UV−Curable Optical Silicone−Modified Materials with Fairly High Tensile Strength, Pencil Hardness, and Good Thermal Stability From 2−Amantadine Functionalized Non−Isocyanate Polyurethane
Nana Sun
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorShuxin Wang
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorPeipei Wu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorHongyu Zhu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorJunyi Li
Sunliky New Material Technology Co., Ltd., Tongxiang, Zhejiang, China
Search for more papers by this authorMengle Liu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorGuoxian Feng
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorWenqing Li
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorCorresponding Author
Meijiang Li
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorCorresponding Author
Guoqiao Lai
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorCorresponding Author
Xiongfa Yang
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorNana Sun
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorShuxin Wang
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorPeipei Wu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorHongyu Zhu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorJunyi Li
Sunliky New Material Technology Co., Ltd., Tongxiang, Zhejiang, China
Search for more papers by this authorMengle Liu
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorGuoxian Feng
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorWenqing Li
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Search for more papers by this authorCorresponding Author
Meijiang Li
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorCorresponding Author
Guoqiao Lai
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorCorresponding Author
Xiongfa Yang
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Silicone Materials Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
Correspondence: Meijiang Li ([email protected]) | Guoqiao Lai ([email protected]) | Xiongfa Yang ([email protected])
Search for more papers by this authorFunding: Financial support from Sunliky New Material Technology Co., Ltd (L2023H01671) and “Pioneer” and “Leading Goose” R&D Program of Zhejiang (2023C01188).
ABSTRACT
Traditional polyurethanes (PUs) are mainly prepared from highly toxcic diisocyanates. They also encounter poor thermal stability with thermal decomposition temperatures not higher than 200°C. Additionally, the pencil hardness of the traditional UV−curable PUs is no more than 2H, which makes them encounter the high risk of being scratched during storage and transportation. To overcome these shortcomings, non−isocyanate polyurethanes (NIPU) are prepared by a safe, environmentally friendly, and greenhouse gas CO2 consuming method, then incorporated rigid 2−amantadine groups to develop UV−curable optical silicone−modified materials. The UV−curable silicone−modified materials exhibit transparency over 90% at 800 nm, pencil hardness of 8−9H, initiate thermal decomposition temperature (Td5) in the range of 223.5−240.5°C, adhesive properties as good as grade 0, tensile strength in the range of 3.66−15.36 MPa. The UV−resistance and solvent−resistance performance are also investigated. It reveals that the UV−curable materials show superior hardness and thermal stability than traditional PUs.
Conflicts of Interest
The authors declare no conflict of interest
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
| Filename | Description |
|---|---|
| macp70042-sup-0001-SuppMat.docx3.6 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1J. Q. Zhang, R. X. Zhai, J. W. Li, et al., “Benzimidazole Functionalized Waterborne Polyurethane with Excellent Mechanical Properties, UV and Corrosion Resistance,” Progress in Organic Coatings 199 (2025): 108945.
- 2S. Jin, H. Jeon, S.-M. Kim, et al., “Self-healable Spray Paint Coatings Based on Polyurethanes with Thermal Stability: Effects of Disulfides and Diisocyanates,” Progress in Organic Coatings 198 (2025): 108931.
- 3F. Cheng, Y. Fan, N. He, et al., “Castor Oil Based High Transparent UV Cured Silicone Modified Polyurethane Acrylate Coatings with Outstanding Tensile Strength and Good Chemical Resistance,” Progress in Organic Coatings 163 (2022): 106624.
- 4J. C. Boyer, L. W. Taylor, and L. A. Nylander-French, “Viability of Cultured human Skin Cells Treated with 1,6-hexamethylene Diisocyanate Monomer and Its Oligomer Isocyanurate in Different Culture media,” Scientifc Reports 11 (2021): 23804.
- 5S. V. Zubkevich, M. Makarov, R. Dieden, et al., “Unique Method for Facile Postsynthetic Modification of Nonisocyanate Polyurethanes,” Macromolecules 57, no. 5 (2024): 2385–2393.
- 6B. Zhu, X. Yang, L. Jiang, T. Chen, S. Wang, and L. Zeng, “A Portable and Versatile Fluorescent Platform for High-throughput Screening of Toxic Phosgene, Diethyl Chlorophosphate and Volatile Acyl Chlorides,” Chinese Chemical Letters 36 (2025): 110222.
- 7S. A. Zimov, E. A. G. Schuur, and F. S. Chapin, “Permafrost and the Global Carbon Budget,” Science 312 (2006): 1612–1613.
- 8B. Grignard, S. Gennen, C. Jérôme, A. W. Kleij, and C. Detrembleur, “Advances in the Use of CO2 as a Renewable Feedstock for the Synthesis of Polymers,” Chemical Society Reviews 48 (2019): 4466–4514.
- 9F. D. Bobbink, A. P. Van Muyden, and P. J. Dyson, “En Route to CO 2 -containing Renewable Materials: Catalytic Synthesis of Polycarbonates and Non-isocyanate Polyhydroxyurethanes Derived from Cyclic Carbonates,” Chemical Communications 55 (2019): 1360–1373.
- 10C. Carré, Y. Ecochard, S. Caillol, and L. Avérous, “From the Synthesis of Biobased Cyclic Carbonate to Polyhydroxyurethanes: a Promising Route towards Renewable Non-Isocyanate Polyurethanes,” ChemSusChem 12, no. 15 (2019): 3410–3430.
- 11T. Theerathanagorn, T. Kessaratikoon, H. U. Rehman, V. D'elia, and D. Crespy, “Polyhydroxyurethanes from Biobased Monomers and CO 2 : a Bridge between Sustainable Chemistry and CO 2 Utilization †,” Chinese Journal of Chemistry 42 (2024): 652–685.
- 12V. Aomchad, À. Cristòfol, F. Della Monica, B. Limburg, V. D'elia, and A. W. Kleij, “Recent Progress in the Catalytic Transformation of Carbon Dioxide into Biosourced Organic Carbonates,” Green Chemistry 23 (2021): 1077–1113.
- 13A. J. Kamphuis, F. Picchioni, and P. P. Pescarmona, “CO 2 -fixation into Cyclic and Polymeric Carbonates: Principles and Applications,” Green Chemistry 21 (2019): 406–448.
- 14L. Guo, K. J. Lamb, and M. North, “Recent Developments in Organocatalysed Transformations of Epoxides and Carbon Dioxide into Cyclic Carbonates,” Green Chemistry 23 (2021): 77–118.
- 15C. Claver, M. B. Yeamin, M. Reguero, and A. M. Masdeu-Bultó, “Recent Advances in the Use of Catalysts Based on Natural Products for the Conversion of CO2 into Cyclic Carbonates,” Green Chemistry 22 (2020): 7665–7706.
- 16M. Alves, B. Grignard, R. Mereau, C. Jerome, T. Tassaing, and C. Detrembleur, “Organocatalyzed Coupling of Carbon Dioxide with Epoxides for the Synthesis of Cyclic Carbonates: Catalyst Design and Mechanistic Studies,” Catalysis Science & Technology 7 (2017): 2651–2684.
- 17W. Yang, S. Qiu, J. Zhang, Z. Cheng, L. Song, and Y. Hu, “Innovative Design and Green Synthesis of Bio-based Non-isocyanate Polyurethanes: Efficient Combination of Cardanol and Carbon Dioxide with High Fire Safety and Robust Adhesion,” Chemical Engineering Journal 482 (2024): 148846.
- 18A. Centeno-Pedrazo, J. Perez-Arce, Z. Freixa, P. Ortiz, and E. J. Garcia-Suarez, “Non-isocyanate Polyurethanes Derived from Carbonated Soybean Oil: Synthesis, Characterization and Comparison with Traditional Vegetable Oil-based Polyurethanes,” Progress in Organic Coatings 197 (2024): 108830.
- 19Y. Zeng and J. Xia, “UV-cured Silicone Pressure-sensitive Adhesive with Adjustable Adhesion and Viscoelastic Properties via Thiol-ene Chemistry,” Progress in Organic Coatings 194 (2024): 108545.
- 20J.-K. Kim, N. Krishna-Subbaiah, Y. Wu, J. Ko, A. Shiva, and M. Sitti, “Enhanced Flexible Mold Lifetime for Roll-to-Roll Scaled-up Manufacturing of Adhesive Complex Microstructures,” Advanced Materials 35 (2023): 2207257.
- 21J. Liu, X. Jiao, F. Cheng, Y. Fan, Y. Wu, and X. Yang, “Fabrication and Performance of UV Cured Transparent Silicone Modified Polyurethane–acrylate Coatings with High Hardness, Good Thermal Stability and Adhesion,” Progress in Organic Coatings 144 (2020): 105673.
- 22J. Fu, L. Wang, H. Yu, et al., “Research Progress of UV-curable Polyurethane Acrylate-based Hardening Coatings,” Progress in Organic Coatings 131 (2019): 82–99.
- 23M. Decostanzi, Y. Ecochard, and S. Caillol, “Synthesis of Sol-gel Hybrid Polyhydroxyurethanes,” European Polymer Journal 109 (2018): 1–7.
- 24X. Feng, M. Li, S. Li, et al., “Fabrication and Properties of Recyclable Tung Oil–based Polymer Coatings Based on Dual Cross-linked Dynamic Covalent Polymer Networks,” Progress in Organic Coatings 192 (2024): 108521.
- 25E. Darroman, N. Durand, B. Boutevin, and S. Caillol, “Improved Cardanol Derived Epoxy Coatings,” Progress in Organic Coatings 91 (2016): 16.
- 26G. Y. Kim, S. J. Sung, M. P. Kim, et al., “Reversible Polymer Networks Based on the Dynamic Hindered Urea Bond for Scratch Healing in Automotive Clearcoats,” Applied Surface Science 505 (2020): 144546.
- 27Y. Yuan, M. Chen, Q. Zhou, and R. Liu, “Synthesis and Properties of UV-curable Cardanol-based Acrylate Oligomers with Cyclotriphosphazene Core,” Journal of Coatings Technology and Research 16 (2019): 179–188.
- 28L.-Y. Wang, F.-Z. Bu, Y.-M. Yu, et al., “A Novel Crystalline Molecular Salt of Sulfamethoxazole and Amantadine Hybridizing Antiviral-antibacterial Dual Drugs with Optimal in Vitro/Vivo Pharmaceutical Properties,” European Journal of Pharmaceutical Sciences 163 (2021): 105883.
- 29F. T. Zahra, A. Saeed, A. Ahmed, H. Ismail, M. U. Ijaz, and F. Albericio, “Synthesis of Amantadine Clubbed N–aryl Amino Thiazoles as Potent Urease, a–amylase & Aglucosidase Inhibitors, Kinetic and Molecular Docking Studies,” RSC Advances 13 (2023): 24988–25001.
- 30L.-Y. Wang, Y.-M. Yu, M.-C. Yu, Y.-T. Li, Z.-Y. Wu, and C.-W. Yan, “A Crystalline Solid Adduct of Sulfathiazole–amantadine: the First Dual-drug Molecular Salt Containing both Antiviral and Antibacterial Ingredients,” CrystEngComm 22 (2020): 3804–3813.
- 31Z. Wang, X. Zhang, L. Zhang, T. Tan, and H. Fong, “Nonisocyanate Biobased Poly(ester urethanes) with Tunable Properties Synthesized via an Environment-Friendly Route,” ACS Sustainable Chemistry & Engineering 4 (2016): 2762–2770.
- 32S. Park, K. Mondal, R. M. Treadway III, V. Kumar, S. Ma, J. D. Holbery, M. D. Dickey, "Silicones for Stretchable and Durable Soft Devices: Beyond Sylgard–184," ACS Applied Materials and Interfaces 10 (2018): 11261–11268.
- 33D. Wei, B. Liao, Q. Yong, et al., “Castor Oil Based Hyperbranched Urethane Acrylates and Their Performance as UV-curable Coatings,” Journal of Macromolecular Science A 55, no. 5 (2018): 422–432.
- 34J. Schweitzer, S. Merad, G. Schrodj, F. Bally-Le Gall, and L. Vonna, “Determination of the Crosslinking Density of a Silicone Elastomer,” Journal of Chemical Education 96 (2019): 1472–1478.
- 35X. T. Chen, W. L. Mao, W. Zhou, et al. ACS Applied Materials and Interfaces 16 (2024): 57512–57523.
