Poly(ethylene oxide) macromonomers. 8. Preparation and polymerization of ι-hydroxypoly(ethylene oxide) macromonomers

Abstract

The potassium alkoxide (3) of tert-butyldimethylsilyl ether of ethylene glycol successfully initiated a living polymerization of ethylene oxide to a controlled degree of polymerization with a narrow distribution. End-capping with p-vinylbenzyl chloride and methacryloyl chloride, followed by desilylation with tetra-n-butylammonium fluoride afforded the corresponding &>-hydroxypoly(ethylene oxide) macromonomers (la and 2a). The radical copolymerization of the macromonomers with styrene and their homopolymerization in benzene have revealed reactivities similar to those of the corresponding -methoxy derivatives. Micellar polymerization in water, however, occurred more rapidly to give an apparently simpler, starlike polymer with a number of hydrophilic, polyethylene oxide) arms with -hydroxy end groups.Research from the Ministry of Education, Science and Culture, Japan. We are greatly indebted to Shinetsu Chemical Co., Ltd., for tert-butyldimethylsilyl chloride.

Synthesis of low molecular weight-hydroxy polycaprolactone macromonomers by coordinated anionic polymerization in protic conditions

“…24 It was stated above that the drastic molecular Should we follow this procedure, v-hydroxy macromonomers will be obtained from initiators disweight decrease owing to the exchange reaction might be seen as a major drawback if dealing with playing masked hydroxyl groups with protecting groups. 13 In the same way, functionalized initiathe synthesis of high molecular weight polymers. This point of view may be totally changed if one tors with phtalimides will be used to get v-aminated macromonomers.…”

Star Poly(ethylene oxide)s from Carbosilane Dendrimers

“…Star PEOs have also been produced by the radical polymerization of ω-hydroxy PEO macromonomers. 7 The method is also limited to low MW PEO, and the product has a wide molecular weight distribution. Extremely high MW stars are obtained when the macromonomer is polymerized in water.…”

Syntheses of Poly(ethylene oxide) Macromonomers Carrying Tertiary Amine and Quaternary Ammonium End Groups

“…1 As usual, styryl or methacryloyl functions have been introduced as a (co)polymerizable end group, say α-end group, of the macromonomer, while the other ω-end group is also feasible to introduce another functionality. So far to our knowledge, hydroxyl, 2,3 carboxylate, [4][5][6] sulfonate, 7,8 aldehyde, 9,10 and perfluoroalkyl 11 groups have been reported. In most cases [3][4][5][6][7][8][9][10][11] some elaborate procedures have been involved either in anionic polymerization of ethylene oxide (EO) or in end-group transformation, while 2-hydroxyethyl methacrylate was used together with a Lewis acid to initiate cationic EO polymerization to give poly(ethylene glycol) monomethacrylate in one step.…”

“…So far to our knowledge, hydroxyl, 2,3 carboxylate, [4][5][6] sulfonate, 7,8 aldehyde, 9,10 and perfluoroalkyl 11 groups have been reported. In most cases [3][4][5][6][7][8][9][10][11] some elaborate procedures have been involved either in anionic polymerization of ethylene oxide (EO) or in end-group transformation, while 2-hydroxyethyl methacrylate was used together with a Lewis acid to initiate cationic EO polymerization to give poly(ethylene glycol) monomethacrylate in one step. 2 Our recent strategy in PEO macromonomer synthesis includes initiation of anionic EO polymerization with a functional alcohol, F-OH, as suggested by the original work by Rempp et al, who used potassium p-isopropenylbenzylate to have a corresponding macromonomer.…”