Reactivity groups, anionic copolymerization

The reactivities of substituted monomers are different from those of the unsubstituted ones. For example, in crosspropagation an electron donating methyl group introduced to the C = C bond of a vinyl monomer makes it less reactive in anionic copolymerization, while it increases its reactivity in a cationic process. Thus, in THF at 25 °C the reactivity of isoprene towards polystyrene anion is lower by about a factor of 2 than that of butadiene (only one end of this bivalent monomer is affected),... 

Haddleton, D. M., et al. (1997). Identifying the nature of the active species in the polymerization of methacrylates inhibition of methyl methacrylate homopolymerizations and reactivity ratios for copolymerization of methyl methacrylate/n-butyl methacrylate in classical anionic, alkyUithium/trialkylaluminum-initiated, group transfer polymerization, atom transfer radical polymerization, catalytic chain transfer, and classical free radical polymerization. Macromolecules, 30(14) 3992-3998. 

To the first category belong the homo- and copolymerization of macromonomers. For this purpose, macromolecules with only one polymerizable end group are needed. Such macromonomers are made, for example, by anionic polymerization where the reactive chain end is modified with a reactive vinyl monomer. Also methacrylic acid esters of long-chain aliphatic alcohols or monofunctional polyethylene oxides or polytetrahydrofurane belong to the class of macromonomers. 

Q = 1.4 and e = 0.46 were determined from the results of the copolymerization of the complex monomer 26 with methacrylic acid. The reactivity of the MA anion (Q = 0.9, e = —1.0) was affected by coordination to the Co(III) complex. In other words coordination, decreased the electron density of the vinyl group. 

The maleimide group can undergo a variety of chemical reactions. The reactivity of the double bond is a consequence of the electron withdrawing nature of the two adjacent carbonyl groups which create a very electron-deficient double bond, and therefore is susceptible to homo- and copolymerizations. Such polymerizations may be induced by free radicals or anions. Nucleophiles such as primary and secondary amines, phenates, thiophenates, carboxylates, etc. may react via the classical Michael addition mechanism. The maleimide group furthermore is a very reactive dienophile and can therefore be employed in a variety of Diels Alder reactions. Bisdienes such as divinylbenzene, bis(vinylbenzyl) compounds, bis(propenylphenoxy) compounds and bis(benzocyclobutenes) are very attractive Diels Alder comonomers and therefore some are used as constituents for BMI resin formulations. An important chemical reaction of the maleimide group is the ENE reaction with allylphenyl compounds. The most attractive comonomer of this family is DABA particularly when tough bismaleimide resins are desired. 

A macromonomer is a macromolecule with a reactive end group that can be homopolymerized or copolymerized with a small monomer by cationic, anionic, free-radical, or coordination polymerization (macromonomers for step-growth polymerization will not be considered here). The resulting species may be a star-like polymer (homopolymerization of the macromonomer), a comblike polymer (copolymerization with the same monomer), or a graft polymer (copolymerization with a different monomer) in which the branches are the macromonomer chains. 

Not all monomers are anionically pol5anerizable. Nevertheless, one can take advantage of the activity of the living ends to introduce reactive end groups at the extremity of homopolymers and then use arch end groups to initiate the polymerization of anionically non polymerizable monomers. This method has been applied to the synthesis of copolymere with polyvinyl and polylactone blocks and of copolymers with polyvinyl and polypeptide blocks One can at last use both anionic and cationic polymerization to prepare block copolymers of tetrahydrofuran with styrene or methylstyrene ... 

Takano et al. employed anionic block copolymerization of a monomer with a reactive functional group and an ordinary monomer [256]. The requirement for this procedure is that the functional group has to be unreacted. This is accomplished using THF as a solvent and short reaction times. Since the multifunctional linking agent has been prepared, subsequent reaction with living chains produces miktoarm stars of the type AnB. In this study n = 13, A is PS, and B is poly-(vinylnaphthalene) (Scheme 88). 

Three events are involved with chain-growth polymerization catalytic initiation, propagation, and termination [3], Monomers with double bonds (—C=C—R1R2—) or sometimes triple bonds, and Rj and R2 additive groups, initiate propagation. The sites can be anionic or cationic active, free-radical. Free-radical catalysts allow the chain to grow when the double (or triple) bonds break. Types of free-radical polymerization are solution free-radical polymerization, emulsion free-radical polymerization, bulk free-radical polymerization, and free-radical copolymerization. Free-radical polymerization consists of initiation, termination, and chain transfer. Polymerization is initiated by the attack of free radicals that are formed by thermal or photochemical decomposition by initiators. When an organic peroxide or azo compound free-radical initiator is used, such as i-butyl peroxide, benzoyl peroxide, azo(bis)isobutylonitrile, or diazo- compounds, the monomer s double bonds break and form reactive free-radical sites with free electrons. Free radicals are also created by UV exposure, irradiation, or redox initiation in aqueous solution, which break the double bonds [3]. 

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