Physical Behavior of Triblock Copolymer Thermoplastic Elastomers Containing Sustainable Rosin-Derived Polymethacrylate End Blocks

Abstract

A rosin-derived polymethacrylate, poly­(dehydroabietic ethyl methacrylate) (PDAEMA), was evaluated as a sustainable end block in triblock copolymer-based thermoplastic elastomers. Triblock copolymers containing glassy PDAEMA end blocks and a rubbery poly­(n-butyl acrylate) (PnBA) midblock were synthesized through atom transfer radical polymerization. The volume fraction of PDAEMA in the triblock copolymer was varied at constant midblock molecular weight. At lower PDAEMA content, the triblock copolymers exhibited microphase separated morphologies lacking long-range order, which transitioned to a well-defined cylindrical morphology as the PDAEMA content was increased. Observed thermal properties were consistent with the presence of distinct PDAEMA and PnBA domains. The order–disorder transition temperature increased with increasing PDAEMA content in the block copolymer, and the Flory–Huggins interaction parameter of PDAEMA/PnBA was strongly temperature-dependent yet small in value. The triblock copolymers exhibited elastomeric behavior at room temperature and accessible order–disorder transitions, appropriate for thermoplastic elastomer applications.

Advances in Rosin-Based Chemicals: The Latest Recipes, Applications and Future Trends

“…It can be prepared using: (i) oxalyl chloride according to Scheme 1 prior to evaporation of unnecessary substances [142], (ii) phosphorus trichloride in chloroform (yield 92.5%) [140] or (iii) thionyl chloride in presence of 4-dimethylaminopyridine [143]. It can be used as a substrate for the synthesis of macroinitiators for atom transfer radical polymerization (ATRP) reactions [142], rosin phosphate esters [140], N -hydroxyethylacrylamide ester of dehydroabietic acid [144], dehydroabietic ethyl methacrylate [145,146], dehydroabietic propargyl ester [147] dehydroabietic hexyl acrylate [148], as well as other intermediates in synthesis of various surfactants [143,149] and medicines [141,150,151].…”

“…Dehydroabietic ethyl methacrylate is a white powder. It can be prepared from dehydroabietyl chloride and hydroxyethyl methacrylate according to Scheme 11, prior to neutralization, drying, evaporation and chromatography [146]. It can be widely used as a monomer in preparation of graft and block copolymers [146,166,167,168,169,170].…”

“…It can be prepared from dehydroabietyl chloride and hydroxyethyl methacrylate according to Scheme 11, prior to neutralization, drying, evaporation and chromatography [146]. It can be widely used as a monomer in preparation of graft and block copolymers [146,166,167,168,169,170]. It is worth noting, that a similar compound dehydroabietic ethyl acrylate is a yellow, viscous liquid, which can be prepared from hydroxyethyl acrylate and dehydroabietyl chloride prior to filtration, precipitation and vacuum distillation [171].…”

Metal Free Reversible-Deactivation Radical Polymerizations: Advances, Challenges, and Opportunities

“…SBMA, which is derived from soybean oil, has long alkyl chains and can decrease the Tg in copolymers. Tang and co-workers used metal free ATRP with PTH as the photocatalyst to obtain polymers with low horizontalstrikeD and could show the synthesis of diblock copolymers with PSBMA as a soft block [268].…”

Preparation and polymerization of isopimaric acid derivatives

“…synthesized a triblock copolymer for pressure‐sensitive adhesives that incorporated rosin structures. A rosin‐derived polymethacrylate, poly(dehydroabietic ethyl methacrylate), has been evaluated as a sustainable end block in triblock copolymer‐based thermoplastic elastomers . Liu et al .…”