Journal of Textile Research ›› 2019, Vol. 40 ›› Issue (10): 13-19.doi: 10.13475/j.fzxb.20181000607

• Fiber Materials • Previous Articles     Next Articles

Kinetics and properties of phosphorus flame retardant copolymerized polyester

CHEN Yong1, WANG Ying1, HE Feng1, WANG Jing1, ZHU Zhiguo1(), DONG Zhenfeng1, WANG Rui1,2   

  1. 1. School of Materials Science and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China
    2. Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing 100029, China;
  • Received:2018-10-09 Revised:2019-07-05 Online:2019-10-15 Published:2019-10-23
  • Contact: ZHU Zhiguo E-mail:clyzzg@bift.edu.cn

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Abstract:

In order to investigate the reaction law and influencing factors of copolymerized phosphorus-based flame retardant polyesters(PET), flame retardant co-PETs was prepared by using 2-carboxyethyl phenyl phosphinic acid (CEPPA) as a co-monomer flame retardant. The kinetic model of the polycondensation reaction of PET and flame retardant co-PETs were established, and the trend and reasons of the kinetic model were analyzed. The structure and properties of polymer were characterized by infrared spectroscopy, differential scanning calorimetry, thermogravimetry, limiting oxygen index and cone calorimetry. The results show that with the increase of the mass fraction of CEPPA, the actiration energy of reaction increases to 106.83 kJ/mol. The glass transition temperature and melting point decreases with the increase of the flame retardant because the group structure of CEPPA is polymerized into the macromolecular chain, which inhibits the crystallization of the PET. PET with the phosphorus content of 1% can achieve the optimal flame retardancy, limit oxygen index can be up to 31%, the ignition time is prolonged obviously, and the peak heat release rate decreases by 24%.

Key words: polyester, kinetics model of polycondensation, flame retardant, phosphorus-containing flame retardant polyester

CLC Number: 

  • TQ311

Fig.1

Change of molecular weight of flame retardant PET of different padditions with time"

Tab.1

Linear regression equations for PET with different padditions"

磷质量
分数/%		 聚合温
度/℃		 回归方程 R2
0.0 275 Mt=203.18t+746.5 0.99
280 Mt=230.90t+1 598.0 0.99
285 Mt=252.49t+1 485.0 0.99
0.6 275 Mt=179.70t+1 411.6 0.97
280 Mt=206.85t+1 178.1 0.97
285 Mt=235.75t+2 376.8 0.96
0.8 275 Mt=157.17t+816.2 0.98
280 Mt=199.14t+366.8 0.96
285 Mt=229.54t+1 501.1 0.97
1.0 275 Mt=138.86t+254.6 0.98
280 Mt=185.91t+691.6 0.98
285 Mt=211.23t+693.3 0.98

Tab.2

Effect of polymerization temperature on apparent reaction rate constant of different systems"

磷质量分
数/%		 K/(g·(mol·min)-1)
275 ℃ 280 ℃ 285 ℃
0.0 203.18 230.90 252.49
0.6 179.70 206.85 235.75
0.8 157.17 199.14 229.54
1.0 138.86 185.91 211.23

Tab.3

Result of activation energies and pre-exponential factors for different polymerization systems"

磷质量分
数/%		 lnK与T-1方程 Ea/
(kJ·mol-1)		 A0/
(g·(mol·min)-1)
0.0 lnK=-6 651T-1 + 17.45 55.30 3.80×107
0.6 lnK=-8 307T-1 + 20.35 69.06 6.86×108
0.8 lnK=-11 596T-1 + 26.23 96.41 2.46×1011
1.0 lnK=-12 849T-1 + 28.40 106.83 2.16×1012

Fig.2

Infrared spectra of PET and flame retardant PET"

Fig.3

DSC spectra of PET and flame retardant PET"

Tab.4

TGA data for PET and flame retardant PET"

样品
编号		 初始分解
温度/℃		 最大分解速
率温度/℃		 最终残
碳量/%
1# 397.7 431.6 22.5
2# 396.0 429.9 21.0
3# 395.0 428.8 20.7
4# 389.9 430.7 21.2
5# 387.3 430.9 17.8
6# 387.1 432.1 16.6
7# 390.0 429.9 22.3
8# 389.2 430.1 23.9
9# 382.9 429.7 17.4
10# 384.1 430.9 19.3
11# 383.7 429.6 18.5
12# 382.8 428.7 18.7

Fig.4

Cone calorimetry test curve of sample. (a)Curve of heat release rate; (b)Curve of total heat release"

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