Polyurethane Composite with Enhanced Mechanical and Damping Properties Filled with Surface-Grafted Hollow Poly(styrene-alt-maleic anhydride) Microsphere
Abstract
1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Surface-Grafting of Hollow PSMA Microsphere
2.3. Preparation of PU Composite Filled with Hollow PSMA Microsphere
2.4. Characterization
3. Results and Discussion
3.1. Characterization of Pristine and Surface-Grafted PSMA
3.1.1. FTIR Spectroscopy Analysis of PSMA
3.1.2. XPS Analysis
3.2. Characterization of Neat PU and PU Composites
3.2.1. FTIR Spectroscopy Analysis of Neat PU and It Composites
3.2.2. TGA and DTG Analysis
3.2.3. Mechanical Properties
3.2.4. Water Uptake Property
3.2.5. Dynamic Mechanical Analysis
3.2.6. XRD Analysis
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Gang, H.; Lee, D.; Choi, K.Y.; Kim, H.N.; Ryu, H.; Lee, D.S.; Kim, B.G. Development of high performance polyurethane elastomers using vanillin-based green polyol chain extender originated from lignocellulosic biomass. ACS Sustain. Chem. Eng. 2017, 5, 4582–4588. [Google Scholar] [CrossRef]
- Fang, Z.; Huang, L.J.; Fu, J.J. Research status of graphene polyurethane composite coating. Coatings 2022, 12, 264. [Google Scholar] [CrossRef]
- Shalygina, T.A.; Voronina, S.Y.; Vlasov, A.Y.; Pasechnik, K.A.; Obvertkin, I.V.; Titov, M.A. The triple-shape memory effect of polyurethane composite material. Tech. Phys. Lett. 2020, 46, 1036–1040. [Google Scholar] [CrossRef]
- Zhang, H.; Zhang, J.; Yun, R.P.; Jiang, Z.G.; Liu, H.M.; Yan, D.P. Nanohybrids of organo-modified layered double hydroxides and polyurethanes with enhanced mechanical, damping and UV absorption properties. RSC. Adv. 2016, 6, 34288–34296. [Google Scholar] [CrossRef]
- Chen, W.Y.; Zhang, D.W.; Wang, H.Y.; Liu, Y.H.; Jin, L.; Gao, H.; Qiao, H.B.; Tian, X.M. A comparative evaluation of mechanically reinforced and heat-resistant organic powder/polyurethane elastomer hybrid composites. Iran. Polym. J. 2024, 33, 105–117. [Google Scholar] [CrossRef]
- Zhao, X.Y.; Jin, R.H.; Niu, Z.H.; Gao, Y.Y.; Hu, S.K. Fabrication of polyurethane elastomer/hindered phenol composites with tunable damping property. Int. J. Mol. Sci. 2023, 24, 4662. [Google Scholar] [CrossRef]
- Zheng, W.J.; Cai, Q.S.; Xiong, L.X.; Zheng, Y.Y. Highly efficient GO-based synergistic intumescent flame retardant/thermoplastic polyurethane for spatial composite film: Insight into flame retardancy and mechanism. J. Therm. Anal. Calorim. 2024, 149, 7289–7300. [Google Scholar] [CrossRef]
- Luo, Z.X.; Zhang, L.Q.; Liang, Y.R.; Wen, S.P.; Liu, L. Improved the dielectric properties of thermoplastic polyurethane elastomer filled with MXene nanosheets and BaTiO3 nanofibers. Polym. Test. 2022, 111, 107592. [Google Scholar] [CrossRef]
- Kaur, R.; Verma, S.K.; Mehta, R. Tailoring the properties of polyurethane pomposites: A comprehensive review. Polym. Plast. Technol. Mater. 2025, 64, 2005–2018. [Google Scholar]
- Wang, H.Z.; Jiao, C.M.; Zhao, L.; Chen, X.L. Preparation and characterization of TiO2-coated hollow glass microsphere and its flame-retardant property in thermoplastic polyurethane. J. Therm. Anal. Calorim. 2018, 131, 2729–2740. [Google Scholar] [CrossRef]
- Dogru, M.H.; Guzelbey, I.H. Investigation of the impact effects of thermoplastic polyurethane reinforced with multi-walled carbon nanotube for soldier boot under the blast load. J. Thermoplast. Compos. 2018, 31, 1078–1089. [Google Scholar] [CrossRef]
- Khatoon, H.; Ahmad, S. A review on conducting polymer reinforced polyurethane composites. J. Ind. Eng. Chem. 2017, 53, 1–22. [Google Scholar] [CrossRef]
- Lei, W.; Fang, C.Q.; Zhou, X.; Li, Y.G.; Pu, M.Y. Polyurethane elastomer composites reinforced with waste natural cellulosic fibers from office paper in thermal properties. Carbohyd. Polym. 2018, 197, 385–394. [Google Scholar] [CrossRef]
- Kong, X.H.; Zhao, L.Y.; Curtis, J.M. Polyurethane nanocomposites incorporating biobased polyols and reinforced with a low fraction of cellulose nanocrystals. Carbohyd. Polym. 2016, 152, 487–495. [Google Scholar] [CrossRef]
- Fan, X.; Zhang, L.; Dong, F.H.; Liu, H.; Xu, X. Room-temperature self-healing polyurethane-cellulose nanocrystal composites with strong strength and toughness based on dynamic bonds. Carbohyd. Polym. 2023, 308, 120654. [Google Scholar] [CrossRef]
- Dong, W.W.; Qian, D.B.; Xi, Y.; Peng, J.L.; Hong, W.H.; Luo, Y.L.; Bai, Y.F.; Zhu, S.G. Preparation and properties of waterborne polyurethane coatings containing polyurethane-coated hollow glass microspheres. Prog. Org. Coat. 2025, 208, 109490. [Google Scholar] [CrossRef]
- Gonte, R.; Balasubramanian, K. Heavy and toxic metal uptake by mesoporous hypercrosslinked SMA beads: Isotherms and kinetics. J. Saudi Chem. Soc. 2016, 20, S579–S590. [Google Scholar] [CrossRef]
- Li, Y.P.; Nie, W.Y.; Chen, P.P.; Zhou, Y.F. Preparation and characterization of sulfonated poly(styrene-alt-maleic anhydride) and its selective removal of cationic dyes. Colloids Surf. A 2016, 499, 46–53. [Google Scholar] [CrossRef]
- Zhu, Z.M.; Sun, F.Q.; Yang, L.T.; Gu, K.Y.; Li, W.S. Poly(styrene-co-maleic anhydride) microspheres prepared in ethanol/water using a photochemical method and their application in Ni2+ adsorption. Chem. Eng. J. 2013, 223, 395–401. [Google Scholar] [CrossRef]
- Guo, X.Y.; Ma, Y.H.; Chen, D.; Peng, W.; Yang, W.T. Preparation of Styrene-Maleic Anhydride Random Copolymer by Stabilizer-Free Dispersion Polymerization. J. Macromol. Sci. A 2012, 49, 1061–1069. [Google Scholar] [CrossRef]
- Yilmaz, E.; Erenler, F.M.; Boztug, A. Synthesis and modification of amine-terminated maleic anhydride-butyl acrylate copolymer and investigation of adsorption properties for cadmium (II) ions (Cd2+). J. Mol. Struct. 2020, 1222, 128924. [Google Scholar] [CrossRef]
- Liang, X.; Su, Y.B.; Yang, Y.; Qin, W.W. Separation and recovery of lead from a low concentration solution of lead(II) and zinc(II) using the hydrolysis production of poly styrene-co-maleic anhydride. J. Hazard. Mater. 2012, 203, 183–187. [Google Scholar] [CrossRef] [PubMed]
- Qiu, G.M.; Zhu, B.K.; Xu, Y.Y. α-Amylase immobilized by Fe3O4/poly(styrene-co-maleic anhydride) magnetic composite microspheres: Preparation and characterization. J. Appl. Polym. Sci. 2005, 95, 328–335. [Google Scholar] [CrossRef]
- Dellacasa, E.; Forouharshad, M.; Rolandi, R.; Pastorino, L.; Monticelli, O. Poly(styrene-co-maleic anhydride) nanoparticles as protein carriers. Mater. Lett. 2018, 220, 241–244. [Google Scholar] [CrossRef]
- Daruwalla, J.; Nikfarjam, N.; Greish, K.; Malcontenti-Wilson, C.; Muralidharan, V.; Christopphi, C.; Maeda, H. In vitro and in vivo evaluation of tumor targeting styrene-maleic acid copolymer-pirarubicin micelles: Survival improvement and inhibition of liver metastases. Cancer Sci. 2010, 101, 1866–1874. [Google Scholar] [CrossRef]
- Larson, N.; Greish, K.; Bauer, H.; Maeda, H.; Ghandehari, H. Synthesis and evaluation of poly(styrene-co-maleic acid) micellar nanocarriers for the delivery of tanespimycin. Int. J. Pharm. 2011, 420, 111–117. [Google Scholar] [CrossRef]
- Deb, P.C.; Rajput, L.D.; Singh, P.K. Polyaniline encapsulated microporous polymer beads and their vapor and gas adsorption behavior. J. Appl. Polym. Sci. 2007, 104, 297–303. [Google Scholar] [CrossRef]
- GB/T 528-2009; Rubber, Vulcanized or Thermoplastic—Determination of Tensile Stress-Strain Properties. Standards Press of China: Beijing, China, 2009.
- Liang, P.Z.; Meng, Z.; Jiang, Z.L.; Nie, J.; He, Y. Investigation of stabilizer-free dispersion polymerization process of styrene and maleic anhydride copolymer microspheres. J. Polym. Sci. Pol. Chem. 2010, 48, 5652–5658. [Google Scholar] [CrossRef]
- Gonte, R.; Balasubramanian, K.; Deb, P.; Singh, P. Synthesis and Characterization of Mesoporous Hypercrosslinked Poly(Styrene Co-Maleic Anhydride) Microspheres. Int. J. Polym. Mater. 2012, 61, 919–930. [Google Scholar] [CrossRef]
- He, Q.L.; Yuan, T.T.; Zhang, X.; Luo, Z.P.; Haldolaarachchige, N.; Sun, L.Y.; Young, D.P.; Wei, S.Y.; Guo, Z.H. Magnetically Soft and Hard Polypropylene/Cobalt Nanocomposites: Role of Maleic Anhydride Grafted Polypropylene. Macromolecules 2013, 46, 2357–2368. [Google Scholar] [CrossRef]
- Le, C.M.Q.; Cao, X.T.; Tu, T.T.K.; Lee, W.K.; Lim, K.T. Facile covalent functionalization of carbon nanotubes via Diels-Alder reaction in deep eutectic solvents. Appl. Surf. Sci. 2018, 450, 122–129. [Google Scholar] [CrossRef]
- Teare, D.O.H.; Schofield, W.C.E.; Roucoules, V.; Badyal, J.P.S. Substrate-independent growth of micropatterned polymer brushes. Langmuir 2003, 19, 2398–2403. [Google Scholar] [CrossRef]
- Briggs, D.; Beamson, G. Primary and secondary oxygen-induced C1S binding-energy shifts in X-Ray photoelectron-spectroscopy of polymers. Anal. Chem. 1992, 64, 1729–1736. [Google Scholar] [CrossRef]
- Calvo-Correas, T.; Gabilondo, N.; Alonso-Varona, A.; Palomares, T.; Corcuera, M.A.; Eceiza, A. Shape-memory properties of crosslinked biobased polyurethanes. Eur. Polym. J. 2016, 78, 253–263. [Google Scholar] [CrossRef]
- Mahmood, K.; Zia, M.K.; Aftab, W.; Zuber, M.; Tabasum, S.; Norseen, A.; Zia, F. Synthesis and characterization of chitin/curcumin blended polyurethane elastomers. Int. J. Biol. Macromol. 2018, 113, 150–158. [Google Scholar] [CrossRef]
- Carriço, C.S.; Fraga, T.; Pasa, V. Production and characterization of polyurethane foams from a simple mixture of castor oil, crude glycerol and untreated lignin as bio-based polyols. Eur. Polym. J. 2016, 85, 53–61. [Google Scholar] [CrossRef]
- Wang, C.W.; Zheng, Y.D.; Xie, Y.J.; Qiao, K.; Sun, Y.; Yue, L.N. Synthesis of bio-castor oil polyurethane flexible foams and the influence of biotic component on their performance. J. Polym. Res. 2015, 22, 1–9. [Google Scholar] [CrossRef]
- Alotaibi, K.M.; Shukla, A.K.; Alshahrani, A.A.; Alzhrani, E.M.; Alotaibi, S.S.; Alswieleh, A. Layer-by-Layer Assembled Nanocomposite Membranes with Functionalized Dendritic Mesoporous Silica Nanoparticles for Selective Heavy Metal Removal. ACS Omega 2025, 10, 28112–28127. [Google Scholar] [CrossRef]
- Wu, D.D.; Tan, Y.; Cao, Z.W.; Han, L.J.; Zhang, H.L.; Dong, L.S. Preparation and characterization of maltodextrin-based polyurethane. Carbohyd. Polym. 2018, 194, 236–244. [Google Scholar] [CrossRef]
- Burkeyeva, G.; Kovaleva, A.; Muslimova, D.; Havlicek, D.; Bolatbay, A.; Minayeva, Y.; Omasheve, A.; Zhakupbekova, E.; Nurmaganbetova, M. Influence of Mineral Fillers on the Curing Process and Thermal Degradation of Polyethylene Glycol Maleate-Acrylic Acid-Based Systems. Polymers 2025, 17, 2675. [Google Scholar] [CrossRef] [PubMed]
- Świtała-Żeliazkow, M. Thermal degradation of copolymers of styrene with dicarboxylic acidsI. Alternating styrene-maleic acid copolymer. Polym. Degrad. Stab. 2001, 74, 579–584. [Google Scholar] [CrossRef]
- Krul’, L.P.; Yakimtsova, L.B.; Egorova, E.L.; Matusevich, Y.I.; Polikarpov, A.P. Heat resistance and thermooxidative stability of copolymers of methyl methacrylate with methacrylic acid and methacrylamide. Russ. J. Appl. Chem. 2011, 84, 859–866. [Google Scholar] [CrossRef]
- Wang, Y.X.; Song, J.Y.; Tian, Q.T.; Song, N.N.; Liang, S.; Tian, C.R.; Qiang, X.L.; Lei, Y.J.; Chen, K.P.; Almásy, L. Understanding water absorption effect on molecular dynamics, microstructures and relaxation behavior of segmented polyurethane elastomers. Polym. Degrad. Stab. 2023, 138, 49970. [Google Scholar] [CrossRef]
- Jin, S.; Hu, J.; Wang, Y.X.; Hong, L. A room-temperature high-damping and high-strength polyurethane elastomer with pendant chains. Colloid Polym. Sci. 2025, 303, 2559–2572. [Google Scholar] [CrossRef]
- Zhang, Z.J.; Jiang, H.; Li, R.; Gao, S.; Wang, Q.; Wang, G.J.; Ouyang, X.; Wei, H. High-damping polyurethane/hollow glass microspheres sound insulation materials: Preparation and characterization. J. Appl. Polym. Sci. 2020, 100, 312–3322. [Google Scholar] [CrossRef]
- Poussard, L.; Burel, F.; Couvercelle, J.P.; Loutelier-Bourhis, C.; Bunel, C. Synthesis of new anionic HTPB-based polyurethane elastomers: Aqueous dispersion and physical properties. J. Appl. Polym. Sci. 2006, 100, 312–3322. [Google Scholar] [CrossRef]
- Senevirathna, S.R.; Amarasinghe, S.; Karunaratne, V.; Koneswaran, M.; Karunanayake, L. The effect of change of ionomer/polyol molar ratio on dispersion stability and crystalline structure of films produced from hydrophilic polyurethanes. J. Appl. Polym. Sci. 2017, 134, 44475. [Google Scholar] [CrossRef]
- Li, C.; Liu, J.W.; Li, J.J.; Chen, F.; Huang, Q.S.; Xu, H.X. Studies of 4,4′-diphenylmethane diisocyanate (MDI)/1,4-butanediol (BDO) based TPUs by in situ and moving-window two-dimensional correlation infrared spectroscopy: Understanding of multiple DSC endotherms from intermolecular interactions and motions level. Polymer 2012, 53, 5423–5435. [Google Scholar] [CrossRef]










| Sample | T5% (°C) | T50% (°C) | Residue at 700 °C (%) | Tdmax-1 (°C) | Tdmax-2 (°C) | Tdmax-3 (°C) |
|---|---|---|---|---|---|---|
| Neat PU | 295.6 | 393.4 | 4.1 | 311.4 | 386.4 | 427.2 |
| PUP | 298.6 | 390.7 | 3.3 | 318.7 | 378.6 | 426.6 |
| PUPB | 291.6 | 383.9 | 2.3 | 312.3 | 371.3 | 422.8 |
| PUPP | 297.4 | 381.1 | 2.6 | 320.7 | 368.9 | 420.3 |
| Sample | Temperature Range (°C) (tanδ > 0.3) | tanδmax | Tg,SS (°C) |
|---|---|---|---|
| Neat PU | 23.7 to 61.5 (37.8) | 0.89 | 41.9 |
| PUP | 24.0 to 68.2 (44.2) | 1.01 | 38.9 |
| PUPB | 26.9 to 66.0 (39.1) | 0.95 | 41.1 |
| PUPP | 25.3 to 65.7 (40.4) | 1.05 | 43.1 |
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |
© 2025 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license.
Share and Cite
Xu, R.; Zhang, J.; Tian, J.; Jiang, Z. Polyurethane Composite with Enhanced Mechanical and Damping Properties Filled with Surface-Grafted Hollow Poly(styrene-alt-maleic anhydride) Microsphere. Polymers 2026, 18, 59. https://doi.org/10.3390/polym18010059
Xu R, Zhang J, Tian J, Jiang Z. Polyurethane Composite with Enhanced Mechanical and Damping Properties Filled with Surface-Grafted Hollow Poly(styrene-alt-maleic anhydride) Microsphere. Polymers. 2026; 18(1):59. https://doi.org/10.3390/polym18010059
Chicago/Turabian StyleXu, Rong, Jun Zhang, Jiafeng Tian, and Zhiguo Jiang. 2026. "Polyurethane Composite with Enhanced Mechanical and Damping Properties Filled with Surface-Grafted Hollow Poly(styrene-alt-maleic anhydride) Microsphere" Polymers 18, no. 1: 59. https://doi.org/10.3390/polym18010059
APA StyleXu, R., Zhang, J., Tian, J., & Jiang, Z. (2026). Polyurethane Composite with Enhanced Mechanical and Damping Properties Filled with Surface-Grafted Hollow Poly(styrene-alt-maleic anhydride) Microsphere. Polymers, 18(1), 59. https://doi.org/10.3390/polym18010059

