Synthesis of Monoacryloxypropyl-POSS-based Hybrid Epoxyacrylate Copolymers and Their Application in Thermally Curable Structural Self-Adhesive Tapes

Abstract

New organic-inorganic hybrid copolymers (EA-POSSs) based on butyl acrylate, glycidyl methacylate, hydroxybutyl acrylate, acryloiloxybenzophenone and acryloxypropylheptaisobutyl-POSS (A-POSS) were prepared via free-radical solution polymerization (FRP) and applied as a component of thermally curable structural self-adhesive tapes (SATs). The EA-POSS with 0.25, 0.5 or 1 mol % of A-POSS exhibited significantly higher dynamic viscosity (ca. +104%), Mw (+61%) and polydispersity (+109%; measured using gel permeation chromatography) as well as lower T g value (−16 • C) in relation to the A-POSS-free copolymer (EA-0). Differential scanning calorimetry (DSC) measurements (one glass transition process) confirmed statistic chain structure of the EA-POSS materials. Replacement of EA-0 by the EA-POSS copolymers in a SATs recipe caused simultaneous improvement of their self-adhesive features, i.e., adhesion (+70%), tack (+21%) and cohesion (+1590%). Moreover, the POSS-based copolymers improved the shear strength of thermally cured Al/SAT/Al overlap joints; the best mechanical resistance (before and after accelerated ageing tests) was observed for the sample containing 0.5 mol % of A-POSS (an increment range of 50-294% in relation to the A-POSS-free joints). Thermogravimetric analysis (TGA) revealed markedly improved thermal stability of the A-POSS-based SATs as well.

Free-Radical Bulk-Photopolymerization Process as a Method of Obtaining Thermally Curable Structural Self-Adhesive Tapes and Effect of Used Type I Photoinitiators

“…A particular kind of the SATs is those with self-adhesive features. They can be prepared, for example, via a UV-photo cross-linking process of reactive acrylate copolymers (obtained in classical free-radical copolymerization process initiated by 2,2′-azobis(isobutyronitryle) and in the presence of organic solvent) compounded with epoxy resin and latent curing agent [ 9 , 10 , 11 , 12 ]. Although the developed method of preparation and modification of SATs gives high results of adhesive and mechanical properties, in recent years a very strong emphasis has been placed on waste-free technologies.…”

Epoxy-Based Structural Self-Adhesive Tapes Modified with Acrylic Syrups Prepared via a Free Radical Photopolymerization Process

“…A UV/heat dual-curable epoxy–acrylate adhesive containing the mentioned core-shell particles exhibits outstanding water resistance [ 15 ]. Applications of epoxyacrylate copolymers (based on BA, GMA, and 2-hydroxyethyl acrylate) prepared by a conventional radical polymerization process in an organic solvent [ 16 , 17 , 18 , 19 ] or by bulk photopolymerization [ 20 ] are also known. In the latter case, the acrylate-type modifier was used in the form of a prepolymer also called acrylic syrup (i.e., a solution of the copolymer in the unreacted monomers).…”

Temperature dependence of methanol and ethanol vapor sorption in polyhedral oligomeric silsesquioxane (POSS) containing methacrylate membranes

“…[15][16][17] Research on applying POSSbased composite materials to gas separation membranes, water treatment, catalyst systems, energy devices, and coating agents has been actively conducted. [18][19][20][21][22][23][24][25][26][27][28] The use of POSS as composite materials, such as nanocomposites and copolymers, improves the durability, thermostability, chemical resistance, and long-term stability, which are essential factors for alcohol separation and adsorption membranes for ethanol concentration and VOC separation. [16][17][18]23,[29][30][31][32][33] Silicon containing polymer membranes have reported to have high gas permeability.…”

“…[18][19][20][21][22][23][24][25][26][27][28] The use of POSS as composite materials, such as nanocomposites and copolymers, improves the durability, thermostability, chemical resistance, and long-term stability, which are essential factors for alcohol separation and adsorption membranes for ethanol concentration and VOC separation. [16][17][18]23,[29][30][31][32][33] Silicon containing polymer membranes have reported to have high gas permeability. 14,34,35 In this study, we focused on a polymer membrane, in which POSS was introduced into the side chain for uniform POSS dispersion and to increase vapor permeability by expanding the polymer gap.…”

“…Its compatibility and physical properties can be changed by introducing an arbitrary organic substituent 15–17 . Research on applying POSS‐based composite materials to gas separation membranes, water treatment, catalyst systems, energy devices, and coating agents has been actively conducted 18–28 . The use of POSS as composite materials, such as nanocomposites and copolymers, improves the durability, thermostability, chemical resistance, and long‐term stability, which are essential factors for alcohol separation and adsorption membranes for ethanol concentration and VOC separation 16–18,23,29–33 .…”