含氮氧自由基和磺酸基共聚物的合成及催化性能

doi:10.16085/j.issn.1000-6613.2017-0886

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

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

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

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/Abstract

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

中图分类号:

TQ317.4

杜慧丽, 崔笑菲, 刘少杰. 含氮氧自由基和磺酸基共聚物的合成及催化性能[J]. 化工进展, 2018, 37(02): 708-713.

DU Huili, CUI Xiaofei, LIU Shaojie. Preparation of copolymers containing nitroxyl radical and sulfonic acid and their catalytic performances[J]. Chemical Industry and Engineering Progress, 2018, 37(02): 708-713.

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含氮氧自由基和磺酸基共聚物的合成及催化性能

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

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