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

doi:10.19491/j.issn.1001-9278.2020.04.014

Abstract

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

CLC Number:

TQ 325.3

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

Figures/Tables 8

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

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

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

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^#

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

Fig. 5. Dynamic thermal stability of the sample

Fig.6. Ultraviolet analysis of thermally degraded PVC samples

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

References 14

1	胡程程, 陈颖, 李晓斌, 等. 氰尿酸钙/锌的制备及其在PVC制品中的应用[J]. 精细化工, 2019, 36(2): 328⁃335.
	HU C C, CHEN Y, LI X B, et al. Preparation of Calcium/Zinc Cyanurate and Its Application in PVC Products[J]. Fine Chemicals, 2019, 36(2): 328⁃335.
2	于静. 复合羧酸镧对PVC热稳定作用研究[J]. 中国塑料, 2014, 28(1): 55⁃59.
	YU J. Thermal Stabilization Effect of Composite Carboxylic Lanthanum on PVC[J]. China Plastics, 2014, 28(1): 55⁃59.
3	李晓斌, 陈颖, 胡程程, 等. 新型PVC辅助热稳定剂乙酰丙酮镁的制备及热稳定性能[J]. 化工进展, 2019, 38(4): 1 862⁃1 871.
	LI X B, CHEN Y, HU C C, et al. Preparation and Properties of a New PVC Auxiliary Heat Stabilizer——Magnesium Acetylacetonate[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1 862⁃1 871.
4	曹先贵, 吴茂英, 刘辉. 二元羧酸单酯金属盐对PVC的热稳定作用—性能递变规律与机理[J]. 中国塑料, 2018, 32(7): 116⁃121.
	CAO X G, WU M Y, LIU H. Hest⁃Stabilizing Effect of Dicarboxylic Acid Monoester Metal Salts on PVC—Law and Mechanism of Performance Evolution[J]. China Plastics, 2018, 32(7): 116⁃121.
5	张伟, 魏忠, 刘志勇，等. PVC稀土热稳定剂的研究进展及发展趋势[J]. 稀土, 2013, 34(5): 69⁃75.
	ZHANG W, WEI Z, LIU Z Y, et al. Research and Development Potential of Rare Earth Thermal Stabilizer for PVC[J]. Chinese Rare Earths, 2013, 34(5): 69⁃75.
6	侯怡, 尹秀招, 刘灵娜, 等. 一种新型PVC 热稳定剂—环氧油酸钙/锌复合热稳定剂的制备及性能研究[J]. 广东化工, 2018, 45(3): 1⁃3.
	HOU Y, YIN X N, LIU L N, et al. Preparation and Properties of a New Type of PVC Thermal Stabilizer⁃Calcium Carbonate/Zinc Composite Heat Stabilizer[J]. Guangdong Chemical Industry, 2018, 45(3): 1⁃3.
7	LI M, ZHANG J W, HUANG K, et al. Mixed Calcium and Zinc Salts of Dicarboxylic Acids Derived from Rosin and Dipentene: Preparation and Thermal Stabilization for PVC[J]. RSC Advances, 2014, 4(108): 63 576⁃63 585.
8	CHEN G A, GU L Q, YAO Y W. A Novel Zinc⁃Containing Additive for the Long⁃Term Thermal Stabilization of Poly(vinyl chloride) [J]. Polymer Degradation and Stability, 2014, 107: 113⁃119.
9	郭晓静, 邬素华, 李为. 用作PVC热稳定剂的环氧油酸盐的制备和应用[J]. 塑料, 2016, 45(5): 75⁃77.
	GUO X J, WU S H, LI W. Application and Preparation of Epoxidized Oleate as Thermal Stabilizers for PVC[J]. China Plastics, 2016, 45(5): 75⁃77.
10	李敏贤, 于静. PVC用液体钙锌热稳定剂及其制备方法: 中国, 201810272066.4[P]. 2019⁃01⁃18.
11	American Society of Testing Materials. ASTM D4202⁃92 Thermal Stability of Poly(vinyl chloride) (PVC) Resin[S]. New York: American Society of Testing Materials, 1992.
12	于静, 李敏贤, 张宁. PVC用三元复合羧酸镧热稳定剂的制备及其性能研究[J]. 中国塑料, 2014, 28(12): 88⁃93.
	YU J, LI M X, ZHANG N. Preparation and Properties of Ternary Composite Carboxylic Lanthanum for PVC[J]. China Plastics, 2014, 28(12):88⁃93.
13	李梅, 王晓川, 吴锦绣, 等. 碱式柠檬酸镧作为PVC 热稳定剂的研究[J]. 稀土, 2017, 38(3): 60⁃67.
	LI M, WANG X C, WU J X, et al. Study on Alkali Type Lanthanum Citrate as a Heat Stabilizer of PVC[J]. Chinese Rare Earths, 2017, 38(3): 60⁃67.
14	杨涛. 亚磷酸酯在聚氯乙烯中的应用[J]. 塑料助剂, 2003, (4): 25⁃28.
	YANG T. Application of Phosphite in Polyvinyl Chloride[J]. Plastics Additives, 2003, (4): 25⁃28.

[1]	YANG Xiaochun, YU Jing, ZHANG Qing. Effects of chitosan on thermal stability of PVC [J]. China Plastics, 2022, 36(7): 68-73.
[2]	DENG Tianxiang, XU Lina, LI Shouhai, ZHANG Yan, YAO Na, JIA Puyou, DING Haiyang, LI Mei. Research progress in grafting and crosslinking modification of PVC [J]. China Plastics, 2022, 36(5): 140-148.
[3]	TANG Yuanjun, LI Xuan, DONG Jun, LI Guoneng, LUO Guanqun, WANG Weimin, XU Yousheng. Multiscale thermogravimetric kinetics of waste polyvinyl chloride plastics [J]. China Plastics, 2022, 36(5): 89-98.
[4]	JIA Yao, ZHANG Ze, YU Zhengfa, CUI Yongyan. Preparation and secondary processing test of dynamic reversible cross⁃linked poly（vinyl chloride） [J]. China Plastics, 2022, 36(3): 82-88.
[5]	YANG Yuxuan, LIU Zhaogang, ZHAO Jingang, HUANG Xubo, CHEN Mingguang, HU Yanhong, WU Jinxiu, FENG Fushan. Synthesis of lanthanum 2，3⁃pyrazinedicarboxylic acid and its stabilizing effect on PVC [J]. China Plastics, 2022, 36(2): 103-110.
[6]	ZHANG Yaocheng, WU Yongzhen, LI Yang, ZHAO Zhu, WANG Guosheng, DING Xuejia. Gimini Quaternary Ammonium Salt⁃modified PVC⁃based Antibacterial Materials for Medical Use [J]. China Plastics, 2021, 35(7): 53-57.
[7]	LIU Xianggui, FANG Wei, SHU Hongbin, ZHENG Genwen, LIU Hai. Preparation and Performance of Hydrotalcite⁃filled PVC Composites [J]. China Plastics, 2021, 35(7): 63-68.
[8]	LI Xianming, ZHANG Ning, LIU Zhengyuan, LIU Luiyuan. Study on Synthesis and Properties of Butyl Stannate Intercalated Hydrotalcite⁃like Compound for PVC [J]. China Plastics, 2021, 35(3): 38-43.
[9]	ZHU Ruixia, GAN Lu, WU Zhixuan. Comparative Analysis of Several Common PVC Engineering Pipes for Water Supply [J]. China Plastics, 2021, 35(3): 50-58.
[10]	ZHAO Jingang, LIU Zhaogang, HAO Wei, LI Mei, HU Yanhong, WU Jinxiu, FENG Fushan, LI Shuai. Effect of Cerium P⁃methyl Benzoate on Thermal Stability of PVC [J]. China Plastics, 2021, 35(2): 14-21.
[11]	GAO Xinxin, JIANG Pingping, SHI Yimin, LENG Yan, ZHANG Pingbo. Preparation and applications of diethylene glycol ether maleate calcium/zinc heat stabilizer [J]. China Plastics, 2021, 35(12): 88-93.
[12]	HUANG Xubo, LIU Zhaogang, ZHAO Jingang, YANG Yuxuan, CHEN Mingguang, WU Jinxiu, HU Yanhong, FENG Fushan. Effect of lanthanum 2⁃benzoyl benzoate on thermal stability of PVC [J]. China Plastics, 2021, 35(12): 94-101.
[13]	WU Tingting, DENG Jianneng, LI Daobin, CAI Guoquan, DENG Shaoxin. Preparation and Application Performance of Epoxidized Neopentylglycol Dioleate [J]. China Plastics, 2021, 35(10): 114-119.
[14]	ZHANG Liang, CHAI Weisheng, WANG Shanshan, LI Wenzhu, WU Qiang, ZHANG Wenbiao, DAI Chunping. Study on Combustion Characteristics of Poly（vinyl chloride）/Bamboo Charcoal Decorative Composites [J]. China Plastics, 2021, 35(1): 37-46.
[15]	Sha LI, Jiayu ZHAN, Yanjun LI, Zhenxin LIU, Feihua YANG. Study on Leaching of Heavy Metal Lead from Unplasticized Poly(vinyl chloride) Drainpipes [J]. China Plastics, 2020, 34(7): 69-73.