聚合诱导相分离制备多孔环氧树脂固化物膜

Preparation of Cured Porous Epoxy Resin Films via Polymerization Induced Phase Separation

摘要

将高反应性脂肪族胺类 593 型固化剂、易挥发溶剂丙二醇甲醚与环氧树脂单体双酚 A-二缩水甘油醚组合成新型体系（Ink），该体系可在室温下快速固化、相分离并去除溶剂。基于聚合诱导相分离技术，25 ℃下的 Ink 经预固化、薄膜固化及最终的高温固化，制得盲孔型环氧树脂固化物膜。使用衰减全反射傅里叶变换红外光谱、相差显微镜及光学显微镜等技术探究固化反应、相分离过程及形貌演变。研究表明：当薄膜固化时间为 120 min 时，Ink 预固化 60、120 min所得盲孔平均孔径分别为 0.50、0.87 μm，延长预固化时间可增大孔径与孔深。此外，以去离子水为反溶剂促进相分离，得到通孔型环氧树脂固化物膜，该流程显著简化了多孔环氧树脂膜的制备。

Abstract

A high-reactivity aliphatic amine curing agent (type 593), a volatile solvent (propylene glycol methyl ether), and an epoxy monomer (bisphenol A diglycidyl ether) were combined into a novel system (denoted as Ink), which enables rapid curing, phase separation, and solvent removal at room temperature. Using the polymerization induced phase separation technique, blind-pore type epoxy cured films were fabricated through precuring and film curing at 25 ℃, followed by a final high-temperature curing step. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), phase contrast microscopy, and optical microscopy were employed to investigate the curing reaction, phase separation process, and morphological evolution. When the film curing time was fixed at 120 min, the average pore diameters of the blind-pore type epoxy films obtained with precuring time of 60 min and 120 min were 0.50 μm and 0.87 μm, respectively, indicating that extending the precuring time increased both pore diameter and depth. Moreover, a through-pore type epoxy cured film was obtained by using deionized water as an antisolvent to promote phase separation. This process significantly simplifies the preparation of porous epoxy cured films.

关键词

多孔环氧树脂固化物 / 聚合诱导相分离 / 脂肪族胺类固化剂 / 相分离动力学 / 固化反应动力学

Key words

cured porous epoxy resin / polymerization induced phase separation / aliphatic amine curing agent / phase separation kinetics / curing reaction kinetics

参考文献

[1] ZHANG W J, WANG H J, TANG Z Y, LAN J L, YU Y H, ZHU Y D, YANG X P . Mechanically robust epoxy resin—based gel polymer electrolyte stabilizing ion deposition for high—performance lithium metal batteries [J]. Materials Chemistry and Physics， 2022， 287： 126324.

[2] SUN Z, WU J, YUAN H, LAN J, YU Y, ZHU Y, YANG X . Self—healing polymer electrolyte for long—life and recyclable lithium—metal batteries [J]. Materials Today Energy， 2022， 24： 100939.

[3] WANG S, ZHAO C, MA W, ZHANG G, LIU Z, NI J, LI M, ZHANG N, NA H . Preparation and properties of epoxy—cross—linked porous polybenzimidazole for high temperature proton exchange membrane fuel cells [J]. Journal of Membrane Science， 2012， 411： 54-63.

[4] MA S, ZHANG L, WANG S, ZHANG H, YOU X, OU J, YE M, WEI Y . Preparation of epoxy—functionalized hierarchically porous hybrid monoliths via free radical polymerization and application in hilic enrichment of glycopeptides [J]. Analytica Chimica Acta， 2019， 1058： 97-106.

[5] SIM K B, BACK J H, HAN G Y, KIM H J . High—performance automotive adhesives with urethane—modified and nanophase—separated epoxy systems [J]. Composites Part A：Applied Science and Manufacturing， 2025， 190： 108652.

[6] SUGIMOTO Y, NISHIMURA Y, UEHARA F, MATSUMOTO A . Dissimilar materials bonding using epoxy monolith [J]. ACS Omega， 2018， 3（7）： 7532-7541.

[7] SAKATA N, TAKEDA Y, KOTERA M, SUZUKI Y, MATSUMOTO A . Interfacial structure control and three—dimensional X—ray imaging of an epoxy monolith bonding system with surface modification [J]. Langmuir， 2020， 36（37）： 10923-10932.

[8] LEE K, CORRIGAN N, BOYER C . Polymerization induced microphase separation for the fabrication of nanostructured materials [J]. Angewandte Chemie International Edition， 2023， 62（44）： e202307329.

[9] ZHAO J, WANG J, LIU Z, ZHANG Y, MI Y . Preparation of porous epoxy resin materials by reaction—induced phase separation regulated using fumed silica [J]. ACS Applied Polymer Materials， 2023， 5（4）： 2859-2866.

[10] LEGUIZAMON S C, POWERS J, AHN J, DICKENS S, LEE S, JONES B H . Polymerization—induced phase separation in rubber—toughened amine—cured epoxy resins: Tuning morphology from the nano— to macro—scale [J]. Macromolecules， 2021， 54（17）： 7796-7807.

[11] TSUJIOKA N, HIRA N, AOKI S, TANAKA N, HOSOYA K . A new preparation method for well—controlled 3D skeletal epoxy resin—based polymer monoliths [J]. Macromolecules， 2005， 38（24）： 9901-9903.

[12] TSUJIOKA N, ISHIZUKA N, TANAKA N, KUBO T, HOSOYA K . Well—controlled 3D skeletal epoxy—based monoliths obtained by polymerization induced phase separation [J]. Journal of Polymer Science Part A: Polymer Chemistry， 2008， 46（10）： 3272-3281.

[13] AZIZ T, HAQ F, FARID A, CHENG L, CHUAH L F, BOKHARI A, MUBASHIR M, TANG D Y Y, SHOW P L . The epoxy resin system: Function and role of curing agents [J]. Carbon Letters， 2024， 34（1）： 477-494.

[14] MI Y, ZHOU W, LI Q, ZHANG D, ZHANG R, MA G, SU Z . Detailed exploration of structure formation of an epoxy—based monolith with three—dimensional bicontinuous structure [J]. RSC Advances， 2015， 5（68）： 55419-55427.

[15] TUCKER S J, FU B, KAR S, HEINZ S, WIGGINS J S . Ambient cure POSS—epoxy matrices for marine composites [J]. Composites Part A: Applied Science and Manufacturing， 2010， 41（10）： 1441-1446.

[16] MORA A S, TAYOUO R, BOUTEVIN B, DAVID G, CAILLOL S . A perspective approach on the amine reactivity and the hydrogen bonds effect on epoxy—amine systems [J]. European Polymer Journal， 2020， 123： 109460.

[17] LIU T, CHEN Z, MA Y, REN Y, TAN J, CHENG Z, ZHU X . Preparation and properties of epoxy adhesives with fast curing at room temperature and low—temperature resistance [J]. ACS Omega， 2024， 9（20）： 22186-22195.

[18] KEZHEN Y, JUNYI S, KAIXIN S, MIN W, GOUKAI L, ZHE H . Effects of the chemical structure of curing agents on rheological properties and microstructure of wer emulsified asphalt [J]. Construction and Building Materials， 2022， 347： 128531.

[19] ZHANG J, ZHOU T, WEN L, ZHANG A . Fabricating metallic circuit patterns on polymer substrates through laser and selective metallization [J]. ACS Applied Materials & Interfaces， 2016， 8（49）： 33999-34007.

[20] WANG Y, HONG Y, ZHOU G, HE W, GAO Z, WANG S, WANG C, CHEN Y, WENG Z, WANG Y . Compatible Ag+ complex—assisted ultrafine copper pattern deposition on poly(ethylene terephtalate) film with micro inkjet printing [J]. ACS Applied Materials & Interfaces， 2019， 11（47）： 44811-44819.

[21] WANG F, ALTSCHUH P, RATKE L, ZHANG H, SELZER M, NESTLER B . Progress report on phase separation in polymer solutions [J]. Advanced Materials， 2019， 31（26）： 1806733.

[22] HANNA E G, YOUNES K, AMINE S, ROUFAYEL R . Exploring gel—point identification in epoxy resin using rheology and unsupervised learning [J]. Gels， 2023， 9（10）： 828.

[23] SURENDRAN A, JOY J, PARAMESWARANPILLAI J, ANAS S, THOMAS S . An overview of viscoelastic phase separation in epoxy based blends [J]. Soft Matter， 2020， 16（14）： 3363-3377.

[24] 王子币, 刘子璐, 韩祥, 王天雨, 刘栋, 陈飞 . 双连续相增韧离子凝胶的制备及水下黏附性能 [J]. 功能高分子学报， 2024， 37（4）： 322-331.

[25] WANG Z B, LIU Z L, HAN X, WANG T Y, LIU D, CHEN F . Preparation and underwater adhesion properties of bi—continuous phases—toughened Ionogel [J]. Journal of Functional Polymers， 2024， 37（4）： 322-331.

[26] VIDIL T, TOURNILHAC F, MUSSO S, ROBISSON A, LEIBLER L . Control of reactions and network structures of epoxy thermosets [J]. Progress in Polymer Science， 2016， 62： 126-179.

[27] SHUNDO A, YAMAMOTO S, TANAKA K . Network formation and physical properties of epoxy resins for future practical applications [J]. JACS Au， 2022， 2（7）： 1522-1542.