Epoxy resins free radical reactions

The addition—reaction product of bisphenol A [80-05-07] and glycidyl methacrylate [106-91-2] is a compromise between epoxy and methacrylate resins (245). This BSI—GMA resin polymerizes through a free-radical induced covalent bonding of methacrylate rather than the epoxide reaction of epoxy resins (246). Mineral fillers coated with a silane coupling agent, which bond the powdered inorganic fillers chemically to the resin matrix, are incorporated into BSI—GMA monomer diluted with other methacrylate monomers to make it less viscous (245). A second monomer commonly used to make composites is urethane dimethacrylate [69766-88-7]. 

Peroxidic groups in oxidized polyolefins have frequently been employed as sources of free radicals to allow grafting of vinyl monomers to polyolefins (2f[). Some of the products from the gas reactions also have interesting potential as reactive sites. For example, chloroformate groups are well known to react with alcohols, and amines 2J[). Thus chloroformate groups could be useful for example in coupling highly oriented polyolefin fibres to resins such as epoxy based systems. 

Epoxy acrylates are also commonly used as oligomers in radiation-curing coatings and adhesives. However, their name often leads to confusion. In most cases, these epoxy acrylates have no free epoxy groups left but react through their unsaturation. These resins are formulated with photoinitiators to cure via uv or electron beam (EB) radiation. The reaction mechanism is generally initiated by free radicals or by cations in a cationic photoinitiated system. The uv/EB cured epoxy formulations are discussed in Chap. 14. 

Unsaturated poly(ester amide) resins were also prepared by reaction between diglycidyl ether of bisphenol-A-based epoxy and unsaturated aliphatic bisamic acids, using a base catalyst (Fig. 5.4). These resins were then blended with styrene to produce homogeneous resin syrups which were cured by using BPO as the free radical initiator. 

The following unsaturated epoxy compounds have been used to prepare via free-radical initiation several different epoxy resins by reaction with methyl methacrylate, butyl acrylate, acrylic acid, styrene (or mixtures of the latter monomers) [86]. 

A different approach was taken by Touhsaent et al. [2081. These authors synthesized two polymers, one of which formed a network, by simultaneous independent reactions in the same container. They have indicated that intercrosslinking reactions are eliminated by combining free radical (acrylate) and condensation (epoxy) polymerization. By this method, they modified an epoxy resin with poly(n-butyl acrylate) polymer. They have found that a two-phase morphology developed, consisting of co-continuous rubber domains (about 0.1—0.5 p-m) within the epoxy resin. The dimensions of the dispersed rubber phase domains and the extent of molecular mixing between the two components were found to depend on the relative reaction rates (or gel time) with respect to the rate of phase separation. Better mechanical properties resulted when the extent of molecular mixing was minimized and heterophase semi-IPNs were produced. 

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