We have demonstrated the validity of a new type of pressure-sensitive adhesion system using block copolymers containing a poly(2-ethylhexyl acrylate) (P2EHA) segment as the low glass transition temperature polymer and a poly(tert-butyl acrylate) (PtBA) or poly(isobornyl acrylate) (PIBoA) segment as the reacting polymer in the presence of a photoacid generator (PAG). This adhesion system can be easily debonded because of a change in the polymer properties of the adhesives by acid-catalyzed deprotection uniquely occurring during the photoirradiation followed by postbaking. We investigated the transformation of PtBA and PIBoA into poly(acrylic acid) using IR spectroscopy and a thermogravimetric analysis in the presence of p-toluenesulfonic acid and the PAGs. The block copolymers with a well-defined molecular structure were then synthesized by atom transfer radical polymerization, and their adhesive properties were evaluated using the 180° peel test. The block copolymers showed superior adhesion property than a random copolymer and polymer blends, due to the microphase separation of the block copolymers. A drastic change in the adhesive strength of the block copolymers was observed in response to the dual external stimuli consisting of UV irradiation and the subsequent heating.

We report the organotellurium-mediated living radical polymerization (TERP) using diphenylditelluride (DT-Ph) and di-n-butylditelluride (DT-Bu) in the presence of a binary azo initiator system consisting of 2,2′-azobis(isobutyronitrile) (AIBN) and 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMVN) with different decomposition rates for the facile synthesis of high-molecular-weight block copolymers containing a polar side group. The block copolymers containing the poly(tert-butyl acrylate) (PtBA) sequence as the reactive segment and the random copolymer sequences of n-butyl acrylate (nBA) or 2-ethylhexyl acrylate (2EHA) with 2-hydroxyethyl acrylate (HEA) as the adhesive segment were synthesized. The concurrent use of the binary initiators was revealed to effectively increase both the polymerization reactivity and the molecular weight of the polymers along with a narrow molecular weight distribution. The produced block copolymers exhibited high performance for the dismantlable adhesion responsible for the dual external stimuli consisting of photoirradiation and postbaking in the presence of a photoacid generator.

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Controlled synthesis of block copolymers as dismantlable adhesives using an organotellurium-mediated living radical polymerization (TERP) for discussion of adhesion strength and failure mode.