聚丁二酸丁二醇酯熔融缩聚增黏特性

doi:10.16085/j.issn.1000-6613.2023-1642

化工进展 ›› 2024, Vol. 43 ›› Issue (10): 5663-5670.DOI: 10.16085/j.issn.1000-6613.2023-1642

• 材料科学与技术 • 上一篇

聚丁二酸丁二醇酯熔融缩聚增黏特性

徐涛¹^,²(), 王勇军¹^,², 林启松², 戴钧明², 查全亮³, 吕汪洋¹^,²(), 陈文兴¹^,²

^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实验室，浙江杭州 310018
^2.浙江省现代纺织技术创新中心，浙江绍兴 312000
^3.绍兴九洲化纤有限公司，浙江绍兴 312000

收稿日期:2023-09-18 修回日期:2023-11-13 出版日期:2024-10-15 发布日期:2024-10-29
通讯作者: 吕汪洋
作者简介:徐涛（1998—），男，硕士研究生，研究方向为生物可降解聚丁二酸丁二醇酯（PBS）的合成。E-mail：202120301064@mails.zstu.edu.cn。
基金资助:
浙江省“尖兵领雁”研发攻关计划(2024SJCZX0028)

Viscosification properties of poly(butylene succinate) by melt polycondensation

XU Tao¹^,²(), WANG Yongjun¹^,², LIN Qisong², DAI Junming², ZHA Quanliang³, LYU Wangyang¹^,²(), CHEN Wenxing¹^,²

^1.National Engineering Laboratory for Textile Fiber Materials & Processing Technology, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China
^2.Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing 312000, Zhejiang, China
^3.Shaoxing Jiuzhou Chemical Fiber Company Limited, Shaoxing 312000, Zhejiang, China

Received:2023-09-18 Revised:2023-11-13 Online:2024-10-15 Published:2024-10-29
Contact: LYU Wangyang

摘要/Abstract

摘要：

为解决生物可降解聚丁二酸丁二醇酯（PBS）长期正常储存过程中易发生降解而导致分子量下降的难题，通过熔融缩聚增黏方法实现了PBS分子量的提升。研究了反应温度、反应时间、初始特性黏度以及熔体膜厚等对PBS特性黏度、分子量、热性能和流变性能的影响。结果表明：PBS分子量随熔融缩聚增黏温度升高而升高；220℃反应60min，PBS特性黏度即可从1.049dL/g升至2.072dL/g；PBS初始黏度越低其增黏速率越高；而PBS的熔体膜厚与其增黏反应速率呈反比；PBS特性黏度的升高导致结晶困难，进而使其熔点下降。流变测试结果表明随着特性黏度升高，PBS熔体强度与热稳定性均提升，能满足重新加工和使用的需求，通过熔融再聚合方法可有效解决PBS因降解而无法满足其后续加工和使用需求的难题。

关键词: 聚合物, 聚合, 聚合物加工, 聚丁二酸丁二醇酯, 熔融缩聚, 热性能, 流变性能

Abstract:

In order to solve the problem of degradation and aging of biodegradable poly (butylene succinate) (PBS) during long-term normal storage, the molecular weight of PBS was improved by melt polycondensation. The viscosity, molecular weight, thermal properties and rheological properties of PBS were studied under various reaction temperatures, reaction time, initial viscosity and melt film thickness. The results showed that the molecular weight of PBS increased with the increasing of melt polycondensation temperatures. The intrinsic viscosity of PBS increased from 1.049dL/g to 2.072dL/g at 220℃ within 60min. The PBS sample possessed lower initial viscosity value indicated faster viscosity increasing rates. The thickness of PBS melt was inversely proportional to its viscosity increasing reaction rate. It was shown that the elevated viscosity values also led to a decrease of crystallization properties and melting point of PBS. The rheological test results showed that with the increase of viscosity, the melt strength and thermal stability of PBS increased, which can meet the needs of reprocessing and use. The melt re-polycondensation process can effectively solve the degradation problems of PBS being unable to meet its subsequent processing and using requirements.

Key words: polymers, polymerization, polymer processing, poly(butylene succinate), melt polycondensation, thermal performance, rheological performance

中图分类号:

TQ31

徐涛, 王勇军, 林启松, 戴钧明, 查全亮, 吕汪洋, 陈文兴. 聚丁二酸丁二醇酯熔融缩聚增黏特性[J]. 化工进展, 2024, 43(10): 5663-5670.

XU Tao, WANG Yongjun, LIN Qisong, DAI Junming, ZHA Quanliang, LYU Wangyang, CHEN Wenxing. Viscosification properties of poly(butylene succinate) by melt polycondensation[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5663-5670.

图/表 12

图1 PBS样品在不同温度下反应60min后特性黏度与损失质量分数的变化曲线

表1 不同增黏温度下的PBS分子量相关参数

增黏温度/℃	特性黏度/dL·g^-1	数均分子量/g·mol^-1	重均分子量/g·mol^-1	多分散系数	端羧基含量/mol·t^-1
200	1.109	23360	38860	1.664	28.20
210	1.891	42960	66680	1.552	18.77
220	2.072	45410	69200	1.524	15.27
230	3.093	63720	99850	1.567	12.68
240	3.234	78760	123900	1.573	13.21

图2 PBS样品在不同温度下反应60min后的分子量分布曲线

图3 PBS样品在220℃下反应不同时间后特性黏度与损失质量分数的变化曲线

表2 不同反应时间下的PBS分子量相关参数

增黏时间/min	特性黏度/dL·g^-1	数均分子量/g·mol^-1	重均分子量/g·mol^-1	多分散系数	端羧基含量/mol·t^-1
0	1.049	22800	38190	1.675	31.10
15	1.105	23700	38920	1.642	27.45
30	1.203	25500	41170	1.614	25.13
45	1.564	40920	64410	1.574	20.22
60	2.072	45410	69200	1.524	15.27
75	2.208	54130	83150	1.536	15.19

图4 220 ℃下反应不同时间后样品的分子量分布曲线

图5 220℃下不同初始黏度样品的特性黏度随时间的变化曲线

图6 220℃下样品的特性黏度与损失质量分数随熔体膜厚变化的曲线

图7 不同温度下反应60min样品的DSC曲线

图8 160℃下熔体流变性能随黏度和频率的变化曲线

图9 不同温度下PBS样品剪切黏度随剪切速率的变化曲线

图10 不同温度下PBS样品熔融指数曲线

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聚丁二酸丁二醇酯熔融缩聚增黏特性

Viscosification properties of poly(butylene succinate) by melt polycondensation

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