新型氢化二聚酸乙二醇醚酯的合成及其增塑PVC性能

doi:10.16085/j.issn.1000-6613.2022-1251

摘要/Abstract

摘要：

以氢化二聚酸和乙二醇醚（乙二醇甲醚、二乙二醇甲醚、三乙二醇甲醚、四乙二醇甲醚）为原料，通过直接酯化法，制备出具有不同乙氧基官能团数目的新型氢化二聚酸乙二醇醚酯（HDA-2n，n=1, 2, 3, 4）增塑剂。利用¹H NMR、¹³C NMR和FTIR确定产物结构，并对HDA-2n增塑后聚氯乙烯（PVC）制品的微观形貌、力学、热稳定、耐迁移、耐挥发等性能进行表征分析。结果表明，HDA-2n的增塑性能随着乙氧基官能团数目的增加而提高；与邻苯二甲酸二辛酯（DOP）增塑后的PVC制品相比，含有乙氧基官能团数目最多的氢化二聚酸(四乙二醇甲醚)酯（HDA-8）增塑PVC后制品的断裂伸长率提高125%，拉伸强度提高11.29MPa，在正己烷中的迁移性降低了14.25%，70℃下的挥发性降低了5.29%，初始热分解温度（T_5%）提高了27.2℃。

关键词: 氢化二聚酸, 醇醚, 氢化二聚酸乙二醇醚酯, 增塑剂, 聚氯乙烯

Abstract:

Novel hydrogenated dimeric acid alcohol ether esters (HDA-2n, n=1, 2, 3, 4) with different number of ethoxy functional units were synthesized from hydrogenated dimeric acid and ethylene glycol ether (ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, tetraethylene glycol methyl ether) via the direct esterification. The structures of resulting products were determined by ¹H NMR, ¹³C NMR and FTIR, respectively. Also, the microstructure, mechanical, thermal stability, migration resistance as well as the volatilization resistance of PVC plasticized by HDA-2n were investigated. The results indicated that the plasticization of HDA-2n increased along with the increase of the number of oxethyl units. Compared with the PVC samples plasticized by dioctyl phthalate (DOP), the elongation at break and tensile strength of the products plasticized by hydrogenated dimeric acid (tetraethylene glycol methyl ether) ester (HDA-8) with the largest number of oxethyl units increased by 125% and 11.29MPa, respectively. Meanwhile, the migration in n-hexane and the volatility (70℃) of PVC/HAD-8 decreased by 14.25% and 5.29%, respectively, while the initial thermal decomposition temperature (T_5%) increased by 27.2℃.

Key words: hydrogenated dimer acid, alcohol ether, hydrogenated dimeric acid alcohol ether ester, plasticizer, polyvinyl chloride (PVC)

中图分类号:

TQ414

黄能坤, 王梓雯, 王文耕, 王学峰, 谈继淮, 朱新宝. 新型氢化二聚酸乙二醇醚酯的合成及其增塑PVC性能[J]. 化工进展, 2023, 42(5): 2638-2646.

HUANG Nengkun, WANG Ziwen, WANG Wengeng, WANG Xuefeng, TAN Jihuai, ZHU Xinbao. Design and synthesis of hydrogenated dimeric acid ethylene glycol ether esters as highly-efficient plasticizers for PVC[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2638-2646.

图/表 15

图1 氢化二聚酸的多种结构

图2 氢化二聚酸乙二醇醚酯的合成反应方程式

表1 PVC薄片原料配方设计

原料	质量/g
PVC	10
增塑剂	4
硬脂酸钙	0.15
硬脂酸锌	0.05

图3 氢化二聚酸（HDA）和氢化二聚酸乙二醇醚酯（HDA-2n）的氢谱（Φ代表氢化二聚酸结构中除羧基以外的其他部分）

图4 氢化二聚酸（HDA）和氢化二聚酸乙二醇醚酯（HDA-2n）的碳谱（Φ代表氢化二聚酸结构中除羧基以外的其他部分）

图5 氢化二聚酸（HDA）及氢化二聚酸乙二醇醚酯（HDA-2n）的红外光谱

图6 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的扫描电镜图

图7 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的力学性能

图8 纯PVC及氢化二聚酸乙二醇醚酯（HDA-2n）增塑后PVC制品的红外光谱

图9 氢化二聚酸乙二醇醚酯（HDA-2n）与PVC分子的相互作用

图10 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的玻璃化转变温度

图11 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的热稳定性

表2 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的T5%

样品	T_5%/℃
PVC-DOP	235.4
PVC-HDA-2	246.3
PVC-HDA-4	252.3
PVC-HDA-6	258.4
PVC-HDA-8	262.6

图12 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的耐迁移性

图13 氢化二聚酸乙二醇醚酯（HDA-2n）及DOP增塑后PVC制品的耐挥发性

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