单氨基改性PBO的AB型新单体的合成

doi:10.16085/j.issn.1000-6613.2016.04.037

化工进展 ›› 2016, Vol. 35 ›› Issue (04): 1197-1202.DOI: 10.16085/j.issn.1000-6613.2016.04.037

单氨基改性PBO的AB型新单体的合成

赵德明, 吴锋, 陈中海, 吴纯鑫, 张建庭, 金宁人

浙江工业大学化学工程学院, 浙江杭州 310014

收稿日期:2015-08-01 修回日期:2015-08-19 出版日期:2016-04-05 发布日期:2016-04-05
通讯作者: 赵德明(1976-),男,博士,副教授.E-mail:dmzhao@zjut.edu.cn.
基金资助:
江苏省重大科技计划支撑项目(BE2011129)及浙江省教育厅项目(Y201121211).

Synthesis of new AB monomers of amino modified PBO

ZHAO Deming, WU Feng, CHEN Zhonghai, WU Chunxin, ZHANG Jianting, JIN Ningren

College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2015-08-01 Revised:2015-08-19 Online:2016-04-05 Published:2016-04-05

摘要/Abstract

摘要： 研究了以4-(甲氧羰基)-2-硝基苯甲酸(β-MNT)与4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)为原料经酰氯化、N-酰化、环合、水解和催化加氢还原等一系列反应合成得到中间体4-((2,4-二羟基-5-硝基)氨甲酰基)-3-硝基苯甲酸甲酯(3-NMNC)、4-(5-硝基-6-羟基-2-苯并唑基)-3-硝基苯甲酸甲酯(3-NMNB)、4-(5-硝基-6-羟基-2-苯并唑基)-3-硝基苯甲酸(3-NNBA)及单氨基改性PBO的AB型新单体4-(5-氨基-6-羟基-2-苯并唑基)-3-氨基苯甲酸(3-AABA),并对环合、水解和催化还原加氢的反应条件进行了优化.结果表明:对于环合反应,以二乙二醇二甲醚为溶剂,PPA为环合脱水剂其中P₂O₅含量84%,w(PPA):w(3-NMNC)=9.5:1,反应温度140℃,反应时间8h,3-NMNB收率73.16%,HPLC纯度99.10%;水解反应,以乙醇与水为溶剂,n(K₂CO₃):n(3-NMNB)= 1.8:1,加热水解2h,3-NNBA收率74.19%,HPLC纯度为98.59%;催化加氢还原反应,甲醇为溶剂,w(10%Pd/C):w(3-NNBA)=1:20,1 MPa氢压,80℃反应5h得3-AABA,HPLC纯度99.43%,收率65.08%.中间体和产物结构经FT-IR、¹³C-NMR和ESI-MS表征确认.

关键词: 4-(5-硝基-6-羟基-2-苯并唑基)-3-硝基苯甲酸甲酯, 4-(5-氨基-6-羟基-2-苯并唑基)-3-氨基苯甲酸, 环合反应, 水解反应, 加氢还原反应

Abstract: Using 4-methoxycarbonyl-2-nitro-benzoic acid (β-MNT) and 4-amino-6-nitroresorcinolhydrochloride (ANR·HCl) as the starting materials, we synthesized the intermediates 4-(5-nitro-6-hydroxybenzoxazole-2-yl)-3-nitro-methyl benzoate (3-NMNC), 4-(5-nitro-6-hydroxybenzoxazole-2-yl)-3-nitrobenzoate (3-NMNB), 4-(5-nitro-6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-NNBA) and the final product 4-(5-amino-6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-AABA) through a series of reaction, including acylchloride, N-acylation, cyclization, hydrolysis and catalytichydrogenation reduction reaction. The optimal cyclization, hydrolysis and catalytichydrogenation reduction conditions were obtained. The experimental results for the cyclization reaction showed that taking diethyleneglycol dimethyl ether as solvent, the polyphosphoric acid(PPA) as dehydrant and the content of P₂O₅ in PPA of 84%, w(3-NMNC):w(PPA)=1:9.5, the reaction temperature of 140℃ and the reaction time of 8h, we obtained the yield of 3-NMNB of 73.16% and its purity was 99.10% as determined by HPLC. The experimental results for the hydrolysis reaction showed that using ethanol and water as solvent, n(K₂CO₃):n(3-NMNB) = 1.8:1 and the reaction time of 2h, we got the yield of 3-NNBA of 74.19% and the purity was 98.59% as determined by HPLC. The experimental results for the hydrogenation reduction reaction showed that using methanol as solvent, w(10%Pd/C):w(3-NNBA)=1:20, pressure of hydrogen of 1.0 MPa, reaction temperature of 80℃, reaction time of 5h, we had the yield of 3-AABA of 65.08% based on 3-NNBA and the purity was 99.43% as determined by HPLC.

Key words: 4-((2,4-dihydroxyl-5-nitrobenzophenonel)carbamoyl)-2,6-dihydroxyl methyl benzoate, 4-(5-nitro-6-hydroxy-2-benzoxazolyl-2,6-dyhydroxy methyl benzoate, cyclization reaction, hydrolysis reaction, hydrogenation reduction reaction

中图分类号:

TQ226.14

赵德明, 吴锋, 陈中海, 吴纯鑫, 张建庭, 金宁人. 单氨基改性PBO的AB型新单体的合成[J]. 化工进展, 2016, 35(04): 1197-1202.

ZHAO Deming, WU Feng, CHEN Zhonghai, WU Chunxin, ZHANG Jianting, JIN Ningren. Synthesis of new AB monomers of amino modified PBO[J]. Chemical Industry and Engineering Progree, 2016, 35(04): 1197-1202.

参考文献

[1] 吴惠英,段亚峰. 耐高温纤维的研究进展与应用[J]. 针织工业,2006
(2):24-27.
[2] 黄玉东. PBO超级纤维研究进展及其表面处理[J]. 高科技纤维与应用,2001,26(1):11-16.
[3] 金宁人,黄银华,王学杰. 超级纤维PBO的性能应用及研究进展[J]. 浙江工业大学学报,2003,31(1):82-87.
[4] 黄美荣,李新贵,王琳. 液晶芳香族聚苯唑纤维的性能[J]. 合成纤维工业,1999,22(3):33-37.
[5] 李玉青,黄英,齐暑华. PBO纤维表面改性的研究进展[J]. 中国胶黏剂,2009,4(18):64-68.
[6] TAN L S,ARNOLD F E,DANG T D,et al. Pseudo-ladder rigid-rod polymers:dihydroxy pendent benzothiazole aromaticheterocyclic polymer and copolymers[J]. Polymer,1994,35(14):3091-3101.
[7] LAMMERS M,KLOP E A,NORTHOLT M G,et al.Mechanical properties and structural transitions in the new rigid-rod polymer fibre PIPD (MS') during the manufacturing process[J]. Polymer,1998,39(24):5999-6005.
[8] 金婷婷,金宁人,何彪,等. 聚1,4-(2,5-二羟基)亚苯基-2,6-苯并二咪唑纤维的制备[J]. 浙江工业大学学报,2012,40(3):265-269.
[9] 赵德明,陈龙,宋嘉彬,等. 2,6-二羟基改性PBO的AB型新单体合成研究[J]. 化工进展,2015,34(2):519-523,533.
[10] 金宁人,张建庭,赵德明,等. 4-(5-氨基-6-羟基-2-苯并唑基)苯甲酸盐的合成、性能及应用[J]. 化工学报,2008,59(10):2680-2686.
[11] 金宁人,孙刚,谢品赞,等. 高选择性合成羟基对苯二甲酸单酯的反应规律及其应用[J]. 化工学报,2012,63(10):3337-3344.
[12] 金宁人,谢品赞,张建庭,等. 高纯度2-羟基对苯二甲酸的合成新技术[J]. 化工学报,2012,63(10):3337-3344.
[13] 金宁人,胡建民,王学杰. AB型聚对苯撑苯并二唑新单体及其制备与应用:200410093359[P]. 2004-07-27.
[14] 丁成. 氨基改性PBO的单体及其有关中间体合成与树脂探索[D]. 杭州:浙江工业大学,2013.
[15] 高鸿宾. 有机化学[M]. 4版. 北京:高等教育出版社,2004.
[16] HIRASHIMA T,MANABE O. Catalytic reduction of aromatic nitro compounds with hydrazine in the presence of iron(Ⅲ) chloride and active carbon[J]. Chemistry Letters,1975(3):260.
[17] JAN K,ZDENEK V. The preparation of 2-amine-4-nitrophenol:CS225036[P]. 1984-02-13.
[18] YUAN L H,SANFORD A R,FENG W,et al. Synthesis of crescent aromatic oligoamides[J]. The Journal of Organic Chemistry,2005,70(26):10660-10669.

单氨基改性PBO的AB型新单体的合成

Synthesis of new AB monomers of amino modified PBO

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