含磷阻燃共聚酯的熔融增黏反应及其动力学

doi:10.13475/j.fzxb.20210101008

纺织学报 ›› 2021, Vol. 42 ›› Issue (11): 9-16.doi: 10.13475/j.fzxb.20210101008

含磷阻燃共聚酯的熔融增黏反应及其动力学

万苏影¹, 包建娜¹, 王滢¹, 张先明¹(), 陈世昌¹, 杨志超², 石教学², 陈文兴¹

1.浙江理工大学纺织纤维材料与加工技术国家地方联合工程试验室, 浙江杭州 310018
2.浙江古纤道绿色纤维有限公司, 浙江绍兴 312000

收稿日期:2021-01-07 修回日期:2021-04-14 出版日期:2021-11-15 发布日期:2021-11-29
通讯作者: 张先明
作者简介:万苏影(1995—),女,硕士生。主要研究方向为阻燃聚酯纤维材料。
基金资助:
浙江省重点研发计划项目(2020C01143);浙江省重点研发计划项目(2021C01020)

Melt polycondensation and kinetics of phosphorus containing flame retardant copolyesters

WAN Suying¹, BAO Jianna¹, WANG Ying¹, ZHANG Xianming¹(), CHEN Shichang¹, YANG Zhichao², SHI Jiaoxue², CHEN Wenxing¹

1. National Engineering Laboratory for Textile Fiber Materials & Processing Technology, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
2. Zhejiang Guxiandao Green Fiber Co., Ltd., Shaoxing, Zhejiang 312000, China

Received:2021-01-07 Revised:2021-04-14 Published:2021-11-15 Online:2021-11-29
Contact: ZHANG Xianming

摘要/Abstract

摘要：

为分析高黏度含磷阻燃共聚酯熔融后增黏反应的影响因素,以2-羧乙基苯基次膦酸(CEPPA)为阻燃剂合成了系列含磷阻燃共聚酯切片,并进行熔融增黏反应,研究反应温度、反应时间及含磷阻燃剂质量分数对阻燃共聚酯增黏效果的影响。结果表明:阻燃单体可成功引入聚酯中;在一定温度范围内,含磷阻燃共聚酯的熔融缩聚增黏效果较好,当温度超过一定范围时降解反应加剧,增黏变得困难;阻燃剂添加量越高,共聚酯黏度增加越困难;缩聚反应动力学研究发现,含磷阻燃共聚酯的反应速率常数随温度的升高而增大,随阻燃剂添加量的增加而减小;反应活化能随阻燃剂添加量的增加而增大,最高达到114.73 kJ/mol;基于正交试验分析熔融增黏反应的影响因素由大到小为反应时间、阻燃剂添加量、反应温度。

关键词: 含磷共聚酯, 阻燃聚酯, 熔融缩聚, 反应动力学, 熔融增黏反应

Abstract:

In order to study the influencing factors for melt polycondensation of high-viscosity phosphorus containing flame retardant copolyesters, flame retardant copolyesters with different phosphorus contents were synthesized by melt-polycondensation with 2-carboxyethyl (phenyl)phosphinic acid (CEPPA) as flame retardant. The melt polycondensation was conducted, and the effects of temperature, time and addition amount of phosphorus-containing flame retardant on intrinsic viscosity of copolyesters were investigated. The results show that the flame retardant is added into polyester successfully. The viscosity of copolyesters is increased significantly within a certain temperature range. When the temperature increases further, the degradation reaction intensified making the increase of viscosity more difficult. The more the addition of flame retardant, the more difficult it is to increase the viscosity. By establishing the reaction kinetics model, it was found that the reaction rate constant of flame retardant copolyesters increases with the increase of temperature, and decreases with the increase of flame retardant content.The activation energy increases with the increase of flame retardant content, the highest reaches 114.73 kJ/mol. The factors for melt polycondensation are analyzed based on the orthogonal experiment. The important order was found to be the reaction time, addition amount of flame retardant and reaction temperature.

Key words: phosphorus containing copolyester, flame retardant polyester, melt polycondensation, reaction kinetics, melt viscosity increasing reaction

中图分类号:

TQ342.92

万苏影, 包建娜, 王滢, 张先明, 陈世昌, 杨志超, 石教学, 陈文兴. 含磷阻燃共聚酯的熔融增黏反应及其动力学[J]. 纺织学报, 2021, 42(11): 9-16.

WAN Suying, BAO Jianna, WANG Ying, ZHANG Xianming, CHEN Shichang, YANG Zhichao, SHI Jiaoxue, CHEN Wenxing. Melt polycondensation and kinetics of phosphorus containing flame retardant copolyesters[J]. Journal of Textile Research, 2021, 42(11): 9-16.

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试样	阻燃剂质量分数/%	特性黏度/ (dL·g^-1)	磷元素含量		端羧基含量/ (mol·t^-1)	LOI 值/%
试样	阻燃剂质量分数/%	特性黏度/ (dL·g^-1)	理论值	实际值	端羧基含量/ (mol·t^-1)	LOI 值/%
PET	0	0.66	0.00	0.00	12.0	22
PEC₁T	1	0.54	1 447.00	1 389.79	14.3	28
PEC₃T	3	0.57	4 343.00	4 265.10	28.9	32
PEC₅T	5	0.55	7 238.00	7 186.09	37.2	36

试样	反应速率常数k/(g·mol^-1·min^-1)			活化能E/ (kJ·mol^-1)
试样	260 ℃	270 ℃	280 ℃	活化能E/ (kJ·mol^-1)
PET	125.79	155.33	206.69	74.83
PEC₁T	101.39	133.22	179.71	81.48
PEC₃T	88.54	114.08	159.12	104.17
PEC₅T	64.86	94.38	148.03	114.73

水平	A 反应温度/℃	B 反应时间/min	C 阻燃剂质量分数/%
1	260	30	0
2	270	60	1
3	280	90	5

试验号	A	B	C	特性黏度增长率/%
1	1	1	1	31.43
2	1	2	2	85.42
3	1	3	3	57.56
4	2	1	2	48.22
5	2	2	3	49.36
6	2	3	1	74.59
7	3	1	3	32.24
8	3	2	1	68.12
9	3	3	2	125.23
K₁	174.41	111.89	174.14
K₂	172.17	202.90	258.87
K₃	225.59	257.38	139.16
极差	17.81	48.50	39.90

含磷阻燃共聚酯的熔融增黏反应及其动力学

Melt polycondensation and kinetics of phosphorus containing flame retardant copolyesters

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