Preparation and properties of novel fluorosilicone thermoplastic vulcanizate with cross-linking–controlled core-shell structure
Yanpeng Wang
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou, 510640 China
Search for more papers by this authorYuan Tang
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorYanrong Ren
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorTao Ding
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorCorresponding Author
Yukun Chen
The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou, 510640 China
Correspondence
Yukun Chen, The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou 510640, China.
Email: [email protected]
Search for more papers by this authorYanpeng Wang
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou, 510640 China
Search for more papers by this authorYuan Tang
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorYanrong Ren
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorTao Ding
School of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004 China
Search for more papers by this authorCorresponding Author
Yukun Chen
The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou, 510640 China
Correspondence
Yukun Chen, The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou 510640, China.
Email: [email protected]
Search for more papers by this authorAbstract
A new fluorosilicone thermoplastic vulcanizate (TPV) composed of poly(vinylidene fluoride) (PVDF), silicone rubber (SR), and fluororubber (FKM) was successfully prepared through dynamic vulcanization. The morphological structure of the TPVs had core-shell elastomer particles dispersed in a continuous PVDF matrix. Furthermore, the cross-linking of core-shell structure was controlled by adopting different curing agent. The effect of cross-linking–controlled core-shell structure on the morphology, crystallization behavior, stress relaxation test, solvent-resistant properties of the obtained TPVs were investigated. It was found that the shell cross-link had a significant influence on the crystallinity of the PVDF phase. The core-shell bicross-linked TPV was found to provide the lowest rate of relaxation. An obvious stress softening phenomenon was observed in the uniaxial loading-unloading cycles in tension. The bicross-linked TPV had good solvent resistant properties. The tensile strength of the bicross-linked TPV was still 12 MPa even after immersed in butyl acetate for 48 hours.
REFERENCES
- 1Cao LM, Huang JR, Chen YK. Dual cross-linked self-healable natural rubber reinforced by tunicate cellulose nanocrystals with improved strength and extensibility. ACS Sustain Chem Eng. 2018; 6(11): 14802-14811.
- 2Liu C, Huang JR, Yuan DS, Chen YK. Design of high strength XSBR/Fe3O4/ZDMA shape memory composite with dual responses. Ind Eng Chem Res. 2018; 57(43): 14527-14534.
- 3Xu CH, Nie JD, Wu WC, Fu LH, Lin BF. Design of self-healable supramolecular hybrid network based on carboxylated styrene butadiene rubber and nano-chitosan. Carbohydr Polym. 2018; 205: 410-419.
- 4Xu CH, Cui R, Fu LH, Lin BF. Recyclable and heat-healable epoxidized natural rubber/bentonite composites. Compos Sci Technol. 2018; 167: 421-430.
- 5Xu CH, Wu WC, Nie JD, Fu LH, Lin BF. Preparation of carboxylic styrene butadiene rubber/chitosan composites with dense supramolecular network via solution mixing process. Compos Part A-Appl S. 2019; 117: 116-124.
- 6Duin MV. Recent developments for EPDM-based thermoplastic vulcanisates. Macromol Symp. 2006; 233(1): 11-16.
10.1002/masy.200690006 Google Scholar
- 7Wu HG, Tian M, Zhang LQ, et al. New understanding of morphology evolution of thermoplastic vulcanizate (TPV) during dynamic vulcanization. ACS Sustain Chem Eng. 2015; 3(1): 26-32.
- 8Coran AY, Patel RP, Williams D. Rubber-thermoplastic compositions part V. Selecting polymers for thermoplastic vulcanizates. Rubber Chem Technol. 1982; 55(1): 116-136.
- 9Ma PM, Xu PW, Zhai YH, Dong WF, Zhang Y, Chen MQ. Biobased poly (lactide)/ethylene-co-vinyl acetate thermoplastic vulcanizates: morphology evolution, superior properties, and partial degradability. ACS Sustainable Chem Eng. 2015; 3(9): 2211-2219.
- 10Liu GC, He YS, Zeng JB, Li QT, Wang YZ. Fully biobased and supertough polylactide-based thermoplastic vulcanizates fabricated by peroxide-induced dynamic vulcanization and interfacial compatibilization. Biomacromolecules. 2014; 15(11): 4260-4271.
- 11Jiang XL, Zhang Y, Zhang YX. Crystallization behavior of dynamically cured polypropylene/epoxy blends. J Polym Sci Pol Phys. 2004; 42(7): 1181-1191.
- 12Simon DÁ, Halász IZ, Karger-Kocsis J, Bárány T. Microwave devulcanized crumb rubbers in polypropylene based thermoplastic dynamic vulcanizates. Polymers-Basel. 2018; 10(7): 767.
- 13Chen YK, Wang WT, Xu CH, Liang XQ, Cao LM. Fully bio-based poly (lactic acid)/poly (methyl methacrylate) grafted natural rubber/natural rubber ternary TPVs with “soft-hard” core-shell continuous rubber phase: balanced stiffness and toughness. ACS Sustainable Chem Eng. 2018; 6(5): 6488-6496.
- 14Liu YT, Cao LM, Yuan DS, Chen YK. Design of super-tough co-continuous PLA/NR/SiO2 TPVs with balanced stiffness-toughness based on reinforced rubber and interfacial compatibilization. Compos Sci Technol. 2018; 165: 231-239.
- 15Yuan DS, Ding JP, Mou WJ, Wang YP, Chen YK. Bio-based polylactide/epoxidized natural rubber thermoplastic vulcanizates with a co-continuous phase structure. Polym Test. 2017; 64: 200-206.
- 16Wang YH, Chen KL, Xu CH, Chen YK. Supertoughened biobased poly (lactic acid)-epoxidized natural rubber thermoplastic vulcanizates: fabrication, co-continuous phase structure, interfacial in situ compatibilization, and toughening mechanism. J Phys Chem B. 2015; 119(36): 12138-12146.
- 17Chen YK, Chen KL, Wang YH, Xu CH. Biobased heat-triggered shape-memory polymers based on polylactide/epoxidized natural rubber blend system fabricated via peroxide-induced dynamic vulcanization: co-continuous phase structure, shape memory behavior, and interfacial compatibilization. Ind Eng Chem Res. 2015; 54(35): 8723-8731.
- 18Wang YP, Zhang CH, Ren YR, Ding T, Yuan DS, Chen YK. Shape memory properties of dynamically vulcanized poly (lactic acid)/nitrile butadiene rubber (PLA/NBR) thermoplastic vulcanizates: the effect of ACN content in NBR. Polym Advan Technol. 2018; 29(8): 2336-2343.
- 19Abolhasani MM, Zarejousheghani F, Naebe M, Guo QP. Does dynamic vulcanization induce phase separation? Soft Matter. 2014; 10(30): 5550-5558.
- 20Wu HG, Tian M, Zhang LQ, Tian HC, Wu YP, Ning NY. New understanding of microstructure formation of the rubber phase in thermoplastic vulcanizates (TPV). Soft Matter. 2014; 10(11): 1816-1822.
- 21Xu CH, Wu WC, Zheng ZJ, Wang ZW, Nie JD. Design of shape-memory materials based on sea-island structured EPDM/PP TPVs via in-situ compatibilization of methacrylic acid and excess zinc oxide nanoparticles. Compos Sci Technol. 2018; 167: 431-439.
- 22Ma LF, Bao RY, Dou R, et al. Conductive thermoplastic vulcanizates (TPVs) based on polypropylene (PP)/ethylene-propylene-diene rubber (EPDM) blend: from strain sensor to highly stretchable conductor. Compos Sci Technol. 2016; 128: 176-184.
- 23Xu CH, Zheng ZJ, Wu WC, Wang ZW, Fu LH. Dynamically vulcanized PP/EPDM blends with balanced stiffness and toughness via in-situ compatibilization of MAA and excess ZnO nanoparticles: preparation, structure and properties. Compos Part B-Eng. 2019; 160: 147-157.
- 24Salaeh S, Cassagnau P, Boiteux G, Wießner S, Nakason C. Thermoplastic vulcanizates based on poly (vinylidene fluoride)/epoxidized natural rubber blends: effects of phenolic resin dosage and blend ratio. Mater Chem Phys. 2018; 219: 222-232.
- 25Ismail SMRS, Chatterjee T, Naskar K. Superior heat-resistant and oil-resistant blends based on dynamically vulcanized hydrogenated acrylonitrile butadiene rubber and polyamide 12. Polym Advan Technol. 2017; 28(6): 665-678.
- 26Padmanabhan R, Naskar K, Nando GB. Investigation into the structure-property relationship and technical properties of TPEs and TPVs derived from ethylene octene copolymer (EOC) and polydimethyl siloxane (PDMS) rubber blends. Mater Res Express. 2015; 2(10): 105301.
- 27Ning NY, Li SQ, Wu HG, et al. Preparation, microstructure, and microstructure-propertiesrelationship of thermoplastic vulcanizates (TPVs): a review. Prog Polym Sci. 2018; 79: 61-97.
- 28Martin G, Barres C, Sonntag P, Garois N, Cassagnau P. Morphology development in thermoplastic vulcanizates (TPV): dispersion mechanisms of a pre-crosslinked EPDM phase. Eur Polym J. 2009; 45(11): 3257-3268.
- 29Antunes CF, Machado AV, van Duin M. Morphology development and phase inversion during dynamic vulcanisation of EPDM/PP blends. Eur Polym J. 2011; 47(7): 1447-1459.
- 30Zhao YS, Liu ZW, Su B, et al. Property enhancement of PP-EPDM thermoplastic vulcanizates via shear-induced break-up of nano-rubber aggregates and molecular orientation of the matrix. Polymer. 2015; 63: 170-178.
- 31Banerjee SS, Bhowmick AK. Tailored nanostructured thermoplastic elastomers from polypropylene and fluoroelastomer: morphology and functional properties. Ind Eng Chem Res. 2015; 54(33): 8137-8146.
- 32Chen YK, Yuan DS, Xu CH. Dynamically vulcanized biobased polylactide/natural rubber blend material with continuous cross-linked rubber phase. ACS Appl Mater Interfaces. 2016; 6(6): 3811-3816.
- 33Yuan DS, Chen ZH, Xu CH, Chen KL, Chen YK. Fully biobased shape memory material based on novel cocontinuous structure in poly (lactic acid)/natural rubber TPVs fabricated via peroxide-induced dynamic vulcanization and in situ interfacial compatibilization. ACS Sustainable Chem Eng. 2015; 3(11): 2856-2865.
- 34Chen YK, Wang YH, Xu CH, Wang YP, Jiang CY. New approach to fabricate novel fluorosilicone thermoplastic vulcanizate with bicrosslinked silicone rubber-core/fluororubber-shell particles dispersed in poly (vinylidene fluoride): structure and property. Ind Eng Chem Res. 2016; 55(6): 1701-1709.
- 35Wang YH, Gong Z, Xu CH, Chen YK. 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”. Mater Chem Phys. 2017; 195: 123-131.
- 36Wang YP, Jiang XJ, Xu CH, Chen ZH, Chen YK. Effects of partial replacement of silicone rubber with fluororubber on properties of dynamically cured poly (vinylidene fluoride)/silicone rubber/fluororubber ternary blends. Polym Test. 2013; 32(8): 1392-1399.
- 37Xu CH, Gong Z, Chen YK, Liang XQ. Improved dispersion in a dynamically vulcanized ternary polymer blend by employing the core-shell concept. Mater Chem Phys. 2017; 199: 98-106.
- 38Nakagawa K, Ishida Y. Annealing effects in poly (vinylidene fluoride) as revealed by specific volume measurements, differential scanning calorimetry, and electron microscopy. J Polym Sci Polym Phys. 1973; 11(11): 2153-2171.
- 39Boyce MC, Yeh O, Socrate S, Kear K, Shaw K. Micromechanics of cyclic softening in thermoplastic vulcanizates. J Mech Phys Solids. 2001; 49(6): 1343-1360.
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