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

Abstract

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

CLC Number:

TQ342.92

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

Melt polycondensation and kinetics of phosphorus containing flame retardant copolyesters

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