Polymers, methacrylates allyl functionalized

Allyltri-n-butylstannane (EC-2) similarly terminates the copper-catalyzed polymerization of MA to give allyl-functionalized polymers via elimination of the stannyl group accompanying the bromine originated from the dormant polymer terminal.346 Allyl a -end PMMA was obtained also by the copper-catalyzed reaction between allyl bromide (EC-3) and the isolated bromine-capped PMMA, although the functionalization was 57%.226 Another allyl derivative (EC-4) similarly leads to methacrylate-based macromonomers quantitatively in the presence of Cu(0).347... 

This involves the use of the Charlesby-Pinner (CP) (22-24) treatment which describes the determination of the gel firaction of the polymer as a function of radiation dose. Figures 4(a) and 4(b) illustrate that pofymers with structures as those shown for Polymers 1 and 2 crosslink when exposed to Co radiation. Polymer 1 has been synthesized with approximately 7 % of the allylic substituent, while the thesis of polymer 2 allowed for 3-4% of the same allylic group. Glass transition temperatures for these pofymers are not quite that of conventional resists such as polymethyl methacrylate (> 100°C), and it is speculated that as allyl content is ino-eased, Tgs will decrease slight. ... 

Well-defined macromonomers of poly(BVE), poly(IBVE), and poly(EVE) with co-methacrylate end group [91] were prepared by living cationic polymerization of the corresponding monomers initiated by trifluoromethanesulfonic add in CH2C12 at -30 °C in the presence of thiolane as a Lewis base. After complete conversion, the polymers were quenched with 37 in the presence of 2,6-lu-tidine or with 41 to produce macromonomers with Mn up to 10,000 g mol-1, with narrow MWD, bearing one polymerizable methacrylate function per molecule. The same polymers were also quenched with 38 in the presence of 2,6-lutidine to give poly(vinyl ether)s with an allylic terminal group. 

Silyl group transfer can also be used to functionalize chain ends. For example, allyl silanes, silyl ketene acetals, and silyl enol ethers [301-304] generate polymers with terminal allyl and methacrylate groups [Eq. (103)]. This type of transfer becomes degradative (termination) if reinitiation with silyl halides is not possible. 

Lipase catalysts have been used for functionalization of polymers. A terminal hydroxy group of poly-(e-CL) was reacted with carboxylic acids using lipase CA catalyst to give end-functionalized polyesters.231 Lipase MM catalyzed the regioselective transesterification of the terminal ester group of oligo (methyl methacrylate) with allyl alcohol.232 In the PPL-catalyzed reaction of racemic 2,2,2-trichloroethyl 3,4-epoxybutanoate with hydroxy-terminated PEG, the... 

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-... 

By far the acrylates are the monomers of choice in UV curable systems. Not only do they cure at extremely rapid rates compared to other monomer systems (acrylic > methacrylic > vinyl > allylic), but they are also available in a wide range of structures which are monofimctional, difunctional, trifunctional, and tetrafunctional. Additionally, as shown in the oligomer section, acrylates can be used to derivatize oligomers or pre-polymers. Commonly in UV curable formulations it is necessary to use a number of monomers in order to achieve a balance between speed of cure and properties of the final film. It is not unheard of to use four or five monomers in a single UV curable formulation. For instance, tri- and tetra-functional acrylates result in highly crosslinked films when incorporated into UV curable resins however, they severely limit the extent and rate of the curing process. Thus, one often combines a tetrafunctional acrylate to increase crosslink density with a mono and/or difunctional acrylate to increase the cure rate. 

The hydrosilylation reaction has also been employed in the reverse way. A poly(dimethyl-siloxane) backbone exhibiting a number of silane (Si-H) functions is reacted with a polystyrene or a poly(methyl methacrylate) fitted at its chain end with allyloxy groups. The latter species can be obtained readily by reacting a living anionic polymer first with oxirane and then with allyl bromide. The hydrosilylation reaction yields poly(dimethylsiloxane- ra/t-styrene) or poly(dimethylsiloxane-graft-mQthyl methacrylate), which have been characterized as such. They exhibit typical behavior of thermoplastic elastomers over a rather broad range of compositions. ... 

As stated in section I, the termination mode of the particular monomer determines the number of functionalities per macromolecular chain. Most monomers undergo both unimolecular and bimolecular termination reactions. It is often observed that both respective monofunctional and bifunctional polymers are formed and well-defined functional polymers cannot be prepared. The use of allylmalonic acid diethylester in free-radical polymerization has been proposed to overcome the problems associated with the aforementioned functionality. In the presence of the allyl compound, the free-radical polymerization of monomers, regardless of their termination mode, proceeds entirely with the unimolecular termination mechanism, as shown in Scheme 9. Because allyl compounds lead to degradative chain transfer, the resulting allyl radical is quite stable due to the allyl resonance. Monofunctional polystyrene, polyvinylacetate, and poly(t-butyl methacrylate) were prepared by using this approach [33]. Subsequently, various macromonomers were derived from these polymers. 

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