{"title":"刚性光敏聚酰亚胺显著提高了紫外线固化环氧丙烯酸树脂的综合性能","authors":"Qiyun Lin, Wenhao Zhang, Lingcheng Chen, Yifan Li, Zhipeng Ning, Xinfu Zhang, Yi Xiao","doi":"10.1021/acsapm.4c01133","DOIUrl":null,"url":null,"abstract":"Epoxy acrylate (EA) resins have excellent light-curing properties and play a crucial role in UV-curable resins, but poor mechanical properties, lower thermal stability, and stronger hydrophilicity hinder their applications in high technic areas such as circuit board printing and electronic packaging. In this study, to enhance UV-curing EA resins, a photosensitive polyimide (PSPI) with a highly rigid and twisted skeleton was developed as a macromolecular cross-linker. This PSPI is featured with a unique diamine monomer that possesses a spirocyclic fluorene-xanthene core double-grafted with methacryloylamino groups. Commercial EA resins (EB600) were blended with varying levels of PSPI to modify the density and structure of the cross-linked network of the EB resins. The methylacrylamide groups branching on xanthene rings in the PSPI participate in radical UV-curing by crossing over with the main-chain helixes, resulting in three-dimensional cross-cured networks and unique structural rigidity of the resins. EB resins with different PSPI contents demonstrate apparently improved overall properties, compared with the nonmodified EB600. Among these cured resins, the overall performance of EB<sub>10</sub>PSPI<sub>1</sub> (weight ratio of EB/PSPI 10/1) was superior. The initial thermal decomposition temperature (<i>T</i><sub>d5%</sub>) of EB<sub>10</sub>PSPI<sub>1</sub> resin is 353 °C, 78 °C higher than that of EB<sub>1</sub>PSPI<sub>0</sub> (without PSPI), and the residual carbon rate is increased by 12.36% at 600 °C. The <i>T</i><sub>g</sub> of EB<sub>10</sub>PSPI<sub>1</sub> resin was 122 °C, while that of EB<sub>1</sub>PSPI<sub>0</sub> resin is only 87 °C. The tensile strength and modulus of elasticity of EB<sub>10</sub>PSPI<sub>1</sub> resin increased by 162 and 246%, respectively, and the hardness increased by 291 MPa compared with EB<sub>1</sub>PSPI<sub>0</sub> resin. In addition, the surface of EB<sub>10</sub>PSPI<sub>1</sub> resin exhibited good hydrophobicity with significantly lower water absorption and swelling rate than that of EB<sub>1</sub>PSPI<sub>0</sub>. Also, EB<sub>10</sub>PSPI<sub>1</sub> exhibits good adhesion capability. Finally, the curing performance of the EB<sub>10</sub>PSPI<sub>1</sub> resin is better, almost doubling the curing speed at weak UV-light irradiation intensities, demonstrating the excellent sensitivity of the PSPI in radical polymerization reactions and the enhancement of the UV-curing network of the EB resin. This study opens a way to comprehensively enhance the thermodynamic and mechanical properties of EB<sub>1</sub>PSPI<sub>0</sub> resins, which is promising in circuit board printing and electronic packaging.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":4.4000,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Rigid Photosensitive Polyimide Significantly Improves the Comprehensive Performance of UV-Curing Epoxy Acrylic Resins\",\"authors\":\"Qiyun Lin, Wenhao Zhang, Lingcheng Chen, Yifan Li, Zhipeng Ning, Xinfu Zhang, Yi Xiao\",\"doi\":\"10.1021/acsapm.4c01133\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Epoxy acrylate (EA) resins have excellent light-curing properties and play a crucial role in UV-curable resins, but poor mechanical properties, lower thermal stability, and stronger hydrophilicity hinder their applications in high technic areas such as circuit board printing and electronic packaging. In this study, to enhance UV-curing EA resins, a photosensitive polyimide (PSPI) with a highly rigid and twisted skeleton was developed as a macromolecular cross-linker. This PSPI is featured with a unique diamine monomer that possesses a spirocyclic fluorene-xanthene core double-grafted with methacryloylamino groups. Commercial EA resins (EB600) were blended with varying levels of PSPI to modify the density and structure of the cross-linked network of the EB resins. The methylacrylamide groups branching on xanthene rings in the PSPI participate in radical UV-curing by crossing over with the main-chain helixes, resulting in three-dimensional cross-cured networks and unique structural rigidity of the resins. EB resins with different PSPI contents demonstrate apparently improved overall properties, compared with the nonmodified EB600. Among these cured resins, the overall performance of EB<sub>10</sub>PSPI<sub>1</sub> (weight ratio of EB/PSPI 10/1) was superior. The initial thermal decomposition temperature (<i>T</i><sub>d5%</sub>) of EB<sub>10</sub>PSPI<sub>1</sub> resin is 353 °C, 78 °C higher than that of EB<sub>1</sub>PSPI<sub>0</sub> (without PSPI), and the residual carbon rate is increased by 12.36% at 600 °C. The <i>T</i><sub>g</sub> of EB<sub>10</sub>PSPI<sub>1</sub> resin was 122 °C, while that of EB<sub>1</sub>PSPI<sub>0</sub> resin is only 87 °C. The tensile strength and modulus of elasticity of EB<sub>10</sub>PSPI<sub>1</sub> resin increased by 162 and 246%, respectively, and the hardness increased by 291 MPa compared with EB<sub>1</sub>PSPI<sub>0</sub> resin. In addition, the surface of EB<sub>10</sub>PSPI<sub>1</sub> resin exhibited good hydrophobicity with significantly lower water absorption and swelling rate than that of EB<sub>1</sub>PSPI<sub>0</sub>. Also, EB<sub>10</sub>PSPI<sub>1</sub> exhibits good adhesion capability. Finally, the curing performance of the EB<sub>10</sub>PSPI<sub>1</sub> resin is better, almost doubling the curing speed at weak UV-light irradiation intensities, demonstrating the excellent sensitivity of the PSPI in radical polymerization reactions and the enhancement of the UV-curing network of the EB resin. This study opens a way to comprehensively enhance the thermodynamic and mechanical properties of EB<sub>1</sub>PSPI<sub>0</sub> resins, which is promising in circuit board printing and electronic packaging.\",\"PeriodicalId\":7,\"journal\":{\"name\":\"ACS Applied Polymer Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2024-07-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Polymer Materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acsapm.4c01133\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Polymer Materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acsapm.4c01133","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Rigid Photosensitive Polyimide Significantly Improves the Comprehensive Performance of UV-Curing Epoxy Acrylic Resins
Epoxy acrylate (EA) resins have excellent light-curing properties and play a crucial role in UV-curable resins, but poor mechanical properties, lower thermal stability, and stronger hydrophilicity hinder their applications in high technic areas such as circuit board printing and electronic packaging. In this study, to enhance UV-curing EA resins, a photosensitive polyimide (PSPI) with a highly rigid and twisted skeleton was developed as a macromolecular cross-linker. This PSPI is featured with a unique diamine monomer that possesses a spirocyclic fluorene-xanthene core double-grafted with methacryloylamino groups. Commercial EA resins (EB600) were blended with varying levels of PSPI to modify the density and structure of the cross-linked network of the EB resins. The methylacrylamide groups branching on xanthene rings in the PSPI participate in radical UV-curing by crossing over with the main-chain helixes, resulting in three-dimensional cross-cured networks and unique structural rigidity of the resins. EB resins with different PSPI contents demonstrate apparently improved overall properties, compared with the nonmodified EB600. Among these cured resins, the overall performance of EB10PSPI1 (weight ratio of EB/PSPI 10/1) was superior. The initial thermal decomposition temperature (Td5%) of EB10PSPI1 resin is 353 °C, 78 °C higher than that of EB1PSPI0 (without PSPI), and the residual carbon rate is increased by 12.36% at 600 °C. The Tg of EB10PSPI1 resin was 122 °C, while that of EB1PSPI0 resin is only 87 °C. The tensile strength and modulus of elasticity of EB10PSPI1 resin increased by 162 and 246%, respectively, and the hardness increased by 291 MPa compared with EB1PSPI0 resin. In addition, the surface of EB10PSPI1 resin exhibited good hydrophobicity with significantly lower water absorption and swelling rate than that of EB1PSPI0. Also, EB10PSPI1 exhibits good adhesion capability. Finally, the curing performance of the EB10PSPI1 resin is better, almost doubling the curing speed at weak UV-light irradiation intensities, demonstrating the excellent sensitivity of the PSPI in radical polymerization reactions and the enhancement of the UV-curing network of the EB resin. This study opens a way to comprehensively enhance the thermodynamic and mechanical properties of EB1PSPI0 resins, which is promising in circuit board printing and electronic packaging.
期刊介绍:
ACS Applied Polymer Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics, and biology relevant to applications of polymers.
The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrates fundamental knowledge in the areas of materials, engineering, physics, bioscience, polymer science and chemistry into important polymer applications. The journal is specifically interested in work that addresses relationships among structure, processing, morphology, chemistry, properties, and function as well as work that provide insights into mechanisms critical to the performance of the polymer for applications.