含氮氧自由基和磺酸基共聚物的合成及催化性能
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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Na Cl O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。
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 Na Cl O 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.
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 Na Cl O 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.
引文
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[3]苏玲,张月成,赵继全.树枝状聚酰胺胺负载TEMPO的合成及其催化分子氧氧化醇的性能[J].分子催化,2014,28(5):400-409.SU L,ZHANG Y C,ZHAO J Q.Synthesis of dendritic polyamidoamine supported 2,2,6,6-tetramethylpiperidine-1-oxyl and its catalytic performance on the oxidation of alcohols with molecular oxygen as oxidant[J].Journal of Molecular Catalysis,2014,28(5):400-409.
[4]NAKAHARA K,IWASA S,SATOH M,et al.Rechargeable batteries with organic radical cathodes[J].Chemical Physics Letter,2002,359:351-354.
[5]FERREIRA P,HAYES W,PHILLIPS E,et al.Polymer-supported nitroxyl catalysts for selective oxidation of alcohols[J].Green Chemistry,2004,6:310-312.
[6]FERREIRA P,PHILLIPS E,RIPPON D,et al.Poly(ethylene glycol)-supported nitroxyls:branched catalysts for the selective oxidation of alcohols[J].Journal of Organic Chemistry,2004,69:6851-6859.
[7]FERREIRA P,PHILLIPS E,RIPPON D,et al.Catalytic oxidation of alcohols using molecular oxygen mediated by poly(ethylene glycol)-supported nitroxyl radicals[J].Applied Catalysis B:Environmental,2005,61:206-211.
[8]POZZI G,CAVAZZINI M,QUICI S,et al.Poly(ethylene glycol)-supported TEMPO:an efficient,recoverable metal-free catalyst for the selective oxidation of alcohols[J].Organic Letters,2004,6:441-443.
[9]LIU S J,CHU X M,WANG H L,et al.Preparation of nitroxide polymer brushes and their applications in the synthesis of an epoxidized soybean oil acrylate as an inhibitor[J].Industrial&Engineering Chemistry Research,2015,54:5475-5480.
[10]刘少杰,王华丽,崔笑菲,等.PEG基氮氧自由基嵌段共聚物的制备及其对伯醇的催化氧化性能[J].高校化学工程学报,2017,31(1):83-89.LIU S J,WANG H L,CUI X F,et al.Preparation of poly(ethylene glycol)-based nitroxyls block copolymers and their selective catalytic oxidation performance on primary alcohols[J].Journal of Chemical Engineering of Chinese Universities,2017,31(1):83-89.
[11]韩晓东,赵志伟,李雪华,等.一种氧化还原石墨烯的稳定水溶液分散体的合成方法[J].化工学报,2016,67(s1):396-401.HAN X D,ZHAO Z W,LI X H,et al.One-step synthesis of stable hydrosoluble dispersion of reduced graphene oxide in presence of poly(sodium 4-styrenesulfonate)[J].CIESC Journal,2016,67(s1):396-401.
[12]孟凡顺.用于光盘存储和太阳能电池菁染料的研究[D].上海:华东理工大学,1999.MENG F S.Study on cyanine dyes for optical disk memory and organic solar cell[D].Shanghai:East China University of Science and Technology,1999.
[13]孟凡顺.菁染料和三苯胺类有机光电功能材料的合成与性能研究[D].上海:华东理工大学,2003.MENG F S.The synthesis and properties of novel opto-electric materials based on cyanine dyes and triphenylamine derivatives[D].Shanghai:East China University of Science and Technology,2003.
[14]ROBERS R M.Acid catalyzed reaction of diarylformamidines with ethyl orthoformate[J].Journal of the American Chemical Society,1949,71:3848-3849.
[15]ROBERS R M,DEWOLFE R H.Ortho esters,imidic esters and amidines.Ⅳ.The mechanism of the reaction of aniline with ethyl orthoformate[J].Journal of the American Chemical Society,1954,76:2411-2414.
[16]ROBERS R M,VOGT P J.Ethyl N-phenylformimidate[J].Organic Syntheses,1955,35:65.
[17]TERENCE R C,VERONA N J.Nickel complex pigments of bis-azomethines:US4508899[P].1985-04-02.