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Exploiting sodium coordination in alternating monomer sequences to toughen degradable block polyester thermoplastic elastomers

DOI: 10.1021/acs.macromol.2c00068 DOI Help

Authors: Georgina L. Gregory (University of Oxford) , Charlotte K. Williams (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Macromolecules

State: Published (Approved)
Published: March 2022
Diamond Proposal Number(s): 29810

Abstract: Thermoplastic elastomers (TPEs) that are closed-loop recyclable are needed in a circular material economy, but many current materials degrade during recycling, and almost all are pervasive hydrocarbons. Here, well-controlled block polyester TPEs featuring regularly placed sodium/lithium carboxylate side chains are described. They show significantly higher tensile strengths than unfunctionalized analogues, with high elasticity and elastic recovery. The materials are prepared using controlled polymerizations, exploiting a single catalyst that switches between different polymerization cycles. ABA block polyesters of high molar mass (60–100 kg mol–1; 21 wt % A-block) are constructed using the ring-opening polymerization of ε-decalactone (derived from castor oil; B-block), followed by the alternating ring-opening copolymerization of phthalic anhydride with 4-vinyl-cyclohexene oxide (A-blocks). The polyesters undergo efficient functionalization to install regularly placed carboxylic acids onto the A blocks. Reacting the polymers with sodium or lithium hydroxide controls the extent of ionization (0–100%); ionized polymers show a higher tensile strength (20 MPa), elasticity (>2000%), and elastic recovery (>80%). In one case, sodium functionalization results in 35× higher stress at break than the carboxylic acid polymer; in all cases, changing the quantity of sodium tunes the properties. A leading sample, 2-COONa75 (Mn 100 kg mol–1, 75% sodium), shows a wide operating temperature range (−52 to 129 °C) and is recycled (×3) by hot-pressing at 200 °C, without the loss of mechanical properties. Both the efficient synthesis of ABA block polymers and precision ionization in perfectly alternating monomer sequences are concepts that can be generalized to many other monomers, functional groups, and metals. These materials are partly bioderived and have degradable ester backbone chemistries, deliver useful properties, and allow for thermal reprocessing; these features are attractive as future sustainable TPEs.

Journal Keywords: Stress; Sodium; Organic polymers; Tensile strength; Polymers

Diamond Keywords: Plastics

Subject Areas: Materials, Chemistry

Instruments: DL-SAXS-Offline SAXS and Sample Environment Development

Added On: 07/03/2022 09:16

Discipline Tags:

Chemistry Materials Science Organic Chemistry Polymer Science

Technical Tags:

Scattering Small Angle X-ray Scattering (SAXS)