MoCl5/EtAlCl2-catalysed nonmetathesis polymerization of norbornadiene

The oligomerization of dicyclopentadiene (DCPD, mixture of endo and exo isomers), 9,10‐dihydrodicyclopentadiene (H‐DCPD), exo‐DCPD, and endo‐DCPD catalyzed by TiCl4/Et2AlCl is studied. Oligomers containing 2,3‐enchained units are obtained in good yields. The endo‐DCPD is less reactive than the exo isomer, exhibiting a reactivity comparable with that of the partially saturated H‐DCPD. While all the products obtained from the oligomerization of the exo isomer and H‐DCPD are amorphous, from the endo isomer, at low DCPD/Ti ratio, a crystalline, stereoregular tetramer having a 2,3‐exo‐disyndiotactic structure is obtained. The results show that the presence of the double bond in the cyclopentene ring, the spatial disposition of the cyclopentene, and the oligomerization conditions play a fundamental role to give a unique crystalline material. Hydrogenation and epoxidation of the obtained products are reported as well.

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Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification

Zanchin

Leone

Pierro

et al. 2017

Macromol. Chem. Phys.

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Cationic polymerization of norbornadiene

Peetz

Moustafa

Kennedy

2003

J. Polym. Sci. A Polym. Chem.

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The polymerization of norbornadiene (NBD) initiated by the 2‐chloro‐2,4,4‐trimethylpentane/titanium tetrachloride system was investigated. Efforts were made to develop conditions for the living polymerization of NBD by the use of proton trap and electron donor in the −35 to −60 °C range however this objective was only partially attained. The molecular weights increased linearly with conversion, and the rate was first‐order in confirmed monomer concentration up to approximately 25%; however, chain transfer became operational beyond this range. The microstructure of polynorbornadiene (PNBD) was investigated by high‐resolution 1H and 13C NMR spectroscopy. According to these techniques, the chain consisted of about equal amounts of exo/exo and exo/endo connected tricyclic repeat units. The head and tail groups were identified and quantitated, and this led to absolute molecular weight determination by integration. Molecular weights obtained by this method and by gel permeation chromatography (relative to polyisobutylene standards) were in good agreement. NMR spectroscopy indicated the presence of small but still identifiable amounts of branching units and their structures. The plot of the glass‐transition temperature against the reciprocal of the number‐average molecular weight was linear and yielded a glass‐transition temperature of 323 °C for the infinite molecular weight polymer. According to thermogravimetric analysis, PNBD was stable up to approximately 250 °C and showed a 5% weight loss at approximately 335 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 732–739, 2003

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A bicyclic conjugated diene monomer, tetrahydroindene, for cationic polymerization and a novel alicyclic hydrocarbon polymer with heat resistance

Mizuno¹,

Satoh²,

Kamigaito³

2006

J. Polym. Sci. A Polym. Chem.

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This study was directed toward the cationic polymerization of tetrahydroindene (i.e., bicyclo[4.3.0]‐2,9‐nonadiene), a bicyclic conjugated diene monomer, with a series of Lewis acids, especially focusing on the synthesis of high‐molecular‐weight polymers and subsequent hydrogenation for novel cycloolefin polymers with high service temperatures. EtAlCl2 or SnCl4 induced an efficient and quantitative cationic polymerization of tetrahydroindene to afford polymers with relatively high molecular weights (number‐average molecular weight > 20,000) and 1,4‐enchainment bicyclic main‐chain structures. The subsequent hydrogenation of the obtained poly(tetrahydroindene) with p‐toluenesulfonyl hydrazide resulted in a saturated alicyclic hydrocarbon polymer with a relatively high glass transition (glass‐transition temperature = 220 °C) and improved pyrolysis temperature (10% weight loss at 480 °C). The new diene monomer was randomly copolymerized with cyclopentadiene at various feed ratios in the presence of EtAlCl2 to give novel cycloolefin copolymers, which were subsequently hydrogenated into alicyclic copolymers with variable glass‐transition temperatures (70–220 °C). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6214–6225, 2006

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MoCl5/EtAlCl2-catalysed nonmetathesis polymerization of norbornadiene

Cited by 11 publications

References 16 publications

Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification

Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification

Cationic polymerization of norbornadiene

A bicyclic conjugated diene monomer, tetrahydroindene, for cationic polymerization and a novel alicyclic hydrocarbon polymer with heat resistance

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