Vinyl Alkyl Ethers

Abstract

T h e literature related to simple urlsubstituted F i n y l allq 1 ethers is reviewed. New data are presented on the purification and properties of the vinyl alkyl ether monomers. Special attention is given to vinyl methyl, vinyl n-butJ 1, and vinyl isobutyl ethers, which have been made available for dekelopment purposes in this country by application o f the Reppe synthesis. Correct physical data on these materials are of special interest both because, the monomers are com-HIS paper discusses simple compounds of the type T CH2=CHOR, where R is an alkyl group free from unsaturation and both the vinyl and R groups are free from halogen or other substitution. Vinyl methyl ether, vinyl n-butyl ether, and vinyl isobutyl ether are the members of the series which received most attention and whose polymers are discussed.The nex data presented from this laboratory comprise the major part of the material under the headings Purification, Physical Properties, and Polymerization, as well as Properties and Stabilization of the Polymers. B large part of the information on

Structurally controlled polymerizations of methacrylates and acrylates

“…SFC trace of an ht-oligomer (M n = 1800) of allyl methacrylate prepared with t-C 4 H 9 Li/MeAl(ODBP) 2 (1/5) in toluene at À95°C clearly showed even±odd alternation with respect to the degree of polymerization; the oligomers with odd-number DP are more abundant than those with even-number DP. 23,55 This is clear experimental evidence for the higher stability of the racemo anion, and also for alternation of r-and mplacements in the propagation reaction.…”

“…For instance, t-C 4 H 9 Li/MeAl(ODBP) 2 a heterotactic speci®c initiator for primary alkyl methacrylates acts as a highly syndiotactic-speci®c initiator for a bulky methacrylate. 24 Combinations of t-C 4 H 9 Li and a bulky aluminium bisphenoxide such as MeAl(ODBP) 2 can also polymerize acrylates in a living manner. 25±27 These initiator systems can provide stereoregular statistical copolymers of methacrylates and acrylates, 25±29 and stereoregular block polymers and block copolymers 30±32 in a living manner.…”

“…Addition of MeAl (ODBP) 2 to t-C 4 H 9 Li decreased the isotacticity of the polymers, in association with an increase of the syndiotacticity, and st-polymers were formed preferentially at a ratio of t-C 4 H 9 Li/MeAl(ODBP) 2 = 1. Further addition of MeAl(ODBP) 2 increased the heterotacticity of the polymers, and at ratios lower than 1/3 highly heterotactic polymers were formed.…”

“…10 Living polymerizations of polar monomers have been developed within these last 20 years 11 but only a few afford stereoregular polymers. In 1992 Yasuda and co-workers 12 found that organolanthanide complexes such as [(C 5 Me 5 ) 2 SmH] 2 give high molecular weight st-poly (methyl methacrylate)s (PMMAs) with narrow MWD in a living manner.…”

The Effect of Counteranions in the Polymerization of Isobutyl Vinyl Ether Initiated by Triphenylmethyl Cation

“…27 Subsequently, Okamura, et al, established from comparisons of TP and other physical properties (X-ray crystallinity and Young's modulus) that TP depended essentially on the steric structure (isotacticity) of the polymer. 24 This is also supported by the IR study of the polymer.…”