油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征

doi:10.19491/j.issn.1001-9278.2020.04.014

中国塑料 ›› 2020, Vol. 34 ›› Issue (4): 84-89.DOI: 10.19491/j.issn.1001-9278.2020.04.014

油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征

李敏贤¹^,², 于静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:2019-11-14 出版日期:2020-04-26 发布日期:2020-04-26
基金资助:
河北省教育厅青年基金项目(QN2019310);唐山市科技计划项目(18130224a);唐山师范学院基金项目(2019B06)

Preparation and Characterization of Calcium/Zinc Benzoate⁃Oleate Liquid Heat Stabilizer

Minxian LI¹^,², Jing YU¹^,²()

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

Received:2019-11-14 Online:2020-04-26 Published:2020-04-26
Contact: Jing YU E-mail:yeyue130@163.com

摘要/Abstract

摘要：

以油酸、苯甲酸、氢氧化钙和氧化锌为主要原料，氧化植物油为溶剂，一锅化反应制备了油酸?苯甲酸钙/锌液体复合热稳定剂。采用刚果红试纸法和热老化法考察了其对聚氯乙烯（PVC）的静态热稳定性能及与辅助热稳定剂β?二酮、亚磷酸苯二异辛酯、季戊四醇间的协同作用。通过转矩流变仪、紫外光谱仪、场发射扫描电子显微镜测试了最优样品对PVC热稳定性能。结果表明，油酸?苯甲酸钙/锌液体复合热稳定剂对PVC的静态热稳定时间可达50 min，与亚磷酸苯二异辛酯具有最好的协同作用，最优样品对PVC的静态热稳定时间可达71 min，动态热稳定时间可达970 s，平衡扭矩37.3 N·m；紫外分析表明其具有较强地抑制共轭数3以上的共轭多烯生成的能力；其与PVC间的相容性较好，能均匀的分散在PVC颗粒表面，60 min前具有较好地抑制PVC降解的能力。

关键词: 聚氯乙烯, 油酸, 苯甲酸, 液体复合热稳定剂

Abstract:

A calcium/zinc benzoate?oleate liquid heat stabilizer was prepared by a one?pot reaction using oleic acid, benzoic acid, zinc oxide and calcium hydroxide as raw materials and oxidized vegetable oil as a solvent, and its static thermal stability and synergistic effect with auxiliary heat stabilizers like beta?dione, phenylenediisooctyl phosphite and pentaerythritol were investigated by means of the Congo red test paper and thermal aging methods. The thermal stability of the stabilized poly(vinyl chloride) (PVC) samples with optimized formulation was measured by torque rheometer, UV?visible spectrometer and scanning electron microscope. The results indicated that the PVC sample stabilized with this composite heat stabilizer achieved a static heat stabilization time of 50 min, and there was a synergistic effect with phenyl diisooctyl phosphite on the stabilization system. The PVC sample exhibited an optimum stabilization time up to 71 min and a dynamic thermal stabilization time up to 970 s, and an equilibrium torque of 37.3 N·m. The UV?visible spectroscopic analysis suggested that this composite heat stabilizer had a strong capability to inhibit the formation of conjugated polyene with more than 3 conjugates. The SEM observation showed that the composite heat stabilizer was uniformly dispersed on the surface of PVC particles due to the good compatibility between two parts, and as a result, the composite heat stabilizer was able to inhibit the degradation of PVC within 60 min.

Key words: poly(vinyl chloride), oleic acid, benzoic acid, liquid composite heat stabilizer

中图分类号:

TQ 325.3

李敏贤, 于静. 油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征[J]. 中国塑料, 2020, 34(4): 84-89.

Minxian LI, Jing YU. Preparation and Characterization of Calcium/Zinc Benzoate⁃Oleate Liquid Heat Stabilizer[J]. China Plastics, 2020, 34(4): 84-89.

图/表 8

图1 钙锌比对液体热稳定剂性能影响

Fig.1 Effect of calcium to zinc ratio on performance of the liquid heat stabilizer

图2 β?二酮用量对液体热稳定剂性能影响

Fig. 2 Effect of the amount of β?diketone on the performance of the liquid heat stabilizer

图3 季戊四醇用量对液体热稳定剂性能影响

Fig. 3 Effect of the amount of pentaerythritol on the performance of the liquid heat stabilizer

图4 亚磷酸苯二异辛酯用量对液体热稳定剂性能的影响

Fig. 4 Effect of the amount of phenyl diisooctyl phosphite on the performance of the liquid heat stabilizer

样品	热老化时间/min
样品	10	20	30	40	50	60	70	80	90	100	110	120
PVC+1^#
PVC+2^#
PVC+3^#

表1 添加不同复合热稳定剂的PVC颜色变化

Tab. 1 Color change of PVC with different compound heat stabilizers

图5 样品的动态热稳定性

Fig. 5 Dynamic thermal stability of the sample

图6 热降解PVC样品的紫外分析

Fig.6 Ultraviolet analysis of thermally degraded PVC samples

图7 不同热降解时间的PVC表面微观形貌

Fig. 7 Microscopic morphology of PVC surface with different thermal degradation time

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油酸⁃苯甲酸钙/锌液体复合热稳定剂的制备与表征

Preparation and Characterization of Calcium/Zinc Benzoate⁃Oleate Liquid Heat Stabilizer

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