芳香族尼龙合成中国专利技术分析

doi:10.16085/j.issn.1000-6613.2016.04.046

摘要/Abstract

摘要： 对近30年芳香族尼龙合成领域申请的中国专利进行了检索和统计,从化学结构、地区分布和申请单位角度总结了专利申请现状,按合成方法对专利技术进行分类讨论.低温溶液缩聚法反应条件温和,但是需采用有机溶剂,成本较高.界面缩聚法反应温度较低,但溶剂消耗量大,需要采用高反应性能的单体.水相溶液缩聚法原料价廉,缩聚过程的升温程序多样,常采用间歇聚合工艺,应用较为广泛.直接熔融缩聚法不用溶剂,压力较低,但是只适用于较易熔融的单体原料.通过本文分析得出,原料中含对苯二甲酸的芳香族尼龙是得到较为深入研究的芳香族尼龙品种,水相溶液缩聚法是最适合工业化的合成方法,未来有望在这些方面取得一定工业化应用成果.

关键词: 半芳香, 尼龙, 间歇式, 溶剂, 聚合

Abstract: The Chinese patents in the field of aromatic polyamide's synthesis were reviewed. We summarized the existing patents based on the chemical structure, regional distribution and application affiliation, respectively. We also made a discussion of the patents based on the synthesis method. The reaction condition of polycondensation at low temperature is easy to achieve, but it needs organic solvent and therefore increases the cost. The temperature of interface polycondensation method is low, but it consumes large amount of solvent, and needs high reactive monomers. The raw materials of aqueous phase polycondensation is cheap, and has various temperature rise programming. It often uses batch operation and is widely applied in many aromatic nylon's synthesis. Direct melt polycondensation requires no solvent, and reacts in low pressure. But it can only be applied to monomers that is easy to melt. We conclude that the aromatic nylons with terephthalic acid as raw material have been studied extensively, while the aqueous phase polycondensation is the most suitable method for industrialization. It is expected to achieve some industrial applications in these areas in future.

Key words: semiaromatic, nylon, batchwise, solvents, polymerization

中图分类号:

TQ323.6

万利, 冯连芳, 顾雪萍. 芳香族尼龙合成中国专利技术分析[J]. 化工进展, 2016, 35(04): 1257-1262.

WAN Li, FENG Lianfang, GU Xueping. Chinese patent analysis of aromatic nylon's synthesis[J]. Chemical Industry and Engineering Progree, 2016, 35(04): 1257-1262.

参考文献

[1] VANNINI M,MARCHESE P,CELLI A,et al. Block and random copolyamides of (poly(m-xylylene adipamide) and poly(hexamethylene isophthalamide-co-terephthalamide):methods of preparation and relationships between molecular structure and phase behavior[J]. Polymer Engineering & Science,2015,55(7):1475-1484.
[2] 姚臻,周亚单,曹堃. 透明聚酰胺的研究进展[J]. 化工进展,2014,33(12):3276-3282.
[3] 鲁尔肯斯 R,克洛姆巴赫 R C B. 基于四亚甲基对苯二酰胺和六亚甲基对苯二酰胺的共聚酰胺:1384847[P]. 2002-12-11.
[4] 加藤公哉,秋田大,松冈英夫. 聚酰胺树脂、聚酰胺树脂组合物以及它们的成型体:102131845[P]. 2011-07-20.
[5] 尼切 J,赫格尔 H,格尔肯斯 S,等. 基于部分芳族的共聚酰胺的模塑料:104448794[P]. 2015-03-25.
[6] 殷炼伟,沈俊毅. 半芳香族聚酰胺的制备方法:104530421[P]. 2015-04-22.
[7] 神田智道,菊地稔,篠原克巳,等. 共聚聚酰胺树脂、其制造方法、树脂组合物和由它们形成的成型品:102648232[P]. 2012-08-22.
[8] 李澜鹏,白富栋,王艳,等. 一种全芳香族聚酰胺的合成方法:104558594[P]. 2015-04-29.
[9] 邢哲,郭润东,李吉东. 一种提高间位芳香族聚酰胺聚合体阻燃性的方法:1683431[P]. 2005-10-19.
[10] 赵清香,刘民英,杨韶辉,等. 一种长碳链稠环半芳香尼龙及其合成工艺:101289535[P]. 2008-10-22.
[11] 罗湘安,曾祥斌,蔡彤旻,等. 一种耐高温尼龙/PEN/PET共聚物及其制法与应用:102634012[P]. 2012-08-15.
[12] 潘育英,刘文良,蔡兴明. 以芳杂环、氯代单体改性的聚芳酰胺树脂的制造方法:101165078[P]. 2008-04-23.
[13] 黄玉东,贺金梅,胡君,等. 一种含噁唑环半芳香聚酰胺及其合成方法:101280057[P]. 2008-10-08.
[14] 李 K-S. 芳族聚酰胺共聚物:103703056[P]. 2014-04-30.
[15] 王凤德,彭涛,陈超峰,等. 一种高强高模杂环芳纶的制备:101787582[P]. 2010-07-28.
[16] MALLON F K. Process for forming an aramid copolymer:WO2013019598[P]. 2013-02-07.
[17] MALLON F K. Process for forming an aramid copolymer:US8921512[P]. 2014-12-30.
[18] 伯西 P,莱恩曼 A,步鲁尔 B. 基于MXD.10聚酰胺的不透性结构:101198653[P]. 2008-06-11.
[19] BUSSL P,LINEMANN A,BRULLE B. MXD.10 polyamide-based barrier structures:WO2006108721[P]. 2006-10-19.
[20] BUSSL P,LINEMANN A,BRULLE B. MXD.10 polyamide-based barrier structures:US20080193691[P]. 2008-08-14.
[21] 霍夫曼 B,霍夫 H,利德洛夫 H-J,等. 共聚酰胺:1745124[P]. 2006-03-08.
[22] HOFFMANN B,HOFF H,LIEDLOFF H,et al. Copolyamides:WO2004055084[P]. 2004-07-01.
[23] 曹煜彤,周助胜,张浩,等. 一种芳香族共聚酰胺纤维的制备方法:102926022[P]. 2013-02-13.
[24] 陈蕾,胡祖明,于俊荣,等. 一种半连续化制备含杂环的共聚芳香族聚酰胺溶液的方法:101985497[P]. 2011-03-16.
[25] 蔡邦肖. 多层聚酰胺复合膜的制备方法:1951549[P]. 2007-04-25.
[26] 俞三传,周勇,高从堦. 高通量聚酰胺反渗透复合膜:1778457[P]. 2006-05-31.
[27] 沢田雅博. 聚酰胺树脂,聚酰胺树脂组合物和其成形制品及其电子部件基板的制造方法:1356348[P]. 2002-07-03.
[28] 中井诚,森本真梨子,竹田裕孝. 半芳香族聚酰胺及其制造方法:102741323[P]. 2012-10-17.
[29] 谷勤翠,张怀忠,杨桂生. 一种长碳链半芳香耐高温聚酰胺的均聚物和共聚物及其合成方法:102153741[P]. 2011-08-17.
[30] 赫韦尔曼弗雷德. 半芳族聚酰胺模塑组合物及其用途:101298517[P]. 2008-11-05.
[31] 拜尔·安德烈亚斯,赫韦尔·曼弗雷德. 部分芳族的聚酰胺模塑组合物及其用途:102372920[P]. 2012-03-14.
[32] 菲利普·布朗德尔,蒂里·布里福德,安尼特·莱恩曼,等. 具有低水分吸收的柔软半芳族聚酰胺:1590461[P]. 2005-03-09.
[33] 冈秀明,原哲也,佐佐木繁. 半芳香族聚酰胺:1590433[P]. 2005-03-09.
[34] 张传辉,蔡彤旻,曾祥斌,等. 一种聚酰胺树脂和其应用以及由其组成的组合物:103087310[P]. 2013-05-08.
[35] 鲁迪·鲁肯斯,罗伯特·康拉德·芭芭拉·克鲁姆巴赫. 半结晶半芳族聚酰胺:101374884[P]. 2009-02-25.
[36] 刘民英,赵清香,付鹏,等. 一种半芳香尼龙的制备方法:101768266[P]. 2010-07-07.
[37] 施特劳赫 J,李斯-索尔 T,格鲁茨奈尔 R-E,等. 由间苯二甲胺和己二酸形成的且端氨基含量小于15mmol/kg的聚酰胺:101296967[P]. 2008-10-29.
[38] 尼切 J,赫格 H,格尔肯斯 S,等. 基于部分芳族的共聚酰胺的模塑料:104448810[P]. 2015-03-25.
[39] 加藤公哉,秋田大,松冈英夫. 聚酰胺树脂、聚酰胺树脂组合物以及它们的成型体:102131845[P]. 2011-07-20.
[40] 维尔思 M. 以共聚酰胺PA-6,I/6,T/6,6和/或PA-6,I/6,T为基的,可拉制和或热成型的,防潮耐变形的阻挡材料:1192449[P]. 1998-09-09.
[41] 佐佐木幸义,坂田范夫,佐久间照章,等. 聚酰胺共聚物及成形品:102482416[P]. 2012-05-30.
[42] RICHARDSON J A,POPPE W,BOLTON B A,et al. Polycondensation process with mean dispersion residence time:US4831108[P]. 1989-05-16.
[43] HURLEY J M,BERSTED B H. Method for reducing mold deposit formation during moldings of polyamide and composition therefore:US6518341[P]. 2003-02-11.
[44] 维尔特泽 K,摩根斯泰恩 G,劳斯曼 P. 连续生产熔点高于265℃的共聚酰胺的方法和装置:1993401[P]. 2007-07-04.
[45] 过井康人,丸山岳,小川薰,等. 聚酰胺的连续制备方法:1678660[P]. 2005-10-05.