Photo Degradation

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Polymer Degradation and Stability 93 (2008) 561e584 www.elsevier.com/locate/polydegstab
Review article
Mechanistic implications of plastic degradation

Baljit Singh*, Nisha Sharma
Department of Chemistry, Himachal Pradesh University, Shimla 171 005, India Received 21 June 2007; received in revised form 6 November 2007; accepted 13 November 2007 Available online 19 November 2007
Abstract Plastics have become an indispensable ingredient of human life. Their enormous use is a matter of great environmental and economic concern, which has motivated the researchers and the technologists to induce different degrees of degradations in the plastic. These degradations can be induced in a better way if their mechanistic implications are properly understood. A better understanding of the mechanism for these degradations is also advocated in order to facilitate the proper use of the alternative waste disposal strategies. In view of the facts concerning the plastic degradation, in this review article, we have discussed various types of polymeric degradations along with their mechanisms, which include photo-oxidative degradation, thermal degradation, ozone-induced degradation, mechanochemical degradation, catalytic degradation and biodegradation. This article also discusses the different methods used to study these degradations and the factors that affect these degradations. 2007 Elsevier Ltd. All rights reserved.
Keywords: Photo-oxidative degradation; Thermal degradation; Ozone-induced degradation; Mechanochemical degradation; Catalytic degradation and biodegradation
1. Introduction Plastics due to their versatility become the essential ingredients to provide a quality to life. These are now rival metals in breadth of use and in severity of applications because of their exibility, toughness, excellent barrier and physical properties and ease of fabrication [1e5]. The accumulation of plastics in the environment is a matter of great concern leading to long-term environment, economic and waste management problems. Degradation of waste plastics through various means becomes one of the alternatives to deal with such problems [6,7]. A wide variety of synthetic polymers absorb solar ultraviolet (UV) radiation and undergo photolytic, photo-oxidative, and thermo-oxidative reactions that result in the degradation of these materials [8,9]. The propensity of plastic products to undergo solar UV radiation induced degradation/ozone-induced degradation has been increased by addition of some additives in these polymers [10,11]. Besides these degradations, biodegradation offers another most
* Corresponding author. Tel.: 91 0177 2830944; fax: 91 0177 2830775. E-mail address: baljitsinghhpu@yahoo.com (B. Singh). 0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymdegradstab.2007.11.008
efcient and attractive route to environmental waste management. The mechanisms involved in the biodegradation are complex due to the interaction of different oxidative processes which are caused by the oxygen present in the air either by the microorganisms or by the combination of the two [12]. On the other hand, sometime the product needs stability instead of degradation. Therefore, depending upon the product applications plastic needs controlled stability. In order to increase the outdoor uses of plastics, the development and production of polymers with increased weathering resistance is required similarly for the use in high temperature applications, polymers need thermal stability [13e15]. To control the stability, understanding of the mechanism is the primary requisite. Keeping in view the facts for the plastic degradation, in this review article, we have mainly discussed the various types of polymeric degradations (photo-oxidative degradation, thermal degradation, ozone-induced degradation, mechanochemical degradation, catalytic degradation and biodegradation) and mechanism followed by these degradations. We have also discussed the various methods used to study these degradations and various factors which affect these degradations.
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2. Types of plastics Plastics can be synthesized via the polymerization (polyaddition or polycondensation) of small molecules and are in general classied into two groups i.e. thermoplastics and thermoset plastics [16]. Thermoplastics are linear chain macromolecules where the atoms and molecules are joined end-to-end into a series of long, sole carbon chains. The bi-functionality necessary to form a linear macromolecule from vinyl monomers can be achieved by opening the double bond and reaction proceeds by a free radical mechanism. Such type of polymerization is known as addition polymerization, polyethylene and polypropylene are the examples [17e19]. On the other hand, thermoset plastics are formed by step-growth polymerization under suitable conditions allowing bi-functional molecules to condense inter-molecularly with the liberation of small by-products such as H2O, HCl, etc. at each reaction step [18]. In this class, the monomers undergo some chemical changes (condensation) on heating and convert themselves into an infusible mass irreversibly [20,21]. 3. Types of plastic degradation Changes in polymer properties due to chemical, physical or biological reactions resulting in bond scissions and subsequent chemical transformations are categorized as polymer degradation [22]. Degradation reects changes in material properties such as mechanical, optical or electrical characteristics in crazing, cracking, erosion, discoloration and phase separation [23]. Depending upon the nature of the causing agents, polymer degradations have been classied as photo-oxidative degradation, thermal degradation, ozone-induced degradation, mechanochemical degradation, catalytic degradation and biodegradation [24]. 3.1. Photo-oxidative degradation Photo-oxidative degradation is the process of decomposition of the material by the action of light, which is considered as one of the primary sources of damage exerted upon polymeric substrates at ambient conditions. Most of the synthetic polymers are susceptible to degradation initiated by UV and visible light. Normally the near-UV radiations (290e400 nm) in the sunlight determine the lifetime of polymeric materials in outdoor applications [25e27]. Polymer degradation occurs mainly in the ether parts of the soft-segments, where photo-irradiation generates ester, aldehyde, formate and propyl end groups [28]. UV radiations have sufcient energy to cleave CeC bond [29]. The most damaging UV wavelength for a specic plastic depends on the bonds present and the maximum degradation therefore occurs at different wavelengths for different types of plastics, e.g. it is around 300 nm for polyethylene (PE) and around 370 nm for polypropylene (PP). Photodegradation changes the physical and optical properties of the plastic. The most damaging effects are the visual effect (yellowing), the loss of mechanical properties of the polymers, the changes in molecular weight and the molecular weight distribution for the same [30e40]. PE and PP lms when exposed to solar UV radiation readily lose their extensibility, mechanical
integrity and strength along with decrease in their average molecular weight [33e37]. Mechanical integrity of polystyrene (PS) is diminished through extensive chain scission during photodegradation [38,39]. Another important study carried out on light-induced damage to PS plastics compounded with ame retardant additives has reduced the risk of re when the plastics have been used as building construction materials [40]. At any given temperature and moisture content, the rate of weathering increases with an increase in UV ux. Tensile stressing of stabilized types of PP in thermo-oxidative and photo-oxidative environment has accelerated embrittlement of the polymers [31]. In one study, tensile stress has been applied at constant load (in the range of 0e6.86 MN/m2) to observe the behavior of stabilized and unstabilized types of isotactic PP in the course of thermo-oxidative aging at 80e130 C, photooxidative aging at 45 C and relative humidity of 65%. From kinetic evaluation of the temperature-dependence of weight changes of unstabilized PP during thermo-oxidative aging, it has been found that the weight losses of unstressed and tension-stressed specimens have obeyed the kinetic equations for a reaction of the rst order [32]. Along with stress, introduction of carbonyl group on polymeric backbone has also accelerated photochemical degradation. PS undergoes photochemical ring-opening reactions, which leads to backbone cleavage by subsequent Norrish Type II reactivity [41,42]. 3.1.1. Mechanism of photodegradation The mechanisms of the degradation and oxidation reactions are determined by the extraneous groups and/or impurities in the polymer, which absorb light quanta and form excited states. Initially short-lived singlet state is transformed to long-lived triplet state [43]. Excited triplet states may cleave the polymer chains and form radical pairs (Norrish Type I reaction) or form pairs of saturated and unsaturated chain ends by hydrogen transfer (Norrish Type II reaction) [44]. The polymer radicals thus formed may add molecular oxygen (in triplet ground state) to peroxy radicals, which abstract hydrogen and form hydroperoxide groups, which absorb UV light or become excited by energy transfer, the weak OeO bonds break and pairs of alkoxy and hydroxyl radicals are formed which may react in various ways, e.g. by hydrogen abstraction, chain scission, rearrangement, etc. and accelerate photodegradation [45]. Double bonds may add excited oxygen molecules in singlet state. In this reaction, the double bond is shifted to an adjacent CeC bond and a hydroperoxide group is formed. Some synthetic polymers, e.g. aromatic polyesters and polyamides, have inherent absorption of UV light, causing excitation, radical formation, oxygen addition, splitting off small molecules, chain scission, etc. Some of these polymers are auto-stabilized towards photodegradation by formation of an oxidized surface layer with high absorption of near UV and visible light of short wavelengths, preventing further penetration of light into deeper layers [46]. In photo-oxidative degradation, mechanism involves autooxidation cycle comprising various steps shown in Scheme 1. 3.1.1.1. Initiation. The absorption of UV light that has sufcient energy to break the chemical bonds in the main polymer
563
Initiation Initiator
. R
i
Ri O2 R H
. . . R
hv Z
* Z *
Z
RiOO RiOOH
.
RiOO
C
Scheme 3.
+ Z
Propagation R
O2
ROO H
.
R
ROO
.
R
ROOH
Termination
. . R
R
ROO
ROOR
Scheme 1.
chain leads to the initiation of mechanism responsible for polymer degradation. It involves a radical chain mechanism for the formation of initial radical. Different initiation steps under varied conditions have been undertaken in different polymers. 3.1.1.1.1. Direct UV initiated photolysis of CeC and CeH bond. Bond dissociation energy of CeC bond (375 kJ/mol) and CeH bond (420 kJ/mol) is equivalent to UV radiation of 320 nm and 290 nm. Thus, direct photolysis of CeC and CeH bond is possible and the radical formed in these reactions become a source of initiation radicals as shown in Scheme 2 [47]. 3.1.1.1.2. Photosensitized cleavage. Photosensitizers are highly photosensitive, readily get excited on exposure to light and are generally employed to bring about effective homolysis of the polymeric chains, which otherwise do not undergo sufcient photo-excitation at the frequency of light available to the system (Scheme 3) [45,48]. 3.1.1.1.3. Catalyst residues as source of generation of radicals. Some metal salts and oxidation products of such residues when added to the polymers act as catalysts to generate initiation radicals (Scheme 4) [48]. Many commercial polymers contain metallic compounds as impurities or deliberately incorporated additives. The bulk of the latter types are pigments, whereas the former include polymerization catalyst residues or debris from processing equipment. Polymerization catalysts such as transition metals (Ti) may remain in polyolens at
2e100 ppm, depending on workup and catalyst efciency. These residues have been implicated in both photo- and thermal stability problems. For example, TiO2 is a well-known photosensitizer for polyamide and polyolen degradation and absorbs at 480 nm. Photosensitization involves the formation of highly reactive species including atomic oxygen, OH, OOH and O2. The primary process involves the promotion of the Ti electron to the conduction band of the semiconductor to form an electron-positive hole pair. The relative proportions of the reactive species depend on the presence of water. No TiO2 sensitization will be observed unless both oxygen and water are present [29]. 3.1.1.1.4. Incorporation of carbonyl groups. Carbonyl groups formed by mild oxidation of polymer during synthesis or processing act as chromophores and become source of the initiation radicals. Carbonyl chromophore absorbs near-UV radiations and subsequently forms radicals following Norrish Type I, Norrish Type II and H-atom abstraction processes (Scheme 5) [49]. 3.1.1.1.5. Introduction of peroxides or site of unsaturation. The peroxides or C]C sites become source of initiation radicals as shown in Scheme 6 [45]. The near UV component of sunlight (280e390 nm) is energetic enough to cleave CeC bond and Ceheteroatom bonds provided that light of the appropriate wavelength is absorbed. Chain oxidation occurs in most of the polymers because of the labile OeO bond present in the macrohydroperoxide eCeOOH, the macroalkoxyl and hydroxyl radicals thus formed may abstract hydrogen from the surrounding polymer matrix to generate alcohol, water and new macroalkyl radicals which can then take part in many cycles of the chain-initiation reactions. In the case of unsaturated polymers, light generated singlet oxygen 1O2 reacts with an unsaturated site by way of an ene reaction and starts chain oxidation (Scheme 6) [29]. 3.1.1.1.6. Reactions of singlet and triplet stage. Reaction of a ketone in a triplet-excited state with ground state oxygen is another potential initiation reaction (Scheme 7). In these reactions, UV light is absorbed by carbonyl or other chromophoric groups and the energy of the excited groups is transferred to oxygen molecules. The resulting excited oxygen species react

uv
H C uv
.H
C
Scheme 2.
TiCl4
hv
hv
TiCl3 O2 , RH
Scheme 4.
Cl
TiO2
TiO2
TiO2
HOO
564
O O
H2 C CH 2 C H2
Type I
CH 2 C H2 CH 2
H2 C C H2
C
CH 2
O Type II
CH 2 H2 C C H2 C CH 2
CH 2
CH 3
OH
RH
Scheme 5.
with vinyl or other unsaturated groups forming hydroperoxide which then initiate free radical reaction mechanism [43]. 3.1.1.2. Propagation reaction. The propagating reactions of auto-oxidation cycle are common to all carbon backbone polymers. These reactions lead to generation of hydroperoxide species (Scheme 8) and are not directly led to backbone cleavage but are the key intermediates to further reactions as shown in Scheme 1. Hydroperoxide species generated in propagating step lead to backbone degradation through cleavage of hydroperoxide OeO bond followed by b-scission (Scheme 9). Polymer backbone cleavage occurs through Norrish Type I and II reactions of chromophores (carbonyl) following bscission route, which is a prevailing route for photo-oxidative degradation. In semi-crystalline polymers, this scission occurs in the amorphous domains. The scission process generates two chain ends that are free to restructure, and can often lead to increase in crystallinity as oxidative degradation proceeds [29,41]. PS undergoes photo-oxidative bulk degradation via a free radical mechanism (Schemes 10 and 11). Oxidative process involves two steps: (1) formation of hydroperoxide and (2) decomposition of these hydroperoxides. Such oxidative reactions are initiated when hydrogen is removed through a photoreaction. The free radical formed on polystyrene reacts with oxygen to form peroxy radical, which can abstract a proton from some other labile positions, thereby forming hydroperoxides and a new radical site. The newly formed hydroperoxide group is subjected to decomposition and resulting ultimately in chain cleavage into ketones and olens [46]. 3.1.1.3. Termination reactions. The termination of photodegradation is achieved by mopping up the free radicals to create inert products. This occurs naturally by combining free radicals or assisted by using stabilizers in the plastic.
O C OH O C
Macroalkyl radicals may combine to give a crosslinked, branched or disproportionated product. Peroxyl radicals eventually terminate by reaction with other radicals to give dialkyl peroxides, carbonyl species or alcohols [29,30]. 3.1.2. Methods for photodegradation 3.1.2.1. Natural weathering method. Outdoor exposure can be performed on samples mounted on testing racks, oriented under standard conditions to expose the material to the full radiation spectrum besides the temperature and humidity of that location [23]. In order to observe the aging of the material, it is characterized with respect to mechanical properties (elongation at break, tensile properties or impact strength) and visible characteristics, such as crack formation, chalking, and changes in color [5]. The alterations in the polymeric materials on exposure can be characterized with FTIR spectroscopy and ultra violet/visible (UV/vis) spectroscopy [50,51]. 3.1.2.2. Articial weathering method/laboratory test. Pure laboratory testing involves using environmental chambers and articial light sources to approximately replicate outdoor conditions but with a greatly reduced test time under highly controlled conditions. Laboratory testing can quickly assess the relative stability of plastics but has the major disadvantage that the quicker the test lower is the correlation to real behavior in the eld [52]. Lundin et al. [53] have studied accelerated weathering of ber-lled PE composites. 3.2. Thermal degradation Under normal conditions, photochemical and thermal degradations are similar and are classied as oxidative degradation. The main difference between the two is the sequence
OH O OH Radical formation via above eq.
C H
CH
CH2 CH2
O2
HC
Scheme 6.
CH CH CH 2

3 1
565
C O
O2
C O
O2
hydroxyacids, aldehyde acids, etc. are also identied in small quantities [65]. 3.2.1. Mechanism of thermal degradation The mechanism of thermal degradation of polymers is an interesting subject, not only from fundamentals of polymer reactions point of view but also in understanding heat-resisting characteristics, polymer processes such as extrusion or injection molding, and the effective utilization of plastic wastes. The thermal degradation of polymers consists of two distinct reactions, which occur simultaneously in the reactor. One is a random scission of links, causing a molecular weight reduction of the raw polymer, and the other is a chain-end scission of CeC bonds, generating volatile products. The chain-end scission takes place at the gaseliquid interface in the working reactor [66]. The type and composition of the pyrolysis products give useful information about mechanism of thermal degradation [67,68]. Thermal dehydrochlorination of poly(vinyl chloride) (PVC) begins with internal allylic chloride and tertiary chloride structural defects formed during polymerization. During thermal degradation, ordinary monomer units are converted into internal allylic chloride defects by a mechanism that may include the abstraction of hydrogen by triplet cation diradicals derived from polyene intermediates. Cyclization reactions seem likely to contribute to the termination of polyene growth [69]. Thermal degradation of the polymers follows either chain end degradation (also known as unzipping route) (Eqs. (1 and 2)) or random degradation route (Eq. (3)) as shown below:
Mn /Mn1 M Mn1 /Mn2 M
hv O2
RCH2CH CHCH2OOH
CH2
RCH
CHCH2OOH
RCH
Radical Reactions
Scheme 7.
of initiation steps leading to auto-oxidation cycle. Other difference includes that thermal reactions occur throughout the bulk of the polymer sample, whereas photochemical reactions occur only on the surface [41]. Thermal degradation of polymers occurs through random and chain degradation (depolymerization reaction) initiated by thermal and UV light [54]. The depolymerization reaction in thermal degradation need not be initiated at terminal end of the macromolecule, instead, imperfections in the chain structure (initiator fragment or a peroxide or ether link) form a weak link from where depolymerization starts. A large number of addition polymers depolymerize at elevated temperature [55], for example, polymethylmethacrylate (PMMA) has been converted almost quantitatively back to the monomer and PE has been decomposed into longer olenic fragments and actually producing little monomer. Thermal degradation above 200 C leads to chain scission and largely depends on impurities like unsaturation sites, head-to-head units, etc. [56]. Polyolens are known to be sensitive to thermal oxidation, due to the impurities generated during their manufacture at high temperatures [57]. Drago et al. [58] have studied thermally stimulated oxidative degradation of high impact PS with nitric acid. Mechanism of oxidation and nitration depends upon temperature and leads to the molecular and chemical heterogeneity and also lowering in mechanical properties of the polymer. PS thermally gets degraded into organic compounds such as phenol, quinine, naphthalene and diphenylamine at the experimental temperature of 350e450 C [59e62]. Complex reactions occurring in thermal degradation of polymers depend on various factors like heating rate, pressure, reaction medium, and reactor geometry. Polymers have high viscosity, which complicates the process by impeding heat and mass transfer [63,64]. Thermo-oxidative degradation of polyesters yields a variety of products such as formaldehyde, acetaldehyde, formic acid, acetic acid, CO2 and H2O. In addition to these compounds, various other compounds like hydroxyaldehydes,
1 2 3
Mn /Mx My
The chain end degradation starts from the end of the chain and successively releases the monomer units. This type of degradation route is also known as depolymerization reaction, which involves successive release of monomer units from the chain ends. Such reactions are the opposite of the propagation step in addition polymerization and occur through free radical mechanism. In this type of degradation, molecular weight of the polymer decreases slowly and large quantity of the monomer is liberated simultaneously. For example, poly amethylestyrene synthesized through anionic mechanism upon heating from 70 C to 60 C undergoes degradation from the chain end carrying the active carbanion in such a manner
CH3 C CH2
CH3 C C(O)OCH3
Scheme 8.
CH3 C CH2
CH3 C C(O)OCH3
566
O O C OH H hv OH
Scheme 9.
O C
H C
that at 60 C, the entire polymer gets converted into the monomer [20]. The major degradation products for uorinated polyacrylate are monomer, dimer, saturated diester, trimer, and corresponding methacrylate along with remarkable amounts of alcohol [67,68]. In general, chain-end degradation occurs when the backbone bonds are weaker than the bonds of the side groups and only with polymer molecules, carrying active chain ends with a free radical, cation, anion, etc. In general, asubstituted vinyl polymers degrade mostly through the process of depolymerization. PMMA, poly a-methyl styrene, PP, polytetrauoroethylene and poly a-methyl acrylonitrile, on pyrolysis, have been converted to their respective monomers almost quantitatively. The unzipping process involves a free radical path [70e72]. Random degradation occurs at any random point along the polymer chain. This is reverse to polycondensation process where the polymer degrades to lower molecular weight fragments but practically no monomer is liberated. For random degradation to occur, the polymer chain does not require necessarily to carry any active site [20]. Polyesters undergo hydrolytic degradation resulting in chain scission. PE also undergoes random degradation through migration of a hydrogen atom from one carbon to another thus generating two fragments [72]. In general, vinyl polymers such as polystyrene, poly(acrylonitrile), etc. are degraded by the random chain scission process. The monomer yield from such polymers is usually low, and the pyrolyzed fragments are ordinarily larger than corresponding monomer unit [71]. For example, poly(ethylene terephthalate) follows random thermal degradation route (Scheme 12); the initial step resulting in scissions leads to carboxyl and vinyl groups [46]. In general, initiation reaction occurs by random chain scission or chain end initiation. This step is followed by de-propagation step forming monomer.
Termination takes place through radical coupling and radical disproportionation (Scheme 13) [73]. Rodryguez-Vazquez et al. [74] while investigating thermal degradation of LDPE at 400 C observed that intra-molecular hydrogen abstraction followed by b-scission is a major degradation route [15]. Radical termination occurred by combination and disproportionation. PS on thermal degradation yields 42% monomer as volatile product in dispropagation reaction (Scheme 14) [18]. Thermal degradation of saturated polymers such as PS follows a hydroperoxide mechanism [20]. Thermal oxidation of PP at 120e280 C results in multiple oxidative chain scission and around 40 volatile compounds are identied by GC/MS technique. Backbone scission route shown by polyolens is b-scission of the macroalkoxyl radicals [29]. 3.2.2. Methods for thermal degradation 3.2.2.1. Batch reactor method. The thermal degradation of waste plastic can be carried out in a glass reactor under atmospheric pressure with denite weight of sample that is loaded into bottom of the reactor for thermal degradation. The purging of the reactor with nitrogen gas at a ow rate of 10 mL/min at 120 C for 60 min is required to remove the physically adsorbed water from the plastic sample. After stopping the nitrogen ow, the reactor temperature is increased to the degradation temperature (430 C) at a heating rate of 3 C min1 and the waste plastic bed temperature is taken as the temperature of the degradation. The gaseous products can be condensed (using a cold-water condenser) to liquid products and trapped in a measuring jar. The quantitative analysis of the liquid products can be performed by using a gas chromatograph equipped with a ame ionization detector, atomic emission detector, an ion chromatograph and mass selective detector. The solid residue can be identied by FTIR spectrometer [75]. 3.2.2.2. Thermogravimetric analysis. Thermogravimetric analysis (TGA) can be used for the investigation of oxidative and thermal degradation of the polymers [76]. The rate of degradation in TGA (da/dt) is dened as the rate of change of the degree of conversion. The degree of degradation or conversion can be calculated in terms of mass as shown below: a W0 W=W0 WN where W0, W and WN are the initial weight, the actual weight at each point of the curve, and the nal weight measured at the end of the degradation process, respectively [77]. In TGA
H C CH2
H C CH2 hv
+H C CH2
H C CH2
O H C CH2 C CH2 O C O2 CH2 H C CH2
Scheme 10.
567
O O C
H H CH2 C CH2
+ OH
O C CH2 H C CH2 O C + H2C C CH2
Scheme 11.
instrument, sample is submitted to constant heating rate from room temperature to 600 C under the nitrogen ow. The reaction products can be analyzed by gas chromatography [78e84]. 3.2.2.3. Pyrolysis GC/MS method. In this method, volatile pyrolysis products at different temperatures can be identied with the help of GC/MS [73]. The pyrolyser is based on a technique in which a small deactivated stainless steel cup loaded with a sample is dropped into a small sized vertical furnace
O C O CH2 CH2
by gravitational free-fall with push button mechanism. This system is designed to provide precise temperature control. Once the system starts, the sample controller stops sampling after 0.5 min and the pyrolysis gases from the samples directly pass into GC/MS analysis system [85]. 3.3. Ozone-induced degradation Atmospheric ozone usually causes the degradation of polymers under conditions that may be considered as normal;
O O C O C O
O C OH + CH2 CH O
O C
O C O C OH O
+ CH
CH
O C O HC CH2 CH CH2
+ CO2
O O C OH CH CH2
O CH
O C O
CH3 CH O
O C O C CH3 + CO
O C O
O C
+ CH3 C
Scheme 12.
568
Initiation R (R)n R R (R)n R
Propagation R (R)n R R (R)n-1 R
+ R
Termination R R R RO RO ROO
+ RO + ROO + RO + ROO + ROO
ROR ROOR ROOR ROR
+ O2 + O2
ROOR
Scheme 13.
when other oxidative aging processes are very slow and the polymer retains its properties for a rather longer time [86e88]. The presence of ozone in the air, even in very small concentrations, markedly accelerates the aging of polymeric materials [89]. This process in saturated polymers is accompanied by the intensive formation of oxygen-containing compounds, by a change in the molecular weight and by impairment of the mechanical and electrical properties of the specimens [5]. Exposure of polymers to ozone results in the rapid and consistent formation of a variety of carbonyl and unsaturated carbonyl products based on aliphatic esters, ketones, and lactones as well as aromatic carbonyl associated with the styrene phase. This follows by a more gradual formation of ether, hydroxyl and terminal vinyl groups with time and concentration [90]. These reactions of ozone with polymers occur with main chains containing C]C bonds, aromatic rings or saturated hydrocarbon links. The reaction proceeds through unstable intermediates such as the bipolar ion or peroxy radicals, which can isomerize or degrade, cause decomposition of macromolecules [91]. Under the inuence of external load, the rate of ozone oxidation and hydrogen atom
abstraction from the polymer chain increases. This is due to the change in hybridization of the reaction centre from the state sp3 to the state sp2 [92e95]. In poly(vinyl alcohol) (PVAL) the chain scission is based on the ozone oxidation of the alcoholic groups of PVAL with formation of ketone groups which in turn are the source of a ketoeenol tautomerism which leads to random chain scission by further ozone attack. PVAL forms a strong hydrogen-bond complex with ozone for which the interaction energy is of the order of 47.3 kJ/mol and it is slowly degraded by ozone. The analysis with FTIR spectra indicates that the nal product is a PVAL oligomer with numerous ketone groups along the main oligomer backbone and with carboxylic end groups [96]. PS is slowly attacked by ozone as compared to unsaturated polymers. The relative yield of products identied from this attack is 35% peroxide, 18% ketone and 47% acid. These products are similar to those expected from free radical chain oxidation processes. Ozen et al. [97] have studied the effect on structural and mechanical properties of packaging lms by ozone exposure and have reported that ozone treatment has affected the PE and polyamide lms differently. It is responsible for formation of oxygen-containing functional groups, degradation of polymeric chains in PE lms and increase in the eCeNe stretching in polyamide. Clough and Gillen [98] have observed that the ozone generated by the action of the ionizing radiation in the air present in the atmosphere surrounding the samples affect the surface of the polymer [98]. This observation has been made during gamma-radiation degradation studies of poly(butadiene-co-styrene) [SBR rubber] and poly(butadiene-co-acrylonitrile) [Buna-n rubber] in the presence of air. The oxides of nitrogen, sulfur, and ozone promote UV-induced oxidative damage of common plastics, particularly in rubber products [11]. Ozone mainly affects vulcanized rubbers with unsaturation in the main polymer chain and causes cracking in stretched form in rubber [17]. Exposure to ozone gas causes change in the mechanical properties of linear LDPE, oriented PP and biaxially oriented nylon [99]. Gatenholm et al. [100] have studied the effect of ozone on the microporous structure of PP. Exposure of isotactic PP to ozone results in surface oxidation which further increases when a microporous membrane has large surface area [100].
OOH CH2 CH CH2 CH CH2 CH CH2 CH O2200 C CH2 CH CH2 CH CH2 C CH2 CH
O CH2 CH CH2 CH CH2 C HO CH2 CH
O CH2 CH CH2 CH CH2 C CH2 CH CH2 C CH2 CHO
Scheme 14.
569
3.3.1. Mechanism of ozone-induced degradation Ozone normally attacks the unsaturation in unsaturated polymers and this reaction generally occurs in three principal steps (Schemes 15 and 16). The rst step is a cycloaddition of ozone to the olen double bond to form ozoneeolen adduct referred to as the primary ozonide which is an unstable species because it contains two very weak OeO bonds. The second step in the ozonolysis mechanism is the decomposition of the primary ozonide to carbonyl compounds and a carbonyl oxide. The carbonyl oxide is considered to be the key intermediate in the C]C bond ozonolysis mechanism. The third step in the ozonolysis mechanism is the fate of the carbonyl oxide, which depends on its source, as well as on its environment. The carbonyl oxide ips over with the nucleophilic oxyanion attacking the carbon atom of the carbonyl group [101e104]. The ozonization of conjugated polymers (polyacetylene, polyphenylacetylene) has showed that the conjugated double bonds of the polyenes react more slowly with ozone than the isolated double bonds of the diene rubbers [86e88]. 3.3.2. Method for ozone degradation 3.3.2.1. Ozone exposure test. Sample of the polymer can be exposed in a HAMPDEN (model 2000-AM ozone cabinet) at 40 C in atmospheres of 50, 100 and 200 ppht (parts per hundred thousand) of ozone in air. Before exposure to ozone atmosphere the specimens are subjected to a deformation of 20% under stress and maintained this way for 72 h in the absence of light. Those samples that in general terms exhibit any crack formation, minimal or even supercial, during the ozone attack assay are termed non-ozone resistant samples and those which do not exhibit any crack formation are termed ozone resistant samples. The samples can be analyzed with FTIR to study the formation of new functional moieties in the sample [90]. 3.4. Mechanochemical degradation Mechanochemical degradation of polymers involves the degradation of polymer under mechanical stress and by strong ultrasonic irradiations [105]. Breakdown of molecular chains under shear or mechanical force is often aided by a chemical reaction and is known as mechanochemical degradation. For example, mastication of rubber can lead to chain breakage and development of plasticity under shear. In the atmosphere of nitrogen at ordinary temperature mastication of rubber does not change the plasticity and molecular weight appreciably, but in the presence of oxygen, degradation occurs rapidly.
This is due to the reason that the rubber molecule breaks into radicals, and oxygen as radical scavenger readily reacts with them, leading to permanent chain breakage, whereas nitrogen is not a radical scavenger and thereby led to radical recombination [18]. The degradation of high molecular weight PS occurs under the turbulent ow and the drag reduction efciency decreases with time due to the mechanical degradation of the polymer molecules [106,107]. In one study mechanical degradation of polymers during their mechanical mixing of binary mixtures of cis-polyisoprene with stereo-regular poly(butadiene), and with butadieneemethylstyrene or butyl rubbers leads to considerable changes in the molecular characteristics of the components [108]. The mechano-degradation of polymers in melts occurs in terms of free radical processes. In this processing, there is a decrease in the width of the molecular weight distribution function, a quantitative correlation between ruptures and crosslinks on the one hand and change in double bond concentration on the other and an increase in long-chain branching due to the reaction of chain-side radicals [109e111]. The mechanochemical degradation of PMMA in the presence of nitroxides acting as chain terminating agents creates macro-radicals, which are used in free radical polymerization reactions [112]. Mechanochemical dechlorination of PVC with various oxide powders, i.e. CaO, Fe2O3, SiO2 and Al2O3, in air reduces the molecular weight of PVC [113]. 3.4.1. Mechanism of mechanochemical degradation When excessive stress is applied, the molecular chain breaks and produces a pair of free radicals, which can take part in subsequent reactions. In the presence of oxygen, the rst reaction results in the formation of peroxy radicals. The most important application of this type of reaction is the mastication of natural rubber to make it processable. Mechanically generated radicals are believed to result from the cleavage of the main backbone segments of polymer chains in the stressed amorphous regions connecting crystallites [114]. High intensity ultrasounds can induce mechanochemical degradation in polymeric materials. Polymer in such a case is subjected to very high vibrations, which are only mechanical forces. As ultrasonic waves pass through the solution, the localized shear gradient produces tear off molecules leading to chain scission and decrease in molecular weight [20]. The relevant mechanism for the observed phenomena has been explained by the interaction of ultrasound and component molecules. In a liquid, upon irradiation of ultrasound, molecules have been exposed to alternate compression and expansion modes, by which bubbles are formed and eventually collapsed. On the molecular level, this implies a rapid motion of solvent molecules to
O O C C O3 C + C
OO+ O C C OC O O OC O O
+C
Scheme 15.
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CH3 CH2 C CH CH2 O3 O CH O O CH2 CH2 CH2
CH3 C CH CH2
CH3 CH2 C
CH3 C CH CH2
H2O Hydrolysis CH 3
CH2
C O
CH3 O
CH
CH2
CH2
CH
CH2
H2O2
Scheme 16.
which the macromolecules embedded in the solvent cannot be adjusted. Thus, friction is generated which causes strain and eventually bond rupture in the macromolecules [115]. In the absence of oxygen, various carbon radicals have been generated from polyolens, PMMA, etc. At low temperature, the radicals from main-chain scission have been detected; upon warming, these attack the polymer matrix and lead to further scission reactions through radical-rearrangement reactions (Scheme 17) [29]. In the presence of oxygen above 113 C, quantitative conversion of macroalkyl to peroxy radicals occurs. Thus mechanical work generates the primary radicals and the oxidation can form the usual oxidation products. In the melt, it is difcult to separate the degradative effect of heat and mechanical work [29]. Gel permeation chromatographic (GPC) studies of the degradation of LDPE and HDPE under high shear conditions have indicated that most of the changes in molecular weight distribution and long-chain branching have occurred from thermal or thermo-oxidative degradation. On the other hand, the orientation of solid PP under high shear
conditions (high draw rates and relatively low temperatures) has produced oxidation products directly as a result of the shear process [116]. Ultrasound is responsible for the breakage of macromolecular CeC bonds and termination reactions of mechano-radicals occur as disproportionation and combination reactions which suppress in the presence of radical scavengers [112].
3.4.2. Method for mechanochemical degradation In mechanochemical degradation polymer is subjected to mechanical stresses through high speed stirring or milling. Agitation, grinding or extrusions are the methods of mechanochemical degradation. The basic phenomenon involved is subjecting the polymer to very powerful shearing force that will break the molecule. Mechanical degradation reduces the average molecular weight of the polymer [117]. Electronspin spectroscopy has graphically demonstrated that stretching, grinding, milling and shearing process has produced free radicals because of main chain fracture [29].
CH 3 CH2 C C O OCH 3 O CH 2
CH 3 mill C 77C C OCH 3 O CH2
CH 3 C C OCH 3 O + CH2
CH 3 C C OCH3 PMMA attack
CH3 CH2 C C O OCH 3 C H O C
CH 3 + C OCH 3 O CH2
CH 3 -scission C C OCH 3
Scheme 17.
CH 3 CH2 C C O OCH 3 C H O
CH 3 C C OCH 3
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3.5. Catalytic degradation Catalytic transformation of waste polymers into hydrocarbons with higher commercial value is a eld of great interest. Polyolens are thermally or catalytically degraded into gases and oils. The interest has been directed towards polyolens (PE, PP, PS) which constitute an important part of industrial and domestic waste. The addition of a catalyst not only improves the quality of products obtained from pyrolysis of plastic wastes, lower the temperature of decomposition, but also enable a given selectivity to a certain product to be achieved. Solid acid catalysts, such as zeolites, favor hydrogen transfer reactions due to the presence of many acid sites. The access of molecules to catalyst reactive sites is limited to the pore size as well as the growth of end products inside the pores. Therefore, zeolite catalysts may produce molecular sieving and shape selectivity [118]. Garforth et al. [119] have investigated catalytic degradation of polyolens using TGA as a potential method for screening catalysts and have found that the presence of catalyst led to the decrease in the apparent activation energy. For polymer degradation, different types of catalysts have been reported in the literature which include PteCo and PteMo supported over SiO2 [120], zeolite catalysts and non-zeolite catalysts [121], transition metal catalysts (Cr, Ni, Mo, Co, Fe) on the support (Al2O3, SiO2) [122], zeolite [123] and zirconium hydride [124]. 3.5.1. Mechanism of catalytic degradation Sekine and Fujimoto [125] have proposed a free radical mechanism for the catalytic degradation of PP using Fe/ activated carbon catalyst. The various steps in catalytic degradation are shown in Scheme 18. In initiation step, random breakage of the CeC bond of the main chain occurs with
heat to produce hydrocarbon radicals. In propagation, the hydrocarbon radical decomposes to produce lower hydrocarbons such as propylene, followed by b-scission and abstraction of H radicals from other hydrocarbons to produce a new hydrocarbon radical. Disproportionation or recombination of two radicals is termination reaction. During catalytic degradation with Fe/activated charcoal (AC) in a H2 atmosphere, hydrogenation of hydrocarbon radical (olen) and the abstraction of the H radical from hydrocarbon or hydrocarbon radical generate radicals, enhancing degradation rate. In a reaction temperature lower than 400 C or a reaction time shorter than 1.0 h, many macromolecular hydrocarbon radicals exist in the reactor, and recombination occurs readily because these radicals cannot move fast. However, with Fe/AC in a H2 atmosphere, these radicals are hydrogenated and therefore recombination may be suppressed. Consequently, it seems as if the decomposition of the solid product is promoted, including low polymers whose molecular diameter is larger than the pore size of the catalysts. Wall et al. [126] have studied the catalytic degradation of waste plastics and have found that when these polymers have been heated above 380 C, they undergo depolymerization and degradation by a free radical chain reaction. 3.5.2. Methods for catalytic degradation 3.5.2.1. Batch autoclave method. The thermal and catalytic degradation of plastic sample can be performed in a batch autoclave. Denite weight of polymer sample and denite weight of catalyst are charged into the reactor. After purging the inner air of the reactor with a reaction gas (H2 or Ar), more reaction gas is added to 4.0 MPa and heated to the reaction temperature while being agitated at 70 times/min. At the end of the reaction, the heaters are removed and the reactor is cooled to ambient temperature in air. The gaseous products can be analyzed through gas chromatography and liquid products can be separated from solid products by suction ltration with an aspirator. The boiling-point distribution of the liquid products is obtained by simulated distillation. The residue from the suction ltration is then washed with toluene, dried in air, and weighed as a solid product. This solid product includes both unreacted product (low polymer) and excessive cracked product (coke precursor or coke). However, the latter is produced on the surface of the catalyst and could not be separated from the former when the reaction temperature is low or the reaction time is short [127]. PP has been pyrolyzed over various catalysts using a laboratory uidized-bed reactor operating isothermally at ambient pressure using zeolite catalysts [121]. Solid phase microextraction has also been used to analyze the products evolved in the thermal degradation of PP [59]. 3.6. Biodegradation
Initiation R1 Propagation R1 R2 Termination R5 R7 Catalysts Fe/ Activated charcoal +H2 R9 R10 R11
Scheme 18.
R2
R1
R2
R3 R4 R2
C2 R4
R6 R8
R5 R7
R6 R8
H H
R9 R10 R11 H H
Biodegradation is a biochemical transformation of compounds in mineralization by microorganisms. Mineralization of organic compounds yields carbon dioxide and water under aerobic conditions, and methane and carbon dioxide under
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anaerobic conditions. Abiotic hydrolysis, photo-oxidation and physical disintegration of polymers may enhance biodegradation of polymers by increasing their surface area for microbial colonization or by reducing molecular weight [128]. Biodegradation has been dened in various ways by different investigators. It is dened as change in surface properties or loss of mechanical strength [129], assimilation by microorganisms [130], degradation by enzymes [131], backbone chain breakage and subsequent reduction in the average molecular weight of the polymers [132,133]. Degradation can occur by any of the above mechanisms alone or in combination with one another. According to ASTM standard D-5488-94d biodegradation is dened as process which is capable of decomposition of materials into carbon dioxide, methane, water, inorganic compounds, or biomass in which the predominant mechanism is the enzymatic action of microorganisms, that can be measured by standard tests, in a specied period of time, reecting available disposal conditions. Biodegradability is also dened as the propensity of a material to get breakdown into its constituent molecules by natural processes (often microbial digestion). The metabolites released by degradation are also expected to be non-toxic to the environment and redistributed through the carbon, nitrogen and sulfur cycles. Biological degradation is chemical in nature but the source of the attacking chemicals is from microorganisms. These chemicals are of catalytic nature e.g. enzymes. The susceptibility of the polymers to microbial attack generally depends on enzyme availability, availability of a site in the polymers for enzyme attack, enzyme specicity for that polymer and the presence of coenzyme if required [134]. Biodegradation can occur at different structural levels, i.e. molecular, macromolecular, microscopic and macroscopic depending upon the mechanism [135]. It has been argued that the phenomenon of degradation in vivo might not be equated with the term biodegradation, since biodegradation implies the active participation of biological entities such as enzymes or organisms in the degradation process [136]. It is, however, difcult to identify the involvement and the role of biological species in in vivo degradation. Both hydrolytic and enzymatic processes may contribute to the degradation to different extent during the different stages of the degradation process. Degradation may begin by hydrolysis, but as the polymer breaks and surface area and accessibility increases, enzymatic degradation may dominate. Thereby biodegradation includes all types of degradation occurring in vivo whether the degradation is due to hydrolysis or metabolic processes. Therefore, biodegradation is also dened as the conversion of materials into less complex intermediates or end products by solubilization, simple hydrolysis or the action of biologically formed entities such as enzymes and other products of the organism. Polymer molecules may, but not necessarily breakdown to produce fragments in this process, but the integrity of the material decreases in this type of process [137]. 3.6.1. Mechanism of biodegradation Biodegradation of polymers occurs through four different mechanisms: solubilization, charge formation followed by
dissolution, hydrolysis and enzyme-catalyzed degradation [138,139]. 3.6.1.1. Solubilization. The hydration of polymers depends on the hydrophilicity of the polymer. The hydration results from disruption of secondary and tertiary structure stabilized by van der Waals forces and hydrogen bonds. During and after hydration, the polymer chains may become water soluble and/or the polymer backbone may be cleaved by chemical or enzyme-catalyzed hydrolysis to result in the loss of polymer strength [140]. For crosslinked polymers, the polymer strength may be reduced by cleavage of either of the polymer backbone, crosslinker or pendent chains. In non-swellable polymer systems, the reduction in the polymer molecular weight may lead to the loss of coherence between polymer chains [141]. Barkay et al. [142] have studied biodegradation of polyaromatic hydrocarbons using a bio-surfactant which have enhanced the solubility and biodegradation of hydrophobic hydrocarbons. 3.6.1.2. Ionization. Some polymers are initially water insoluble but become solubilized by ionization or protonation of a pendent group. Polyacids become soluble at high pH and become hydrophilic [143]. Cellulose acetate phthalate becomes water soluble at a pH > 6, while poly(vinyl acetate phthalate) and hydroxyl propyl methyl cellulose phthalate are ionized at a lower pH [144]. 3.6.1.3. Hydrolysis. Water insoluble polymers containing pendent anhydride or ester groups may be solubilized if anhydride or esters hydrolyze to form ionized acids on the polymer chain. For example, poly(methacrylate) and poly(methyl methacrylate) which are esters derived from poly(acrylic acid) and poly(methacrylic acid), respectively, are not water soluble but become water soluble upon hydrolysis of the pendent esters, and subsequent ionization of the carboxylic group [145]. Chain length of ester group and degree of substitution exert the effect on anaerobic biodegradation [146]. Hydrolysis of the polymer backbone is most desirable since it produces low molecular weight by-products. Natural polymers undergo degradation by hydrolysis whereas synthetic polymers are water insoluble. They tend to be more crystalline and this property account for their water-insolubility [147]. For hydrolysis to occur, the polymer has to contain hydrolytically unstable bonds, which should be reasonably hydrophilic for the access of water. Biodegradable polymers include esters and ester derivative polymers [148e151]. Polyesters are degraded mainly by simple hydrolysis. The rst stage of the degradation process involves non-enzymatic, random hydrolytic ester cleavage and its duration is determined by the initial molecular weight of the polymer as well as its chemical structure [152,153]. 3.6.1.4. Enzyme-catalyzed hydrolysis. Enzymes function as catalysts for a specic reaction or a series of reactions, such as oxidation, reduction, hydrolysis, esterication, synthesis and molecular inter-conversions [154]. Hydrophobic polymers
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with no hydrolyzable bonds such as PE, PP, PMMA and PS are expected to be the most stable [21]. Wool et al. [155] have studied degradation of PEestarch composites enzyme diffusion, which results in the back-diffusion of small molecules to the surface for further assimilation by microorganisms [155]. The enzymatic degradation of certain natural polymers follows the unzipping or chain-end degradation mechanism. For example, b-amylase degrades starch to maltose, beginning with the chain ends [20]. Chattopadhyay and Madras [156] have studied the lipase catalyzed degradation of poly(vinylacetate) (PVAc) and observed that the ester bonds in the side chains are broken specically to yield oligomers with acid and alcohol groups. There are many side branches in PVAc because chain transfer to the methyl groups in the acetate groups of PVAc takes place frequently during the polymerization of vinyl acetate. Enzymatic degradation of poly(3-caprolactone) has been successfully carried out in supercritical carbon dioxide (scCO2). Candida antarctica lipase has smoothly catalyzed the hydrolytic degradation in scCO2 to give oligo(3-caprolactone) [157]. 3.6.1.5. Microbial degradations. Microbial degradation results from the action of naturally occurring microorganisms such as bacteria, fungi, algae, etc. The product so formed is not visible and need not be screened after composting [158]. The production of biodegradable plastics that get decomposed completely in nature have received remarkable attention globally as they are totally ecofriendly and helpful in waste landll management. Addition of natural polymers to thermoplastics having long-term potential is one of the approaches to enhance biodegradability [159]. To prepare biodegradable plastic involves adding special additives to the synthetic polyolens, which make it susceptible to microbial degradation, and these additives also disconnect the continuity of CeC chain of polyolen. Few additives having hydrophilic groups make plastic hydrophilic and susceptible for photo- and chemical degradation. Modication of backbone through copolymerization and through anchoring monosaccharide with polyolen or blending with nutrients and biodegradable llers makes the plastic degradable [160e163]. These micronutrients help the growth of specic microorganisms thus inducing biodegradability and through incorporation of polar functional groups which can serve as point of microbial attack [164,165]. Generally, polyolen constitutes a non-biodegradable class of plastic and in order to make it degradable, research has been carried out on biological degradation of PE. Biodegradation of PE occurs through two mechanisms: hydro-biodegradation and oxo-biodegradation [166]. These two mechanisms work successfully on the modied PE (by additive starch) making the material hydrophilic. The starch present in the composite has been catalyzed by amylase enzyme. Chiellini et al. [167] have reported the oxidative degradation of PE lm containing pro-oxidant additives. Some strains of the bacteria such as Pseudomonas aeruginosa, Pseudomonas uorescens and fungi Penicillium simplicissimum have been reported as the most commonly used organisms for the plastic degradation [168,169]. Sielicki et al. [170] have studied the microbial
degradation of [b-14C] PS and 1,3-diphenylbutane in soil and liquid enrichment cultures, and it has been determined by 14CO2 evolution from applied [14C] PS. Metabolism of 1,3-diphenylbutane appeared to involve the attack by a monooxygenease to form 2-phenyl-4-hydroxyphenylbutane followed by a further oxidation and subsequent ssion of the benzene ring to yield 4-phenylvaleric acid and an unidentied 5-carbon fragment via the classic meta-ssion pathway. The basal salt medium (water containing trace elements) triggered auto-oxidation of the pro-oxidant through decomposition of trace hydroperoxides, which in synergistic combination with biodegradation of the starch, eventually initiated autooxidation of the LDPE matrix [171]. Hadad et al. [172] have isolated thermophilic bacterium strain of Brevibacillus borstelensis for the degradation of LDPE and have studied the effect of UV photo-oxidation on the extent of biodegradation of PE which has enhanced the extent of biodegradation. Gilmore et al. [173] have carried out degradation study of six types of plastics and plastic blends in municipal wastewater. Samples consist of 6% starch in PP, 12% starch in linear LDPE, 30% polycaprolactone in LDPE, and poly(-hydroxybutyrateco-hydroxyvalerate) (PHB/V), a microbially produced polyester in activated sludge of 5 months and found no sign of degradation of blended samples except PHB/V, which has showed a considerable loss of mass and a signicant loss of tensile strength in municipal wastewater. Biodegradable polymers can be synthesized by the modication of natural polymers by blending and fermentation [174e180]. NakajimaKambe et al. [181] have isolated, puried and characterized polyurethane (PU) degrading enzymes from Comamonas acidovorans [182,183]. These enzymes are cell-associated membrane bound PU-esterase and an extracellular PU-esterase. The membrane bound enzyme provides cell mediated access to the hydrophobic polyurethane and extracellular enzyme stick on surface. 3.6.2. Methods for biodegradation The most important factor in determination of biodegradation is the proper selection of test procedure based on the nature of plastic and the climatic conditions of the study environment [184]. There are wide varieties of methods currently available for measuring the biodegradability of polymeric materials [185]. Several test methods to assess the potential biodegradability of plastics have been developed by International Standard Organization (ISO) [186] and American Society for Testing and Materials (ASTM) [187]. Biodegradation can be characterized with loss of weight, change in tensile strength, change in dimensions, change in chemical and physical properties, carbon dioxide production, bacterial activity in soil and change in molecular weight distribution [188,189]. 3.6.2.1. Soil burial method. Soil burial method is one of the frequently used methods for the determination of biodegradability of plastic [185,190]. In this method, biodegradation test is performed under natural conditions or laboratory conditions. Sample with denite weight and dimension is buried in specic depth in the soil for different time intervals. After
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a specied time, sample is taken out of soil, thoroughly rinsed with distilled water following immersion in distilled water and after that dried at 50 C for 24 h in a vacuum oven. Sample is allowed to equilibrate to ambient temperature and humidity for at least 24 h before measurement. In one study starche plastic lms buried in a forest soil have developed rapid colonization (15 days later) by fungal hyphae and showed degradation of the starch granules on the lms [191]. 3.6.2.2. Pure culture method. In pure culture method, specic bacteria and fungi can be applied for degradation of polymers. In laboratory conditions, isolated microorganism strain has been allowed for sufcient growth in different nutrient media [160,172,188]. In pure culture method, pre-weighed disinfected lms are aseptically added to sterilized culture medium and lms in culture medium are incubated with shaking for 24 h before inoculation to ensure asepsis. Culture medium is inoculated with spores from a specic microorganism and is incubated with shaking at 125 rpm for 4 weeks at optimal growth temperature for the selected microorganism. Four replicates are prepared for each different pretreated lm. The sample is weighed after washing with 70% ethanol and drying at 45 C until equilibrated. Each of the different lms is then compared with the corresponding uncultured material [192,193]. The presence of microbes can be conrmed by using a microscope [194]. 3.6.2.3. Compost method. In this method, the denite weight of the dry plastic is subjected to the mixture of denite amount of mature compost and then incubated at 58 C with maintained moisture content at 65%. Biodegradation is measured based on the amount of material carbon converted to gaseous carbon dioxide [195]. Nature of compost affects the degree of degradation [196e198]. Unexpected trends have been reported for the biodegradation of plastics in the compost stored at 20 C, 4 C and 20 C for different periods. Viable cells in the compost stored at 20 C is expected to be fewer than those in the compost stored at 4 C and 20 C, because microbes may be under stress or even be killed due to the formation of ice crystals at the subzero temperature. Mesophilic bacteria and mesophilic actinomycetes [the mesophilic microorganism live at medium temperatures (20e45 C)] are fewer in number in the compost stored at 20 C than in the compost stored at the other two lower temperatures contrary to expectation. In contrast, both thermophilic bacteria and thermophilic actinomycetes [thermophilic microorganism thrive above 45 C and some live at or even above the boiling point of water] are fewest in the compost stored at 20 C as expected, indicating that thermophilic microbes are more susceptible to stress in the freezing conditions than the mesophilic ones. Activity of the extracellular enzymes plausibly excreted by the microbes in the compost decreased as a result of the storage [196]. Shape of the plastic sample [185] and additives in the compost [199] effect the plastic degradation in the compost. Vermiculite, a clay mineral, can be activated and used as a solid matrix in place of mature compost. The composting
test method based on activated vermiculite is a comprehensive system for the assessment of the environmental impact of biodegradable plastics. Activated vermiculite affects neither the biodegradation rate nor the nal biodegradation level. On the other hand, possible metabolic intermediates and polymeric residues left after biodegradation can be recovered more easily from activated vermiculite than from mature compost, a very complex organic matter. Therefore, at end of the test it has been possible to determine the carbon balance that is by taking into account both the evolved CO2 and a polymeric residue extracted from vermiculite [200]. 3.6.2.4. An aerobic degradation in the presence of sewage sludge. Because of enriched environment of sewage sludge, the microbes present are more diverse in composition than other disposed methods encountered [140]. In laboratory conditions, samples have been inoculated with sewage microbes. Gaseous CO2 and CH4 are monitored by headspace analysis using GC/MS [201]. 4. Factors affecting polymer degradation Degradation is dened as a process which leads to a deterioration of any physical property of a polymer [17]. In general, the degradation process affects the thermal stability, mechanical properties, crystallinity and lamellar thickness distribution and begins in the amorphous/crystalline interface [56]. Degradations of plastic affected by various factors are given below: 4.1. Chemical composition Chemical composition of the polymers plays a very important role in their degradation. Presence of only long carbon chains in the thermoplastic polyolens makes these polymers non-susceptible to degradation by microorganisms. By the incorporation of the heterogroups such as oxygen in polymer chain makes polymers labile for thermal degradation and biodegradation [20]. Presence of heteroatom in the polymer chain affects the strength of neighboring CeH bonds of the polymer and promotes carbanion formation in the presence of bases. Linear saturated polyolens are resistant to oxidative degradation. Presence of unsaturation in the polymer chain makes them susceptible to oxidation, for example natural rubber is more susceptible to degradation than PE [3]. Amorphous regions in the polymer have been reported to be more labile to thermal oxidation as compared to crystalline areas because of their high permeability to molecular oxygen [17]. Oxidation rates depend on the reactivity of the peroxy radicals formed and on the dissociation energies of available carbonehydrogen bonds in the polymer substrate. A polymer with no hydrogen at all or with unreactive methyl and phenyl groups shows resistance to oxidation [17]. 4.2. Molecular weight Increase in molecular weight of the plastic decreases the rate of plastic degradation [202]. It has been reported that
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some microorganisms utilize polyolens with low molecular weight faster as compared to high molecular weight polyolens [203,204]. Linear polyolens with molecular weight lower than 620 support microbial growth [205]. It is easy to form the ozone adduct in low molecular weight olens which rearranges to ozonide and during this operation, if the polymer chain is under tension during reaction, the broken chain ends separate out before rearrangement to ozonide occurs [17]. 4.3. Hydrophobic character Petrochemical-based plastic materials are not easily degraded in the environment because of their hydrophobic character and three-dimensional structure [203]. Hydrophobicity of PE interferes with the formation of a microbial bio-lm, thus decreases the extent of biodegradation [172]. 4.4. Size of the molecules Size of the molecules in the polymers affects their mechanical degradation, thermal degradation and biodegradation. These degradations increase as the size of the molecule decreases [20]. 4.5. Introduction of functionality Introduction of carbonyl groups in polyolens makes these polymers susceptible to photodegradation. As the number of chromophores increases the rate of photodegradation increases due to the more sites, which are available to absorb more photons and to initiate the reaction for degradation. The carbonyl chromophore absorbs near-UV radiation and form radicals by the Norrish Type I, II and H-abstraction processes for photochemical degradation. Chromophores other than carbonyl group pC]O such as metalemetal bond if incorporated in polymer backbone induce photodegradability. In such a case, metalemetal bond cleaves homolytically on irradiation [206]. Polyolens undergo slow sulfonation and oxidative degradation by reagents based on concentrated sulfuric acid. In chromic acid, sulfonation results in more rapid oxidative degradation of PP with a slower attack on PE. Relative rates of attack on CeH sites are 4600:75:1 for tertiary:secondary: primary (Scheme 19) [207]. To observe the effect of hydrophilic moieties on the degradations of the polymers, Singh and Sharma [208] have carried out biodegradation study of pure PS and grafted PS
that is [PS-g-poly(AAc)], [PS-g-starch] and [PS-g-poly(AAc)co-starch] lms by soil burial method. It has been observed that 37% degradation has occurred in PS when modied with starch after 160 days and no degradation has been seen in the case of PS grafted with poly(AAc). This is because starch is a natural hydrophilic polymer and has more susceptibility for bacterial and fungal degradations in soil as ambient environment available for their growth. This is possible due to scissoring caused by the microorganism in some chains at the site of grafting and polymer chains may get breakdown and decrease the number of carbon atom in the chains [208]. It has also been observed by Wool and co-workers that the following exposure to soil test conditions, micrographs of thin lms clearly showed the colonization of microorganisms within channels of the matrix that has been initially occupied by starch [155]. Apart from weight loss, change in color of the starch modied PS lms has also been observed. FTIR spectra have shown that with passage of time, the soil microorganisms have consumed starch portion of the grafted product [208]. 4.6. Additives Non-polymeric impurities (such as residues of polymerization catalysts, transformation products of additives), llers or pigments affect the resistance to degradation. Yang et al. [209] have reported that the thermal stability slightly decreases and the ash content increases when the ligno-cellulosic ller loading increases in the sample. The dispersion and interfacial adhesion between the ligno-cellulosic ller and thermoplastic polymer are the important factors affecting the thermal stability of the composite system [209]. Metals act as good pro-oxidants in polyolens making polymer susceptible for thermo-oxidative degradation. For example, manganese (Mn) is a suitable metal participating in metal combination for pro-oxidant activity. Upon activation by heat in the presence of oxygen, pro-oxidants have produced free radicals on the polyethylene chain which have undergone oxidation and have changed the physical properties of the polymers [4]. In addition, the pro-oxidant catalyzes the reaction of chain scission in the polymer, producing low molecular mass oxidation products, such as eCOOH, eOH, C]O group containing products [210]. Traces of transition metals have accelerated thermal oxidative processes of polyolens by inducing hydroperoxide decomposition [21]. For example, TiO2 delustrant has made the polyamides susceptible for heat- and lightinduced oxidation [29]. Oxidation of plastic (polyolen) is
R CH2 C H CH2
R chromic acid 80-100C CH2 C O Cr (OH)3

Scheme 19.
R CH2 H2O CH2 C OH O C H , CH2 CH2
O C CH2 ,
O C OH
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inuenced by the amount of pro-oxidant additives, chemical structure, morphology of plastic sample and the surface area [211]. Chain-breaking (hindered phenol) antioxidants inhibit the oxo-biodegradation of the polyolens under thermooxidative conditions during service [212]. Photo-stabilizers decrease the chances of photodegradation of plastic materials. Effective light absorbers such as benzotriazoles, benzophenones, and phenyl esters, as well as hindered amine light stabilizers are presently used in plastic formulations intended for outdoor use (usually at a 0.05e2.0 wt.% level) [213]. Many transition metal ions are effective accelerators for peroxidation and hence for the biodegradation of the hydrocarbon polymers. Since the sequence of reactions shown in Scheme 20 leads to the rapid buildup of hydroperoxides in the polymer, peroxidation cannot be controlled by chain-breaking antioxidants such as the hindered phenols since the latter are rapidly destroyed by hydroxyl and peroxyl radicals (Scheme 20) [212]. As the antioxidants and the stabilizers make polyolens resistant to degradation, the use of pro-oxidant additives can therefore make them oxo-biodegradable by making polymer hydrophilic and also catalyze breakdown of high molecular weight polyolen to lower molecular weight product [213]. Susceptibility towards biodegradation of polyolens enhances by blending with starch or other polyesters and biodegradation depends upon the type of polymer and the blend composition [214]. Along with this ller, pro-oxidants accelerate the process of biodegradation. Averous and co-workers [215] have studied the effect of ligno-cellulosic fractions from wheat straw as natural llers in composites of a polyolen (a copolymer of PE and PP) and a biodegradable polyester [poly(butylenes adipate-co-terephthalate)] [216,217]. It has been observed from the study that amount of natural composites affects the degradation of the composites. In another case grafting of the wheat starch had affected the tensile strength of the composites [218]. 4.7. Chemical bonding Linkage affects the degree of degradation in plastic. In thermoplastic, head-to-head addition of monomer units and tail-to-tail addition of monomer units during addition polymerization create weak points which make the plastic susceptible for degradation. Head-to-head linkage in PMMA enhances
thermal degradation of the polymer [219]. Branching in polymer chain increases thermal degradation [3,20]. Crosslinking decreases the rate of photodegradation by locking the polymer structure and preventing lamellar unfolding because these actions prevent the separation of photo-produced radicals and favor the radicaleradical combination [41]. 4.8. Methods of synthesis Methods of synthesis show the noteworthy effect on the stability of the polymers [220]. For example, anionic polymerized PS showed more photo-stability than free radically formed polymer due to the presence of peroxide residue in the latter, which is labile for photodegradation [221]. PP synthesized by bulk polymerization and by ZieglereNatta catalyst is more susceptible towards photodegradation as compared to copolymerized PP [222]. 4.9. Effect of substituents Substituents effect the degradation processes in many polymers containing labile a-hydrogen in the repeating units and modify the reaction course profoundly even if the mainchain scission reactions prevail. For ethylene and 1-substituted ethylene, chain-end scission reactions are predominant, producing either little or up to 50% monomer as volatiles. In 1,1-Disubstituted ethylene, repeated units apparently favored 100% monomer yield, whereas chlorine as substituents did not favor chain end degradation route [18]. Thermal stability of a polymer decreases as the number of substituents on polymer backbone increases. Phenyl group in styrene unit of PS makes CeC backbone labile for thermal degradation. Based on the same fact PE shows more thermal stability as compared to PP and polyisobutylene. The effect of substituent groups on the stability of the backbone CeC bond is apparent from the comparison of the bond dissociation energies for CeC bond (in kcal/mol), CH3eCH3 88, CH3CH2CH3 85, (CH3)3 CCH3 80 and C6H5CH2CH3 70. In PVC, the presence of allylic positioned chlorine atom favored dehydrochlorination of the polymeric chain as double bond activated the release of chlorine radical as shown in Scheme 21. The elimination of the rst molecule of HCl and consequent formation of a double bond on PVC chain subsequently activates the neighboring chlorine atom which has assumed the nature of an allylic chlorine, causing elimination of another HCl molecule, with the process continuing to repeat
CH2 CHCl CH2 CHCl CH CHCl
Iron Catalysed Peroxidation of Hydrocarbon Polymers Fe2+ Fe3+
POOH
Fe3+ Fe2+
+ PO + OH + POO + P +
P
+ POOH + +
PH PH
+ H+
CH2 O 2 / PH POOH O2 / PH POOH CH2 CHCl CH CH CH CHCl CHCl CH2 CH CH CHCl
+ Cl
POO PO
POOH POH
+ HCl
Scheme 20.
Scheme 21.
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itself nally producing a conjugated polyene structure by an autocatalytic effect [18,29]. Contrary to this, all substituents not always reduce thermal stability of the polymeric systems. For example, the presence of electronegative groups as uorine in teon increases the thermal stability of the polymer due to high dissociation energy (108 kcal/mol) of CeF bond [3,20]. Aromatic groups in a polymeric backbone increase the thermal stability. 4.10. Effect of stress Stress has signicant effect on polymer degradation. Tensile stress increases the rate of photodegradation whereas compressive stress retards the photodegradation rate. Stress changes the quantum yields of the reactions that lead to bond photolysis, the efciency of radical recombination following homolysis, and changes the rate of the radical trapping reaction (Scheme 22) [41,220]. The polymer morphology is one of the key factors to interpret the effect of stress on degradation rates. Higher stress causes signicant morphological changes, including the straightening of the polymer chains in the amorphous regions. When stretched bonds are cleaved by light, the probability of radical recombination decreases as compared to non-stressed polymer because entropic relaxation of the chain drives the radicals apart and prevents their efcient recombination because of their increased separation [41]. Stress induces a chain orientation that is more favorable for degradation, apparently due to chain conformation that becomes more susceptible to hydrogen abstraction [223]. Stress also effects the thermooxidative degradation [32]. Degradation of stressed specimens occurred with considerably higher rate as compared to the unstressed state and is marked by a decrease in apparent activation energy as well as by an increased rate of crack development. The cracks developed in the direction perpendicular to the tensile stress and have the shape of hollow funnels widening outward. An accelerated embrittlement of the polymer occurred due to the tensile stressing of stabilized types of PP in thermo-oxidative and photo-oxidative environments, manifested particularly by a marked decrease of elongation at break [32]. 4.11. Environmental conditions Biodegradation of polymer depends upon environmental conditions such as moisture, temperature, oxygen, and suitable population of microorganisms [4]. In warm climates when the relative humidity exceeds above 70%, the rate of polymer degradation by the microorganisms increases [17]. High
temperature and high humidity enhance hydrolytic degradation of the polymers. Temperature of the material and the presence of moisture show a considerable synergistic effect on the photodegradation of the polymeric materials [11]. Moisture promotes the light-induced degradation due to the fact that under high humidity soluble photo-stabilizers might leach out of the plastic matrix, reducing the effectiveness of the light stabilizer and leading to degradation. The presence of high humidity, particularly at the higher temperatures tends to increase the photo-damage in polymers such as thermoplastic polyester elastomers [39]. Even a small increase in solar UV level dramatically accelerates the deterioration processes in plastics at high temperature [224]. It is the synergistic effect of high temperature and solar UV radiation that is responsible for the rapid degradation of the polyethylene lms under these conditions [224]. Weathering is a degradation process and as such is temperature dependent, i.e. it will occur more rapidly at higher temperatures. The general rule is that for every 10 C increase in temperature the reaction rate will double. Tropical areas therefore suffer not only from an increase in UV exposure but also faster reaction rates because of the increased temperatures. Humidity also affects the degradation processes; most weathering processes are considerably slower in hot dry climates than in hot wet climates [30]. Oxygen affects the mechanochemical degradation of rubber at ambient temperature. For instance, degradation has been found to be almost absent when rubber is masticated in an atmosphere of nitrogen. However, when the process has been repeated in the presence of a small amount of oxygen or air, degradation has been observed very quick and signicant. This is because during degradation free radicals are produced at the end of the scissor fragments of the chain. In nitrogen, however, the primary radicals formed under shear immediately recombine to give no effective chain breakage. Oxygen due to its radical scavenger nature readily reacts with the free radicals formed at the fragmented ends of the polymer molecule and renders the chain break permanent [65]. Thermal dehydrochlorination of PVC in the presence of oxygen occurs faster than the inert atmosphere [213]. During processing, carbon radicals are formed from chain scission because of strong shear forces. These radicals then react with oxygen to form peroxy radicals, and nally, hydroperoxides [225]. 5. Plastic materials: future perspectives, challenges and other issues Various types of plastics may be of use in packages, biomedical products, electronic components, non-returnable goods, construction materials, etc. However, an important
homolysis
M k recombination
X = trap 2 M X
Scheme 22.
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aspect of these materials for a sustainable society is to predict their lifespan. How a material affects its environment is always important [226,227]. Sustainability, industrial ecology, ecoefciency, and green chemistry are the new principles that are guiding the development of the next generation of plastic products and processes. Ecofriendly, biodegradable polymers are the major breakthrough in plastic and polymer industries. Bio-based economy is challenging to agriculture, forestry, academic, society, and industry to develop and commercialize agricultural based new materials. A grand challenge facing government, industry, and academia in the relationship of our technological society to the environment is reinventing the use of materials. To address this challenge, collaboration from an interdisciplinary group of stakeholders will be necessary. An emerging approach to this grand challenge seeks to embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for using and creating new materials chemists [212,228e230]. 5.1. Sustainable polymers Polymer material has brought not only tremendous wealth for human being, but also unfortunately the serious environmental problems. We must solve these problems through sustainable development which can be carried out in two ways: (1) recycling the waste plastic and (2) developing environmental friendly polymer materials [231]. The term sustainable is often assumed to be synonymous with renewable. Sustainable polymers also have to be industrially acceptable and biodegradable. The ideal biopolymer is of renewable biological origin and biodegradable at the end of its life. Biopolymers include polysaccharides such as cellulose and starch, carbohydrate polymers produced by bacteria and fungi, protein polymer derived from soy protein and animal protein based biopolymers such as wool, silk, gelatin, and collagen. On the other hand, polylactic acid (PLA), PVA, and poly(butylenes succinate) (PBS) are examples of polymers that have synthetic origin but are also biodegradable. The extremely high price of petroleum and the growing environmental problems are some of the driving forces in looking towards renewable source based plastics to meet the challenges [212,232,233]. 5.2. Plastic recycling Recycling is an expanding area of the chemical industry in general, plastic recycling and waste management in particular being closely examined in academia, commercial organizations and governmental institutions. Finding suitable solutions can lead to the recycling of potentially hazardous materials on the one hand and production of acceptable commercial products with little or no outlay in raw materials on the other. The recycling of post-consumer plastics is of increasing importance as land lling and incineration becomes more expensive and environmentally risky. In addition to reducing the amount of plastic waste requiring disposal, recycling plastic can have several other advantages such as conservation of
non-renewable fossil fuels, reducing energy consumption, reducing carbon dioxide emissions, and many others [234]. A fairly new utilization of plastic waste is conversion of post-consumer plastic waste into oil by two methods that is direct liquefaction and pyrolysis followed by hydroprocessing of the pyrolysis liquids [235]. Post-consumer waste plastics can be used in cement-based composite. Also, mechanochemical treatment can be used to develop composite plastic materials from post-consumer plastic waste [236]. Recycling plastic usually involves processes such as melting, shredding or granulation of waste plastics. An option with great potential is feedstock recycling, which includes a variety of processes like pyrolysis, catalytic conversion, depolymerization and gasication, designed to transform plastic waste into hydrocarbon products for use in the preparation of recycled polymers, rened chemicals or fuels. Despite not being used extensively, feedstock recycling is attracting increasing scientic and commercial attention as an alternative with the potential to absorb very large amounts of plastic wastes. The application of catalysts is giving feedstock recycling a new impulse that is expected to put this technology at the forefront of plastic management [237e239]. 5.3. Biodegradable plastics: as an alternative to the existing petrochemical-based polymers Advanced technology in petrochemical polymers has brought many benets to mankind. Synthetic- and petroleum-based polymers are extremely stable and are commonly used in agriculture, food packaging, fast-food restaurants, and on military and commercial ships. However, their attractive stability is counterbalanced by two problems: polymers contribute to the demand for expensive imported oil and their great resistance to biodegradation. Petroleum reserves will be exhausted in less than a century. It is therefore necessary to nd another raw material for the fuel area, but also for plastic industry. The shortage and high cost of fossil resources require that alternative resources and processes must take over in the near future. Biodegradable polymers are now being considered as an alternative to the existing petrochemical-based polymers [175,240]. New applications based on synthetic polyester-based biodegradable polymers have been commercialized, especially in the packaging industry, paper coating and garbage bags. These polyesters are made using modied polyethylene polymerization processes and as blends. A second class of biodegradable polyesters includes polylactic acid (PLA) and thermoplastic starch-based polymers. These polyesters environmentally degrade into water and carbon dioxide when exposed to microorganisms and water in composting piles. A third type of biodegradable plastics includes aliphatic co-polyesters such as polyhydroxyalkanoates or PHAs produced by bacteria. Potato, corn and wheat starch are renewable raw materials for starch-based plastics [241]. Fully biodegradable synthetic polymers are commercially available since 1990. Among these biopolymers, PLA was extensively studied in medical implants, suture, and drug delivery systems since 1980s due
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to its biodegradability. PLA has been attractive for disposable and biodegradable plastic substitutes due to its better mechanical properties. However, PLA is still more expensive than conventional plastics. Also, the degradation rate is still slow as compared to the waste accumulation rate. The newly developed plastics from this research could provide possible solutions to the problem. Also, the plastics from this proposed research could be used as biomedical and pesticide slowreleasing carrying matrix. The industrial-scale production of PLA from lactic acid generated by fermentation now provides a renewable resources-based polyester as a commodity plastic for the rst time [242e246]. Starch may offer a substitute for petroleum-based plastics. Starch is a renewable, degradable carbohydrate biopolymer that can be puried from various sources by environmentally sound processes. It is a relatively low-cost polymer available from agricultural surplus with potential thermoplasticity. However, it needs water for processing and the water content of the product inuences its stability. Another widely available carbohydrate material is cellulose, which is biodegradable, but cannot be thermally processed, because it decomposes before melting. Chemical modications can improve thermoplasticity but decreases biodegradability. While numerous attempts have been made using starch and a few other carbohydrates as components in various formulations for biodegradable plastics, generally the major technical problem is the need to strike a balance between stability and moldability. Water content and molecular weight are two keys to this balance. The nal products should be biodegradable after fullling the requirements of their use, however, they must be stable during the application. The stability requires a low water content and resistance to water. On the other hand, most agricultural polymers use water as a plasticizer during molding. High molecular weight provides better stability and physical strength but decreases the moldability [2,240,241,247,248]. Synthetic hydrophobic biodegradable polymers are available since 1990. However, these synthetic polymers are usually more expensive than petroleum polymers and also have a slow degradability. Blending starch with these degradable synthetic polymers has recently become the focus of researchers [2,56]. This will increase the cost and decrease the mechanical strength properties of the blends. Potato, corn and wheat starch are renewable raw materials for starch-based plastics [161e163,249]. 5.4. Biodegradable plastics: limitations and obstacles for use While a number of alternatives have emerged, one of the main limitations for synthetic biodegradable polymers such as polyesters and starch-based blends is higher cost compared to synthetic polymers. Another serious obstacle is a lack of suitable infrastructure for sorting, recycling and composting solid wastes. Development of process technology for completely biodegradable polymers is generally costly. Either the cost of monomers is prohibitive for its commercialization or the polymerization technology is not yet competitive with
the conventional processes. Further research and development efforts are necessary to make the biodegradable polymers cost effective. Another drawback in the development of completely biodegradable polymers is the limited availability of monomers. Processability, performance limitations, cost, and rate of degradation present formidable obstacles to widespread adoption. Bio-based polymers such as cellulose and starch are not so conducive to mechanical recycling, and they also have a lower caloric value on incineration [228,176,211, 250e252]. 5.5. Future directions Any decision to use a degradable polymer should be based on a good understanding of where and how the product will degrade, recognize and minimize life cycle environmental impacts (not just end of life), and deliver real commercial benet [228,252]. 6. Conclusion It is concluded from the foregone discussion that understanding about the mechanism can go a long way in helping the researchers and the technologists to induce the different types of degradation in the plastic. These degradations can further be enhanced by the addition of the additives in the plastic and by understanding the various factors responsible for these degradations. It is also concluded from this discussion that plastic degradation could be enhanced by its modication with natural polymers and this acquaintance can further be exploited for environmental waste management. Acknowledgement This article is prepared from the literature collected for the project sponsored by the Ministry of Environment and Forest. The authors wish to thank the Ministry of Environment and Forest, Government of India, for providing the nancial assistance for the project. References
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Polymer Degradation and Stability 93 (2008) 561e584 www.elsevier.com/locate/polydegstab

Mechanistic implications of plastic degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

OH O OH Radical formation via above eq.

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

O H C CH2 C CH2 O C O2 CH2 H C CH2

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

Initiation R (R)n R R (R)n R

Propagation R (R)n R R (R)n-1 R

+ RO + ROO + RO + ROO + ROO

ROR ROOR ROOR ROR

O CH2 CH CH2 CH CH2 C HO CH2 CH

O CH2 CH CH2 CH CH2 C CH2 CH CH2 C CH2 CHO

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

CH3 CH2 C CH CH2 O3 O CH O O CH2 CH2 CH2

CH 3 mill C 77C C OCH 3 O CH2

CH 3 C C OCH3 PMMA attack

CH3 CH2 C C O OCH 3 C H O C

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

R chromic acid 80-100C CH2 C O Cr (OH)3

R CH2 H2O CH2 C OH O C H , CH2 CH2

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

Iron Catalysed Peroxidation of Hydrocarbon Polymers Fe2+ Fe3+

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

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