Preparation and applications of diethylene glycol ether maleate calcium/zinc heat stabilizer

doi:10.19491/j.issn.1001-9278.2021.12.015

Abstract

Abstract:

Diethylene glycol ether maleate （MD） was prepared using maleic anhydride and diethylene glycol ether as raw materials without a catalyst， and its molecular structure was determined to be ester groups， ether bonds， and carbon?carbon double bonds. This intermediate product was respectively reacted with calcium acetate and zinc acetate to prepare diethylene glycol ether maleate calcium/zinc salt （MD?Ca/Zn）. The structure of the resultant product was further analyzed with FTIR spectroscopy， indicating that its molecule contains ether bond， ester group， carbon?carbon double bond， and carboxylate structure. This indicated that it could be used as a heat stabilizer for PVC. The thermal stabilizing effect of the MD?Ca/Zn was verified through the Congo red， thermal aging， thermogravimetry， electrical conductance measurements as well as the comparation the commercially available calcium/zinc stearate. Its thermal stabilization mechanism was analyzed and explored. Furthermore， the synergistic effect of the MD?Ca/Zn with an auxiliary heat stabilizer， β?diketone （stearoyl benzoyl methane）， was investigated. The results indicated that the PVC compound exhibited an optimal thermal stability at an MD?Ca/Zn mass ratio of 2∶1， and its initial whiteness and static stabilization time reached 40 min and 35 min， respectively. The thermal stability could be further improved by combination with 10 % β?diketone in the total amount of heat stabilizers.

Key words: diethylene glycol ether maleate calcium/zinc salt, heat stabilizer, synergistic effect, poly（vinyl chloride）

CLC Number:

TQ314.24⁺5.1

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.

Figures/Tables 10

Fig.1. FTIR spectra of MD and MD?Ca/Zn

Tab.1. Color changes of PVC samples of calcium/zinc system measured by heat aging oven method

热稳定剂成分	静态稳定时间/min
空白样	5.5
MD?Ca	18
MD?Ca/Zn=3∶1	28
MD?Ca/Zn=2∶1	35
MD?Ca/Zn=1∶1	30
MD?Ca/Zn=1∶2	17
MD?Zn	9
CaSt₂/ZnSt₂=2∶1	25

Tab.2. Congo Red test

Fig.2. Standard conductivity curve

Fig.3. Conductivity test curves

Fig. 4. TG curves of different systems

Fig.5. Weight loss rate in two stages

热稳定剂成分	180 ℃热老化时间/min
热稳定剂成分	0	10	20	30	40	50	60	70	80
MD?Ca/Zn=2∶1
10%β?二酮

Tab. 3. Color change of PVC test piece of β?diketone/Ca/Zn composite system

Fig.6. Thermal stability mechanism of maleic anhydride

Fig.7. Synergistic mechanism of Ca/Zn in MD?Ca/Zn

References 16

1	唐伟，陈语.我国PVC热稳定剂的现状与发展趋势［J］.聚氯乙烯，2017， 45（8）：11⁃16.
2	杨惠娣.聚氯乙烯及其热稳定剂现状与发展趋势［J］.中国塑料，2019， 33（4）：111⁃119.
	YANG H D. Current situation and development trends of PVC and its stabilizers［J］.China Plastics，2019， 33（4）：111⁃119.
3	张鸿，蒋平平，潘杰，等.马来酸单三甘醇酯钙/锌热稳定剂的制备及其对PVC制品热稳定性能影响的研究［J］.中国塑料，2019， 33（8）：76⁃82.
	ZHANG H，JIANG P P，PAN J，et al. Preparation of calcium/zinc triglycol ester acid maleate heat stabilizer and its effect on thermal stability of PVC products［J］.China Plastics，2019， 33（8）：76⁃82.
4	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.
	LI M X，YU J. Preparation and characterization of calcium/zinc benzoate⁃oleate liquid heat stabilizer［J］. China Plastics，2020， 34（4）：84⁃89.
5	张鸿，蒋平平，HARYONO，等.马来酸单甘油酯钙/锌的制备及在PVC中的应用［J］.塑料，2019， 48（6）：6⁃10.
	ZHANG H，JIANG P P，HARYONO，et al. Preparation of calcium/zinc monoglyceride maleate and its application in PVC products［J］.Plastics，2019， 48（6）：6⁃10.
6	李国兴.马来酸酐类聚氯乙烯热稳定剂的研究［D］.重庆：西南大学， 2017.
7	孙佳莹，白梦遥，王茹，等.乙基双马来酰胺酸类物质对聚氯乙烯的热稳定及修复性能的影响［J］.高分子材料科学与工程，2019， 35（12）：76⁃80.
	SUN J Y，BAI M Y，WANG R，et al. Effect of ethyl bismaleamic acid on thermal stability and repair performance of polyvinyl chloride［J］.Polymer Materials Science & Engineering，2019， 35（12）：76⁃80.
8	LI M，ZHANG J W，XIN J N，et al. Design of green zinc⁃based thermal stabilizers derived from tung oil fatty acid and study of thermal stabilization for PVC［J］.Journal of Applied Polymer Science，2017， 134（14）：10.1002/app.44679.
9	丁士文，贾光，杨金霞，等.多元羧酸类稀土热稳定剂的制备方法：中国，CN105482286A［P］. 2014⁃09⁃17.
10	李梅.油脂/松脂源多元酸基PVC钙锌复合热稳定剂的合成及其作用机理研究［D］.北京：中国林业科学研究院， 2015.
11	张宁.二元羧酸稀土复合热稳定剂的制备与性能研究［J］.工程塑料应用，2014（3）：99⁃103.
	ZHANG N. Study on preparation and properties of rare earth dicarboxylate compound thermal stabilizer［J］.Engineering Plastics Application，2014（3）：99⁃103.
12	LI Y P，LI D G，HAN W Y，et al. Facile synthesis of di⁃mannitol adipate ester⁃based zinc metal alkoxide as a bi⁃functional additive for poly（vinyl chloride）［J］.Polymers （Basel），2019， 11（5）：10.3390/polym11050813.
13	WANG M，XIA J L，JIANG J C，et al. A novel liquid Ca/Zn thermal stabilizer synthesized from tung⁃maleic anhydride and its effects on thermal stability and mechanical properties of PVC ［J］.Polymer Degradation and Stability，2016，133：136⁃143.
14	李梅，黄坤，李守海，夏建陵.油脂/松脂源PVC钙锌复合热稳定剂的研究进展［J］.塑料助剂，2017，24（2）：8⁃12.
15	黄元旦，蒋平平，李志莹，等.生物基单硬脂酸甘油酯锌合成及其在PVC制品中的应用［J］.塑料，2015， 44（5）：53⁃57.
	HUANG Y D，JIANG P P，LI Z Y，et al. Synthesis of bio⁃based glycerol monostearate zinc and its application in PVC products［J］.Plastics，2015， 44（5）：53⁃57.
16	YE F，YE Q F，ZHAN H H，et al. Synthesis and study of zinc orotate and its synergistic effect with commercial stabilizers for stabilizing poly（vinyl chloride）［J］.Polymers （Basel），2019，11（2）：10.3390/polym11020194.

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