生物基<italic style="font-style: italic">δ</italic>-己内酯与<italic style="font-style: italic">L</italic>-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究

王丽颖; 沈勇; 李志波

doi:10.11777/j.issn1000-3304.2023.23290

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生物基δ-己内酯与L-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究

研究论文 | 更新时间：2024-09-20

- 生物基δ-己内酯与L-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究
  增强出版
- Properties Study of Thermoplastic Elastomers Prepared by Sequential Ring-opening Copolymerization of Bio-based δ-Caprolactone and L-lactide
- 高分子学报 2024年55卷第5期页码：582-593
- 作者机构：
  
  1.生态化工国家重点实验室培育基地青岛科技大学化工学院
  2.山东省高等学校生物基高分子材料重点实验室青岛科技大学高分子科学与工程学院青岛 266042
- 作者简介：
  
  E-mail: shenyong@qust.edu.cn
  zbli@qust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23290
  中图分类号：
- 纸质出版日期：2024-05-20，
  
  收稿日期：2023-12-21，
  
  录用日期：2024-01-30
- 稿件说明：
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王丽颖, 沈勇, 李志波. 生物基δ-己内酯与L-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究. 高分子学报, 2024, 55(5), 582-593

Wang, L. Y.; Shen, Y.; Li, Z. B. Properties study of thermoplastic elastomers prepared by sequential ring-opening copolymerization of bio-based δ‍-caprolactone and L-lactide. Acta Polymerica Sinica, 2024, 55(5), 582-593
王丽颖, 沈勇, 李志波. 生物基δ-己内酯与L-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究. 高分子学报, 2024, 55(5), 582-593 DOI： 10.11777/j.issn1000-3304.2023.23290.

Wang, L. Y.; Shen, Y.; Li, Z. B. Properties study of thermoplastic elastomers prepared by sequential ring-opening copolymerization of bio-based δ‍-caprolactone and L-lactide. Acta Polymerica Sinica, 2024, 55(5), 582-593 DOI： 10.11777/j.issn1000-3304.2023.23290.

摘要

发展可再生、可降解脂肪族热塑性弹性体有望部分替代目前广泛使用的聚苯乙烯型热塑性弹性体材料，对于解决塑料污染问题具有重要意义. 本工作以商品化的生物基单体

-己内酯和

-丙交酯为原料，利用有机碱(

-BuP

)/脲二元催化体系实现其顺序开环聚合，成功制备得到聚乳酸-

-聚(

-己内酯)-

-聚乳酸三嵌段共聚物. 这些三嵌段共聚物随软硬段比例不同表现出不同的力学性质. 在硬段体积分数较高时(0.30

hard

0.45)，三嵌段共聚物表现出热塑性弹性体性质，具有较高的断裂伸长率和弹性回复率. 在硬段体积分数较小时(

hard

0.22)，三嵌段共聚物与环氧大豆油混合后可作为压敏胶使用.

Abstract

It is of significance to develop renewable and

biodegradable aliphatic thermoplastic elastomers

which are promising replacement of the widely used polystyrene-based thermoplastic elastomer materials and are expected to partially address the end-of-life issue of plastics. Poly(lactic acid)‍-

-poly(

‍-caprolactone)‍-

-poly(lactic acid) triblock copolymer was successfully prepared by sequential ring-opening copolymerization of commercial bio-based

‍-caprolactone and

-lactide in the presence of an organobase (

-BuP

)/urea as binary catalytic system. These triblock copolymers exhibited different microphase separation structures and mechanical properties depending on the composition of soft and hard segments. As the volume fraction of the hard segment (

hard

) increased from 0.22 to 0.34

the microphase separation structure of the sample gradually changed from spheres to hexagonally packed cylinders

and finally to lamella. When

hard

was in the range of 0.3‍0‒‍0.45

the triblock copolymers behaved as thermoplastic elastomers (TPEs) with high elongation at break (

=600%‍‒‍1000%) and good tensile strength (

=10‍-‍20 MPa). The samples with

hard

~0.35 exhibited high elastic recovery (

~90%)

high resilience (~70%) and low residual strain (

10%). When the samples possessed comparable molecular weight of soft segment

the elastic recovery and resilience gradually decreased while the residual strain increased as

hard

decreased from 0.34 to 0.22. The triblock copolymers that possessed a relatively lower volume fraction of the hard segment (

hard

0.22) can be used as pressure-sensitive adhesives after mixing with epoxy soybean oil (ESO). The 180° peel strength of PSA can be further adjusted by changing the composing triblock copo

lymers and the ratio of copolymers to ESO. The 180° peel adhesion tests showed that the peel strength of PSA-1 was (3.0±0.4) N/cm

and that of PSA-2 was (0.3±0.05) N/cm

which can be used as kraft paper tape and post-it note

respectively.

关键词

热塑性弹性体压敏胶三嵌段共聚物开环聚合脂肪族聚酯

Keywords

Thermoplastic elastomersPressure-sensitive adhesivesTriblock copolymerRing-opening polymerizationAliphatic polyester

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DOI：10.11777/j.issn1000-3304.2023.23290

摘要

Abstract

关键词

Keywords

references