Xianyi Chen

Synthesis by ATRP of poly(ethylene‐co‐butylene)‐block‐polystyrene, poly(ethylene‐co‐butylene)‐block‐poly(4‐acetoxystyrene) and its hydrolysis product poly(ethylene‐co‐butylene)‐block‐poly(hydroxystyrene)

Diblock copolymers of poly(ethylene-co-butylene) and polystyrene or poly(4-acetoxystyrene) are synthesized by atom transfer radical polymerization (ATRP) using a 2-bromopropionic ester macroinitiator prepared from commercial monohydroxyl functional narrow dispersity hydrogenated polybutadiene (Kraton Liquid Polymer, L-1203). ATRP carried out in bulk and in xylene solution with cuprous bromide and two different complexing agents 2,2′-bipyridine (bipy) and 1,1,4,7,10,10-hexamethyltriethylenetetraamine (HMTETA) yielded well-defined diblock copolymers with polydispersities around 1,3. The diblock copolymer with poly(4-acetoxystyrene) was hydrolyzed to the corresponding poly(4-hydroxystyrene) sequence.

Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization

Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow dispersed materials with phenolic groups which were substantially free from crosslinkages. Gel permeation chromatographic (GPC) analysis of these polymers revealed different extents of molecular weight distribution (MWD) broadening for the hydrolysis products for the different structures. On the other hand, by NaOH catalyzed deprotection, the 4-acetoxystyrene polymers including triblock copolymer poly(4-acetoxystyrene-b-isobutylene-b-4-ace-toxystyrene) suffered from some degrees of coupling or even gelation, except for poly-(styrene-b-4-acetoxystyrene-b-styrene) which also by this method could be conveniently converted to its phenolic product.

Synthesis of 1‐chloro‐1‐phenylethyl‐telechelic polyisobutylene, a new potential macroinitiator by living cationic polymerization

1-Chloro-1-phenylethyl-telechelic polyisobutylene (PIB) was synthesized by living carbocationic polymerization (LCCP). LCCP of isobutylene was induced by a difunctional initiator in conjunction with TiCl4 as coinitiator in the presence of N,N-dimethylacetamide in CH2Cl2/hexane (40:60 v/v) solvent mixture at −78°C. After complete isobutylene conversion a small amount of styrene was added leading to a rapid crossover reaction and thus to the attachment of short outer polystyrene (PSt) blocks to the PIB segment. Quenching the living polymerization of styrene yielded 1-chloro-1-phenylethyl terminal groups. The resulting telechelic polymer (Cl-PSt-PIB-PSt-Cl) is a potential new macroinitiator for atom transfer radical polymerization of a variety of vinyl monomers.