Living cationic polymerization of vinyl ethers with a urethane group

Abstract

To study the possibility of living cationic polymerization of vinyl ethers with a urethane group, 4‐vinyloxybutyl n‐butylcarbamate (1) and 4‐vinyloxybutyl phenylcarbamate (2) were polymerized with the hydrogen chloride/zinc chloride initiating system in methylene chloride solvent at −30 °C ([monomer]0 = 0.30 M, [HCl]0/[ZnCl2]0 = 5.0/2.0 mM). The polymerization of 1 was very slow and gave only low‐molecular‐weight polymers with a number‐average molecular weight (Mn) of about 2000 even at 100% monomer conversion. The structural analysis of the products showed occurrence of chain‐transfer reactions because of the urethane group of monomer 1. In contrast, the polymerization of vinyl ether 2 proceeded much faster than 1 and led to high‐molecular‐weight polymers with narrow molecular weight distributions (MWDs ≤ ∼1.2) in quantitative yield. The Mn's of the product polymers increased in direct proportion to monomer conversion and continued to increase linearly after sequential addition of a fresh monomer feed to the almost completely polymerized reaction mixture, whereas the MWDs of the polymers remained narrow. These results indicated the formation of living polymer from vinyl ether 2. The difference of living nature between monomers 1 and 2 was attributable to the difference of the electron‐withdrawing power of the carbamate substituents, namely, n‐butyl for 1 versus phenyl for 2, of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2960–2972, 2004

Synthesis of poly(vinyl ether)-based, ABA triblock-type thermoplastic elastomers with functionalized soft segments and their gas permeability

“…Toluene (solvent for polymerization), tetrahydronaphthalene, and heptane (internal standards for gas chromatography), and ethyl acetate (CH 3 COOEt; added base) were purified as already reported. 39 …”

“…[6][7][8][9] Thanks to the stable living propagating species derived from vinyl ethers, living polymerization is possible for vinyl ethers with not only alkyl (linear 10,11 and cyclic [12][13][14][15][16][17] ) substituents but also a variety of functional substituents including halide, [18][19][20][21][22][23][24] olefin, 25,26 ether, [27][28][29][30] ester, [31][32][33][34][35][36] amide, 37 imide, 38 and urethane 39 linkages. With such tolerance for a broad range of the substituents, sequential living polymerization of vinyl ether monomers provides synthetic design of new thermoplastic elastomers with a wide range of properties like hydrophobicity to hydrophilicity, flexibility to rigidity, various reactivity, and specific functions.…”

Living cationic polymerization of vinyl ethers with a tricyclodecane or tricyclodecene unit: Synthesis of new poly(vinyl ether)s with high glass‐transition temperature

“…To prepare such new elastomeric polymers consisting totally of poly(vinyl ether) backbones, the controlled synthesis of poly(vinyl ether)s with high T g is necessary. Our previous approach to obtain poly(vinyl ether)s with high T g involved the synthesis of poly(vinyl ether)s with urethane groups in their side chains 14…”

Synthesis and characterization of novel poly(cycloalkyl methacrylate) bearing fused‐ring structure and its copolymers

“…The molecular weights of the polymers were also determined by GPC in THF with polystyrene standards for the calibration. The white polymeric materials were filtered and purified by redissolving in aminimum quantity of THF and then precipitated into methanol following a standard literature procedure 21. A Waters 510 Pump connected through three series of Styragel HR columns (HT‐3, HT‐4, and HT‐5) and a Waters 410 Differential Refractometer were used for analsis of the samples.…”

“…Tricyclodecane‐based polymers are another class of materials with a bulky cycloaliphatic unit in the ester group. Tricyclodecyl methacrylates and bis(hydroxymethyl)tricyclodecane have been reported for their use in optical polymers; they have excellent nonyellowing characteristics and are also widely used in the photo curing industry 14–21. Here, we report the synthesis and characterization of methacrylate monomer and copolymers based on mono(hydroxymethyl)tricyclodecane.…”