Metathesis and addition polymerization of novel Me3Si- and Me3Ge-substituted tricyclononenes

被引：22

作者：

Bermeshev, Maxim ^{[1
]}

Bulgakov, Boris ^{[1
]}

Demchuk, Dmitry ^{[2
]}

Filatova, Marina ^{[1
]}

Starannikova, Lyudmila ^{[1
]}

Finkelshtein, Eugene ^{[1
]}

机构：

[1] RAS, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

[2] RAS, ND Zelinsky Inst Organ Chem, Moscow 119991, Russia

来源：

POLYMER JOURNAL | 2013年 / 45卷 / 07期

基金：

俄罗斯基础研究基金会;

关键词：

2+2+2]-cycloaddition; addition polymerization; gas-transport properties; metathesis polymerization; POLYMERS; POLYNORBORNENES; PHOTORESISTS; GE;

D O I：

10.1038/pj.2012.211

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Addition and ring-opening metathesis polymerizations of new monomers (Me3Si- and Me3Ge-substituted tricyclononene and tricyclononadienes) were studied. Addition polymerization was carried out on Pd- and Ni-catalyst systems activated by B(C6F5)(3) and/or methylalumoxane. New addition polymers were obtained with good yields up to 70% and with molecular weights (M-w) up to 5.6 x 10(5). Metathesis polymerization was performed using the first-generation Grubbs catalyst. The yields of the first obtained metathesis polymers were higher than 80%, and the M-w values were up to 8.8 x 10(5). It was revealed that the cyclobutene double bond in the studied tricyclononadienes is inactive in both metathesis and addition polymerizations. The relative activities of the substituted tricyclononene-7 and the corresponding tricyclononadiene-3,7 in the metathesis copolymerization were defined using H-1 NMR spectroscopy. It was found that the novel addition polymer poly[(3-trimethylgermyl)tricyclononene-7] possesses high gas-transport parameters (for example, P(O-2) = 660 Barrers, P(CO2) = 3850 Barrers) and solubility-controlled permeation of gaseous hydrocarbons (alpha (n-C4H10/CH4) = 17.3).

引用

页码：718 / 726

页数：9

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