磺酸化聚苯乙烯微球催化合成N-(乙氧基亚甲基)苯胺
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摘要
首先通过无皂乳液聚合制得聚苯乙烯(PS)种子乳液,再加入苯乙烯磺酸钠继续进行无皂乳液聚合,得到核壳结构的苯乙烯-苯乙烯磺酸钠共聚物微球(PS-Na SS@PS),然后酸化,得到表面磺酸化的苯乙烯-苯乙烯磺酸微球(PS-HSS@PS)。以PS-HSS@PS作为可回收的催化剂合成N-(乙氧基亚甲基)苯胺,并与对甲苯磺酸、商品化的强酸阳离子交换树脂的催化性能进行对比,结果表明,PS-HSS@PS的磺酸基含量和加入量对催化性能影响较大,磺酸基含量较高的PS-HSS@PS催化性能优异,产物收率可达97%,其活性优于强酸阳离子交换树脂(收率89%),与对甲苯磺酸相当(收率98%),且循环使用性能良好,循环使用5次,收率仍可达97%左右。
Polystyrene( PS) seed emulsion was first prepared by soap-free emulsion polymerization.Then,seeded emulsion polymerization of sodium p-styrenesulfonate and styrene was carried out to give styrene-styrene sulfonate copolymer microspheres( PS-Na SS @ PS) with core-shell structure. Finally,surface-sulfonated microspheres( PS-HSS@ PS) were obtained by treatment of PS-Na SS@ PS with HCl aqueous solution. PS-HSS @ PS as a recoverable catalyst was used to synthesize ethyl Nphenylformimidate,and its catalytic performance compared with that of p-toluene sulfonic acid and commercially available strong acidic cation-exchange resin. The results showed that the content of sulfonic group and the addition amount of PS-HSS @ PS had a great influence on the catalytic performance. The PS-HSS @ PS with higher content of sulfonic group exhibited a higher catalytic activity. The yield of ethyl N-phenylformimidate on PS-HSS@ PS was up to 97%. The activity of PSHSS@ PS was higher than that of strong acidic cation-exchange resin( 89%),and comparable to that of p-toluene sulfonic acid( 98%). Furthermore,PS-HSS@ PS had an excellent recyclability,and the yield of ethyl N-phenylformimidate could still reach about 97% even after recycling for five times.
Polystyrene( PS) seed emulsion was first prepared by soap-free emulsion polymerization.Then,seeded emulsion polymerization of sodium p-styrenesulfonate and styrene was carried out to give styrene-styrene sulfonate copolymer microspheres( PS-Na SS @ PS) with core-shell structure. Finally,surface-sulfonated microspheres( PS-HSS@ PS) were obtained by treatment of PS-Na SS@ PS with HCl aqueous solution. PS-HSS @ PS as a recoverable catalyst was used to synthesize ethyl Nphenylformimidate,and its catalytic performance compared with that of p-toluene sulfonic acid and commercially available strong acidic cation-exchange resin. The results showed that the content of sulfonic group and the addition amount of PS-HSS @ PS had a great influence on the catalytic performance. The PS-HSS @ PS with higher content of sulfonic group exhibited a higher catalytic activity. The yield of ethyl N-phenylformimidate on PS-HSS@ PS was up to 97%. The activity of PSHSS@ PS was higher than that of strong acidic cation-exchange resin( 89%),and comparable to that of p-toluene sulfonic acid( 98%). Furthermore,PS-HSS@ PS had an excellent recyclability,and the yield of ethyl N-phenylformimidate could still reach about 97% even after recycling for five times.
引文
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[12]Yang Nanhuang(杨南煌),Xie Deming(谢德明),Chen Ying(陈英).Polystyrene sulfonate by solution polymerization[J].Journal of Jinan University:Natural Science(暨南大学学报:自然科学版),2006,27(5):724-728.
[13]Ouyang Xinping(欧阳新平),Tan Chunmei(谭春枚),Qiu Xueqing(邱学青),et al.Synthesis of water-soluble styrene and styrene sulfonate copolymer and its dispersion and stable effect for suspension[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2010,24(4):681-687.
[14]Brijmohan S B,Swier S,Weiss R A,et al.Synthesis and characterization of cross-linked sulfonated polystyrene nanoparticles[J].Ind Eng Chem Res,2005,44:8039-8045.
[15]Xiao J Z,Zhang Z B,Nie J.Preparation,characterization and catalytic activity of polystyrene with pendent perfluoroalkylsulfonylimide groups[J].Journal of Molecular Catalysis A:Chemical,2005,236:119-124.
[16]Zhang Z B,Zhou S Y,Nie J.Polymer-supported sulfonimide as a novel water-tolerant Br9nsted acid catalyst for esterification of equimolar carboxylic acids and alcohols[J].Journal of Molecular Catalysis A:Chemical,2007,265:9-14.
[2]Meng Fanshun(孟凡顺).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(华东理工大学),2003.
[3]Roberts R M.Acid catalyzed reaction of diarylformamidines with ethyl orthoformate[J].Journal of the American Chemical Society,1949,71:3848-3849.
[4]Roberts 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.
[5]Roberts R M,Vogt P J.Ethyl N-phenylformimidate[J].Organic Syntheses,1955,35:65.
[6]Terence R C,Verona N J.Nickel complex pigments of bisazomethines:US4508899[P].1985-04-02.
[7]Okuhara T.Water-tolerant solid acid catalysts[J].Chemical Reviews,2002,102:3641-3666.
[8]Peng Baoxiang(彭宝祥),Wang Guangrun(王光润),Wang Jinfu(王金福).Synthesis of isopropenyl acetate(IPA)by esterification catalyzed by srong acidic cation-exchange resin[J].Fine Chemicals(精细化工),2007,24(7):719-723.
[9]Dang Zaiqing(党在清),Yang Jiangao(杨建高).Synthesis of ptert-butylphenol catalyzed by thermal stable strong acidity cation exchange resin[J].Technology&Development of Chemical Industry(化工技术与开发),2009,38(5):8-10.
[10]Zhao Zhigang(赵志刚),Shao Taili(邵太丽),Qin Guozheng(秦国正),et al.Ability of cation exchange resin H-732 as catalyst for esterification[J].Chemical Industry and Engineering Progress(化工进展),2012,31(7):1592-1596.
[11]Zhang Bo(张博),Wan Zhuanxin(万转欣),Huang Chunwei(黄纯伟),et al.Synthesis of per-O-acetylated carbohydrates catalyzed by cation exchange resin[J].Chemical Reagents(化学试剂),2012,34(9):826-828.
[12]Yang Nanhuang(杨南煌),Xie Deming(谢德明),Chen Ying(陈英).Polystyrene sulfonate by solution polymerization[J].Journal of Jinan University:Natural Science(暨南大学学报:自然科学版),2006,27(5):724-728.
[13]Ouyang Xinping(欧阳新平),Tan Chunmei(谭春枚),Qiu Xueqing(邱学青),et al.Synthesis of water-soluble styrene and styrene sulfonate copolymer and its dispersion and stable effect for suspension[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2010,24(4):681-687.
[14]Brijmohan S B,Swier S,Weiss R A,et al.Synthesis and characterization of cross-linked sulfonated polystyrene nanoparticles[J].Ind Eng Chem Res,2005,44:8039-8045.
[15]Xiao J Z,Zhang Z B,Nie J.Preparation,characterization and catalytic activity of polystyrene with pendent perfluoroalkylsulfonylimide groups[J].Journal of Molecular Catalysis A:Chemical,2005,236:119-124.
[16]Zhang Z B,Zhou S Y,Nie J.Polymer-supported sulfonimide as a novel water-tolerant Br9nsted acid catalyst for esterification of equimolar carboxylic acids and alcohols[J].Journal of Molecular Catalysis A:Chemical,2007,265:9-14.