Unsaturated polyesters additive

Unsaturated Polyesters. There are two approaches used to provide flame retardancy to unsaturated polyesters. These materials can be made flame resistant by incorporating halogen when made, or by adding some organic halogen compound when cured. In either case a synergist is needed. The second approach involves the addition of a hydrated filler. At least an equal amount of filler is used. 

Diacyl peroxides are used in a broad spectmm of apphcations, including curing of unsaturated polyester resin compositions, cross-linking of elastomers, production of poly(vinyl chloride), polystyrene, and polyacrjlates, and in many nonpolymeric addition reactions. 

TriaUyl cyanurate is used as a comonomer in small amounts with methacrylate esters and unsaturated polyesters. The addition of 5% or more of TAC to MMA in castings improves heat and solvent resistance as weU as thermooxidative stabUity (99). For optical appUcations, up to 20% TAC has been suggested. Reactivity ratios for TAC and methacrylate esters have been reported (100). 

Polyester Resins. Reinforced polyester resins are thermosets based on unsaturated polyesters from glycols and dibasic acids, either or both of which contain reactive double bonds. The ratio of saturated to unsaturated components controls the degree of cross-linking and thus the rigidity of the product (see Polyesters, unsaturated). Typically, the glycols and acids are esterified until a viscous Hquid results, to which an inhibitor is added to prevent premature gelation. Addition of the monomer, usually styrene, reduces the viscosity to an easily workable level. 

Unsaturated polyester resin powders can provide a colored and finished exterior molded surface or a finish ready for painting. Normally, a primer/sealer must be appHed to molded articles prior to painting. In addition to the unsaturated polyester resin, multifimctional unsaturated monomers such as triaHyl cyanurate (TAC) [101-37-1] or diaHyl phthalate (DAP) [131-17-9] suitable peroxide initiators (qv) or mixtures thereof, and mold release agents (qv) are used to formulate the coating powder (46). 

An alternative route to cross-linking is to start with a linear polymer and then cross-link the molecules by tying the molecule through some reactive group. For example, it is possible to cross-link unsaturated polyesters by an addition polymerisation across the double bond as shown schematically in Figure 2.12. 

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. 

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. 

High-temperature cement formulations are basically polymer concrete. Mainly unsaturated polyesters or vinyl ester resins with allylphthalate as vinyl monomer are in use [927]. Cming is achieved with peroxides, which decompose sufficiently fast at temperamres between 120° and 200° C. Polymer concrete requires additional materials, which compensate shrinkage. 

Development of the third class, i.e. unsaturated polyester resins, remained rather slow until the late 1930s, but after commercial production of maleic anhydride by catalytic oxidation of benzene began in 1933, maleic anhydride and fumaric acid rapidly became the most important sources of unsaturated groups in polyesters. The mechanism of drying of these resins on their own and with the addition of drying oils (i.e. unsaturated compounds such as linseed oil) was... 

Glycolysis is also conducted to create polyols for unsaturated polyester usage. The PET can be dissolved in DEG to create polyols with ether linkages [30], The reaction can be carried out with propylene glycol [31] or by reacting with an unsaturated dibasic acid [32] and needed additives and catalysts [33],... 

Low-profile additives, which control shrinkage, have emerged as a distinct science and class of additive. Unsaturated polyester resins, as do all thermosetting polymers, shrink when cured. Low-profile additives are a major class of additives used to control shrinkage, which vastly improves surface quality. This science is credited with the opening of automotive markets where surface quality is of prime importance. In exterior automotive body panels, Class A surfaces are required for market acceptance. 

Low-profile additives are generally materials such as poly (vinyl acetate), polystyrene, polyethylene or polycarbonate. During the unsaturated polyester cure cycle, the low-profile additives separate into a second phase, which expand to counteract the shrinkage of the curing unsaturated polyester resin. Material development and the science of low-profile additives have helped create substantial markets for unsaturated polyesters. Their use in automotive markets, where Class A show room quality surfaces is a requirement, is an example of this. 

In addition, fillers can be used for both cost reduction and property modification. Table 21.3 presents some examples of typical fillers and their effects on the unsaturated polyester resin formulation properties. 

There are perhaps hundreds of miscellaneous unsaturated polyester resin construction applications. These would include window frames, doors, cabinet enclosures, electrical boxes, etc. In addition, recent developments bode well for unsaturated polyesters in construction markets. Concrete rebar, bridge construction and general infrastructure repair are examples of growing construction applications. 

Sheet molding compounds (SMCs) and bulk molding compounds (BMCs) are the dominant materials used in automotive applications. These composites of unsaturated polyester resin, fillers and fiberglass have advantages of high stiffness, heat resistance and low coefficient of expansion. Coupled with low creep resistance, which is a distinct advantage over thermoplastic competition, and low-profile additives, which can yield Class A surfaces, these materials are well suited for applications from exterior body panels to under the hood components. 

This technique involves the dispersion of a nanomaterial in a monomer (Fig. 4.8). This step requires a certain amount of time that depends on the polarity of the monomer molecules, the surface treatment of the nanomaterial, and the swelling temperature. For thermoplastics, the polymerization can be initiated either by the addition of an agent or by an increase in temperature. For thermosets such as epoxies or unsaturated polyesters, a curing agent or peroxide can be added in order to initiate the polymerization. Functionalized nanomaterials can improve their initial dispersion in the monomer and consequently in the composites. In the case of layered materials, such as clays or graphene, the most important step is the penetration of the monomer between the sheets, thus allowing the polymer chains to exfoliate the material. The... 

Uses. About 60% of the MA produced is used to make unsaturated polyester and aikyd resins, which are formed by reaction of MA with glycols. Polyester resins are used in the fabrication of glass fiber reinforced parts. Applications include boat hulls, automobile body parts, patio furniture, shower stalls, and pipe. Aikyd resins are mostly used in coatings (paint, varnish, lacquers, and enamels). MA also is widely used as a chemical intermediate in the manufacture of plasticizers and dibasic acids (fumaric, maleic, and succinic). About 15% of MA production goes into the manufacture of viscosity index improvers and dispersants used as additives in lube oils. Several agricultural chemicals are based on maleic anhydride, the best known being Malathion. 

Uses of MA include unsaturated polyester resins (63%), lubricating oil additives (11%), copolymers (8%), alkenyl succinic anhydrides (5%), malic acid (3%), fiimaric acid (2%), and agricultural chemicals (2%). 

The mechanism of reduction of NG absorption in halopolyesters (chloropolyesters and bromopolyesters) and filled unsaturated polyesters and halopolyesters (after addition of fillers) has already been proposed by us [322] and accordingly, techniques for reduction of NG migration have been suggested [323-325]. 

Navale, P.B., Athar, J., Diwakar, R.P., Sadakale, V.G., and Agrawal, J.P. (1999) Unsaturated polyester with melamine based additives for inhibition of DB rocket propellants. Proc. Polymer 99 (Polymers Beyond AD 2000), IIT Delhi, Jan. 12-15,1999, pp. 778-781. 

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