Unsaturated polyester thermosetting plastic

Thermosetting unsaturated polyester resins constitute the most common fiber-reinforced composite matrix today. According to the Committee on Resin Statistics of the Society of Plastics Industry (SPl), 454,000 t of unsaturated polyester were used in fiber-reinforced plastics in 1990. These materials are popular because of thek low price, ease of use, and excellent mechanical and chemical resistance properties. Over 227 t of phenoHc resins were used in fiber-reinforced plastics in 1990 (1 3). PhenoHc resins (qv) are used when thek inherent flame retardance, high temperature resistance, or low cost overcome the problems of processing difficulties and lower mechanical properties. 

Thermosets A number of thermosets have been used as adhesives. Phenolic resins were used as adhesives by Leo Baekeland in the early 1900s. Phenolic resins are still used to bind together thin sheets of wood to make plywood. Urea resins have been used since 1930 as binders for wood chips in the manufacture of particle board. Unsaturated polyester resins are used for body repair and PUs are used to bond polyester cord to rubber in tires, and vinyl film to particle board, and to function as industrial sealants. Epoxy resins are used in the construction of automobiles and aircraft and as a component of plastic cement. 

DMTA is a very interesting tool for characterizing heterogeneous materials in which domains of distinct Tg values coexist. The most interesting cases involve modified thermosets of different types (see Chapter 8). Examples are the use of rubbers (e.g., liquid polybutadiene and random copolymers), or thermoplastics (e.g., polyethersulphone or polyetherimide in epoxy matrices or poly(vinyl acetate) in unsaturated polyesters), as impact modifier (epoxies), or low-profile additives (polyesters). The modifier-rich phase may be characterized by the presence of a new a peak (Fig. 11.10). But on occasions there may be superposition of peaks and the presence of the modifier cannot be easily detected by these techniques. If part of the added polymer is soluble in the thermoset matrix, its eventual plasticizing effect can be determined from the corresponding matrix Tg depletion, and the... 

For commodity applications, there are four major classes of resins that are used in FRP applications. They are phenolic resin, epoxy resin, unsaturated polyester resin, and epoxy vinyl ester resins. A more complete description of these types of resins and their many variations can be found in Handbook of Thermoset Plastics. This is not a comprehensive list of resins used in composite manufacture, as commodity materials like polyurethanes and isocyanurate resins are sometimes used as well to make FRP parts. However, these materials are not covered in this chapter owing to their limited use, but, the principals of fire safety that apply for the resins described subsequently apply to these materials as well. 

As a preliminary step in the manufacture of unsaturated polyester thermoset plastic one uses low molecular weight linear polyester (Mr 10,000) obtained by a polycondensation of polyglycols with saturated and unsaturated dicarboxylic acids. The precondensate can then be dissolved and stored in the stabilized comonomer, e.g. styrene, with which it will be crosslinked later. The crosslinking polymerization reaction between the polyester chains and the styrene bridges is initiated with the help of organic peroxides which are added dispersed in plasticizers. The reaction begins at 60-90 °C and then proceeds exothermally. In addition to this a cold hardening reaction can also be carried out. For this reaction cold accelerators are necessary, e.g. tertiary amines or cobalt naphthenate. 

Plastics can be placed into two main categories, thermoplastic and thermoset. Thermoset plastics are irreversibly formed into a permanent shape often by applying heat. Thermosets caimot be softened and remoulded on heating and have few applications in food packaging, except for the iimer linings used for can coatings and many adhesives, as used, for example, in multilayer materials. A limited range of food contact materials is made from thermosets, predominantly melamine resins and unsaturated polyesters used in tableware and utensils. 

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. 

Alkyd resins have been the workhorse for the coatings industry over the last half century. The term alkyd was coined to define the reaction product of polyhydric alcohols and polybasic acids, in other words, polyesters. However, its definition has been narrowed to include only those polyesters containing monobasic acids, usually long-chain fatty acids. Thus thermoplastic polyesters typified by polyethylene terephthalate (PET) used in synthetic fibers, films, and plastics and unsaturated polyesters typified by the condensation product of glycols and unsaturated dibasic acids (which are widely used in conjunction with vinylic monomers in making sheet molding compounds or other thermosetting molded plastics) are not considered as part of the alkyd family and are beyond the scope of the present discussion. 

This chapter will deal with the chemistry and applications of epoxies, phenolics, urethanes, and a variety of current vogue high-temperature polymers. Applications in fiber-reinforced plastics will be discussed in the individual sections on resin chemistry where appropriate. Separate sections will deal with adhesives and sealants. Adhesives are most important because, as early history demonstrates, they led the way to the application of resins in aerospace. A section is also included on silicone and polysulfide sealants. Although these materials are elastomers rather than resins, no discussion of aerospace polymers would be complete without some mention. Some major thermosetting polymers have been omitted from this review. Among these are the unsaturated polyesters, melamines, ureas, and the vinyl esters. Although these products do find their way into aerospace applications, the uses are so small that a detailed discussion is not warranted. 

One of the major uses of diallyl esters is in the preparation of reinforced plastics. In this application, a lyoven fabric or mat prepared from glass or other fibers is saturated with a liquid resin or monomer containing a peroxide catalyst. The liquid resin may be a diallyl ester, a mixture of an unsaturated polyester resin and a vinyl or allyl monomer, or a mixture of monomer and prepolymer. The resih-monomir-fiber combination is placed in a mold and under the influence of heat and pressure is converted to a thermoset reinforced material. The steps are outlined in Fig. 15-42. 

Synthetic thermosets which cure on heating to solids, e.g., amino plastics, epoxides, phenolic resins, unsaturated polyesters, polyaromatics, and furanes. 

Reinforced plastics are composites in which a resin is combined with a reinforcing agent to improve one or more properties of the resin matrix. The resin may be either thermosetting or thermoplastic. Typical thermosetting resins used in RPs include unsaturated polyester, epoxy, phenolic, melamine, silicone, alkyd, and diallyl phthalate. In the field of reinforced thermoplastics (RTFs), virtually every type of thermoplastic material can be, and has been, reinforced and commercially molded. The more popular grades include nylon, polystyrene, polycarbonate, polyporpylene, polyethylene, acetal, PVC, ABS, styrene-acrylonitrile, polysulfone, polyphenylene sulfide, and thermoplastic polyesters. 

The matrix in reinforced plastics may be either a thermosetting or thermoplastic resin. The major thermosetting resins used in conjunction with glass-fiber reinforcement are unsaturated polyester resins and, to a lesser extent, epoxy resins. These resins have the advantage that they can be cured (cross-linked) at room temperature, and no volatiles are liberated during curing. 

Polyester resins (alkyds) were commercialized for coatings use in 1926, and unsaturated polyesters were used as thermoset fiberglass composite matrix resins in the 1940s, but the early resins made poor adhesives. When flexibilized resins appeared in the 1950s, they were used as adhesives. Today, unsaturated polyesters are widely used as adhesives for thermoset plastics bonding, and even for metal bonding in most countries, but are seldom used as adhesives in the United States, where the more expensive epoxy adhesives are used in similar applications. The saturated polyesters, used as thermoplastic hot-melt adhesives, seem to have appeared in the literature first in the 1954—1957 period. 

The term styrenic describes the family of major plastic products that use styrene as their key building-block PS, expanded polystyrene (EPS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), styrene-butadiene rubber (SBR) and unsaturated polyester resin (UP). Among these, UP is the only thermoset and will... 

All TP or TS matrix property can be improved or changed to meet varying requirements by using reinforcements. Typical thermoplastics used include TP polyesters, polyethylenes (PEs), nylons (polyamides/ PAs), polycarbonates (PCs), TP polyurethanes (PURs), acrylics (PMMAs), acetals (polyoxymethylenes/POMs), polypropylenes (PPs), acrylonitrile butadienes (ABSs), and fluorinated ethylene propylenes (FEPs). The thermoset plastics include TS polyesters (unsaturated polyesters), epoxies (EPs), TS polyurethanes (PURs), diallyl phthalates (DAPs), phenolics (phenol formaldehydes/PFs), silicones (Sis), and melamine formaldehydes (MFs). RTSs predominate for the high performance applications with RTFs fabricating more products. The RTPs continue to expand in the electronic, automotive, aircraft, underground pipe, appliance, camera, and many other products. 

The terms reinforced plastics (RP) and composites refer to combinations of plastic materials and reinforcing materials, usually in fiber form (chopped fibers, porous mats, woven fabrics, continuous fibers, etc. see Fig. 7-1). Both thermoset (TS) and thermoplastic (TP) resins are used. When modern RP industry started in 1940, glass-fiber-reinforced unsaturated polyester (TS), low pressure or contact pressure, curing resins were used. Today about 60 percent of the plastics industry uses many different forms of glass fiber-polyester composites. In this chapter the abbreviation RP will be used, and in references to polyester resin it will refer only to TS, as relatively little TP polyester is used in RPs. 

Fibre reinforced plastics. The most wide-spread reinforcement is glass fibre as roving, chopped strand mat, fabric, etc. The most usual matrix materials are unsaturated polyesters and epoxy resins as thermosets. In glass fibre reinforced thermoplastics (e. g. ABS, PA, PPO), the length of the glass fibres is 1 to 3 mm. Other reinforcing fibres are aramide, asbestos, boron, carbon, etc. 

Polyesters. Main chain of their macromolecules is characterized by repeated — CO—O— groups. Unsaturated polyester resins are thermosets used mainly for manufacturing glass fibre-reinforced plastics products. The most wide-spread type of thermoplastic polyesters are polymers of an aromatic dicarboxylic acid (mainly terephthalic acid) and an aliphatic diol (e. g. ethyleneglycol or butanediol). The most important representatives of this group are poly(ethylene terephthalate) and poly-(butylene terephthalate). Polyarylate aromatic polyester is a high-temperature thermoplastic of an aromatic dicarboxylic acid (terephthalic acid) and an aromatic diol (bisphenol-A). In the chemical sense, polycarbonate is also a polyester. 

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