Stereoselective synthesis and polymerization of Exo-5-trimethylsilylnorbornene

被引：33

作者：

Alentiev, Dmitry A. ^{[1
]}

Bermeshev, Maxim V. ^{[1
,2
]}

Starannikova, Lyudmila E. ^{[1
]}

Bermesheva, Evgeniya V. ^{[1
,3
]}

Shantarovich, Viktor P. ^{[4
]}

Bekeshev, Valentin G. ^{[4
]}

Yampolskii, Yuri P. ^{[1
]}

Finkelshtein, Eugene Sh. ^{[1
]}

机构：

[1] Russian Acad Sci, AV Topchiev Inst Petrochem Synth, 29 Leninsky Prospekt, Moscow 119991, Russia

[2] DI Mendeleyev Univ Chem Technol Russia, 9 Miusskaya Sq, Moscow 125047, Russia

[3] IM Sechenov First Moscow State Med Univ, Trubetskaya Str 8,Bldg 2, Moscow 119991, Russia

[4] Russian Acad Sci, NN Semenov Inst Chem Phys, 4k1 Kosygina St, Moscow 119991, Russia

来源：

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY | 2018年 / 56卷 / 12期

关键词：

addition polymerization; gas permeability; microporous materials; norbornenes; ROMP polymerization; ADDITION-TYPE POLYNORBORNENE; GAS PERMEATION PARAMETERS; SI(CH3)(3) SIDE-GROUPS; FREE-VOLUME; FUNCTIONALIZED POLYNORBORNENES; SEPARATION MEMBRANES; MOLECULAR-PROPERTIES; MONOMER UNIT; 193; NM; QUADRICYCLANE;

D O I：

10.1002/pola.29003

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Herein the stereoselective two-step synthesis of pure exo-5-trimethylsilylnorbornene is reported. The monomer proved to be highly reactive in both metathesis and addition polymerization. ROMP polymerization was catalyzed by the first-generation Grubbs catalyst. High-molecular-weight saturated addition polymers were prepared using nickel or palladium complexes as precatalysts and Na+[B(3,5-(CF3)(2)C6H3)(4)](-) and/or MAO as cocatalysts. The obtained addition polynorbornenes are highly gas permeable and microporous materials possessing large free volume and BET surface area (up to 540 m(2)/g). The influence of the substituent orientation (exo- vs. exo-/endo-mixture) on polymer properties was established. The metathesis polymer based on exo-isomer exhibits 1.5- to 2-fold increase of permeability coefficients for all gases in comparison to the similar polymer based on the mixture of exo- and endo-isomers. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1234-1248

引用

页码：1234 / 1248

页数：15

共 48 条

[11] [2σ+2σ+2π]-Cycloaddition of quadricyclane to partially methylated chlorosilylalkenes [J].

Chapala, Pavel P. ;

Bermeshev, Maxim V. ;

Lakhtin, Valentin G. ;

Genaev, Alexander M. ;

Tavtorkin, Alexander N. ;

Finkelshtein, Eugene Sh. .

MENDELEEV COMMUNICATIONS, 2015, 25 (05) :344-345

[12] DIELS-ALDER REACTION OF ALPHA, BETA-UNSATURATED TRIHALOSILANES WITH CYCLOPENTADIENE [J].

CUNICO, RF .

JOURNAL OF ORGANIC CHEMISTRY, 1971, 36 (07) :929-&

[13] THE TEMPERATURE-DEPENDENCE OF POSITRON LIFETIMES IN SOLID PIVALIC ACID [J].

ELDRUP, M ;

LIGHTBODY, D ;

SHERWOOD, JN .

CHEMICAL PHYSICS, 1981, 63 (1-2) :51-58

[14] New amorphous fluoropolymers of tetrafluoroethylene with fluorinated and non-fluorinated tricyclononenes. Semiconductor photoresists for imaging at 157 and 193 nm [J].

Feiring, AE ;

Crawford, MK ;

Farnham, WB ;

Feldman, J ;

French, RH ;

Junk, CP ;

Leffew, KW ;

Petrov, VA ;

Qiu, WM ;

Schadt, FL ;

Tran, HV ;

Zumsteg, FC .

MACROMOLECULES, 2006, 39 (09) :3252-3261

[15]

Finkelshtein E., 2017, MEMBRANE MAT GAS VAP, P143, DOI DOI 10.1002/9781119112747.CH6

[16] Addition-type polynorbornenes with Si(CH3)3 side groups:: Synthesis, gas permeability, and free volume [J].

Finkelshtein, E. Sh. ;

Makovetskii, K. L. ;

Gringolts, M. L. ;

Rogan, Yu. V. ;

Golenko, T. G. ;

Starannikova, L. E. ;

Yampolskii, Yu. P. ;

Shantarovich, V. P. ;

Suzuki, T. .

MACROMOLECULES, 2006, 39 (20) :7022-7029

[17] Addition polymerization of silyl-containing norbornenes in the presence of Ni-based catalysts [J].

Finkelshtein, E. Sh. ;

Makovetskii, K. L. ;

Gringolts, M. L. ;

Rogan, Y. V. ;

Golenko, T. G. ;

Lakhtin, V. G. ;

Filatova, M. P. .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2006, 257 (1-2) :9-13

[18] Substituted polynorbornenes as promising materials for gas separation membranes [J].

Finkelshtein, E. Sh ;

Bermeshev, M. V. ;

Gringolts, M. L. ;

Starannikova, L. E. ;

Yampolskii, Yu P. .

RUSSIAN CHEMICAL REVIEWS, 2011, 80 (04) :341-361

[19]

Goodall B.L., 2003, LATE TRANSITION META, P101

[20] Highly permeable polymer materials based on silicon-substituted norbornenes [J].

Gringol'ts, M. L. ;

Bermeshev, M. V. ;

Syromolotov, A. V. ;

Starannikova, L. E. ;

Filatova, M. F. ;

Makovetskii, K. L. ;

Finkel'shtein, E. Sh. .

PETROLEUM CHEMISTRY, 2010, 50 (05) :352-361

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