抗氧剂耐迁移化技术的研究应用进展

doi:10.19491/j.issn.1001-9278.2020.12.016

中国塑料 ›› 2020, Vol. 34 ›› Issue (12): 92-102.DOI: 10.19491/j.issn.1001-9278.2020.12.016

抗氧剂耐迁移化技术的研究应用进展

李晨洋¹^,², 公维光³, 孟鑫¹^,²(), 曹齐茗¹^,², 姚中阳¹^,²

^1.华东理工大学化工学院，上海市多相尺度重点实验室，上海 200237
^2.华东理工大学化工学院产品工程系，上海 200237
^3.华东理工大学体育新材料研发中心，上海 200237

收稿日期:2020-05-08 出版日期:2020-12-26 发布日期:2020-12-26

Research and Application Progress of Antioxidant Anti⁃migration Technology

LI Chenyang¹^,²,GONG Weiguang³,MENG Xin¹^,²(),CAO Qiming¹^,², YAO Zhongyang^1,2

^1.Shanghai Key Laboratory of Multiphase Measurement，School of Chemical Engineering，East China University of Science and Technology，Shanghai 200237，China
^2.Department of Product Engineering，School of Chemical Engineering，East China University of Science and Technology，Shanghai 200237，China
^3.Research & Development Center for Sports Materials，East China University of Science and Technology，Shanghai 200237，China

Received:2020-05-08 Online:2020-12-26 Published:2020-12-26
Contact: MENG Xin E-mail:mengxin@ecust.edu.cn

摘要/Abstract

摘要：

抗氧剂对抑制聚烯烃材料的氧化具有重要作用，但其在制品中易迁移、易挥发，降低了抗氧化效率。综述了近年来通过抗氧剂大分子化、聚合物封装和无机载体固载，实现抗氧剂耐迁移化的研究进展。其次，提出了目前抗氧剂耐迁移化技术存在的问题及改进方法，并对其发展前景做出展望。

关键词: 聚烯烃, 抗氧剂, 耐迁移化

Abstract:

Antioxidants play an important role in preventing the oxidation of polyolefin materials. However， they are easy to migrate and volatilize， resulting in a reduction in antioxidation efficiency. Therefore， it is of great significance to improve the anti-migration of antioxidant. This paper introduced the recent research progress in antioxidant migration resistance through macro?molecularization， polymer encapsulation and inorganic particle immobilization. Furthermore， the existing problems and improvement methods of current antioxidant migration resistance technology were proposed， and the its development trend in future was prospected.

Key words: polyolefin, antioxidant, anti-migration, macro-molecularization

中图分类号:

TQ314

李晨洋, 公维光, 孟鑫, 曹齐茗, 姚中阳. 抗氧剂耐迁移化技术的研究应用进展[J]. 中国塑料, 2020, 34(12): 92-102.

LI Chenyang, GONG Weiguang, MENG Xin, CAO Qiming, YAO Zhongyang. Research and Application Progress of Antioxidant Anti⁃migration Technology[J]. China Plastics, 2020, 34(12): 92-102.

图/表 17

图1 双功能抗氧剂TAIC3S3Ph的制备及抗氧剂CA1的结构式(根据文献[5]修改)

Fig.1 Preparation of bifunctional antioxidant TAIC3S3Ph and molecular structure of CA1(revised according to reference[5])

图2 抗氧剂BM46TBPP的分子结构式

Fig.2 Molecular structure of BM46TBPP

图3 抗氧剂EVOAP、POE?A的合成示意图[8]

Fig.3 Preparation of EVOAP and POE?A[8]

图4 降冰片烯聚合型抗氧剂的合成[10]

Fig.4 Synthesis of norbornene polymerized antioxidant[10]

图5 封装抗氧剂纳米球粒结构[11]

Fig.5 Encapsulated antioxidant nanosphere structure[11]

图6 静电纺丝封装酚类抗氧剂的结构[11]

Fig.6 Structure of encapsulated phenolic antioxidant synthesized by electrospinning[11]

图7 抗氧剂AO?KH550?SiO2?TiO2制备过程[16]

Fig.7 Preparation of AO?KH550?SiO2?TiO2[16]

图8 AO?MWCNT?B的制备过程[19]

Fig.8 Preparation of AO?MWCNT?B[19]

图9 抗氧剂AO?80的化学固载和物理吸附过程[21]

Fig.9 Chemical immobilization and physical adsorption process of AO?80[21]

图10 PPSQ的制备过程

Fig.10 Preparation of PPSQ

图11 聚丙烯样品的氧化诱导温度随水解时间变化关系

Fig.11 Relationship between oxidation induction temperature and hydrolysis time of PP samples

图12 抗氧剂HNTs?4010NA的固载过程[23]

Fig.12 Immobilization process of HNTs?4010NA[23]

图13 样品SBR#4和SBR#6的耐迁移及老化后力学性能果[24]

Fig.13 Test results of migration resistance and mechanical property of SBR#4 and SBR#6 after aging[24]

图14 RD在橡胶中的迁移过程[25]

Fig.14 Migration process of RD in rubber[25]

图15 插层抗氧剂分子结构式

Fig.15 Molecular structure of intercalation antioxidant

图16 AO?OM?MMt的制备过程[33]

Fig.16 Preparation of AO?OM?MMt[33]

图17 霍夫曼消除反应释放抗氧剂机理[31]

Fig.17 Mechanism of antioxidant release by Hoffman elimination reaction[31]

参考文献 37

1	姜日元，齐姝婧，卢春阳，等. 国内外聚乙烯生产及供需情况分析预测［M］. 化学工业， 2019， 37： 26⁃32，41.
2	谭捷. 我国聚丙烯供需现状及未来发展分析［J］. 塑料助剂， 2019（4）：5⁃12，18.
	TAN J. Supply⁃Demand Status and Future Development Analysis of Polypropylene in China［J］. Plastics Additives， 2019（4）：5⁃12，18.
3	冯亚青，陈立功. 助剂化学及工艺学［M］.第二版. 北京：化学工业出版社， 2015： 49⁃52.
4	LI G Y， KOENIG J L. A Review of Rubber Oxidation［J］. Rubber Chemistry and Technology， 2005， 78（2）：355⁃390.
5	FISCHER J， METZSCH⁃ZILLIGEN E， ZOU M Y， et al. A Novel Class of High Molecular Weight Multifunctional Antioxidants for Polymers Based on Thiol⁃Ene Click Reaction［J］. Polymer Degradation and Stability， 2020， 173：109099.
6	MENG X， JIANG Z W， XIN Z， et al. Antioxidation and Mechanism of Phosphites Including the Free Phenolic Hydroxyl Group in Polypropylene［J］. Journal of Applied Polymer Science， 2017， 134（15）：44696.
7	孟鑫，蒋泽文，公维光. 亚磷酸酯⁃酚双功能抗氧剂对聚丙烯氧化稳定性的影响［J］. 塑料助剂， 2019（1）：28⁃33.
	MENG X， JIANG Z W， GONG W G. Impact of the Phosphite⁃Phenol Bifunctional Antioxidant on the Oxidative Stability of Polypropylene［J］. Plastics Additives， 2019（1）：28⁃33.
8	MANTEGHI A， AHMADI S， ARABI H. Covalent Immobilization of Phenolic Antioxidant on Ethylene Copolymers： An Efficient Approach Toward Enhanced Long⁃term Stabilization of Polypropylene［J］. Polymer， 2016， 104：31⁃39.
9	MANTEGHI A， AHMADI S， ARABI H. Enhanced Thermo⁃oxidative Stability through Covalent Attachment of Hindered Phenolic Antioxidant on Surface Functionalized Polypropylene［J］. Polymer， 2018， 138：41⁃48.
10	XUE B Y， OGATA K， TOYOTA A. Synthesis of Polymeric Antioxidants Based on Ring⁃Opening Metathesis Polymerization （ROMP） and Their Antioxidant Ability for Preventing Polypropylene （PP） from Thermal Oxidation Degradation［J］. Polymer Degradation and Stability， 2008， 93（2）：347⁃352.
11	MAQSOUDLOU A， ASSADPOUR E， MOHEBODINI H， et al. Improving the Efficiency of Natural Antioxidant Compounds via Different Nanocarriers［J］. Advances in Colloid and Interface Science， 2020， 278：102122.
12	DALMOLIN L F， KHALIL N M， MAINARDES R M. Delivery of Vanillin by Poly（lactic⁃acid） Nanoparticles： Development， Characterization and in Vitro Evaluation of Antioxidant Activity［J］. Materials Science and Engineering： C， 2016， 62：1⁃8.
13	MARCET I， WENG S H， SÁEZ⁃ORVIZ S， et al. Production and Characterisation of Biodegradable PLA Nanoparticles Loaded with Thymol to Improve Its Antimicrobial Effect［J］. Journal of Food Engineering， 2018， 239：26⁃32.
14	GIMENEZ⁃ROTA C， PALAZZO I， SCOGNAMIGLIO M R， et al. Β⁃Carotene， Α⁃Tocoferol and Rosmarinic Acid Encapsulated within PLA/PLGA Microcarriers by Supercritical Emulsion Extraction： Encapsulation Efficiency， Drugs Shelf⁃life and Antioxidant Activity［J］. The Journal of Supercritical Fluids， 2019， 146：199⁃207.
15	BRUNI G P， OLIVEIRA J P D， GÓMEZ⁃MASCARAQUE L G， et al. Electrospun Β⁃carotene⁃loaded SPI： PVA Fiber Mats Produced by Emulsion⁃electrospinning as Bioactive Coatings for Food Packaging［J］. Food Packaging and Shelf Life， 2020， 23：100426.
16	LI G， WANG F， LIU P， et al. Antioxidant Functionalized Silica⁃coated TiO₂ Nanorods to Enhance the Thermal and Photo Stability of Polypropylene［J］. Applied Surface Science， 2019， 476：682⁃690.
17	ZHONG B C， SHI Q F， JIA Z X， et al. Preparation of Silica⁃supported 2⁃mercaptobenzimidazole and Its Antioxidative Behavior in Styrene⁃butadiene Rubber［J］. Polymer Degradation and Stability， 2014， 110：260⁃267.
18	LIN J， LUO Y F， ZHONG B C， et al. Enhanced Interfacial Interaction and Antioxidative Behavior of Novel Halloysite Nanotubes/Silica Hybrid Supported Antioxidant in Styrene⁃butadiene Rubber［J］. Applied Surface Science， 2018， 441：798⁃806.
19	SHI X M， WANG J D， JIANG B B， et al. Hindered Phenol Grafted Carbon Nanotubes for Enhanced Thermal Oxidative Stability of Polyethylene［J］. Polymer， 2013， 54（3）：1 167⁃1 176.
20	ZHANG J H， ZHANG H， CHEN F B， et al. Improving Stability of Mechanical Properties for Nitrile Butadiene Rubber Composite by Carbon Nanotube with Antioxidant Loading Distribution［J］. Polymer Composites， 2019， 40（S2）：E1172⁃E1180.
21	ZHANG J H， ZHANG H， WANG S T， et al. Antioxidant⁃loaded Carbon Nanotube to Sustain a Long⁃term Aging⁃protection for Acrylonitrile⁃butadiene Rubber［J］. Polymer Degradation and Stability， 2017， 144：93⁃99.
22	TANG H Y， LIU P， LU M， et al. Thermal⁃oxidative Effect of a Co⁃condensed Nanosilica⁃based Antioxidant in Polypropylene［J］. Polymer， 2017， 112：369⁃376.
23	FU Y， ZHAO D T， YAO P J， et al. Highly Aging⁃resistant Elastomers Doped with Antioxidant⁃loaded Clay Nanotubes［J］. ACS Applied Materials & Interfaces， 2015， 7（15）：8 156⁃8 165.
24	FU Y， YANG C， LVOV Y M， et al. Antioxidant Sustained Release from Carbon Nanotubes for Preparation of Highly Aging Resistant Rubber［J］. Chemical Engineering Journal， 2017， 328：536⁃545.
25	ZHONG B C， LIN J， LIU M L， et al. Preparation of Halloysite Nanotubes Loaded Antioxidant and Its Antioxidative Behaviour in Natural Rubber［J］. Polymer Degradation and Stability， 2017， 141：19⁃25.
26	BERLIER G， GASTALDI L， SAPINO S， et al. MCM⁃41 as a Useful Vector for Rutin Topical Formulations： Synthesis， Characterization and Testing［J］. International Journal of Pharmaceutics， 2013， 457（1）：177⁃186.
27	LI C， QIU X L， LU L X， et al. Preparation of Low⁃density Polyethylene Film with Quercetin and Α⁃tocopherol Loaded with Mesoporous Silica for Synergetic⁃release Antioxidant Active Packaging［J］. Journal of Food Process Engineering， 2019， 42（5）：e13088.
28	FENG Y J， JIANG Y， HUANG Q， et al. High Antioxidative Performance of Layered Double Hydroxides/Polypropylene Composite with Intercalation of Low⁃molecular⁃weight Phenolic Antioxidant［J］. Industrial & Engineering Chemistry Research， 2014， 53（6）：2 287⁃2 292.
29	ZHANG Q， JIAO Q， LEROUX F， et al. Antioxidant Intercalated Zn⁃containing Layered Double Hydroxides： Preparation， Performance and Migration Properties［J］. New Journal of Chemistry， 2017， 41（6）：2 364⁃2 371.
30	ZHANG Q， LEROUX F， TANG P G， et al. Low Molecular Weight Hindered Amine Light Stabilizers （HALS） Intercalated MgAl⁃Layered Double Hydroxides： Preparation and Anti⁃aging Performance in Polypropylene Nanocomposites［J］. Polymer Degradation and Stability， 2018， 154：55⁃61.
31	DINTCHEVA N T， AL⁃MALAIKA S， MORICI E， et al. Thermo⁃oxidative Stabilization of Poly（lactic acid）⁃based Nanocomposites through the Incorporation of Clay with In⁃built Antioxidant Activity［J］. Journal of Applied Polymer Science， 2017， 134（24）： DOI：10.1002/app.44 974.
32	DINTCHEVA N T， AL⁃MALAIKA S， ARRIGO R， et al. Novel Strategic Approach for the Thermo⁃ and Photo⁃ Oxidative Stabilization of Polyolefin/Clay Nanocomposites［J］. Polymer Degradation and Stability， 2017， 145：41⁃51.
33	DINTCHEVA N T， AL⁃MALAIKA S， MORICI E. Novel Organo⁃Modifier for Thermally⁃stable Polymer⁃layered Silicate Nanocomposites［J］. Polymer Degradation and Stability， 2015， 122：88⁃101.
34	BEDIAKO E G， NYANKSON E， DODOO⁃ARHIN D， et al. Modified Halloysite Nanoclay as a Vehicle for Sustained Drug Delivery［J］. Heliyon， 2018， 4（7）：e00689.
35	FAN Q Q， HAN G P， CHENG W L， et al. Effect of Intercalation Structure of Organo⁃Modified Montmorillonite/Polylactic Acid on Wheat Straw Fiber/Polylactic Acid Composites［J］. Polymers， 2018， 10（8）：896.
36	HÁRI J， POLYÁK P， MESTER D， et al. Adsorption of an Active Molecule on the Surface of Halloysite for Controlled Release Application： Interaction， Orientation， Consequences［J］. Applied Clay Science， 2016， 132/133：167⁃174.
37	杨春. 一维无机纳米管负载缓释防老剂制备高性能耐老化橡胶的研究［D］. 北京：北京化工大学， 2017.

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抗氧剂耐迁移化技术的研究应用进展

Research and Application Progress of Antioxidant Anti⁃migration Technology

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