Mechanistic Investigation of Nucleating Agent Calcium Hexahydrophthalate in Retarding the Crystallization of Linear Low-density Polyethylene

Xuan Sha; Wei Peng; Guang-quan Li; Jia-chun Feng

doi:10.11777/j.issn1000-3304.2025.25195

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Mechanistic Investigation of Nucleating Agent Calcium Hexahydrophthalate in Retarding the Crystallization of Linear Low-density Polyethylene

Research Article | 更新时间：2025-12-18

- Mechanistic Investigation of Nucleating Agent Calcium Hexahydrophthalate in Retarding the Crystallization of Linear Low-density Polyethylene
- Acta Polymerica Sinica Vol. 56, Issue 12, Pages: 2371-2380(2025)
- 作者机构：
  
  1.复旦大学高分子科学系聚合物分子工程全国重点实验室上海 200433
  2.中国石油石油化工研究院兰州化工研究中心兰州 730060
- 作者简介：
  
  Jia-chun Feng, E-mail: jcfeng@fudan.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25195
  CLC：
- CSTR：32057.14.GFZXB.2025.7469
- Received：15 August 2025，
  
  Accepted：18 September 2025，
  
  Published Online：12 November 2025，
  
  Published：20 December 2025
- 稿件说明：
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沙璇, 彭伟, 李广全, 冯嘉春. 成核剂六氢邻苯二甲酸钙减缓线性低密度聚乙烯结晶的机理探究. 高分子学报, 2025, 56(12), 2371-2380

Sha, X.; Peng, W.; Li, G. Q.; Feng, J. C. Mechanistic investigation of nucleating agent calcium hexahydrophthalate in retarding the crystallization of linear low-density polyethylene. Acta Polymerica Sinica, 2025, 56(12), 2371-2380
沙璇, 彭伟, 李广全, 冯嘉春. 成核剂六氢邻苯二甲酸钙减缓线性低密度聚乙烯结晶的机理探究. 高分子学报, 2025, 56(12), 2371-2380 DOI： 10.11777/j.issn1000-3304.2025.25195. CSTR： 32057.14.GFZXB.2025.7469.

Sha, X.; Peng, W.; Li, G. Q.; Feng, J. C. Mechanistic investigation of nucleating agent calcium hexahydrophthalate in retarding the crystallization of linear low-density polyethylene. Acta Polymerica Sinica, 2025, 56(12), 2371-2380 DOI： 10.11777/j.issn1000-3304.2025.25195. CSTR： 32057.14.GFZXB.2025.7469.

摘要

添加成核剂是高分子工业中优化产品质量、提高生产效率的重要手段. 研究发现，在线性低密度聚乙烯(LLDPE)中加入成核剂Hyperform

HPN-20E时，存在整体结晶速率下降的现象. 一般认为其可归因于成核剂加入后结晶温度提高导致的晶体生长变慢，但这一现象与大多数高分子添加成核剂后同时提高结晶温度和结晶速率的普遍现象不一致. 为进一步探究这一问题，本工作合成了上述成核剂的有效成分-六氢邻苯二甲酸钙(Ca-HHPA)，系统考察了其对一种茂金属线型低密度聚乙烯(mLLDPE)结晶行为的影响. 结果表明，Ca-HHPA虽可显著促进mLLDPE中具有高结晶能力链序列的成核，但成核密度增加对提高结晶速率的贡献不及结晶温度升高后生长速率降低的效果；同时，Ca-HHPA加入后会抑制弱结晶能力链序列的成核，使其在更低温度下结晶. 两种因素共同作用，导致整体结晶速率减缓.

Abstract

The introduction of nucleating agents is an important approach

to improve product quality and production efficiency in the polymer industry. Interestingly

it has been observed that the addition of the nucleating agent Hyperform

HPN-20E into linear low-density polyethylene results in a decrease in the overall crystallization rate. Although this reduction is commonly explained by the decreased crystal growth rate at higher crystallization temperatures

it contradicts the general behavior observed in most nucleated polymer systems

where both crystallization temperature and crystallization rate increase. To further elucidate this unusual behavior

the active component of HPN-20E

calcium hexahydrophthalate (Ca-HHPA)

was synthesized

and its influence on the crystallization behavior of a linear low-density polyethylene prepared by metallocene catalyst (mLLDPE) was systematically investigated. Our results reveal that Ca-HHPA promotes nucleation of these segments with high crystallization ability

while the increase in nucleation density contributes less to the crystallization rate than the reduction in growth rate caused by the elevated crystallization temperature. Meanwhile

the Ca-HHPA addition inhibits nucleation of segments with lower crystallization ability

leading to their crystallization at a greater undercooling. The combination of these two effects results in the observed decrease in the overall crystallization rate.

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