Crystallization Behavior of Poly(vinylidene fluoride-hexafluoropropylene) Copolymer under High-pressure External Fields

Zi-qi Wang; Zheng-song Hu; Chong-yang Wang; Yan-ping Liu; Chun-guang Shao; Zhen Wang

doi:10.11777/j.issn1000-3304.2026.26018

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Crystallization Behavior of Poly(vinylidene fluoride-hexafluoropropylene) Copolymer under High-pressure External Fields

Research Article | 更新时间：2026-07-08

- Crystallization Behavior of Poly(vinylidene fluoride-hexafluoropropylene) Copolymer under High-pressure External Fields
- Acta Polymerica Sinica Vol. 57, Issue 7, Pages: 1619-1632(2026)
- 作者机构：
  
  1.郑州大学橡塑模具国家工程研究中心材料成型与模具技术教育部重点实验室郑州 450002
  2.郑州大学力学与安全工程学院郑州 450001
- 作者简介：
  
  Yan-ping Liu, E-mail: ypliu@zzu.edu.cn
  Zhen Wang, E-mail: wangz@zzu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26018
  CLC：
- CSTR：32057.14.GFZXB.2026.7608
- Received：24 January 2026，
  
  Accepted：21 April 2026，
  
  Online First：17 June 2026，
  
  Published：20 July 2026
- 稿件说明：
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王紫琪, 胡正松, 王重阳, 刘艳萍, 邵春光, 王震. 高压外场下聚偏氟乙烯-六氟丙烯共聚物的结晶行为. 高分子学报, 2026, 57(7), 1619-1632.

Wang, Z. Q.; Hu, Z. S.; Wang, C. Y.; Liu, Y. P.; Shao, C. G.; Wang, Z. Crystallization behavior of poly(vinylidene fluoride-hexafluoropropylene) copolymer under high-pressure external fields. Acta Polymerica Sinica (in Chinese), 2026, 57(7), 1619-1632.
王紫琪, 胡正松, 王重阳, 刘艳萍, 邵春光, 王震. 高压外场下聚偏氟乙烯-六氟丙烯共聚物的结晶行为. 高分子学报, 2026, 57(7), 1619-1632. DOI： 10.11777/j.issn1000-3304.2026.26018. CSTR： 32057.14.GFZXB.2026.7608.

Wang, Z. Q.; Hu, Z. S.; Wang, C. Y.; Liu, Y. P.; Shao, C. G.; Wang, Z. Crystallization behavior of poly(vinylidene fluoride-hexafluoropropylene) copolymer under high-pressure external fields. Acta Polymerica Sinica (in Chinese), 2026, 57(7), 1619-1632. DOI： 10.11777/j.issn1000-3304.2026.26018. CSTR： 32057.14.GFZXB.2026.7608.

摘要

共聚单元含量是调控聚偏氟乙烯-六氟丙烯(P(VDF-HFP))共聚物结构与性能的关键因素. 本工作以不同六氟丙烯(HFP)含量的样品为实验对象，通过施加不同温度与压力条件，系统探究了P(VDF-HFP)熔体在高压外场下的结晶行为以及相结构与形态演变. 结果表明，随着HFP含量增加，高压下伸直链晶体(ECCs)的形成逐渐受到抑制. 这主要归因于HFP大的侧基体积，在热力学和动力学上均阻碍了高压六方相(h相)的增厚生长，导致ECCs含量及熔点均降低. 另一方面，HFP单元的引入显著促进了高压诱导的极性

相生成，且随着HFP含量增加，

相先后以ECCs和折叠链片晶(FCCs)的形式出现. 高压外场下，HFP对

相形成的促进作

用可能源于其空间位阻效应，不仅有利于全反式(

TTTT

)构象的产生，同时有助于稳定高压诱导的

TTTT

构象，防止无法增厚的h相在结晶过程中松弛为

‑FCCs. 在此过程中，

相发生明显的晶格膨胀，对应的(110)晶面间距甚至接近

相，表明少量HFP单元以缺陷形式进入晶格，降低了晶体有序度. 此外，引入HFP还有效避免了材料的热降解，这一加工特性为实际材料应用带来了优势.

Abstract

The composition of copolymer units plays a crucial role in determining the structure and performance of poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) copolymers. This study employed samples with varying HFP contents to systematically investigate the crystallization behavior of P(VDF-HFP) melts under high-pressure external fields

as well as the evolution of their phase structures and morphologies under different temperature and pressure conditions. The results demonstrated that an increase in the HFP copolymer unit content progressively suppresses the formation of extended chain crystals (ECCs) under high pressure. This suppression can be primarily attributed to the large side group volume of HFP

which thermodynamically and kinetically hinders the growth of the high-pressure hexagonal (h) phase. Consequently

both the ECC content and melting point decreased. Conversely

the introduction of HFP significantly enhanced the generation of the polar

-phase induced by high pressure. As the HFP content increased

the

-phase emerged successively in the form of ECCs and folded chain crystals (FCCs). Under high-pressure external fields

the promoting effect of HFP on

-phase formation is likely due to its steric hindrance

which facilitates the generation of the all-

trans

(

TTTT

) conformation and stabilizes the

TTTT

conformation

induced by high pressure. This stabilization prevents the h-phase

which cannot thicken

from relaxing into

-FCCs during crystallization. During this process

the

-phase exhibits significant lattice expansion

with the (110) interplanar distances approaching those of the

-phase. This suggests that a small number of HFP units were incorporated into the lattice as defects

which reduced the crystalline order. Furthermore

unlike pure PVDF

the incorporation of HFP effectively mitigates the thermal degradation of the material while significantly promoting the formation of the

-phase under high pressure. This characteristic provides substantial advantages for practical applications of the material.

关键词

Keywords

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