哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

doi:10.19491/j.issn.1001-9278.2020.07.012

中国塑料 ›› 2020, Vol. 34 ›› Issue (7): 74-79.DOI: 10.19491/j.issn.1001-9278.2020.07.012

哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

于静¹^,², 李敏贤¹^,²

^1.唐山师范学院化学系，河北唐山 063000
^2.唐山市绿色专用化学品重点实验室，河北唐山 063000

收稿日期:2020-03-08 出版日期:2020-07-26 发布日期:2020-07-26
基金资助:
河北省教育厅青年基金项目(QN2019310);河北省教育厅科学研究计划项目(Z2019013);唐山师范学院基金项目(2019B06)

Synthesis of Piperazinyl Monobutyric Amic Acid Calcium/Zinc and Its Thermal Stabilization for PVC

Jing YU¹^,², Minxian LI¹^,²

^1.Department of Chemistry, Tangshan Teacher College, Tangshan 063000, China
^2.Tangshan Key Laboratory of Green Specialty Chemicals, Tangshan 063000, China

Received:2020-03-08 Online:2020-07-26 Published:2020-07-26

摘要/Abstract

摘要：

以丁二酸酐、哌嗪、氯化钙、氯化锌为原料，通过两步反应制备了哌嗪基单丁酰胺酸钙/锌（PSACa/Zn）热稳定剂。采用元素分析、电感耦合等离子体原子发射光谱仪（ICP?OES）和傅里叶变换红外光谱仪（FTIR）对产品结构进行表征，通过刚果红试纸法、转矩流变仪法、热失重法考察了PSACa/Zn对PVC的热稳定性能，并筛选了PSACa和PSAZn的最佳配比。结果表明，PSACa和PSAZn对PVC的静态热稳定时间分别可达74.5、41.5 min，优于硬脂酸钙（CaSt₂）、硬脂酸锌（ZnSt₂）热稳定剂；PSACa和PSAZn复配使用时，以m_PSACa∶m_PSAZn=1∶1时性能最佳，对PVC静态热稳定时间可达92 min，动态热稳定时间可达905 s；发现PSACa/Zn对PVC的长期热稳定性良好。

关键词: 聚氯乙烯, 钙/锌热稳定剂, 哌嗪, 酰胺酸

Abstract:

A piperazinyl monobutyric amic acid calcium/Zinc (PSACa/Zn) thermal stabilizer was synthesized by a two?step reaction using succinic anhydride, piperazine, calcium chloride and zinc chloride as raw materials, and its chemical structure of the synthesized product was characterized by elemental analysis, inductively coupled plasma atomic emission spectrometry and Fourier?transform infrared spectroscopy. The thermal stabilization effect of PSACa/Zn on PVC was investigated by a Congo red paper method, torque rheometer and thermogravimetric analysis (TGA), and an optimum mass ratio of PSACa/PSAZn was achieved. The results indicated that the static thermal stability time of PVC modified with PSACa and PSAZn reached 74.5 and 41.5 min, respectively, which was better than the stabilization effect of calcium stearate and zinc stearate. With the combination of PSACa and PSAZn (m_PSACa∶m_PSAZn = 1∶1), the modified PVC exhibit a static thermal stabilization time of 92 min, and a dynamic thermal stabilization time of 905 s. PSACa/Zn has a long?term thermal stabilization effect on PVC according to the thermal analysis result.

Key words: poly (vinyl chloride), calcium/zinc thermal stabilizer, piperazine, amic acid

中图分类号:

TQ325.3

于静, 李敏贤. 哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究[J]. 中国塑料, 2020, 34(7): 74-79.

Jing YU, Minxian LI. Synthesis of Piperazinyl Monobutyric Amic Acid Calcium/Zinc and Its Thermal Stabilization for PVC[J]. China Plastics, 2020, 34(7): 74-79.

图/表 7

产物		质量分数/%				分子式
产物		C	H	Ca	Zn	分子式
PSACa	理论值	44.44	4.94	12.35	—	C₁₂H₁₆O₆N₂Ca
PSACa	实测值	43.85	5.01	12.18	—	C₁₂H₁₆O₆N₂Ca
PSAZn	理论值	41.26	4.58	—	18.62	C₁₂H₁₆O₆N₂Zn
PSAZn	实测值	40.98	4.71	—	18.45	C₁₂H₁₆O₆N₂Zn

表1 合成产物的元素分析

Tab.1 Elemental analysis of the products

图1 PSACa和PSAZn的FTIR谱图

Fig.1 FTIR spectra of PSACa and PSAZn

图2 不同PVC体系的静态热稳定时间

Fig.2 Static thermal stability time of different PVC systems

图3 PSACa和PSAZn质量比对PVC热稳定性能的影响

Fig.3 Effect of mass ratio of PSACa and PSAZn on thermal stability of PVC

图4 PSACa/Zn和Cast2/Znst2对PVC的动态热稳定性能对比

Fig.4 Comparison of dynamic thermal stability of PSACa/Zn and Cast2/Znst2 on PVC

图5 PVC样品的TG曲线

Fig.5 TG curve of PVC samples

图6 PVC样品的DTG曲线

Fig.6 DTG curve of PVC samples

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哌嗪基单丁酰胺酸钙/锌的合成及对PVC热稳定性研究

Synthesis of Piperazinyl Monobutyric Amic Acid Calcium/Zinc and Its Thermal Stabilization for PVC

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