Addition-Type Polynorbornenes with Si(CH3)3 Side Groups: Synthesis, Gas Permeability, and Free Volume
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- 作者：E. Sh. Finkelshtein ; K. L. Makovetskii ; M. L. Gringolts ; Yu. V. Rogan ; T. G. Golenko ; L. E. Starannikova ; Yu. P. Yampolskii ; V. P. Shantarovich ; T. Suzuki
- 刊名：Macromolecules
- 出版年：2006
- 出版时间：October 3, 2006
- 年：2006
- 卷：39
- 期：20
- 页码：7022 - 7029
- 全文大小：101K
- 年卷期：v.39,no.20(October 3, 2006)
- ISSN：1520-5835
文摘
Polymerization of norbornene bearing Si(CH3)3 groups in the 5-position with the opening of doublebonds and its copolymerization with 5-(n-hexyl)norbornene were realized in the presence of nickel(II) naphthenate/methylaluminoxane catalyst system. The completely saturated homopolymer containing Si(CH3)3 group (APNSi)and a copolymer containing both Si(CH3)3 and n-hexyl side groups (ACPNHSi) were prepared. The polymershave molecular mass of about 300 000 and a high glass transition temperature (Tg > 340 
es/entities/deg.gif">C). Gas permeationproperties of the polymers obtained were studied. APNSi reveals unusually high gas permeation parameters, e.g.,P(O2) of about 800 Barrer for different samples. This polymer also exhibits solubility controlled gas permeation:the permeability coefficients increase in the series of n-alkanes C1-C4 when the size of the penetrant increases.Free volume in addition type substituted polynorbornenes was studied using positron annihilation lifetimespectroscopy (PALS). This method indicated that very large sizes of free volume elements are characteristic forAPNSi what explains its great gas permeability. Another interesting feature of this polymer is an independenceof the annihilation parameters (lifetimes es/gifchars/tau.gif" BORDER=0 >i and intensities Ii) of temperature in a wide range of its variation.Thus, APNSi is a novel representative of high free volume, high permeability glassy polymers, and it is a potentialmaterial for gas separation membranes.