Functionalization of polyisobutylene and polyisobutylene oligomers via the ritter reaction,Journal of Polymer Science

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Functionalization of polyisobutylene and polyisobutylene oligomers via the ritter reaction
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2018-02-05 , DOI: 10.1002/pola.28961
Corey M. Parada ₁ , Robson F. Storey ₁

Affiliation

The Ritter reaction, that is, reaction of a carbocation with a nitrile, was carried out on polyisobutylene (PIB) using a variety of reaction conditions. End quenching of PIB carbocations with acrylonitrile under living polymerization conditions (methyl chloride (MeCl)/hexane 60/40 (v/v) solvent mixtures at −70 °C) resulted in either tert‐chloride end groups or loss of chain‐end fidelity via carbocation rearrangement, as evidenced by NMR spectroscopy. Exo‐olefin functionalized PIB substrates were also reacted with nitriles under a variety of reaction conditions including various acid and solvent medium combinations. In all cases, the result was either no reaction or PIB that had undergone severe backbone degradation, as determined via NMR spectroscopy and gel permeation chromatography. Finally, the Ritter reaction was performed on a series of exo‐olefin functionalized oligoisobutylenes using acrylonitrile as the nitrile and either 60/40 dichloromethane/hexane or excess acrylonitrile as the solvent. In 60/40 dichloromethane/hexane, significant carbocation rearrangement and/or degradation resulted in a variety of isomeric, acrylamide‐functionalized oligomers. In excess acrylonitrile, the desired Ritter reaction was the only reaction observed, resulting in the smooth formation of the terminal acrylamide. The various N‐oligoisobutylacrylamides thus obtained represent new hydrophobic monomers useful for the introduction of hydrophobic moieties into acrylamide‐based water‐soluble polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 840–852

中文翻译：

通过Ritter反应将聚异丁烯和聚异丁烯低聚物官能化

Ritter反应，即碳阳离子与腈的反应，是使用多种反应条件在聚异丁烯（PIB）上进行的。在活性聚合条件下（甲基氯（MeCl）/己烷60/40（v / v）溶剂混合物在-70°C下）用丙烯腈对PIB碳阳离子进行末端淬灭会导致叔氯化物端基或链端保真度降低如核磁共振波谱所证实的，通过碳正离子重排。o烯烃官能化的PIB底物还在各种反应条件下与腈反应，包括各种酸和溶剂介质组合。在所有情况下，结果都是没有反应或PIB经历了严重的骨架降解，这是通过NMR光谱和凝胶渗透色谱法确定的。最后，在一系列exo上进行Ritter反应使用丙烯腈作为腈并以60/40二氯甲烷/己烷或过量的丙烯腈为溶剂的烯烃官能化的异丁烯。在60/40二氯甲烷/己烷中，显着的碳阳离子重排和/或降解导致产生各种异构体，丙烯酰胺官能化的低聚物。在过量的丙烯腈中，所需的Ritter反应是唯一观察到的反应，导致末端丙烯酰胺的平滑形成。由此获得的各种N-低聚异丁基丙烯酰胺代表了新的疏水性单体，可用于将疏水性基团引入基于丙烯酰胺的水溶性聚合物中。©2018 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2018，56，840-852

更新日期：2018-02-05

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