Oxyethylation and carbonation of telechelic polyisobutylene anions

Nemes, Sándor; Peng, K. L.; Wilczek, Lech; Kennedy, Joseph P.

doi:10.1007/bf00297316

Cited by 11 publications

(7 citation statements)

References 9 publications

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“…6 Such conditions naturally lead to tert-chloride functionality at the chain end, 7 and postpolymerization dehydrochlorination would still be required to synthesize exo-olefin telechelic PIB. [8][9][10] Olefin-terminated PIB has been subjected to numerous postpolymerization transformations, including hydroboration-oxidation, 11 hydroformylation, 12 epoxidation, 13 ozonolysis, 14,15 lithiation, 16 sulfonation, 17 hydrosilylation, 18 and hydrobromination. 19 The terminal unsaturation has also been used as a Friedel-Crafts alkylating agent 20 and a substrate for the free radical addition of thiols.…”

Section: Introductionmentioning

confidence: 99%

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

2010

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Alkoxybenzenes were used to end-quench TiCl 4 -catalyzed quasiliving isobutylene polymerizations initiated from 2-chloro-2,2,4-trimethylpentane or 5-tert-butyl-1,3-di(1-chloro-1-methylethyl)benzene at -70 °C in 40/60 (v/v) hexane/methyl chloride. The alkoxybenzene/chain end molar ratios were in the range 2.5-4. Effective alkoxybenzene quenchers included those with simple alkyl groups, such as anisole and isopropoxybenzene, haloalkyl tethers, such as (3-bromopropoxy)benzene and (2-chloroethoxy)benzene, and even those with hydroxyl and amine functionality, such as 4-phenoxy-1-butanol and 6-phenoxyhexylamine. Alkylation was generally quantitative and occurred exclusively in the para position; multiple alkylations on the same alkoxybenzene were not observed. The alkylation reactions were tolerant of temperatures ranging from -70 to -30 °C and were unimpeded by the presence of endo-or exo-olefin termini. In situ cleavage of the ether linkage of anisole and isopropoxybenzene termini allowed single pot syntheses of phenol-terminated polyisobutylenes.

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Section: Introductionmentioning

confidence: 99%

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

2010

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“…Among the available processes some gave incompletely COOH-functionalized products6•25'26 and another was deemed cumbersome. 27 The best process to date seemed to be that developed by Liao and Kennedy28 which was A solution of 20 g of HO-PIB-OH (2 wt % in THF) was added dropwise to charges of 40-fold excess (to suppress chain extension) of adipoyl chloride. The THF solvent employeed by the earlier authors28 consumed 2-5% of the PIB end groups, probably by the following side reaction: By substitution of benzene for THF this side reaction has been avoided and useful products were obtained.…”

Section: Ho-pib-ohmentioning

confidence: 99%

Novel Thermoplastic Elastomers: Polyisobutylene-block-polyamide Multiblocks

Zaschke¹,

Kennedy²

1995

Macromolecules

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“…Низкомолекулярные (M n = 500 -5000 г/моль) моно-и дифункциональные полиизобутилены с концевыми олефиновыми группами являются важными интермедиатами для синтеза полимеров с концевыми первичными гидроксильными [1][2][3][4][5][6][7][8], альдегидными [9], карбоксильными [4; 10-12], бромидными [3], хлоридными [4], аминными [3; 13-15], гидросилильными [16], алкоксисилильными [6], фенильными [17; 18], а также эпоксидными [19], метакрилатными [3; 20] и многими другими [21][22][23][24] группами.…”

Section: Introductionunclassified

Complexes of aluminum, iron(III), and gallium(III) chlorides with ethers in synthesis of highly reactive polyisobutylene

Kostjuk¹

2020

Journal of the Belarusian State University. Chemistry

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In this review, the latest achievements in the field of cationic polymerization of isobutylene catalyzed by the complexes of conventional Lewis acids with ethers are presented. The experimental and computational data on the influence of steric structure and basicity of ether used for the preparation of the Lewis acid-ether complex on the catalyst activity and regioselectivity of β-H abstraction are discussed here. Complexes of metal halides with linear (Bu2O) and moderately branched (iPr2O) ethers of moderate basicity (pKa from –4.3 to –5.4) displayed the highest activity and regioselectivity in the cationic polymerization of isobutylene affording highly reactive polyisobutylene (HR PIB) – the key intermediate in the preparation of motor oil and fuel additives. The review is also focusing on the adaptation of the developed catalytic system to the industry, which consists in using non-polar hydrocarbon solvents, high temperatures and monomer concentrations.

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Oxyethylation and carbonation of telechelic polyisobutylene anions

Cited by 11 publications

References 9 publications

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

Novel Thermoplastic Elastomers: Polyisobutylene-block-polyamide Multiblocks

Complexes of aluminum, iron(III), and gallium(III) chlorides with ethers in synthesis of highly reactive polyisobutylene

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Oxyethylation and carbonation of telechelic polyisobutylene anions

Cited by 11 publications

References 9 publications

End-Quenching of TiCl4-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

End-Quenching of TiCl4-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

Novel Thermoplastic Elastomers: Polyisobutylene-block-polyamide Multiblocks

Complexes of aluminum, iron(III), and gallium(III) chlorides with ethers in synthesis of highly reactive polyisobutylene

Contact Info

Product

Resources

About

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization

End-Quenching of TiCl₄-Catalyzed Quasiliving Polyisobutylene with Alkoxybenzenes for Direct Chain End Functionalization