化工进展 ›› 2018, Vol. 37 ›› Issue (02): 708-713.DOI: 10.16085/j.issn.1000-6613.2017-0886

• 精细化工 • 上一篇    下一篇

含氮氧自由基和磺酸基共聚物的合成及催化性能

杜慧丽, 崔笑菲, 刘少杰   

  1. 河北科技大学化学与制药工程学院, 河北 石家庄 050018
  • 收稿日期:2017-05-15 修回日期:2017-10-19 出版日期:2018-02-05 发布日期:2018-02-05
  • 通讯作者: 刘少杰,副教授,研究方向为功能高分子材料合成。
  • 作者简介:杜慧丽(1991-),女,硕士研究生。
  • 基金资助:
    国家自然科学基金项目(21304030)。

Preparation of copolymers containing nitroxyl radical and sulfonic acid and their catalytic performances

DU Huili, CUI Xiaofei, LIU Shaojie   

  1. College of Chemical & Pharmaceutical Engineering, Hebei University of Science & Technology, Shijiazhuang 050018, Hebei, China
  • Received:2017-05-15 Revised:2017-10-19 Online:2018-02-05 Published:2018-02-05

摘要: 以2,2-偶氮二异丁腈为引发剂,苯乙烯磺酸钠(SSS)、甲基丙烯酸-2,2,6,6-四甲基哌啶醇酯(TMPM)为单体,采用自由基聚合的方法制备出无规共聚物P (TMPM-co-SSS)。然后用3-氯过氧苯甲酸将其氧化为含氮氧自由基的共聚物P (TMA-co-SSS)。最后用盐酸酸化,得到含氮氧自由基和磺酸基的双功能共聚物P (TMA-co-HSS)。在NaClO油水两相氧化体系下,研究了P (TMA-co-HSS)对苯甲醇的选择性催化氧化性能。结果表明,P (TMA-co-HSS)催化性能较好,收率最高可达89%,并且回收方便,重复使用3次活性未见明显降低。同时研究了P (TMA-co-HSS)作为固体酸催化剂在合成N-(乙氧基亚甲基)苯胺反应中的催化性能,并与对甲苯磺酸和聚苯乙烯磺酸的催化性能进行了对比。结果表明,P (TMA-co-HSS)催化性能优异,收率可以达到97%,远高于聚苯乙烯磺酸,与对甲苯磺酸相当,而且循环使用5次后,收率未见明显降低。

关键词: 共聚物, 催化剂, 催化, 氧化

Abstract: With 2,2'-azobis(2-methylpropionitrile) as the initiator, and sodium p-styrene sulfonate (SSS) and 2,2,6,6-tetramethylpiperidine-4-yl-1-oxyl (TMPM) as the monomers, the copolymer of P(TMPM-co-SSS) was synthesized via free radical copolymerization. Followed by oxidizing it with the mchloroperbenzoic acid, the nitroxyl copolymer of P(TMA-co-SSS) was obtained. Finally acidified by the hydrochloric acid, the bifunctional copolymer of P(TMA-co-HSS) was obtained. Selective catalytic oxidation performances of P(TMA-co-HSS) for benzyl alcohol in a biphasic water-oil NaClO oxidation system were studied. The results showed that the catalytic activity of P(TMA-co-HSS) was good and the yield was up to 89%. Furthermore, the copolymers had excellent recyclability and the activity was not decreased significantly after 3 cycles. The catalytic performance of P (TMA-co-HSS) as a solid acid catalyst for the synthesis of ethyl N-phenylformimidate was also studied. Its catalytic performance was compared with p-toluene sulfonic acid and PHSS. The results showed that the catalytic activity of P(TMA-co-HSS) was excellent and the yield was up to 97%, comparable to p-toluene sulfonic acid. Furthermore, P(TMA-co-HSS) had excellent recyclability and the activity was not decreased significantly after 5 cycles.

Key words: copolymer, catalyst, catalysis, oxidation

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