Curing of Unsaturated Polyester: Network Formation R. F.Toorkey, K. C. Rajanna, and P. K. Sai Prakash’ ‘Osmania University, Hyderabad-500 007, India While the words polymer and polymerization have be- ‘come common to students at different levels of the chemis- ‘try curriculum, very few experiments are demonstrated to clear the various doubts that arise from a study of these versatile products. "AS a means of explaining and enthusing students to the polymer field, we demonstrate the erose-linking reaction of| fan unsaturated polyester resin (UP) dissolved in styrene {co-monomer solvent), The reaction is initiated by the use of methyl ethyl ketone peroxide (MEKP) and accelerated by cobalt octoate (Co.Oct), "The purpose of the paper is to give details ofthe various saps invlred in the demonsaton; whith ale alo to explain some concepts like polymerization, cross-link! thermoplastic. thermoset, and inhibition. A simple ada tional experiment by hand lay-up technique making use of glass fiber (GF) can demonstrate the industrial signifi- ‘cance of the glass fiber reinforced produets. ‘Chemistry of Unsaturated Polyster Resins Resin Formation Linear UP resins are condensation polymers prepared by reaction of diols with appropriate acids and/or anhy- rides. Propylene glycol (PG), maleic anhydride (MA) and phthalic anhydride (PA) are usually the main reactants. A segment of polyester obtained from PG, MA, and PA might have the following structure. 2 general purpose low reactivity poly(propylene maleate phthalate). Source of UP, M/S. Bakelite Hylam Ltd., Sanathnagar, Hyderabad, grade HSR-8112. “Methl ethyl ketone peroxide (MEKP) (initiator): A {50% MEKP solution in dibuty] phthalate having an active oxygen content of 7-9% has been used. Cobalt Octoate (promoter); Approximately 18%~20% cobalt octoate solution in low boiling white spirit (50-60 °C) having a cobalt content of 3%, N.N-Dimethylaniline solution (second promoter 6% VA solution of N.N-dimethylaniline (DMA) ing white spirit (50-60 °C) isa second promoter. Pyridine solution (inkibitor) ; A 6% VIV sotution of pyridine in a mixture of solvents was prepared to obtain a clear solution. (n-Hexane(65-70 °C) = 42 mL, Styrene = 42 mL, Acetone (double distilled) = 10 ml), synthesis grade (B. Merck) pyridine = 6 mI. Procedure ‘The demonstration can be earried out in a wide-mouth stainless steel container having a capacity of 125 ml, or it also can be done in a plasticlined paper cup (2). ‘Testing can be performed in the 25-50 °C temperature range to obtain reasonable reaction times. Initiate the reaction by dispersing 0.5 mL of Co-Oct in 50 g UP ina suitable container, followed by addition and mix- ing of 0.5 mL MEKP. Simultaneously start stopwatch to record gel time. The reacting mass is probed periodically with a glass rod. The gel time is recorded as the A Tow boil- he he ‘time required for the mass to attain a rubbery con- 00~cH=cH-co-o-bcto-0 HoHrO-CO-cH=cH-co— sistency after initiator addition. This is recorded as the base gel time. The steps are shown schemal cally in Figures 1 and 2. Effect of DMA Solution ‘Appreciable cis-trans isomerization generally occurs dur- ing polyesterification of unsaturated acids and anhydrides. Suc isomerization is marked particularly with maleic anhy- ride, which becomes incorporated into the polymer chains mostly as fumarate groups. Itis at these unsaturated sites thatthe eross linking occurs with styrene. Cross Linking Crosslinking at room temperature is generally initiated by using a peroxy compound and a metal salt. The cross- linking reaction is a free radical catalyzed eopolymeriza- tion between UP and styrene. The free radicals are gener- ated by the redox decomposition of the peroxide by cobalt fons according to the following chain reaction. ROOH + Co!*+RO' + OH" + Co? OOH + Co™ > ROO’ +H* + Co? ‘This cyclo is repeated until all the hydroperoxide has ‘been decomposed (7) ‘Chemicals Usod Unsaturated polyster resin (UP): Approximately 65% solide in styrone as reactive comonomer. The resin used is Tutor fo whom corespondence shoud be addressed. 872 Journal of Chemical Education A similar procedure is adopted for observing the action of DMA solution (second promoter). After the resin is weighed out (50 g) and accelerator (0.5 mL.) added, 0.6 a (UP rein ein) NC-CH-CHe)” nIGHe-CH—CH) (Syren ee (uP reonenany | cota 09 ag dics pedod ck be mn ben ogre pe (Cres.nies ptt feeniae Figure 1. A representation of polyester golatonicross linking.L “pereper t te pote po4 oreton where a 4. ‘Ma male anhydride moity = deat moiety P= phthalic antyeride moiety Xe stone Figura 2. Cross nkedioued poyestar ean. ml, of DMA promoter is added and dispersed, followed by addition of 0.5 mL MEKP, simultaneously starting a stop- watch. There is a dramatic reduction in gel time when DMA\s used. Indicative gel times at 25 °C are 25 min and 8-4 min, respectively, without and with DMA addition. ‘The gel times recorded at 50 °C are between 4-5 min and 1-2 min, respectively, without and with DMA addition. ‘Because cross linking is an exothermic process a ther- mometer of 0-250 °C range can be introduced into the rub- bery mass and the peak exotherm and time for peak ‘exotherm also ean be noted, These values help in deter- mining the cure rate of the polyester. + Caution: Extreme care is required becouse the temperature an reach 150°C t0 170 °C, However, it must be remembered that the thermometer introduced for recording temperature should be removed ‘a8 soon as the exotherm has reached its peak and tempera- ture begins to decline, because as the gelled mass cools it shrinks. Failure to remove the thermometer will result in breakage. ‘The higher the temperature at which the reaction is con- ucted the lower will be the gel time. This is true for both types of reactions in which DMA is present or absent, Etfect of Variation of Pyridine Solution When the above experiment is repeated, using pyridine solution (inhibitor), the gel time increases. A range of el times eould be obtained by using 0.1 to 08 mLof pyridine solution, If the three experiments are conducted side by side, con- cepts such as acceleration, inhibition, exotherm, and ther- ‘moset stage can be conveyed in a colorful and simple main- Note 1. Technique for Hand-layup ‘This is a simple manual method for the production of «glass reinforced plastic (GRP). Material Requirements ‘+50 gf cm x5 em glass cloth squares (Crom chopped strand mat). + Promoted unseturated payer resin The quantity of the resin required is approximately half the woight of the glass dech squares in this case 25 "The resn ie promoted hy Ca et at 1 ‘bart per hundred parts UR + A2.5:em ordinary paint brush, + Methyl ethyl Ketone peroxide (50% solution). Quantity of [MEKP used is atthe rate of 1 phr af promoted resin, Procedure Weigh tho resin and add cobalt octoate (promoter) at the level of 1 phr. Mix thoroughly and then add MEKP at the same level ie., 1 phr. Mix to obtain uniform dispersion. [Now the resin is ready for use for hand-layup experiment, ‘Ona flexible polyethylene sheet apply a thin layer of the (catalyzed) resin with the help of a paint brush. Now place the first square of glass cloth onto this layer of resin and brush some more resin onto it. Dab the glass cloth with the brush to promote resin penetration into the cloth. Align the ‘edges of the next square with the first square and repeat the process, alternating with resin application and firmly pressing the layers of glass cloth with the brush, continue till the glass eloth is ovor. When the resin has been used up, wash the beaker with acetone or stryene, followed by detergent and water. Allow the assembly to set and hard- en, Approximately 1 h is sufficient at 25 °C. Peel off the laminate from the polyethylene sheet. The final product is 2 GRP laminate, which is used widely in industry and ex. hibits characteristic toughness and hardness of glass rein- foreed plasties (GRP). Caution, ‘Do not build up more than 2-3 mm at a time, cexzothorm, and resultant warping of the laminate. ‘Same people are allergic to ase fiber cloth; hence, handle ‘with rubber gloves ‘Aller the laminate has sot and hardened, the edges are arp. Trim the edges with a hacksaw or crcular saw. 1 Under no eireumstances should MEK? and Co.ot be mixed directly because of the possibilty ofa violent reaction Note 2 Suggested equivalents to HSR-S112 are Freeman Chemi- cals Co. UP resin-(Siypol 40-2417), Reichold Chemieals- Polylite (81-001), and AC Hatrick (NZ) Ltd.-Polylite 610), ‘Arange of UP resins are available from reputed manufae- turers, and due to compositional differences gel times will vary, it maybe necessary, therefore, to adjust promoter, acel- ‘erator, and initiator concentrations to achieve gelation in the ‘required time. The present study was conducted on alow re- activity orthophthalate maleate resin (general purpose type). Similar resin available may be tried. 1e to ‘Some of the Resin Suppliers and Their Product Names ‘Supplier Trade name ‘Aslor Ghorical Lid, Polastor Bayer UK Lid Leguval BPChomecals Ld. Collovond Cray Valley Products Lis, Synoiac ule UK Li, Vestopal ‘Scottadar Go. Lid. Cystic Felonold Chomica Lia. Freoman Gremical Li, Polyito low reactiy polyte 31-001) ‘typo! medium reaciy resin 40 2817), ‘AG Hatrik (NZ) Lid, _Palyite (610) —_ Note 3 ‘The thermoset state that is characterized by insolubility and infusibility can be demonstrated by breaking a small piece of the gelled mass and putting it into a test tube con- taining acetone whorein it swolls but does not go into solu- tion. (The base UP resin easily dissolves in acetone.) Fur- ther, a piece of the gelled polyester, if held above a flame will not melt but eatehos fire and, burns with a sooty flame, Literature Cited 1 ani KI rama hy, Chapa st a New ek 2 Stam LB Sith De Mor Pos Me Grom, eo rk 198 Volume 73 Number April 1996 373