热塑性聚氨酯在退火过程中的粘弹性演变及其与节段结晶的关系

IF 4.1 2区 化学 Q2 POLYMER SCIENCE Chinese Journal of Polymer Science Pub Date : 2024-11-07 DOI:10.1007/s10118-024-3219-0
Jian-Wen Shan, Yan-Bo Zhu, Ling-Ling Ni, Peng-Ju Pan
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引用次数: 0

摘要

热塑性聚氨酯(TPU)的粘弹性性能对其加工至关重要。本文以聚己内酯(PCL)二醇、二苯基甲烷-4,4′-二异氰酸酯(MDI)和1,4-丁二醇(BDO)为原料制备了不同的tpu,并研究了三种不同硬段含量的tpu在热退火过程中的粘弹性行为。TPU的存储模量(G′)在中退火温度(Ta)区随时间增加,但在高温和低温区保持不变。损耗模量(G″)随时间的增长比G′的增长慢。在中等温度下,由于硬段逐渐结晶,在重复频率(ω)扫描过程中,G′和G″均增加。这表明晶粒主要抑制大尺寸单元的弛豫。随着TPU中硬段含量的减少,G′和G″的增量减弱。对于高硬段含量的TPU,仅在中Ta下进行一次频率扫描测试,即可观察到宽度为3个数量级的完整高弹性平台。此外,在频率扫描测试(等温退火)过程中,硬段晶粒不断长大,导致G′和G″随着ω在低ω区急剧增大。
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Viscoelastic Property Evolution of Thermoplastic Polyurethane during Annealing Treatment and Its Correlation with Segmental Crystallization

Viscoelastic properties of thermoplastic polyurethane (TPU) is of fundamental importance for its processing. In this work, we prepared different TPUs from polycaprolactone (PCL) diol, diphenylmethane-4,4′-diisocyanate (MDI), and 1,4-butanediol (BDO), and investigated the viscoelastic behavior of three TPUs with different hard segment content during thermal annealing process. The storage modulus (G′) of TPU increases over time in a medium annealing temperature (Ta) region, but remains unchanged at both high and low temperature regions. The growth of loss modulus (G″) over time is slower than that of G′. At medium Ta, both G′ and G″ increase during the repeating frequency (ω) sweep, due to the gradual crystallization of hard segments. This indicates that the crystallites primarily restrain the relaxation of unit with large size. The increments of G′ and G″ are weakened when the content of hard segment in TPU is decreased. For TPU with high content of hard segments, a complete high elastic platform with a width of 3 orders of magnitude was observed only through one frequency scan test at medium Ta. In addition, the crystallites of hard segments grow up continuously during frequency scan test (isothermal annealing treatment) and cause the extreme increase in G′ and G″ with ω in low ω region.

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来源期刊
Chinese Journal of Polymer Science
Chinese Journal of Polymer Science 化学-高分子科学
CiteScore
7.10
自引率
11.60%
发文量
218
审稿时长
6.0 months
期刊介绍: Chinese Journal of Polymer Science (CJPS) is a monthly journal published in English and sponsored by the Chinese Chemical Society and the Institute of Chemistry, Chinese Academy of Sciences. CJPS is edited by a distinguished Editorial Board headed by Professor Qi-Feng Zhou and supported by an International Advisory Board in which many famous active polymer scientists all over the world are included. The journal was first published in 1983 under the title Polymer Communications and has the current name since 1985. CJPS is a peer-reviewed journal dedicated to the timely publication of original research ideas and results in the field of polymer science. The issues may carry regular papers, rapid communications and notes as well as feature articles. As a leading polymer journal in China published in English, CJPS reflects the new achievements obtained in various laboratories of China, CJPS also includes papers submitted by scientists of different countries and regions outside of China, reflecting the international nature of the journal.
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