Synthesis of comb‐shaped poly(methyl methacrylate)‐b‐poly(polytetrahydrofuran acrylate) under ⁶⁰Co γ‐ray irradiation

Abstract

Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under 60Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under 60Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]0/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002

Syntheses and Characterizations of Block Copolymers Prepared via Controlled Radical Polymerization Methods

“…For example, in order to prepare comb-shaped copolymers with a handle as shown in Scheme 3.13 [74], the following polymerization steps were adopted. The first step is to create a comb polymer by the homopolymerization of poly(tetrahydrofuran) acrylate (PTHFA) at room temperature using LPI-6 as initiator.…”

“…After isolation and purification, the PTHFA-SC(S)Ph polymer obtained was used as macroinitiator in the successive polymerization of MMA at room temperature under 60 Co irradiation, forming a PMMA handle block. A block copolymer LPB-8 with controlled branch chain length and number of grafts was obtained [74]. The PTHFA macromonomers were synthesized by the cationic ring-opening polymerization of tetrahydrofuran (THF) with acryloyl chloride/AgClO 4 as initiator.…”

A Novel Strategy to Synthesize Double Comb‐Shaped Water Soluble Copolymer by RAFT Polymerization

“…[2][3][4] Several articles on the controlled free radical polymerization of macromonomers have been published. [18][19][20][21] The ATRP of the macromonomer polyvinyl ether terminated methacrylate proceeded in a living fashion and gave products with fairly narrow polydispersities (M w =M n ). [18] However, the researchers did not mention whether they obtained pure polymacromonomers; all gel permeation chromatography (GPC) traces showed mixtures of the macromonomer and its polymers.…”

“…In our previous investigation, pure comb-shaped poly(polytetrahydrofuran acrylate) and poly[poly(ethylene oxide) methyl ether acrylate] were prepared by 60 Co irradiation polymerization in the presence of dithiobenzoate esters, and their self-assembly under appropriate conditions displayed very interesting structures. [20,21] We predict that a new architectural copolymer, comb-shaped polymer-block-polymer-block-combshaped polymer, which is called a double comb-shaped polymer, may show more rich morphologies. Although various comb-shaped copolymers have been synthesized by the macromonomer technique, no investigations into the synthesis of double comb-shaped copolymers have been reported to the best of our knowledge.…”

Synthesis and characterization of block comb‐like copolymers P(A‐MPEO)‐block‐PSt

“…However, the researchers did not mention whether they obtained pure polymacromonomers; all gel‐permeation chromatography (GPC) traces showed mixtures of the macromonomer and its polymers. In our previous research, pure comb‐shaped poly(polytetrahydrofuran acrylate) was prepared by controlled radical polymerization of poly(tetrahydrofuran acrylate) using 1‐(ethoxylcarbonyl)prop‐1‐yl dithiobenzoate) as an initiator under 60 Co irradiation 24. In order to study the self‐organization behaviour of comb‐shaped block copolymers, poly[(ethylene oxide) methyl ether acrylate]‐ block ‐polystyrene, well‐defined comb‐shaped copolymers with narrow molecular weight distribution are necessary.…”