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ABA triblock copolymers are used as thermoplastic elastomers (TPEs) for a wide variety of applications. Herein, we describe incorporation of sugar-based glassy components to create sustainable triblock copolymers as alternatives for commodity TPEs. Poly(glucose-6-acrylate-1,2,3,4-tetraacetate) [PGATA] and poly(acetylated acrylic isosorbide) [PAAI] end blocks were chain-extended from a poly(n-butyl acrylate) [PnBA] midblock. PAAI-PnBA-PAAI exhibited excellent adhesion properties: peel = 8.74 N cm-1, loop tack = 2.96 N cm-2, no shear failure up to 100 h, and shear adhesion failure temperature (SAFT) = 60 °C. Although similar peel adhesion and higher loop tack were observed for PGATA-PnBA-PGATA, the shear strength and SAFT were moderate (18 h and 42 °C, respectively). PAAI-PnBA-PAAI are tough elastomers and demonstrated high stress and elongation at break (σ = 6.5 MPa and ϵ = 620%, respectively) while the GATA-based analogue exhibited weaker tensile properties (σ = 0.8 MPa and ϵ = 476%). To address this, the anomeric hydroxyl groups of GATA units were selectively deprotected to promote self-complementary hydrogen bonding in the glassy domains, resulting in 80% enhancement in the ultimate tensile stress at break (σ = 1.5 MPa). This study aims to demonstrate effects of noncovalent interactions, such as chain entanglements and self-complementary hydrogen bonding, to enhance the adhesion and mechanical performance of sugar-derived TPEs.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation under the Center for Sustainable Polymers (CHE-1413862). The authors acknowledge Dr. David Giles and Leon Lillie for their feedback and helpful discussions. Part of this work was carried out in the College of Science and Engineering Polymer Characterization Facility, University of Minnesota, which has received capital equipment funding from the NSF through the UMN MRSEC program under Award DMR-1420013. Synchrotron SAXS data were obtained at the DuPont− Northwestern−Dow Collaborative Access Team (DNDCAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University. Use of the APS at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357.
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Reporting period for MRSEC
- Period 5