Polymer reaction unsaturated polyester

Thermosetting polymers are usually liquids at room temperature. They are eonverted to solids by combining with other liquid reactants in the presence of liquid or paste catalysts. Heat may be applied to hasten the setting reaction. Unsaturated polyesters constitute the largest volume, followed by polyurethanes and polyureas. Phenol-, urea- and melamine-formaldehyde resins are used in large volumes in laminates, but these contain little or no mineral filler. Epoxies are a relatively low volume market for fillers. 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

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). 

Unsaturated polyesters are a group of polymers and resins used in coatings or for castings with styrene. These polymers normally have maleic anhydride moiety or an unsaturated fatty acid to impart the required unsaturation. A typical example is the reaction between maleic anhydride and ethylene glycol ... 

Although low-molar-mass aliphatic polyesters and unsaturated polyesters can be synthesized without added catalyst (see Sections 2.4.1.1.1 and 2.4.2.1), the presence of a catalyst is generally required for the preparation of high-molar-mass polyesters. Strong acids are very efficient polyesterification catalysts but also catalyze a number of side reactions at elevated temperature (>160°C), leading to polymers of inferior quality. Acid catalysts are, therefore, not much used. An exception is the bulk synthesis of hyperbranched polyesters reported in Section 2.4.5.1, which is carried out at moderate temperature (140°C) under vacuum in the presence of p-toluene sulfonic acid catalyst. The use of strongly acidic oil-soluble catalysts has also been reported for the low-temperature synthesis of polyester oligomers in water-in-oil emulsions.216... 

There are two types of cure reactions of thermosetting resins step (e.g., epoxies, phenolics, urethanes) and chain (e.g., unsaturated polyesters, vinyl esters, acrilates) polymerizations. In the first type, the size of the polymer chain increases because of the linking of the oligomers (e.g., monomers, dimers, etc.) to themselves. Short chains can be linked to long ones in a condensation reaction. In the second case, the size of the polymer chain increases because of... 

In these polyurethane/unsaturated polyester mixtures chemical reactions and physical entanglements proceed simultaneously during processing and in the mold. The final goal of this process is the formation of a polymer composite with interpenetrating networks. These networks provide... 

As a second example, there is a wide variety of breakdown products and oligomeric products that may be formed from the reactive monomers that are the building blocks of plastics. For plastics, the general assumption has been that any side-reaction products and breakdown products are likely to be significantly less toxic than the monomers, and so restricting the migration of the monomer was accepted as an indirect way to limit any hazard from the oligomers also. Whilst this approach is probably acceptable for addition polymers, such as those made from the unsaturated monomers vinyl chloride, butadiene and acrylonitrile where the unsaturated monomer is far more noxious than their products, the validity of this means of indirect control is questionable for condensation polymers such as polyesters and for polyethers formed from epoxide monomers. 

Unsaturated polyesters with terminal hydroxyl or carboxyl groups can also react at the same time with isocyanate groups and a vinyl monomer, such as styrene, to produce hybrid polymers. Two kinds of reactions, the NCO-OH addition reaction and radical polymerization by the vinyl groups, can occur. In parallel to the two reactions, interference between the two reactions also can occur. Detailed studies on the interference reactions were studied by Hsu et al. (190). 

Polyester-based resins are also used in bulk plastics in fiberglass reinforced fabrications such as boats, auto body repairs, and for very large structures such as industrial vessels and pipes, and ships for mine sweeping [10]. This technology uses a combination of polycondensation and vinyl-type (chain reaction) technologies to obtain the final composite product. The viscous, still fluid resin used for layup is a linear unsaturated polyester of relatively low-molecular weight. Unsaturation is introduced into the backbone of the polymer by using maleic anhydride to replace a part of the phthalic anhydride (e.g., Eq. 21.4). 

Since the decomposition reaction occurs at a specific temperature, the performance of these fillers depends on the properties of the polymers in which they are used. For example, Mg(0H)2 performs better in polyethylene than AlfOI I) because it remains stable during compounding and decomposes at a temperature closer to the decomposition of PE (300-400 C). In unsaturated polyesters, Al(0H)3 starts to release water at 200°C. The major endothermic peak occurs at 300°C with a heat of decomposition of 300 kJ/mol. About 90% of the water is released between 200 and 400 C. A considerable amount of heat is absorbed before the polymer is affected. The water also dilutes combustible gases and hinders the access of oxygen to the polymer surface. Figure 12.8 shows the difference between talc and a fire retardant filler in PP." Talc causes an increase in the combustion rate as its concentration increases, whereas Mg(OH)2, used at a sufficient concentration (above 20%), decreases the rate of combustion. 

Morphology. Phase inversion in polymer mixtures occurs when the volume fraction of the dispersed phase becomes equal to or exceeds 0.5 (14). The driving force is to minimize the interfacial energy of the system. This is not the case here because the volume fraction of the rubber-rich phase at phase inversion is about 0.85. After inversion, the fraction of the continuous rubber-rich phase is only 0.28, and it increases to 0.63 at 12.5% rubber content. Initially, the components are fully soluble and compatible, but as the reactions proceed, the molecular weight of the products increases and phase separation results. The ability to separate and invert is dependent on the viscosity of the medium. The unsaturated polyester forms a gel at conversions as low as 2 to 5%, and both the ability to separate and to invert is impeded. Thus the morphology depends on the two competing effects of phase inversion and... 

Other modifications of vegetable oils in polymer chemistry include the introduction of alkenyl functions, the study of novel polyesters and polyethers and the synthesis of semi-interpenetrating networks based on castor oil (the triglyceride of ricinoleic acid) [42], and also the production of sebacic acid and 10-undecenoic acid from castor oil [44]. Additionally, the recent application of metathesis reactions to unsaturated fatty acids has opened a novel avenue of exploitation leading to a variety of interesting monomers and polymers, including aliphatic polyesters and polyamides previously derived from petrochemical sources [42, 45]. 

Crosslinking - Reaction or formation of covalent bonds between chain-like polymer molecules or between polymer molecules and low-molecular compounds such as carbon black fillers. As a result of crosslinking, polymers such as thermosetting resins may become hard and infusible. Crosslinking is induced by heat, UV or electron-beam radiation, oxidation, etc. Crosslinking can be achieved either between polymer molecules alone as in unsaturated polyesters or with the help of multifunctional crosslinking agents such... 

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