Polyester-styrene resins unsaturated

Preparation and Cure of Unsaturated Polyester/Styrene Resin... 

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... 

Bisphenols is a broad term that includes many chemicals with the common chemical structure of two phenolic rings joined together by a bridging carbon. Bisphenol A is a monomer widely used in the manufacture of epoxy and phenolic resins, polycarbonates, polyacrylates and corrosion-resistant unsaturated polyester-styrene resins. It can be found in a diverse range of products, including the interior coatings of food cans and filters, water containers, dental composites and sealants. [4]. BPA and BP-5 were selected for testing by the whole... 

Among the emerging pollutants of industrial origin, Bisphenol A [2,2 bis(4-hydroxydiphenyl)pro-pane] (BPA) has special relevance since it was one of the first chemicals discovered to mimic estrogens as endocrine disrupters.147 This compound was first reported by Dianin in 1891.1411 BPA is produced in large quantities worldwide, mainly for the preparation of polycarbonates, epoxy resins, and unsaturated polyester-styrene resins.149 The final products are used in many ways, such as coatings on cans, powder paints, additives in thermal paper, in dental composite fillings, and even as antioxidants in plasticizers or polymerization inhibitors in polyvinyl chloride (PVC). To a minor extent, BPA is also used as precursor for flame retardants such as tetrabromobisphenol A or tetrabromobisphenol-S-bis(2,3-dibromopropyl) ether.150 This substance can enter the environment... 

Figure 9.1 Cure exotherms for urethane methacrylate/methyl methacrylate resins (a), compared with unsaturated polyester/styrene resins (b)...

The practical consequences of an auto-acceleration effect on exotherm and conversion are illustrated by the exotherm curves in Figure 9.1. The urethane methacrylate/methyl methacrylate resin that shows auto-acceleration at all oligomer/monomer ratios is compared with an unsaturated polyester/styrene resin, which only shows an autoacceleration (or gel effect ) at high alkyd/styrene ratios. The urethane methacrylate oligomer copolymerised with styrene shows virtually the same exotherm behaviour as the unsaturated polyester for equivalent styrene/oligomer unsaturation ratios. 

Other common radical-initiated polymer processes include curing of resins, eg, unsaturated polyester—styrene blends curing of mbber grafting of vinyl monomers onto polymer backbones and telomerizations. 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

The free radicals then initiate curing by attacking residual double bonds in acrylic oligomers and monomers, or in styrene and unsaturated polyester resins. Since most pigments absorb u.v. radiation and can prevent it reaching sufficient photoinitiator molecules, this technique is best suited to transparent coatings or thin pigmented layers (e.g. inks). 

About 8,000 metric tons of peroxides were consumed in 1972. This consumption was strongly stimulated by the rapid growth in reinforced plastics (Ref 23). The largest volume product is benzoyl peroxide which is used in polystyrene and polyester markets for such items as toys, automobiles, furniture, marine, transportation and mil requirements. Also, methyl ethyl ketone peroxide is used in large volumes to cure (as a catalyst) styrene-unsatur-ated polyester adhesive resins used in mil ammo adhesive applications, as well as in glass fiber reinforced plastic products such as boats, shower stalls, tub components, automobile bodies, sports equipment, etc. The monoperesters are growing slowly because of some substitution of the peroxydicarbonates and azo compds (Refs 8,9 23)... 

For example, the molecular weight of unsaturated polyesters is controlled to less than 5000 g/mol. The low molecular weight of the unsaturated polyester allows solvation in vinyl monomers such as styrene to produce a low-viscosity resin. Unsaturated polyesters are made with monomers containing carbon-carbon double bonds able to undergo free-radical crosslinking reactions with styrene and other vinyl monomers. Crosslinking the resin by free-radical polymerization produces the mechanical properties needed in various applications. 

The unsaturated polyester-styrene combination, is used as the resin matrix, in Fibre-reinforced plastics (FRP) structures. These resins also find use as decorative coatings. 

Maleic anhydride [R1 equals -CH=CH- in Eq. (2.7) cis isomer] is reacted with aliphatic diols to form low molar mass unsaturated polyesters, UP. For molar masses higher than 1000 g/mol, products are diluted with a liquid vinyl monomer, most often styrene. This reactive mixture, generally called unsaturated polyester, UP resin, can be transformed into crosslinked polymers through a free-radical chain polymerization (see Sec. 2.3). 

Figure 8.3 Phase diagram for styrene (S)-unsaturated polyester (UP) prepo-lymer-PVAc ternary blends at T = 23°C,-D- UP Mn = 1690 g.moMand Mw/ Mn = 7.5 -o- UP Mn = 1480 g.mor1 and Mw/ Mn = 3.1. The dashed triangle represents the formulation range of typical industrial UP resins. (Reprinted from Suspene et al., 1991, Copyright 2001, with permission from Elsevier Science)...

Thermoset plastics have also been pyrolysed with a view to obtain chemicals for recycling into the petrochemical industry. Pyrolysis of a polyester/styrene copolymer resin composite produced a wax which consisted of 96 wt% of phthalic anhydride and an oil composed of 26 wt% styrene. The phthalic anhydride is used as a modifying agent in polyester resin manufacture and can also be used as a cross-linking agent for epoxy resins. Phthalic anhydride is a characteristic early degradation product of unsaturated thermoset polyesters derived from orf/io-phthalic acid [56, 57]. Kaminsky et al. [9] investigated the pyrolysis of polyester at 768°C in a fiuidized-bed reactor and reported 18.1 wt% conversion to benzene. 

The efficiencies of benzoin derivatives in promoting the light induced hardening of styrene-containing unsaturated polyester resins have been found to vary considerably (7), benzoin alkyl ethers and a-alkylated benzoins being more reactive than benzoin itself. However, as photoinitiators for the polymerization of bulk methyl methacrylate, benzoin and benzoin methyl ether exhibit comparable efficiencies (20), and this is also indicated for polymerisation of methyl acrylate in tert-butanol (21). The relative photoinitiating efficiencies of benzoin derivatives may be influenced by several factors, some of which will depend on the nature of the monomer system and the environment in which the polymerizations are carried out. 

For laboratory use and, perhaps, for small-volume production, another first stage can be added. Microreactors, which require much less solvent, are being studied for fluorina-tion,6 DNA chips, and other uses.7 A variation on item 2 is the use of a polyhydroxyester based on aromatic epoxy resins and aliphatic carboxylic acids to reduce the loss of styrene from unsaturated polyester resins by 95-99%.8... 

Since the cross-linking of polyester-styrene system occurs by a free-radical chain-reaction mechanism across the double bonds in the polyesters with styrene providing the cross-links, the curing reaction does not give rise to volatile by-products (unlike phenolic and amino resins) and it is thus possible to cure without applying pressure. This fact as well as that room temperature cures are also possible makes unsaturated polyesters most useful in the manufacture of large structures such as boats and car bodies. 

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