邻苯二甲酸二(乙二醇醚)酯绿色合成及增塑PVC性能

doi:10.16085/j.issn.1000-6613.2020-2289

摘要/Abstract

摘要：

以邻苯二甲酸酐和低毒型乙二醇醚（乙二醇甲/乙/丁醚、二乙二醇甲/乙/丁醚）为原料，固体酸 $S O 4 2 -$ /TiO₂为催化剂，采用直接酯化法催化合成邻苯二甲酸二(乙二醇醚)酯（酯化率?97.0%），并利用傅里叶红外光谱（FTIR）、¹H核磁共振（¹H NMR）确定产物结构。对合成产物邻苯二甲酸二(乙二醇醚)酯的基本物性（酯含量、酸度、黏度、加热减量等）及其增塑后聚氯乙烯（PVC）制品的力学性能、热稳定性以及抗迁移性能进行测试。结果表明，邻苯二甲酸二(乙二醇醚)酯的增塑性能与其结构中乙氧基数目成正比，而与其末端烷基碳链长度呈现先增加后下降趋势。与邻苯二甲酸二辛酯（DOP）增塑后PVC制品（PVC/DOP）相比，邻苯二甲酸二(二乙二醇乙醚)酯增塑后PVC制品（PVC/DEEEP）的断裂伸长率和拉伸强度分别提高87.4%和3.4MPa，初始热分解温度（T_5%）提高21.5℃。

关键词: 催化, 酯化, 邻苯二甲酸醇醚酯, 环保增塑剂, 聚氯乙烯树脂, 聚合物加工

Abstract:

Environment-friendly plasticizers of dialkyloxy phthalates were synthesized via direct esterification using phthalic anhydride and low toxic alcohol ethers (ethylene glycol methyl/ethylene/butyl ether, diethylene glycol methyl/ethylene/butyl ether) as feedstocks. Under the catalytic of of $S O 4 2 -$ /TiO₂, the_{esterification rate of the reaction was higher than 97.0%, and the structure of purified product was confirmed by FTIR and ¹H NMR. The basic physical properties of dialkyloxy phthalate esters including ester content, acidity, viscosity and heating loss, were studied and then they were used as plasticizers for PVC resin. The results indicated that the plasticizing properties of dialkyloxy phthalate including mechanical properties, thermal stability and migration resistance of plasticized PVC were related to the length of ethoxyl group and terminal alkyl chain in their structures, and the plasticizing properties were increased as increasing the number of ethoxyl groups. However, with increasing length of alkyl carbon chain in the structure of dialkyloxy phthalate esters, the properties of plasticized PVC increased at first and then decreased. Compared with the PVC plasticized by traditional DOP (PVC/DOP), the elongation at break, tensile strength and thermal decomposition temperature (T_5%) of PVC plasticized by diethylene glycol monoethyl ether phthalate (PVC/DEEEP) were increased by 87.4%, 3.4MPa and 21.5℃, respectively.}

Key words: catalysis, esterification, phthalates, environment-friendly plasticizer, polyvinyl chloride(PVC) resin, polymer processing

中图分类号:

TQ414

王凡, 谷佳泽, 胡兵, 谈继淮, 朱新宝. 邻苯二甲酸二(乙二醇醚)酯绿色合成及增塑PVC性能[J]. 化工进展, 2021, 40(11): 6315-6322.

WANG Fan, GU Jiaze, HU Bing, TAN Jihuai, ZHU Xinbao. Green synthesis of phthalate-based alkoxy esters and application as high efficient plasticizers for PVC resin[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6315-6322.

图/表 11

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实验编号	酯化率/%
1	97.4
2	97.4
3	97.3

实验编号	酯化率/%
1	97.4
2	97.4
3	97.3

产物	反应温度/℃	酯化率/%
DMEP	160～180	98.7
DEEP	160～180	99.0
DBEP	160～180	99.2
DMEEP	190～215	97.4
DEEEP	190～215	97.4

产物	反应温度/℃	酯化率/%
DMEP	160～180	98.7
DEEP	160～180	99.0
DBEP	160～180	99.2
DMEEP	190～215	97.4
DEEEP	190～215	97.4

项目	DMEP	DEEP	DBEP	DMEEP	DEEEP	DBEEP
酸度（以邻苯二甲酸单酯计）/%	0.12	0.09	0.02	0.12	0.09	0.02
水分/%	≤0.20	≤0.20	≤0.20	≤0.20	≤0.20	≤0.20
密度（20℃）/g·cm^-3	1.2114	1.1508	1.1025	1.2114	1.1508	1.1025
黏度（25℃）/mPa·s	35	—	30	180.8	140.6	78.0
加热减量/%	≤0.4	≤0.4	≤0.4	≤0.4	≤0.4	≤0.4
色度	≤200	≤150	≤150	≤200	≤200	≤200