Applications of Composite Antioxidants in Coal⁃based Polypropylene

doi:10.19491/j.issn.1001-9278.2021.02.014

Abstract

Abstract:

A series of coal-based PP （S1003） were prepared by using different ratios of 1010/168 composite antioxidants to calcium stearate， and their thermal oxidative stability and processing stability were analyzed through oxidation induced time （OIT） test， multiple extrusion test and yellow index test at different temperatures. The results indicated that the OIT value of S1003 increased with an increase in the concentration of antioxidant 1010 in the main and auxiliary antioxidant system at the same temperature， presenting an excellent ability to capture oxygen free radicals. At the same time， the MFRs of the samples with formula 3 and formula 4 showed a slow increasing trend， indicating that the thermal oxidative degradation of S1003 was inhibited effectively. In addition， the distribution trend in yellow index showed that the color change resistance for the samples obtained from repeated extrusion was improved with an increase in the concentration of antioxidant 168. It was concluded that a proper ratio for the antioxidant composite could improve the antioxidant performance of S1003. Such a result is of great significance for the optimizing the formula proportion of composite antioxidants and prolonging the service life of coal?based PP materials.

Key words: polypropylene, composite antioxidant, thermal oxidative stability, processing stability

CLC Number:

TQ325.1⁺5

LIU Yi, GUO Xiaodong, BAO Lulu, SHU Cheng, LI Yonglun, WANG Yong, LI Guofeng, DU Shanming. Applications of Composite Antioxidants in Coal⁃based Polypropylene[J]. China Plastics, 2021, 35(2): 84-89.

Figures/Tables 7

References 15

1	BUSICO V， CIPULLO R. Microstructure of Polypropylene［J］. Progress in Polymer Science， 2001， 26（3）：443⁃533.
2	包璐璐，韩李旺，杨廷杰，等. 聚丙烯生产工艺技术及其产品进展［J］. 广州化工， 2019， 47（14）：14⁃16，44.
	BAO L L， HAN L W， YANG T J， et al. Research Pro⁃gress on Polypropylene Production Technology and Products［J］. Guangzhou Chemical Industry， 2019， 47（14）：14⁃16，44.
3	洪定一.聚丙烯-原理、工艺与技术（第二版）.北京：中国石化出版社，2011：452⁃477.
4	GALLI P ， VECELLIO G. Polyolefins： The Most Promising Large-Volume Materials for the 21st Century［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2004，42：396⁃415.
5	王海鹰，贾冰茹，吴立豪. 抗氧剂在聚合物中的应用［J］. 塑料科技， 2011， 39（12）：83⁃86.
	WANG H Y， JIA B R， WU L H. Application of Antioxidant in Polymer［J］. Plastics Science and Technology， 2011， 39（12）：83⁃86.
6	LI M J， HSUAN Y G. Temperature and Pressure Effects on the Degradation of Polypropylene Tape Yarns—Depletion of Antioxidants［J］. Geotextiles and Geomembranes， 2004， 22（6）：511⁃530.
7	刘一鸣，胡贵，吴智华. 抗氧剂对无规共聚聚丙烯抗紫外光老化性能的影响［J］. 塑料科技， 2012， 40（12）：84⁃88.
	LIU Y M， HU G， WU Z H. Effect of Antioxidants on the Anti⁃Ultraviolet Aging Behavior of Polypropylene Random Copolymer［J］. Plastics Science and Technology， 2012， 40（12）：84⁃88.
8	YAKIMETS I， LAI D W， GUIGON M. Effect of Photo⁃Oxidation Cracks on Behaviour of Thick Polypropylene Samples［J］. Polymer Degradation and Stability， 2004， 86（1）：59⁃67.
9	KOTEK J， KELNAR I， BALDRIAN J， et al. Structural Transformations of Isotactic Polypropylene Induced by Heating and UV Light［J］. European Polymer Journal， 2004， 40（12）：2 731⁃2 738.
10	王洪山，郭琛，孙亚斌. 酚类抗氧剂及结构优化［J］. 石油化工应用， 2010， 29（7）：1⁃6.
	WANG H S， GUO C， SUN Y B. Phenolic Antioxidants and Their Structure Modification［J］. Petrochemical Industry Application， 2010， 29（7）：1⁃6.
11	李国锋，包璐璐，郭晓东，等. 快速注塑薄壁制品聚丙烯专用料的助剂研究进展［J］. 广州化工， 2020， 48（10）：20⁃23.
	LI G F， BAO L L， GUO X D， et al. Research Progress on Additives for Rapid Injection Thin⁃Walled Polypropylene［J］. GuangZhou Chemical Industry， 2020， 48（10）：20⁃23.
12	张永鹏，陈俊，郭绍辉，等. 受阻酚类抗氧剂的研究进展及发展趋势［J］. 塑料助剂， 2011（3）：1⁃7.
	ZHANG Y P， CHEN J， GUO S H， et al. Research Progress and Development Tendency of Hindered Phenol Antioxidant［J］. Plastic Additives， 2011（3）：1⁃7.
13	LUGAO A B， CARDOSO E C L， HUTZLER B， et al. Temperature Dependent Oxidative⁃Induction Time （TOIT） of Irradiated and Non⁃Irradiated Polypropylene—A New Method［J］. Radiation Physics and Chemistry， 2002， 63（3/4/5/6）：489⁃492.
14	SCHMID M， AFFOLTER S. Interlaboratory Tests on Polymers by Differential Scanning Calorimetry （DSC）： Determination and Comparison of Oxidation Induction Time （OIT） and Oxidation Induction Temperature （OIT）［J］. Polymer Testing， 2003， 22（4）：419⁃428.
15	孟鑫，石靖，裘志浩，等. DSC加速老化试验方法在PP寿命估算中的应用［J］. 工程塑料应用， 2012， 40（5）：74⁃76.
	MENG X， SHI J， QIU Z H， et al. Life Predication of Polypropylene Using Accelerated Aging Method Based Differential Scanning Calorimetry［J］. Engineering Plastics Application， 2012， 40（5）：74⁃76.

样品编号	1010含量/g	168含量/g	1010∶168的质量比	硬脂酸钙/g
1^#	3	0	-	1.5
2^#	2	1	2∶1	1.5
3^#	1.5	1.5	1∶1	1.5
4^#	1	2	1∶2	1.5
5^#	0.6	2.4	1∶4	1.5
6^#	0	3	-	1.5

样品编号	1010含量/g	168含量/g	1010∶168的质量比	硬脂酸钙/g
1^#	3	0	-	1.5
2^#	2	1	2∶1	1.5
3^#	1.5	1.5	1∶1	1.5
4^#	1	2	1∶2	1.5
5^#	0.6	2.4	1∶4	1.5
6^#	0	3	-	1.5

样品编号	氧化温度与时间关系	E_a /kJ·mol^-1	b
1^#	ln t=-59.05+28 826(1/T)	-239.659 364	28 826
2^#	ln t=-48.53+24 043(1/T)	-199.893 502	24 043
3^#	ln t=-60.28+29 212(1/T)	-242.868 568	29 212
4^#	ln t=-58.1+27 938(1/T)	-232.276 532	27 938
5^#	ln t=-35.80+17 437(1/T)	-144.971 218	17 437
6^#	ln t=-26.77+11 767(1/T)	-97.830 838	11 767

样品编号	氧化温度与时间关系	E_a /kJ·mol^-1	b
1^#	ln t=-59.05+28 826(1/T)	-239.659 364	28 826
2^#	ln t=-48.53+24 043(1/T)	-199.893 502	24 043
3^#	ln t=-60.28+29 212(1/T)	-242.868 568	29 212
4^#	ln t=-58.1+27 938(1/T)	-232.276 532	27 938
5^#	ln t=-35.80+17 437(1/T)	-144.971 218	17 437
6^#	ln t=-26.77+11 767(1/T)	-97.830 838	11 767

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