Group transfer polymerization graft copolymers

Group-Transfer Polymerization. Living polymerization of acrylic monomers has been carried out using ketene silyl acetals as initiators. This chemistry can be used to make random, block, or graft copolymers of polar monomers. The following scheme demonstrates the synthesis of a methyl methacrylate—lauryl methacrylate (MMA—LMA) AB block copolymer (38). LMA is CH2=C(CH2)COO(CH2) CH2. 

Aldol group transfer polymerization of ferf-butyldimethylsilyl vinyl ether [62] was initiated by pendant aldehyde functions incorporated along a poly(methyl methacrylate) (PMMA) backbone [63]. This backbone was a random copolymer prepared by group transfer polymerization of methyl methacrylate (MMA) and acetal protected 5-methacryloxy valeraldehyde. After deprotection of the aldehyde initiating group, polymerization proceeded by activation with zinc halide in THF at room temperature. The reaction led to a graft copolymer with PMMA backbone and poly(silyl vinyl ether) or, upon hydrolysis of the ferf-butyldimethylsilyl groups, poly(vinyl alcohol) branches. 

Following quantitative methylation of the co-fert-chloro site by trimethyl aluminum, the methylated polyisobutylene methacrylate macromonomer was co-polymerized with MMA by Group Transfer Polymerization [87]. PMMA-g-PIB graft copolymers with controlled MW and composition were obtained. The structure and physical properties were determined by the [MMA]/[MA-PIB] and [MMA]/[Initiator] ratios. 

After synthesis, the methacryloxy-terminated PDMS macromonomers were purified, and the macromonomers were copolymerized with methyl methacrylate using free-radical, anionic, and group transfer polymerization. Detailed descriptions of the polymerization are provided by DeSimone (1990) and Hellstern (1989). In addition to well-defined graft copolymers, there is... 

Figure 9.17 Experimentally determined CCD profiles for PMMA-g-PDMS copolymers prepared by group transfer polymerization using 20,000 molecular weight grafts (A) Hexane extracted before fractionation and (B) Hexane extracted and CO2 extracted before fractionation (tabulated data in Hellstern, 1989).

The triflated polysilanes were also used to initiate the polymerization of methyl methacrylate by group transfer polymerization. The initiation sites were prepared in-situ using equimolar amounts of triflic acid and arylsilanes, methyl-propionate and triethylamine. Tris(dimethylaminosulfonium) bifluoride was the catalyst. It was found by degradation studies that each polysilane chain contains on average 2.7 PMMA branches. No additional details were reported on the characterization of these graft copolymers. 

Trimethyl-5-chloro-l-hexyl methacrylate was used as initiator for the polymerization of isobutylene, leading to macromonomers with methacrylate end-groups [185]. Group transfer polymerization of these macromonomers with MMA provided P(MMA-g-isobutylene) graft copolymers (Scheme 53). 

More examples concerning the synthesis of macromonomers by group transfer polymerization and the subsequent formation of graft copolymers are given in Table 4. 

Table 4. Graft Copolymers Prepared by Macromonomers Synthesized by Group Transfer Polymerization...

Emulsion polymerizations of vinyl acetate in the presence of ethylene oxide- or propylene oxide-based surfactants and protective coUoids also are characterized by the formation of graft copolymers of vinyl acetate on these materials. This was also observed in mixed systems of hydroxyethyl cellulose and nonylphenol ethoxylates. The oxyethylene chain groups supply the specific site of transfer (111). The concentration of insoluble (grafted) polymer decreases with increase in surfactant ratio, and (max) is observed at an ethoxylation degree of 8 (112). 

If (P ) is terminated by a chain transfer to a solvent or a monomer, a graft copolymer is formed, or, if the termination is from a combination, a crosslinked network polymer is formed. If the pre-existing polymer (B) contains an end group that itself is photosensitive (or can produce a radical by interacting with photoinitiator) and in the presence of a vinyl monomer (A), block copolymer of type AB can be produced if the photosensitive group is on one end of the polymeric chain. Type ABA block copolymer can be produced if the polymer chain (B) contains a photosensitive group on both ends. 

The isopropyl group discourages P-H transfer, leading to the exclusive formation of Al-PEs. The Al-PEs can be readily transformed to a variety of functionalized PEs and to PE-based and polar polymer-based block and graft copolymers, using established methods. The selective synthesis of vinyl- and Al-terminated PEs with Zr-FI catalysts shows the critical importance of the substituent on the imine-N for polymerization catalysis. 

Free radical polymerization of styrene, of acrylate and of methacrylate monomers in solutions at 60° C in the presence of this preformed polymer produced graft copolymers in high efficiency, the chain transfer constants for these mercapto groups with styrene and methyl methacrylate being similar to those found with simple mercaptans (80, 85). 

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