钛系和锑系催化剂对阻燃聚酯制备的影响

doi:10.19398/j.att.202104043

现代纺织技术 ›› 2022, Vol. 30 ›› Issue (4): 94-101.DOI: 10.19398/j.att.202104043

钛系和锑系催化剂对阻燃聚酯制备的影响

俞雨农¹, 郑兵², 蒲新明², 冯卫芳³, 张顺花¹

1.浙江理工大学材料科学与工程学院,杭州 310018;
2.万凯新材料股份有限公司,浙江海宁 314415;
3.正凯纺织有限公司,杭州 311223

收稿日期:2021-04-22 出版日期:2022-07-10 网络出版日期:2022-08-25
通讯作者:张顺花,E-mail:zshhzj@163.com
作者简介:俞雨农(1995-),男,杭州人,硕士研究生,主要从事高分子材料合成与加工技术方面的研究。
基金资助:
海宁市协同创新项目(20210102);萧山区重科技计划项目(20202105)

Effect of titanium and antimony catalysts on the preparation of flame retardant polyester

YU Yunong¹, ZHENG Bing², PU Xinming², FENG Weifang³, ZHANG Shunhua¹

1. College of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China;
2. Wankai New Materials Co., Ltd., Haining 314415, China;
3. Zhengkai Textile Co., Ltd., Hangzhou 311223, China

Received:2021-04-22 Published:2022-07-10 Online:2022-08-25

摘要/Abstract

摘要： 为了探究不同种类催化剂对阻燃聚酯聚合工艺及性能的影响,选用了两种钛系催化剂和一种锑系催化剂,以2-羧乙基苯基次磷酸为阻燃单体,采用直接酯化法合成阻燃改性共聚酯,探讨了不同的催化剂对合成共聚酯性能的影响。结果表明:两种钛系催化剂制备的阻燃聚酯(Ti-PET)的缩聚反应时间都长于锑系阻燃聚酯(Sb-PET),其特性黏度低于Sb-PET的;使用乙二醇钛作为催化剂制备的阻燃聚酯呈深黄色,采用自制的Ti/Zn催化剂制备的阻燃聚酯呈淡黄色;热分析测试表明:两种Ti-PET的熔点(T_m)、峰顶温度(T_p)都高于Sb-PET,其熔融热焓和结晶热焓都高于Sb-PET;其热稳定性更好,残碳量高;阻燃性能测试表明,3种阻燃聚酯的极限氧指数均在29.5% 左右,UL-94测试结果都达到V-0级。

关键词: 阻燃聚酯, 钛系催化剂, 锑系催化剂, 聚合

Abstract: In order to explore the influence of different types of catalysts on the polymerization process and properties of flame-retardant polyester, two kinds of titanium-based catalysts and one kind of antimony-based catalyst were selected to synthesize flame-retarded modified copolyesters by direct esterification methodusing 2-carboxyethyl (phenyl)phosphinicacid as the flame retarded monomer, and the influence of different catalysts on the performance of the copolyester was discussed. The results show that the polycondensation reaction time of the flame-retardant polyester (Ti-PET) prepared by the two titanium-based catalysts is longer than that of the flame-retardant polyester (Sb-PET) prepared by the antimony-based catalyst, and the intrinsic viscosity of the two Ti-PETs is lower than that of Sb-PET; the flame-retardant polyester prepared with ethylene glycol titanium catalyst is dark yellow, and the flame-retardant polyester prepared with self-made Ti/Zn catalyst is light yellow; DSC test shows that the melting temperature (T_m) and peak temperature (T_p) of two kinds of Ti-PET are higher than those of Sb-PET, and their melting enthalpy and crystallization enthalpy are also higher thanthose of Sb-PET; TG test shows that Ti-PET has good thermal stability and high residual carbon content; the fire performance test shows that the flame retardant performance of the three flame retardant polyesters is not much different, the limiting oxygen index is about 29.5%, and the UL-94 test results have reached the V-0 level.

Key words: flame-retardant polyester, titanium-based catalyst, antimony catalyst, polymerization process

中图分类号:

TB34

俞雨农, 郑兵, 蒲新明, 冯卫芳, 张顺花. 钛系和锑系催化剂对阻燃聚酯制备的影响[J]. 现代纺织技术, 2022, 30(4): 94-101.

YU Yunong, ZHENG Bing, PU Xinming, FENG Weifang, ZHANG Shunhua. Effect of titanium and antimony catalysts on the preparation of flame retardant polyester[J]. Advanced Textile Technology, 2022, 30(4): 94-101.

参考文献

[1] BUTSTRAEN C, SALAUN F, DEVAUX E, et al. Application of flame-retardant double-layered shell microcapsules to nonwoven polyester[J]. Polymers, 2016, 8(7): 267-281.
[2] SAMPERI F, PUGLISI C, ALICATA R, et al. Thermal degradation of poly(ethylene terephthalate) at the processing temperature[J]. Polymer Degradation and Stability, 2004, 83(1): 3-10.
[3] ZHAO H, WANG Y Z, WANG D Y, et al. Kinetics of thermal degradation of flame retardant copolyesters containing phosphorus linked pendentgroups[J]. Polymer Degradation and Stability,2003,80(1): 135-140
[4] 闫梦祥,张思源,王总帅,等.磷系阻燃剂阻燃PET的研究进展[J].中国塑料,2017,31(10):1-5.
YAN Mengxiang,ZHANG Siyuan,WANG Zongshuai, et al. Research progress in phosphorus flame retardants for polyesters[J]. China Plastics,2017,31(10):1-5.
[5] 俞雨农,蒲新明,郑兵,等.磷系阻燃聚酯的制备及其性能[J].浙江理工大学学报(自然科学版),2021,45(2):205-211.
YU Yunong, PU Xinming, ZHENG Bing, et al. Preparation and properties of phosphorus flame retardant polyester [J]. Journal of Zhejiang Sci-Tech University (Natural Sciences Edition),2021,45(2):205-211.
[6] 张日东,陈勇伟,周岚,等.2-羧乙基苯基次膦酸的胺化处理及其在尼龙6中的阻燃应用[J].浙江理工大学学报(自然科学版),2015,33(7):447-451.
ZHANG Ridong,CHEN Yongwei,ZHOU Lan, et al.Amination of 2-carboxyethyl phenylphosphonic acid and its flame retardant application in nylon 6 [J]. Journal of Zhejiang Sci-Tech University(NaturalSciences),2015,33(7):447-451.
[7] 黄意龙,龚静华,杨曙光,等.磷系阻燃共聚酯的结构与性能[J].功能高分子学报,2012,25(4):410-416.
HUANG Yilong,GONG Jinhua,YANG Shuguang, et al. Structure and properties of phosphorus flame retardant copolyester [J]. Journal of Functional Polymers,2012,25(4):410-416.
[8] WANG L S,WANG X L,YAN G L. Synthesis,characterisation and flame retardancebehaviour of poly(ethylene terephthalate) copolymer containing triaryl phosphine oxide[J]. Polymer Degradation and Stability,2000,69(1): 127-130.
[9] 李顶松,曹睿,赵玲.聚酯反应催化剂的研究[J].聚酯工业,2020,33(2):32-34.
LI Dingsong,CAO Rui,ZHAO Ling, et al.Study on catalyst for polyester reaction[J]. Polyester Industry,2020,33(2):32-34.
[10] 郑晓旭,梁建荣,汪子翔,等.环保型PET用钛系催化剂的研究进展[J].合成纤维工业,2020,43(6):59-63.
ZHENG Xiaoxu,LIANG Jianrong,WANG Zixiang, et al. Research progress of environmental friendly titanium catalyst for PET[J].China Synthetic Fiber Industry,2020,43(6):59-63.
[11] 马楷,刘绍英,王公应.聚丁二酸乙二醇酯合成的研究进展[J].中国塑料,2012,26(5):1-6.
MA Kai,LIU Shaoying,WANG Gongying. Research progress in synthesis of poly(ethylene glycol succinate)[J]. China Plastics,2012,26(5):1-6.
[12] 章瑛虹.钛系聚酯催化剂催化活性的影响因素研究[J].合成纤维工业,2012,35(4):8-11.
ZHANG Yinghong. Influential factors on catalytic activity of titanium catalyst for polyester[J]. China Synthetic Fiber Industry,2012,35(4),8-11.
[13] 张大省.钛系催化剂在聚对苯二甲酸乙二醇酯合成中的应用[J].纺织导报,2020(1):48-52.
ZHANG Daxing. Titanium catalyst for the synthesis of polythylene terephthalate[J]. China Textile Leader,2020,1(6):48-52.
[14] 俞雨农.阻燃改性聚酯的制备及性能研究[D].杭州:浙江理工大学,2021.
YU Yunong. Preparation and Performance of Flame Retardant Modified Polyester[D].Hangzhou: Zhejiang Sci-Tech University, 2021.

[1]	谢尚栋, 孙黎江, 朱开阳, 陈世昌, 陈文兴. Ti-Al双金属催化剂制备PEIT共聚酯及其热性能[J]. 现代纺织技术, 2022, 30(5): 89-96.
[2]	何佳灵, 王滢. 基于钛系催化剂制备的聚酯性能分析[J]. 现代纺织技术, 2022, 30(3): 47-51.
[3]	王延蒙, 秦鹏, 张文国. 基于分段聚合和卡尔曼滤波的纱线直径时间序列预测[J]. 现代纺织技术, 2022, 30(2): 41-47.
[4]	盛婷, 张佳文, 徐天祺, 胡叶蕾, 易玲敏. 基于纳米粒子改性短链含氟整理剂的棉织物拒水拒油整理[J]. 现代纺织技术, 2022, 30(2): 169-177.
[5]	刘凡，赵晓明，郑煜昊，赵润德. 导电聚合物/磁性粒子复合吸波材料的研究进展[J]. 现代纺织技术, 2021, 0(6): 7-18.
[6]	吴跃亚，蒲新明，郑兵，张顺花. 微量氧化石墨烯改性聚酯的制备及性能研究[J]. 现代纺织技术, 2021, 0(4): 96-101.
[7]	崔妞妞,张彩玉,李家炜,顾健军,戚栋明,厉巽巽,陈玉霜. 温度响应涂层棉织物的制备及其可逆润湿性能研究[J]. 现代纺织技术, 2021, 0(3): 84-88.
[8]	杨丹，刘丽妍，韩永良. 增强型中空纤维膜界面处理及结合强度表征进展研究[J]. 现代纺织技术, 2021, 0(2): 22-28.
[9]	李伟翔，易玲敏，钟申洁，左甜. 有机硅型杂化乳液的制备及其在棉织物防水整理中的应用[J]. 现代纺织技术, 2020, 0(4): 78-83.
[10]	胡静，陈智杰，谢子文，王刚，冯梦龙，李家炜，黄骅隽，戚栋明. 高颜料含量的聚丙烯酸酯包覆改性颜料的制备及其在水相介质中的分散稳定性[J]. 现代纺织技术, 2020, 0(4): 64-70.
[11]	邓成浩，汪进前，李朝利，盖燕芳. 改性纳米TiO2/丙烯酸酯复合乳液的制备及研究[J]. 现代纺织技术, 2019, 0(05): 1-5.
[12]	张德立，喻进华，田厚宽. 静电纺丝聚合物纳米纤维力学性能表征及凝聚态结构研究进展[J]. 现代纺织技术, 2019, 0(03): 10-15.
[13]	赵敏，张德锁，陈宇岳，林红. HBP-NH-2调控掺金纳米二氧化钛的制备及其光催化性能研究[J]. 现代纺织技术, 2018, 0(04): 52-57.
[14]	董雅婕，梅顺齐，孔令学. 离心转子法制备纳米纤维技术研究[J]. 现代纺织技术, 2017, 0(06): 81-86.
[15]	易玲敏，叶星星. 不同温度下酸催化有机硅单体开环共聚制备含氢硅油的研究[J]. 现代纺织技术, 2017, 0(02): 50-53.

钛系和锑系催化剂对阻燃聚酯制备的影响

Effect of titanium and antimony catalysts on the preparation of flame retardant polyester

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics