Tripolymers from Butyl Rubber Polymerization

Minckler, L. S.; Small, A. B.

doi:10.1021/i360003a018

I&EC Product Research and Development

1962

DOI: 10.1021/i360003a018

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Tripolymers from Butyl Rubber Polymerization

L. S. Minckler¹,

A. B. Small²

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1967

1979

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Cationic copolymerization of isobutene and conjugated small‐ring dienes

Tsao

Lenz

1979

J. Polym. Sci. Polym. Chem. Ed.

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Synopsisl-Methyl-3-methylenecyclobutene (MMCB) and 1,2-dimethylenecyclobutane (DMCB) copolymerized readily with isobutene with aluminum chloride as initiator in methyl chloride solution at temperatures from -95 to -78OC. No polymers were obtained with methylenecyclobutene (MCB) under similar conditions. The copolymerization of MMCB with isobutene took place through a 1,5-addition reaction while that of DMCB through both 1,2-and l,4-addition reactions. Large amounts of gel were present in the copolymers obtained from DMCB if the reaction was carried to high conversion. The commonly observed effects of dienes (i.e., rate retardation and molecular weight depression) on cationic copolymerization reactions were observed but to a much higher degree with these small ring dienes. The thermal crosslinking behavior of the resulting copolymers was investigated. In conjunction with the copolymerization studies, homopolymers of MMCB, DMCB, and 3,3-dimethyl-l-isopropylidene-2-methylenecyclobutane (IMCB) were prepared and their chemical structures examined.

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Cationic copolymerization of isobutene and conjugated small‐ring dienes

Tsao

Lenz

1979

J. Polym. Sci. Polym. Chem. Ed.

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Thermally reversible polymer systems by cyclopentadienylation. I. A model for termination by cyclopentadienylation of olefin polymerization

Kennedy

Castner

1979

J. Polym. Sci. Polym. Chem. Ed.

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The reaction between tert‐butylchloride (t‐BuCl) and dimethylcyclopentadienylaluminum (Me2AlCPD) was studied as a model for initiation by the tert‐butyl cation (t‐Bu⊕) and termination by cyclopentadienylation by the Me2Al(CPD)Cl⊖ counteranion of isobutylene polymerization. All reaction products formed in this model system have been identified and quantitatively determined. A comprehensive scheme that indicates pathways to these products was developed (scheme III). It is proposed that the predominant product, tert‐butylcyclopentadiene (t‐BuCPD), arises in the collapse of the t‐Bu⊕‐Me2Al(CPD)Cl⊖ ion pair, mainly by CPD⊖ transfer to the tert‐butyl cation. The minor products are neopentane (t‐BuMe) and isobutylene (i‐C4H8), which are probably formed, respectively, by Me⊖ transfer to and proton loss from the t‐butyl cation. Cyclopentadienylation selectivity increases by lowering the temperature and extrapolation of results suggests 100% cyclopentadienylation at −55°C. The t‐BuCl/Me2AlCPD ratio strongly influences the overall reaction pathway. The reaction is first order in t‐BuCl with ΔEa of ca. 7 kcal/mole (1,2‐dichloroethane or chlorobenzene solvents, +24 to −29°C). Indirect evidence indicates that the kinetic product of cyclopentadienylation is 5‐t‐BuCPD and that this isomer cannot be tert‐butylated; that is, the initiation of 5‐t‐BuCPD polymerization by t‐Bu⊕ is sterically unfavorable. Detailed analysis of the chemistry and kinetics of the t‐BuCl/Me2AlCPD model system holds important clues to the controlled polymerization of olefins leading to macromolecules with cyclopentadiene (CPD) termini.

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Contributions to the Mechanism of Isobutene Polymerization. IV. Effect of Conjugated Dienes

Kennedy

Squires

1967

Journal of Macromolecular Science: Part A - Chemistry

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Tripolymers from Butyl Rubber Polymerization

Cited by 3 publications

References 1 publication

Cationic copolymerization of isobutene and conjugated small‐ring dienes

Cationic copolymerization of isobutene and conjugated small‐ring dienes

Thermally reversible polymer systems by cyclopentadienylation. I. A model for termination by cyclopentadienylation of olefin polymerization

Contributions to the Mechanism of Isobutene Polymerization. IV. Effect of Conjugated Dienes

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