Free-radical chain copolymerizations

The most common and most versatile technique for the production of synthetic hydrogels is the free radical (chain) copolymerization of monofunctional and multifunctional vinyl monomers. Gels can also be created by the step (e.g., con-... 

Typical Free Radical Chain Copolymerization Reactivity Ratios at 60°C... 

Table 4 Typical free-radical chain-copolymerization reactivity ratios...

Unlike the polyurethanes and other previously discussed mortars, polyester cements are produced by a free radical chain copolymerization of a liquid unsaturated polyester and styrene. While most polyester composites are reinforced by fiber glass, polyester mortars are usually filled with silica, clay or alumina trihydrate (ATH). 

Despite numerous efforts, there is no generally accepted theory explaining the causes of stereoregulation in acryflc and methacryflc anionic polymerizations. Complex formation with the cation of the initiator (146) and enoflzation of the active chain end are among the more popular hypotheses (147). Unlike free-radical polymerizations, copolymerizations between acrylates and methacrylates are not observed in anionic polymerizations however, good copolymerizations within each class are reported (148). 

Photoinduced free radical graft copolymerization onto a polymer surface can be accomplished by several different techniques. The simplest method is to expose the polymer surface (P-RH) to UV light in the presence of a vinyl monomer (M). Alkyl radicals formed, e.g. due to main chain scission or other reactions at the polymer surface can then initiate graft polymerization by addition of monomer (Scheme 1). Homopolymer is also initiated (HRM-). 

In this section, the important concepts related to the formation of hydrogels by free radical copolymerization/cross-linking are examined. Greater depth beyond the scope of this chapter can be obtained from textbooks on polymer chemistry and the papers cited herein. As stated earlier, almost all gels produced from monomers for pharmaceutical applications are synthesized by free radical chain polymerizations. 

The polymerization of a mixture of more than one monomer leads to copolymers if two monomers are involved and to terpolymers in the case of three monomers. At low conversions, the composition of the polymer that forms from just two monomers depends on the reactivity of the free radical formed from one monomer toward the other monomer or the free radical chain of the second monomer as well as toward its own monomer and its free radical chain. As the process continues, the monomer composition changes continually and the nature of the monomer distribution in the polymer chains changes. It is beyond the scope of this laboratory manual to discuss the complexity of reactivity ratios in copolymerization. It should be pointed out that the formation of terpolymers is even more complex from the theoretical standpoint. This does not mean that such terpolymers cannot be prepared and applied to practical situations. In fact, Experiment 5 is an example of the preparation of a terpolymer latex that has been suggested for use as an exterior protective coating. 

The free radical initiated copolymerization of CH2CHOAc with CO has been reported 25>. Copolymers with up to 30 mol% CO were obtained. At 60 °C, the monomer reactivitry ratios were rVA = 0.24, rco = 0.33. The magnitude of rc0 indicated the possibility of the presence of vicinal CO groups in the polymer chain. Indeed, the results of a periodate oxidation of the copolymer showed that 30 % of the CO were present in 1,2-diketo structures. The acetate groups in the copolymer could be hydrolyzed in the presence of methanolic NaOH. However, the IR and the UV-vis spectra of the hydrolyzed copolymer showed the presence of significant amounts of a,P-unsaturated carbonyl structures, formed by the base induced dehydration. 

Comparison of the Two Reactions Step-Growth Polymerization in More Detail Making PET in the Melt Interfacial Poly condensation Chain-Growth Polymerization in More Detail Free Radical Chain Polymerization Going One Step Better Emulsion Polymerization Copolymerization Ionic Chain Polymerization It Lives ... 

The free-radical chain polymerization of maleimides and the iV-substitnted derivatives has been extensively and both homo- and copolymerization... 

The two monomers enter into the copolymer in overall amounts determined by their relative concentrations and reactivities. The chain copolymerization may, however, be initiated by any of the chain initiation mechanisms, namely, free-radical chain initiations considered in the preceding chapter, or ionic chain initiations, which will be described in a later chapter. Chain copolymerizations involving more than two monomers are generally referred to as multicomponent copolymerizations. For systems of three monomers, the specific term terpolymerization is commonly used. 

To predict the course of a copolymerization we need to be able to express the composition of a copolymer in terms of the concentrations of the monomers in the reaction mixture and the relative reactivities of these monomers. In order to develop a simple model, it is necessary to assume that the chemical reactivity of a propagating chain (which may be free-radical in a radical chain copolymerization and carbocation or carboanion in an ionic chain copolymerization) is dependent only on the identity of the monomer unit at the growing end and independent of the chain composition preceding the last monomer unit [2-5]. This is referred to as the first-order Markov or terminal model of copolymerization. 

The maleimide group in BMI can undergo a wide range of possible reactions, either in the neat resin or copolymerized, with other monomers. The predominant reaction is the free radical chain reaction of the double bond ([20, 21] and references therein), which, due to the difunctionality of BMI monomers, results in a crosslinked three-dimensional network. Maleimides have been shown to undergo copolymerization with a number of monomers including methyl methacrylate [22, 23], styrene [22-24], acrylonitrile [22] and... 

The analysis of copolymer composition in Section 4.6.4.1 has been carried out using the terminal model which assumes that radical reactivity is solely determined by the terminal unit on the free-radical chain. The terminal model has been successfully applied to represent the monomer and copolymer compositions for a wide variety of systems, mostly studied at ambient pressure. This model is, however, not capable of describing both copolymer composition and copolymerization kinetics with a single set of reactivity ratios [63]. 

The copolymerization of hydrophobically modified monomers should exhibit similar behavior, but opposite in direction to ionogenic monomers. Increasing hydrophobe size and solubility diflPerences with the nonionic monomer should make it difficult to obtain significant spacings between hydro-phobic monomers in chain-growth copolymerizations. In view of what has been delineated in surfactant-micelle (40) and ionogenic monomer behaviors, a multitude of unique structural possibilities could be obtained in hydrophobically modified copolymers synthesized by free-radical chain-growth processes. 

Anionic copolymerizations have been investigated by applying the classical Mayo-Lewis treatment which was originally developed for free-radical chain reaction polymerization [198]. The copolymerization of two monomers (Mj and M2) can be uniquely defined by the following the four elementary kinetic steps in Scheme 7.21, assuming that the reactivity of the chain end (Mj" or ) depends only on the last unit added to the chain end, that is, there are no penultimate effects. 

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