Carboxylate-terminated poly methyl

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Carboxylated polyesters were prepared by extending hydroxyl-terminated polyester segments with dianhydrides. Carboxylated polyesters which were soluble in common lacquer solvents were effective in improving the adhesion of coatings on a variety of substrates when 1-10% was blended with cellulose acetate butyrate, poly(vinyl chloride), poly(methyl methacrylate), polystyrene, bisphenol polycarbonates, and other soluble polymers. 

Polypropylene imine) dendrimers (see Scheme 1 for structure) have been constructed step by step onto an amine functionalized polystyrene [38, 130, 131]. The challenge in this synthesis is finding conditions for the polypropylene imine) synthesis under which the low MW polystyrene (MW=3200) is soluble [38]. Similar poly(imine) dendrimers with carboxylic acid end groups have also been prepared [130]. The polypropylene imine) dendrimer has also been synthesized on an amino-terminated poly(2-methyl-2-oxazoline) [132]. 

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. ... 

Previous extensive studies of carboxylic acid functionalized poly(ethylene) films (PE—CO2H) [207-209], of SAMs terminated in ionizable acids and bases [100], of mixed SAMs of carboxylic acid- and methyl-terminated alkanethiolates [210], and of SAMs of dialkyl sulfides on gold [211] have established the utility of contact angle titration in characterizing the wetting properties of interfaces. We... 

The synthesis, starting from a bifunctional initiator followed by quenching the double-headed living ends, gives homotelechelic polymers (method B). Carboxylate-capped telechelic poly(isobutyl vinyl ether) has been obtained in this way [82], where the adduct of a bifunctional vinyl ether with trifluoroacetic acid is the initiator, and the quencher is the malonate anion. For method C, a bifunctional trimethylsilyl enol ether, CH2=C[OSi(CH3)3]C6H4OCH2CH20C6H4[(CH3)3SiO]C=CH2, is a useful terminator (chain coupler) for vinyl ethers [142,147] and a-methyl-styrene [159] (see also Section VI.B.4). 

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... 

In the same way, Oishi et al. [256] used IEM to functionalize oligomers carrying an acid function obtained by polymerization of chiral acrylamides. Chiral polyacrylamide macromonomers were synthesized from 2-methacryloyloxyethyl isocyanate and prepolymers, i.e., poly[(S)-methyl-benzyl acrylamide] or poly(L-phenylalanine ethylester acrylamide) with a terminal carboxylic acid or hydroxyl group. Radical homopolymerizations of polyacrylamide macromonomers were carried out under different conditions to obtain the corresponding optically active polymers, as shown in Scheme 52. 

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