Production of alkyd resins and their paints: Effect of catalyst on their properties

D Doulia, S Rokotas and K Georgopoulou

i

Chemical Engineering Department, National Technical University of Athens, Zografou Campus, GR157 80, Athens, Greece

Keywords
,~\i~,yd resin catalysts, film prope! tie's~ paints, physicocherr~icai p!o.~el tiesr p! ot.ess tir'e

Summaries
Production of alkyd resh~s and their paints: Effect of catalyst on their properties
Modified aiq~d resins were produced b}, aicoholysis of soya bean oil with pentaer?h! itol followed vdl I . lJ~ by esierificatior! with penfaerythlito! and p.htha!k: anhyd!-icie "~-;,~ caEaiysts . with different cc,rents, including LiOq, bub4 tin oxide and dibutTi tin chiorid6 were used for aicohoiysis anti/or esteri,ica tion reactions. [he effect os the catal)st or, rise reduction or the process time of alk'/ds, and their physicochemicaJ and Film p!.pelties, wel e investigated >.nd evaluated [he cablvtic s}~stern iiOH 00/% - dibul?i tin chloride 02% proved to be the best catalb,st s?stern foiio~,~ed by LiOH 0.07%. ]he coaiing fihr~ characteristics of t~,~,opaints, r with selected a!{',~ds, were measured and compa-ed

La production des resines alkydes et de leurs peintures : elfet d'un catalyseur sur leurs proprietes
Des r~}sines aikjdes modifi@s ont et#; produltes gr'ace 8 i'alcooiyse de l'huiie de s';,ja avec is pen tael },th! itoi suivi de i'(S.slerification avee ie pentaer,,4hritol et i'anhvd! ide phthaiique Piusieurs catai,,~seurs ayant de dif.~rents contenus, v cor~pds LiOH, i'exyde de ;~ub;h}tain, le chlerul e de dibutyi~.bin, orit ~te uti!b(,s pour i'alcooi'>,se et/ou i'Oste~iqcation, i'effet du cata!?seul sur ia dh-~in~stion du tents du process.s des aikydes, st sur burs propri~.tes ph),'sicochimiques et de film, a eta} etudie. Le s},,steme catai)'tique l..iOH 0,07% ch!oru!-e de dib,4b@.iain 0,2% s'est r~ontre is reel!bur s}'st@-qe catal}s s.,ivi de iiOH 0,0/% Lea ca! acteristiques de film de rev~tement de deux peintul es qh.~i ~.taient -u~mul@s avec des a!kjdes seieetionn0s ont eta} rnesu~@s et compa~ @s.

Die Produktion yon AIkydharzen [md ihrer Anstriche: Der Effekt yon Katal[yse auf ihre Eigenscha~ten
bloclifi,,ierte s wurden hergestellt rnittels s yon 5o2s mit Pentaer'tthritol ur]d nachblger!de~ Esterifizie! ung rail: Pentaervth itoi und Phthalisch~.n s idt.n. ~9'iI ve~wen@ten verschiedene ~f, ataiysatoren mit unterschiediichem inha!t, z.B i_i014, Butylzinkoxid .nd Dibut),!zinkch!orid, ~Jr die Aikohoi},se und/oder dis Esterifizielung, und studierten die Wi!-kung des F,~ataiysators slf die b!ersteiiungseit del /-'Jkyde, ih!e Ph'fsiochernie und Fi!rr~eigenschafien Ein .'/,~atai?satorsystem bestehend aus LiOH 0.0/% und Dibusr163 02% stei!te >ich als das efiektivste hera~Is, gefolgt t~on LiOH 0079.8. Die, Filmeigelsschafien yon 7','~,eik31 ben die mit ausge~,,,9.hitenAik)'den hergeetei it wul cien, ve!den gemessen und vergiiche~s.

D DeLliia, S Reketas and g Geergopeubu

Chemical Engineering Departrrent, ~',ationai Technical Ur!iversi,:}, of Athens, Zoglafou Campus, GR..!57 80, Athens, Greece -el: +30 2! 07723122 Fax: +30 2!0,,723163 Emaii: ddouiia@chemeng ntua.gr

Cepydght OCCA206,6

Introduction
The polyester obtained by the esterifica tion of a polybasic acid with a pol3&ydric alcohol is commonly referred to as an alkyd resin. A typical member of the alkyd resin family is made fi'om phthalic anhydride and maleic acid, and glycerol m~d/or pentaeuthritol and/or other poly ols, The resins are hard and have very good stability, gloss and gloss retention, weathering resistance a~d fast--duing characteristics, Due to the low chemical and alkali resistance, the alkyds are usually modified with monobasic acids or oils such as soya, linseed, coconut etc, constituting the main volume of alkyds in production. ~ Their main difference from other polyester resins is that they contain unsaturated fatty acid side groups} The basic reac~ons of processing alkyd resins via the monoglycetide process are: alcoholysis of the oil by a part of the poiyol used, and esterification by a polyacid and the remainder of the polyol, The oil and part of the polyol are mixed and heated to a temperature between 240 and 270'C in the presence of a catalyst which is generally alkaline (eg NaOH, KOH, LiOH, CaO and PbO), oi" without a catalyst ff the reaction proceeds at around 270~ s,4 The quantities of the catalyst used are around 0.01 to O.05%w/w with respect to the oil. The mixture obtained from alcoholysts contains monoester (more than 40%, irrespective of the reaction conditions), as well as diester, triester and glycerol. The monoglyceride content is sufficient to homogenise the reaction medium and allow the process to proceed to the second stage, Monoglycerides and diglycerides, generated during the first phase, take part in the polymerisation by undergoing numerous transesterification reactions. Esteri fication is operated either as a catalytic process (faster and milder temperature conditions) or a conventional high tern perature process. The selection of the catalyst is based on its effectiveness and on economical criteria. The catalytic esterification process yields alkyd resins with a lower viscosity (lower average molecular weight) and better results are obtained by preventing the resins from gelation compared with a high--temperature process under the same reaction conditions/: Various catalysts have been used for the esterification reactions of polyesters for use as coating resins. In particular., alkaline catalysts such as LiOH, Ca salts, acidic catalysts SUCh a s HsPO 4, HCI, H2SO4, and organotin catalysts, have been reported in the relevant literature. ~-~~ Also,

organotin compounds have been used as catalysts for the alcoholysis and esterification reactions in alkyd manufa.cture, n There is, generall Z a global effort to replace the conventional homogeneous catalysts of the above reactions with economical and eco fiiendly heterogeneous catalysts that have similar effecriveness and selectM ty but without the formation of by products or wastes. The cata154ic reac tivity of zeolite< cation--exchange resins, enz3;mes and metal compounds (hydroxides, alkoxides, organic polymeric salts etc), and the related mechanisms of esterification and transesterification reaction, have thus been reported in the relevant literature, !~ !6 Apart from resins, alkyd paints contain a suitable solvent (usually mineral spirits), a set of driers and other additives which irrorove perforlTkance/' Modified alkyd resins have been extensively used in paints and coatings. Alkyds rn W be old fashioned, but they are inexpensive and effective, Future trends will be driven by economic, quality and environmental pressures along '~ith competition from other materials. Price reductions of paint con~onents is a continuous demand. ~,!r In the last two decades, the research effort has focused on the cost reduction of alkyds and the dr?ing chernistry of alk3,ds mainly because of tighter environmental legislation. 7he reduction of VOC (volatile organic corroound 9 emissions from paints can be achieved mainly either by the replacement of solvent borne paints with water borne paints or by the pro duction of solvent-borne products with a lower solvent content, .Q~other topic is the role of metal catalysts, which may affect not only the process time of alkyds, but also the properties of alkyd resins and the paints derived from them5 ~ Paint drying includes the solvent evaporation and the oxidative drying related to a lipid autoxidation process. The polyunsaturated fatty acids of alkyd resins are prone to autoxida tion leading to product formation of cross linked Non volatile) species and numerous other oxygen containing compounds. ~-~ In this work, a variety of catalysts were used in the synthesis of modified longoil alkyd resins (~qth an oil length of 65%) by alcoholysis and esterification, The effect of the catalyst on the reduction of the process time and the physioochemical and coating film characteris tics of the resultant prepared resins were investigated. In addition, b.~:o paints were tbmmlated containing selected alkyd resins, and their technical coating

properties were examined and compared,

Experimental Materials
Technical-grade soya bean oil, pentaerythritol, phthalic anhydride, xylene and white spirit were used in the preparation of alkyd resins. The catalysts used were LiOH, in powder fo~rc~, of 99% purity (HELM AG), dibutyl tin chloride, white powder (R2 Sn C12: R butyl) with corn position: Sn 51 to 54% and chlorides 2% (Atochem), butyl tin oxide (RSnOJ (Atochem). The components of the paints, namel3; soya lecithin, titanimn dioxide, white spirit, etc, were also of technical grade, Synthesis of alkyd resins by a l c o h o l y s i s e s t e r i f i c a t i o n of' otis The process applied for the preparation of the alkyd resin included two stages, in the first stage, soya bean oil (600g), together with an initial quantity of pentaerythritol (72g) and the selected cat& lyst were introduced into a four necked round bottom flask connected with a water condenser, a mechanical stirrer and a Pt 100 thermocouple. ~[he flask was placed in an electric jacket heater. 'Ihe flask mixture was heated gradually up to 250~ under stirring. The alco iholysis reaction occurred mainly at 250~ The duration of the reaction depended on the type of the catalyst used, The reaction progress was monitored, and periodically sarr~les fl'om the reactor mixture were obtained. The alcoholysis reaction was considered complete when one volmne of a sam ple, mixed with three volumes of absolute alcohol, did not give an opaque solution, but gave a clear solu tion when cooled at room temperature. lhis test is based on the solubility of monoglycerides in absolute alcohol, while the triglycerides were not dis solved in this solvent, In the second stage, the remaining mnount of pentaerythritol (72g) was added to the alcoholysis mixture followed by phthalic anhydride (256g), the catalyst (whenever used) and the reflu>soivent (xylene). ~[he mixture was heated. I h e distillation began at about 190 to 210~ and the water, which was lbrmed, was distilled out as an azeotrope with xylene. Both water and xylene were condensed and collected :in the receiver, attached to the water condenser, and separated by gravity. Later, the temperature of the reaction rr~xture was gradually raised to 230~

qi!i!!ii!ii!:i!iii,i!!8 i!{)ii!i!i,!ii liii i ili!,!i!i:ii!:ili! !i)! !ii!i!ili i !i!ii{

iili!

!ii!ii iii i!ilii !!i ! iiiiill! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i !il

and maintained constant until an acid value of 15 was obtained. At that time, the total reaction time was recorded, A sample was withdrawn periodically from the reaction system and its acid value was determined. After the corn pletion of the reaction, the reaction mixture was cooled to an ambient tern perature mid dissolved in white spirit (60%~<&v). The characterisation of the alkyd resin followed. Monitoring the viscosity during the reaction was not possible because the quantity was too small to allow the collection of a number of samples. Preparation of solvent-based paints Two paints were prepared with two resins selected from among the seven produced, The typical composition of the paint is given in Table 1. The experimental apparatus for the paint preparation consisted of a high speed agitator connected to an electric motor. The weighed raw materials, namely half of the resin, the white pig merit, the extender, the dispersing and the a_ntisettling agents were placed in a metal vessel and dispersed for one hour, Then, the rest of the resin was added and the mixture was agitated for art additional half hour, ~]naily, the solvent and the driers (lead octoate and cobalt octoate) were added, the paint mixed, the antiskinning agent (methyl ethyl ketoxime) was then a d d e d and the paint was agitated manually and left for one day before testing. The prepared paints were checked for fineness of grinding, to be less than 20Bm, according to the ISO 1524 standard. Analytical and test methods The resins obtained by the procedure mentioned above were in the form of a solution in white spiflt, Each resin was evaluated for its total process time (for alcoholysis and eserification) and its acid value (ISO 3682). The resins were also tested for their physicochemical and film forming properties. [n particu ]at, the determination of the dtTying time was based on the ASfM standard D 1640 :method, which was measured on a 100pro wet film on a glass substrate, applied from the resin solution in white spirit (60%), 24 hours after the addition of the appropriate quantity of dr)ing agents. The viscosity of the diluted resin (dPa s) was :measured at 25~ (ISO 2431), For the hardness, a film of the alkyd resins diluted at 50% non-volatile (NV) matter, in which drying agents were a d d e d one day befbre the film application, was applied at 100pro wet film thickness on a glass panel. Because the resin was dissolved in white spirit at 60% non volatile matter (solid content 60% w/w), a dilution down to 50% NV (solid content 50% w/w) was made by adding the appropriate quantity of solvent. The amount of drying agents was negligible, The hardness was measured using a Koenig pendulum, according to the standard method ISO 1522, 24 hours, 48 hours and 72 hours after the film application. The film fomnng properties of the two paints p r o d u c e d were also examined. The film (100[tm wet thick hess) was applied on a glass plate, and the duing time and the ihardness (24 hours, 48 hours and 72 hours) measure ments were perforated by the same methods applied to the resins, In addition, the gloss of the coating film (100bm~ wet thickness) was measured using an electronic gloss meter (Sheen Instruments Ltd, TiJ-Oloss) at 20 ~ and 60 ~ according to ISO Standard 2813, and the whiteness index, according to ASTM standard C-313 was measured using a portable spectrocolorimeter (Sheen Instruments Ltd, Micromatch) with 10 ~ observer and 45/0 geomet U.

Results and Discussion

Seven alkyd resins were prepared using the same p r o c e d u r e and the same reagents but '~vith a different catalytic system, The ream which was produced with catalyst LiOH at 0.07% content in Ncoholyas and no additional catalyst was used in the esterification stage, was considered for comparison reasons as 'the conventional resin'. '[he duration of the process ,,,.,as significantly ~]'ected by the type and content of tile catalyst in the alcoholysis m~d/or esterification reactions, The results of the alcoholysis reaction time, esterification reaction time and overall process time of the resins for each catalytic system are given in Table 2, It is evident that LiOH at 0.07% content was proven to be a very eft)ctive catalyst lbr the alcoholysis reaction because it decreased the reaction rime to 1.33 hours (a decrease of 46.8% with regard to 2.5 hours of reaction time of alcohol ysis without a catalyst). Using no addi tional catalyst in the esterification reac tion (conventional resin), the total process time rose to 9.33 hours, The increase of the LiOH content from 0.07 to 0.14% had no influence on the alcoiholysis time and consequently on the overall process time, In addition, the use of LiOH at 0,07% in both reactions led to a decrease of esterification reaction time of only 3.1% (wqth regard to that of the conventional resin), thereby being unimportant in temps of cost, The o~gan ic metal catalysts were proven to be inef fbctive for decreasing the duration of the esterificaiion reaction when no catalyst was added in the stage of alcoholysis. In these cases, an increase in the esteritica tion time was observed, ranging front

lable 1- Formulation of alkyd paint

Reagent
i 2 3 4 5 6 8 9 All<#d resin Titanium dioxide (rutiie) Bentone SD I i ~<ji,i-,in(soya) Bariu-~ sNphae Lead octoate (30%)
vDus
..... <'J~

Amount %0 (~'/w)
515.0 205.0 2.0 ~7 200.0 4.!
0.,~

function
BJnde~ Whii,e pign~ent Antisett!ing agem ~"<, m~~,v -, s,ms Extencer Drying ager!t
~'3.,,3 d g , . .

Supplier
DuPont Rl~eox Sova ~' "'" , ,el,a> Baser Servo
SsI%~O

k' .,/o)

.................................................................................................................................

Methyl ei,hyl i<etoxime WhJi,e spirit

}6 66.0

AiXi>'inning agent Solvent

Servo Shell Hellas

-fable 2: Effect of catalytic system on the pr~ess time Ior the synthesis of modified alkyd resins by the alceholysis-esterification method

Experiment Atcohoty5is number catalyst %

1 2 3 4 5 6 7
.:,, .,.,..., .,,,,,,,.... ,,,,,..,..,., ,,,..,,..,,..,,..,

77me

(hours)
!33 133 133 25O 2 50 !33 133
,,,,,..,..,.,., ,.,..,,,,,,,,,-,,,...

Est~'Hfication catalyst %
No additional catalyst he additiona! catal!,st LiOH 0.0,, % Oibu:h,i tin c,hlo~ide (0.2%) Buvi tin oxide (o2%) Dibu>! tin chlq ide (0.2 %) Bu%/l tin oxide (0298)
,,,,,,--,.-,.-,,,,,,,,,...,,,.,,,,,,,..., ..... ,,,,,,,,,,,,,,,,,,,.,,,,,,,,

Time Totatprocess (hours) time (hours)

800 8 00 /,,5 8 83 9 25 500 566 9.33 9 33 9.08 I 1.33 !]./5 6.33 6.99
.,,,,,,,,,,,,,,,,.,,

iJOH 0.07 LIOH 0.14 LiOH 0.0/ Psocatalyst ho catalyst LiOn 0.0/ LiON 0.0/
...-,-,,.,,,,,,,.........,-,-,,,.......

,,..,..,..,.,.,.,.,..,.,..,.,.,.,.,.,.,.,.,.,..,..,.,, ,,..,,,,,,,,,.....,,,,,.,,.,..,..,

+ + + ;+ + + :+ { ;+ + + + + (@ ! + + + ) ; :+ + + + + :? + i+ r

+++++i :++: ++: ++ ++: ;+ :+ :+ ;:+ :++ + +++ :+::+;++: :+ :++ ;;++: + :++: {+ +;+ ;+: :p+~:a{~aii+ +; ;a :a+a::e+R~;+::++;+++a+; +~+ +~+::: ~4: +:g ++t/a~:++ ++ ++el+:+:+++++~ ++ +: +;
10.4% to 15,6%, by using dibutyl tin chloride and butyl tin omde respectively at 0.2% content, compared with the esterification reaction time of the conventional resin. The selection of LiOH (0.07%) as the catalyst for the alcoholysis and an organic metal catalyst (0.2%) for the esterification resulted in a significant reduction of esterification reaction times (37.5% and 29.3% fbr dibutyt tin chlo ride and butyl tin oxide respectively) and of the overall process time of the alkyd resins (32% and 25% respectively). Consequently, dibu@ tin chloride was superior compared with butyl tin oxide catalyst with regard to decreasing the process time. The order of the catalyst effectiveness in decreasing the overall process time (alcoholysis - esterification) was as follows: idOH 0.07 % dibu@ tin chloride 0.2% > LiOH 0.07% bu@ tin oxide 0.2% > LiOH 0.07% LiOH 0.07% > LiOI-{ 0.07% (or LiOH 0.14%) no additional catalyst; no catalyst dibutyl tin chloride 0.2% > no catalyst buUl tin oxide 0.2%. The change in the acid value against time during the ester ification reaction of the selected alkyds :produced using a different catalytic system is given in Figures I and 2. The physicochemical and film coating properties of the alkyd resins investigat.ed, namely the @ml acid value, viscosit> hardness and duing time, are given in 'Ihble 3. It is obvious flint the properties (viscosit> hardness and @ying time val ues) of the alk3~d produced with LiOH 0.14%/no additional catalyst, although similaL were inferior in comparison with those of the conventional resin (catalyst LiOH 0,07%/no additional catalyst) and the resin produced with a catalytic system (LiOH 0,07?4/LiOH 0,07%). Also, the d~2ing time of the resin produced with LiOH added in both reactions was higher than that of the conventional resin, while the values of the other properties (viscosity, hardness and production time) were the stone or very close. Therefore, the conventional resin is preferable because the quantity of cata lyst and therefore the cost of the catalyst is lower. The properties of the h~o resins pre pared with the organic metal catalysts in the esterification reaction were similar, Comparing their properties with those of the conventional resin, the latter proved to be better. It should also be kept in mind that the organic catalysts are much more expensive tha~q LiOH, The two resins produced using a combination of catalysts for the alcoholysis and esterifi cation reactions showed excellent prop erties and very low process times, with dibutyl tin chloride being slightly better.

!il!ii iii i!ilii !!i ! ii i il ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i ! i !il

+ ) ; + + [ + + :; @ : + p ; : @ + + : ;+ + : { + ; + :+ !+ + :+ + ;+ :+ ; :+ { + :+ + :@ + + > + ;@ :: + + : ;+ } + + { + :+ + + :i + + s :+ + + + 8 + + + + :: + + :+ @ @ + + + + @ + + + + ;+ :+ + + + :} + :+ :+ ++ + ; :+ ~ ~ ! :+ ~ :+ :i + + ~+ + + + + : + :+ + ~ + l ~ + i + ~ + : + + + : + ~ , R : + : + : + R : + + : ~ g + + +:i g + i :~ : ; + + + ~ :+ :+ ,: ; +

+1
m

+1
|

5 -! ~ LiOH0 . 0 ~ Mm ar~dit~on~lmtal~t E | m LiOH0.14% Mno adCtional mlalyst E | j ~,, tiOH O.OW/oMLiOfi 0 . 0 ~ [

O J,

"I

3.17 3.33 3.67 4.25 5.00 5.17 5.75 6.25 g,42 8.75 7.17 7.50 7.75 8.00
Time(+mms)

Figure 1 : Rate of the esterification reaction based on the charNe of acid value against time in the alkyd process using as catalyst LiOH in alcoholysis (A) and LiOH or not in esterification (E) and in comparison with that of the conventional alb/d (LiOH in A/no additional catalyst in E)

~5

25-

105-

~, [iOH0.~ Mm mtal~t [

No catalyst t~/dibutyl tin ehlmide0.2% [

R0 m~l~st Mb~tyl tin oxide0.2% [ LiOH0.07%Mdi~.tyl tin ~hlodde0.~ [ x [iOH 0.07% ~,/hutyJtin oxide02% [

2.42

3.0~

3.67

a.92

4.42

4.92

5+12

S.92

7.0~

7.S~

8.25

925

lime ( ~ r s )

Figure 2: Rate of the esterification reaction based on the cha~ge of acid value against time in the alkyd process using different organic catalysts in esterification (E) and LiOH in alcoholysis (A) in comparison with that of the conventional alkyd (LiOH in A/no additional catalyst in E)

~!i~!i~@~!i~+~ii!~i!~i:~i~i~i~i~!)~!~!~i i~i~+ i}~i ~!!~ !~!i !~i~ !~!~i !!i;!~~ !~ i:~ !;;!i !:!~!;~i !~~ !i~ i!+! ~!!~i ~+~! i!~:~i ~!~!;~ !i@~i !+@i i~+ i!:!~i ~~ !~ !~!i ! i~!i~@)i~i~!i~i!~!i{:ii:@~i~i!~ii~!@i!@ii!~!~!i!i~!~:!~!i~!;~!~:~!~!~i ~i~i~@~i !!~!~i i~;!ii!i~;~i ;i~ii!~i i+i~ !)!i @~i~@~!i!!~:~!!i~:~i

~!~+:~!~!~ifi!:!:~!i!i~i~i!i!++i ~!~i!~!~i!i~i!i~i~+i~:~+i~i!~!i~i~ii~i~i~!N~;i!i~i~!~i!~N;~!~i~!N~iN!ii!!~!~i~!~!!~!~!~N~!~!~!~!~i~+}~++!:~i ~i~!~i!~!~!i~l~i~!i!~i~+~i~i!~!~i~i~i!~i~!~!i~J~i~i~i~!i~i:i!!~i~i~i:i~!i!~i~i~

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Table 3: Properties of the a l ~ d resins produced by alcohoiysis (A)-esterilcation (E) pr~ess with various catalytic systems

i!i:::::i
7. Sumtsova L A, Z M Kudrova, G L Yukhnovstdi, B M Rudenko and R R Popenker, Soviet Union Patent 622822, 23rd Februal 7 1976, 1978 8. Lu B~ G Peng~ S Xu, Y Meng~ G Liu, D Li and X Zha.ng, Improvement of ested~dng technolo D, for alkyd resins. Part II. Heterogeneous cat alytic effect on estedficadon of alkyd resins', ~;Akao Gong~.'e (journal written in Chinese), g5, I-6, 1985 9. Istratescu S, V DanciuIescu, A Nistor, V Pilca, N Dobre, A Barbulescu~ N Dan, S Rasnoveanu, M Mddovan, E Anton and T Muresan~ Romania Patent 10965& 31st August 1994 10. Radiff L S and L ] Prendny, 'Catalysts for use in the acidolysis, alcoholysis and esterification reactions of polyesters for coating resins', h,d\,ax-~ces m ,~oe~a E ,ecb:~o~eg], ACT '98, Internaional Conference, 3rd Katowice, Poland, 20th to 23rd October, 1998 11. Seshadri S R, 'Catalysts for alkyd production', 'eolifa-~e~sPes Coleuv ~ouv~M, 185, (4363), 12, 1995 12. Yadav C D and M B Thathagar, 'Esterification of maleic acid with ethanol over cation exchange resin catalysts', Re~ctic~r~ a_~d~v.~mtiorta~ %b2mers, 52, 99 110, 2002 13. Gryglewicz S, 'Alkaline earth metal compounds as alcoholysis catalysts for ester oils synthesis', Xpp~ied Cave!L-sisk. Ger~e;~, 192, 2 3 - 8 , 2000 14. Ram M S and S Palaniappan, 'Benzoyl peroxide o~dda.tion route to pal)aniline salt and its use as cat alyst in the esterification reactionL ~o~a.v~;zd o~ M0~.ec~lea C~vs s Chern~c~, 201, (1-2), 28{-96, 2003 15. Karayanidis G E C P Roupakias, D N Bikiaris and D S Achilias, 'Study of various catalysts in the synthesis of poly(propyleneterephthalate) and mathematical meddling of the ester ification reaction', Pol,/me~, 44~ 931 42, 2003. I6. Barrault ], Y Pouilloux, J M Clacens, V Hove and C Bancquart, 'Catalysis and fine chemisW', C~ta~?sis '~oda'L /'~4"~..,,,;i~ @iiiiiiiiii, ," ~; 75, 177-81,2002 17. Schoff C K, 'OrgaNc coatings: 1'he i i ~ G ~ i ~ ~ 4 . r ~ S ; paradoxical materials'~ Progress in Orgaff~c Ceas 52, 21 7, 2005. ? ~b9 18. Oyman Z O, W Ming, F Miccich6, E Oosween, ] van F[averen and R van der Linde, 'A promising environmentally-friendly manganese-based catalyst for alkyd emulsion coaings', Pel'dmer, 45, 7431--6, 2004 19. Gorkum R and E Bouwman, 'The oxidative d@ng of alkyd paint cata.l ysed by metal complexes', Coo:dinat%n C~-~ewiatryRe\4ev.,,~ 249, (17-.18), 1709--.28, 2005

Catalyst % AlE
I JOH 0 07!I-o addJtioFal ~.~,yo,~' ...... ~t I!,vh '~" ' 0.141no addilJonai cabi;,st

Acid value
l!i.. 0 ~r, C ,.... 1~.,~,..7 15.0 (, . It: ,~.~ 14.5

V~scosity Drying time (dPas) (hours)

2:2) 2.750 2.833 . . . . 3 083 3 500 3.1 .... . 5 / > >'~;' .Ju . .

Non volatile matter %

s,;~ ,sue" 5880 . box . '} 6040 :""~ s o o"n'
~000

Hardness, oscfl Konig 24h

19 18 i~ ,. 20 "!9
!1'~

48h .:>~~
!8 20 2! P0
1t
, .

/2h
,'4 22 24 25 24 23 24

!0
. 5! 21J !20 .
! ~ i

i<,' ,.,.,~ ~, , A - , ~ I_.,,.~d I r~H '- "~

No catalvsb'dJbutvi

tin ~ c H~,0.2 NO cure, -i q .vsi .. ,u ,b ~ ~ ., . . ,-, = tin oxide 0.2 l iOH' 0 " ' " ~-'&,} t,,' d//'d!l,' tin chloride 0 2
,

o..o

tin oxide

I_i(;H ,9 0//but}ll ,9.'2

4 . q. . . . . . ! e ~ -" d ! ,.J.

2 ~50 2 !50

b'~ . . .> . A ~ 'o ",r, .

. .

18
. !8 .

20 20

Ta net ,~, . ',,,alue

_.

?0

,~a

P4

Table 4: Coating properties of the paints from selected modiled alkyd resim

Alkyd resin

Drying time (hours)

40 35

Gloss 20 +
6:34

Whiteness index
8~ 4 82 0

Hardness.oscifi goen(q 24 h
~~ !5

50 +
8o,: 876

48
lq I/

/2
19 !8

C,,rv,,m..~ Combined r'

a,

r-', i,~ . e l ,, if J- catalyst . if rid s and so additional catal;st ,rot esterari,:.ation p,,.,u~,.e., ,~,~,! . oo7% . . for a!cot]oivs , .. ~,p~educed witr~ ~~tsl., ~t~ . . . . .Jail . 0.07% fOl aicohok,sis aiid ~"&[utv!,% chiol ide 0.2% f,]~ este~i~icaticq ~

Therefore, l~e conventional resin mrd that produced with LiOH dibub, l tin chloride were selected for paint formu lations because they had the best prop erties as well as lower process times and cost. The coating properties of their films (drying time, gloss, whiteness and hardness) are given in Table 4, The values of the properties of both paints were almost similar. Particularly t h e gloss, >.,hiteness and hardness values were very close to each other. The selection of the best paint with regard to their properties can be focused on their film drying time. It is obvious that the combined paint, containing the alkyd prepared with two catalysts, was suped or, demonstralng lower duing lines.

References
1. Weiss K D, 'Paint and coatings: A mature industry in transition'~ P~og PobB~; ScL 22, 203 45, 1997 2. Spyros A, 'Quantitative determina tion of the distribution of free hydrovlic and carbovlic groups in unsaturated polyester and alkyd resin by 31P-NMR spectroscopy', lou~r~ai o~ hpp~ied Po!vme~ Science, 8a, 1635 42, 2End February 2002 3. Delig W P and N Tuck, Resirr~ ~or %wdace Coathkg~ II, (2nd edition), (ed) PKT Oldring, 58 60, ]ohn Wiley & Sons, Chichester, 2000, ISBN 0471978957 4, Chanem N A and A EI-M Fawzia, 'Clycerdysis step in the production of oil modified alkyd resins. I. Rate and extent of monoglyceride farina tion from two mixed tdglycerides', ~ovs~xe0~o~ P~>_t l~eda~dkog,}, aK (498), 381 6, 1966 5. Lu B, G Peng, Y Meng, C Liu, Q Zhang, D Li and X Cui, 'improvement of esterification of alkyd resin. "v'.Relation between performance a.nd molecular weight disu-ibution of alkydsL ~,.~'tia~Go~_~e (journal written in Chinese)~ 3, 9 12, 1988 6. Courley S and ] E B Purvis, GB Patent 697318, 14th March 1950

Conclusions
The effect of a catalytic system used in the modified alkyd processes, which included alcoholysis and esterification reactions, is significant with regard to the reduction el process times as well as the improvement of the coating properties of alkyds and the paints derived from them. The catalytic systern (LiOH/dibutyl tin chloride) proved more effective than the com;entiona] catalyst (LiOH/no additional catalyst).

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