Macromonomers, poly methacrylate terminated

Kaneko et al. have reported the preparation of EPR macromonomers, which is useful to synthesize PMMA-g-EPR graft copolymers [106]. Graft copolymers possessing a poly(methacrylate) backbone and EPR branches were successfully synthesized by the copolymerization of EPR macromonomers with MMA. Methacryloyl terminated EPR, which were EPR macromonomers, were prepared by the sequential end functionalization of EPRs with vinylidene end group via hydroalumination, oxidation, and esterification (Fig. 20). The ATRP method can be used for the copolymeriza-... 

Block-Type Brushes by Sequential Polymerization The sequential hving polymerization of two macromonomers or a macromonomer with a conventional comonomer forms either block-block- or block-coil-type brush structures. For example, giant rod-coil amphiphilic block copolymer bmshes were prepared via a stepwise metallocene-catalyzed polymerization [58]. In the first step, a concentrated solution of methacryloyl end-functionalized PS macromonomer (DP = 18.3, MWD = 1.05) was polymerized by the organosamarium(iii) catalyst in THF. After PS macromonomer was completely consumed, the active center remained living, and tert-butyl methacrylate tert-butyl methacrylate (tBMA) as a comonomer was added to grow the second block. After termination by ethanol, the poly(tert-butyl methacrylate) (PtBMA) coil block was hydrolyzed into a hydrophihc block, poly(methacrylic acid) (PMAA). The final product consisted of a hydrophobic PS brush block and a hydrophihc PMAA coil. The hydrophilic PMAA coil collapsed in nonpolar solvents, which forced the block-coil CPBs to self-assembled into giant micelles with PMAA as the core component and the stiff PS brush block as the shell to stabihze the micelles. 

MethacrylatE-terminated poly(L-lacUc acid) macromonomer, Mn=2800 Methacrylate-terminated poly(D,L-lactlc acid) macromonomer, M,=3350 2-Hydroxyethyl methacrylate 2-Acetoxyethyl methacrylate... 

Methacrylate-terminated poly(L-lactic acid) macromonomer, Mn=4500 Acrylate-terminated poly(L-lactic acid) macromonomer, M =26W 82-Hydroxyethyl acrylate DPE dipheiryl ether Determined by Jaacks method... 

Star polymers exhibiting three different branches (PS, PDMS, and poly( er -butyl methacrylate) were prepared in a similar way, the first being the preparation of PDMS macromonomers containing a terminal nonpolymeriz-able DPE entity. Thus, a living PS is reacted with the PDMS macromonomers to create active sites on DPE. These sites served subsequently as initiators for the anionic polymerization of tert- mXy methacrylate [89]. Stadler and coworkers have used that reaction to generate polystyrene-arm-polybutadiene-arm-poly(methyl methacrylate) [90]. 

Comb-shaped polymers are derived from polymerizing or copolymerizing macromonomers. Macromonomers can be synthesized by a variety of synthetic techniques. Asami and co-workers prepared a methacrylate-terminated polystyrene by anionic polymerization. The macromonomer was then polymerized using GTP [41] to yield an oligomer with a polystyrene backbone and PMMA grafts. McGrath and co-workers prepared a poly(dimethyl siloxane) macromonomer end-capped with a methacrylate group. This macromonomer was polymerized by GTP to yield a comb-shaped polymer with PDMS branches [19]. 

A methacryl-type polyester macromonomer was synthesized by lipase PF-catalyzed polymerizahon of DDL using vinyl methacrylate as terminator ( terminator method ), in which the vinyl ester terminator was present from the beginning of the reachon (Scheme 17). In using divinyl sebacate as terminator, the telechelic polyester having a carboxylic acid group at both ends was obtained. Various non-protected thiol compounds were used as inihator or terminator for the thiol end-funchonalizahon of poly(8-CL). ... 

A similar procedure was also used for the synthesis of methacrylate functional poly(a-MeS) [80]. Thus, 31 was used in conjunction with SnBr4 in CH2C12 at -78 °C, to obtain the macromonomer with Mns substantially (-50%) higher than the theoretical value. This was probably due to the formation of terminated low MW oligomers with indanyl end group structure. The eliminated proton was as-... 

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. 

Pentadienyl-terminated poly(methyl methacrylate) (PMMA) as well as PSt, 12, have been prepared by radical polymerization via addition-fragmentation chain transfer mechanism, and radically copolymerized with St and MMA, respectively, to give PSt-g-PMMA and PMMA-g-PSt [17, 18]. Metal-free anionic polymerization of tert-butyl acrylate (TBA) initiated with a carbanion from diethyl 2-vinyloxyethylmalonate produced vinyl ether-functionalized PTBA macromonomer, 13 [19]. 

No general method for naming macromonomers has been proposed so far, so that there is a great variety of terms used. Throughout this review we always clearly state the nature of the polymeric chain and the nature of the terminal polymerizable function. For instance, co-methacryloyl-polytetrahydrofuran refers to a poly-THF chain bearing at the chain end a methacrylic ester function. 

CCT of benzyl methacrylate leads to a mixture of poly(benzyl methacrylate) macromonomers from which the dimer macromonomer could be isolated.516 When the benzyl dimer is used as a RAFT chain-transfer agent, PMMA with a- and co-terminal benzyl methacrylate units is obtained. Catalytic hydrogenation of the a,co-benzyl terminal methyl methacrylate polymer results in the evolution of toluene and formation of a,co-dicarboxyl functional telechelic PMMA. 

Poly(2-alkyl oxazoline)s having methacrylate or acrylate end groups were prepared by two methods [182]. a) Living polyoxazoline chains, prepared using methyl p-toluene sulphonate as initiator, were end-capped by reaction with metal salts or tetraalkylammonium salts of acrylic or methacrylic acid or a trialky-lammonium salt or trimethylsilyl ester of methacrylic acid (functional termination). b) The living polymers were terminated with water in the presence of Na2C03 to provide hydroxyl-terminated chains. Subsequent acylation with acry-loyl or methacryloyl chloride in the presence of triethylamine led to the formation of the macromonomers. The procedures are outlined in the following Scheme 51. 

The exo-olefin is a precursor to a variety of chain-end-functionalized polymers via postpolymerization reaaions as shown in Scheme 37. Hydroxy-functionalized PIB has been utilized as a precursor for the preparation of RAFT macromo-lecular CTAs and carboxylic acid end-fimctionalized polymers. Telechelic PIB diols have been prepared using p-dicumyl chloride/BCU initiator system followed by dehydro-chlorination, hydroboration, and alkaline peroxide oxidation. Aldehyde end-fiinctionalized PIBs have been used to prepare carboxyl- and hydroxyl-terminated poly-mers. Carboxylic acid-functionalized PIBs have also been prepared from the oxidation of the methyl ketone-functionalized PIBs." The hydroxyl-functionalized PIBs have also been used to prepare methacrylate macromonomers by their reaction with methacryloyl chloride in the presence of triethylamine. The homopolymerization and copolymerization of these maaomonomers with methyl methacrylate were also reported. Cyanoacrylate-funaionalized PIBs prepared via the hydroxyl-functionalized PIB were also reported by Kennedy et al. ... 

Single-step synthesis of polyester macromonomers was achieved by lipase-catalyzed polymerization of lactones in the presence of vinyl esters acting as terminator ( terminator method ) (187,188). A methacryl-type poly(DDL) macromonomer was obtained using vinyl methacrylate (12.5 or 15 mol% based on DDL) and lipase PF as terminator and catalyst, respectively. By the addition of divinyl sebacate, the telechelic polyester having a carboxylic acid group at both ends was synthesized. 

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