Acyclic diene metathesis (ADMET) polymerization using a well-defined ruthenium based metathesis catalyst

被引:41
作者
Brzezinska, K
Wolfe, PS
Watson, MD
Wagener, KB
机构
[1] UNIV FLORIDA,DEPT CHEM,GAINESVILLE,FL 32611
[2] UNIV FLORIDA,CTR MACROMOLEC SCI & ENGN,GAINESVILLE,FL 32611
关键词
D O I
10.1002/macp.1996.021970622
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A series of alpha,omega-dienes have been exposed to Ru(Cl-2)(CH=Ph)(PCy(3))(2), [Ru] 3, metathesis catalyst under acyclic diene metathesis (ADMET) conditions, and the products were compared with those obtained previously using Schrock's well defined Mo and W alkylidenes. High molecular weight polymers can be synthesized using [Ru] 3 if lower monomer to catalyst ratios (with respect to [Mo] 1 and [W] 2 are used. Monomer structure plays a role since 1,9-decadiene produces molecular weights typical of ADMET chemistry, whereas 1,5-hexadiene produces only oligomers. This decrease in reactivity is attributed to a manifestation of intramolecular pi-complexation of the tethered olefin in 1,5-hexadiene polymerizations. Substituents at the 2-position of alpha,omega-dienes also affects polymerization in that only dimers can be produced from 2-methyl-1,5-hexadiene, a result similar to the same reaction performed with [W] 2. Diallyl ether oligomerizes effectively in the presence of [Ru] 3 with a ratio of cyclics to oligomers comparable to results obtained with [Mo] 1 and [W] 2.
引用
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页码:2065 / 2074
页数:10
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