Polyester resins, preparation

Unsaturated polyester resins prepared by condensation polymerization constitute the largest industrial use for maleic anhydride. Typically, maleic anhydride is esterified with ethylene glycol [107-21-1] and a vinyl monomer or styrene is added along with an initiator such as a peroxide to produce a three-dimensional macromolecule with rigidity, insolubiUty, and mechanical strength. 

Although monobasic acid is an optional component in polyester preparation, a large variety of such acids are often used. In addition to naturally occurring fatty acids, other monobasic adds used in polyester resin preparation include benzoic acid,p-terr-butylbenzoic acid, rosin (abietic add) and levopimaric acid. A mixture of benzoic acid and p-rm-butylbenzoic acid resulted in a fast drying time and improved the performance of the... 

Unsaturated polyester resins prepared from epoxides and MA are usually conducted in a manner which gives only the maleate copolymer. This necessitates heating the resin for several hours at 200°C, to bring about the needed maleate-fumarate isomerization. The isomerization may be facilitated by a variety of catalysts, reducing both the temperature and time needed to... 

P.J. Apice, Unsaturated polyester resins prepared from phosphoric acid esters, US Patent 3 433 854, assigned to Allied Chem., March 18, 1969. 

Glyptal (thermosetting polyester) resins prepared by Smith from the condensation... 

About 2 X 10 Ib/year of 1 2 epoxypropane is produced in the United States as an intermediate in the preparation of various polymeric materials including polyurethane plastics and foams and polyester resins A large fraction of the 1 2 epoxypropane is made from propene by way of its chlorohydrm... 

Chlorendic Acid. Chlorendic acid [115-28-6] and its anhydride [115-27-5] are widely used flame retardants. Chlorendic acid is synthesized by a Diels-Alder reaction of maleic anhydride and hexachlorocyclopentadiene (see CyclopentadlENE and dicyclopentadiente) in toluene followed by hydrolysis of the anhydride using aqueous base (60). The anhydride can be isolated directly from the reaction mixture or can be prepared in a very pure form by dehydration of the acid. The principal use of chlorendic anhydride and chlorendic acid has been in the manufacture of unsaturated polyester resins. Because the esterification rate of chlorendic anhydride is similar to that of phthalic anhydride, it can be used in place of phthalic anhydride in commercial polyester... 

As a dibasic acid, malic acid forms the usual salts, esters, amides, and acyl chlorides. Monoesters can be prepared easily by refluxing malic acid, an alcohol, and boron trifluoride as a catalyst (9). With polyhydric alcohols and polycarboxyUc aromatic acids, malic acid yields alkyd polyester resins (10) (see Alcohols, polyhydric Alkyd resins). Complete esterification results from the reaction of the diester of maUc acid with an acid chloride, eg, acetyl or stearoyl chloride (11). 

Uses. About 35% of the isophthahc acid is used to prepare unsaturated polyester resins. These are condensation products of isophthahc acid, an unsaturated dibasic acid, most likely maleic anhydride, and a glycol such as propylene glycol. The polymer is dissolved in an inhibited vinyl monomer, usually styrene with a quinone inhibitor. When this viscous hquid is treated with a catalyst, heat or free-radical initiation causes cross-linking and sohdification. A range of properties is possible depending on the reactants used and their ratios (97). 

Polycarbonates. Polyarjiates are aromatic polyesters commonly prepared from aromatic dicarboxylic acids and diphenols. One of the most important polyarylates is polycarbonate, a polyester of carbonic acid. Polycarbonate composite is extensively used in the automotive industry because the resin is a tough, corrosion-resistant material. Polycarbonates (qv) can be prepared from aUphatic or aromatic materials by two routes reaction of a dihydroxy compound with phosgene accompanied by Hberation ofHCl(eq. 5) ... 

This monomer is prepared by reacting cyanuric chloride with excess allyl alcohol in the presence of sodium hydroxide at 15-20°C. Laminates based on polyester resins containing triallyl cyanurate are claimed to be able to withstand a temperaure of 250°C for short periods. 

Aircraft radomes, ducting, spinners and other parts are often prepared from polyester resins in conjunction with glass cloth or mat. The principal virtue here is the high strength/weight ratio possible, particularly when glass cloth is used. Land, sea and air transport applications account for almost half the polyester resin produced. 

Over the years many blends of polyurethanes with other polymers have been prepared. One recent example is the blending of polyurethane intermediates with methyl methacrylate monomer and some unsaturated polyester resin. With a suitable balance of catalysts and initiators, addition and rearrangement reactions occur simultaneously but independently to give interpenetrating polymer networks. The use of the acrylic monomer lowers cost and viscosity whilst blends with 20% (MMA + polyester) have a superior impact strength. 

As small molecule fragments resulting from the initiator may plasticize the polymer and lower performance, approaches have been developed to avoid this. A dihydroxyamine can be used to form a polyester [52]. This accelerator gave a modest increase in the strength of unsaturated polyester resins. A polymerizable tertiary amine has been prepared by the reaction of A-methylaniline with glycidyl methacrylate [53] (Scheme 8). 

Polyester-based networks are typically prepared from polyester prepolymers bearing unsaturations which can be crosslinked. The crosslinking process is either an autoxidation in the presence of air oxygen (alkyd resins) or a copolymerization with unsaturated comonomers in the presence of radical initiators (unsaturated polyester resins). It should also be mentioned that hydroxy-terminated saturated polyesters are one of the basis prepolymers used in polyurethane network preparation (see Chapter 5). 

By depolymerizing PET waste with a polyol and subsequently condensing the oligomeric product with a polycarboxylic acid or anhydride, polyester resins are produced which have wide industrial applications. Depending on the polyol and polycarboxylic acid or anhydride used, saturated resins, alkyd resins, or unsaturated resins are obtained. PET wastes have been used for the production of alkyd resins in water thinnable paints. The materials obtained from the reaction of PET with a mixture of fatty acids high in linoleic acid content and trimethylolethane have been used in the preparation of water-dispersible coatings. Products of the depolymerization of PET with trimethylolpropane and pentaerythritol are used in the manufacture of high-solids paints. In the first step, PET is depolymerized with trimethylopropane and pentaerythritol at temperatures of 230-240°C. The final paint compositions contain 30-50% of PET depolymerization products.12... 

Thermoplastic resins, self-reinforced, 26 Thermoplastics, preparation of, 257-258 Thermoplastic step-growth polymers, 3 Thermosetting polyester resins, 29-31 Thermosetting resins, 3-4, 19 Thermotropic compounds, 49 THF. See Tetrahydrofuran (THF) Thiobisphenol S (TBPS), 364 Thionyl chloride, 80 activation of, 111 3,3 -linked polymers, 480 Tin-amine coordination complex, 234 Tin compounds, 86, 232-233... 

Unsaturated polyesters (UPs), 4, 18, 19 from PET waste, 560-561 Unsaturated polyester/styrene resin, preparation and cure of, 101 Unsaturated polyester thermosetting resins, syntheses of, 101-103 Unstirred interfacial process, 155 U-Polymer, 77... 

Unsaturated polyester resins (UPRs) Uralkyd resins, 202 Urea-methylol reaction, 410 Urethane alkyds, 241 Urethane coatings, 202 Urethane elastomers, implanted, 207 Urethane foams, tests for, 244 Urethane gels, 205 Urethane-grade ATPEs, 223 Urethane-grade polyol types, 212 Urethane-grade raw materials, 246 Urethane hydrogel, preparation of, 250-251... 

IPNs are found in many applications though this is not always recognised. For example conventional crosslinked polyester resins, where the polyester is unsaturated and crosslinks are formed by copolymerisation with styrene, is a material which falls within the definition of an interpenetrating polymer network. Experimental polymers for use as surface coatings have also been prepared from IPNs, such as epoxy-urethane-acrylic networks, and have been found to have promising properties. 

Both pigmented and unpigmented polyurethane paints have been prepared using a polyester resin containing hydroxyl functional groups and the biuret trlmer of hexamethylenedllsocyanate as a crosslinker. The molar ratio of hydroxyl/isocyanate has been chosen 1.0 and the pig-ment/binder ratio 0.6. 

The largest single use of maleic anhydride is in the preparation of unsaturated polyester resins. It is first esterihed with a polyalcohol (two or more hydroxyls) and then the double bond is copolymerized (crosslinked) with a vinyl monomer such as styrene to form a rigid structure. Such resins are usually reinforced with hberglass (FRP). Maleic anhydride is also used to make oil additives and agricultural chemicals. 

Earlier studies at the ITRI have demonstrated the effectiveness of tin(IV) oxide, both in its anhydrous and hydrous forms, as a flame- and smoke-retardant additive for laboratory-prepared polyester resin formulations (J5j. In a recent study, carried out in collaboration with a major U.K. company, a number of inorganic tin additives have been incorporated into a commercial brominated polyester resin. Although this resin, which contains 28% by weight bromine, is intrinsically flame-retardant, giving samples with an 01 of ca. 41 and which meet the UL94-VO classification, formulations with improved flame and smoke properties are sought. 

Finally, glass-reinforced unsaturated polyesters are well known as building materials for boats, yachts and cars and generally termed fibre-glass resin . The preparation, properties and applications of these unsaturated polyesters are summarized in Chapter 21, while the chemistry and properties of a new unsaturated polyester resin for fibre-reinforced composite materials are discussed in Chapter 22. 

GENERAL PROCEDURE FOR THE PREPARATION OF UNSATURATED POLYESTER RESIN FROM A POLYETHER POLYOL... 

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