Skip to main content
SpringerLink
Log in

Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends

  • Research Article
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

Methyl vinyl silicone rubber (MVQ)/polypropylene (PP) thermoplastic vulcanizate (TPV) combines the good melt processability, recyclability and sealing performance as well as biosafety, stain and fluid resistance, and thus it is especially suitable in bio-safety areas and wearable electronic devices, etc. Nevertheless, the compatibility between MVQ and PP phases is poor. A big challenge on the compatibilization of MVQ/PP blends is that neither MVQ nor PP contains any reactive groups. In this study, a dual reactive compatibilizer composed of ethylenemethyl acrylate-glycidyl methacrylate terpolymer (EMA-co-GMA) and maleic anhydride grafted polypropylene (PP-g-MAH) was designed for the compatibilization of MVQ/PP blends. During melt blending, a copolymer compatibilizer at the MVQ/PP interface can be formed because of the in situ reaction between EMA-co-GMA and PP-g-MAH. The thermodynamic predict of its compatibilization effect through calculating the spreading coefficient of the in situ formed copolymer indicates that it can well compatibilize MVQ/PP blends. The experimental results show that under the GMA/MAH molar ratio of 0.5/1, the interface thickness largely increase from 102 nm for non-compatibilized blend to 406 nm, and the average size of MVQ dispersed phase largely decreases from 2.3 µm to 0.36 µm, the Tg of the two phases shifts toward each other, the mixing torque and mechanical properties of the blend are increased, all indicating its good compatibilization effect. This study provides a good compatibilizing method for immiscible MVQ/PP blends with no reactive groups in both components for the preparation of high performance MVQ/PP TPVs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ning, N.; Li, S.; Wu, H.; Tian, H.; Yao, P.; Hu, G. H.; Tian, M.; Zhang, L. Preparation, microstructure, and microstructure-properties relationship of thermoplastic vulcanizates (TPVs): a review. Prog. Polym. Sci. 2018, 79, 61–97.

    Article  CAS  Google Scholar 

  2. Wang, H. S.; Zhang, X. H.; Zhu, Y. L.; Song, Z. H.; Qiao, J. L. One-step process to make electrically conductive thermoplastic vulcanizates filled with MWCNTs. Chinese J. Polym. Sci. 2012, 30, 138–142.

    Article  CAS  Google Scholar 

  3. Fan, J.; Huang, J.; Cao, L.; Yin, S.; Chen, Y. Mechanically robust, reprocessable shape memory fluorosilicon materials using β-H elimination reaction and in situ interfacial compatibilization. Indust. Eng. Chem. Res. 2020, 59, 12745–12754.

    Article  CAS  Google Scholar 

  4. Wu, H.; Tian, M.; Zhang, L.; Tian, H.; Wu, Y.; Ning, N.; Chan, T. W. New understanding of morphology evolution of thermoplastic vulcanizate (TPV) during Dynamic Vulcanization. ACS Sustain. Chem. Eng. 2015, 3, 26–32.

    Article  Google Scholar 

  5. Shen, Y.; Tian, H.; Pan, W.; Feng, J.; Wang, D.; Ning, N.; Tian, M.; Zhang, L. Unexpected improvement of both mechanical strength and elasticity of EPDM/PP thermoplastic vulcanizates by introducing β-nucleating agents. Macromolecules 2021, 54, 2835–2843.

    Article  CAS  Google Scholar 

  6. Hu, X.; Kang, H.; Li, Y.; Geng, Y.; Wang, R.; Zhang, L. Preparation, morphology and superior performances of biobased thermoplastic elastomer by in situ dynamical vulcanization for 3D-printed materials. Polymer 2017, 108, 11–20.

    Article  CAS  Google Scholar 

  7. Yao, P.; Wu, H.; Ning, N.; Zhang, L.; Tian, H.; Wu, Y.; Hu, G. H.; Chan, T. W.; Tian, M. Microstructure and properties of bromo-isobutylene-isoprene rubber/polyamide 12 thermoplastic vulcanizate toward recyclable inner liners for green tires. RSC Adv. 2016, 6, 30004–30013.

    Article  CAS  Google Scholar 

  8. Matchawet, S.; Kaesaman, A.; Vennemann, N.; Kummerlöwe, C.; Nakason, C. Optimization of electrical conductivity, dielectric properties, and stress relaxation behavior of conductive thermoplastic vulcanizates based on ENR/COPA blends by adjusting mixing method and ionic liquid loading. Indust. Eng. Chem. Res. 2017, 56, 3629–3639.

    Article  CAS  Google Scholar 

  9. Garois, N.; Sonntag, P.; Hong, S.; Martin, G.; Galpin, D. 2011, U.S. Pat., 0281984A1.

  10. Li, S. Q.; Tian, H. C.; Hu, G. H.; Ning, N. Y.; Tian, M.; Zhang, L. Q. Effects of shear during injection molding on the anisotropic microstructure and properties of EPDM/PP TPV containing rubber nanoparticle agglomerates. Polymer 2021, 229, 124008.

    Article  CAS  Google Scholar 

  11. Fan, J.; Yan, M.; Huang, J.; Cao, L.; Chen, Y. Fabrication of smart shape memory fluorosilicon thermoplastic vulcanizates: the effect of interfacial compatibility and tiny crystals. Indust. Eng. Chem. Res. 2019, 58, 15199–15208.

    Article  CAS  Google Scholar 

  12. Gong, K.; Tian, H.; Liu, H.; Liu, X.; Hu, G. H.; Yu, B.; Ning, N.; Tian, M.; Zhang, L. Grafting of isobutylene-isoprene rubber with glycidyl methacrylate and its reactive compatibilization effect on isobutylene-isoprene rubber/polyamides 12 blends. Indust. Eng. Chem. Res. 2021, 60, 16258–16266.

    Article  CAS  Google Scholar 

  13. Dong, W.; Wang, H.; He, M.; Ren, F.; Wu, T.; Zheng, Q.; Li, Y. Synthesis of reactive comb polymers and their applications as a highly efficient compatibilizer in immiscible polymer blends. Indust. Eng. Chem. Res. 2015, 54, 2081–2089.

    Article  CAS  Google Scholar 

  14. Li, H.; Hu, G. H. The early stage of the morphology development of immiscible polymer blends during melt blending: compatibilized vs. uncompatibilized blends. J. Polym. Sci., Part B: Polym. Phys. 2001, 39, 601–610.

    Article  CAS  Google Scholar 

  15. Yu, C.; Shi, D.; Wang, J.; Shi, H.; Jiang, T.; Yang, Y.; Hu, G. H.; Li, R. K. Y. Effect of a dual compatibilizer on the formation of co-continuous morphology of immiscible polymer blends. Materials & Design 2016, 107, 171–177.

    Article  CAS  Google Scholar 

  16. Rong, C.; Chen, Y.; Chen, C.; Hu, L.; Wang, H.; Li, Y. Toward simultaneous compatibilization and nucleation of fully biodegradabe nanocomposites: effect of nanorod-assisted interfacial stereocomplex crystals in immiscible polymer blends. Compos. Part B: Eng. 2022, 234, 109708.

    Article  CAS  Google Scholar 

  17. Wang, H.; Chen, J.; Li, Y. Arrested elongated interface with small curvature by the simultaneous reactive compatibilization and stereocomplexation. Macromolecules 2020, 53, 10664–10674.

    Article  CAS  Google Scholar 

  18. Li, Q.; Lin, G.; Chen, S.; Zhang, L.; Song, Y.; Geng, C.; Qu, S.; Jing, Y.; Liu, F.; Liang, Z. Enhancing mechanical performance and wet-skid resistance of emulsion styrene butadiene rubber/natural rubber latex composites via in-situ hybridization of silanized graphene oxide and silica. J. Appl. Polym. Sci. 2022, 139, 52083.

    Article  CAS  Google Scholar 

  19. Liu, X.-x.; Wang, Y.-f.; Zhang, N.-z.; Shanks, R. A.; Liu, H. S.; Tong, Z.; Chen, L.; Yu, L. Morphology and phase composition of gelatin-starch blends. Chinese J. Polym. Sci. 2014, 32, 108–114.

    Article  CAS  Google Scholar 

  20. Wang, X.; Peng, S.; Chen, H.; Yu, X.; Zhao, X. Mechanical properties, rheological behaviors, and phase morphologies of high-toughness PLA/PBAT blends by in situ reactive compatibilization. Compos. Part B: Eng. 2019, 173, 107028.

    Article  CAS  Google Scholar 

  21. Ji, W. Y.; Feng, L. F.; Zhang, C. L.; Hoppe, S.; Hu, G. H.; Dumas, D. A concept of reactive compatibilizer-tracer for studying reactive polymer blending processes. Aiche J. 2016, 62, 359–366.

    Article  CAS  Google Scholar 

  22. Deng, S. H.; Bai, H. W.; Liu, Z. W.; Zhang, Q.; Fu, Q. Toward supertough and heat-resistant stereocomplex-type polylactide/elastomer blends with impressive melt stability via in situ formation of graft copolymer during one-pot reactive melt blending. Macromolecules 2019, 52, 1718–1730.

    Article  CAS  Google Scholar 

  23. Wei, B.; Lin, Q.; Zheng, X.; Gu, X.; Zhao, L.; Li, J.; Li, Y. Reactive splicing compatibilization of immiscible polymer blends: compatibilizer synthesis in the melt state and compatibilizer architecture effects. Polymer 2019, 185, 121952.

    Article  CAS  Google Scholar 

  24. Prakashan, K.; Gupta, A. K.; Maiti, S. N. Effect of compatibilizer on micromehanical deformations and morphology of dispersion in PP/PDMS blend. J. Appl. Polym. Sci. 2007, 105, 2858–2867.

    Article  CAS  Google Scholar 

  25. Wei, B.; Chen, D.; Wang, H.; You, J.; Wang, L.; Li, Y.; Zhang, M. In-situ grafting of carboxylic acid terminated poly(methyl methacrylate) onto ethylene-glycidyl methacrylate copolymers: one-pot strategy to compatibilize immiscible poly(vinylidene fluoride)/low density polyethylene blends. Polymer 2019, 160, 162–169.

    Article  CAS  Google Scholar 

  26. Rajan, K. P.; Al-Ghamdi, A.; Ramesh, P.; Nando, G. B. Blends of thermoplastic polyurethane (TPU) and polydimethyl siloxane rubber (PDMS), part-I: assessment of compatibility from torque rheometry and mechanical properties. J. Polym. Res. 2012, 19, 9872.

    Article  Google Scholar 

  27. Robert, C.; de Montigny, F.; Thomas, C. M. Tandem synthesis of alternating polyesters from renewable resources. Nat. Commun. 2011, 2, 586.

    Article  PubMed  Google Scholar 

  28. Wang, H.; Fu, Z.; Dong, W.; Li, Y.; Li, J. Formation of interfacial janus nanomicelles by reactive blending and their compatibilization effects on immiscible polymer blends. J. Phys. Chem. B 2016, 120, 9240–9252.

    Article  CAS  PubMed  Google Scholar 

  29. Wang, H.; Fu, Z.; Zhao, X.; Li, Y.; Li, J. Reactive nanoparticles compatibilized immiscible polymer blends: synthesis of reactive SiO2 with long poly(methyl methacrylate) chains and the in situ formation of janus SiO2 nanoparticles anchored exclusively at the interface. ACS Appl. Mater. Interfaces 2017, 9, 14358–14370.

    Article  CAS  PubMed  Google Scholar 

  30. Zolali, A. M.; Favis, B. D. Toughening of cocontinuous polylactide/polyethylene blends via an interfacially percolated intermediate phase. Macromolecules 2018, 51, 3572–3581.

    Article  CAS  Google Scholar 

  31. Yao, N.; Wang, H.; Zhang, L.; Yue, D.; Tian, M. One-pot solvothermal synthesis of silane-functionalized carbon nanodots as compatibilizers for the immiscible TPU/MVQ blends. Appl. Surf. Sci. 2020, 530, 147124.

    Article  CAS  Google Scholar 

  32. Mahmud, M. B.; Anstey, A.; Shaayegan, V.; Lee, P. C.; Park, C. B. Enhancing the mechanical performance of PA6 based composites by altering their crystallization and rheological behavior via in-situ generated PPS nanofibrils. Compos. Part B: Eng. 2020, 195, 108067.

    Article  CAS  Google Scholar 

  33. Jańczuk, B.; Wójcik, W.; Zdziennicka, A. Determination of the components of the surface tension of some liquids from interfacial liquid-liquid tension measurements. J. Colloid Interface Sci. 1993, 157, 384–393.

    Article  Google Scholar 

  34. Yu, F.; Huang, H. X. Simultaneously toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane blend via enhancing interfacial adhesion by hydrophobic silica nanoparticles. Polym. Test. 2015, 45, 107–113.

    Article  CAS  Google Scholar 

  35. Fu, Z.; Wang, H.; Zhao, X.; Li, X.; Gu, X.; Li, Y. Flame-retarding nanoparticles as the compatibilizers for immiscible polymer blends: simultaneously enhanced mechanical performance and flame retardancy. J. Mater. Chem. A 2019, 7, 4903–4912.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 51525301).

Author information

Authors and Affiliations

  1. Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing, 100029, China

    Han-Bin Wang, Bing Yu, Nan-Ying Ning, Ming Tian & Li-Qun Zhang

  2. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Bing Yu, Nan-Ying Ning, Ming Tian & Li-Qun Zhang

  3. Shandong Dawn Polymer Material Co., Ltd., Longkou, 265700, China

    Hong-Chi Tian & Shi-Jia Zhang

Authors
  1. Han-Bin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hong-Chi Tian
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shi-Jia Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bing Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Nan-Ying Ning
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ming Tian
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Li-Qun Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Nan-Ying Ning or Ming Tian.

Ethics declarations

The authors declare no interest conflict.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, HB., Tian, HC., Zhang, SJ. et al. Excellent Compatibilization Effect of a Dual Reactive Compatibilizer on the Immiscible MVQ/PP Blends. Chin J Polym Sci 41, 1133–1141 (2023). https://doi.org/10.1007/s10118-023-2945-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-023-2945-z

Keywords

Search

Navigation