Enhanced Mechanical and Adhesion Properties in Sustainable Triblock Copolymers via Non-covalent Interactions

Abstract

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.

Sub‐3 V ZnO Electrolyte‐Gated Transistors and Circuits with Screen‐Printed and Photo‐Crosslinked Ion Gel Gate Dielectrics: New Routes to Improved Performance

“…Photo‐Patternable Ion Gel, Synthesis, and Preparation : Poly[(styrene‐ r ‐vinylbenzyl azide)‐ b ‐poly(ethyl acrylate)‐ b ‐poly(styrene‐ r ‐vinylbenzyl azide)] (SEAS‐N3) was synthesized via reversible addition−fragmentation chain transfer (RAFT) polymerization and a post polymerization reaction . The detailed synthetic procedures have been described in a previous report .…”

Loop-stabilized BAB triblock copolymer morphologies by PISA in water

“…The first one, named (C12-TTC)2-BA and commercially available, has a C12 alkyl chain end-group and has already been used for the synthesis of triblock copolymer under homogeneous conditions. 38,39 The second one, (C4-TTC)2-BA, has a short C4 alkyl chain and was synthesized according to a previously established protocol. 35 They were used in the solution polymerization of DMAc in DMF in presence of AIBN as an initiator.…”

Predicting the Mechanical Response of Polyhydroxyalkanoate Biopolymers Using Molecular Dynamics Simulations

“…Therefore, as a specific challenge, one needs to find PHA polymer motifs and compositions that exhibit superior mechanical properties, allowing them as a viable alternative of conventional packaging materials [20]. Tailoring the mechanical properties can be achieved either by combining monomers with diverse chemistries to form either copolymers or blends [22][23][24][25] or by adding plasticizers to the polymer matrix [26,27]. To accelerate the rational design of PHA-based polymers, the chemical design space has to be efficiently explored and the structure-property relationships established to identify new polymers with enhanced properties [28].…”