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New Understanding of Morphology Evolution of Thermoplastic Vulcanizate (TPV) during Dynamic Vulcanization

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State Key Laboratory of Organic−Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
§ Department of Materials Science and Engineering, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, 24061, United States
*Tel.: 86 10 64434860. Fax: 86 10 64433964. E-mail: [email protected] (M.T.).
*Tel.: 86 10 64434860. Fax: 86 10 64433964. E-mail: [email protected] (N.N.).
Cite this: ACS Sustainable Chem. Eng. 2015, 3, 1, 26–32
Publication Date (Web):November 19, 2014
https://doi.org/10.1021/sc500391g
Copyright © 2014 American Chemical Society
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Abstract

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Thermoplastic vulcanizates (TPVs) have attracted considerable attention as typical “green” polymers in recent years and have been widely used in industry because they combine the excellent resilience of conventional elastomers and the easy recyclability of thermoplastics. With a new understanding of the formation and agglomeration of the rubber nanoparticles in ethylene propylene diene monomer/polypropylene (EPDM/PP) TPV, we revealed a new mechanism for the morphology evolution of TPV during dynamic vulcanization (DV). The phase inversion in TPV is dominated by the formation and agglomeration of the rubber nanoparticles rather than the elongation and breakup of the cross-linked rubber phase as previously reported. The size of the rubber agglomerates increases with increasing DV time and then remains constant after DV. In addition, we studied the relationship between the cross-linking of the rubber phase, formation and agglomeration of the rubber nanoparticles, and phase inversion and variation of the rubber network during DV. This study provides guidance to control the microstructure of TPV in preparation of high performance TPV products for automobile and electronic applications.

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Characteristics of the used materials (Table S1), photographs of the disintegrated samples in hot xylene for various times (Figure S1), result of RPA testing for samples C–F (Figure S2), and schematic representation of a rubber nanparticle and rubber nanoparticles agglomerate (Figure S3). This material is available free of charge via the Internet at http://pubs.acs.org.

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  5. Michael W. Bodley and J. Scott Parent . A New Approach to Dynamic Vulcanization: Use of Functional Nitroxyls to Control Reaction Dynamics and Outcomes. Industrial & Engineering Chemistry Research 2017, 56 (43) , 12247-12255. https://doi.org/10.1021/acs.iecr.7b02681
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  8. Youhong Wang, Kunling Chen, Chuanhui Xu, and Yukun Chen . Supertoughened Biobased Poly(lactic acid)–Epoxidized Natural Rubber Thermoplastic Vulcanizates: Fabrication, Co-continuous Phase Structure, Interfacial in Situ Compatibilization, and Toughening Mechanism. The Journal of Physical Chemistry B 2015, 119 (36) , 12138-12146. https://doi.org/10.1021/acs.jpcb.5b06244
  9. Piming Ma, Pengwu Xu, Yinghao Zhai, Weifu Dong, Yong Zhang, and Mingqing Chen . Biobased Poly(lactide)/ethylene-co-vinyl Acetate Thermoplastic Vulcanizates: Morphology Evolution, Superior Properties, and Partial Degradability. ACS Sustainable Chemistry & Engineering 2015, 3 (9) , 2211-2219. https://doi.org/10.1021/acssuschemeng.5b00462
  10. Sayan Basak. Thermoplastic elastomers in biomedical industry – evolution and current trends. Journal of Macromolecular Science, Part A 2021, 58 (9) , 579-593. https://doi.org/10.1080/10601325.2021.1922086
  11. Guodian Zhu, Zhuoxi Li, Jingqi Shang, Jiao Ding, Yuanyuan Li, Guoqiang Yin. Flow mark defects reduction of injection‐molded polypropylene by dynamically vulcanized polyolefin elastomer. Polymer Engineering & Science 2021, 61 (9) , 2276-2286. https://doi.org/10.1002/pen.25756
  12. Shangqing Li, Hongchi Tian, Guo-Hua Hu, Nanying Ning, Ming Tian, Liqun Zhang. Effects of shear during injection molding on the anisotropic microstructure and properties of EPDM/PP TPV containing rubber nanoparticle agglomerates. Polymer 2021, 229 , 124008. https://doi.org/10.1016/j.polymer.2021.124008
  13. Nikoo Ghahramani, Krishnan A. Iyer, Antonios K. Doufas, Savvas G. Hatzikiriakos. Rheological modeling of thermoplastic vulcanizates (TPVs) using the Kaye–Bernstein, Kearsley, Zapas (K–BKZ) constitutive law. Physics of Fluids 2021, 33 (8) , 083107. https://doi.org/10.1063/5.0061474
  14. Yufeng Lei, Anqiang Zhang, Yaling Lin. Interpenetrating covalent adaptable networks with enhanced mechanical properties and facile reprocessability and recyclability. Polymer Chemistry 2021, 12 (28) , 4052-4062. https://doi.org/10.1039/D1PY00623A
  15. Zi Wen Cui, Yuan Rong Jing, Su Su Liu, Guang Yong Liu. Systematic investigation on the effect of crosslinking agent type and dosage on the performance of TPU / MVQ based thermoplastic vulcanizates. Journal of Applied Polymer Science 2021, 138 (26) , 50630. https://doi.org/10.1002/app.50630
  16. Nikoo Ghahramani, Shiling Zhang, Krishnan Iyer, Antonios K. Doufas, Savvas G. Hatzikiriakos. Melt fracture and wall slip of thermoplastic vulcanizates. Polymer Engineering & Science 2021, 61 (4) , 942-958. https://doi.org/10.1002/pen.25588
  17. Xiaolong Pan, Zhaozhao Wang, Long Chen, Wenhao Li, Jian Hu, Jie Hu, Xiao Wu, Jianming Zhang, Yongxin Duan. Dependence of microstructure and properties of polypropylene/bromo‐isobutylene‐isoprene rubber thermoplastic vulcanizates on the molding process. Journal of Applied Polymer Science 2021, 138 (2) , 49659. https://doi.org/10.1002/app.49659
  18. Aizeti Burgoa, Aitor Arriaga, Kepa Zulueta, Eva Maria Acuña, Jose Manuel Laza, Ricardo Hernandez, Jose Luis Vilas. Experimental investigation of the nonlinear quasi-static and dynamic mechanical behaviour of novel PA6/XHNBR thermoplastic vulcanizates: Linking mechanical nonlinearities to microstructural features. Materials Today Communications 2020, 25 , 101395. https://doi.org/10.1016/j.mtcomm.2020.101395
  19. Nikoo Ghahramani, Krishnan A. Iyer, Antonios K. Doufas, Savvas G. Hatzikiriakos. Rheology of thermoplastic vulcanizates (TPVs). Journal of Rheology 2020, 64 (6) , 1325-1341. https://doi.org/10.1122/8.0000108
  20. Qinjun Pan, Guojie Zhao, Hua Deng, Qiang Fu. Balanced physical properties for thermoplastic silicone vulcanizate‐based polymer composites containing functional filler. Polymer Composites 2020, 41 (10) , 4307-4317. https://doi.org/10.1002/pc.25713
  21. Jiarui Hou, Ming Zhong, Xiaolong Pan, Long Chen, Xiao Wu, Zhengqing Kong, Yuan Yuan, Shouke Yan, Jianming Zhang, Yongxin Duan. Fabricating 3D printable BIIR/PP TPV via masterbatch and interfacial compatibilization. Composites Part B: Engineering 2020, 199 , 108220. https://doi.org/10.1016/j.compositesb.2020.108220
  22. Tao Peng, Fei Lv, Zhou Gong, Liming Cao, Xuesong Yan, Ling Ge, Saifudin Abubakar, Yukun Chen. Design of PP/EPDM/NBR TPVs with tunable mechanical properties via regulating the core-shell structure. Polymer Testing 2020, 90 , 106767. https://doi.org/10.1016/j.polymertesting.2020.106767
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  24. Francesco Ciardelli, Stefano Dossi, Andrea Galanti, Andrea Magri, Stefano Riolo. Molecular evolution during dynamic vulcanization of polyolefin mixtures for lead‐free thermoplastic vulcanized. Polymers for Advanced Technologies 2020, 31 (4) , 864-872. https://doi.org/10.1002/pat.4821
  25. Shangqing Li, Hongchi Tian, Hanguang Wu, Nanying Ning, Ming Tian, Liqun Zhang. Coupling effect of molecular weight and crosslinking kinetics on the formation of rubber nanoparticles and their agglomerates in EPDM/PP TPVs during dynamic vulcanization. Soft Matter 2020, 16 (9) , 2185-2198. https://doi.org/10.1039/C9SM02059D
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  30. Qiang Wu, Jiafeng Fang, Minghuan Zheng, Yan Luo, Xu Wang, Lixin Xu, Chunhui Zhang. Morphology Evolution and Rheological Behaviors of PP/SR Thermoplastic Vulcanizate. Polymers 2019, 11 (1) , 175. https://doi.org/10.3390/polym11010175
  31. Zhaoyang Wei, Nanying Ning, Ming Tian, Liqun Zhang, Jianguo Mi. Microscopic theory of heterogeneous phase inversion in rubber/plastic blends. Polymer 2018, 150 , 177-183. https://doi.org/10.1016/j.polymer.2018.07.032
  32. Nanying Ning, Shangqing Li, Hanguang Wu, Hongchi Tian, Pengjun Yao, Guo-Hua HU, Ming Tian, Liqun Zhang. Preparation, microstructure, and microstructure-properties relationship of thermoplastic vulcanizates (TPVs): A review. Progress in Polymer Science 2018, 79 , 61-97. https://doi.org/10.1016/j.progpolymsci.2017.11.003
  33. Chao-Qun Li, Jun-Wei Zha, Zhi-Jun Li, Dong-Li Zhang, Si-Jiao Wang, Zhi-Min Dang. Towards balanced mechanical and electrical properties of thermoplastic vulcanizates composites via unique synergistic effects of single-walled carbon nanotubes and graphene. Composites Science and Technology 2018, 157 , 134-143. https://doi.org/10.1016/j.compscitech.2018.01.038
  34. Yasamin Kazemi, Adel Ramezani Kakroodi, Amir Ameli, Tobin Filleter, Chul B. Park. Highly stretchable conductive thermoplastic vulcanizate/carbon nanotube nanocomposites with segregated structure, low percolation threshold and improved cyclic electromechanical performance. Journal of Materials Chemistry C 2018, 6 (2) , 350-359. https://doi.org/10.1039/C7TC04501H
  35. Shangqing Li, Yafei Lv, Jian Sheng, Hongchi Tian, Nanying Ning, Liqun Zhang, Hanguang Wu, Ming Tian. Morphology development of POE/PP thermoplastic vulcanizates (TPVs) during dynamic vulcanization. European Polymer Journal 2017, 93 , 590-601. https://doi.org/10.1016/j.eurpolymj.2017.06.019
  36. Youhong Wang, Zhou Gong, Chuanhui Xu, Yukun Chen. Poly (vinylidene fluoride)/fluororubber/silicone rubber thermoplastic vulcanizates prepared through core-shell dynamic vulcanization: Formation of different rubber/plastic interfaces via controlling the core from “soft” to “hard”. Materials Chemistry and Physics 2017, 195 , 123-131. https://doi.org/10.1016/j.matchemphys.2017.04.016
  37. Keiichi Kuboyama. Polymer Blend. Seikei-Kakou 2017, 29 (7) , 249-253. https://doi.org/10.4325/seikeikakou.29.249
  38. M. Haghnegahdar, G. Naderi, M. H. R. Ghoreishy. Microstructure and Mechanical Properties of Nanocomposite Based on Polypropylene/Ethylene Propylene Diene Monomer/Graphene. International Polymer Processing 2017, 32 (1) , 72-83. https://doi.org/10.3139/217.3286
  39. Korn Taksapattanakul, Tulyapong Tulyapitak, Pranee Phinyocheep, Polphat Ruamcharoen, Jareerat Ruamcharoen, Fabienne Lagarde, Mathieu Edely, Philippe Daniel. Raman investigation of thermoplastic vulcanizates based on hydrogenated natural rubber/polypropylene blends. Polymer Testing 2017, 57 , 107-114. https://doi.org/10.1016/j.polymertesting.2016.11.016
  40. Nanying Ning, Xiangyan Li, Hongchi Tian, Yueqing Hua, Hongli Zuo, Pengjun Yao, Liqun Zhang, Youping Wu, Guo-Hua Hu, Ming Tian. Unique microstructure of an oil resistant nitrile butadiene rubber/polypropylene dynamically vulcanized thermoplastic elastomer. RSC Advances 2017, 7 (9) , 5451-5458. https://doi.org/10.1039/C6RA24891H
  41. Joyeeta Dutta, Padmanabhan Ramachandran, Kinsuk Naskar. Scrutinizing the influence of peroxide crosslinking of dynamically vulcanized EVA/TPU blends with special reference to cable sheathing applications. Journal of Applied Polymer Science 2016, 133 (29) https://doi.org/10.1002/app.43706
  42. W. Pongdong, C. Kummerlöwe, N. Vennemann, A. Thitithammawong, C. Nakason. Property correlations for dynamically cured rice husk ash filled epoxidized natural rubber/thermoplastic polyurethane blends: Influences of RHA loading. Polymer Testing 2016, 53 , 245-256. https://doi.org/10.1016/j.polymertesting.2016.05.026
  43. Li-Feng Ma, Rui-Ying Bao, Rui Dou, Shao-Di Zheng, Zheng-Ying Liu, Rui-Yan Zhang, Ming-Bo Yang, Wei Yang. Conductive thermoplastic vulcanizates (TPVs) based on polypropylene (PP)/ethylene-propylene-diene rubber (EPDM) blend: From strain sensor to highly stretchable conductor. Composites Science and Technology 2016, 128 , 176-184. https://doi.org/10.1016/j.compscitech.2016.04.001
  44. Hanguang Wu, Ming Tian, Liqun Zhang, Hongchi Tian, Youping Wu, Nanying Ning, Guo-Hua Hu. Effect of Rubber Nanoparticle Agglomeration on Properties of Thermoplastic Vulcanizates during Dynamic Vulcanization. Polymers 2016, 8 (4) , 127. https://doi.org/10.3390/polym8040127
  45. Pengjun Yao, Hanguang Wu, Nanying Ning, Liqun Zhang, Hongchi Tian, Youping Wu, Guohua Hu, Tung W. Chan, Ming Tian. Properties and unique morphological evolution of dynamically vulcanized bromo-isobutylene-isoprene rubber/polypropylene thermoplastic elastomer. RSC Advances 2016, 6 (14) , 11151-11160. https://doi.org/10.1039/C5RA26171F
  46. Pengjun Yao, Hanguang Wu, Nanying Ning, Liqun Zhang, Hongchi Tian, Youping Wu, Guo-Hua Hu, Tung W. Chan, Ming Tian. Microstructure and properties of bromo-isobutylene–isoprene rubber/polyamide 12 thermoplastic vulcanizate toward recyclable inner liners for green tires. RSC Advances 2016, 6 (36) , 30004-30013. https://doi.org/10.1039/C6RA00131A
  47. Hanguang Wu, Pengjun Yao, Nanying Ning, Liqun Zhang, Hongchi Tian, Youping Wu, Ming Tian. A novel dielectric elastomer by constructing dual-network structure of carbon nanotubes and rubber nanoparticles in dynamically vulcanized thermoplastic elastomer. RSC Advances 2016, 6 (39) , 32932-32939. https://doi.org/10.1039/C6RA01463A
  48. Lifeng Ma, Ruiying Bao, Zhengying Liu, Wei Yang, Mingbo Yang. Effect of cross-linking degree of EPDM phase on the electrical properties and formation of dual networks of thermoplastic vulcanizate composites based on isotactic polypropylene (iPP)/ethylene–propylene–diene rubber (EPDM) blends. RSC Advances 2016, 6 (78) , 74567-74574. https://doi.org/10.1039/C6RA14731C
  49. Nanying Ning, Yueqing Hua, Hanguang Wu, Liqun Zhang, Shemao Wu, Ming Tian, Hongchi Tian, Guo-Hua Hu. Novel heat and oil-resistant thermoplastic vulcanizates based on ethylene-vinyl acetate rubber/poly(vinylidene fluoride). RSC Advances 2016, 6 (94) , 91594-91602. https://doi.org/10.1039/C6RA19335H
  50. Pranab Dey, Kinsuk Naskar, Golok B. Nando. Theoretical and morphological evaluation of dynamic viscoelasticity and thermo-mechanical characteristics of TPV composites. Polymer 2015, 70 , 161-172. https://doi.org/10.1016/j.polymer.2015.06.024

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