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Ind. Eng. Chem. Res. 1987, 26, 194-198

Unsaturated Polyester Resins from Poly(ethy1ene terephthalate) Waste. 1. Synthesis and Characterization?
Utpal R. Vaidya and Vikas M. Nadkami*
Polymer Science and Engineering Group, Division of Chemical Engineering, National Chemical Laboratory, Pune 41 1 008, India

Fiber-grade poly(ethy1ene terephthalate) waste was depolymerized by using different amounts of propylene glycol. These glycolyzed products were reacted with maleic anhydride and mixed with styrene monomer to get unsaturated polyester resins. T h e processing characteristics like viscosity, gel time, and exotherm temperature of the resins were investigated with respect to the amounts of styrene monomer, initiator, and accelerator. The resins were compared with the conventional general purpose resin and were found t o be comparable in their processibility. T h e resins offer a new class of unsaturated polyesters to the fiber-reinforced plastics (FRP) processors. Fiber-reinforced plastics form a versatile class of materials that are increasingly replacing conventional structural materials such as metals, wood, and concrete in engineering applications. These materials, commonly termed FRP, offer a high strength-to-weight ratio, excellent corrosion resistance, ease of fabrication, and versatility of product design in comparison with metals. Although both thermosets and thermoplastics are used as matrix materials for fiber reinforcement, the thermosets constitute the major segment. Among the thermoseting resins, unsaturated polyesters and epoxies are the most commonly used matrix materials for FRP. The world consumption of unsaturated polyester resins in composites was of the order of about 1 X lo6 metric tons in 1985, whereas that of epoxies in FRP uses was only about 1.5 X lo5 metric tons in the same year (MPI, 1986). The unsaturated polyester (UP) resins are thus commercially important for the reinforced plastics markets. Besides their low cost, the UP resins can be tailor-made to meet specific requirements by proper choice of their chemical building blocks. The UP resins are made by the reaction of aliphatic diols with unsaturated and saturated diacids. The most commonly used diols &e ethylene glycol (EG), propylene glycol (PG), and neopentyl glycol (NPG). The use of PG offers better hydrolytic resistance relative to EG, since the ester linkages are shielded by the pendant methyl groups. A further improvement in hydrolytic resistance is achieved by using NPG because of the presence of two pendant methyl groups in its structure that enhances the steric protection for the ester linkage. The saturated diacids used as monomers in UP resins include phthalic anhydride, isophthalic acid, adipic acid, succinic acid, etc. The aromatic acids impart rigidity, whereas the aliphatic acids are used to give flexibility. The choice of the acid monomer is governed by the desired combination of properties in the final product. The unsaturated acid monomers used are maleic anhydride and fumaric acid. Of the two, the former is more common because of its higher reactivity. It is thus possible to achieve a wide range of properties by proper selection of the monomers. The general purpose (GP) resin is prepared by polycondensation of PG, maleic anhydride, and phthalic anhydride (Parkyn et al., 1967). When phthalic anhydride is replaced by isophthalic acid, certain properties such as heat distortion temperature (HDT) and chemical resistance are improved (Boeing, 1969). This effect is expected to be more prominent when terephthalic acid (TPA) is used as the diacid. This is because the chain linearity increases as one goes from ortho to meta and from meta to parQnkages, thereby improving the packing ability of the polymer chains. However, the direct use of TPA in the synthesis of UP resins is restricted due to its high melting point and processing difficulties arising from its sublimation during the course of the reaction. The major use of TPA is in the manufacture of poly(ethylene terephthalate) commonly termed as PET, which is a versatile thermoplastic that is used in synthetic fibers, extruded films, moulded engineering components, and blow moulded bottles. The worldwide production of P E T is above 1 X lo6 metric tons/year. With such a large consumption, the effective utilization of P E T waste is of considerable commercial and technological significance. P E T waste may be converted into extruded or moulded articles after repelletizing, or it may be depolymerized to yield raw materials for resin synthesis. Recycling of segregated waste by blending in small quantities with virgin monomer, bis(hydroxyethy1)terephthalate, is a possibility. However it often lowers the quality of the final product (Sittig, 1981). It is, therefore, desirable to break down the polymer into smaller fragments or oligomers. PET can also be fully depolymerized into dimethyl terephthalate (DMT) (Matsuura et al., 1975; Hemmi et al. 1973; Ligorati et al. 1972; Heinze et al., 1969; Sittig, 1981). This regenerated DMT can be recycled with fresh DMT. However, the regenerated DMT exhibits a significantly higher carboxyl content, adversely affecting the product quality. It is more economical to convert P E T into low molecular weight oligomers by glycolysis, in the presence of a transesterification catalyst (Matsuura et al., 1975; Etienne and Soulas, 1969; Miura et al., 1968; Rustagi et al., 1977; Mueller et al., 1972; Ostrowski, 1975). When glycolysis is carried out using EG, the oligomers may be directly recycled into the polycondensation stage in P E T manufacturing. However, this also lowers the prbduct quality. Glycolysis can also be carried out using other glycols such as PG, and the oligomers can be used in the synthesis of unsaturated polyesters by reaction with maleic anhydride (Toshima, 1975; Miyake et al., 1975; Makimura and Miyake, 1978; Tong et al., 1983). There are two distinct advantages of the process. Firstly, the P E T waste is converted into a commercial value added product, and 0 1987 American Chemical Society

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correspondence should be addressed.

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