Macromonomers polymerizable double bond

If the DC photoiniferter having a polymerizable double bond, i.e., a monomer iniferter, is successively used as both monomer and iniferter, macromonomers and graft copolymers would be obtained according to Eq. (54) [188] ... 

All these cationic deactivation processes were performed with oxolane as the monomer and with various initiators such as triethyloxonium tetrafluoroborate and benzoyl, acetyl or propionyl hexafluoroantimonate. Efficient difunctional cationic initiators such as adipoyl- or terephthaloyl hexafluoroantimonate) can also be used 42 to synthesize bifunctional macromonomers containing at both chain ends a polymerizable double bond. 

Our team also realized the synthesis of macromonomers with a polymerizable double bond by using peculiar transfer agents. For instance, telomeriza-tions of (meth)acrylates were performed in the presence of cysteamine, i.e., thiol with an amine group, leading to PMMAs with an amine at the chain end [253]. However, amines enable the Michael addition onto the double bond activated by the carbonyl group. Hence, before performing the telom-erization, the amine group is protected (chlorhydrate salt) and recovered by a simple basification of the solution (Scheme 48). 

The polymerizable double bond may be obtained by functionalizing the amine with a monomer such as methacrylate glycidyl ether or isocyanoethyl methacrylate (IEM), i.e., reaction of amine with an epoxy or isocyanate group. We chose to functionalize the amine by using maleic anhydride to get highly stable (thermally) maleimide macromonomers [162], as shown in Scheme 49. 

Like the telomerization process, ATRP enables the synthesis of two different types of macromonomers either with a polymerizable double bond or with a polycondensable group. As depicted in Sect. 3.1 on the design of the macromonomers, the polycondensable groups also comprise groups that afford ring-opening polymerization. 

Synthesis of Macromonomers with a Polymerizable Double Bond... 

Scheme 64 Different routes to obtain macromonomers with a polymerizable double bond 3.4.1.1...

The critical survey of the research work carried out in the field of macromonomers exemplifies the great variety of the approaches that have been chosen for the synthesis of these macromolecules fitted with polymerizable terminal groups mostly carbon-carbon double bonds. 

End-functionalized polymers with polymerizable groups such as double bonds and heterocycles of course provide macromonomers allyl, vinyl ester, vinyl ether, lactone, and epoxy are examples of such a category whose a-ends are not susceptible or have little susceptibility to metal-catalyzed radical polymerization. As discussed above, for example, allyl chloride and bromide (FI-33 and FI-34) are effective initiators to be used for styrene with CuCl and CuBr catalysts,161 while allyl compounds with remote halogens such as FI-35 and FI-36 allow the polymerization of methacrylates with high initiation effi-... 

Macromolecular monomers or macromonomers are ohgomers or polymers having a polymerizable functional group at the end of chain. The double bond allows copolymerization reactions in which the length and the number of grafts obtained can be controlled. Macromonomers can be synthesized by ionic route but also by radical route as discussed below. 

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