{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,16]],"date-time":"2026-06-16T17:28:32Z","timestamp":1781630912610,"version":"3.54.5"},"reference-count":50,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2024,4,29]],"date-time":"2024-04-29T00:00:00Z","timestamp":1714348800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Materials with monolithic structures, such as epoxy monoliths, are used for a variety of applications, such as for column fillers in gas chromatography and HPLC, for separators in lithium-ion batteries, and for precursor polymers for monolith adhesion. In this study, we investigated the fabrication of epoxy monoliths using 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C) as the tetrafunctional epoxy and 4,4\u2032-methylenebis(cyclohexylamine) (BACM) as the amine curing agent to control pore diameters using polyethylene glycols (PEGs) of differing molecular weights as the porogenic agents. We fabricated an epoxy monolith with micron-order pores and high strength levels, and which is suitable for the precursors of composite materials in cases where smaller PEGs are used. We discussed the effects of the porous structures of monoliths on their physical properties, such as tensile strength, elongation, elastic modulus, and glass transition temperatures. For example, epoxy monoliths prepared in the presence of PEGs exhibited an elastic modulus less than 1 GPa at room temperature and Tg values of 175\u2013187 \u00b0C, while the epoxy bulk thermoset produced without any porogenic solvent showed a high elastic modulus as 1.8 GPa, which was maintained at high temperatures, and a high Tg of 223 \u00b0C. In addition, the unique adhesion characteristics of epoxy monolith sheets are revealed as a result of the combinations made with commercial epoxy and acrylic adhesives. Epoxy monoliths that are combined with conventional adhesives can function as sheet-type adhesives purposed with avoiding problems when only liquid-type adhesives are used.<\/jats:p>","DOI":"10.3390\/molecules29092059","type":"journal-article","created":{"date-parts":[[2024,4,29]],"date-time":"2024-04-29T10:33:36Z","timestamp":1714386816000},"page":"2059","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Control of Pore Sizes in Epoxy Monoliths and Applications as Sheet-Type Adhesives in Combination with Conventional Epoxy and Acrylic Adhesives"],"prefix":"10.3390","volume":"29","author":[{"given":"Yoshiyuki","family":"Kamo","sequence":"first","affiliation":[{"name":"Advanced Technology R&D Center, Mitsubishi Electric Corporation, 8-1-1, Tsukaguchi-Honmachi, Amagasaki, Hyogo 661-8661, Japan"},{"name":"Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Akikazu","family":"Matsumoto","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, Japan"},{"name":"Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,4,29]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2012.03.046","article-title":"Sample displacement chromatography as a method for purification of proteins and peptides from complex mixtures","volume":"1239","author":"Gajdosik","year":"2012","journal-title":"J. Chromatogr. A"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"9901","DOI":"10.1021\/ma051409h","article-title":"A new preparation method for well-controlled 3D skeletal epoxy resin-based polymer monoliths","volume":"38","author":"Tsujioka","year":"2005","journal-title":"Macromolecules"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1294","DOI":"10.1002\/jssc.201200084","article-title":"Preparation and Applications of Hybrid Organic-Inorganic Monoliths: A Review","volume":"35","author":"Zhu","year":"2012","journal-title":"J. Sep. Sci."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1002\/jssc.201600774","article-title":"Advances in the Development and Applications of Organic-Silica Hybrid Monoliths","volume":"40","author":"Zajickova","year":"2017","journal-title":"J. Sep. Sci."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"6308","DOI":"10.1021\/cm060645j","article-title":"Epoxy-based Monoliths. A Novel Hydrophilic Separation Material for Liquid Chromatography of Biomolecules","volume":"18","author":"Nguyen","year":"2006","journal-title":"Chem. Mater."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2343","DOI":"10.1021\/am300552q","article-title":"New Monolithic Capillary Columns with Well-Defined Macropores Based on Poly(styrene-co-divinylbenzene)","volume":"4","author":"Hasegawa","year":"2012","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2767","DOI":"10.1002\/jssc.201300431","article-title":"Organic monoliths for highperformance reversed-phase liquid chromatography","volume":"36","author":"Liu","year":"2013","journal-title":"J. Sep. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/j.chroma.2013.08.010","article-title":"Advances in the development of organic polymer monolithic columns and their applications in food analysis\u2014A review","volume":"1313","author":"Jandera","year":"2013","journal-title":"J. Chromatogr. A"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"250","DOI":"10.1021\/ac504059c","article-title":"Advances and recent trends in the field of monolithic columns for chromatography","volume":"87","author":"Svec","year":"2015","journal-title":"Anal. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2859","DOI":"10.1021\/acsapm.3c00088","article-title":"Preparation of Porous Epoxy Resin Materials by Reaction-Induced Phase Separation Regulated Using Fumed Silica","volume":"5","author":"Zhao","year":"2023","journal-title":"ACS Appl. Polym. Mater."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"7422","DOI":"10.1039\/c1cc12402a","article-title":"Fabrication of mesoporous polymer monolith: A template-free approach","volume":"47","author":"Okada","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"7810","DOI":"10.1039\/C4CC01693A","article-title":"A nanodiamond\/CNT\u2013SiC monolith as a novel metal free catalyst for ethylbenzene direct dehydrogenation to styrene","volume":"50","author":"Liu","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1016\/j.talanta.2016.12.071","article-title":"Preparation of a poly(styrene-co-DPHA-co-EDMA) monolith and its application for the separation of small molecules and biomacromolecules by HPLC","volume":"165","author":"Wang","year":"2017","journal-title":"Talanta"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4453","DOI":"10.1021\/ma5009258","article-title":"Trajectory of Critical Point in Polymerization-Induced Phase Separation of Epoxy\/Oligoethylene Glycol Solutions","volume":"47","author":"Hara","year":"2014","journal-title":"Macromolecules"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1016\/j.memsci.2007.04.045","article-title":"Investigation of Corrugation Phenomenon in the Inner Contour of Hollow Fibers during the Non-Solvent Induced Phase-Separation Process","volume":"299","author":"Bonyadi","year":"2007","journal-title":"J. Membr. Sci."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2847","DOI":"10.1016\/j.polymer.2012.04.029","article-title":"Facile Fabrication of Polycarbonate Monolith by Non-Solvent Induced Phase Separation Method","volume":"53","author":"Xin","year":"2012","journal-title":"Polymer"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"239","DOI":"10.1016\/S0376-7388(00)85130-3","article-title":"Microporous Membrane Formation via Thermally Induced Phase Separation 1. Solid Liquid-Phase Separation","volume":"52","author":"Lloyd","year":"1990","journal-title":"J. Membr. Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3212","DOI":"10.1016\/j.polymer.2014.05.031","article-title":"Facile Fabrication of Poly(methyl methacrylate) Monolith via Thermally Induced Phase Separation by Utilizing Unique Cosolvency","volume":"55","author":"Yoneda","year":"2014","journal-title":"Polymer"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3272","DOI":"10.1002\/pola.22665","article-title":"Well-Controlled 3D Skeletal Epoxy-Based Monoliths Obtained by Polymerization Induced Phase Separation","volume":"46","author":"Tsujioka","year":"2008","journal-title":"J. Polym. Sci. Part A Polym. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"828","DOI":"10.1002\/jssc.200401836","article-title":"Characterization of polyacrylamide based monolithic columns","volume":"27","author":"Plieva","year":"2004","journal-title":"J. Sep. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1016\/j.jcis.2008.06.012","article-title":"Formation of porous epoxy monolith via concentrated emulsion polymerization","volume":"325","author":"Wang","year":"2008","journal-title":"J. Colloid Interface Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"257","DOI":"10.1007\/s10971-015-3851-9","article-title":"Bio-inspired highly hydrophobic surface with ecdysis behavior using an organic monolithic resin and titanium dioxide photocatalyst","volume":"77","author":"Sakai","year":"2016","journal-title":"J. Sol-Gel Sci. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"177","DOI":"10.1016\/j.matlet.2009.10.037","article-title":"Co-continuous monolithic titania prepared by organic polymer monolith as pore template","volume":"64","author":"Kubo","year":"2010","journal-title":"Mater. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1900683","DOI":"10.1002\/adem.201900683","article-title":"Lubrication Characteristics of Epoxy Resin-Based Monolithic Thin Films with a Well-Defined Porous Morphology","volume":"21","author":"Shimizu","year":"2019","journal-title":"Adv. Eng. Mater."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1431","DOI":"10.1038\/s41598-021-80978-2","article-title":"Co-continuous network polymers using epoxy monolith for the design of tough materials","volume":"11","author":"Tominaga","year":"2021","journal-title":"Sci. Rep."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"125433","DOI":"10.1016\/j.polymer.2022.125433","article-title":"Non-destructive observation of internal structures of epoxy monolith and co-continuous network polymer using X-ray CT imaging for elucidation of their unique mechanical features and fracture mechanism","volume":"263","author":"Tominaga","year":"2022","journal-title":"Polymer"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7532","DOI":"10.1021\/acsomega.8b00920","article-title":"Dissimilar Materials Bonding Using Epoxy Monolith","volume":"3","author":"Sugimoto","year":"2018","journal-title":"ACS Omega"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"10923","DOI":"10.1021\/acs.langmuir.0c01481","article-title":"Interfacial Structure Control and Three-Dimensional X-ray Imaging of an Epoxy Monolith Bonding System with Surface Modification","volume":"36","author":"Sakata","year":"2020","journal-title":"Langmuir"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1080\/15583724.2019.1650063","article-title":"Multifunctionality in epoxy resins","volume":"60","author":"Capricho","year":"2020","journal-title":"Polym. Rev."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2430","DOI":"10.1002\/1097-4628(20000912)77:11<2430::AID-APP11>3.0.CO;2-P","article-title":"Multifunctional Epoxy Resins: Synthesis and Characterization","volume":"77","author":"Mustata","year":"2000","journal-title":"Sci. Appl. Polym. Sci."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"132031","DOI":"10.1016\/j.cej.2021.132031","article-title":"Flame-Retardant multifunctional epoxy resin with high performances","volume":"427","author":"Liu","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"6866","DOI":"10.1039\/C6TA09005B","article-title":"Fabrication of surface skinless membranes of epoxy resin-based mesoporous monoliths toward advanced separators for lithium ion batteries","volume":"5","author":"Sakakibara","year":"2017","journal-title":"J. Mater. Chem. A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"529","DOI":"10.1038\/s41428-023-00872-8","article-title":"Study on the Deformation and Fracture of Epoxy Monoliths through Mechanical Tensile and Compressive Tests and X-ray CT Imaging","volume":"56","author":"Aragishi","year":"2024","journal-title":"Polym. J."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"102454","DOI":"10.1016\/j.ijadhadh.2019.102454","article-title":"A review of research advances in epoxy-based nanocomposites as adhesive materials","volume":"96","author":"Jojibabu","year":"2020","journal-title":"Int. J. Adhes. Adhes."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"106005","DOI":"10.1016\/j.porgcoat.2020.106005","article-title":"Peelable coatings: A review","volume":"150","author":"Wagle","year":"2021","journal-title":"Prog. Org. Coat."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"115610","DOI":"10.1016\/j.compstruct.2022.115610","article-title":"Effects of resin pre-coating treatment and fibre reinforcement on adhesive bonding between CFRP sheet and concrete","volume":"292","author":"Yang","year":"2022","journal-title":"Compos. Struct."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"116680","DOI":"10.1016\/j.indcrop.2023.116680","article-title":"A formaldehyde-free bio-composite sheet used as adhesive with excellent water-wet bonding performance","volume":"198","author":"Zhu","year":"2023","journal-title":"Ind. Crops Prod."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1002\/pen.760140211","article-title":"A method for estimating both the solubility parameters and molar volumes of liquids","volume":"14","author":"Fedors","year":"1974","journal-title":"Polym. Eng. Sci."},{"key":"ref_39","unstructured":"(2003). Adhesives Determination of Tensile Lap-Shear Strength of Rigid-to-Rigid Bonded Assemblies (Standard No. ISO 4587:2003)."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"95","DOI":"10.1016\/0032-3861(61)90010-6","article-title":"The mechanism of the crosslinking of epoxide resins by amines","volume":"2","author":"Smith","year":"1961","journal-title":"Polymer"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1522","DOI":"10.1021\/jacsau.2c00120","article-title":"Network formation and physical properties of epoxy resins for future practical applications","volume":"2","author":"Shundo","year":"2022","journal-title":"JACS Au"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1007\/3-540-15546-5_2","article-title":"Mechanics and mechanisms of fracture of thermosetting epoxy polymers","volume":"72","author":"Kinloch","year":"1985","journal-title":"Adv. Polym. Sci."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"8833","DOI":"10.1016\/S0032-3861(01)00341-X","article-title":"Thermomechanical properties and morphology of blends of a hydroxy-functionalized hyperbranched polymer and epoxy resin","volume":"42","author":"Ratna","year":"2001","journal-title":"Polymer"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"104505","DOI":"10.1016\/j.reactfunctpolym.2020.104505","article-title":"A hydroxyl-containing hyperbranched polymer as a multi-purpose modifier for a dental epoxy","volume":"149","author":"Xing","year":"2020","journal-title":"React. Funct. Polym."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"4650","DOI":"10.1002\/pola.24909","article-title":"Effect of Water Addition on the Cure Kinetics of an Epoxy-Amine Thermoset","volume":"49","author":"Choi","year":"2011","journal-title":"Polym. Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"4370","DOI":"10.1021\/ma070423m","article-title":"Theoretical Study on Mechanisms of the Epoxy-Amine Curing Reaction","volume":"40","author":"Ehlers","year":"2007","journal-title":"Macromolecules"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"529","DOI":"10.1007\/s13233-018-6075-3","article-title":"Comparison of Hydrogenated Bisphenol A and Bisphenol A Epoxies: Curing Behavior, Thermal and Mechanical Properties, Shape Memory Properties","volume":"26","author":"Wei","year":"2018","journal-title":"Macromol. Res."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"6073","DOI":"10.1039\/D1SM00529D","article-title":"Dynamic behaviour of water molecules in heterogeneous free space formed in an epoxy resin","volume":"17","author":"Yamamoto","year":"2021","journal-title":"Soft Matter"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"93","DOI":"10.1016\/0376-7388(95)00281-2","article-title":"Evidence for spinodal decomposition and nucleation and growth mechanisms during membrane formation","volume":"111","author":"Nunes","year":"1996","journal-title":"J. Mem. Sci."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"389","DOI":"10.1070\/PU1979v022n06ABEH005571","article-title":"Spinodal decomposition (phase transitions via unstable states)","volume":"22","author":"Skripov","year":"1979","journal-title":"Sov. Phys. Uspekhi"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/9\/2059\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:36:21Z","timestamp":1760106981000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/9\/2059"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,4,29]]},"references-count":50,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2024,5]]}},"alternative-id":["molecules29092059"],"URL":"https:\/\/doi.org\/10.3390\/molecules29092059","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,4,29]]}}}