DEPARTMENTOFINDUSTRIAL

MANAGEMENTANDTECHNOLOGY

SCHOOLOFCHEMICALENGINEERING

Poly(butylenesuccinate):APromisingBiopolymer

EIRINIADAMOPOULOU

Supervisors
C.D.Papaspyrides,Professor
S.Vouyiouka,Lecturer

Athens,2012

ACKNOWLEDGEMENTS

My thesis would not have been possible without the support of several thoughtful and generous
individuals.ForemostIwanttothankmysupervisorsMrPapaspyrideswhogavemetheopportunityto
work with his team and Mrs Vouyiouka for the knowledge I gained in this field and of course for the
scientificguidance.
I would also like to thank my friends and my parents for their unwavering support over the years
dedicatingtheirjob.
This thesis is dedicated to everybody who helped me and has been by my side all over these months.
Furthermore,Ithankalsomyfamilyandallmyfriendsforalwaysbeingbymyside.

ABSTRACT
Since1976,plasticsplayamajorroleineverydaylifeandtheyhavebeenthemostusedmaterial
intheworld.Plasticsareoftenselectedovertraditionalmaterialsbecauseoftheirsuperiorproperties
andlowercost.Theirversatilityenablestheiruseinapplicationsrangingfromclothingandpackagingto
hightechcomposites.Currentlymanufacturersandresearchersaretargetinginnewbiobasedproducts
able to be used in several applications with packaging in first position. Owing to its biodegradability,
wide processing window, and balanced mechanical properties, poly(butylene succinate) (PBS) and its
copolymershaveattractedmuchinterest.
ThispaperdealswithPBS,thisfairlynewbutalotpromisingbiopolymer.PBSsynthesizedfrom
succinicacidand1,4butanediolexhibitsbalancedperformanceinthermalandmechanicalpropertiesas
well as thermoplastic processability compared with other common plastics. In this paper, synthesis,
processability, properties, biodegradability and recycling of PBS and its copolymers will be outlined. In
addition,industrialproductionandapplicationswillbebrieflysummarized.
In Chapter 1 PBS monomers are presented.The synthesis of succinic acid and butanediol, are
brieflyreviewed,focusingonbiobasedproductionmethods.Moreoverwepresentthemanufacturesof
thesebuildingblocksworldwide.
In Chapter 2 PBS preparation processes are described. Twostep transesterification
polymerization, direct polymerization, condensation polymerization followed by chain extension,
enzymaticpolymerizationanddirectpolyesterificationundermicrowaveirradiationaretheoneswelay
out about. Except of PBS homopolymer, we also introduce the copolymers and branched PBS
preparationprocesses.Industrialproductionisalsoreviewed.
InChapter3,characterizationandcriticalpropertiesofthe biopolymerarepresented,focusing
onmolecularweightdetermination,gelpermeationchromatography,endgroupanalysis,viscosity,melt
flow index, thermal /mechanical properties and transition, melting and thermal degradation and
crystallization.
InChapter4,processingandapplicationsofPBSarebrieflydescribed.Severaltypesofadditives
andprocessingmethodssuchasextrusion,injectionmoldingandthermoformingaredefined.Moreover
thereisareviewonallpossibleapplicationfieldsofPBS.
In Chapter 5, we get through degradability and recycling of PBS. Non enzymatic and enzymatic
hydrolytic degradation, environmental biodegradation and thermal degradation are presented. PBS
possiblerecyclingtechniquesreviewedaremechanicalrecycling,chemicalrecyclingandincineration.

Contents
CHAPTER1:POLY(BUTYLENESUCCINATE)BUILDINGBLOCKS(PBSMONOMERS)........................................10
1.1.SUCCINICACIDTECHNOLOGYANDPROPERTIES.........................................................................................10
1.1.1.INTRODUCTION.................................................................................................................................................10
1.1.2.PROPERTIESOFSUCCINICACIDANDITSAPPLICATIONS...............................................................................................11
1.1.3.SUCCINICACIDPRODUCTIONMETHODS..................................................................................................................15
1.1.4.FERMENTATIONFEEDSTOCKANDMICROORGANISMSINBIOBASEDPRODUCTIONOFSUCCINICACID...................................21
1.1.5.ADVANTAGESANDDISADVANTAGESOFBIOBASEDSUCCINICACIDPRODUCTION..............................................................25
1.2.MANUFACTURERSOFSUCCINICACID........................................................................................................26
1.2.1BIOAMBERINC...................................................................................................................................................27
1.2.2.MYRIANTCORPORATION.....................................................................................................................................29
1.2.3ROYALDSMN.V.ANDROQUETTEFRERESS.A.COLLABORATION................................................................................31
1.2.4.BASF,PURAC,DNPANDMBICOMPANIES............................................................................................................32
1.3.BUTANEDIOLTECHNOLOGYANDPROPERTIES............................................................................................33
CHAPTER2:DEVELOPMENTOFPOLY(BUTYLENESUCCINATE)PREPARATIONPROCESSES..........................37
2.1.INTRODUCTION.........................................................................................................................................37
2.2.STATEOFTHEARTINHOMOPOLYMERSPOLY(BUTYLENESUCCINATE)PREPARATIONPROCESSES..............38
2.2.1.TWOSTEPTRANSESTERIFICATION/ESTERIFICATIONPOLYMERIZATIONROUTEFORPBSSYNTHESIS.......................................40
2.2.2.DIRECTPOLYMERIZATIONFORPBSSYNTHESIS.........................................................................................................42
2.2.3.CONDENSATIONPOLYMERIZATIONFOLLOWEDBYCHAINEXTENSIONFORPOLY(BUTYLENESUCCINATE)................................43
2.2.4.ENZYMATICPOLYMERIZATION(LIPASECATALYZED)SYNTHESISOFPOLY(BUTYLENESUCCINATE).........................................45
2.2.5.DIRECTPOLYESTERIFICATIONUNDERMICROWAVEIRRADATION...................................................................................46
2.3.STATEOFTHEARTINCOPOLYMERANDBRANCHEDPBSPREPARATIONPROCESSES..................................47
2.3.1.POLY(BUTYLENESUCCINATE/ADIPATE)COPOLYMER(PBSA).....................................................................................48
2.3.2.POLY(BUTYLENESUCCINATECOBUTYLENETEREPHTHALOYLDIOXYDIBENZOATES)(PBST)...............................................49
2.3.3.PBSCOPOLYMERSFILLEDWITHTALC.....................................................................................................................51
2.3.4.OTHERCOPOLYMERS..........................................................................................................................................51
2.3.5.BRANCHEDPBS................................................................................................................................................54
2.3.6.PBSBLENDSANDNANOCOMPOSITES.....................................................................................................................55
2.4.CATALYSISINPOLY(BUTYLENESUCCINATE)PREPARATION........................................................................57
2.5.INDUSTRIALPRODUCTIONOFPOLY(BUTYLENESSUCCINATE).....................................................................59
2.5.1.SHOWAHIGHPOLYMERBIONOLLE.......................................................................................................................60
2.5.2.SKCHEMICALSSKYGREEN................................................................................................................................62
2.5.3.MITSUBISHICHEMICALGSPLA..........................................................................................................................62
2.5.4.BIOAMBERMODIFIEDPBS(MPBS)......................................................................................................................63
2.5.5OTHERINDUSTRIES..............................................................................................................................................64
CHAPTER3:CHARACTERIZATIONANDCRITICALPROPERTIESOFPOLY(BUTYLENESUCCINATE)..................65
3.1.METHODSFORPOLY(BUTYLENESUCCINATE)MOLECULARWEIGHTDETERMINATION................................65
3.1.1.GELPERMEATIONCHROMATOGRAPHY...................................................................................................................65
3.1.2.ENDGROUPCONCENTRATIONSANALYSIS................................................................................................................66
3.1.3.SOLUTIONVISCOSITY..........................................................................................................................................68

3.2.MELTFLOWINDEX....................................................................................................................................69
3.3.THERMALPROPERTIESANDTRANSITIONS.................................................................................................71
3.3.1.MELTINGANDTHERMALDEGRADATION.................................................................................................................71
3.3.2.CRYSTALLIZATION...............................................................................................................................................75
3.4.MECHANICALPROPERTIES.........................................................................................................................81
CHAPTER4:PROCESSINGANDAPPLICATIONSOFPOLY(BUTYLENESUCCINATE)..........................................85
4.1.MODIFICATIONOFPOLY(BUTYLENESUCCINATE):USEOFADDITIVES.........................................................85
4.1.1.ANDIOXIDANTSANDSTABILIZERSINPBS................................................................................................................85
4.1.2.ANTIMICROBIALADDITIVESINPBS........................................................................................................................86
4.1.3 COLORANTADDITIVESINPBS...........................................................................................................................86
4.1.4BIODEGRADABILITYACCELERANTS..........................................................................................................................86
4.1.5ADDITIVESAIDRECYCLING....................................................................................................................................86
4.1.6FLAMERETARDANTS...........................................................................................................................................87
4.1.7PROCESSINGAIDS...............................................................................................................................................88
4.1.8STARCHADDITIVES..............................................................................................................................................88
4.1.9PLASTICIZERADDITIVESFORPBS............................................................................................................................89
4.2.PROCESSINGOFPOLY(BUTYLENESUCCINATE)...........................................................................................89
4.2.1.INTRODUCTION.................................................................................................................................................89
4.2.2.EXTRUSION.......................................................................................................................................................92
4.2.3INJECTIONMOLDING............................................................................................................................................94
4.2.4THERMOFORMING..............................................................................................................................................96
4.3.APPLICATIONFIELDSOFPOLYBUTYLENESUCCINATE..................................................................................97
4.3.1.AGRICULTURE...................................................................................................................................................99
4.3.2.PACKAGING....................................................................................................................................................101
4.3.3.MEDICINE......................................................................................................................................................102
4.3.4.DAILYNECESSITYANDOTHERFIELDS....................................................................................................................103
4.3.5.POTENTIAL,NEARFUTUREAPPLICATIONSOFPBS..................................................................................................103
CHAPTER5:DEGRADATIONANDRECYCLINGOFPOLY(BUTYLENESUCCINATE)...........................................105
5.1.DEGRADABILITYOFPBS............................................................................................................................105
5.1.1.NONENZYMATICHYDROLYTICDEGRADATIONOFPBS.............................................................................................105
5.1.2.ENZYMATICHYDROLYTICDEGRADATIONOFPBS....................................................................................................109
5.1.3.ENVIRONMENTALBIODEGRADATIONOFPOLY(BUTYLENESUCCINATE).........................................................................112
5.1.4.THERMALDEGRADATIONOFPBSANDITSCOPOLYMERS..........................................................................................115
5.2.PBSRECYCLINGTECHNIQUES....................................................................................................................116
5.2.1.MECHANICALRECYCLING...................................................................................................................................117
5.2.2.CHEMICALRECYCLING.......................................................................................................................................120
5.2.3.INCINERATION.................................................................................................................................................123
CONCLUSIONS................................................................................................................................................124
REFERENCES...................................................................................................................................................126

Tableoffigures
FIGURE1.1.SUCCINICACIDMARKETSHARES...........................................................................................................13
FIGURE1.2.SUCCINICACIDDERIVATIVES..................................................................................................................14
FIGURE1.3.PRODUCTIONOFSUCCINICACIDFROMDIFFERENTISOLATES(IA,IB,IC,IIB,IIC,IIIBANDIIICARE
DIFFERENTTYPESOFSTRAINS)USINGVARIOUSSYNTHETICCARBONSOURCES......................................................23
FIGURE1.4.SUCCINICACIDMARKET2010................................................................................................................27
FIGURE1.5.BIOSUCCINICANDPRODUCTIONPROCESS...........................................................................................28
FIGURE1.6.BIOBDOPRODUCTIONPROCESS...........................................................................................................36
FIGURE2.1.PBSENDPRODUCTAPPLICATIONS.........................................................................................................38
FIGURE2.2.PBSPRODUCTIONPROCESSTHROUGHTRANSESTERIFICATIONPOLYMERIZATION..............................41
FIGURE2.3.PBSCOPOLYMERSPRODUCTIONPROCESS.............................................................................................48
FIGURE3.1.VARIATIONOFTHECOOHCONTENTWITHTIMEDURINGPOLYCONDESATIONOFPBSATDIFFERENT
TEMPERATURES.........................................................................................................................................................67
FIGURE3.2.VARIATIONOFTHEOHCONTENTWITHTIMEDURINGPOLYCONDESATIONOFPBSATDIFFERENT
TEMPERATURES.........................................................................................................................................................67
FIGURE3.3.RELATIONSHIPWITH
w
M ,MFRANDPROCESSINGMETHODS..............................................................71
FIGURE3.4.DSCCURVESINTHEHEATINGPROCESSFORAPBSRESINISOTHERMALLYCRYSTALLIZEDATTCS.......72
FIGURE3.5.CONVENTIONALDSCTRACESOFTHEMELTINGBEHAVIORAFTERTHENONISOTHERMAL
CRYSTALLIZATION......................................................................................................................................................73
FIGURE3.6.TMDSCTRACESOFTHEMELTINGBEHAVIORAFTERTHENONISOTHERMALCRYSTALLIZATION...........74
FIGURE3.7.COPOLYESTERMELTINGTEMPERATUREANDHEATOFFUSIONASAFUNCTIONOFCOMPOSITION...75
FIGURE3.8.PBSCRYSTALLIZEDAT70C(A)AND90C(B)ASOBSERVEDUNDERTHEPOLARIZEDOPTICAL
MICROSCOPE..............................................................................................................................................................76
FIGURE3.9.ATOMICFORCEMICROSCOPEOFPBSBANDEDSPHERULITES...............................................................76
FIGURE3.10.AFMIMAGESOFTHELAMELLAEINAPBSBANEDSPHERULITE...........................................................77
FIGURE3.11.TYPICALXRAYDIFFRACTIONDIAGRAMMOFMELTCRYSTALLIZEDPBSFILM...................................79
FIGURE3.12.WAXDDIAGRAMMOFPBST..................................................................................................................80
FIGURE3.13.WAXDDIAGRAMMOFPBSA................................................................................................................80
FIGURE3.14.DSCDIAGRAMMOFPBSF......................................................................................................................81
FIGURE3.15.TENSILESTRENGTHDEPENDINGONTEMPERATUREFORTHREETYPESOFPOLYESTERS....................82
FIGURE3.16.TENSILEPROPERTIESOFLINEARANDLONGCHAINBRANCHEDPBSWITHDIFFERENTBUTANEDIOL
CONTENT.....................................................................................................................................................................83
FIGURE3.17.MECHANICALPROPERTIESOFPBST......................................................................................................84
FIGURE4.1.PLASTICSPYRAMIDDATA:PLASTICSEUROPE2008..............................................................................87

FIGURE4.2.DYNAMICCOMPLEXVISCOSITY(|*|)(A),STORAGEMODULUS(B),LOSSMODULUS(C),AND
DAMPINGFACTOR(D)ASAFUNCTIONOFFREQUENCEOFLINEARPBSANDLONGCHAINBRANCHEDPBS..........90
FIGURE4.3.TYPICALDRYINGSYSTEM........................................................................................................................91
FIGURE4.4.TYPICALSINGLESCREWEXTRUDER........................................................................................................92
FIGURE4.5.TYPICALINJECTIONMOLDINGASSEMBLY...............................................................................................94
FIGURE4.6.TYPICALVACCUMTHERMOFORMINHASSEMBLY..................................................................................96
FIGURE4.7.AGRICULTURALMULCHINGFILMS.......................................................................................................100
FIGURE4.8.COMPOSTABLEBAGS............................................................................................................................101
FIGURE4.9.FOODPACKAGINGANDUTENSILS........................................................................................................102
FIGURE5.1PBSANDPBSADEGRADATIONRATEAT30C........................................................................................106
FIGURE5.2WEIGHTREMAINING(%)COMPAREDWITHDAY0VALUESDEGRADATIONINPHOSPHATEBUFFERED
SOLUTION.................................................................................................................................................................106
FIGURE5.3MW(%)REMAININGCOMPAREDWITHDAY0VALUESDEGRADATIONINPHOSPHATEBUFFERED
SOLUTION.................................................................................................................................................................107
FIGURE5.4.SEMPICTURESOFDEGRADEDPBSCRYSTALLIZEDATDIFFERENTTEMPERATURESAFTERHYDROLYSIS
FOR9DAYSA)MELTQUENCHEDB)ISOTHERMALLYCRYSTALLIZED25CC)ISOTHERMALLYCRYSTALLIZED60CD)
MELTQUENCHEDANDANNEALEDAT75C.............................................................................................................108
FIGURE5.5.WEIGHTLOSSOFPBSCRYSTALLIZEDATDIFFERENTTEMPERATURES.................................................109
FIGURE5.6.MASSREMAININGOFVARIOUSPBSANDPBSLSAMPLESASAFUNCTIONOFTIME.THESAMPLESWERE
INCUBATEDWITHLIPASEPS1AT508CANDPH6.0................................................................................................110
FIGURE5.7.PBSTWEIGHTLOSSDEGRADEDBYLIPASEFROMPSEUDOMONAS......................................................111
FIGURE5.8.PBSAWEIGHTLOSSDEGRADEDBYLIPASEFROMCANDIDACYLINRACEA...........................................111
FIGURE5.9.SEMMICROGRAPHSOFPBSHOMOPOLYMERANDPBSACOPOLYESTERSAFTERSOILBURIAL............113
FIGURE5.10.PBSDEGRADATIONINACTIVATEDSLUDGEA)BEFOREDEGRADATIONB)1WEEKC)2WEEKSD)4
WEEKSE)6WEEKSF)10WEEKS................................................................................................................................114
FIGURE5.11.BIODEGRADATIONOFPBSINACTIVATEDSLUDGEWITHVISCOSITYA)1,793DL/GB)1.049DL/G..114
FIGURE5.1.BIODEGRADABLEMATERIALRECYCLING.............................................................................................118
FIGURE5.2.PBSHOMOPOLYMERMWAGAINSTTHENUMBEROFREPROCESSINGWITHOUTWATER................119
FIGURE5.3.PBSMWAGAINSTIMMERSIONANDREPROCESSING..........................................................................119
FIGURE5.4.THEBENDINGPROPERTIESOFPBSAGAINSTTHENUMBEROFREPROCESSING.................................120
FIGURE5.5.THEBENDINGPROPERTIESOFPBSAGAINSTTHENUMBEROFREPROCESSING.................................120

ListofTables
TABLE1.1.IDENTIFICATIONOFTHEACTUALANDPOTENTIALPATHWAYSFROMSUGAR........................................11
TABLE1.2.PHYSICALPROPERTIESOFSUCCINICACID................................................................................................12
TABLE1.4.SUCCINICACIDPRODUCTIONBYVARIOUSMICROORGANISMS..............................................................24
TABLE1.5.COMPARISONBETWEENCHEMICALANDFERMENTATIVEROUTES.........................................................26
TABLE1.6.BIOAMBERSSUCCINICACIDCHEMICALPROPERTIES..............................................................................28
TABLE1.7.MYRIANTSSUCCINICACIDCHEMICALPROPERTIES.................................................................................30
TABLE2.1.PBSANDITSCOPOLYMERSPRODUCTIONPARAMETERS.........................................................................38
TABLE2.2.PBSANDCOPOLYMERSPRODUCERS........................................................................................................60
TABLE2.3.PHYSICALPROPERTIESOFBIONOLLEANDITSGRADES............................................................................61
TABLE2.4.PHYSICALPROPERTIES..............................................................................................................................62
TABLE2.5.PHYSICALPROPERTIESOFGSPLAGRADES...............................................................................................63
TABLE3.1.MELTFLOWINDEXMEASURESFORBIONOLLE........................................................................................70
TABLE3.2.UNITCELLPARAMETERSOFTHEAANDBFORMSOFPBS.......................................................................78
TABLE3.3.PROPERTIESOFPBSANDITSGRADES.......................................................................................................84
TABLE4.1.MELTFLOWRATEANDPROCESSINGMETHODSFORDIFFERENTPBSGRADES.......................................91
TABLE4.2.OPTIMUMDRYINGCONDITIONS..............................................................................................................92
TABLE4.3.PROCESSINGDATAFOREXTRUSIONMOULDING.....................................................................................93
TABLE4.4.PROCESSINGDATAFORINJECTIONMOULDING......................................................................................95
TABLE4.5.ADVANTAGESANDDISADVANTAGESOFTHEPROCESS...........................................................................97
TABLE4.6.INDUSTRIESANDDEGRADABLEPOLYMERSAPPLICATIONS(PBS,PLA,PHBECT.)....................................98
TABLE4.7.GLOBALMARKETOFBIODEGRADABLEPOLYMERS(MILLIONLBS)..........................................................98
TABLE4.8.MAINAPPLICATIONSFORPBSANDPBSAINGLOBAL...............................................................................99
TABLE4.9.PBSPOTENTIALFUTUREAPPLICATIONS.................................................................................................104
TABLE5.1.POLYMERSTRUCTUREANDBIODEGRADABILITYINDIFFERENTENVIRONMENTS..................................112

ListofSchemes
SCHEME1.1.MOLECULARFORMULAFORSUCCINICACID........................................................................................10
SCHEME1.2.HYDROGENATIONOFMALEICACIDTOSUCCINICACID.........................................................................15
SCHEME1.3.BACTERIABASEDPRODUCTIONOFSUCCINICACID..............................................................................15
SCHEME1.4.YEASTBASEDPRODUCTIONOFSUCCINICACID....................................................................................15
SCHEME1.5.REACTIVEEXTRACTIONFORSUCCINICACID........................................................................................16
SCHEME1.6.SUCCINICACIDFROMMALEICANHYDRIDE..........................................................................................17
SCHEME1.7.SUCCINICACIDTHROUGHELECTROREDUCTIONOFMALEICACID........................................................17
SCHEME1.8.SUCCINICACIDPRODUCTIONFROMACETYLENE,CARBONMONOXIDEANDWATER.........................17
SCHEME1.9.SIMPLIFIEDMETABOLICMAPOFE.COLIFERMENTATIONFORSUCCINICACIDPRODUCTION............19
SCHEME1.10.CHEMISTRYOFTHECONVERSIONOFSUCCINICACIDTOBUTANEDIOL/TETRAHYDROFURAN.........34
SCHEME1.11.REACTIONSCHEMEOFMALEICANHYDRIDEHYDROGENATIONTO
BUTANEDIOL/TETRAHYDROFURAN............................................................................................................................35
SCHEME2.1.POLY(BUTYLENESUCCINATE)REPEATINGUNIT....................................................................................37
SCHEME2.2.PBSSYNTHESISTHROUGHTRANSSTERIFICATIONPOLYMERIZATION...................................................41
SCHEME2.3.TWOSTAGESMELTPOLUCONDESATIONFORMULA............................................................................42
SCHEME2.4.PBSCHAINEXTENSIONWITHBISOXAZOLINEASACHAINEXTENDER.................................................44
SCHEME2.5.THECHAINEXTENSIONOFHOPBSOHWITHABCWITHORWITHOUTTHEPTSACATALYST.............45
SCHEME2.6LIPASECATALYZEDCONDENSATIONPOLYMERIZATIONFORPBS.........................................................46
SCHEME2.7.SYNTHESISOFPBSUNDERMICROWAVEIRRADIATION.......................................................................47
SCHEME2.8.PBSACOPOLYMERSSYNTHESIS.............................................................................................................48
SCHEME2.9.CHEMICALSTRUCTIRESOFMONOMERSANDOLIGOMERS..................................................................49
SCHEME2.10.PBSTCOPOLYMERSSYNTHESIS...........................................................................................................50
SCHEME2.11.PBESTSTRUCTURALUNIT....................................................................................................................51
SCHEME2.12.PBESTSYNTHESIS.................................................................................................................................52
SCHEME2.13HIGHMOLECULARPBSF.......................................................................................................................52
SCHEME2.14.SYNTHESISROUTEOFPB
X
I
Y
E
Z
S............................................................................................................53
SCHEME2.15.SYNTHESISOFLONGCHAINBRANCHEDPBS......................................................................................54
SCHEME2.16PBSASTARCHBLEND.........................................................................................................................55
SCHEME2.17.FORMATIONOFURETHANEBONDSINHIGHMOLECULARPBS..........................................................56
SCHEME5.1.THERMALDEGRADATIONMECHANISMOFPBS..................................................................................116

10

CHAPTER1:POLY(BUTYLENESUCCINATE)BUILDINGBLOCKS
(PBSMONOMERS)

1.1.Succinicacidtechnologyandproperties
1.1.1.Introduction
In2004,theU.S.DepartmentofEnergy(DOE)[1]releasedareportidentifying12chemicalsthat
could be produced from sugars, through microbial fermentation. These building blocks were of great
interestbecausetheycouldbeconvertedintovarioushighvaluebiobasedchemicalsandmaterials.The
maincriteriaforthetop12chemicalswerethefollowing:
1)multiplefunctionalitiessuitableforfurtherconversionasderivativesormolecularfamilies
2)productionfrombothlignocellulosicsandstarch
3)acarbonnumberclassificationframeworkofonetosixcarboncompounds(C1C6monomers)
4)nonaromaticsderivedfromlignin
5)notalreadysupercommoditychemicals
6)strategicfitforlignocellulosicandstarchbiomasswithinthebiorefinery
7)valueofthebuildingblockanditsderivativesasareplacementornovelchemical
8) the technical complexity of each part of the pathway transformation (sugars to building blocks and
buildingblockstoderivatives)
9)thebuildingblockspotentialtoproducefamiliesorgroupsofsimilarderivatives
Atthetopofthelistwassuccinicacid.Succinicacidisanimportantplatformmoleculederived
frompetrochemicalorbiobasedfeedstocksandcanbetransformedintoawiderangeofchemicalsand
polymers.Petroleumorcoalbasedsuccinicacidischeaperthanbiobasedbutwithfuturedevelopment
itwillbecomecompetitive.Concerningsuccinicacid,itsmolecularformulaanditsactual andpotential
pathwaysfromsugarareshowninscheme1.1andTable1.1respectively.

HO
O
O
OH

Scheme1.1.Molecularformulaforsuccinicacid

11

Table1.1.Identificationoftheactualandpotentialpathwaysfromsugar[1]
Building
block
Yeastof
fungal
Bacterial
Yeastof
fungal
Bacterial
Chemicaland
catalyticprocesses
Biotransformation
Succinic
acid
Aerobicfermentation
Anaerobic
fermentation
CHEMenzymetransformations
x x x x

1.1.2.Propertiesofsuccinicacidanditsapplications
Succinic acid or butanedioic acid belongs to dicarboxylic acids. Their general formula is
HOOC(CH
2
)nCOOH,wheren=0foroxalicacid,n=1formalonicacid,n=2forsuccinicacid,n=3forglutaric
acidetc.Therangeofcarbonchainlengthisfrom2,andlongerthanC24isveryrare.Carboxylicacids
have industrial application directly or indirectly through their derivatives, such as acid halides, esters,
salts,andanhydrideforms.Dicarboxylicacidsareusefulinavarietyofindustrialapplicationsincluding:
Plasticizersforpolymers
Biodegradablesolventsandlubricants
Engineeringplastics
Epoxycuringagent
Adhesiveandpowdercoating
Corrosioninhibitor
Perfumeryandpharmaceutical
Electrolyte
Therearealmostinnumerableestersobtainedfromcarboxylicacids.Estersareformedthrough
condensation reaction between an acid and an alcohol. Lower chain esters are used as flavoring base
materials, plasticizers, solvent carriers and coupling agents. Higher chain compounds are used as
components in metalworking fluids, surfactants, lubricants, detergents, oiling agents, emulsifiers,
wetting agents textile treatments and emollients. They are also used as intermediates for the
manufactureofavarietyoftargetcompounds.Estersprovideawiderangeofviscosity,specificgravity,
vapor pressure, boiling point, and other physical and chemical properties for the proper application
selections.
Focusingonsuccinicacid,itoccursnaturallyinplantandanimaltissues.Itplaysasignificantrole
in intermediary metabolism (Krebs cycle) in the body. Krebs cycle (also called citric acid cycle,

12

tricarboxylicacidcycle)isasequenceprocessofenzymaticreaction,inwhichatwocarbonacetylunitis
oxidizedtocarbondioxideandwatertoprovideenergyintheformofhighenergyphosphatebonds.
Succinicacidisacolorlesscrystallinesolid,solubleinwater,slightlydissolvedinethanol,ether,
acetone and glycerin, not dissolved in benzene, carbon sulfide, carbon tetrachloride and oil ether. The
propertiesofsuccinicacidarelistedinthetable1.2.[2,3].

Table1.2.Physicalpropertiesofsuccinicacid[3]
CASNumber 110156
Appearance WhiteCrystallineProduct
MolecularFormula (CH
2
COOH)
2

PhysicalState Odorlesswhitecrystals
MolecularWeight 118.09g/mole
MeltingPoint 188C
BoilingPointDecomposes at235C
SpecificGravity 1.5625C/4C
Assay(drybasis) 99.5%w/w
Solubility
100g/100mlat100Cinwater
7.69g/100mlat25C
ResidueonIgnition 0.025%w/w
LeadContent 2mg/kg
ArsenicContent 3mg/kg
MoistureContent 0.5%w/w
pKA1 4.21
pKA2 5.64

Traditionally, succinic acid is used in four application regions [4]. The largest one is as a
surfactant, extender and foaming agent. The second region is as an ion chelator, where it is used in
ordertopreventthecorrosionandspotcorrosionofmetalintheelectroplatingindustry.Thethirdisas
an acidulant, a pH regulator and flavoring agent in the food and drink industry and the fourth is the
production of pharmaceutical products, including antibiotics, amino acids, and vitamins. The total
marketsizeforthesefourexistingusesofsuccinicacidismorethan$400.000.000peryearconcerning
acurrentworldwideuseofabout20.00030.000tons/year,withanincreasingrateof10%ayear[5].

13

Figure1.1.Succinicacidmarketshares[4]

In addition, succinic acid is an important chemical building block and the world market of its
derivatives has a potential that is estimated to be 270.000 tons/year [5,6]. Taking into account the
current improvements in the microbiological succinic acid production, which will lead to a competitive
price, the production routes from succinic acid will become economically more viable and more
important.
A major group of possible succinic acid derivatives consists of: butanediol, tetrahydrofuran,
gammabutyrolactone, adipic acid, Nmethyl pyrrolidinone, 2pyrrolidinone, succinic acid esters and
succinatesalts(figure1.2)[7].Butanediolandsuccinicacidpolyesters(suchaspoly(butylenesuccinate),
PBS)aregoingtobepresentedlaterinmoredetail.
Butanediol:isarawmaterialusedfor thesynthesisoffilms,fibers,engineering plasticsandadhesives.
Biological routes are the most widespread used. There is a great interest in biobased butanediol
concerningthereductionoftheuseofpetroleumbasedfeedstocksinlightofglobaloilprices.
Tetrahydrofuran(THF):isasolventandkeyingredientofadhesives,printinginks,andmagnetictapes.It
is also suggested as a feedstock for an alternative of the adipic acid production via carbonylation, but
thisrouteisnotthatcompetitivewiththecurrentone[8].Ontheotherhand,THFisaprecursorforthe
production of poly (tetramethylene ether glycol) (PTMEG), used in the production of polyurethane
polymer[9,4].
Gammabutyrolactone(GBL):isusedasasolventforpolymersandalcohols,asachemicalintermediate,
a raw material for pharmaceuticals, and as a component of herbicides, pharmaceuticals and rubber
additives[10,11].TheGBLcanalsobeconvertedto2pyrrolidone.Morethan230.000tonsofGBLare
producedperyearworldwide.

PLASTICINDUSTRY
ELECTROPLATING
INDUSTRY
FOODINDUSTRY
PHARMACEUTICALS

14

Adipicacid:isarawmaterialchemicalusedinthemanufactureoflubricants,foamsandfoodproducts.
Benzene is the main feedstock for adipic acid production but there are also two alternative methods
involvingsuccinate[4,8,12].Adipicacidisalsotheprecursortonylon6,6.
Pyrrolidinones:arematerialsthatcanbederivedfromGBL,andaddressalargesolventmarket.Succinic
acid through the fermentative production of diammonium succinate can be directly converted to
pyrrolidinones.
Succinate salts: could replace current salts by offering improved performance characteristics and more
neutraleffectsonsurfacesandtheenvironment.Succinicsaltsmayalsobeusedasadditivestoanimal
feed.

Figure1.2.Succinicacidderivatives[4]

15

1.1.3.Succinicacidproductionmethods
The common method of synthesis of petrochemical succinic acid is the catalytic hydrogenation
ofmaleicacidoritsanhydride(scheme1.2).
HO
H
H
OH
O O
3 atm H
2
Pd
OH
O
H
H
H
H
O
O

Scheme1.2.Hydrogenationofmaleicacidtosuccinicacid

The lack of renewability and the rising price of the fossil resources have limited the use of
petrochemicalsuccinicacidforawiderangeofapplications.Consequently,theinterestforfermentation
methodsarisesrapidly.Biosuccinicacidisproducedbyfermentationofstarchoroligosaccharides(C5,
C6 sugars) containing renewable resources. This fermentation of carbohydrates may also yield other
valuable chemicals, such as lactic acid, acetic acid, formic acid, and alcohols. The yield of all these
chemicals may vary according to the microorganism and cultivation technology used. The forlumas of
thefermentationreactiosarepresentedinschemes1.3and1.4.

glucose +CO
2
+ KOH K
2
SA (succinicsalt) +ATP (energy)
K
2
SA (succinic salt) +H
2
SO
4
(sufuric acid) K
2
SO
4
(salt) +H
2
SA (succinic acid)

Scheme1.3.Bacteriabasedproductionofsuccinicacid

glucose +CO
2
H
2
SA (succinicacid) +ATP (energy)

Scheme1.4.Yeastbasedproductionofsuccinicacid

Although there are a few industries producing biobased succinic acid in commercial scale, it is
important to mention that a minimum productivity of 2,5 g/l/h needs to be achieved in order for the
process to be economically competitive. In addition, it is essential for commercial fermentations to
operateusingminimalnutrients.Expensivenutrientcomponents,suchasyeastextractandbiotin,must

16

be eliminated. The nutrient requirements should be limited to the use of corn steep liquor or
equivalent. In an ideal situation, the fermentation is carried out at low pH, most preferably without
requiring any neutralization. The cost of neutralization is not necessarily cost prohibitive, but the
conversionofthesalttothefreeaciddoesaddsignificantcost[1].
When succinic acid is synthesized from petrochemical sources, it is labeled as chemically
produced, whereas succinic acid from bioproduction is considered naturally produced as it is sourced
frombiomass[4]. This distinctionofchemicalversusnaturalproductioncan change theareasinwhich
succinic acid can be used as well as affect the selling price. Industries, such as foods and
pharmaceuticals will prefer to use succinic acid produced from renewable resources to avoid potential
healthhazardsfromproductionresidues,eventhoughtheproductisidenticalthroughbothproduction
methods[13].

PetrochemicalProductionofsuccinicacid
Succinicacid ismostcommonlyproducedby hydrogenationof maleicanhydrideormaleicacid
or recovered from a byproduct stream in the production of adipic acid. Some industrial petrochemical
routesappliedforsuccinicacidproductionare:
Separation of succinic from a mixture of different carboxylic acids after paraffins oxidation.The
followingreactionsoccurinthereactiveextractionofcarboxylicacidswithtertiaryamineextractants
(scheme1.5).

(I) HA H
+
+A
-
(II) R
3
N +H
+
R
3
NH
+
(III) R
3
NH
+
+A
-
R
3
NHA
(IV) R
3
N +HA R
3
NHA

Scheme1.5.Reactiveextractionforsuccinicacid

Catalytic hydrogenation of maleic acid or transmaleic acid. The reaction from maleic anhydride to
succinic acid begins by hydrolysis, breaking one of the single bonds between carbon and oxygen,
formingmaleicacid.Theadditionofhydrogenbreaksthecarboncarbondoublebondandcompletes
thereaction,formingsuccinicacidasitisshowninscheme1.6:

17

H
2
(g) H
2
(l) (1)
catalyst
C
4
H
4
O
4
+H
2
(l) C
4
H
6
O
4
(2)

Scheme1.6.Succinicacidfrommaleicanhydride

Electrochemical synthesis from maleic anhydride in a bipolar membrane or nonmembrane cell. The
electroreduction of maleic acid is a two electron, irreversible, diffusionlimited process as shown in
scheme1.7:

HOOC - CH
CH - COOH +2H
+
+2e
-
HOOC - CH
2
- CH
2
- COOH

Scheme1.7.Succinicacidthroughelectroreductionofmaleicacid

Production from acetylene, carbon monoxide, and water catalyzed by [CO(CO)

4
] in an acid medium
underapressureof2,9449,03MPaat80250C.Themethodsknownforthepreparationofsuccinic
acidcompriseatleasttwostagesaccordingtotheequationsinscheme1.8:

CH
CH +2CO +2CH
3
OH
Co
CH
3
OOC - CH
2
- CH
2
- COOH
3
H
+
+2H
2
O
HOOC - CH
2
-CH
2
- COOH +2HCH
3
OH
1)
2)
CH
CH +2CO +K
2
CO
3
[K
2
Ni(CN)
4
]
KOOC - CH
2
- CH
2
- COOK
2HCl
HOOC - CH
2
- CH
2
- COOH +2KC

Scheme1.8.Succinicacidproductionfromacetylene,carbonmonoxideandwater

Amongthem,electrochemicalsynthesisfrommaleicanhydrideisagenerallyappliedprocessfor
succinicacid,whichhastheadvantageofhighyield,lowcost,highpurityofthefinalproduct,andvery
lowornowasteformation.Succinicacidproduced bytheelectrochemicalprocesscanbe usedinfood
andpharmaceuticals[14].Theusedmaleicanhydrideisproducedfromnbutaneorbenzene[15,13].
Various heterogeneous catalysts have been studied concerning the aqueous phase
hydrogenationofmaleicacid tosuccinicacid.Pd/Al
2
O
3
catalyst,inatrickle bedtypereactor.Effectsof

18

PtorPdonvarioussupportsintheaqueousphaseofhydrogenationhavealsobeeninvestigated.Ithas
been reported to reach a 99,5% yield when a mixture of maleic acid, water and Pd/C catalyst is
autoclaved at 100 C with hydrogen bubbling .The hydrogenation of maleic acid in aqueous cobalt
chlorideandpotassiumchloridesolutionshasbeenreportedtogive41%succinicacidinthepresenceof
a Zn/Hg catalyst and 22% in its absence. Succinic acid has also been prepared chemically by treating
maleicacidwith50%H
3
PO
2
atroomtemperatureinaqueousNaOH/EtOHwithanaverageyieldof83%.
Ruisalsoknowntobeagoodcatalystforhydrogenationinthepresenceofwater.Further,itischeaper
thanPdandPtanditisequallyeffectiveforhydrogenationoffumaricacidtosuccinicacid.Succinicacid
mayalsobeobtainedathighyieldsbythehydrationofsuccinicanhydrideinanautoclaveat200C.
Although the yields in some of the above processes are good, their practicability is limited by
several factors such as: the requirement of adding a supporting electrolyte in the electrochemical cell,
the saturation of the medium with succinic acid before electrolysis, the need for costly catalysts or
reagents, and the separation of supporting electrolyte, catalyst and/or unreacted reagents from the
reactionmixture/product.
Except hydrogenation, succinic acid can be synthesized in excellent yields by the galvanostatic
reductionofmaleicacidatstainlesssteel,CuandPbcathodesinanionexchangemembraneflowcell.
This method demonstrates the advantages of using a highly conductive solid ion exchange membrane
filmbetweenthetwoelectrodesinaflowcell,whichemploysacatholytewithoutsupportingelectrolyte
for the electroreduction of maleic acid. Hence, the requirement of additional separation steps,
otherwiserequiredinconventionalmethods,ismaderedundant.Cyclicvoltammetricstudiesindicatea
twoelectrondiffusionlimitedirreversiblereductionofmaleicacidtosuccinicacid[16].
Industries producing petrochemical succinic acid all over the world are following patented
routesregardingcatalysts,waterreductionandhighyieldatalowcostbysupplyinganaqueoussolution
ofmaleicacid.Inthiscasethesolutionhasaconcentrationof1060wt%,preferably2040wt%andthe
hydrogenpressureissetatabout550kg/cmat60150C.

BiobasedProductionofsuccinicacid
Succinicacidcanbeproducedthroughfermentationbybacteriaisolatedfromruminantanimals,
convertingglucosetosuccinicacid,alongaportionofthereductivecycleoftricarboxylicacid(TCA)cycle
[17]. Fermentation production has attracted interest the last decades regarding increased knowledge
and metabolic technology. To have an economically viable biosuccinic acid process, it should be
competitive with the current applied chemical process. Based on the petrochemical analogue (maleic
anhydride),theU.S.DepartmentofEnergyhavesetthetargetedproductionpriceofbiosuccinicacidat
0,45 dollars/kg. The most important parameters determining the viability of a method are: 1) yield 2)
(purity)and3)productionrate.Onlyyieldisrelatedtothecostofrawfeedstock.Wilke[18,6]calculated

19

thatayieldof100%,arateof3g/l/handpurityupto250g/lwouldresultinatotalproductioncostof
0,45dollars/kg.
First reaction step in a typical fermentation process is glucose conversion to glucose6
phosphatebyhexokinase.Nextfollowstheproductionofphosphoenolpuryvate(PEP),fromwhichthe
metabolic route can take one of two paths depending on the amount of CO
2
available in the system.
WithamblesupplyofCO
2,
themicroorganismfavorssuccinicacidproduction.Onthecontrary,ifthereis
not enough CO
2
the metabolic pathway leads to different end products, such as formate, ethanol and
acetate[7].Nextreactionishydrogenationinordertoproducemalate,whichisconvertedtofumarate
byfumarasewithwaterremoval.Inthisway,succinateinionicstateisformed,whichiscommonasthe
pHrangeofproductionisabovepKavaluesforsuccinicacid[4].Succinicacidasanendproductcanbe
created by protonating the succinate ion. A theoretical yield of succinic acid production has been
estimated to 1,17 moles per mole of glucose based on stoichiometry by McKinlay [7]. All the reaction
stepsareshowninscheme1.10.

Scheme1.9.SimplifiedmetabolicmapofE.Colifermentationforsuccinicacidproduction[7]

Fermentationisaproductionmethodthathasbyproducts.Aceticacid,formicacidaresomeof
them and they are observed in concentrations 9,2 g/l and 6,1 g/l respectively. Although the values are
reallysmallcomparingtosuccinicacidproductionof27,2g/l,theseparationisthemostexpensiveand
time consuming step of the whole process [19]. Concerning the downstream purification cost, this
normally accounts more than 60 % of the total production cost and it is crucial to develop a more
economicalprocesspurificationprocessforsuccinicacid.

20

Several methods for the succinic acid recovery and purification have been developed including
reactive extraction, ion exchange resins, electrodialysis, precipitation and nanofiltration [20]. Glassner
and Datta [21] suggested a conventional electrodialysis system to remove succinic acid from the
fermentation broth after ultrafiltration. In this method, ionized compounds are separated from non
ionizedcompoundsbyionexchange.HongandHong[22]havestatedthatelectrodialysiscouldbeused
in conjunctionwithother separationmethods,notablyaminebasedextraction[20]. Electrodialysisisa
method that has significant potential, but there are also some shortcomings with using this system on
anindustrialscale.Oneofthemostglaringproblemsisthatelectrodialysisrequiresenergytofunction.
Given that energy costs are on the rise and electricity may come from nonrenewable resources, it
would seem counterintuitive to use this method, since the intent of succinic acid production via
fermentation is to reduce the use of fossil fuels and provide a more environmentally friendly process
[23].Asuccinicacidpurityof80%canbeachieved.
Precipitating succinic acid out of solution is a separation process that was first proposed by
Datta [24]. In this process, after the fermentation reaches completion, solids are centrifuged and
separated out of the fermentation broth by addition of calcium dihydroxide, which simultaneously
neutralizes the fermentation broth. Succinic acid is recovered by filtration and further purified by acid
and ion exchangers. Precipitation appears to be the most common and simplest method for succinic
acidseparation,butitisalsooneofthemostinefficientprocessesfromanenvironmentalandeconomic
standpoint.Withthisdownstreamprocess,apurityof95%canbeachieved.
Theextractionofsuccinicacidwithanaminebasedextractionmethodhasbeeninvestigatedby
Huh[26]. It is a promising method of separation because separation is possible insitu at room
temperature and pressure, so no pretreatment is required for this method to function properly [26].
Thisprocessisbasedonreversiblereactionbetweenextractantandextractedcarboxylicacid.Thereare
additionalstepsthatmust takeplacetocontinue theprocessof separatingandpurifyingsuccinicacid,
such as vacuum distillation and crystallization, but given that the byproduct organic acids have been
removed,thisstepbecomeseasier,reachingafinalpurityof99,8%withayieldof73,1%[20,23].
Nanofiltration is a relatively new method for separating out the different byproducts of the
fermentation broth from succinate. Kang and Chang [27] studied how two different nanofiltration
membranes separated the main products of glucose fermentation by A. succinogenes, including
succinate, formate, and acetate. The results indicated that the filters had a very high retention of
succinate, the only divalent ion product [20]. While nanofiltration shows promise there are still some
aspectsoftheprocessthatarenotaddressed,suchasthepriceofmembranes,membranefoulingand
theapplicationofthisseparationmethodinrealfermentorbroth.

21

1.1.4.Fermentationfeedstockandmicroorganismsinbiobasedproductionofsuccinic
acid
Among many fermentation feedstock studied, cane molasses, whey, glycerol, lignocellulosic
hydrolyzatesandcerealshaveproventobeadequateforfermentationprocesses.Canemolassesisaby
product of sugar industry consisting of water, carbohydrates, heavy metals, colloids, vitamins and
nitrogenouscompounds[15].Wheyisasidestreamfrommilkindustryanditisalreadyusedinseveral
fermentation processes with great success. Succinate production is one of them as well. Glycerol is
increasingconsiderablyduetobiodieselproduction.Itismeanttobeaverysuitablecarbonsourcefor
succinicacidproductionbyA.succiniproducens,withhighyieldsandlessbyproducts.
Lignocellulosic material can also serve as a carbon source and replace glucose. Untreated
hydrolysates can be used but with approximately half of the productivity of the alkaline treated
material.Atlast,anovelbiorefiningconcepthasbeenintroducedregardingthebiosynthesisofsuccinic
acidfromwheatflour.
Various microorganisms and strains have been reported to produce succinic acid. However the
choice of the production host is very diverse. A.succinogenes and A. succinoproducens were the first
identifiednaturalsuccinicoverproducers.
A.succinogenesisafacultativeanaerobic, capnophilic, mesophilic,pleomorphic, Gramnegativerod
andmemberofthePasteurellaceaefamilyisolatedfrombovineruminal.Thisstrainshowsadistinctive
abilitytoproducearelativelylargeamountofsuccinicacidfromabroadrangeofcarbonsourcessuch
as arabinose, cellobiose, fructose, galactose, glucose, lactose, maltose, mannitol, mannose, sorbitol,
sucrose, xylose or salicin under anaerobic condition [28]. Guettler et al. [29] investigated also 130Z
strain which was able to produce larger amounts of succinic acid and were more resistant to it.
A.succinogenes variants can produce succinate up to 110 g /l at a yield of 8387 % if the pH is
maintainedwithmagnesium[28,30].Strain130Zproduced66,4g/lsuccinicacidbyconsuming98,3g/l
ofglycolafter84hoffermentation.Comparedtotheothermajorproducersofsuccinicacid,thereare
several advantages of this bacterium including tolerance to high levels of substrate, high resistance to
product inhibition, and high production rate. It also has a high tolerance of oxygen, low production of
unwanted acid byproducts and can use a number of substrates in comparison to other succinic acid
producingbacteria.ManysourcesstatethatActinobacillussuccinogenesisthemicroorganismofchoice
forcreatinganindustrialprocess,havingahightoleranceofsuccinicacid[31].
A.succinoproducensisastrictlyanaerobic,capnophilic,mesophilic,pleomorphic,gramnegative
spiral rod and an opportunistic pathogen, isolated from the throat and feces of a beagle dog [32]. The
broad spectrum of carbon sources it ferments has allowed succinate production of several complex
sugar mixtures originating from for instance wood hydrolysates and whey. Lee et al. [20] reported the

22

useofglycerolascarbonsourcewhichleadstoanincreasedsuccinicyield(1,33mole/mole).Astypicala
capnophilic A. succiniciproducens, requires high carbon dioxide for efficient growth. Addition of
hydrogengastothesparginggascanalsoincreaseyieldsandproductionratesandthatbecauseofthe
increase in NADH in the cell. Lee et al. reported also a maximum succinic acid yield of 0,91 mole/mole
andamaximumproductivityof1,8g/l/h.
M.succiniciproducensisafacultativeanaerobic,capnophilic,mesophilic,gramnegativerodand
similartoA.succinogenes,andamemberofthePasteurellaceaefamily.M.succiniciproducensferments
a wide variety of substrates and hydrolysates [17]. A disadvantage of this strain is the auxotrophies
exhibitions. In contrast to A. succinogenes, M. succiniciproducens has a complete TCA cycle and can
efficiently grow in aerobic as well as in anaerobic conditions. It produces succinic acid as a major
product,aceticandformicacidsasthesecondmajoronesfromvariouscarbonsourcesunder100%CO
2

condition at pH of 6,07,5. M. succiniciproducens leads to a succinic acid productivity of 3,9 g/l/h [17].
Moreover,theefficientandeconomicalproductionofsuccinicacidwaspossiblebyusingawheybased
mediumcontainingcornsteepliquorinsteadofyeastextract.Inbatchcultures,thefinalsuccinicacid
concentration of 11,73 g /l was obtained from the pretreated wood hydrolysate based medium,
resulting in a succinic acid yield of 56% and a succinic acid productivity of 1,17 g/ l/ h while the
correspondingcontinuousculturesgavethesuccinicacidyieldandproductivityof55%and3,19g/l/h,
respectively[33].
E.coliunderanaerobicconditionsproducesamixtureoforganicacids.Inordertoincreasethe
yieldofsuccinicacidinrelativetootheracids,differentE.colimutantshavebeendeveloped.Twosuch
mutantsareAFP184andAFP111.TherecombinantEscherichiacoliAFP184strainshowedaproduction
rate and yield substantially higher those of natural producers. Productivity up to 3 g/ l/h was obtained
by dualphase fermentations of sugar in high concentrations. E.coli AFP184 is a strain easy to handle
produce succinic from glucose, fructose, xylose and mixtures of glucose and fructose and xylose with
productivityintherangeof1,52,9g/l/h[34].
E. coli AFP111 is being used to ferment sugars derived from wood wastes and plant crop
residues. This novel E. coli strain has been patented for the production of succinic acid from corn
derivedglucose,anditisbeinggeneticallyengineeredtoimprovetheconversionratesofdifferenttypes
ofsugarsveryefficiently[1].In2002succinicacidproductionwasexaminedinE.coliAFP111usingdual
phase fermentations, which comprise an initial aerobic growth phase followed by an anaerobic
production phase. Using the best transition time, fermentations achieved a final succinic acid
concentrationof99,2g/lwithanoverallyieldof110%andproductivityof1,3g/l/h.
Enterococcus faecalis RKY1 was also reported to produce succinic acid with a high productivity
of up to 17,1 g/ l/ h starting from 80 g/ l fumarate and glycerol in a continuous fermentation process

23

[35,36,37]. The yield of bioconversion was enhanced about 1,2 times by addition of glucose and the
amountofsuccinateproducedin the highcellcultureisaboutthreetimeshigherthanwasthe casein
the low cell culture. The maximum concentration of 65,9 g/l succinate was obtained at pH 7.0. These
resultsindicatethatEnterococcussp.RKY1straincanproducesuccinatefromfumarateatasignificantly
higher yield and higher rate than any amplified E. coli. Since glycerol, a renewable resource, derived
fromthemanufactureofbiodieselfuelcanbeusedasstartingmaterial,theadvantagesofusingglycerol
asasubstrateincludethatsuccinatecanbeproducedwithacheaperrawmaterialinhighconcentration
withhighpurityandhighyield,permittingeconomicrecoveryofsuccinicacid.
In2011Raja[38]isolatedanovelsuccinicacidproducingbacteriumfromcowbovinerumenand
studied succinic acid production using different synthetic carbon sources such as glucose, sucrose,
fructose,dextrose,starchandcelluloseanddifferentcrudecarbonsourcessuchasricestraw,sorghum
stalk, baggase and sugar mill waste (figure 1.3.). The fermentation process was carried out under CO
2

atmospherewithN
2
gas.TheeffectofpH,temperatureandinitialdextroseconcentrationwerestudied
andoptimized.Theoptimumfermentationconditionsforthenewlyisolatedstrainwerefoundtobe:pH
6,5, temperature 30C and initial dextrose concentration 10 g/L. At these optimized condition, the
maximumproductionofsuccinicacidwasfoundtobe15g/l.

Figure1.3.Productionofsuccinicacidfromdifferentisolates(Ia,Ib,Ic,IIb,IIc,IIIbandIIIcaredifferenttypes
ofstrains)usingvarioussyntheticcarbonsources[38]

For an economical biobased succinic production, several improvements should be made,

including limiting the use of low cost amino acids, high yield and inexpensive carbon sources. The
optimization of a biosuccinate production process is been the topic of many research in the past two
0
2
4
6
8
10
12
14
16
Ia Ib Ic IIb IIc IIIb IIIc
C
o
n
c
e
n
t
r
a
t
i
o
n

(
g
/
l
)
Strain
Glucose
Sucrose
Dextrose
Starch
Fructose
Cellulose

24

decades. Although some of the process performances are very promising, many problems have been
uncoveredovertheyears.Productionrateandbyproductformationshouldbethepointsofattention.
Novel ways to increase the production rate should be developed and potential byproduct formation
pathways should be investigated. In conclusion performances of succinic acid production by various
microorganismsaregatheredintable1.4.

Table1.4.Succinicacidproductionbyvariousmicroorganisms
Microorganisms
Fermentation
strategy
Feedstock Time(h)
Succinicacid
concentration
(g/l)
Yield
(g/g)
Productivity
(g/l/h)
A.Succinogenes Repeatbatch Glucose 38,5 33,9 0,86 0,88
130Z Batch Glucose 84 66,4 0,67 0,79
M.
succiniproducens
Batch
Glucose 7,5 14 0,70 1,87
Batch
Whey 11 13,5 0,72 1,22
A.
succiniproducens
Continuous Whey 0,085/h 24 0,72 2,10
Fedbatch
Glucoseand
glycerol
22 29,6 0,97 1,35
Batch Glucose 30 33 0,93 1,10
RecombinantE.
coli

AFP111 Dualphase
fedbatch
Glucose 76 99,2 1,10 1,30
AFP184
Dualphase
fedbatch
Glucose 24 45,4 0,92 2,84
Fructose 27,7 0,46 1,54
Xylose 29,2 0,69 1,79

Glucoseand
Fructose
52 0,73 2,89

Glucoseand
Xylose
31,2 0,57 1,73

25

1.1.5.Advantagesanddisadvantagesofbiobasedsuccinicacidproduction
Compared to the chemical process, the fermentation process has both advantages and
disadvantages. One of the obvious advantages is the mild conditions that require less energy input.
Moreover,fermentationischaracterizedbytheindependenceofthefossilfeedstockandthefixationof
CO
2
. Theoretically, succinate fermentations consume 1 mole of CO
2
per mole of succinate produced,
while1moleofglucoseand2moleofCO
2
aretransformedinto2moleofsuccinate.Themanufacturing
processproducesalsolesstoxicwasteresultinginthesamechemicalasinpetrochemicalproduction.
Ontheotherhand,fermentation proceduresrequirelargeoccupationspaceofthefactoryand
muchlongerfermentationtime.Theyalsoimplylargeamountsofaqueoussolutionsofsaltswhichpose
an ecological problem. In addition, the complicated separation and purification steps of the final
productleadtoahighproductioncost.Fermentationreactionhasalsoproblems,becausecellsareliving
organisms and as production takes place, product inhibition can occur and cell growth and synthesis
stopbecausemoreenergyisrequiredtomaintaincells[17].Moreover,byproductsofthefermentation
(acetate,formate,etc.)leadtoadistortionofthebalance.Theycanlimitsuccinicacidproductionaswell
astakeawayfromthecarbonsourceusedbythebacteriatomakethemainproduct,reducingtheyield
ofthedesiredproduct[25].Theideaofalteringorganismsinawaytoreduceoreliminatebyproducts
hasbeensuggestedandsomeworkhasbeendonetoalterthegeneticcodeofbacteriatoensurethat
onlyspecificgenesareexpressed,limitingthenumberofundesirableproducts[20].
Until recently, the main problem of fermentatively produced succinic acid was the price. The
costismostlyincreasedbytherequirednutrientsandthebyproductrecovery.Thepriceofnutrientsis
higherthanthepriceof carbohydrate nutrients,so ithas tobe partofeconomic consideration.Efforts
havebeenmadetolowerthepricebymakingtheproductionprocessmoreefficient.Ontheotherhand,
maleic acid price rose seriously in the past couple of years. The main difference between the two is
therefore slowly diminishing, creating opportunities for succinic acid as substitute of maleic acid,
especially since industrial demand of the later is still increasing. A general comparison between
fermentationandpetrochemicalproductionisshowninthetable1.5.

26

Table1.5.Comparisonbetweenchemicalandfermentativeroutes
Petrochemicalproduction Fermentation
Origin Nonrenewablefeedstock(petrochemicals) Biobasedfeedstock(carbohydrates)
Price Cheaperthanrenewablesources Downstreamprocesseshighcost
Routes Developedroutes
Establishedtechnology
Routesunderconstantimprovement
Newtechnologies
Yield
High
Sideproducts
Dilutedmedia
Longreactiontime
Disadvantages
Availabilityexpectedtodecreaseintime
Highenergydemands
Catalystsdisposalissues
Sensitivityofmicroorganisms
Nutrientrequirements
Complicatedproductrecovery
Wastes
Public
awareness
Decreasingpopularity Increasedinterest

1.2.Manufacturersofsuccinicacid
The global market for succinic acid in terms of revenue was estimated to be worth $182,8
million in 2010 and is expected to reach $496,0 million by 2016, growing at an annual growth rate of
18,7 % from 2011 to 2016. Currently, 35.000 tons of succinic acid are processed annually, though
estimationspredictariseto2.000.000tonsperyearin2020.
EuropeandNorthAmericadominatetheglobalsuccinicacidmarketandtogetherbothofthem
account for 66 % of the global succinic acid demand in 2010. AsiaPacific is expected to be the fastest
growing market in the near future owing to the rapid advancement and increasing demand from key
countries such as China and India. In 2010, Europe dominated the global succinic acid market,
accounting for 35 % of the overall consumption. America and Asia are the second and third largest
succinic acid consuming regions, accounting for 31% and 28% of the overall market as presented in
figure1.4.

Si
interest i
continuou
1.2.1Bio
Bi
company
purificatio
company
technolog
acid is 97
characteri

nce biobase
n the prod
uslyfocusing
amberInc.
ioAmber is
s proprieta
on process
is producin
gytoconvert
7 % biobased
isticsoftheir
0%
5%
10%
15%
20%
25%
30%
35%
ed succinic a
uction of b
ongainingm
the world's
ary technolo
and chemic
ng biosuccin
tsuccinicaci
d, as it has
rbiobasedch
U.S.A.
Figure1.4.S
cid demand
biobased suc
marketshare
s first and
ogy platfor
cal catalysis
nic acid, PBS
idintobutan
been certifi
hemicalfori
EUROP
27
SuccinicAcidM

is increasin
ccinic acid
eandimprov

only dedic
rm combine
to convert
S and they
nediolandT
ied by the U
industrialuse

PE A
Market2010[
g rapidly, m
and its der
veprofitabili
cated bioba
es industria
t renewable
are current
Tetrahydrofu
United State
earepresen
ASIA
39,40,41]
any industri
ivatives. Ma
ty.
ased succini
al biotechno
e feedstocks
tly finalizing
ran(THF).B
es Departme
tedintable
OTHERS

ies are show

arket partic
ic acidcom
ology, an
s into chem
g the pilotin
BioAmbersb
ent of Agricu
1.6.
wing strong
ipants are
pany. The
innovative
micals .The
ng of their
biosuccinic
ulture. The

28

Table1.6.BioAmberssuccinicacidchemicalproperties[42]
Appearance PowderColorwhite
Odor Odorless
pH(1%inwater) 2.42.8
Meltingpoint 184192C
Kst,Pmax Kst=51barm/sPmax=7,4bar
Min.FlammabilityEnergy >1.000mJ
Min.FlammabilityTemp.(cloud) 620C
Watersolubility Moderatelysoluble

BioAmberhasdevelopedafermentationanddownstreammethodtoproducebiosuccinicacid
usingraw materialsfromagricultureor forestry,asanalternative topetroleumderivatives. Their main
rawmaterialsareglucoseorsucroseandCO
2
.Thebiobasedproductionprocessisbasedonsmallsugar
requirement than most other renewable products need, because 25 % of the carbon in its biosuccinic
acid originates from carbon dioxide. Moreover, there are no byproducts such as ammonium sulphate
sincethereisa100%recycleofammonia.Productionstepsareshowninfigure1.5.

Figure1.5.BioSuccinicandproductionprocess[42]
Inoculum
Bacteria
Glucose
O
2
Growth phase
Glucose
Minerals
O
2
Bioconversion
Glucose
O
2
Purification Evaporation Crystalization
Succinic acid

29

ThecompanyhasademonstrationplantinPomacleinFranceproducingbiosuccinicacidatan
industrialscaleof3.000MT/year,sinceJanuary2010.Theproductionisgoingunderacommercialscale
of a 350.000 l fully automated pilot fermentors. The facility is integrated into an existing biorefinery
that supplies the biosuccinic acid plant with glucose, carbon dioxide, steam, ammonia and process
water.
BioAmber expects to establish 3 production plants worldwide for biosuccinic acid production.
ThefirstonewouldbeinSarnia,Ontario(Canada).Thefacilitywillhaveinitialcapacityofapproximately
17.000 MT/year of biosuccinic acid and is expected to be operational in 2013, able to reach a total
capacity of 34.000 MT/year, while up to year 2017 70.000 MT/year. Its feedstock will be corn. The
secondplantisgoingtobeestablishedinThailandwithanannualcapacityof65.000MTofbiosuccinic
acid. The plantisexpectedtobeoperationalin2014usingcassavaandsugarcanefeedstock.Thelast
one facility to be built pursuant to BioAmbers will either be in North America or Brazil, with a target
annualcapacityof65.000MT.
BioAmber's 350.000 liter fermenter in Pomacle, which started operating on January 2010, has
now produced 221 tons of biosuccinic acid. The company has supply agreements for the sale of over
84.000 tons of biosuccinic acid and derivatives over the next five years, of course, coming from its
planned succinic acid facilities in Sarnia and Thailand. The company estimates its succinic acid will be
costcompetitivewithoilpriceaslowas$35/barrelofcrudeoilandcornpriceat$6.50/bushel.

1.2.2.MyriantCorporation
MyriantTechnologiesLLC[43]wasformedinJune2009byBioEnergyInternationalLLCandhas
already developed proprietary fermentation technology, through the commercial production of D ()
lactic acid. Currently, Myriant expands production including succinic acid, fumaric acid and malic acid.
Generally,itisacompanyfocusedonthedevelopmentandcommercializationofproprietarybiocatalyst
technology for conversion of renewable feedstocks, into high value biobased chemicals, cost
competitivewithpetrochemicals.
Myriant has developed a new process for the production of succinic acid that it is still
demonstrated on a pilot scale producing tonsized samples. Myriant has created a microbial platform
for the manufacture of high value specialty chemicals competitive to that petroleum based. The
production of chemicals from renewable feedstocks requires the use of microbes to convert sugars
contained in the biomass into desired products. In particular, the company has developed a novel
system that transforms genetically microbial hosts through the chromosome and not just the cell wall,
makingtheresultingorganismmuchmorestableatlargescaleproduction.Thepatentedprocessused,

30

depends on lower cost feedstock (sugar instead of oil), milder and less expensive operating conditions
(consumelessenergy)andrequirelowercapitalinvestmentbecausetherearefewerproductionsteps.
While Myriant's initial commercial production of succinic acid will rely on first generation
fermentation technologies for conversion of biomass containing readily accessible sugars to high value
products, the company is also trying to develop advanced methods that consume cellulosic biomass.
Myriant has developed core science and engineering competencies to support the development of
robust,economicallyviableprocessesfortherecoveryoffermentablesugarsfromcellulosicfeedstocks.
Concerning cellulosic technology, specially designed microbial systems convert different sugars
into various high value specialty chemicals. Carbon dioxide generated in the production is consumed
during specialty chemical production. Lignin byproduct from the sugar separation is burned as an
energy source for the biorefinery or sold as an ingredient for downstream use. Water usage and
fertilizer runoff are decreased for cellulosic biomass (compared to products such as corn and sugar
beets). The process consumes less energy and water while wastes production is minimum. The
characteristicsoftheirbiobasedchemicalareshownintable1.7.

Table1.7.Myriantssuccinicacidchemicalproperties[44]
Color whitecrystallinesolid
Molecularweight 118,09
Meltingpoint 188C
Boilingpoint 235(1atm)
Density 1.57g/cm
3

Solubilityinwater,0C 2.8
Solubilityinwater,100C 121
Solubilityinchloroform Insoluble
pK1,inwaterat25C 4.16
pK2,inwaterat25C 5.61
Assay 99.5wt%
Moisture <0.5wt%
Ash <0.025wt%
Pb <2ppm

31

Sulfate 500ppmmax
Cl 10ppmmax
As 2ppmmax
Fe 5ppmmax
N 10ppmmax
UnsaturatedCompounds 0.2wt%max
Packaging
25kgpolybags
1000kgSuperSack

Myriant has already constructed its 13.392 tons commercial succinic acid facility in Lake
Providence, Louisiana. It is expected to start up its production of biobased succinic acid in 2013. The
facility will be the world's largest biobased succinic acid plant and the company plans to expand it to
75.892MT/yearbyearly2014.ThecompanyuntilnowwasfocusedmostlyinD()lacticacidproduction
atcommercialscalesinceJune2008.

1.2.3RoyalDSMN.V.andRoquetteFrresS.A.collaboration
Royal DSM N.V. [39] creates innovative products and services in Life Sciences and Material
Sciencesgloballyinawiderangeofmarketsandapplicationsincludinghumanandanimalnutritionand
health, personal care, pharmaceuticals, automotive, coatings and paint, electrical and electronics, life
protectionandhousing.
ROQUETTE [45] is one of Europes largest starch and starchderivatives businesses. ROQUETTE
derivesover650productsfromsixmilliontonsofmaize,wheat,peasandpotatoes.Itservescustomers
all over the world in the food, paper/board, biochemicals, chemicals, pharmaceuticals, cosmetics and
animalnutritionsectors.
The companys production facility uses starch derivatives as feedstock, but in longer term the
aspirationistoswitchtosecondgenerationfeedstock(cellulosicbiomass).Thecurrentlybiotechnology
based route, could result in up to 40 % reduction in energy requirements compared to the traditional
method,andhaveapositiveimpactonreducingCO
2
emissions,ascarbondioxideisactuallyusedinthe
productionprocess.
Since 2007, Roquette has applied several patents concerning succinic acid production through
fermentation. Patent FR 2925068 A1 implies a production method using E. coli in anaerobic conditions

32

withCO
2
andMgOadditions.Anotherpatentedinvestigationinvolvesathreestepfermentationprocess
withanaerobicfermentationstepwithE.coliandMgO,withastepofsuccinateionsproductionthrough
anaerobicconditionsandalaststepofthetransformationofionstosuccinicacid.
In 2009, the two companies decided to join a venture regarding the production of biobased
succinicacid.DSMandROQUETTEhavedevelopedamethodtoproducesuccinicacidfromstarchusing
an innovative enzymebased fermentation technology based on white biotechnology. The same year,
they constructed a demonstration plant in Lestrem, France which has been running at full capacity. In
2010 the first testing volumes of biobased succinic production (Succinium project) proved that their
biological route could be commercially viable. n May 2011, DSM and the French starch and starch
derivatives company Roquette Frres announced that they will build a commercial scale plant for the
production of biobased succinic acid. With a capacity of about 10 ktons per year, the plant will be
Europes largest biobased succinic acid facility. It is expected to come on stream in the second half of
2012 located in Cassano Spinola in Italy. By the end of 2011 / beginning of 2012 the facility was
supposedtobescaleduptofullcommercialindustrialproductionwithacapacityofabout10ktonsper
year.

1.2.4.BASF,Purac,DNPandMBIcompanies
BASF and CSM and Purac explore a joint venture for the production of biobased succinic acid.
The companies have been conducting research under a joint development agreement on biobased
succinicacidsince2009.Thecomplementarystrengthsinfermentationanddownstreamprocessingled
tothedevelopmentofasustainableandhighlyefficientmanufacturingprocessbasedonaproprietary
microorganism. The companies aim for a 25.000 tons capacity fermentation production plant at the
PuracsitenearBarcelona,Spain,withtheintentiontostartupby2013atthelatest[46,47,41].
Anothercompanythatismovingtowardlargescaleproductionofbiomassderivedsuccinicacid
is DNP, formerly Applied CarboChemicals. The company has acquired the intellectual property to
transform cropbased sugars into succinic acid. DNP's process for making succinic acid starts with a
microbialfermentation.However,itusesastrainofE.colidevelopedattheDepartentof Energyinthe
mid1990saspartoftheagency'sAlternativeFeedstocksProgram.
Atlast,MBIestablishedin1981hasahistoryofdevelopingbiobasedchemicalsandagricultural
feedstocks into chemicals derived from fermentation processes. In 1996, the company patented the
process for the production of succinic acid from sugars and more specifically from a unique isolated
bacterium. MBI scientists knowing that the rumen, one of the four compartments of the bovine
stomach,wasawarm,voluminousholdingvatdevoidofoxygenandbrimmingwithmicrobesthatdigest
and ferment an endless supply of wellmasticated feedstuffs collected rumen samples and isolated a

33

novel succinic acid producer. At this point, MBI has scaledup the benchtop fermentation process for
theproductionofsuccinicacidtoa1.000gallonfermentationprocessatitspilotplantinLansing,Mich.

1.3.Butanedioltechnologyandproperties
Butanediol(BDO)isarawmaterialforanumberofchemicalsyntheses,includingpoly(butylene
terephthalate) (PBT) and poly(butylene succinate) (PBS) resins, used for the synthesis of films, fibers,
engineeringplasticsandadhesives.
Butanediol (BDO) industry appears to be in the center of a technological revolution. Biological
routestoBDOarebeingperfectedwhichoffertremendouspromisetonewparticipants.Withtheglobal
demand for butanediol estimated at 1,4 million MT in 2010, BDOs growth will continue to be derived
from its almost exclusive use as an intermediate to synthetize other chemicals and polymers at an
annualaveragerateof4,8percentuntil2015[48].ThereisagreatinterestinBioBDOconcerningthe
reductionoftheuseofpetroleumbasedfeedstocksinlightofglobaloilprices.
TheglobalBDOindustryhasalreadywitnessedseveraltechnologicalupheavalsinthepast.The
first phase started with the development of BDO from acetylene by Dr. Reppe in the 1930s. In 1970
MitsubishiChemicalIndustriesintroducedthebutadieneacetoxylationprocess.Itwasnotuntilthelate
1980s and early 1990s that another new technology was commercialized for BDO production, when
ARCOexploiteditsBDOprocessfrompropyleneoxide.Theearly1990ssawanotherdevelopment,this
timebythetechnologycompany/engineeringcontractorDavy(nowDavyProcessTechnology)basedon
the esterification of maleic anhydride (made from either nbutane or benzene) with ethanol, followed
by hydrogenation of the ethyl ester to diethyl succinate, then GBL, and finally BDO, typically with a
tetrahydrofuran (THF) coproduct (scheme 1.11). In 1998, a commoditization through technology
improvements took place, including a drive to worldscale BDO plants with the introduction of SISAS
maleic anhydridebased integrated BDO/THF/GBL technology, producing around 110.000 MT/year of
BDOequivalents(acombinationofBDO,THF,GBL,andNMPexpressedastonsofBDOconsumed)[48].
As innovations in BDO/THF technology continue, and improvements in the maleic anhydride
based BDO routes are still being made, new developments emerge for the production of BDO using
renewable resources. As before, a whole new set of firms threatens to dramatically alter the BDO
landscape through technological advances. Several of the companies are welladvanced in their
construction and/or commercialization plans. Many of these developments are centered on the
production of biobased succinic acid production, which can subsequently be converted to BDO/THF
using conventional means, such as the Davy approach, in which the succinic acid would first be
convertedtothedimethylesterandthenundergovaporphasehydrogenolysistoBDO/THFmixtures.

34

HO
O
O
OH
CH
3
OH
-H
2
O
H
2
-H
2
O
BDO/THF
H
3
CO
O
O
OCH
3
H
2
-CH
3
OH
BDO/THF

Scheme1.10.ChemistryoftheconversionofsuccinicacidtoButanediol/Tetrahydrofuran

Other developing technologies to BDO include routes from biomass, polyhydroxyalkanoate

(PHA) and direct fermentation of sugar using E. coli bacteria. A promising process for butanediol
productionistheliquidphasehydrogenationofmaleicanhydrideasshowninscheme1.12.Anystageof
the multistep hydrogenation of maleic anhydride to butanediol is known to be catalyzed by copper
basedcatalysts[9,49,50,51].

35

O
O
O
H
2
O
O
O
2H
2
-H
2
O
O
O
2H
2
-2H
2
HO
OH
-2H
2
O
O
maleic anhydride
succinic anhydride
Y-butyrolactone 1,4- Butanediol Tetrahydofuran

Scheme1.11.Reactionschemeofmaleicanhydridehydrogenationtobutanediol/tetrahydrofuran

Anotherpatentteachesconcerningbutanediolproductionpresentsaprocessthrough:
supplyingtoafirsthydrogenationzoneafeedstreamcomprisingmaleicacid
reacting in the first hydrogenation zone, the maleic acid feedstock and hydrogen in contact with a
catalystcomprisingpalladium,toproduceareactionproductcomprisingsuccinicacid
supplyingtoasecondhydrogenationzone,thereactionproductofthefirsthydrogenationzone.
reactinginthesecondhydrogenationzone,thereactionproductfromthefirsthydrogenationzoneand
hydrogen in contact with a catalyst comprising palladium, to produce a product stream comprising at
leastoneofgammabutyrolactone,1,4butanediolandtetrahydrofuran.
BioAmber is one of the industries that supplies BDO producers with the biobased alternative
thatiscleaner,cheaperandofhigherpurity.ThecompanyincollaborationwithMitsui&Co.isgoingto
reach a production capacity of about 50.000 tons/year. BioAmber has exclusive license to DuPonts
hydrogenationtechnology(figure1.6.)anditisestimatedthatliquidphasehydrogenationtechnologyis
thelowestcostroutetoBDOviasuccinic(bio)ormaleic(petro).Theusedtechnologyislessdependent
onsugarpricevolatility,becauseofitshighyield.

36

Figure1.6.BioBDOproductionprocess[42]

GenomaticaandTate & Lyleis another companies collaboration for the production of

GenomaticasBioBDO.TheGenomaticaprocessproducesthesameBDOproductthatiscurrentlymade
from a variety of petroleumderived feedstocks, but uses 100% renewable feedstocks instead. A
demonstrationscale facility has been constructed in Decatur, Illinois, for the scaleup of the BioBDO
process. The company is ramping its process to 13.000liter fermenters followed by an integrated
downstream process for BDO recovery and purification. The company has been successfully producing
at pilot scale in 3.000 liter fermentation tanks since the first half of 2010. Current feedstocks for the
genomatica platform consist of refined sugars such as sucrose from sugarcane or sugar beets, and
dextrose from corn or cassava, but in the current future the company plans to utilise cellulosic sugars
from biomass and synthesis gas, or syngas, from municipal solid waste as the cheaper feedstocks
become available. Genomaticas technology is covered by multiple patents, including US patent
80067214B2[52].

Inoculum
Bacteria
Glucose
O
2
Growthphase
Glucose
Minerals
O
2
Bioconversion
Glucose
O
2
Purification
Hydrogenation
DuPontcatalysts
Seperation/
distillation
1,4Butanediol

37

CHAPTER2:DEVELOPMENTOFPOLY(BUTYLENESUCCINATE)
PREPARATIONPROCESSES

2.1.Introduction
Poly (butylene succinate) (PBS) and its copolymers are a family of biodegradable polyesters
synthesized from succinic acid, butanediol, or other dicarboxylates and alkyldiols. PBS is a white
crystallinethermoplasticwithdensityof1,25g/cm
3
meltingpoint(T
m
)intherangeof90C120Cand
a low glass transition temperature (T
g
) of about 45 C to 10 C. It has generally excellent mechanical
properties and processability. Like other aliphatic polyesters, it is thermal stable up to approximately
200Candbecauseofitsgoodbiodegradability,ithasattractedintenseattentionfrombothacademic
andindustry.PBSrepeatingunitisasitisshowninscheme2.1:

HO C
O
(CH
2
)
2
C
O
O
(CH
2
)
4
O
H
n

Scheme2.1.Poly(butylenesuccinate)repeatingunit

PBSwascurrentlyproducedbycondensationpolymerizationofpetrochemicalsuccinicacidand
butanediol, both of which are usually derived from maleic anhydride. Nowadays, poly(butylene
succinate) is a particularly important, technically produced biodegradable polyester for three reasons.
Firstly, succinic acid can be a biogenic monomer, i.e.it is a monomer based on renewable resources.
Secondly, the rates of hydrolysis of polysuccinates are higher than those of polyesters derived from
higher aliphatic dicarboxylic acids and thirdly, the melting temperature, and thus, the heat distortion
temperatureofPBSisthehighestofallpolysuccinatederivatives.
Because of its excellent mechanical properties it can be applied to a range of end applications
viaconventionalmeltprocessingtechniques,suchasinjection,extrusionorblownprocess.Newgrades
of PBS copolymers have also been produced with a high recrystallization rate and high melt tension,
suitableforpreparingstretchedblownfilmsandhighlyexpandedfoams.
PBS applications in general include mulch film, packaging film, bags and flushable hygiene
products.Owingtothesteadygrowthofthemarketforbiodegradableplastic,thedemandisexpected
to increase rapidly. It can also substitute for poly(ethylene terephthalate) (PET), polypropylene (PP),
replacepolyolefinsandpolystyreneinsomeapplications,andadditionallyitcanreplacepoly(lacticacid)

(PLA) in s
polyethyle
materials

2.2.Stat
process
Sy
opening r
However
ofsynthet

several appli
ene (PELD),
includingpa
teofthea
es
ynthetic biod
eactions/cha
itisdifficult
ticandgreen
Raw
Materia
PBS
PBS
ications. Scie
high densit
per,natural
artinhom
degradable
ain extensio
tosynthesiz
ntechnology
Tabl
l
C
titanium
titanium
entists also
ty polyethyle
fibreandwo
Figure2.
mopolyme
polymers ar
n. Polyester
zehigh mole
y,highmolec
le2.1.PBSan
Catalyst
m(IV)butoxid
m(IV)butoxid
38
suggest sub
ene (PEHD)
ood.
.1.PBSendpr
erspoly(b
re mostly sy
rs have been
ecular weigh
cularweight
ditscopolym
Condi
de
180
de
60m
230
bstitution po
and polypr
roductapplica
utylenesu
ynthesized t
n first synthe
ht polyesters
polyestersa
mersproductio
itions Mw
0C
M
59
M
104
min
0C
M
7.
otential is hi
olylene, as w
ations
uccinate)
hrough poly
esized by W
intheinitia
recommerc
onparameters
w/Mn So

n
M
.500

w
M
4.100
T
20

n
M
000
Ch
20
ighest for lo
well as non

preparati
ycondensatio
W.H. Carother
alstage. Wit
ciallyavailabl
s
ources
Tserki
006[53]
hrissafis
005[54]
ow density
polymeric
ion
on or ring
rs in 1935.
hprogress
lenow.

39

PBS
Chainextenders:2,2(
(1,4phenylene)bis(2
oxazoline)(PBOX)and
adipoyl
biscaprolactamate(ABC)

180240C
chain
extension
for0,5h
andat
reduced
pressureto
2mmHgfor
2,5h

Xu
2010[55]

prePBS
PBS
ptoluenesulfonicacid
(pTSA
180200C
2h

w
M
14.500
(prePBS)
Huang
2010[56]

PBS
Biscaprolactamateas
chainextenderandp
toluenesulfonicacidas
catalyst
Chain
extensionat
200240C
under
reduced
pressure

Zhao
2007[57]

PBS
Candidaantarctica
lipaseB
8095C
21h

n
M
38.000
Azim
2006[58]
PBS distannoxane
20min
microwave
irradiation
200W
220C
N
2

atmosphere
w
M
=23.500
Velmathi
2005[59]
PBS tetranbutoxytitanate

n
M
59.000
Mochizuki
1997[60]
PBS

n
M
77.000

w
M
141.000
Ahn
2001[61]
PBS titanium(IV)butoxide
w
M
=92.940
Rizzarelli
2004[62]
PBS
dibutyltindilaurateor
dibutyltinoxide
N
2
flow
Sonnenschein
2010[63]
PBS distannoxane
azeotropic
conditions
atmospheric
pressure
72h

n
M
117.000

w
M
277.000
Ishii
2001[64]

40

PBS
SnCl
2
,Ti(OiPr)
4
,
Ti(OBu)
4
,Sn(Oct)
2
,
Zn(Ac)
2
,p
toluenesulfonate(p
TS),
12h
w
M
=79.000

Sun
2007[65]
PBS SnCl
2
70h

n
M
24.800
Zhu
2003[66]
PBS
Bismuthbased
compounds
80C
48h

n
M
30.000
Lahcini
2010[67]
PBS
triflatesofsodium,
magnesium,aluminum,
zinc,tin(II),scandium,
andhafnium
80C

n
M
35.000

Buzin
2008[68]
PBS zincacetatedihydrate

n
M
53.000
Taniguchi
2002[69]
PBS
Sc(OTf)
3

160C
180C
10h

n
M
20.900

n
M
30.700
Takasu
2003[70]
PBST
tetrabutyltitanate
(TBT)

Du
2007[71]
Branched
PBS
titaniumisopropoxide
Kim
2001[72]
PBEST Ti(BuO)
4

38.5h
235C

Kint
2003[73]
PBSF Ti(OBu)
4

200C
20h

Nikolic
2003[74]

2.2.1. Twostep transesterification/Esterification polymerizationroute for PBS

synthesis
Tsansesterificationinvolvesreactionofdimethylsuccinatewithbutanediolinthepresenceofa
catalystandisthefirststepofthesyntheticprocedurefollowedbypolycondesationinmeltorsolution
(figure 2.2.). Butanediol and dicarboxylic ester are added at a molar ratio of 1,1:1,0 (slight excess of
butanediolduetoitssidereactiontoTHF)andtitanium(IV)butoxideisusedascatalyst(typicallyat0.05

41

mol%ofmonomers).Thisreactioncantakeplaceat180CandmayresultinPBSwithnumberaverage
molecularweight(
n
M )of59.500andweightaveragemolecularweight
w
M of104.100[53,75].

Figure2.2.PBSproductionprocessthroughtransesterificationpolymerization

ATransestrificationpolymerizationformulaofPBSfromdimethylsuccinateandbutanediolisas
itfollows:

HO(CH
2
)
4
OH +CH
3
OO(CH
2
)
2
COOCH
3
H[O(CH
2
)
4
OOC(CH
2
)
2
CO]
n
O(CH
2
)
4
OH+CH
3
OH

Scheme2.2.PBSsynthesisthroughtranssterificationpolymerization

A twostage melt polycondensation method (esterification and polycondensation) was also

studiedbyChrissafis[54]usingsuccinicacidandappropriateglycolsinamolarratio1:1,1andtitanium
(IV) butoxide as a catalyst (10,3 mol/mol succinic acid). The reaction mixture was heated at 190 C
underargonatmosphereinordertoremoveoxygen.PBSpresentedmeltingat112C,glasstransitionat
44 C and cold crystallizaon at 6.6 C. The polycondesaon followed took place under vacuum to
avoidexcessivefoamingandtominimizeoligomersublimation.Thereactioncontinuedforabout60min
at230C.

BDO
SUCCINICACID
TRANSESTERIFICATION POLYCONDESATION
CATALYST
PBS

42

First step: Esterification

n HOOC-CH
2
CH
2
-COOH +n HO-R-OH
190
C
Ti(OC
4
Hg)
4
-H
2
O
Oligomers -OROC-CH
2
CH
2
-C-
n
O O
Second step: Polycondesation
230
C
Ti(OC
4
Hg)
4
high vacuum
-H
2
O
HO-R-OH
Polyesters
-OROC-CH
2
CH
2
-C
O O
R =- CH
2
CH
2
- PESU
R =- CH
2
CH
2
CH
2
- PPSU
R =- CH
2
CH
2
CH
2
CH
2
- PBSU

Scheme2.3.Twostagesmeltpolycondesationformula

However there is an intrinsic difficulty in synthesizing high molar mass aliphatic polyesters
throughthe conventional polycondensationmethod,dueto thecompetitive reactionsof condensation
anddegradation,whichsimultaneouslytakeplaceespeciallyinthemeltstate.

2.2.2.DirectpolymerizationforPBSsynthesis
Directpolycondensationisamethodbasedonstoichiometricamountsofdiacidsanddiolsinthe
presence of a catalyst. Direct polymerization can be conducted in two ways: 1) direct melt
polymerization of succinic acid and butanediol 2) solution polymerization of the same two reactants .
Both methods have been examined intensively the current years, studying the efficiency of different
temperaturesandcatalystsapplied.

43

Direct melt polymerization for PBS is a direct polymerization method starting from dicarboxyl
acidanddiol,producingPBSofhighmolecularweight.Solutionpolymerizationisamodifiedmethodof
direct melt polymerization in which the monomers and the polymerization initiators are dissolved in a
liquidsolvent,suchasxyleneordecahydronaphthaleneatthebeginningofthepolymerizationreaction.
ThekeystoobtaininghighmolecularweightPBSareasfollows:
Thewaterformedduringesterificationmustberemovedfromthesystem
Esterificationmustbecarriedoutatthepropertemperature
A sufficiently high vacuum is required to remove the butanediol and the small amount of water
formed in the polycondensation stage. The Technical Institute of Physics and Chemistry, Chinese
AcademyofSciences,hasappliedthecoldtraptechniqueintheflowlineofaPBSpreparation.Itis
reportedthatthecoldtrapcanreach120Candsocausethesmallmolecularmaterialformedin
the condensationstageto condenseandcankeepa stablehighvacuumandimprovetheremoval
of small molecular compounds. Consequently, PBS with high Mw can be prepared via this
technology
Catalysts with high reactivity and that are resistant to hydrolysis must be chosen to improve the
molecular weight of PBS and to shorten the reaction time. At the same time, a thermal stabilizer
andendcappingreagentareincorporatedtoreducedegradationduringpolycondensationandthe
followingthermalprocessing.

2.2.3. Condensation polymerization followed by chain extension for poly(butylene

succinate)
The chain extension process is a formerly developed production methodology. Compared with
the direct melt condensation polymerization, an additional step is carried out to further improve the
molecularweightofPBS.AchainextenderwithtwofunctionalgroupscanreactwiththeterminalOH
or COOH of PBS. Ideally, a chain extender molecule will couple two PBS chains. A variety of chain
extendershavebeeninvestigatedthroughyearsfortheimprovementofPBSmolecularweight.
Xuetal.[55]estimatedbisoxazolineasachainextender.Extensionreactions(scheme2.4.)were
carried out at 180240C using 2,2((1,4phenylene)bis(2oxazoline) (PBOX) and adipoyl
biscaprolactamate(ABC) as combined chain extenders. PBOX and ABC melting points were 249C and
7273C respectively. Prepolymer of PBS was stirred and heated under nitrogen to 180240C. The
chain extenders PBOX and ABC were added at molar ratios of (1/2)PBOX/COOH1.0 and (1/2)ABC/
OH1.0, and the reaction mixture was homogeneously mixed. The chain extension was conducted at
normalpressurefor0,5handatreducedpressureto2mmHgfor2,5h.Huang[56]studiedalsochain

44

extension of PBS with 2,2 (1,4phenylene)bis(2oxazoline) using ptoluenesulfonic acid (pTSA) as a

catalyst (00.15 wt %). There is no doubt that higher molecular weight polyesters were obtained from
thecatalyzedreactionthanfromthe noncatalyzed one.However,animproperlyhighamountofpTSA
andahightemperaturecancausebranchingoracrosslinkingreaction.Underoptimalconditions(180
200C), PBS with an intrinsic viscosity of 0,82 dL/g in a 20 mL of chloroform (CHCl
3
) solvent, was
synthesized.
N
O
R
N
O
+2HO-C-R-C-OH
O O
HO-C-R-C-OCH
2
CH
2
NH-C-R-C-RNHCH
2
CH
2
-O-C-R-C-OH
O
O O O O O
2 C -OH +CH
2
-CH -R CH -CH
2
O
O
O
C - O -CH
2
-CH -R -CH- CH
2
-O-C
O
OH OH
O

Scheme2.4.PBSchainextensionwithbisoxazolineasachainextender

Biscaprolactamate was aslo investigated as chain extender [57]. HOterminated poly(butylene

succinate)(HOPBSOH)wassynthesizedthroughmeltcondensationpolymerizationfromadipicacidor
succinic acid, with excess of butanediol (scheme 2.5.). Chain extension was carried out at 200240C
underreducedpressure.Thechainextensionproceedsthrough theeliminationofcaprolactamringsin
the chain extenders, the adipoyl groups or the terephthaloyl groups couple the hydroxylterminated
polyesters together and make the molecular weight of PBS increased, whether acid catalyst such as p
toluenesulfonic acid was present or not. Chainextended PBS with intrinsic viscosity of 0.871.25 dL/g
wasobtainedat30C.

45

HO - PBS - OH +(CH
2
)
5
C - N- C - (CH
2
)
4
- C -N -C (CH
2
)
5
O O O O
200 -240
o
C
with or without p-TSA
PBS - O -C - (CH
2
)
4
-C - O - PBS
+2 HN - C (CH
2
)
5
O O
O

Scheme2.5.ThechainextensionofHOPBSOHwithABCwithorwithoutthepTSAcatalyst

In this process, the polycondensation conditions are not that critical comparing to those of
directmeltpolycondensation.Ontheotherhand,chainextensionreactionshavethedisadvantagethat
incorporationofthechainextendercanreducethebiosafetyandaffectthebiodegradabilityoftheend
PBSproduct,whichisimportantespeciallyforpackagingapplication.

2.2.4. Enzymatic polymerization (lipasecatalyzed) synthesis of poly(butylene

succinate)
LipasecatalyzedsynthesisofPBSisarecentlydevelopedmethod,whichisfulfilledatmilderconditions
without residual metal salt. Lipases are renewable catalyst with high catalytic activities both for the
condensation polymerization and ringopening polymerization of lactones under mild reaction
conditions.Thelipasecatalyzedpolymerizationisconsideredasanewstrategyforthegreenproduction
of biobased plastics [76]. PBS synthesized by lipase catalysis has a narrower polydispersity index than
polycondesationmethods.However,theremaininglipasemaycauseaprobleminthefollowingthermal
processing.
In 2006, Azim et al. [58] reported Candida antarctica lipase B catalyzed synthesis of PBS, from
the monophasic reaction mixtures of diethyl succinate and butanediol (scheme 2.6.). Lipase B (0,61 g,
dried under 0,1 mmHg vacuum at 25 C for 24 h) was added to a solution of diethyl succinate (4,00 g,
22,96 mmol) and butanediol (2,07 g, 22,96 mmol) in diphenyl ether (12,14 g). PBS with
n
M of 2.000,
4.000, 8.000, and 7.000 was produced at 60, 70, 80, and 90C, respectively. The low molecular weight
was due to precipitation after polymerization for 510 h, limiting the growth of the polyester chain
length.Tomaintainamonophasicreactionmixture,thepolymerizationtemperaturewasincreasedfrom
80to95Cafter21h.TheresultwasanincreaseinthePBSmolecularweightto
w
M 38.000.

46

CH
3
CH
2
O
OCH
2
CH
3
O
O
+
HO
HO
Lipase B
solution or bulk
vacuum
heat
O
O
O
O
n

Scheme2.6LipasecatalyzedcondensationpolymerizationforPBS

Another work was that of Briassoulis according to which PBS production was made through a
twostepsprocessbeginningwiththeproductioncyclicoligomerbythelipasecatalyzedcondensationof
dimethylsuccinateand1,4butanediolinadilutetoluenesolutionusinglipasefromCandidaAntarctica.
Thepolymerizationofcyclicoligomersproceededwithoutproducingacondensationbyproduct,suchas
water and a lower alcohol, in 90C for 48 h. Following, a ringopening polymerization of the cyclic
oligomertookplaceinamoreconcentratedsolutionorinbulkwiththesamelipasein120Cfor24h.In
order to produce highmolecularweight polyester, the ringopening polymerization of cyclic oligomers
could become a new revolutionary means of manufacturing polyesters that are now typically
synthesizedbyapolycondensationreaction.

2.2.5.Directpolyesterificationundermicrowaveirradation
AnecofriendlymethodforPBSsynthesishasbeenstudiedbyVelmathi[59].PBShasbeenproducedby
thedirectesterificationof adicarboxylicacidanda diolusingdistannoxane catalyst under microwaves
(scheme 2.7.).The optimum parameters were found to be a catalyst concentration of 2 mol %, a bulk
polymerization method,a reactiontemperatureof220C,astoichiometryof 1:1,2ofdicarboxylicacid
anddiol,respectively,andamicrowaveirradiationtimeof20min.ThePBSsynthesizedwasobtainedin
81,3% yield with a
w
M of 23.500. The reaction took place under a N
2
atmosphere at a maximum
microwavepowerof200W.

47

OH
OH
O
O
+
HO
OH
catalyst , 200
o
C
microwave, N
2
O
O
O
O
n

Scheme2.7.SynthesisofPBSundermicrowaveirradiation

Bothmeltandsolutionpolymerizationofsuccinicacidandbutanediolwereattempted.Concerningbulk
polymerization,thereactiontimewasfixedat20and30minandwith2mol%ofthecatalystmaximum
w
M 9.600and12.200wereobtainedrespectively.Inthecaseofsolutionpolymerization,thepolymer
withthemaximum
w
M 19.300wasformedwith2mol%ofthecatalystin30minutes.Comparedto
thebulkpolymerization,theyieldobtainedwaslowinmostcases,whichmightbeaconsequenceofthe
decalin(anonpolarsolvent),whichisamicrowaveinactivesolventresultinginapoormicrowaveeating
effect.WithanincreaseintheirradiationtimetherewasanincreaseinMwofthepolymerobtained.
Theadvantagesofthismethod,suchasshortreactiontime,freedomofsolvent,andperforming
under atmospheric pressure, makes it possible to synthesize aliphatic polyesters in a rapid and
ecofriendlywaywithoutanysolventandundermildconditionscomparedtotheconventionalmethods.

2.3.StateoftheartinCopolymerandbranchedPBSpreparationprocesses
Inordertoimprovethepropertiesandthebiodegradationrate,PBScopolymersandbranched
structures have been synthesized. PBS copolymers are obtained from succinic acid or succinate,
butanediol, and other dicarboxylic acids, such as adipic acid, terephthalic acid, succinic acid with
substituted side groups, sebacic acid, or alkylenediols such as 1,3propanediol, or other substituted
glycols.Usually,copolymerizationleadstoadecreaseddegreeofcrystallinity,depressedheatdistortion
temperature and higher molecular weight by incorporating a suitable chain extending agent in the
polymerizationstage.
Branching has been also proved effective in enhancing processability in the processes involved
with elongational flow, such as fiber spinning, film blowing, vacuum forming, and foaming. Branching

48

also increases the melt strength and confers a tensionhardening property on the polymer, which is of
helpforuniformextensioninthepolymerprocessing,inwhichahighdegreeoforientationisrequired.
The production process of PBS copolymers can be through the twostep transesterification
route, and the raw material inputs are butanediol and binary acid, using a highefficiency catalyst for
polymerization.MostimportantPBScompolymerswillbedescribedinthefollowingsection.

Figure2.3.PBScopolymersproductionprocess

2.3.1.Poly(butylenesuccinate/adipate)copolymer(PBSA)
In 2002, Ahn et al. [61] produced poly(butylene succinate/adipate) copolymer by reacting
butanediol and dicarboxylic acids under N
2
atmosphere. Esterification reaction took place for 2 h at
190C and then the active catalyst titanium isopropoxide was added prior to deglycolization reaction
whichtookplacearthetemperatureof220C.Thestructuresofthesecopolyestersarepresentedinthe
scheme2.8.
HOCCH
2
COH +HOCCH
2
CH
2
CH
2
CH
2
COH +HOCH
2
CH
2
CH
2
CH
2
O
O
O
O
190
o
C
N
2
gas flow, -H
2
O
HO(CH
2
)
4
O - C(CH
2
)
2
CO(CH
2
)
4
OC(CH
2
)
4
C -OH
m
220
o
C
Ti[OCH(CH
3
)
2
]
4
, reduced pressure
C(CH
2
)
2
CO(CH
2
)
4
OC(CH
2
)
4
C
n
O O
O O

Scheme2.8.PBSAcopolymerssynthesis

BDO
BINARYACID
TRANSESTERIFICATION POLYCONDESATION
CATALYST
PBSCOPOLYMER

49

Nikolic et al. [77] obtained a twostep transesterification reaction in the melt for PBSA
production.Butanediol,dimethyladipateanddimethylsuccinatewerethereactantsusingTi(OBu)
4
asa
catalyst.Acopolymerwithamolecularweight73.000wasattained.
High molecular weight biodegradable PBSA copolymers was also obtained from butanediol,
dimethyl esters of succinic and adipic acid, with the incorporation of hexamethylene diisocyanate as
chainextender.Thereactiontookplaceatat140Cfor1hundernitrogeninlet[53].
Regarding properties, in the case PBSA, tensile strength decreases with the introduction of the
secondary component (adipate), exhibiting a tendency similar to that of the other physical properties.
PBS is the polyester with the highest tensile strength, while the copolymers of PBSA shows improved
elongation[61].

2.3.2.Poly(butylenesuccinatecobutyleneterephthaloyldioxydibenzoates)(PBST)
A series of liquid crystalline aromatic/aliphatic random poly(butylene succinatecobutylene
terephthaloyldioxydibenzoates)(PBSTs)copolymerswerepreparedbymeltpolycondensationofanew
mesogenic monomer dimethyl 4,40(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and
1,4butanediol,usingtetrabutyltitanate(TBT)ascatalystandhexamethylenediisocyanatewasusedas
chainextender[71].

OH
OH
B
H
OH
O O
HO
T
H
HO
OH
O
O
S
H
OH
O
OH
BS
H
O
O
OH O
OH
O O
BT
H
OH
O O
OH
BTB
H
O
O
O
O
O
O
O
O
O O
BS
BT

Scheme2.9.Chemicalstructiresofmonomersandoligomers[78]

50

Investigation carries out by several scientists indicated that increased temperature and excess
chain extender could not only activate the chain extension reaction, but also accelerate the side
reactions, such as branching or crosslinking, reducing the solubility of the products. Therefore,
ameliorated chain extension need to be conducted to reduce the possibility of crosslinking. Chain
extension temperature and chain extender content were both factors affecting chain extension
reactions. Therefore, a stable chain extension method by decreasing the reaction temperature and
reducingthediisocyanatecontentwasintroduced.
IntheprocessofPBSTsynthesisusingasmallexcessofthedioloverthe diesters,ispresented
belowinscheme2.10.

nH
2
CO-C(CH
2
)
2
-C-OCH
2
+1.2(n+m) HO-(CH
2
)
4
-OH +mH
2
CO-C-
O
O O
-OOC -COO
COCH
3
O
O(CH
2
)
4
OOC(CH
2
)
2
CO/
m
O(CH
3
)
2
OOC-
-OOC-
-
-COO-
-CO/
m
3

Scheme2.10.PBSTcopolymerssynthesis

Moreover Xu et al. [55] in order to increase the thermal and mechanical properties of PBS
preparedaseriesofpotentiallybiodegradableliquidcrystallinearomatic/aliphaticrandomcopolyesters
by melt polycondensation of MTB, dimethyl succinate, and butanediol. A twostep polycondensation
technique was followed as well and the
w
M values of the copolyesters were in the range of 24.400 to
53.600g/mol.ItwasalsofoundthatT
m
,crystallizationbehaviourandhydrolyticdegradationrateofthe
copolyesters decreased gradually with increasing the MTB content. In comparison the elongations at
breakincreasedremarkablywithincreasingMTBcontent.
Honda et al. [78] synthesized PBST and revealed the effect of aromatic block unit on their
enzymatic degradation under a lipase, and the biodegradability of PBST copolyester could be tailored
withincreasingthepopulationofaliphaticbutylenesuccinateblock.

51

2.3.3.PBScopolymersfilledwithtalc
Talcisahighlyfunctionaladditivethatenhanceskeypropertiesofnumerousresins.Inaddition
to being a costeffective filler, talc can effectively provide antiblocking, reinforcement, and improved
barrierproperties.Duringpolymerprocessing,talc,asthesoftestmineral,minimizesequipmentwear.It
alsodecreasesmoldshrinkage,andimprovesendproductmachining.
Plastics exhibit increased stiffness, reduced mold shrinkage, improved heat stability and lower
materialcostswhenfilledwiththeappropriatelysizedtalc.Impactstrengthcanbemaintainedwhenthe
particlesizeiscarefullycontrolledtoa1to2micron,ultrafinemedianparticlesizewhilemaintaininga
minimumtopsize.Inadditiontosize,talcparticleshapeandparticleaspectratiocanbeusedtofurther
optimize these properties. alc with an aspect ratio of 10 to 1 when melt compounded with a
homopolymer will provide a 250 percent increase in flexural modulus too. Polyester gel coat barrier
properties are improved with the addition of fine ground, platy talc. Talc also functions well as a
nucleatingagentduringmeltcompounding.
The block copolymers can be produced by any well known polymerization or copolymerization
procedure including sequential addition of monomer techniques, incremental addition of monomer
techniqueorcouplingtechnique.Thetalcmaybeaddedwiththepolyesterreactantsbeforepolyester
is prepared or the talc may be blended with the polyester after its preparation by conventional
techniques [80]. It has recently been discovered that the incorporation of talc filled into thermoplastic
polyesters which have been modified by the incorporation of a butadienebased modifier, causes the
degradation of the polyester. So these talc filled thermoplastic polyester compositions degrade during
the mixing of the composition as well as during further processing operations such as extrusion and
injectionmolding[80,81].

2.3.4.Othercopolymers
A new copolyester poly(butylene succinatecoethylene succinatecoethylene terephthalate)
(PBEST), was synthesized via direct polycondensation from three prepolymers of butylene succinate,
ethylene succinate and ethylene terephthalate. PBEST has excellent elongation behavior and
biodegradability at a certain composition. Particularly, its elongation at break is around 1200 % when
PBEScontains78mol%ofPESand22mol%ofPBS.
HO-[CCH
2
CH
2
COCH
2
CH
2
O]
m
-H
O
O

Scheme2.11.PBESTstructuralunit

52

All the synthesized copolyesters have an intrinsic viscosity ranging from 0,62 to 0,86 dl/g (in
CHCl
3
at 20 0,1 C) within a reaction time range of 38,5 h. In particular, a longer reaction time is
needed for polyesters with a higher content of poly(ethylenesuccinate) PES, indicating that Ti (BuO)
4

catalyst was not so highly efficient for the synthesis of copolyesters containing high content of (PES)
prepolymeralthoughitwasaveryefficientcatalystforsynthesisofothercopolyesters.
HOOCCH
2
CH
2
COOH +HOCH
2
CH
2
CH
2
CH
2
OH HO-[CCH
2
CH
2
COCH
2
CH
2
CH
2
CH
2
O]
n
-H
O O
HOOCCH
2
CH
2
COOH +HOCH
2
CH
2
OH HO-[CCH
2
CH
2
COCH
2
CH
2
O]
m
-H
O O
HOOC
COOH +HOCH
2
CH
2
OH
HO -[C
O
COCH
2
CH
2
O]
k
-H

Scheme2.12.PBESTsynthesis[82]

For the synthesis of PBEST copolyesters, the reaction temperature reached around 235 C, which was
abovethetemperatureoftheesterbondcleavageinprepolymers,thusleadedtothepossibilityofester
exchange reaction. Meanwhile, a long reaction time was also assumed to be in favor of the ester
exchangereaction[82].
AnothercopolymerbasedonPBSisthealiphaticpoly(butylenesuccinatecobutylenefumarate)
(PBSF), which is synthesized by a two step transesterification reaction. PBSF copolymers show slightly
higher melting and crystallization temperatures than the corresponding homopolyester, PBS. The
incorporationofdoublebondsinto thepolymerchainsmakesthemstifferwhichin turnhastheeffect
of increasing the melting temperature. All the copolyesters are less thermally stable than PBS
homopolymer and increasing content of fumaric residues the stability is decreased. The trend was
opposite in air. Although the copolyesters are less stable than PBS, their stability increases with
increasingfumaratecontent.Also,thecopolyestersaremorestableinairthaninnitrogenasaresultof
thermal degradation inhibition because of the oxygen and that these inhibitory reactions take place at
the double bonds. The highest biodegradability was observed for the copolyesters containing 5 and 10
mol%offumarateunits.

- C (CH
2
)
2
CO(CH
2
)
4
O-
O O
x
CCH
CHCO(CH
2
)
4
O
O O
y

Scheme2.13HighmolecularPBSF

53

Starting from the dimethyl esters (dimethyl succinate and dimethyl fumarate) and butanediol
with a diol excess and Ti(OBu)
4
as a catalyst. Reaction temperature was maintained under vacuum at
200 C for 20 h [75]. In order to prevent reaction on the double bond of the fumaric acid, the
transesterificationreactionwascarriedoutat200Cforlongerperiodsoftime,1220hdependingon
the composition of the reaction mixture. The key to the successful synthesis of highmolecular weight
aliphatic polyesters is the combination of a highly effective catalyst and the proper choice of
polymerizationconditions,suchasthereactiontemperatureandreactiontime,whichwoulddiminished
sidereactionsonthereactivedoublebondsofthefumaricmoieties.
Another aliphatic copolyester poly(butylene succinate co isosorbide succinate co
polyethyleneoxide succinate) (PBxIyEzS) was synthesized by the twostage melt polycondensation
methodcomposingofesterificationandpolycondensationinthepresenceofdimethylsuccinate(DMS),
1,4butanediol (BDO), isosorbide (ISO) and poly(ethylene glycol) (PEG). PBxIyEzS copolyesters
synthesizedfromthreedifferentdiolmoieties(BDO,ISOandPEG)havehighmolecularweightsandthey
aresuitabletobeusedinfieldswhereflexiblematerialsareneeded.Biodegradablecopoloyestersbased
on renewable resources were successfully synthesized by the transesterification and polycondensation
inthemeltfrompoly(butylenesuccinate),poly(ethyleneglycol)andisosorbide.ComparedtopurePBS,
the PBxIyEzS copolyesters showed lower crystallization temperature, melting temperature and
crystallinity while a significant increase in glass transition temperature with increasing isosorbide
content[83].
OMe
OMe
O
O
+
O
O
OH
H
OH
H
+HO-(CH
2
)
4
-OH +H -(O-CH
2
-CH
2
)
k
-OH
1. esterification 100
o
C 2h - 230
o
C 3h
2. polycondesation 230
o
C 4h
-O -(CH
2
)
4
-O
O
O
x
O
+
O
O
O
H
H
O
O
)
y
(O-CH
2
CH
2
)
k O
O
O
z

Scheme2.14.SynthesisrouteofPB
x
I
y
E
z
S

54

2.3.5.BranchedPBS
Kim et al. [72] produced long branched poly(butylene succinate), by introducing a branching
agent, trimethylol propane (TMP) and titanium isopropoxide as a reaction catalyst. It was found in the
samestudythatT
m
isslightlydecreasedasthecontentofmodifierisincreased.However,crystallization
temperature(T
c
)wasnotablydecreasedwithincreasingthemodifiercontent.ThereductioninT
m
andT
c

results from the fact that chain branching reduces molecular regularity and retards crystallization. The
numberaverage molecular weight is decreased with TMP content while the weightaverage molecular
weightisincreased.
LongchainbranchedPBSwasalsosynthesized,using1,2,4butanetriolasalongchainbranching
agentandTi(OBu)
4
asacatalyst.Theresultsoftheresearchshowedthatwiththeincreasingof1,2,4BT
segments,thecrystallizationtemperaturesandglasstransitiontemperaturesincreaseslightly,whilethe
relative crystallinity degree decreases gradually. The viscoelastic properties of branched PBS under
shear flow were different from the linear PBS. The complex viscosities of longchain branched PBS
increasedincomparisonwiththoseoflinearPBS.Concernigng
n
M itwasfirstincreasedgraduallyand
thendecreasedslightlywiththeincreasingof1,2,4BTsegments[84].

(m+n)
OH
OH
O
O
(m)
OH
OH
(n) OH
OH
OH
*
O
O
O
O
O
O
O
O
O
OR
m
n
+2(m+n)H
2
O
OH
OH
OH
OH
O
O
O
O +
+
*
*
O
O
O
O
m
n

Scheme2.15.SynthesisoflongchainbranchedPBS[84]

55

2.3.6.PBSblendsandnanocomposites
Starch is totally biodegradable, environmentally friendly and low cost material. Nevertheless,
sincestarchishighlysensibletowaterandhasrelativelypoormechanicalpropertiescomparedtoother
petrochemical polymers, its use is limited. So the solution is to blend it with other synthetic polymers
(scheme 2.16). A lot of research work deals with the development of blends of starch with synthetic
biodegradablepolymers.Theseblendspresentseveraladvantages[85].
The blending process is low cost compared to the cost of the development of new synthetic
materials.Thesekindsofblendsareintendedtobemorebiodegradablethantraditionalones.PBSwas
blended with granular corn starch [86]. Increasing the starch content, the elongation at break and the
tensilestrengthweredecreased.Onthecontrary,theadditionofstarchfillerssignificantlyimprovedthe
degradationrate.Thestudiesofblendsofstarchwithaliphaticpolyesters(PCL,PBS,andPHBV)showed
in all cases that only a modest level of starch is possible. To improve compatibility between the starch
and the aliphatic polyester, a compatibilizer was used. It contains an anhydride functional group and
wasincorporatedontothepolyesterbackbone.Thetensilestrengthobtainedforsuchblendswasclose
tothatofsyntheticpolyester,onlywithasmallamountofcompatibilizer[87].

O
O
CH
2
OH
OH
OH
O
O
CH
2
OH
OH
OH
O
O
CH
2
OH
HO
OH
O
O
CH
2
OH
HO
OH
O
CH
2
O
OH
OH
O
O
O
HOH
2
C
HO
OH
O
O
CH
2
OH
OH
OH

Scheme2.16PBSAstarchblend

56

For certain applications, biopolyesters cannot be fully competitive with conventional

thermoplastics since some of their properties are too weak. Therefore, to extend their applications,
these biopolymers have been formulated and associated with nanosized fillers, which could bring a
largerangeofimprovedproperties(stiffness,permeability,crystallinity,thermalstability).SinhaRayet
al. [88] first reported structure and properties of PBS/clay nanocomposites (PBSCN) obtained by melt
intercalation. Other studies [88, 89] investigated the effect of the organoclay type on the composites
structures and properties. High molecular weight PBS was synthesized by a coupling reaction with a
chain extender, namely the hexamethylene diisocyanate (OCNC
6
H
12
NCO), resulting in urethane
moietiesandterminalhydroxylgroups.After manyresearchestesting metalbasedcatalysts (dibutyltin
dilaurate Sn(Bu)
2(
Lau)
2,
titanium(IV) butoxide Ti(OBu)
4
and antimony(III) oxide Sb
2
O
3
) for the
esterification reaction, Sn(Bu)
2
(Lau)
2
appeared to be the most appropriate one. Sinha Ray et al. also
reported PBSAbased nanocomposites. Cloisite30B appeared the most suitable nanofiller for PBSA
basednanocompositespreparedbymeltintercalation.

O
C
N
O
H
N
H
C
O
O
=PBS

Scheme2.17.FormationofurethanebondsinhighmolecularPBS

A last, rice husk (RHF) and wood flour (WF) are two of the agromaterials that can be used as
reinforcing fillers in biodegradable polymer biocomposites. RHF is an agricultural waste material
generatedinriceproducingcountries,especiallyintheAsian,Pacific,andNorthAmericanregions.Most
ofthisricehuskisusedasabeddingmaterialforanimalsandtheindustrialapplicationsofthismaterial
are limited. Therefore, the use of rice husk in the manufacture of agromaterialfilled biodegradable
polymer biocomposites is attracting much attention because of the potential biomass energy. With
increasingagroflourcontentinthePBSbiocomposites,therewasamorerapiddecreaseinthetensile
strength, notched Izod impact strength, and percentage weight loss of the biocomposites by bacteria
and fungi during the natural soil burial test. Agroflourfilled PBS biocomposites are environmentally
friendly and degradable materials that can be considered as alternatives to conventional plastic
materialsforpacking,injectionmolded,anddisposableproducts[90].

57

2.4.Catalysisinpoly(butylenesuccinate)preparation
PBSsynthesisismainlycarriedoutwithtitanium(IV)isopropoxide,titanium(IV)isobutoxideor
titanium (IV) nbutoxide [60,91,92]. It is generally accepted that titanium and specially
tetrabutoxytitaniumisthemostactivecatalystfortransesterificationpolymerization[93].Mochizukiet
al. [60, 91] synthesized PBS with
n
M up to 59.000 using tetranbutoxy titanate as a catalyst and
polyphosphoric acid as a thermal stabilizer. Using titanium (IV) isopropoxide, Ahn et al. [61] produced
PBS with
n
M of 77.000 and
w
M of 141.000. Rizzarelli [63] starting from dimethyl succinate and
butanediol in the presence of titanium (IV) butoxide, obtained high molar mass polymers with a Mw
92.940.
Sonnenschein et al. [63] also studied PBS synthesis through polycondensation of succinic acid
with butanediol using dibutyl tin dilaurate or dibutyl tin oxide as catalyst .Samples of 1.000 g/mol or
2.000 g/mol were synthesized under N
2
flow. Germanium and antimony metal oxides can also display
desirablecatalyticefficiency,whentheyareassociatedwithhydroxyacids,whichareactingaschelating
agents. However, this catalytic system exhibits lower efficiency compared to a titanium one [53,75].
Thesecatalystsappeartobelesseffectivethanalkoxides,buthavetheadvantagesofbeingwaterstable
and soluble in ethylene glycol at room temperature. The ability of metal oxides to catalyze PBS
transesterification was clearly improved by the presence of hydroxy acids. Nevertheless, when the
concentration of these compounds became too high, the efficiency of the catalytic mixture began to
decline.Thisdecreaseinefficiencyislinkedtothequantityofhydroxylacidaddedsincetheinsertionof
hydroxyacidunitsinPBSchainsdecreasestheproportionofactivehydroxylPBSendgroupsthatplay
adominantroleintransesterification[94].
Ishiietal.[64]reportedonestepsynthesisofPBSbydistannoxanecatalyzedpolymerizationof
succinic acid and butanediol in a twophase system of solvent (decalin) and molten polymer under
azeotropic conditions at atmospheric pressure. When the reaction time was extended to 72 h in the
presenceof0.001mol%ofcatalyst,PBSwithMnof117.000andMwof277.000wasobtained.
At the National Sun Yatsen University, researchers [65] examined the effect of different
catalysts, such as SnCl
2
, Ti(OiPr)
4
, Ti(OBu)
4
, Sn(Oct)
2
, Zn(Ac)
2
, and p toluenesulfonate (pTS), on the
molecularweightofsolutionpolymerizedPBS.Amongthesecatalysts,SnCl
2
showedthemostpromising
result, producing PBS with a
w
M of 79.000 after a 12 h reaction. Utilizing a new water trap that
contains a 4 molecular sieve, Zhu et al. [66] synthesized PBS with
n
M of 24.800 after
polycondensation for 70 h with SnCl
2
as a catalyst and dimethyl benzene as the solvent and water
removingagent.

58

Takasu et al. [95] gave emphasis to rare earth triflates as catalysts for the room temperature
directpolycondensationofdicarboxylicacids.Bismuthbasedcompoundsascatalystscanleadtoa
n
M
upto30.000afterabulkpolymerizationat80Cforover48h[67].
Buzin et al. [68] is another one who examined polycondensations with the triflates of sodium,
magnesium,aluminum,zinc,tin(II),scandium,andhafnium.Polycondensationsandmodelexperiments
provedthatmosttriflatescatalyzedtheformationoftetrahydrofuranfrombutanediolabove100Cand
that the highest
n
M values were achieved with Bi (OTf)
3
. At temperatures of 80 C the number
average molecular weights up to 35.000 and at temperatures up to 120C
n
M <10.000 were not
obtained. PBS homopolymer produced by the ordinary melt polycondensation with zinc acetate
dihydrateasthecatalyst,obtainedanumberaveragemolecularweightof53.000withapolydispersity
in
w
M /
n
M of1.9.TheT
m
andT
g
weredeterminedtobe114Cand34C,respectively[69].
In order to reduce side reactions and consumption of energy, low temperature
polycondensation methods have recently attracted increasing interest. For instance, 2,2dibutyl1,3
stannepane reacts at room temperature exothermically with succinyl chloride, but the
n
M of the
resultingPBSgradeswaslow,duetorapidcrystallizationoftheoligoesters.Themostversatileapproach
yielding any kind of aliphatic polyesters with moderate to high
n
M is the polycondensation of diols
with dicarboxylic dichlorides catalyzed by pyridine at temperatures <20 C. Yet, this approach is
particularly expensive and not suited for upscaling. Ueda and coworkers claimed that high molar mass
PBSmaybeobtained,whenbutanediolandsuccinicacid,werestirredwithorwithoutcatalystat120C,
followed by heating to 200210 C in refluxing decalin. The addition of decalin had the purpose to
remove the liberated water azeotropically and to maintain a biphasic reaction mixture, so that the
polycondensation proceeded at the highest possible monomer (and oligomer) concentration. However
itisdemonstratedthatthecombinationoftheUedamethodwithnontraceBicatalysts,representsa
satisfactory approach to the preparation of PBS. This conclusion is supported by the finding that the
commercialPBShasaninherentviscosityofonly0.40dL/g,whenmeasuredundertheconditionsofthis
work.
Recently, new catalysts have been developed that are based on rareearth metals, such as
Sc(OTf)
3
orSc(NTf
2
)
3
.Thesecatalystsarecapableofachievingthebulkpolycondensationofmethylester
of succinic acid with butanediol under mild conditions (35 C). Moreover, these catalysts can be
recoveredandreusedbysolubilizationinchloroformandextractionwithwater.Polycondensationtimes
at such temperatures remain very long (>50 h), and the final number average molar mass of
n
M ,
ranging from 5.000 to 12.000 g/mol is relatively low [53,75]. Takasu [70] demonstrated that Sc (OTf)
3

59

cancatalyzenotonlytheesterificationofPBSbutalsoetherificationasasidereaction,whichdepends
on the chain length (methylene number) of the diols. The catalyst makes it possible to prepare
biodegradablepolyesters,havinga
n
M over10.000evenat35C.Thepolycondensationat160Cand
180Cfor10hgivesaPBSpolymerwitha
n
M of20.900and30.700respectively,eveninthepresence
of 0,1 mol % catalyst. Direct polycondensation using the recovered catalyst gave PBS with a
n
M of
14.300.
In summary, metal ranking is Ti > Ge > Zr> Sn > Hf > Sb > Bi. Despite the fact that Tibased
catalysts are highly efficient, they should be used with caution due to the important degradation
reaction that they induce. That was particularly outlined by the carboxylic acid endgroups contents,
yellownessindexesandreducedviscosities,whichweremeasureduponageing.Residualmetalsinthese
materials are difficult to remove, because of strong metalester interactions. These metals can cause
undesirableeffectsontheenvironmentuponmaterialdisposal,limitpolymeruseinapplicationssuchas
electronics,andmaybeunacceptablecomponentsofmedicalmaterials.Furthermore,thecombination
of high reaction temperatures and organometallic catalysts can lead to monomer/ polymer
decompositionreactionsand,hence,discolorationanddecreasedproductmolecularweight.

2.5.Industrialproductionofpoly(butylenessuccinate)
ThefirstattemptforPBSsynthesiswasmadein1931byCarothers.ThePBSobtainedwasoflow
molecular weight, less than 5.000, and was weak and brittle. In 1993, Showa High Polymer produced
highmolecularweightPBSunderthetrademarkBionolle,whichwassynthesizedviameltcondensation
polymerization followed by a chainextension method [96]. However chainextended PBS was not
suitable for some applications. Thereafter, researchers and companies attempted to manufacture high
molecular weight PBS via direct melt polycondensation. In 2003, Mitsubishi Chemicals introduced GS
Pla.Afterthreeyears,HexingChemical,AnhuiproducedPBSthroughdirectmeltpolycondensationand
in 2007, Xinfu Pharmactical built a PBS production line with onestep polymerization technology [97].
ThemajormanufacturersofPBSanditscopolymersarelistedinTable2.2.

60

Table2.2.PBSandcopolymersproducers
Manufacturer Product
HexingChemical,China
PBSandcopolymers
Bioamber RenewablemodifiedPBS(mPBS)
XinfuPharmaceutical,China PBS,PBSA
JinfaTech,China PBSA
AnqingHexingChemicalCo,China PBS
BASF,Germany Ecoflex
Eastmann,USA EastBio
Showa,Japan Bionolle
MitsubishiChemical,Japan GSPla
MitsubishiGaschemicals,Japan Iupec
NipponShokubai,Japan Lunare
Ube,Japan ETERNACOLL3050
IreChemical,Korea Enpol
SKChemicals Skygreen

2.5.1.ShowaHighpolymerBionolle
ShowaHighpolymer,partoftheShowaDenkoGroupinJapanwasthefirstcompanytoproduce
a commercial biodegradable PBS polymer with the trade name Bionolle. Grades of Bionolle are
poly(butyleneSuccinate)(#1000series),poly(butylenesuccinateadipatecopolymer)(#3000series)and
poly(ethylene succinate) (tentatively #6000 series). Showa Denko has selected Myriant as its global
supplierofbiosuccinicacidasarawmaterial[98].
These polymers were first produced through polycondensation reaction of butanediol with aliphatic
dicarboxylic acids and in case of need for higher molecular weights, coupling reaction was carried out
with coupling agents acting as chain extenders (e.g. hexamethylene diisocyanate). Chain extension of
HOPBSOH with diisocyanate can produce PBS with a relatively high molecular weight in a range of
about20.000200.000andweightaveragemolecularweight(
w
M )atabout40.0001.000.000[99,100].
The esterification reaction can be carried out at 160C 230C for 516 h preferably under
nitrogen gas atmosphere. Then, transesterification is carried out at 170C 230C for 216 h under a
decreased pressure. However in view to the reaction rate and the prevention of decomposition, it is
preferabletoperformthereactionat180C210Cunderhighvaccumstate[99,100].

61

Bionolle is a semicrystalline polymer and flexible. The polymer was designed to have the
processibility of polyethylene with physical properties similar to those of poly(ethylene terephthalate)
[88]. It has high flexibility, excellent impact strength, and thermal and chemical resistance. It can be
processed easily and is the best choice to blend with poly(lactic acid). Showa Denko produces also
Bionollederivedfrombiobasedsuccinicacid.Usingmorethan60%ofstarchasarawmaterial,theend
product Bionolle Starcla is a biobased environmentally friendly polymer, which returns to nature
becauseitiscompletelybiodegradable.PhysicalpropertiesofBionolleareshowninTable2.3below.
Showa Denko K.Ks Bionolle family of biodegradable plastics have received numerous green
certifications from associations across the globe including the GreenPla label by the Japanese
BioPlastics Association (JBPA), the OK Compost mark by AIBVincotte (AVI) and the Belgian based
certificationandscreeningbody,foritscapacitytocompletelybiodegrade.

Table2.3.PhysicalpropertiesofBionolleanditsgrades[96,98]

Units PBS PBSA

Density
g/l 1.260 1.230
Heatofcombustion KJ/g 23.6 23.9
Heatdeflection
temperature(at0.45MPa)
C 97 69
Crystallinty % 3545 41
Meltingpoint(Tm) C 114115 114
Glasstransition C 32 45
Grade 1001MD 1020MD #1903 3001MD 3020MD
MFR(190,2.16kg) g/10min. 1.5 25 4.5 1.4 25
Crystallization
temperature
C 75 76 88 50 53
Flexuralmodulus MPa 660 640 690 320 340
Tensileyieldstrength MPa 32 34 39 19 19
Tensilebreakstrength MPa 57 21 35 47 34
Tensileelongation % 700 320 50 900 400
Structure Linear
Longchain
branch
Linear

62

Bionolleiscommercialavailableuntil1994.ShowaHighpolymerconstructedapilotplantwitha
capacity of 10 tons/year in 1991 and a semicommercial plant with a capacity of 3.000 tons/year in
1993.In2002Showadoubleditscapacityto6.000tons/year[60].ShowaHighPolymersellsBionollefor
3,50 per kilo and expects this price to go down only marginally to 3,00 per kilo [98]. Since the raw
materialhasthemostinfluenceonthecostprice,Showaclaimsthatthepercentageofcostsattributed
to the feedstock will increase (from 50 % in 2003 to 85 % in 2030). Showas projections are in sharp
contrast to the expected decrease in raw material cost (both in absolute terms and relative to total
costs)whichisexpectedforthebiobasedroute.

2.5.2.SKChemicalsSkyGreen
SK Chemicals, Korea is also reported to have a small plant producing PBS and PBSA with the
trademark SkyGreen BDP (Table 2.4). SkyGreenis a series of aliphatic polyester and aliphatic/aromatic
copolyesterthatisdegradedintowaterandcarbon dioxideby microorganisms.This producthasbeen
mainly developed on the basis of the SK Chemicals PET technology and there is no other chemical
linkagethanesterinitsmolecularstructure[101].

Table2.4.Physicalproperties[102]
Density 1.27g/cm
3
Tensilestrengthbreak 26MPa
Elongationbreak 70%
Flexuralmodulus 2150MPa
Heatdistortiontemperature(0.455MPa) 74
o
C
MeltingPoint 110C

2.5.3.MitsubishiChemicalGSPla
Mitsubishi Chemical produces biobased PBS named as GS Pla[60]. Succinic acid obtained
through glucose fermemtation processes, butanediol and lactic acid are used as raw materials, which
throughadirectdehydrationpolycondensationaretransformedtoPBS[103].
ThemainGSPlacharacteristicsaresafety,workabilityandmoldingproperties.GSPlaisaliphatic
polyesteravailableforvariousmoldingprocesses,likeinflation,extrusion,injectionandblow.Moreover
itcan presentgreat compatibilitywith otherbiodegradableresins.Asfarasdegradationisconcerned,
the polymer can be decomposed into water and carbon dioxide by microorganisms in the natural
environment.PhysicalpropertiesofBionolleareshowninTable2.5.

63

Table2.5.PhysicalpropertiesofGSPlagrades[104]
Physicalproperties
GSPlagrades
FZ91P AZ91T AD92W GZ95T
Densityg/cm
3
1,26 1.26 1.24 1.51
GlasstransitiontemperatureC 22 24 36 24
MeltingpointC 115 110 88 110
TensilestrengthMPa 40 55 50 33
Tensileelongationatbreak 250 450 800 5
FlexuralmodulusMPa 650 550 300 1.800
IzodimpactstrengthkJ/m 9 10 35 5

2.5.4.BioamberModifiedPBS(mPBS)
Bioamber using biobased succinic acid as a raw material produces renewable modified
poly(butylenesuccinate)plastic(mPBS).ThisrevolutionarymodifiedPBShasbetterperformancethan
other biodegradable polymers sold today, with heat resistance above 100 C, excellent strength
properties and the ability to be processed in existing production equipment. Bioamber is the first
companytocommercializePBSwithrenewablecontentabove50%[105].
These new composites are engineered and designed at the molecular level using BioAmbers
proprietary technology to meet enduser requirements for high performance, biodegradable
plastics.The uniformity, performance and processability of mPBS in existing equipment has been
confirmed by a number of end users, with applications ranging from foodservice cutlery and coffee
cup lids to plates, bowls, straws and stirrers, as well as non food contact applications such as razor
handles,sheets,filmsandfibers.
AmongthebasicchracteristicsandbenefitsofmPBSare:
o Highheatdistortiontemperature,upto110C(230F)
o Highstrengthandstiffness
o Goodductilityandstrength
o Greatprocessability
o Dropinexistingproductionequipment
o Injectionmoldingandextrusiongrades
o Meetsglobalbiodegradabilitystandards
o Gradesthatcanbeusedinfoodcontact
o Flexibilitytousepetroleumand/orrenewablerawmaterials

64

2.5.5Otherindustries
Anqing Hexing Chemical Co. Ltd.is a high technology enterprise producing PBS based on
biologicaltechnology.Itcanbeappliedforfieldssuchaspackage,tableware,cosmeticsbottle,medicine
bottle, oneoff medical supplies, agricultural films, pesticides, fertilizing slowrelease materials and
biologicalmedicalmacromoleculematerialsetc[106].
IRE is another big company producing PBS with the trademark EnPol. These polymers are
produced through the polycondensation reaction of glycols and dicarboxylic acids with IRes self
developed catalyst and process technology [78]. EnPol polymers are stable in the atmosphere, but
biological decomposition commences when exposed to bacteria or fungi and moisture. Living micro
organismstransformEnPolpolymersintowater,carbondioxideandbiomass.Inaddition,EnPolpolymer
completely decompose in normal composting conditions without any harmful byproducts, and
harmless to the environment at every stage of decomposition process. Ire produces several EnPOl
gradessuchas:
o EnPol G4560 [PBS] whose mechanical property can be a adjusted by changing melting flow
index(M.F.I)dependingonthepurposeofproductinpolycondensationprocess
o EnPolG4560J[PBS].ItsT
m
andspecificgravityaresameasthoseofG4560butitsMFIishigher
thanthatofG4560.
These polymers can be applied as disposable goods (cup, knife, spoon, fork, razor, straw, golf
tee), films (compost bag, trash bag, shopping bag, packaging film, shrink film, blister film, etc.),
agriculture and horticulture (mulch film, plant pot, rope or string, clip, etc), fishing gear (fishing net,
Fishing trap, rope, fishing line) and containers (tray, food containers, bottles, shampoo, detergent,
beverage).
China Materials Holding Ltd produces high molecular weight PBS from butanediol and succinic
acid in the presence of catalyst through one of the two production methods: the chain extension
process or the direct polycondensation process patented by the Technical Institute of Physics and
ChemistryoftheChineseAcademyofSciencesIPCCAS.TheyinitiallyengagedIPCCAStoinvestigateinto
the feasibility of constructing a 20.000 tones per year PBS production facility adopting its direct
polycondensationprocessin2008.InJuly2009,theyenteredintoaletterofintentwithIPCCASforthe
licensingofthispatentedprocesstoconstructa20.000tonesperyearPBSproductionfacility,aswellas
settingupajointresearchlaboratorytoresearchintonewPBSformulationsandpotentialapplications.
Subsequently in December 2009, the company entered into a formal technology licensing agreement
with IPCCAS under which they were granted a nonexclusive license to use the relevant PBS resin
polymerization technologies in their PBS production facilities and our 500 liter PBS laboratory facility
adoptingtheIPCCASprocess[107].

65

CHAPTER3:CHARACTERIZATIONANDCRITICALPROPERTIES
OFPOLY(BUTYLENESUCCINATE)

3.1.Methodsforpoly(butylenesuccinate)molecularweightdetermination
3.1.1.Gelpermeationchromatography
MolecularweightofsynthesizedPBScanbedeterminedusinggelpermeationchromatography
(GPC). Polystyrene is used as a standard with a low polydispersity in order to make a calibration curve
andchloroformasaneluentataflowraterangingbetween0.8mL/min1mL/min[108,109].GPCcan
be performed at 40 C [64], 35C [53, 75] or room temperature. Shah et al. [110] used
hexafluoroisopropanol (HFIP) as an eluent and the molecular weight was measured relative to
poly(methylmethacrylate)(PMMA)at40C.
Another way to measure the weightaverage molecular weight (
w
M ), numberaverage
molecular weight (
n
M ), and molecular weight distribution (
w
M
/
n
M ) for polymers is size exclusion
chromatography(SEC) usingSEC columnswitharefractiveindex detector.Chloroformwasusedasthe
eluentat1.0mL/mininthiscasetoo.TheSECsystemiscalibratedwithpolystyrenestandardshavinga
narrow molecular weight distribution [76]. Except chloroform for SEC analysis, tetrahydrofuran
stabilized with hindered phenol can also be used as mobile phase at the velocity of 1.0 mL/ min.
HoweverPBSpresentsapoorsolubilityinTHF.
Lahciniinhisstudy[67]inordertoestimatethemolecularweightoftheobtainedpolymers,he
has taken into account that several research groups reported that direct comparison with polystyrene
standardsin chloroformoverestimates therealmolecularweightsby5080% (dependingonchemical
structureandmassrange).Thisoverestimation correspondsto correctionfactorsintherangeof0,55
0,67. When the SEC measurements of three PBS samples were evaluated via the universal calibration
method it was found that the direct calibration with polystyrene causes an overestimation of
n
M and
w
M by80100%.
The difference between several researchers and their results can only be explained by the
different starting points used for the evaluation of the elution curves. In the case of polycondensation
themaximumofthefrequencydistributionisusuallythedimericspecies(regardlessiflinearorcyclic).
Therefore, polycondensates contain a high molar fraction of oligomers, which is important for the
calculation of
n
M even when their mass fraction is low. If the evaluation of the elution curve begins

66

with the mass of the dimer (around 400 Da) with a mass of 2000 Da or with a mass of 5000 Da may
resultinavariationofMnbyafactorof10,whereastheinfluenceon
w
M issmall.Therefore,
n
M values
of polycondensates published without definition of the mass range used for their calculation are
absolutelymeaningless.
Moreover,thedifferenceofthemolecularweightdetectedbyGPCfromthatcalculatedbythe
hydroxyl number is due to different methods of the measurements. Molecular weight calculated from
the hydroxyl number is the absolute molecular weight. But
n
M and
w
M detected by GPC are relative
molecularweight.ThenumberaveragemolecularweightMnofPBScanalsobecalculatedfromintrinsic
viscosity[]values,usingtheBerkowitzequation:
n
M =3,29x10
4
[]
1,54
[93].
InastudydonebyKimetal.[72]itisproventhatconcerningbranchedPBSthenumberaverage
molecular weight (
n
M ) decreased with increasing branching agent content, while the weightaverage
molecular weight (
w
M ) increased. This means that the polydispersity index increased with increasing
branching agent content. Molecular weights and polydispersities of the PBSA and PBSA/starch blends
were determined by GPC using chloroform. PBSA solutions of varying concentration were used to
prepare a calibration curve of molecular weight. However, because of the insolubility of starch in
chloroform, only the PBSA component of the blends could be detected in the chromatograms [86]. In
thefollowingtableMn,MwandMw/Mnresultsfromseveralbibliographicalsourcesarepresented.

3.1.2.Endgroupconcentrationsanalysis
Todeterminethenumberofmolesofapolymer,theanalysismethodmustrespondequallyto
eachmoleculewithoutregardtoitschainlength.Themonomermoleculesattheendsofthechainmust
in some way be different from the chain itself. For a linear polymer (i.e., one in which there are no
bonds, called crosslinks, between the chains) every molecule has two end groups, which may be
identical or different. If the end groups can be analyzed, the number of polymer molecules may be
calculated using simple stoichiometric relationships. Using this end group analysis method Mn can be
easilydetermined.
Carboxylendgroupcontent(COOH)canbedeterminedbyatitrationmethodusingchloroform
as a solvent at room temperature, NaOH in methanol as a standard and phenol red as indicator. For
hydroxyl groups (OH) the polyester is dissolved just in chloroform [54]. An equation used for the
calculationofthecarboxylicacidendgroupscontent(CC)is:
CC(
eq
/g
polym
)=[(V
eq
xC
NaOH)
/m
polym
]x10
3

67

where, CC is the carboxylic acid end groups content, Veq is the volume of the solution, C
NaOH
is the
NaOHconcentrationandm
polym
isthemolarmassofthepolymer.
Itishasbeenprovedthatcarboxylicacidendgroupscontentcanbeincreasedwiththequantity
of catalyst contained in the polymer [94] and decrease constantly with time at all temperatures [111].
Carboxyl end groups are reducing only by esterification reaction, but it is interesting to note that after
thefirstpolycondensationhouraplateauinthecarboxylendgroupvaluesisalmostreached.

Figure3.1.VariationoftheCOOHcontentwithtimeduringpolycondesationofPBSatdifferent
temperatures[93]

Asfarashydroxylgroupsareconcerned,aninitialabruptreductiontakesplaceatthebeginning
of the polycondensation reaction, while afterwards this reduction levells off. This reduction was more
pronounced at higher temperatures. The values of the hydroxyl end groups do not show the plateau
observedinCOOHendgroupsinsteadtheycontinuouslydecrease.

Figure3.2.VariationoftheOHcontentwithtimeduringpolycondesationofPBSatdifferent
temperatures[93]

68

Velmathi et al. [59] produced PBS polymers and analysed their end group using
1
NMR
spectroscopy.Theresultsshowedapeakcorrespondingtothethemainpolymerchain,andaverysmall
triplet at 2,5 ppm corresponding to the methylene protons of the succinic acid end group. This
observationsuggestedtheformationofCOOHendgroupsofthepolymerchain.Averysmallbroadpeak
at3,3ppmwasalsofoundandassignedtoterminalOHprotons.Amultipletat3,6ppmcorrespondsto
theOconnectedmethyleneprotonsoftheendgroupandamultipletatd1,6ppmwasassignedtothe
methylene protons. These peaks are similar to butanediol peaks confirming the presence of a diol end
group.
Chrissafis et al. [54] estimated COOH 79 eq/10
6
and OH 58 eq/10
6
end groups and proved
also that end groups and mainly carboxyl groups can accelerate the thermal decomposition of PBS
polyesters. On the other hand concering enzymatic degradation, it is known that the initial weight
decrease is much lower for the carboxyl endcapped PBS in comparison with that of the hydroxyl end
capped PBS. This fact suggests that the carboxyl endcapping with bulky group efficiently retards the
enzymaticreaction,whilethehydroxylendcappinghasnoeffect[20].

3.1.3.Solutionviscosity
Solution intrinsic viscosity ([]) measurements of PBS are usually performed in a suitable
viscometer at 25 C in chloroform solvent. An equation then for the calculation is the SolomonCiuta
equation
=[2 {t/t
0
- ln(t/t
0
) -1}]
1/2
/C

wherecistheconcentrationofthesolution,tistheflowtimeofsolutionandt
0
istheflowtimeofpure
solvent[93].
TheintrinsicviscosityofPBShomopolymerisintherangeof0,14to0,64dl/g,dependingonthe
amount of OH and COOH terminal groups [55]. Chainextended PBS presents an intrinsic viscosity of
0.871.25dL/g[57]andcopolyestersbetween0.46and0.83dl/g.ThevaluesoftheNewtoniancomplex
viscosity(measuredat130C)which couldalsobeusedasanindicatorofthemolecularweightof the
polyesters,areintherangefrom13,4to250Pas[77].Yashiro[112]andLahcini[67]havemeasuredthe
inherentviscosityusingdichloromethaneasasolventinsteadofchloroform.
It is widely documented that a high degree of branching in a polymer backbone provides
enhancedsolubility,lowerviscosityandlowercrystallinity,forthecaseofsymmetricchainsthatreadily
crystallize, than a linear polymer of equal molecular [] of a branched chain to a linear chain,
conventionallydenotedasg,isemployedasbelow

69

g'=
[n]
branched
[n]
linear

ThevalueofgiseasilydeterminedusingtheprocedureofHudsonetal.,whereamultianglelaserlight
scattering (MALLS) detector and a viscosity detector are coupled with SEC [113]. The value of []
branched is measured directly using the viscosity detector and [] linear is calculated using the Mark
Houwink relationship []
linear
=KM
w
a
. The parameters, K and a, are the MarkHouwink

constants for a
linearpolymer.Foralinearchain,g

andgareequalto1anddecreaseasthelevelof

branchingincreases
[114].

3.2.Meltflowindex
PBS is a typical thermoplastic and can be processed via various methods, such as extrusion,
injectionmolding,filmblowing,fiberspinning,andthermoforming.However,itsprocessabilitydepends
on rheological properties. PBS is a shearthinning melt, which demonstrates decreasing viscosity with
the increase of shear rate. For film blowing, strainhardening, the tensile viscosity improves with the
tension rate, is preferred for a stable process line. To obtain the goal, long branches were introduced
intothePBSpolymerchain.
The traditional melt index test (ASTMD 1238) is widely used in the plastics industry to
characterize polymer processability. Melt flow index method is now used in a wide variety of
thermoplastics. It comprises measurement of the mass flow rate of a polymer through an orifice of
specifieddimensionsunderprescribedconditionsofload,temperature,andpositionofadrivingpiston
intheplastometerbarrel.
However, the results must be interpreted cautiously, because polymers are usually processed
under conditions that are far removed from those of the melt index test and the method suffers from
several severe shortcomings. First, the measured flow rates are not always steadystate values. The
actual results may be very sensitive to the details of the measurement procedure, especially for low
melt index polymers. Second, and more important, melt index values cannot be expected to be very
useful predictors of processability since most commercial thermosplastics are shear thinning and are
actually processed at much higher shear rates than those prevailing during the meltflow index
measurement[115].
Variationsoftheprocedurehavebeendevisedfordifferentpolymersandprocessabilityranges.
Thatmakeseasiertorelatethemeltindexofapolymertosomecharacteristicsofitsmolecularweight
distributionsincethelatterispresumablytheunifyingfactorwherebyrelationscanbeestablished
betweenpolymerizationconditionsandproductproperties.

70

The flow rate of PBS and its copolymers is determined as a function of applied load with the
mass flow rate expressed in gram mass per 10 min measured at 190 C. Some measures of melt flow
indexesarepresentedintable3.2.

Table3.1.MeltflowindexmeasuresforBionolle
PBSgrade MFR(g/10min) Bibliographicalsources
Bionolle1020 29
ShowaHighPolymerCo.Ltd[98]
ToyoseikiCo.Ltd.[116]
Bionolle1003 5
Bionolle3001 1
Bionolle3001 1.5
ShowaHighPolymerCo.LtdEurope[98]
Labuzeketal.[117]
PBS 20
SKChemicalCo.(Seoul,SouthKorea)[101]
Kimetal.[90]
Bionolle1001 1,5
NationalSunYatSenUniversity[65]

Bionolle1903 4,5
Bionolle1020 25
Bionolle1020x30 22
PBSA3001 1,4
PBSA3020 25
PBSA3001 0.81.8
ShowaHighpolymerCo.Ltd[98]
KrystynaTwarowskaSchmidt[118]

Asshownin Figure3.3themeltflowrate(MFR)of PBSisdesignedbycontrolling

n
M and
w
M
forittobeprocessedbysuchmethodsasthoseusedforpolyolefins.

71

Figure3.3.Relationshipwith
w
M ,MFRandprocessingmethods[96]

3.3.Thermalpropertiesandtransitions
3.3.1.Meltingandthermaldegradation
The thermal parameters characterizing PBS and its copolymers and also affect the application
and processing of the polymer are: glasstransition temperature, melting point, heat distortion
temperature, thermal degradation temperature, etc. These thermal parameters can be obtained via
differentialscanningcalorimetry,dynamicmechanicalanalysis,thermogravimetricanalysis,etc.
DSCmeasuresareperformedusingaDSCanalyzer.TheDSCscansarerecordedunderanitrogen
atmosphere in a temperature range 140150 C at a heating rate of 10 C /min. The melting
temperatureisdeterminedfromtheinitialscanasthetemperatureofthemainpeakintheDSCcurves.

The glass
change.
Th
molecular
varies wit
found tha
ataconst

Figure3.4.
was 10K/m
temperatu
curvesatT

Yo
lamellae f
resultsfro
preformed
Q
inorderto
ofPBScry
transition te
he PBS hom
r weight and
th the therm
t PBS shows
antcoolingr
DSCcurvesin
min. Three m
re.Inaddition
Tc=85and80
oo and Im [1
formed durin
om the melti
dmetastable
iuetal.[121
ogivethed
ystallizednon
emperature
opolymer ha
d the therma
mal history,
s twothree
rate,whichw
ntheheating
melting peaks
n,asmallpea
8C[119]
120] have d
ng the previ
ingofrecry
elamellaele
1]carriedou
irectevidenc
nisothermall
is calculated
as a melting
al history of
e.g., the cry
melting end
wasascribed
processfora
appear in th
kSappearsev
emonstrated
ous isotherm
ystallizedcry
adstolamel
utexperimen
cestosuppo
yfromthem
72
d from the D
g point arou
the sample
ystallization
otherms upo
totherecry
PBSresiniso
he DSC curve
videntlyatth
d that the m
mal crystalliz
stallitesduri
llarthickenin
ntsusingmo
orttheprop
melt.TMDSC
DCS scans as
nd 112116
preparation
temperatur
on crystallizi
ystallizationa
othermallycry
es and are ex
elowertemp
middle endot
zation, wher
ingthe heat
ng.
dulatedtem
osedmodels
Cisarelative
the midpoin
6C, which m
n. The meltin
e [10]. Yasu
ing nonisoth
andmelting
stallizedatTc
xpressed as A
eratureofpea
therm corre
reas the high
ingscan.The
mperaturemo
sexplaining
lynewtherm
nt of the hea
mainly depen
ng temperat
uniwa et al.
hermally from
mechanism.

cs.Theheatin
A, L, and H f
akHasshown
esponds to t
hest endoth
ereorganizat
odulatedDS
themelting
malanalysis
at capacity
nds on the
ure of PBS
[119] also
m the melt

ngratescan
from a low
nintheDSC
he original
erms peak
tionofthe
C(TMDSC)
behaviour
technique,

73

whichappliesasinusoidaltemperatureoscillation(modulation)onalinearheating/coolingconventional
DSCandmakesthetotalheatflow(suchasthatfromconventionalDSCfigure3.5.)tobeseparatedinto
the heat capacityrelated (reversible) and kinetic (nonreversible) components. Thus, the endothermic
signals can be detected in both reversible and nonreversible scans, whereas the crystallization
exotherms only contribute to the nonreversible signal. This makes TMDSC (figure 3.6.) a very powerful
technique for the separation of exotherms (including crystallization and recrystallization) from glass
transitions,reversiblemelting,orotherheatcapacityrelatedevents.Alltheresultsobtainedconfirmed
once more that the double melting behaviour of PBS crystallized nonisothermally from the melt at a
constantcoolingrateoriginatesinthemeltingandrecrystallizationofthecrystallitesofthelowmelting
endothermwithlowthermalstability.

Figure3.5.ConventionalDSCtracesofthemeltingbehaviorafterthenonisothermalcrystallization[121]

74

Figure3.6.TMDSCtracesofthemeltingbehaviorafterthenonisothermalcrystallization.IntheconventionalDSC
traces,thecoolingratesareshowninthefigure;intheTMDSCtraces,thethreecurvesfromthetoptothebottom
arenonreversibleheatflow(NR),totalheatflow(T)andreversibleheatflow(R),respectively[121]

In both isothermal and nonisothermlal crystallization, they found that the rate of the
recrystallizationdecreasedwiththemolecularweight.PBSwithlowmolecularweightreorganizesmore
easily and shows multiple melting peaks over a wider temperature range than that with higher
molecularweight.
Thethermogravimetricanalysis(TGA)ofPBSrevealsthatthispolyestershowsweightlossof5,
50,and90%at325,400,and424C,respectively,inair.Itshouldbe noted thatthisdoesnotindicate
that PBS polymer chains are thermally stable up to 325C. On the contrary, PBS shows thermal
degradation when extruded at 200C, which is implied by the decrease of the shear viscosity with
prolongedtime.ThethermaldegradationtemperaturesofPBSarealmostthesameinnitrogenandair
[74].
ConcerningtheeffectofthechosenpolymerizationcatalystonPBSthermalproperties,forTi,Zr
and Sn based catalysts, glass transition temperatures, crystallization temperatures and melting
temperatures do not change much. However copolymers synthesized with GeO
2
/lactic acid based
catalystsarestatisticalcopolyesterswithsmallermeltingtemperatures(from110Cto102C)although
theglasstransitiontemperatureremainsunchanged[94].
The thermal properties of PBS copolymer depend on the copolymer composition. The melting
temperatureanddegreeofcrystallinitydecreasewiththeincreaseofthecomonomercontentwhenitis
more than 30 mol %. When the comonomer content is less than 15 mol%, the copolymers still have a
melting temperature higher than 100C, which is preferred for real applications. This phenomenon is

probably
chainacta
[71].
Th
the chem
succinicac
copolyme
transition
on their
compositi

3.3.2.Cry
PB
strength,
thedegre
mainlyde
Whencrys

due to the f
asanimpuri
hedependen
ical structur
cid,adipica
rization wit
temperatur
composition
onisshown
Figure3.7.
ystallization
BS is a semi
and flexibilit
eofcrystalli
pendsonth
stallizedfrom
fact that the
ity,disturbin
nceofthegl
re of the com
cid,andpro
h benzyl su
re.Forexam
n. The varia
inFigure3.6
Copolyester
n
icrystalline p
ty and its tra
inity.Concer
hecrystallizat
mquiescent
e segments
ngcrystalgro
lasstransitio
monomer un
panediolres
uccinic acid
ple,PBSAco
ation in cop
6.
meltingtemp
polyester. Its
ansparency a
rningthecry
tiontemper
melt,PBSfo
75
of the exten
owthandlow
ontemperat
nit. Copolym
sultsinadec
and tereph
opolymersex
polymer me
peratureandh

s mechanica
and biodegra
ystallization
ature,andt
ormsspherul
nder or the
weringthere
ureonthec
merization w
creasedglas
thalic acid
xhibitedani
elting tempe
heatoffusion
al properties
adability dep
behaviorof
hickeningof
itesasprese
other polym
egularityofc
copolymerco
with methyl s
stransition
brings abou
ntermediate
erature and
nasafunction
s such as te
pend on the
PBS,thethi
fthelamella
entedinFigu
mer in macro
copolymerm
ompositionv
succinic acid
temperature
ut an increa
ebehaviour
heat of fu

nofcompositi
ensile streng
e crystal stru
icknessofth
aeoccursby
re3.7.
omolecular
mainchains
varieswith
d, dimethyl
e,whereas
ased glass
depending
usion with
ion[53]
gth, impact
ctures and
helamellae
annealing.

76

Figure3.8.PBScrystallizedat70C(a)and90C(b)asobservedunderthepolarizedopticalmicroscope [121]

Thesizeandthe morphologyofthespherulitesareaffectedpredominantlybythecrystallization
temperature.Abandedspheruliteconsistingofcircularbrightandgraybirefringent bandsformsovera
wide range of temperatures, with further increase of temperature, the regular bands disappear and a
coarsegrained morphology prevails. Besides the normal spherulite morphology, some spherulites
demonstrate a peculiar winglike region. The results of the atomic force microscope observing PBS film
areshowninFigure3.8.

Figure3.9.AtomicforcemicroscopeofPBSbandedspherulites[121]

Thedetailed imagesobtainedfromtheatomicforcemicroscope revealthatthePBSspherulite

consists of radiating lamellar crystals, which splay and branch consecutively during growth, leading to

77

fillingofthewholespace.Thissuggeststhatthecooperativetwistingofthelamellarcrystalsleadstothe
formationofthebandedspherulite.

Figure3.10.AFMimagesofthelamellaeinaPBSbanedspherulite[121]

ThethicknessofPBSlamellarcrystalsdependsonthecrystallizationtemperature.Thethickness
of the crystalline lamellar core increases steadily and that of the amorphous layer decreases with
increase of the crystallization temperature. But the total degree of crystallinity varies little with
temperature.ThisresultsuggeststhatthesurfaceofPBSlamellaemightconsistirregularlyofmethylene
or ester bonds in order to accommodate the chains to smoothly increasing thickness of the lameallae.
PBS single crystals grown from solution show terracelike and leaflike shapes depending upon growth
temperature. The lamellar thickness increases smoothly with temperature, but not stepwisely, to
accommodate the repeating units. This suggests lamellar surfaces composed irregularly of both ester
bondsandmethyleneunits[122].Crystallizationtemperatures(T
c
)rangefrom70to100C[120].

78

The unit cell parameters can be determined from the wide angle Xray diffraction patterns of
thesinglecrystals,films,orfibers.PBShastwocrystallinemodifications:aandbform,dependingonthe
crystallization conditions. The a form appears when PBS is crystallized from a quiescent melt, whereas
thebformoccursundermechanicalstress.Bothofthemodificationsbelongtothemonoclinicsystem.
The unit cell contains two molecular chains; the cell dimensions for the a form are a = 0.523 nm, b =
0.912nm,c(fiberaxis)=1.090nm,andb=123.9fortheaform[122]anda=0.584nm,b=0.832nm,
c(fiberaxis)=1.186nm,andb=131.6forthebform[5]aspresentedinTable3.3.too.

Table3.2.UnitcellparametersoftheaandbformsofPBS[55]
Crystallinemodifications aform bform
Crystalsystem monoclinic monoclinic
Spacegroup P2
1
/n P2
1
/n
Celldimensions
a(nm) 0,523(2) 0,584(5)
b(nm) 0,912(3) 0,832(11)
c(nm) 1,090(5) 1,186(7)
() 123,9(2) 131,6(5)
Volume(nm
3
) 0,4315(30) 0,4320(80)
Observeddensity(g/cm
3
) 1,28
Calculateddensity(g/cm
3
) 1,33 1,32
Number of chains running
throughtheunitcell
2 2

UsingtheXRDanalysisforthecrystallinemodificationsaandbtheresultsobtainedshowthat
the 2 peak at 19,6, 21,5, 22,5, and 28,8 corresponds to (020), (021), (110), and (111) deflection,
respectively [121,123]. Studying the bulk crystallization behavior of PBS films under various thermal
conditions with respect to their crystallinity and spherulite morphology. The main characteristic
diffraction peaks results were the same (figure 3.11), but they have also mentioned that the
isothermally crystallizedPBShasthesame crystalstructure (aformcrystalmodificationof PBS)evenif
crystallizationtemperaturesaredifferent.

79

Figure3.11.TypicalXraydiffractiondiagrammofmeltcrystallizedPBSfilm

SincethecaxisdimensionofPBSisshorterthanthatofthefullyextendedchain,thePBSchain
includestransconformationsaswellasgauche.Themolecularconformationsoftheaandbformsare
T
7
GTGandT
10
,respectively,whereT,G,andGindicatetrans,gauche,andgaucheminus,respectively.
Thebformhasamoreextendedchainconformationthantheaform.Thesolidstatetransitionbetween
theaandbformsisreversibleundertheapplicationandreleaseofstrain[55].
The crystalline structure of PBS copolymers varies with the copolymer composition. The
crystallinities of the chainextended PBS is presented 12.3 % lower than that of PBS prepolymer [56].
Poly(butylene succinatecobutylene terephthalate) (PBST) demonstrates a PBStype crystalline
structure when the content of butylene terephthalate units is less than 30 mol % and shows a
poly(butylene terephthalate) type crystalline structure when the content of butylene terephthalate
unitsishigherthan40mol%,asdemonstratedinFigure3.12.

80

Figure3.12.WAXDdiagrammofPBST[55]

Poly(butylenesuccinatecoadipate)(PBSA),exhibitsalowerdegreeofcrystallinitythanboth
therespectivehomopolyestersPBSandPBA.Crystallizationtemperature(T
c
)decreasedwithincreasing
branchingagentcontent[124].However,copolyesterPBSAshowsthesameXRDpatternasPBS,proving
that the patterns of copolyesters depend strongly on the composition of the predominant crystal unit
[53].

Figure3.13.WAXDdiagrammofPBSA[53]

The characteristic peaks for the copolyester PBSF prove that with increasing unsaturation, the
peakpositionsareshiftedto higher2values,whichcanbeassignedtoasmalldecrease oftheunitcell
dimension.Thepeakpositionsin thediffractogramsofthecopolyestersshowthatthereis nochangein

81

the type of the crystal lattice and that the unsaturated copolyesters crystallize in a monocliniccrystal
latticesimilartohomopolymer[74].

Figure3.14.DSCdiagrammofPBSF[74]

3.4.Mechanicalproperties
PBS has mechanical properties similar to those of polyolefins such as polyethylene. PBS
possesses good tensile strength and impact strength, moderate rigidity, and hardness, and is a typical
toughpolymer.Physicalforces,suchasheating/cooling,freezing/thawing,orwetting/drying,cancause
mechanicaldamagesuchasthecrackingofpolymericmaterials.Propertiessuchastensilestrengthare
very sensitive to changes in the molar mass of polymers, which is also often taken directly as an
indicatorofdegradation[125].
Comparing PBS with other polyesters such as polyethersulfone, polyphenylene sulfide (PPS),
polylacticacid(PLA),PBSischaracterizedasahardandtoughmaterial.Asitcanbeseeninfigure3.14
the mechanical properties are both temperature and polyester type dependent. An increase in
temperature leads to higher tensile strengths. Comparing polyethylene succinate with PBS the former
exhibits higher Youngs modulus, although the latter exhibits higher tensile strength especially at high
temperaturesandhigherelongationatbreakvaluesatalltemperatures[93].

82

Figure3.15.Tensilestrengthdependingontemperatureforthreetypesofpolyesters[93]

The bending strength of PBS if it is immersed in water was investigated and it was found to
decrease as the immersion time and the immersion temperature increased due to the chemical
degradation of PBS caused by hydrolysis. If it is also reprocessed an unusual increase both in the
bendingstrengthandinthemolecularweightofPBStakeplace.Toestimatetheeffectsofthematerial
recyclingonthemechanicalpropertiesofPBS,twomajoraffecterswereconsidered:oneistheeffectof
thenumberofreprocessingtimesandtheotheristheeffectoftheusageenvironment.Previousstudies
revealedthattherepetitionofprocessinghadadetrimentaleffectonthestrengthofthepolymer[126].
Copolymerization is a facile method to upgrade the mechanical properties of PBS. The large
degreesofchainbranchescanenhancethehorizontaltensilestrengthandtearingstrengthofpolymer
films.Jinetal.[11,123]examinedtheeffectofethylandnoctylbranchesonthepropertiesofPBSand
concluded that the addition of ethyl branches as well as noctyl branches into PBS improved the
biodegradation properties, the elongation at break, and the tear strength without notable decrease of
tensilestrengthandtensilemodulus.Wangetal.[84]examinedtheeffectofmolfractionofbutanediol
segmentsonthetensilepropertiesoflinearPBS.Infigure3.16(a)itisshownthatlongchainbranched
PBS exhibits higher tensile strength than that of linear PBS and increases gradually with increasing the
butanediolsegmentscontent.Infigure3.16.(b),itcanbeseenthattheelongationatbreakoflongchain
branched PBS is lower than that of linear PBS and decreases gradually as the concentration of
butanediol segments increased. The above results showed that the longchain branches can enhance

83

the tensile strength of linear PBS; however, the elongation at break decreases gradually with the
increasingofbutanediolsegmentscontent.

Figure3.16.TensilepropertiesoflinearandlongchainbranchedPBSwithdifferentbutanediolcontent

Concerning fillers, it has to be mentioned that poor compatibility between the filler and the
polyester matrix is an issue of concern having a deteriorating influence in the mechanical properties
[127]. The most popular additive is starch, which makes such plastic more susceptible to microbial
attackhowever,itmaycausepoormechanicalpropertiesofcompositematerial.Mechanicalproperties
aredependentonsuchfactorsasfillervolume,fillerparticlesizeandshape,andthedegreeofadhesion
of the filler to the polymeric matrix. Small amounts of starch significantly altered the elongation,
however,thenegativeimpactofstarchadditionsonelongationappearedtoplateauatthehigherstarch
concentrations[86].
Aromaticmonomergroupscanalsobeincorporatedintothemainchainofaliphaticpolyesters
for improving their mechanical properties. The introduction of terephthalate units increased the
copolyestersmechanicalpropertiesbutdecreaseditsdegradationrate.ThehomopolymerPBSexhibits
themaximumtensilestrength19,3MPa.PBSAcopolymers,whichconsistmainlyofamorphousregions,
exhibit quite low mechanical properties as a result of their low crystallinity and molecular weights.
Elongation at break increased with increasing adipate unit (2040 mol %) content, due to the
introductionofmoreflexiblegroupsintocopolymermacromolecularstructure.However,inthecaseof
equimolarity there was a reduction in copolymer elongation, which could be attributed to the low
molecular weight values, observed [53]. Figure 3.17 demonstrates the variation of the mechanical
propertiesofPBSTwiththecopolymercomposition.

84

Figure3.17.MechanicalpropertiesofPBST[53]

InthefollowingtabletypicalmechanicalpropertiesofPBSarepresented.

Table3.3.PropertiesofPBSanditsgrades[128,69]
Properties PBS PBSA PBSL
Tensilestrength 34 19 540
Elongationatbreak 560 807 94
Izodimpactstrength 300 >400

85

CHAPTER4:PROCESSINGANDAPPLICATIONSOF
POLY(BUTYLENESUCCINATE)

4.1.Modificationofpoly(butylenesuccinate):useofadditives
Biodegradable polymers derived from renewable resources are attracting lots of interest and
publicity, more and more. However lots of studies are required concerning availability, cost,
performance, and processability. Bipolymers and among them PBS do need help from additives to
addressinherentweaknessesinprocessability,physicalpropertiesandprerformance.
Additivescanberankedinthreelevels.Thefirstoneinvolvestraditionaladditivesthathaveno
adverse effect on health or the environment and do not compromise resins compliance with
compostability standards. The second level includes renewable additives derived from natural sources,
but not necessarily biodegradable, for use in durable products. Third are additives that are both
renewableandbiodegradable,whichareagoodfitforsingleuseorshortlivedproducts.
Additives can range in a variety of materials from silicon to wood flour, each having its own
uniquepurposeanduse[129].Thechoiceofwhichadditiveisneededdependsonwhatisdemandedof
the end product polymer. Additives are usually combined with polymers in a matrix form, integrating
the polymer and additive together. The molecular structure of the polymer is altered so that the
additive is incorporated within the very structure of the plastic, altering the properties depending on
whichadditiveisincluded.Thisallows uniformstrengtheningof thematerial aswellasreplacingsome
volumethat wouldotherwisebefilledwithpolymer,whichcan oftenleadtoalessexpensiveproduct.
WhenadditivesareaddedtheymustmeetstandardsforcompostableplasticssuchasASTMD6400and
itsEuropeanUnioncounterpart,EN13432.

4.1.1.AndioxidantsandstabilizersinPBS
From packaging to agricultural film, additives that prevent polymer damage from ultraviolet light are
becoming more requested. The additive's high opacity reportedly blocks 100 % of UV light, extending
productshelflifewhilemaintainingtheglossofthepolymer.Theantioxidantsandthestabilizersmake
the polymers resistant to degradation. Poly(ethylene oxide), PEO, is one of these additives. In several
studies,itwasshownthatPBS,modifiedwithPEOpresentsbetterbiodegradabilitypropertiescompared
to PBS modified with polytetramethylene oxide (PTMO), due to the increased hydrophilicity of the
former[130].

86

4.1.2.AntimicrobialadditivesinPBS
Antimicrobial properties that can be added to polymers by using additives are of great interest. In
medical applications, microbe growth constitutes a threat on multiple surfaces. Additives that can
encounterthisproblemhavealreadybeendeveloped.Antimicrobialadditivesprotectpolymersdurably
from microbial infestation, destruction, stains and odors. Except of that additives for controlling
bacterial growth also exist. Many of them contain silver, trichlosan, or proprietary agents that kill
variousmicroorganisms.

4.1.3 ColorantadditivesinPBS
Colorants are additives that mainly improve the aesthetic of the biopolymer and improve the
characteristics of the final product line, offering denesting, antistatic, slip, antiblock and ultraviolet
protection. They are made from nonpolymeric, nonpetroleumbased carrier materials while avoiding
relianceonheavymetalsorhalogensintheirformulations.Thenewcolorantscanbeusedinextrusion
andblowmoldingprocesses.

4.1.4BiodegradabilityAccelerants
The biodegradability of PBS and most biopolymers is what makes them more attractive for packaging
applications, though they may require some help degrading. Thus, companies have sought ways of
makingthesepolymerstrulyandrapidlybiodegradable.Forexample,thereisacompliantmasterbatch
thatisdesignedtolowerthemolecularweightofthepolymer,speedingoxidativedegradationinitiated
bysunlight,heat,oroxygen.Itcanbeintegratedwithconventionalprocessesandhighspeedmolding.
Thespecificmasterbatchloadinglevel(typically1%4%)dictatestheshelflifeofthepolymers.

4.1.5AdditivesAidRecycling
Otheradditivesenabletheuseofmorerecycledresininproducts.Suchanadditivecangiveextraclarity
and reduce the yellow discoloration associated with recycled resin content. Meanwhile, some
companies have already introduced viscositymodifying additives that aid the incorporation of the
recycledpolymer.

87

4.1.6FlameRetardants
Flame retardants are new and improved tye of additives that do not contain undesirableor dangerous
ingredients, such as halogens. Polymers including flame retardants are meant to meet the smoke
density and flamespread limits of the standard. In figure 4.1. the pyramid of plastics indicates that
commoditypolymersarethemostflammable.

Figure4.1.PlasticspyramidData:PlasticsEurope2008

Measuring the limiting oxygen index (LOI) can identify whether the material is of low or high
flammability. A high LOI indicates a lower flammability. According to a recent research by Wang et al.
[131] intumescent flame retardant poly(butylene succinate) (IFRPBS) composites with enhanced fire
resistancewerepreparedusinggrapheneassynergist.Thelimitingoxygenindex(LOT)valuesincreased
from 23 for the pure PBS to 31 for IFRPBS with 20 wt % IFR loading. The addition of graphene further
improved the LOI values of the composites and exhibited excellent antidripping properties. The UL94
VUmaterialswereobtainedwithaformulationof18wt%IFRand2wt%graphene.
Themainretardantselectioncriteriaarethefollowing:
Efficiency/cost
Easeofcompounding
Adequatethermalstability
Corrosivityissues
Physicalproperties
Appearance
Compatibility
Environment/toxicity

88

UVStability/weathering
Electricalproperties
Although effective at reducing flammability, flameretardant additives and fillers have
disadvantagesaswell.Theirpoorcompatibility,highvolatilityand otherdeleteriouseffectscanchange
properties ofpolymers. Besides, addition of many fireretardants producessootandcarbon
monoxideduringcombustion.Halogencontaining materials cause even more concerns on
environmentalpollution.

4.1.7ProcessingAids
Plastics process aids are indispensible tools for productivity. Fluoropolymerbased meltprocessing aids
effectively coat and lubricate the walls of process equipment, reducing torque and improving output.
Mold release agents can add to the bottom line in injection molding, especially when they can be
incorporatedintotheplastic.

4.1.8Starchadditives
StarchbasedpolymershavealreadybeenpresentedinChpater2,paragraph2.3.6.asPBSblends.Inthis
parahrpah starch will be described from the point of an additive. Due to the relatively cheap cost of
starch additives and its availability, this technique is cost effective and enhances currently used food
packagingpolymers[132].Usingthisadditivecan providesome biodegradationatafasterrateaswell
as provides strengthening properties from the starch additive itself. Fangs group [133] showed that
increasedpercentagesofstarchbasedadditive,whencombinedwithpolymers,showedimprovedstrain
curves when force was applied. Though the study focused mostly on film based processing and
mechanical function, it did show positive results toward the stability of such polymers. These starch
based polymers can also be thermally processed and can undergo extrusion, injection molding,
compression, and film casting [124]. Lius group showed extensive work on processing techniques that
can be used on starchbased materials as well as phase transitions during processing. They also tested
processing properties of the starchbased polymers by observing effects of water, glycerol, citric acid
and other plasticizers and additives. His group showed that after processing, there was some loss in
mechanical function due to temperature changes during processing. The group also showed that
processing needed to be controlled and mechanical function of the polymers was based largely on the
processing technique and control of moisture within each stage, as an increase in moisture greatly
affectedthemechanicalfunctionintheendstageofprocessing.

89

4.1.9PlasticizeradditivesforPBS
Cellulose acetate butyrate (CAB) esterified by acetyl and butyryl groups is a brittle and transparent
materialthatithasalreadybeenusedasaphotofilmandacoatingmaterial.Someresearchersreported
that CAB can act as a plasticizer too for some polymers and specially polyesters. CAB is available as a
biomassbasedplasticizer,andalsoasaninhibitorforthebiodegradationofPBS.Biobasedfurfuralwas
alsolistedasagoodplasticizerforPBS[134].

4.2.Processingofpoly(butylenesuccinate)
4.2.1.Introduction
Biodegradablepolymerscanbeprocessedbymostconventionalplasticsprocessingtechniques,
with some adjustments of processing conditions and modifications of machinery. PBS has the best
processability among the general degradable polymers and it can be processed by injection molding,
extrusion molding or blow molding using conventional polyolefin processing equipment, lowering
barriertoswitchtoPBSfromotherpolymers.Dependingontheenduse,eachPBSgradeisprocessedin
a diffent way. Low melt flow rate grades can produce sheet, film and bottles, and high melt flow rate
grades can be used for lamination extrusion, injection molding, and fiber extrusion. Grades containing
longchainbranchesshowhighmeltstrengthandsuitableforproductionoffoamedproducts.
Processability of the polymer depends on thermal stability, viscosity, melt strength and
crystallization rate, etc. Thermal stability of PBS materials is sensitive to water content, the content of
residualcarboxylicacidterminalsandthemolecularstructureofpolymerchains.
As already mentioned, according to PBS grade a different process is followed. So, PBS with a
w
M less than 100.000 can be used for extrusion and injection molding and PBS with higher
w
M or
longchain is more appropriate for film blowing and casting, where high melt strength branches is
necessary[96].

In
is demons
viscosity,
addition, e
ofstretche
is required
the transp
methodsa

Figure4.2.D
factor
nfigure4.2.t
strated that
the storage
entanglemen
edblownbo
d. In order t
parency of t
accordingto
Dynamiccomp
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therheologic
t a small am
and loss m
nts of longc
ottlesandhig
to manage th
the end prod
polymergra
plexviscosity(
tionoffreque
calbehavior
mount of lon
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ghlyexpande
hat, nucleati
duct. Talc an
adearegathe
90

(|*|)(a),sto
enceoflinear

oflinearPB
ng branches
he terminal
hes result in
edfoams[96
ing agents c
nd cyclodext
ered.

oragemodulus
PBSandlong
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region due
high melt te
6].Intofastp
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hedPBSispr
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ultaneously
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In
excessive
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of less th
performed
dryingsys
(Po
(Polybu
(P
n prior to m
hydrolysis (
Inordertoa
an 500 part
dbyusinga
temisshow
Table4.1.M
Grade
PBS
lybutylenes
PBSA
tylenesuccin
PBAT
olybutylene
terepthala
melting proc
(molecular w
avoidthisde
ts per millio
commercial
ninfigure4
Meltflowratea
uccinate)
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adipate
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weight drop
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91
andprocessin

T
m
(C
110
e)
90
120
PBS, the pol
p) which can
hepolymer
fore process
recirculating
ptimumdryi
re4.3.Typical

ngmethodsfo
C) Pro
I
Ext
E
Ex
lymer must
n compromi
shouldbesu
sing. The dr
g,dehumidifi
ngcondition
ldryingsystem
ordifferentPB
ocessingmet
InjectionMo
trusion,Film,
ExtrusionCo
trusion,Film
be dried s
se the phys
ufficientlydr
rying operat
iedhotaird
nsintable4.2
m
BSgrades
ethods
olding
,Sheet,
oating
m,Sheet
sufficiently t
sical propert
riedtoamoi
tion is most
ryingsystem
2.
to prevent
ties of the
isturelevel
efficiently
m.Atypical

92

Table4.2.Optimumdryingconditions[135,136]
Dryingtemperature 65C70C
Dryingtime 612h
Airflowofdryair
>0,065m
3
/minperkg/h
Dewpointofdryair <30C
Residualmoisturecontent <0,05%(500ppm)
Dryinghoppercapacity 612timesextruderoutputperhour
Height/diameterratio >2:1,3:1isbetterforplugflow
Insulation Insulatewelltoimprovenergyefficiency
Monitoring Inletairtemperatureanddewpoint

4.2.2.Extrusion
PBS polymer can be processed easier than any other biopolymers and the film produced does
not resemble typical biofilms. According to GmbH & Co. KG company, working on PBS cast film
processing, the material is supplied in moisture proof bags and provided that it is not exposed to the
atmospheric moisture for a long period, no predrying is required. Its set point temperature is about
180C and it is similar to those of many conventional polyolefines. PBS exhibits good draw down from
the die lips and the film can be effectively edgepinned using electrostatics. The film produced at last,
has excellent stiffness and mechanical properties and no tendency to yellowing is pbserved. A typical
singlescrewextruderisshowninfigure4.4.

Figure4.4.Typicalsinglescrewextruder

Ratto et al. [86] produced PBSA with granular corn starch through extrusion blown film
processing. All samples were dried at 55C or 70C for several hours before processing. The mixed
powdersthenwereprocessedintoblownfilmsusingasinglescrewextruderwithfourheatedzonesand
a blown film die. The film thickness varied from 0,070,18 mm. Constant mix times, screw speeds and

93

temperatureprofilesfortheextrusionprocessweremaintainedinordertominimizeanyalternationsin
thefilmsandanyeffectsfromprocessingparameters.Pivsaetal.[137]withthesamemethodprepared
polymer blends of PLA, PBSA and PBAT.This time, the blends were prepared using a twinscrew
extruder.Beforeextrusion,PLA,PBSAandPBATresinweredriedat80Cfor8hinanoveninorderto
remove any trace of moisture to prevent potential hydrolytic degradation during the melt processing.
The mixture of PLA/PBSA/PBAT was manually premixed by tumbling in a plastic ziplock bag, and
subsequently fed into the extruder for melt compounding. The extrudate was cooled in a water bath
and subsequently granulated by a pelletizer. The polymer sheets (thickness 2 mm) of polymer blends
werepreparedbycompressionmoulding.
According to SK Chemicals [135] producing SKYGREEN, this material offers the high melt
viscosity and noncrystalline properties required for a successful extrusion blow moulding. In the
following table all processing data for the production of a 6 mm extruded sheet are presented.
Moreoversomeprocessingdetailsthatshouldbetakenintoconsiderationhavetobementioned:
If extrusion stopped from more than 15 20 minutes, the temperature inside should be
reducedtoabout150Csoastoavoidexcessivedegradationofthepolymer
When restarting the machine or on initial startup extrusion should begin as soon as
possibleafterthemachinereachedthedesirableconditions
Onmachineshutdownitisrecommendedthatpurgingmaterialsshouldnotbeused

Table4.3.Processingdataforextrusionmoulding[135]
Extruder 45mmsinglescrew,L/D=30/1,100rpm,vaccum=40mbar
Extrudertemperature
Zone1:180C
Zone2:245C
Zone3:265C
Zone4:260C
Zone5:240C
Meltpressure 83bar
Die
Zone1:247C
Zone2:249C
Roll
1:45C
2:54C
3:63C

94

Reactiveextrusion(REx)isanattractiverouteforpolymerprocessinginordertocarryoutmelt
blending, and various reactions including polymerization, grafting, branching and functionalization as
well. It is a special process in which individual components are first bonded by a chemical reaction.
Usinganextruderforconductingchemicalmodificationshasproventobeanefficientwayforlowcost
productionandprocessingmethods,whichenhancesthecommercialviabilityandcostcompetitiveness
ofthematerials.Thefactorthatdetermineswhetherthedesiredobjectiveoftheextrusionismetisthe
screwgeometryusedintheextruder.Thescrewgeometrycontrolstheresidencetime,thepowerinput,
and the extent of mixing imparted to the melt in the extruder [138]. There are two main challenges in
using an extruder for reactive processes: a) reaction time that can be varied from seconds to minutes.
However reaction kinetics should be fast enoughto achieve 100% reactant consumption within the
extruderandb)undesirablesidereactionsoccurringbecauseoffreeradicalsgeneratedatthebeginning
of reactions. One of the common undesirable reactions in peroxide initiated processes is the polymer
degradation (backbone chain scission) and undesirable intrapolymer crosslinking rather than inter
polymer crosslinking. For this reason process condition should always be optimized [139]. Lindstrom
[124]studiedreactiveextrusionasatoolforsynthesizingstarchPBSpolymerreactiveblends.

4.2.3Injectionmolding
Injection molding is one of the most widely used polymer processing method in the plastics
industry.Itischaracterizedbylowcost,highproductionratesanddimensionalaccuracyoftheproduct.
Molten polymer is injected into a mold cavity at high speeds and then is allowed to cool and solidify
beforeitisejectedofthepartfromthemold[140].Atypicalinjectionmoldingmachineispresentedin
figure4.5.

Figure4.5.Typicalinjectionmoldingassembly

95

Thepreparationofcomplexinjectionmoldedpartssometimesinvolvestheuseofmultiplegates
where polymer melts from different gates meld to form the molded part (weldline). For example, for
the fabrication of short fiber reinforced jute/PBS biodegradable composites, weldlines are created
whenever polymer flow fronts meet, due to the presence of cores, pins or the use of multiple gates.
Weldlinesarealsoformedwhenjettingoccursalongtheflowpathsuchasnearthegate.Thepresence
ofweldlinessignificantlyreducesthestrengthofinjectionmoldedparts.Injectionmouldingparameters
such as the temperature and viscosity of the molten polymer, mold temperature, moulding
clamp/hold/back pressure and mold cooling have been shown to influence weldline properties. In
terms of material parameters, the type and properties of the matrix resin, molded part thickness, the
presenceoffillersorreinforcingfibersandimpactmodifiersplayasignificantrole.Thecombinedeffects
ofprocessingparametersandmaterialpropertiesultimatelydeterminetheabilityofthetwomeltflows
toknittogetherhomogeneously[141].
Reviewing Sk Chemicals sheet injection moulding guide for SKYGREEN [136], the main
processingdataarepresentedinthetablebelowinrelationwithgeneralguidlinewfrotheprocess:
Injectionspeed:slowtomediumandscrewspeed50100rpm
Cushionsize:minimu(313mm)anddecompressionisheldtominimizedrooling
Backpressure:0,31MPaisenoughtogiveuniformmeteringandreduceaireentrapment
Holdpressure/time:toeliminatesinkorvoids,butavoidoverpacking

Table4.4.Processingdataforinjectionmoulding[136]
Screwtype Generalpurpose,l/D=18/1to20/1,compressionration2,5:1to3,5:1
Temperature
(C)
Mould Nozzle C2 C3 C4 Feeding
40 245 245 245 210 240
Pressure(bar)
1
st
pressure:2
2
nd
pressure:40,40,35
Backpressure:5
Speed(mm/sec)
V12:8
V21:8
Time(sec)
Injection:2
Hold:15
Cooling:15
Cycle:36
Screw
Refillspeed:50%
Rpm:100
Strike:62mm

Comparing to extrusion molding, injection moulded products are removed from moulds after
coolingwhileextrusionmouldedproductsaretypicallycarriedalongaconveyor,cooledandcut tothe
desired length. Moulded products are generally packaged by manual and/or automated means for
transportation.

96

4.2.4Thermoforming
Thermoforming is commonly used for forming packaging containers that do not have
complicatedfeaturesandgenerallytoshapethermoplasticsheetintodiscreteparts.Thebasicprinciples
andkeyparametersforthisprocessingtechnologyarethefollowing:
Heatthethermoplasticsheetuntilitsoftens
Forcethehotandpliablematerialagainstthecontoursofamoldbyusingeithermechanical,air
orvacuumpressure
Heldagainstmoldandallowtocool,andplasticsretainsitsshape
Speedofvacuumapplicationvacuumshouldbeappliedasquicklyaspossible
emperatureofthemoldthemoldisnormallyatroomtemperature,ortemperaturebelow
solidificationpointoftheplastic
Sizeofthebubble
Plugsize

Figure4.6.Typicalvaccumthermoforminhassembly

Thermoforming process is differed from other plastic processing because the material is not
melted, lower pressures are required to thermoform (the mold materials is less sturdy materials
comparedtootherprocessings).Thetechniquesofformingprocesscanbegroupedintoseveraltypes:
FundamentalVacuumforming

97

Pressureforming
Plugassistforming
Reversedrawforming
Freeforming
Matcheddieforming
Themostimportantsheetpropertyisthickness(variationinthicknessoverthesheetshouldbe
keptunder5%).Theuniformityfromsheettosheetisdesired,sothattheprocessingparametercanbe
keptconstant,i.e.meltindex,ifonesheethasalowermeltindexthananother,theamountofheatto
achievethesameformationwillbehigherthaninthesheetwithlowermeltindex.Othervariablesthat
might change from sheet to sheet are density, molecular orientation, etc. The advantages and
disadvantagesoftheprocessarepresentedinthetablefollowing.

Table4.5.Advantagesanddisadvantagesoftheprocess
Advantages Disadvantages
Lowmachinecost Highcostofrawmaterials(sheets)
Lowtemperaturerequirement Highscrap
Lowmoldcost Limitedpartshapes
Lowpressurerequirement Olyonesideofpartdefinedbymold
Largepartseasilyformed Inherentwallthicknessvariation
Fastoldcycles Internalstressescommon

4.3.Applicationfieldsofpolybutylenesuccinate
As with conventional plastics, biopolymers have a very broad application spectrum.
Poly(butylene succinate) as a polymer being able to decompose naturally into water and CO
2
under
specific conditions (contact with soil, light, heat, natural water), has already become of great
environmental awareness as a promising alternative to common plastics. Due to its mechanical
properties, processability and heat resistance, PBS and its copolymers can be used in a wide range of
applicationsinvariousindustries.Sofar,PBShasfoundapplicationsinagriculture,fishery,forestry,civil
engineering, packaging and other fields in which recovery and recycling of materials after use is
problematic.
According to National Research Center of Engineering Plastic of IPCCAS the characteristics of
differentindustriesregardingtheapplicationofdegradablepolymersaresetoutinTable4.6andTable
4.7depictstheglobalmarketofbiodegradablepolymersinseveralapplications.

98

Table4.6.Industriesanddegradablepolymersapplications(PBS,PLA,PHBect.)
I
n
d
u
s
t
r
y

T
e
c
h
n
i
c
a
l

B
a
r
r
i
e
r

P
o
l
i
c
y

E
n
v
i
r
o
n
m
e
n
t

I
n
d
u
s
t
r
y

c
o
n
c
e
n
t
r
a
t
i
o
n

N
e
c
e
s
s
i
t
y

f
o
r

d
e
g
r
a
d
a
b
l
e

m
a
t
e
r
i
a
l
s

P
r
o
p
o
r
t
i
o
n

o
f

c
o
s
t

i
n
c
r
e
m
e
n
t

A
p
p
l
i
c
a
t
i
o
n
s

C
o
n
s
u
m
e
r

c
o
n
c
e
r
n

Packaging Low
Very
favourable
Low High Higher
Packaging
bags,films
andbottles
Concern
Agricultural
andforestry
High Normal Higher Normal Higher
Plastic
sheeting
and
pesticide
container
Normal
Daily
necessity
Low Normal Low Normal Higher
disposable
razors,
toys,
toothbrush
es,diaper
pants,bibs,
electronics
and
business
equipment
Normal
Medical High Favourable Higher High Normal
Medical
container
and
syringe
Concern

Table4.7.Globalmarketofbiodegradablepolymers(millionlbs)[142]
Application 2006 2007 2012
CompoundAnnual
GrowthRate(%)
Compostbags 173 242 587 19,4
Loosefillpackaging 152 161 214 5,7
Otherpackaging
(includesmedical,
hygieneproducts)
51 59 48 23,4
Miscellaneous
(unidentified
polymers)
33 54 171 25
TOTAL 409 516 1.200 17,3

ShowaHighPolymeristhecompanywithonofthebiggestproductionusingPBSanditsgrades
in several applications. Agricultural mulch film, foamed cushioning, food packaging and engineering

99

worksmaterial,stretchedblownbottlesandhighlyexpandedfoamsaresomeofthem.InTable4.8the
mainproductionofShowaispresented.

Table4.8.MainapplicationsforPBSandPBSAinglobal[142]
Sector
%oftotalproduction
2003
%oftotalproductionin
2020
Packaging(includes
compostbag10%today,
7,5%in2020)
25 57,5
Building 5 7,5
Agriculture 50 15
Transporation 10 10
Furniture 4 5
Electricalappliancesand
electronics
2 5
Houseware 4 5
Others
Total 100 100

4.3.1.Agriculture
Forthisapplication,themostimportantpropertyofbiodegradablepolymersandspeciallyPBSis
in fact their biodegradability. Starchbased polymers are the most used biopolymers in this area. They
meetthebiodegradabilitycriteriaandhaveasufficientlifetimetoact.
Plastic films are widely used in agriculture for greenhouse coverings, fumigation and mulching.
All principal grades of polymers (plastics, coatings, elastomers, fibres, watersoluble polymers) are
utilizedinapplicationswhichincludethecontrolledreleaseofpesticidesandnutrients,soilconditioning,
seed coatings, gel plantings and plant protection. As the scope of the application fields is growing,
degradable plastics are also of interest as agricultural mulches and agricultural planting containers.
Using degradable materials in agriculture is a good way to produce useful soilimproving materials,
reducingsimyltaneouslylabouranddisposalcost.
Multch films are mainly produced by low density polyethylenes, poly(vinyl chloride),
polybutyleneorcopolymersofethylenewithvinylacetate.Agriculturalmulcheshelpwithplantgrowth
and at the end of their life can photodegrade in the fields thereby avoiding the cost of removal. The

100

plastic films are desirable because they conserve moisture, reduce weeds and increase soil
temperatures,improvingtherateofgrowthinplantsinthatway.Attheendoftheseason,thefilmcan
beleftintothesoil,whereitisbiodegraded.Duringdegradationperiod,mulchesbreakdownintosmall
smallbrittlepieceswhichpassthroughharvestingmachinerywithoutdifficultyanddonotinterferewith
subsequent planting. Reducedporosity films can be more effective reducing the escape of volatile
chemicals, i.e. nematocides, insecticides, herbicides, etc., and therefore allow for lower application
rates.

Figure4.7.Agriculturalmulchingfilms

Anotherapplicationmentionedbeforeisthecontrolledrelease(CR)ofbiologicallyactivechemicalstoa
target species at a specified rate and for a predetermined time. The active agent can be dissolved,
dispersed or encapsulated by the polymer matrix or coating, or is a part of the macromolecular
backbone or pendent side chain. The polymer used in this case serves primarily to control the rate of
delivery, mobility, and period of effectiveness of the chemical component. The principal advantage of
controlledreleaseapplicationisthatlesschemicalsareusedforaspecificperiodsotheimpactonnon
target species decreases and leaching, volatilization, and degradation are limited. The macromolecular
natureofpolymersisthekeytolimitingchemicallossesbytheseprocesses[143].Anotherapplicationis
the bands of sowing, which contain seeds regularly distributed as well as nutriments [144]. In marine
agriculture,biopolymersareusedtomakeropesandfishingnets.Theyarealsousedassupportforthe
marinecultures.

101

4.3.2.Packaging
Most of the packaging that holds the food we consume is neither renewable nor natural.
Concerning packaging, it has to be paid attention to the physical characteristics influenced by the
chemicalstructure,molecularweight,crystallinityandprocessingconditionsofthepolymersused.The
physical characteristics required in packaging depend on what item will be packaged as well as the
environment in which the package will be stored. Except of biodegradability, biopolymers have other
characteristics too as air permeability, low temperature sealability etc [145]. For example, items which
mustbekeptfrozenforaperiodoftimerequirespecialpackagingandfooditemsthereisnodoubtthat
require more stringent packaging requirements than nonperishable goods. The challenge in packaging
industryisthedevelopmentofbiodegradablepackagingmaterialseitherusingbiodegradablepolymers
themselves or combining polymers which are truly biodegradable into a laminate film or a film blend
whichhaspropertiesasgoodasthosefoundinsyntheticlaminates.

Figure4.8.Compostablebags

Using PBS, packaging industry is moving a step in the right environmental direction. A PBS
applicationiscompostablewastebagsinordertocollectorganicwasteandcarrierbags,whichcanalso
be used as organic waste bags. These bags help reduce landfill by increasing the volume of collected
organicwasteandmoreoverimprovethecompostingprocessandcompostquality.Foodpackagingfor
snackfoodsalesandfilmpackagingforfoodswithshortshelflifewhichrequireattractivepresentation,
or to extend shelf life. These include compostable pouches, netting and (foam) trays for (organically
produced)fruitandvegetables,andrecentlyalsofreshmeat,platescutleryandbags.Thesepackagings
havetheadvantageofcompositionafterusealongwithanyremainingfoodscraps.Spoiledfoodstuffs
canberecoveredviacompostingwithnoneedforseparationofpackagingandcontentsatpointofsale.

102

Figure4.9.Foodpackagingandutensils

Moreover, PBS is applied in rigid packaging such as containers and bottles. Bottles made from
poly(lactic acid) (PLA) are used for nonsparkling beverages and dairy products. Bhatia et al. [146] have
studiedthecompatibilityofbiodegrdablePLAandPBSblendsforpackagingapplications.Theresultsof
the research showed that both polymers are incompatible beyond 20 wt% of PBS in PLA. However,
compositions 90/10, 80/20 (PLA/PBS) seem to be compatible. The shear viscosity of the blend system
exhibited shear thinning behavior similar to biodegradable polymers. Blends of up to 20 wt% PBS
contentinPLAareexpectedtoovercomethedeficienciesofpolylacticacidsuchasbrittleness,flexural
properties,heatdistortiontemperatureandimpactstrengthforapplicationsinfoodpackaging,compost
bags,andotherbiodegradabledisposablebags.
Scientists should pay attention when choosing the right material or grade each time in order
to avoid migration phenomena of hazardous substances into the food or drinks. A small amount of
oligomer remains in PBS and it can possible move to products' surface. For this reason, applications
which the plateout causes problems, purified grades of the polymers are used. By a purification
process,theamountofoligomerinpurifiedgradesisaboutonethirdofthatingeneralgrades.

4.3.3.Medicine
Biopolymers in order to be used in medical applications should abide several conditions.
Biodegradabale polymers should have three important properties: biocompatibility, bioabsorbility and
mechanicalresistance.Currentapplicationsincludesurgicalimplantsinvascularororthopaedicsurgery
and plain membranes, but they are also widely used as porous structure in tissue engineeringbecause
they typically have good strength and an adjustable degradation speed [147]. Biodegradable polymers

103

are also used as implantable matrices for the controlled release of drugs inside the body. Synthetic
polymers are used more widely that others in biomedical implants and devices because they can be
fabricatedintoseveraldifferneshapes.
PBS is a promising material concerning bone and cartilage repair [148]. It presents better
processability than PLA and it has also higher mechanical properties than PE or PP. For medical
instruments and materials PBS it is also used a resin in several blends. The resin may be a PBS
copolymer, or a mixture of PBS and a copolymer of PBS with polylactic acid or poly (3
hydroxyalkanoate). However in cases of insufficient biocompatibility it can be enhanced by plasma
treatment.

4.3.4.Dailynecessityandotherfields
Biopolymers are also used in other special applications such as in the automotive, electronics,
constructionsectorsandeverydaynecessities.Inautomotivesector,bioplasticsandbiocompositesaim
topreparelightercarsusingnaturalfibersinplasticcarparts.Starchbasedpolymerscanalsobeused
as additive in the manufacturing of tires, reducing as a result the resistance to the movement and the
consumptionoffuelandinfinegreenhousegasemissions.
Asfarasconstructionsectorisconcerned,inflammabilityisthemainpropertyobtainedthrough
biopolymersreplacingsyntheticfibers.Therearealsomanyotherapplicationswhichdonotfitintoany
ofthepreviouscategoriesconcerningeverydayneccesities.

4.3.5.Potential,nearfutureapplicationsofPBS
Some grades however present technical problems. Especially, the resin properties have to be
improvedinorderforindividualenduseapplications.Forexample,inthecaseofbeveragebottlesthe
water and alcohol permeability and gas barrier property of carbon dioxide must be improved, and for
applications in horticultural, agricultural and construction fields, the biodegradability in soil must be
improved. For diaper application for aged people biodegradable material with super water absorbency
andelasticpropertyisneededandmustbedeveloped.NewgradeofPBSwillbedesignedwithabreak
through conception of a new macromolecule structure for various applications such as pressure
sensitive adhesives, aqueous emulsions, inks, paints and coatings. Worldwide potential demands for
biodegradablepolymerswillbequitesignificant,oncethetechnicalproblemsdiscussedaboveshouldbe
resolved. In the following Table 4.9. a few potential applications of PBS in the near future are
presented.

104

Table4.9.PBSpotentialfutureapplications[96]
Processingmethods Potentialapplications
Injectionmolding Cutlery,brush,container
Meltblow Nonwovenfabric,filters
Multifilament Conjugatedfiber(coreand
sheath),knotlessnet,rascal
wovennet,nonwoven(planting,
diaper,disposablemedical
supplies,sanitarynapkin)
Monofilament Fishingline,net,rope
Yarn(flatandsplit) Clothandnet,plantingtape
Film(castingandTdie) Paperlamination,multilayers
Film(tubular) Compostingbag,shoppingbag
Film(oriented) Shrinkfilm
Flexiblepackaging cushion
Sheetextrusion Foodtray,card
Foaming Softpackaging,cup,vessel
Blowmolding(direct) Shampoobottle,drugbottle
Bloqmolding(injection) Cosmeticbottle
Blowmolding(stretch) Beveragebottle

105

CHAPTER5:DEGRADATIONANDRECYCLINGOFPOLY(BUTYLENE
SUCCINATE)

5.1.DegradabilityofPBS
Degradable plastics including PBS and its copolymers can decompose to the environment,
degrade into CO
2
and water, through naturally occurring degrading enzymes and microorganisms.
Consequently, these biodegradable plastics will find wider and wider applications as disposable film or
articles. PBS can be degraded through hydrolytic degradation, enzymatic degradation, and
biodegradation in environmental conditions, such as burial, activated sludge, and compost. The
biodegradation rate of PBS and its copolymers depends on several parameters such as: chemical
structure,crystallinity,macroscopicshapeofthearticlesanddegradationconditions.

5.1.1.NonenzymatichydrolyticdegradationofPBS
HydrolyticdegradationofPBSandPBSAwascarriedoutoveratemperaturerangeof180300C
forperiodsofupto30min.Thehydrolyticdegradationtemperaturewassettobemuchhigherthanthe
T
m
of PBS (114 C) and PBSA (94 C) to melt the polymers completely and, therefore, to elevate their
hydrolytic degradation rate. Succinic acid and adipic acid at degradation temperatures of 250300 C
wererecoveredatmaximumyieldsof6580%,whereasbutanediolwasrecoveredatamaximumyield
ofonly30%,probablybecauseofitsdecomposition,althoughtheTOCvaluesreachedabout90%ofthe
theoretical values. Such low monomer yields or differences between TOC and monomer yields are
probably a result of the decomposition of the formed monomers [149]. The higher hydrolytic
degradationrateofPBScomparingtothatofPBSAcopolymersdegradationrateisshowninFigure5.1

106

Figure5.1PBSandPBSAdegradationrateat30C[150]

pHhasaconsiderableeffectontherateofhydrolyticdegradation.AtpH13,PBScanlose38%
of its weight after degradation for 9 days. At pH 10.6, the weight loss of PBS can reach 23 % after
hydrolyticdegradationfor27days.AtpH7.2,theweightlossislessthan10%after9weeks,butinthe
followingperiod,thedegradationacceleratesgreatly.MorespecificallyPBSloses75%ofitsweightafter
15weeks,asshowninFigure5.2[151].

Figure5.2Weightremaining(%)comparedwithday0valuesDegradationinphosphatebuffered
solution[151]

A traditional way to follow hydrolytic degradation is to measure the weight loss. There is a
significant difference in the hydrolysis rate depending on the degradation media. PBS aged in water

107

showedupto8%higherweightlossthanPBSagedinphosphatebuffer.Inthehydrolyticdegradation,
themolecularweightdecreasessteadilywithtime,whichindicatesthathydrolyticdegradationproceeds
viarandomchainscission,asrevealedinFigure5.3

Figure5.3Mw(%)remainingcomparedwithday0valuesDegradationinphosphatebufferedsolution
[151]

Hydrolytic degradation of PBS is also affected by polymers morphology, which controls the
diffusionofwaterintothepolymermatrix.Water penetratesatahigherrateintheamorphousregion
than in the crystalline region, which results in a higher hydrolysis rate in the amorphous region. The
higherdegradationrateintheamorphousregionisattributedtotheeasierdiffusionofwatermolecules
into the interior of polymers. The central part of the spherulites and spherulitic impinging lines is
degraded first, followed by the other parts of the spherulites. Moreover, the internal structure of the
spherulitealsoplayedanimportantroleinhydrolyticdegradation.

108

Figure5.4.SEMpicturesofdegradedPBScrystallizedatdifferenttemperaturesafterhydrolysisfor9days
a)meltquenchedb)isothermallycrystallized25Cc)isothermallycrystallized60Cd)meltquenchedandannealed
at75C[108]

Oneofthemostimportantparametersthataffectshydrolysisrateisagingtemperature.During
agingat37Ctheamountofsuccinicacidand1,4butanediolincreasedslowlyasafunctionofhydrolysis
time. The amount of 1,4butanediol detected was slightly higher than the amount of succinic acid and
thisisprobablybecauseoftheexcessof1,4butanediolusedduringthesynthesisofPBS.Asexpected
there was a large increase in hydrolysis rate and amount of monomers formed when the aging
temperature was raised from 37C to 70C. The excess of butanediol over succinic acid was also seen
during the first weeks at 70 C. However, after 34 weeks the hydrolysis rate accelerated significantly
and the amount of monomers increased rapidly between 4 and 12 weeks [108]. Figure 5.5 shows the
degradation profile of PBS samples crystallized at different temperatures. PBS isothermally crystallized
at 60C underwent the fastest hydrolytic degradation, whereas that quenched and then annealed at
70Cdemonstratedthelowestdegradationrate,indicatingtheimportanceofcrystallinity.

109

Figure5.5.WeightlossofPBScrystallizedatdifferenttemperatures[108]

Hydrolytic degradation is also a potential method for monomer recovery of PBS after its use,
belongingto chemicalrecyclingapproach (asitwill bepresentedinparagraph5.2.2). Toovercome the
very slow rate of hydrolytic degradation in the solid state, owing to the highly hydrolysis resistant
crystalline residues (or extended chain crystallites), hydrolytic degradation in the melt has been
developedwithouttheaidofacatalyst[149].

5.1.2.EnzymatichydrolyticdegradationofPBS
AfterseveralstudiesithasbeenshownthatPBS,anditscopolymersareenzymaticallydegraded
by lipases such as Rhizopus delemar, Rhizopus arrhizus, Mucor miehei, Pseudomonas sp , Aspergillus
niger,Chromobacteriumviscosum, Rhizopusorizae, andRhizopusniveus.The enzymatic degradationof
aliphatic polyesters depends on the chemical structure and the highly ordered structure as regards its
specificsolidstatemorphologyanddegreeofcrystallinity[152].
Crystallinity has been singled out as the factor that affects mostly enzymatic degradation of
polymers. It is long known that the degradation of aliphatic copolyesters is faster with respect to the
singlehomopolyesters.Themeltingtemperatureofpolyestershasalsoastrongeffectontheenzymatic
degradationofpolymers.ThehighertheT
m
,thelowerthebiodegradationofthepolymer[153].

T
lactate)(P
of PBSL a
enzymatic
conditions
molecular
andfilms
6.0for2w

Co
with incre
degreeof

Taniguchi et
PBSL)withlip
re readily h
c hydrolysis.
s, the enzym
r orientation
showedweig
weeksasitis
Figure5.6.M
oncerning al
easing aroma
crystallinity
al. [69] exam
paseoriginat
ydrolyzed b
Since the p
matic hydro
. However,
ghtlossesab
sshowninfig
Massremainin
incub
liphaticarom
atic comono
demonstrat
mined enzym
tedfromPse
y the action
olymer films
olysis should
PBS fiber ha
bout6and7
gure5.6.
ngofvariousP
batedwithLip
matic PBS co
omer conten
ethehighes
110
matic hydro
eudomonasce
n of the lipa
s of PBS and
d depend no
as a much lo
76%afterbe
PBSandPBSL
pasePS1at50
opolymers,
nt [78, 154].
stdegradatio
lysis of PBS
epacia.Ithas
ase, compari
d PBSL are r
ot only on
ower degrada
eingincubate
samplesasa
08CandpH6.
the enzyma
For PBSA c
onrateinlipa
and poly(bu
sbeenfound
ng to those
eadily hydro
the crystall
ation rate th
edwithLipa
functionoftim
0[69]
tic biodegra
opolymers, t
asesolution
utylene succ
dthatthedr
e of PBS und
olyzed under
inity but al
han PBS film
asePSat50

me.Thesamp
adation rate
those with t
[60,77].
inatecoL
rawnfibers
dergo little
r the same
so on the
. PBS fiber
0CandpH
pleswere
decreases
the lowest

111

Figure5.7.PBSTweightlossdegradedbylipasefromPseudomonas[151]

Figure5.8.PBSAweightlossdegradedbylipasefromcandidacylinracea[77]

It is known that polymer degradation usually proceeds in a selective manner, with the
amorphousregionsbeingpreferentiallydegradedascomparedtocrystallineones.Bothsurfaceerosion
andtheweightloss,takeplace.Themolecularweightandmolecularweightdistributiondonotchange
duringtheenzymaticdegradationbecauseonlythepolymeronthesurfaceofthesubstrateisdegraded
andthelowmolecularweightdegradationproductsareremovedfromthesubstratebysolubilizationin
thesurroundingaqueousmedium.

112

The enzymatic degradation is not affected by the molecular weight of aliphatic polyesters and
thedegradationtrendsforlowmolecularweight(
w
M :6300)andhighmolecularweight(
w
M :29,000)
poly(butylene succinate) are similar. The lack of any dependence of the enzymatic degradation on
molecularweightwouldindicatethatthelipasesproducedbymicroorganismsareendotypeenzymes.
Thatmeansthattheseenzymesrandomlysplitbondsinthepolymerchains.Thus,thevariationsinthe
rate of enzymatic degradation are not attributable to molecular weight differences in the series of
synthesizedpolyestersbuttotheirchemicalstructure[155].

5.1.3.Environmentalbiodegradationofpoly(butylenesuccinate)
PBSanditscopolymerscanbedegradedincompost,moistsoil,naturalwater,activatedsludge
and sea water. In the following table the relation between Bionolle grades (PBS, PBSA) and
biodegradabilityispresented.

Table5.1.Polymerstructureandbiodegradabilityindifferentenvironments[96]
Degradationenvironments PBS PBSA
Hotcompost normal Rapid
Moistsoil Normal Rapid
Seawater Slows Rapid
Waterwithactivatedsludge slow Slow

Degradation in soil is also affected by the same parameters as enzymatic hydrolysis, although
there is a difference in their degradation mechanism, since in the case of soil burial the effect of
microorganisms arises on the surface of the polymer. Microorganisms in the soil extract liquid can
degradePBSandthepHofthedegradationliquiddoesnotchangesignificantly.

113

Figure5.9.SEMmicrographsofPBShomopolymerandPBSAcopolyestersaftersoilburial[53]

ThepercentagesofdegradingbacteriaforPBSin thesoilenvironment have beenestimated to

be 0,26,0 % of the total colonies with Bacteria phylogenetically related to the genus Roseateles
showing the highest degrading activity of all examined [156]. The biodegradability of PBS copolymers
also depends on the copolymer composition and the content of the aromatic comonomers [157]. For
the aliphatic copolyesters, the greatest biodegradability occurs at about 3050 mol% comonomer
content.
Kasuya et al. [158] studied PBS degradation in different environmental natural waters. Results
showed that the rate of biodegradation of chemosynthetic polyesters is dependent not only on the
chemicalstructureofmonomericunitsbutalsoonthesourceofnaturalwaterused.Morespecifically,
therateofbiodegradationdecreasedinthefollowingorder: seawaterfrom the bay>freshwaterfrom
theriver>freshwaterfromthelake>seawaterfromthePacificOcean.
BiodegradationofPBSanditscopolymersinactivatedsludgeisfasterthaninsoilburial.ForPBS
film, a considerable change in the film morphology could be observed after it had been immersed in
activatedsludgefor2weeks.After10weeksofbiodegradation,bigholeswereobservedinthePBSfilm,
asshowninFigure5.10.

114

Figure5.10.PBSdegradationinactivatedsludgea)beforedegradationb)1weekc)2weeksd)4weekse)
6weeksf)10weeks[55]

The molecular weight has a considerable effect on biodegradation of PBS in activated sludge.
Afterbiodegradationfor12weeks,PBSwithintrinsicviscosity1,049dl/ghasaweightlossofabout80
%,whichismuchlargerthantheweightlossofPBSwithanintrinsicviscosityof1,79dl/g,about16%.

Figure5.11.BiodegradationofPBSinactivatedsludgewithviscositya)1,793dl/gb)1.049dl/g[55]

115

Concerning PBS copolymers, the biodegradation rate depends on their chemical structure. For
PBSA copolymers, the biodegradation rate in activated sludge improves with increase of the butylene
adipate content from 0 to 20 mol %. For PBS copolymers with substituted succinic acid as the
comonomer, at the same comonomer content of 10 and 20 mol %, the degradation rate follows the
order PBSM > PBSA > PBSBS > PBS. For PBST copolymer, with increase of butylene terephthalate
comonomers, the biodegradability increases first, and then decreases sharply. It is observed that the
aromaticunitsarenotsosusceptibletobiodegradationasthealiphaticunits.
Biodegradation in compost is the best way to examine whether a plastic is biodegradable or
compostable.PBSpowdershowsadegradationratecomparabletothatofthefilm.PBSpelletdegrades
moreslowlyandshowsafinalweightlossoflessthan15%afterdegradationincompostfor3months.
The biodegradation rate of PBS in compost depends on the shape and the size of the specimen
[159,160]. PBSA powder has biodegradation rate similar to that of the film [159]. PBSA has a higher
biodegradationratethanPBS.TheweightlossofPBSAandPBSisaround90and55%afterdegradation
in60Ccompostfor3months[160].
Both in nitrogen and in air, the temperatures of the beginning of degradation of the
copolyesters PBSF are lower than the corresponding temperature for PBS. Moreover, their stability
increases with increasing fumarate content. Also, the copolyesters are more stable in air than in
nitrogenandthiscanleadtotheconclusionthatoxygeninhibitsthethermaldegradationreactionsand
thattheseinhibitoryreactionstakeplaceatthedoublebonds.Thethermogravimetricanalysiscurveof
PBSrevealsthatthispolyestershowsweightlossof5,50,and90%at325,400,and424C,respectively,
inair.ItshouldbenotedthatthisdoesnotindicatethatPBSpolymerchainsarethermallystableupto
325C[74].

5.1.4.ThermaldegradationofPBSandItsCopolymers
Rizzarellietal[161]examinedthethermooxidationmechanismsofcommercialPBSpolyesters.
Thermal oxidation was performed for 0.5, 1, 2, 2.5, 3,3.5, 5 and 6 h at 170 C, in atmospheric air and
thermal degradation procedure took place under nitrogen flow at 240 C for 60, 75, 90,105,120 and
135 min, at 250 and 260 C for 1 h. The results obtained showed that thermal oxidation produces a
significant reduction of the molar mass of the polyesters, promoting the formation of PBS oligomers
withdifferentendgroups.Theidentificationofthestructuresandendgroupsattachedtotheoligomers
producedisreallyimportant,sincetheendgroupsrevealtheparticularmechanismthathasbeenactive
inthethermaldegradation.
The initial step in this process consists of a hydrogen abstraction from the methylene group
adjacent to the ester linkage, leading to the formation of a hydroperoxide intermediate. Remarkably,

116

the hydroperoxide intermediate (I) decomposes by radical rearrangement reactions via the hydroxyl
ester (III) or from the radical (II) which may follow two different pathways. These three degradation
pathwayshavebeenrevealedtobetimeresolved,showingadifferentinductionperiod.
Thermal degradation experiments were also performed showing a decomposition pathway
through a bhydrogentransfer bond scission, followed by the production of succinic anhydride from
succinicacidendmoleculesviaacyclisationdecompositionmechanism.

O(CH
2
)
4
OCO(CH
2
)
2 CH
O
O
CH
2
CH
2
H
(CH
2
)
2
OCO(CH
2
)
2
CO

hydrogen transfer
O(CH
2
)
4
OCO(CH
2
)
2
COOH + CH
2
CH(CH
2
)
2
OCO(CH
2
)
2
CO
O(CH
2
)
4
OH +
O
O
O

Scheme5.1.ThermaldegradationmechanismofPBS[161]

PBSpresentsagoodthermostabilitysincenosignificantweightloss,0.8%forPBS,occurreduntil
300 C. From preliminary studies of the monomers, it was found that succinic acid degrades at
temperatures close to 200 C while butylene glycol evaporates at slightly higher temperatures,
nevertheless lower than 300 C. Consequently, it can be concluded that the number of methylene
groupsofuseddiolforpolyesterpreparationhasacrucialeffectonitsthermalstability.Asthenumber
ofmethylenegroupsincreases,thermalstabilitydecreases[54].Thethermaldegradationtemperatures
of PBS are almost the same in nitrogen and air [74]. The mechanism of thermal degradation however
should be examined not only as a degradation route but as a way to synthesize new compounds,
includingpolymers,oligomers,andmonomers.

5.2.PBSrecyclingtechniques
Majority of plastic processing companies recycle inhouse thermoplastic scrap, which is
produced as sprues, offcuts or trimmings. Most of this material is reworked as addition to virgin
feedstock,whileanumberofreactionstakeplace,whicharedetrimentaltothepropertiesofapolymer.

117

These may be oxidation, crosslinking, decomposition and molecular mass reduction. To reduce
degradation,antioxidantandstabilizersareused,eitheridenticaltothoseusedintheoriginalmaterial,
or if new applications are envisaged, those appropriate to the new use. Lower grade scrap, which is
dirty, contaminated and consists of mixed colors but is single polymer type, may be converted to low
grade colored or filled compounds, suitable for use in many standard fabrication processes. Similarly,
thermosetwastecanbeusedbutonlyasgroundorshreddedfillers.Therecyclingofpolymermaterials
isofincreasingimportancenowadays.Themainpolymersrecyclingtechniquesaremechanicalrecycling,
chemicalrecyclingandincineration.
Generally, for any viable and sustainable recycling processthe following criteria must be
satisfied:
consistentandabundantsupplyoffeedstock
materialsmustnotbenecessarilymonopolymericoruncontaminated
existenceofasignificanteconomicadvantageinusingrecycledmaterials
reprocessingtechnologymustbedevelopedandavailable
theremustbemarketforthenewproducts

5.2.1.Mechanicalrecycling
Among the methods referred above, there have been several reports that suggested material
recyclingasoneofthemostefficientandreliablemethodstodealwithpolymersrecycling,sincedirect
reprocessingcanbeefficientlycarriedout[162,163].
The mechanical recycling process involves several steps: separation of plastics by resin type,
washingtoremovedirtandcontaminants,grindingandcrushingtoreducetheparticlesize,extrusionby
heat and reprocessing into new plastic goods. Mechanical recycling of plastics is limited by the
compatibility between the different types of polymers because this can cause dramatically changes in
new polymer properties and therefore applications. Another problem with mechanical recycling is the
presenceinplasticaddition,mostpolymerssuffercertaindegradationduringtheiruseduetoeffectsof
temperature, ultraviolet radiation oxygen and ozone. That is the reason for lower properties and
performanceofrecycledpolymerscomparingwiththevirginonew.
Kanemura et al. [126] examined PBS as a promising biodegradable and reprocessable material
used for material recycling in water. It turned out that using the biodegradable PBS could induce the
total reduction of the environmental burdens in the material recycling, where uncollected waste,
discardedmaterialsandmateriallossescaneventuallybiodegradetoreducetheoverallenvironmental
load.Moreover,itwasfoundthatthemechanicalpropertiesofPBSwereenhancedafterreprocessing,
whichcouldnotbeobservedinothertypesofbiodegradablematerialssuchasPLA.

118

Figure5.1.Biodegradablematerialrecycling[126]

More specifically, the effects of the reprocessing properties of PBS in water are affected as preseted
below:
Accordingtotheresultsofthethreepointbendingtest,therewashardlyanydegradationobserved
PBS up to the third reprocessing cycle at 140C. When immersed to water, on the contrary, the
molecular weight of PBS was reduced due to the chemical degradation. However, the molecular
weight of the immersed PBS became higher after reprocessing, indicating the cure of the chemical
degradationowingtotheresynthesisofthePBSduringthereprocessing.

Products
Collection
Wasteplastic
Uncollectible Disposal
Biodegrade Biodegrade
Biodegrade Loss
Reprocessing

The be
immer
eventu
bendin
remova

Figure5
ending stren
sion time in
ually affected
ngstrengthw
alofthecrac
5.2.PBShomo
Figure
ngth of PBS
ncreased. D
d the bendin
washigherth
cksandvoid
opolymerMw
e5.3.PBSMw
materials im
egradation
ng strength.
hanthatoft
sthathaveb
119
wagainstthen

wagainstimme

mmersed in
was caused
Concerning
heimmersed
beencreated
numberofrep
ersionandrep
water at hig
by hydroly
g the reproce
done.Thisi
donthesurf
processingwit
processing[12
gh temperat
ysis due to
essed mater
mprovement
faceofthede

thoutwater[

26]
ture decreas
the immers
rial after imm
tispossibly
egradedPBS
126]
sed as the
sion which
mersion its
duetothe
S.

120

Figure5.4.ThebendingpropertiesofPBSagainstthenumberofreprocessing[126]

Figure5.5.ThebendingpropertiesofPBSagainstthenumberofreprocessing[126]

5.2.2.Chemicalrecycling
Chemical recycling also know as feedstock or tertiary recycling is a method based on the
decompositionofpolymersbymeansofheat,chemical,orcatalyticagentinordertoyieldavarietyof
products ranging from the chemical monomers to a mixtures of compounds. Nevertheless, feedstock
recycling is more limited by process economy than by technical reasons. The profitability of the
technique is mostly determined by the degree of separation required in raw wastes, the value of the
products obtained, and the capital investments in the processing facilities. Chemical (monomer)

121

recoveryistotallyeffectivefortherecyclingofbiodegradableplasticsandspeciallypolyesterslikePBS,
whicheasilyundergohydrolysisanddecomposeintomonomerssuchasorganicacidsandpolyols.
During the chemical depolymerization process, the polymer is cracked to the original monomer in the
presence of different reagents. Recycled monomers are identical to those used in the preparation of
virgin polymers. Chemical depolymerization is the most established method of plastic feedstock
recycling, even though it is restricted to the recycling of condensation polymers and there are no
applicationsofdecompositionofotherpolymers.Dependingonthechemicalagentusedtobreakdown
the polymer, different depolymerization routes are envisaged: for instance glycolysis, methanolysis,
hydrolysisandammonolysis.
Thermal treatment is a collective term to describe different methods and processes developed
forbreakingdownpolymericmaterialssimplybytreatmentathightemperatureinaninertatmosphere.
Theyaremainlyusedforthefeedstockrecyclingofadditionpolymers,whereascondensationpolymers
are preferably depolymerised by reaction with certain agents. Thermal degradation of plastics and
rubberproceedsthrougharadicalmechanism,whichmayinvolvethreedifferentpathways:
Randomscissionleadingtotheformationofsmallerpolymericfragmentsasprimaryproducts
Endchainscission,whereasmallmoleculeandalongchainpolymericfragmentareformed.
Abstractionoffunctionalsubstituentstoformsmallmolecules
Inmanycases,severalofthesepathwaysoccursimultaneously.Duringthethermaldegradationofmany
polymers,otherreactionsmayalsooccuratthesametime.
PBSbeinga biodegradablepolyerand duetoitshighhydrolyzabilityin the presenceofwater
hasahighpotentialformonomerrecoverybyhydrolyticdegradationafteritsuse.However,monomer
recovery through hydrolytic degradation in the solid state should be avoided because the highly
hydrolysis resistant crystalline residues (or extended chain crystallites) are formed and their very slow
degradationwillcauselowmonomeryieldinalimitedshortperiodorwilltakealongtimetogiveahigh
yield.Firthisreasonhydrolyticdegradationofbiodegradablepolyestersinthemeltdasbeendeveloped.
Tsujietal.[149]haveexaminedhydrolytic degradationofPBS andPBSAas arecycle/recovery
method. At degradation temperatures of 250300 C, the yields of succinic acid and of butanediol
reachedabout6580%and30%,respectively,althoughthetotalorganiccarbon(TOC)valuesreached
about 90 % of the theoretical values. Low monomer yields or differences between TOC and monomer
yieldsareprobablyaresultofthedecompositionoftheformedmonomers.However,itisbelievedthat
afurtheroptimizationofhydrolyticdegradationconditionswillresultinhighermonomeryields.
Enzymes are also used for chemical recycling of plastics. The substrate specificity of enzymes
may be the most excellent feature although it is also important in that reactions can be carried out at
normal temperature and under normal pressure, thereby saving energy costs and requiring no organic

122

solvent responsible for environmental pollution. In general, bioprocesses require high costs and hence
aredisadvantageousinthispointwithoutanydoubt,butitisagreatmerittoachieveextractionofhigh
puritymonomerswithoutseparation.Toestablishenzymaticrecycling,thepremiseisthepresenceofa
strongplasticdegradingenzyme.
Nakajima et al. [155] have made several experiments on findind the appropriate enzyme for
polymer decomposition and monomer recovery for PBSA. Biodegradable plastics are most suitable for
biochemical monomer recycling because they must be degraded by specific enzyme containing
environmental microorganisms as it is already presented in paragraph 5.1.2. Indeed, there have been
manyreportsregardingtheisolationofbacteriaandfungithatcandegradetheseplasticsfromvarious
environmental sources. Most reported PBSAdegrading microorganisms, however, can only degrade
emulsions or films (with thickness b50 m) but not solid plastics. Nakajima screened and identified a
novel bacterium that has high PBSA monomerization activity. Strain TB71 could completely
monomerize the solid PBSA. The amounts of succinic acid and adipic acid, however, were much lower
thanthatofbutanediol.
Inrecentyearsanothermethodreceivingmuchattentionforrecyclingpolymersisdegradation
performed under sub and supercritical water conditions. In experiments held by the Kasetsart
Universitywithinathesis,[164]succinicacidandbutanediolwereextractedusingdifferentadsorbents
forpolarextraction,namelysilicagel,florisilandpolystyrenedivinylbenzene(PSDVB)assolidphaseto
extractthedegradedcomponents.ItwasfoundthatthePSDVBsolidphasewaschosenforextraction
ofsuccinicacidandbutanedioldegradedproductsbecauseofthierhigherextractedyieldfromaqueous
matrixes than those obtained from silica gel and florisil. The advantages of the method are usage of
environmental friendly solvent, low organic solvent consumption, cheap and nontoxic reagent,
relativelysimpleequipment,andaneaseinfurtherproductrecycling.
At last, great attention should be paid concerning PBS recycling in order to be used for
packaging. Any polymer whether virgin or recycled must meet the appropriate standards for food
contact. Thus, the recycling process must not only produce reconstituted polyester with appropriate
physicalandchemicalcharacteristics,butmoreoverbesufficientlypuretomeetfoodqualitystandards.
According to patent EP 1084171B1 [165], a method of recycling PBS and other polyesters of sufficient
highpuritytomeetfoodpackagingrequirementsisconsistingfromthefollowsteps:
Extrudingameltofcleanedpostconsumerpolyester
Solidifyingandpelletizingthepostconsumermelt
Blendingthepostconsumerpolyesterwithvirginpolyesterprepolymerresin
Polymerizingtheblendinsolidstate

123

5.2.3.Incineration
Incinerationofpolymerscanalsobeseenasarecoverymethodsinceplasticscouldreplacethe
application of other oil based fuels. It can be viewed that the plastic application is the first purpose of
oil, and energy production is the secondary task. Indeed incineration with energy reclamation is
consideredasarecoverymethodand,duetotheirhighenergycontent,polymersarevaluablefuels.
As a result of the combustion, several non combustible gases and vapors can evolve, such as
volatile lowmelting heavy metals and a wide variety of acid gases.If these gases are discharged
uncontrolled into the atmosphere along with the fly ash they can constitute a high level of emission
leadin to global warming and pollution. A welloperated incinerator can virtually eliminate most of the
flyashandwhateverhazardouschemicalsadheretotheash.
Incineration process however has the advantage that the plastics have high calorific value. For
this reason incineration plants have to be modified for efficient combustion of the polymers and
regulation of the gas emissions to ensure that no toxic gases are released. Energy recovery through
incinerationisanessentialpartofanoverallwastemanagementscheme[166].
Concerning PBS, it can be incinerated with less problems to the furnace as its combustion heat is
relatively low and does not generate toxic or acid gases. Specifically, when incinerated, the heat of
combustion and the generation of carbon dioxide are about one half and two thirds of conventional
polyolefinrespectively.ScientistshavingstudiedPBSbehaviorthinkthatthispolymerisbetterthanPE
forincinerationsinceithaslowerBTUs.

124

CONCLUSIONS
Poly(butylene succinate) (PBS) and its copolymers are a family of biodegradable polymers with
excellent biodegradability, thermoplastic processability and balanced mechanical properties. In this
paper,productionofthe monomerssuccinicacidandbutanediol,synthesis,processing,propertiesand
recycling of PBS and its copolymers were reviewed. The main coclusions after studying and reviewing
thebibliographyarethefollowing:

Physical properties and biodegradation rate of PBS materials can be varied in a wide range
throughcopolymerizationwithdifferenttypesandvariouscontentsofmonomers

PBS has the best processability among the general degradable polymers. Due to its wide
temperature window for thermoplastic processing, the resin is suitable injection molding,
extrusion molding or blow molding using conventional polyolefin processing equipment,
loweringbarriertoswitchtoPBSfromotherpolymer

Mechanical properties of PBS are almost the same with polyethylene and polypropylene so it
cansatisfythegeneralrequirementsforuseinplastics

PBSs thermal deformation temperature is approximately 100C which can be increased after
property alteration. PBS has a good heat resistance performance compared to other fully
biodegradable polymers and is able to meet the heat resistance requirement of daily articles,
suchascold/hotdrinkpackagingandfoodcontainers

PBSisbasicallystableintheatmospherebutbiodegradableinsoil,seawaterandcompost.Itcan
maintain a stable performance in a relatively long storage and usage period while being
degradedquicklyafteruse

PBS has great flexibility and it has emerged as a biodegradable material potentially for a wide
range of applications, such as packaging materials, food containers, packaging films, garbage
bags, disposable medical devices, hygiene products, textiles and covering materials for
landscapingpurposes.Itcanalsobeblendedwithothercompounds,suchasstarchandadipate
copolymers,enablingamoreeconomicaluse

125

PBS copolymers are fully biodegradable synthetic aliphatic/aromatic copolyesters having a

melting point between 100C and 120C and are in solid form under room temperature. Comparing to
toPBShomopolymer,PBScopolymershavethefollowingcharacteristics:
EnhancedtensilestrengthandtearstrengthsothatthepackagingbagmadebyPBScopolymer
cancarryheavierweightandbereused
Higher transparency and suitable for use in the packaging of food and cigarette and as
advertisingmaterials
Improving the compatibility of degradable polymers with other materials, such as starch, PLA
and PHB so that the toughness and processability of the mixed degradable materials will be
enhanced.
Therefore, PBS copolymers are believed to be the most suitable degradable material to be used in
packaging,filmsandfibrematerialsintermsofitsmechanicalpropertiesandprocessability.

At the present stage, petroleum or coal based succinic acid is still cheaper than biobased feedstock.
With future development of fermentation technology and the finding of new microbial strains, bio
based succinic acid will become competitive and so PBS will be one of the most preferable
biodegradablepolymersespeciallyforpackagingapplications.

126

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