聚对苯二甲酸丙二醇酯-聚四氢呋喃嵌段共聚物的合成与表征

doi:10.13475/j.fzxb.20250300101

纺织学报 ›› 2025, Vol. 46 ›› Issue (11): 19-25.doi: 10.13475/j.fzxb.20250300101

聚对苯二甲酸丙二醇酯-聚四氢呋喃嵌段共聚物的合成与表征

董海良¹^,²^,³, 卫婷³, 况军³, 陈烨¹^,²()

1.东华大学先进纤维材料全国重点实验室, 上海 201620
2.东华大学材料科学与工程学院, 上海 201620
3.中石化(上海)石油化工研究院有限公司, 上海 201208

收稿日期:2025-02-21 修回日期:2025-08-14 出版日期:2025-11-15 发布日期:2025-11-15
通讯作者: 陈烨(1982—),男,教授,博士。主要研究方向为高保形纤维及循环再生。E-mail:chenye@dhu.edu.cn。
作者简介:董海良(1988—),男,博士生。主要研究方向为生物基聚酯新材料。
基金资助:
上海市自然科学基金面上项目(24ZR1400200)

Synthesis and characterization of poly(trimethylene terephthalate)-block-poly(tetramethylene glycol) copolymers

DONG Hailiang¹^,²^,³, WEI Ting³, KUANG Jun³, CHEN Ye¹^,²()

1. State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
2. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
3. Sinopec Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, China

Received:2025-02-21 Revised:2025-08-14 Published:2025-11-15 Online:2025-11-15

摘要/Abstract

摘要：

针对以不同软硬段质量比合成的聚对苯二甲酸丙二醇酯嵌段聚四氢呋喃(PTT-b-PTMG)尚缺乏系统性研究的现状,采用直接酯化-熔融缩聚方法合成了系列不同硬度的PTT-b-PTMG共聚酯,借助红外光谱仪、核磁共振仪、凝胶渗透色谱仪、乌氏黏度计、差示扫描量热仪、热重分析仪、X射线衍射仪等仪器,对PTT-b-PTMG共聚酯的结构与性能进行表征。结果表明:随软段含量增加,PTT-b-PTMG共聚酯的特性黏度、分子量增加,分子序列结构中的PTT硬段链段长度变短,邵氏硬度、熔点、结晶温度下降,而所有共聚物在室温下都具有与均聚PTT 相同的晶体结构;随软段含量增加,拉伸强度、拉伸模量下降,断裂伸长率提升;共聚酯具有良好的热稳定性。

关键词: 聚对苯二甲酸丙二醇酯, 直接酯化, 软段含量, 嵌段共聚酯, 硬度, 分子序列结构, 热塑性聚酯弹性体

Abstract:

Objective To enrich the variety of traditional polybutylene terephthalate-based thermoplastic polyether ester elastomer and address the poor elastic recovery performance in the field of fiber materials, new types of thermoplastic polyether ester elastomer (TPEE) were synthesized by direct esterification and melt polycondensation using bio-based poly(trimethylene terephthalate) as hard segment contents, aiming to achieve a series of poly(trimethylene terephthalate)-block- poly(tetramethylene glycol) (PTT-b-PTMG)with different hardness. This study aims to investigate the effects of different soft segment contents on the structure and properties of PTT-b-PTMG, so as to provide support for the development and application of the thermoplastic polyether ester elastomer.
Method A series of PTT-b-PTMG copolymers with different hardness were synthesized by direct esterification melt polycondensation. The structure and properties of PTT-b-PTMG copolyesters were characterized by FT-IR, ¹H-NMR, gel permeation chromatography (GPC), viscosity analyzer, differential scanning calorimeter (DSC), thermogravimetry (TG), wide-angle X-ray diffraction (WAXS), etc.
Results The results showed that PTT-b-PTMG copolyester was successfully synthesized evidenced by FT-IR, ¹H-NMR, and GPC analysis and the soft segment mass fraction calculated by ¹H-NMR spectra were close to the theoretical addition value.The influences of soft segment contents on the structure and properties of PTT-b-PTMG copolyesters were studied by changing the soft segment contents. The results showed that as the content of soft segments increase, the intrinsic viscosity and molecular weight of copolyesters increased with the increase of soft segments ratio from 0% to 60%. With the increase of soft segments content, the length of PTT hard segment segments in the molecular sequence structure decreased from 16.3 to 4.5, the elongation at break increased from 49% to 542%, the tensile strength decreased from 26 MPa to 13 MPa, the Young's modulus decreased from 2 012 MPa to 62 MPa and the Shore hardness decreased from 65 to 38. WAXS revealed that all copolymers had the same crystal structure of homo-PTT at room temperature. With the increase of soft segments content, melting point shifted from 223.2 ℃ to 178.7 ℃ with the enthalpy of melting decreased from 43.2 J/g to 16.2 J/g and crystallization temperature shifted from 178.0 ℃ to 132.5 ℃with the enthalpy of crystallization decreased from 49.0 J/g to 19.5 J/g. The thermal degradation performance showed that all copolyester had good thermal stability, with the increase of soft segments content, the residual carbon content decrease from 6.8% to 1.0%, when the content of soft segments is 60%, the thermal stability of the copolyester show better than other content, slightly worse than pure PTT.
Conclusion A series of PTT-b-PTMG copolyesters were successfully synthesized by direct esterification and melt polycondensation. The crystal structure of PTT-b-PTMG copolyesters was found to be consistent with that of PTT by WAXS. With the increase of soft segment content, the intrinsic viscosity and molecular weight of the copolyesters increased, the mean chain length of the hard segment PTT of the molecular sequence structure decreased, the hardness, melting point and crystallization temperature decreased, and the crystallization property deteriorated. The thermal stability results suggest that copolyesters have good thermal stability, and the residual carbon content decreases with the increase of soft segment content. In addition, the increase of soft segment content leads to the change of mechanical properties, the decrease of tensile strength and tensile modulus, and the increase of elongation at break. In this paper, the properties of PTT-b-PTMG with different proportion of soft and hard segments are studied. By changing the content of soft segments, the hardness, tensile modulus, elongation at break and other mechanical properties could be precisely controlled. This work provides more raw material options for the application in the field of TPEE elastic fiber materials.

Key words: poly(trimethylene terephthalate), direct esterification, soft segment content, block copolymer, hardness, molecular sequence structure, thermoplastic polyether ester elastomer

中图分类号:

TQ334

董海良, 卫婷, 况军, 陈烨. 聚对苯二甲酸丙二醇酯-聚四氢呋喃嵌段共聚物的合成与表征[J]. 纺织学报, 2025, 46(11): 19-25.

DONG Hailiang, WEI Ting, KUANG Jun, CHEN Ye. Synthesis and characterization of poly(trimethylene terephthalate)-block-poly(tetramethylene glycol) copolymers[J]. Journal of Textile Research, 2025, 46(11): 19-25.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20250300101

http://www.fzxb.org.cn/CN/Y2025/V46/I11/19

图/表 13

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表3

PTT-b-PTMG共聚酯的热稳定性能"

样品编号	T_5%/℃	T_25%/℃	$T 50 %$ /℃	T_max/℃	W_f/%
S₀	367.5	388.0	399.3	399.7	6.8
S₃₀	364.2	384.9	398.0	401.7	4.7
S₄₀	361.7	386.5	399.2	402.7	3.1
S₅₀	360.2	387.2	398.0	403.1	2.2
S₆₀	365.0	388.8	401.0	405.0	1.0

表3

图9

表4

参考文献 12

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样品编号	W_PTMG/%	M_n ×10³/ (g·mol^-1)	M_w×10³/ (g·mol^-1)	M_w/M_n	L_n
S₀	—	38.6	71.3	1.84	—
S₃₀	28.0	40.8	77.3	1.89	16.3
S₄₀	39.4	42.2	79.4	1.84	9.4
S₅₀	49.7	43.9	81.3	1.85	6.5
S₆₀	61.1	46.6	82.9	1.78	4.5

样品编号	T_m/℃	ΔH_m(J·g^-1)	T_p/℃	ΔH_c(J·g^-1)
S₀	223.2	43.2	178.0	49.0
S₃₀	213.7	38.8	169.1	35.1
S₄₀	209.5	32.2	165.1	35.0
S₅₀	194.9	22.0	157.5	19.6
S₆₀	178.7	16.2	132.5	19.5

样品名称	拉伸模量/MPa	断裂强度/MPa	断裂伸长率/%
S₀	2 012±3.2	26±0.3	49±10
S₃₀	289±3.5	24±0.2	387±15
S₄₀	178±2.6	21±0.3	353±13
S₅₀	107±2.1	17±0.2	395±16
S₆₀	62±2.3	13±0.5	542±14

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聚对苯二甲酸丙二醇酯-聚四氢呋喃嵌段共聚物的合成与表征

Synthesis and characterization of poly(trimethylene terephthalate)-block-poly(tetramethylene glycol) copolymers

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