新型栲胶聚丙氧基醚酯的合成及增塑PVC性能

doi:10.16085/j.issn.1000-6613.2022-1893

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4847-4855.DOI: 10.16085/j.issn.1000-6613.2022-1893

新型栲胶聚丙氧基醚酯的合成及增塑PVC性能

谈继淮¹(), 余敏¹, 张彤彤², 黄能坤¹, 王梓雯¹, 朱新宝¹()

^1.南京林业大学化学工程学院，江苏南京 210037
^2.阜阳师范大学化学与材料工程学院，安徽阜阳 236037

收稿日期:2022-10-12 修回日期:2022-11-22 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 谈继淮,朱新宝
作者简介:谈继淮（1988—），男，博士，副教授，研究方向为多功能生物基助剂。E-mail：jihuaitan@njfu.edu.cn。
基金资助:
国家自然科学基金青年基金(32101467);江苏省自然科学基金青年基金(BK20210619)

Manufacturing of tannin polypropoxy ether carboxylates as efficient and improved migration resistance plasticizers for PVC

TAN Jihuai¹(), YU Min¹, ZHANG Tongtong², HUANG Nengkun¹, WANG Ziwen¹, ZHU Xinbao¹()

^1.College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
^2.School of Chemistry and Materials Engineering, Fuyang Normal University, Fuyang 236037, Anhui, China

Received:2022-10-12 Revised:2022-11-22 Online:2023-09-15 Published:2023-09-28
Contact: TAN Jihuai, ZHU Xinbao

摘要/Abstract

摘要：

以工业级杨梅栲胶粗品为原料，通过环氧丙烷醚化和脂肪酸（乙酸、丁酸和油酸）直接酯化的方式，构建增塑性能高、抗迁移性能好的栲胶聚丙氧基醚酯增塑剂（TEPEA、TEPEB和TEPEO）。利用凝胶渗透色谱仪、核磁共振氢谱、傅里叶变换红外光谱对栲胶聚丙氧基多元醇和栲胶聚丙氧基醚酯的分子量和结构进行表征，并对栲胶聚丙氧基醚酯增塑剂增塑后聚氯乙烯（PVC）制品（PVC/TEPEA、PVC/TEPEB和PVC/TEPEO）的表观形貌、力学性能、耐低温性能、耐挥发性能和耐溶剂迁移性能进行测试。此外，通过合成低分子量栲胶聚丙氧基乙酸酯（LTEPEA），并将其增塑后的PVC制品（PVC/LTEPEA）与PVC/TEPEA、PVC/TEPEB和PVC/TEPEO进行综合性能差异比较，研究丙氧基对栲胶基增塑剂综合性能的影响。结果表明，栲胶聚丙氧基醚酯增塑后PVC制品的综合性能与其结构中丙氧基聚合度及酯基上的烷基碳链长度有关；丙氧基聚合度大且酯基上碳链最短的栲胶聚丙氧基乙酯（TEPEA）增塑后的PVC制品的增塑、耐挥发和抗迁移性能均优于传统石油基邻苯二甲酸二辛酯（DOP）增塑后的PVC制品（PVC/DOP），表明TEPEA可作为主增塑剂替代有毒的DOP。

关键词: 栲胶, 聚氯乙烯, 栲胶聚丙氧基醚酯, 生物基增塑剂, 抗迁移

Abstract:

Novel tannin polypropoxy ether carboxylates (TEPEC) equipped with excellent plasticization and migration resistances for PVC resin were synthesized through the propoxylation of tannin extracts derived from waste bark and then esterification with fatty acid (acetic acid, butyric acid, and oleic acid). Then the structures of tannin-based polypropoxy polyol and its esters (TEPEA, TEPEB and TEPEO) were confirmed by GPC, ¹H NMR and FTIR. The performances including surface morphology, tensile property, low temperature resistance and volatility resistance, as well as migration resistances of PVC samples plasticized by tannin polypropoxy ether carboxylates (PVC/TEPEA, PVC/TEPEB and PVC/TEPEO) were systematically investigated and respectively compared with that of neat PVC and PVC blended with dioctyl phthalate (PVC/DOP). Additionally, low molecular weight tannin polypropoxy ether acetate (LTEPEA) was also synthesized and used as a reference to evaluate the effect of propoxy unit on the properties of PVC samples plasticized by tannin polypropoxy ether carboxylates. The results indicated that the overall performances of PVC samples plasticized by tannin polypropoxy ether carboxylates were dependent on their structures, where the performances of PVC plasticized by tannin polypropoxy ether carboxylates holding largest propoxy units and shortest methyl group (PVC/TEPEA) were better than PVC samples blended with others plasticizers (PVC/TEPEB, PVC/TEPEO and PVC/DOP). All of the results suggested that tannin polypropoxy ether acetate (TEPEA) had a great potential to totally the traditional petro-based DOP applied in PVC industry.

Key words: tannin extracts, polyvinyl chloride, tannin polypropoxy ether carboxylates, bio-based plasticizer, migration resistance

中图分类号:

TQ414

谈继淮, 余敏, 张彤彤, 黄能坤, 王梓雯, 朱新宝. 新型栲胶聚丙氧基醚酯的合成及增塑PVC性能[J]. 化工进展, 2023, 42(9): 4847-4855.

TAN Jihuai, YU Min, ZHANG Tongtong, HUANG Nengkun, WANG Ziwen, ZHU Xinbao. Manufacturing of tannin polypropoxy ether carboxylates as efficient and improved migration resistance plasticizers for PVC[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4847-4855.

图/表 7

图1 “一锅”两步法合成栲胶聚丙氧基醚酯（TEPEC）

图2 栲胶聚丙氧基醚酯的结构表征

图3 PVC制品的力学性能

图4 PVC制品的玻璃化转变温度

图5 PVC制品的SEM图

图6 栲胶聚丙氧基醚酯与PVC相互作用

图7 增塑后的PVC制品的抗迁移性能

参考文献 16

1	TAN Jihuai, WANG Fan, WANG Wengeng, et al. Waste fatty acid-based methyl tetraglycol ester derived from dimer acid manufacturing as an efficient and biodegradable plasticizer for poly(vinyl chloride)[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(40): 13573-13581.
2	吴海龙, 农桂叶, 曹宇, 等. 聚氯乙烯用环保型增塑剂的研究进展[J]. 包装工程, 2022, 43(7): 118-124.
	WU Hailong, NONG Guiye, CAO Yu, et al. Research progress of environmentally-friendly plasticizers in PVC[J]. Packaging Engineering, 2022, 43(7): 118-124.
3	TAN Jihuai, ZHANG Tongtong, WANG Fan, et al. One-pot and industrial manufacturing of cardanol-based polyoxyethylene ether carboxylates as efficient and improved migration resistance plasticizers for PVC[J]. Journal of Cleaner Production, 2022, 375: 133943.
4	PAN Siyu, HOU Delong, CHANG Jinming, et al. A potentially general approach to aliphatic ester-derived PVC plasticizers with suppressed migration as sustainable alternatives to DEHP[J]. Green Chemistry, 2019, 21(23): 6430-6440.
5	ZHU Huichao, YANG Jianjun, WU Mingyuan, et al. Vanillic acid as a new skeleton for formulating a biobased plasticizer[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(45): 15322-15330.
6	JIA Puyou, MA Yufeng, ZHANG Meng, et al. Designing rosin-based plasticizers: Effect of differently branched chains on plasticization performance and solvent resistance of flexible poly(vinyl chloride) films[J]. ACS Omega, 2019, 4(2): 3178-3187.
7	黄能坤, 王梓雯, 王文耕, 等. 新型氢化二聚酸乙二醇醚酯的合成及其增塑PVC性能研究[J].化工进展, 2023, 42(5): 2638-2646.
	HUANG Nengkun, WANG Ziwen, WANG Wengeng, et al. 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.
8	TAN Jihuai, FU Qinghe, QU Yongquan, et al. Direct transformation of fatty acid-derived monomers from dimer acid manufacturing into valuable bio-plasticizers with high plasticization and compatibilization[J]. Journal of Cleaner Production, 2021, 289: 125821.
9	朱光前, 申伟. 世界木材资源及中国木材市场前景[J]. 中国人造板, 2022, 29(7): 36-40.
	ZHU Guangqian, SHEN Wei. World wood resources and china’s wood market prospect[J]. China Wood-Based Panels, 2022, 29(7): 36-40.
10	ZHANG Tongtong, YU Changlei, YU Min, et al. Multifunctional tannin extract-based epoxy derived from waste bark as a highly toughening and strengthening agent for epoxy resin[J]. Industrial Crops and Products, 2022, 176: 114255.
11	Maëva BOCQUÉ, VOIRIN Coline, LAPINTE Vincent, et al. Petro-based and bio-based plasticizers: Chemical structures to plasticizing properties[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2016, 54(1): 11-33.
12	MA Yufeng, SONG Fei, HU Yun, et al. Highly branched and nontoxic plasticizers based on natural cashew shell oil by a facile and sustainable way[J]. Journal of Cleaner Production, 2020, 252: 119597.
13	ROSA Joyce Rover, DA SILVA Ingrid Souza Vieira, DE LIMA Caroline Stefany Marques, et al. Production of polyols and new biphasic mono-component materials from soy hulls by oxypropylation[J]. Industrial Crops and Products, 2015, 72: 152-158.
14	Jason D’SOUZA, GEORGE Ben, CAMARGO Rafael, et al. Synthesis and characterization of bio-polyols through the oxypropylation of bark and alkaline extracts of bark[J]. Industrial Crops and Products, 2015, 76: 1-11.
15	TAN Jihuai, LIU Bowen, FU Qinghe, et al. Role of the oxethyl unit in the structure of vegetable oil-based plasticizer for PVC: An efficient strategy to enhance compatibility and plasticization[J]. Polymers, 2019, 11(5): 779.
16	CHEN Jie, LIU Zengshe, JIANG Jianchun, et al. A novel biobased plasticizer of epoxidized cardanol glycidyl ether: Synthesis and application in soft poly(vinyl chloride) films[J]. RSC Advances, 2015, 5(69): 56171-56180.

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新型栲胶聚丙氧基醚酯的合成及增塑PVC性能

Manufacturing of tannin polypropoxy ether carboxylates as efficient and improved migration resistance plasticizers for PVC

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