Journal of Textile Research ›› 2021, Vol. 42 ›› Issue (03): 64-70.doi: 10.13475/j.fzxb.20200700907

• Fiber Materials • Previous Articles     Next Articles

Kinetic study on synthesis of bottle polyester using Ti-Mg catalyst

GUAN Zhenyu1,2,3, ZHOU Wenle1, ZHANG Yumei2,3(), WANG Huaping2,3   

  1. 1. Shanghai Research Institute of Petrochemical Technology, China Petroleum & Chemical Corporation, Shanghai 201208, China
    2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
    3. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
  • Received:2020-07-03 Revised:2020-12-07 Online:2021-03-15 Published:2021-03-17
  • Contact: ZHANG Yumei E-mail:zhangym@dhu.edu.cn

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Abstract:

In order to study the effect of activity and hydrolysis resistance of titanium magnesium composite catalyst (TMPC) on the properties of high viscosity polyester for bottle production, the hydrolysis characteristics of the TMPC catalyst, molecular weight of polyester, acetaldehyde (AA) content and color of polyester were investigated, and the kinetics of esterification, melt polycondensation and solid-state polycondensation of different catalytic systems were studied in detail. The results show that TMPC is resistant to hydrolysis and has obvious catalytic effects on esterification and polycondensation. TMPC was found to be 36 times as active as antimony catalyst under the same polymerization conditions. The polycondensation time was proved 60 minutes shorter than that of ethylene glycol antimony (EGA), and the activity energy of esterification is lower than that of EGA and ethylene glycol titanium (EGT). The solid-state polycondensation rate of TMPC is close to that of EGA, and the activation energy is slightly higher than that of EGA. The high viscosity polyester with number-average molecular weight of 25 734 g/mol was obtained by solid-state polycondensation. The color phase of the product is similar to that of EGA catalyzed polyester, and the acetaldehyde content was as low as 0.59 μg/g, which could be used as a green and efficient catalyst for high viscosity bottle grade polyester.

Key words: Ti-Mg catalyst, bottle polyester, high viscosity polyester, polymerization kinetics, acetaldehyde content

CLC Number: 

  • TQ342.2

Tab.1

Performance of PET synthesized by different catalyst systems"

催化剂 缩聚工艺 催化剂用量/
(μg·g-1)		 稳定剂 特性黏度
(dL·g-1)		 数均分子量/
(g·mol-1)		 色相 端羧基含量/
(mol·t-1)		 乙醛含量/
(μg·g-1)
L b
EGA 熔融 180 PPA 0.741 14 746 85.9 3.23 29 88.00
固相 0.989 26 154 86.4 6.76 21 0.66
EGT 熔融 6 TEP 0.756 15 387 88.6 6.23 20 95.00
固相 0.966 25 167 87.1 8.48 11 0.87
TMPC 熔融 5 TEP 0.771 16 136 88.3 3.58 18 87.00
固相 0.974 25 734 87.6 7.10 9 0.59

Fig.1

Infrared spectra of PET basic chips synthesized by different catalytic systems. (a) ATR-IR of three kind of PET;(b) Local enlarged view after normalized"

Fig.2

Esterification kinetics of different catalytic systems. (a)Fit curve of relationship between esterification time and esterification rate; (b)Fit curve of relationship between T-1 and ln K"

Tab.2

Esterification activation energies of different catalyst systems"

催化剂 酯化时间/min 反应活化能/(kJ·mol-1)
EGA 105 24.4
EGT 92 20.9
TMPC 90 17.1

Fig.3

Melt polycondensation kinetics of different catalytic systems. (a) Fit curve of relationship between M ˉ n and polycondensation time at 286 ℃; (b)Fit curve of relationship between T-1 and lnK "

Tab.3

Polycondensation activation energies of different catalyst systems"

催化
剂		 温度/
℃		 K/(g·mol-1·
min-1)		 线性回归方程 ΔE/
(kJ·mol-1)
EGA 271 68.87 lnK=-10 209(1/T)+22.98 95.05
276 78.51
281 97.34
286 112.16
EGT 271 72.53 lnK=-9 838(1/T)+22.35 81.76
276 84.31
281 99.98
286 117.47
TMPC 271 102.10 lnK=-7 921(1/T)+23.38 65.82
276 116.87
281 129.58
286 152.27

Fig.4

Relationship between intrinsic viscosity and acetaldehyde content in solid state polymerizationprocess at 220 ℃"

Fig.5

Solid state polymerization kinetics of different catalytic systems. (a)Fit curve of relationship between t1/2 and M ˉ n at 220 ℃; (b)Fit curve of relationship between T-1 and lnK "

Tab.4

Solid state polymerization activation energies of different catalyst systems"

催化
剂		 固相缩聚
温度/℃		 K/(g·mol-1·
min-1)		 线性回归方程 ΔE/
(kJ·mol-1)
EGA 215 288.11 lnK=-2 250(1/T)+10.27 18.70
220 301.66
225 317.20
230 330.56
EGT 215 261.52 lnK=-2 504(1/T)+10.70 20.81
220 276.03
225 290.81
230 304.62
TMPC 215 270.06 lnK=-2 460(1/T)+10.64 20.44
220 285.61
225 299.60
230 314.43
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