Synergistic antioxidant effect of phosphonite P⁃EPQ and hindered phenol in polypropylene

doi:10.19491/j.issn.1001-9278.2024.08.004

Abstract

Abstract:

Hydrogen peroxide clearance experiments and thermogravimetric analysis were conducted to compare the antioxidant activity and thermal stability of tetrakis（2，4⁃di⁃tert⁃butylphenyl） 4，4'⁃biphenylene diphosphonate （Hostanox P⁃EPQ） and tris（2，4⁃di⁃tert⁃butylphenyl） phosphite （Irgafos 168）. The results demonstrated that due to its higher phosphorus content and unique P—C bond in the structure， P⁃EPQ exhibited superior antioxidant performance and thermal stability. Furthermore， hindered phenolic antioxidants Irganox 1010 and Irganox 1076 were selected to be compounded with P⁃EPQ to investigate their synergistic antioxidant effects in isotactic polypropylene （iPP）.The comparison of changes in melt volume flow rate （MVR） and yellowing index （YI） during multiple extrusion， as well as the oxidation induction period （OIT） in oxygen atmosphere of iPP stabilized by compound antioxidants indicated that the combination of antioxidant 1010 and P⁃EPQ exhibits a significant synergistic effect. When the mass ratio of 1010 to P⁃EPQ was 6/4， the stabilized iPP had the optimal overall stability performance. At this stage， the MVR and YI of antioxidant⁃modified sample after the fifth extrusion were only 19.8 % and 79.9 % of pure iPP， while the OIT at 180 ℃ significantly increased from 0.8 min to 74.8 min.

Key words: phosphite, antioxidative performance, polypropylene, compound system, synergistic effect

CLC Number:

TQ325.1⁺4

SHAO Haofeng, JIAO Longjie, GONG Weiguang, MENG Xin. Synergistic antioxidant effect of phosphonite P⁃EPQ and hindered phenol in polypropylene[J]. China Plastics, 2024, 38(8): 20-25.

Figures/Tables 12

样品	抗氧剂的质量比（w₁/w₂）
	受阻酚抗氧剂		亚磷酸酯抗氧剂
	A（Irganox 1010）	B（Irganox 1076）	C（Hostanox P⁃EPQ）
iPP	0	0	0
iPP/C₁₀	0	0	10
iPP/A₂/C₈	2	0	8
iPP/A₄/C₆	4	0	6
iPP/A₆/C₄	6	0	4
iPP/A₈/C₂	8	0	2
iPP/A₁₀	10	0	0
iPP/B₂/C₈	0	2	8
iPP/B₄/C₆	0	4	6
iPP/B₆/C₄	0	6	4
iPP/B₈/C₂	0	8	2
iPP/B₁₀	0	10	0

Tab.1. Content of the antioxidant components in different PP samples

一段温度/℃	二段温度/℃	三段温度/℃	四段温度/℃	五段温度/℃	六段温度/℃	七段温度/℃	喂料转速/r·min^-1	主机转速/r·min^-1
195	235	235	235	235	235	200	20	120

Tab.2. Parameter setting of the extruder

Fig.1. Appearance photos of different phosphite reaction solution after adding saturated KI solution and standing for 15 min

抗氧剂	氢过氧化物清除能力
P⁃EPQ	227.6±2.7
168	174.3±2.6

Tab.3. Hydroperoxide scavenging capacity of the phosphite

Fig.2. TG and DTG curves of P⁃EPQ and 168

抗氧剂	$T 5 %$ /℃	$T 10 %$ /℃	$T m a x$ /℃	$R 600$ /%
P⁃EPQ	266	286	333、391、460	11.9
168	257	270	331	0.9

抗氧剂	$T 5 %$ /℃	$T 10 %$ /℃	$T m a x$ /℃	$R 600$ /%
P⁃EPQ	266	286	333、391、460	11.9
168	257	270	331	0.9

Tab.4. Thermo stability of P⁃EPQ and 168

样品	第一次挤出	第三次挤出	第五次挤出
iPP	22.2	43.5	63.6
iPP/A₁₀	9.6	12.5	17.2
iPP/B₁₀	10.0	14.0	19.5
iPP/C₁₀	7.0	10.3	13.4

Tab.5. Melt volume flow rate of the iPP stabilized by various antioxidants alone

Fig.3. Melt volume flow rate of the iPP stabilized by compound systems after being extruded several times

Fig.4. Oxidation induction period of the iPP stabilized by various antioxidants

Fig.5. Oxidation induction period of the iPP stabilized by compound systems

样品	第一次挤出	第三次挤出	第五次挤出
iPP	1.5	11.7	20.4
iPP/A₁₀	4.4	15.6	24.6
iPP/B₁₀	4.7	13.0	19.9
iPP/C₁₀	2.3	3.4	6.8

Tab.6. YI of the iPP stabilized by various antioxidants

Fig.6. YI of the iPP stabilized by compound systems

References 9

1	窦立岩，汪丽梅. 聚丙烯研究进展及应用［J］. 山东化工， 2023， 52（18）： 104⁃105，108.
	DOU L Y， WANG L M. Research progress and application of polypropylene ［J］. Shandong Chemical Industry， 2023， 52（18）： 104⁃105，108.
2	颜安，翁长永，刘毓敏. 聚丙烯改性技术及其产品应用进展［J］. 现代化工， 2022， 42（S2）： 58⁃61.
	YAN A， WENG C Y， LIU Y M. Advances on polypropylene modification technology and application of modified polypropylene ［J］. Modern Chemical Industry， 2022， 42（S2）： 58⁃61.
3	赵建光，高杰. 聚丙烯产品的性能及其应用进展［J］. 化工设计通讯， 2020， 46（07）： 58⁃64.
	ZHAO J G， GAO J. The properties and application progress of polypropylene products［J］. Chemical Design Communications， 2020， 46（07）： 58⁃64.
4	ZHANG Y， LI H， LUO Z， et al. Synthesis of polyethylene‐grafted phosphite antioxidant and its antioxidant behavior in polypropylene ［J］. Macromolecular Chemistry and Physics， 2020， 221（7）： 1900540.
5	LIU Q， WEI P， CONG C， et al. Synthesis and antioxidation behavior in EPDM of novel macromolecular antioxidants with crosslinking and antioxidation effects ［J］. Polymer Degradation and Stability， 2022， 205： 110155.
6	XIA H， GAO H， SUN Q， et al. Puerarin， an efficient natural stabilizer for both polyethylene and polypropylene ［J］. Journal of Applied Polymer Science， 2020， 137（48）： 49599.
7	TATRAALJAI D， TANG Y， PREGI E， et al. Pomegranate extract for the processing stabilization of polyethylene ［J］. Journal of Vinyl and Additive Technology， 2022， 28（2）： 321⁃330.
8	TOCHACEK J， MATUSKA R， POLACEK P， et al. The role of organic phosphite primary structure in the overall stabilization performance in polypropylene ［J］. Polymer Testing， 2017， 57： 126⁃132.
9	ALLEN N S， EDGE M， HUSSAIN S. Perspectives on yellowing in the degradation of polymer materials： inter⁃relationship of structure， mechanisms and modes of stabilisation ［J］. Polymer Degradation and Stability， 2022， 201： 109977.

[1]	SONG Wenlan, SONG Wenxing, LI Bing, LIU Qian, OUYANG Yuge, TIAN Huafeng, GUO Gaiping. Research progress in BOPP films of capacitors for enhancing dielectric and electric energy storage [J]. China Plastics, 2024, 38(7): 138-143.
[2]	SHEN Qiangfeng, LYU Mingfu, XU Yaohui. Study on autoclave foaming properties of metallocene polypropylene [J]. China Plastics, 2024, 38(7): 55-61.
[3]	XU Chen, LUO Bofei, LIU Tengteng, XING Jingkai. Research progress in modification of polypropylene with nucleating agent [J]. China Plastics, 2024, 38(7): 79-85.
[4]	YANG Lian, JIANG Jing, JIA Caiyi, XIE Yuehan, WANG Xiaofeng, LI Qian. Preparation of polyamide 6 microfiber reinforced polypropylene composite and its property of chemical foam injection molding [J]. China Plastics, 2024, 38(6): 12-18.
[5]	DONG Yapeng, ZHAO Tianjiao, WANG Meizhen, CUI Wenju, LIN Fuhua, WANG Bo. Effect of long chain fatty acid sodium/sodium arylamide fatty acid compounding nucleating agent on properties of polypropylene [J]. China Plastics, 2024, 38(6): 60-65.
[6]	XIE Bo, TU Zhigang, ZHOU Xianjin, ZHAG Shangxian, XIONG Ligui, YANG Ting. Development of heat shrinkable BOPP packaging film with low friction coefficient [J]. China Plastics, 2024, 38(6): 78-81.
[7]	ZHANG Yi, HUANG Yating, WEI Yongbao, TANG Wei, QIAN Lijun. Study on pyrolysis mechanism of intumescent flame⁃retardant system based on reaction force field [J]. China Plastics, 2024, 38(5): 66-72.
[8]	GUO Minghai. Studies on structure and properties of high⁃impact copolymerized polypropylene with high melt flow rate [J]. China Plastics, 2024, 38(5): 7-13.
[9]	GUO Jiang, XU Mengyi, LI Hui, HUANG Xiang, LIN Hao, JIANG Shengbao, CHEN Shang, CHEN Cheng. Preparation and dielectric properties of polypropylene/ZrO₂composite materials [J]. China Plastics, 2024, 38(3): 44-48.
[10]	WANG Peng, YAO Cheng, LIU Gang, CAI Xipeng, JIA Lei, WANG Kai, CHEN Long. Structural characteristics and electrical insulating properties of BOPP films based on different stretching modes [J]. China Plastics, 2024, 38(3): 54-58.
[11]	RUAN Fangtao, WU Hao, ZHU Jinwei, SU Yongsheng, CHEN Zhuolin, WANG Guofeng, WANG Hongjie. Effect of TEOS modification and long straw fiber orientation on properties of PP/SF composites [J]. China Plastics, 2024, 38(2): 14-19.
[12]	XU Yaohui, TANG Yiwen, GUO Peng, LYU Mingfu. Effect of ion modification on viscoelasticity of broad molecular weight distribution polypropylene [J]. China Plastics, 2024, 38(1): 7-13.
[13]	LI Dan, ZHAO Biao, CHEN Ke, WANG Fan, ZHANG Jingyu, ZHANG Fengbo, PAN Kai. Research progress in preparation and applications of hollow polypropylene fiber [J]. China Plastics, 2023, 37(9): 109-114.
[14]	DONG Dangfeng. Effect of content of recycled polyethylene/recycled polypropylene/recycled sulfur slag complex modifiers on properties of modified asphalt [J]. China Plastics, 2023, 37(8): 101-106.
[15]	WANG Wenhui, ZHU Huihao, LI Guo, WANG Yu, WU Fan, LIN Zhenbin, MA Yulu, XIE Linsheng. Preparation and optimization of PP/PC light diffusing materials for ultraviolet shielding effect [J]. China Plastics, 2023, 37(8): 8-12.