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Soft, Formstable (Co)Polyester Blend Elastomers.

ABSTRACT: High crystallization rate and thermomechanical stability make polylactide stereocomplexes effective nanosized physical netpoints. Here, we address the need for soft, form-stable degradable elastomers for medical applications by designing such blends from (co)polyesters, whose mechanical properties are ruled by their nanodimensional architecture and which are applied as single components in implants. By careful controlling of the copolymer composition and sequence structure of poly[(L-lactide)-co-(ε-caprolactone)], it is possible to prepare hyperelastic polymer blends formed through stereocomplexation by adding poly(D-lactide) (PDLA). Low glass transition temperature T_g ≤ 0 °C of the mixed amorphous phase contributes to the low Young's modulus E. The formation of stereocomplexes is shown in DSC by melting transitions T_m > 190 °C and in WAXS by distinct scattering maxima at 2θ = 12° and 21°. Tensile testing demonstrated that the blends are soft (E = 12-80 MPa) and show an excellent hyperelastic recovery R_rec = 66-85% while having high elongation at break ε_b up to >1000%. These properties of the blends are attained only when the copolymer has 56-62 wt% lactide content, a weight average molar mass >140 kg·mol^-1, and number average lactide sequence length ≥4.8, while the blend is formed with a content of 5-10 wt% of PDLA. The devised strategy to identify a suitable copolymer for stereocomplexation and blend formation is transferable to further polymer systems and will support the development of thermoplastic elastomers suitable for medical applications.

SUBMITTER: Neffe AT

PROVIDER: S-EPMC8230036 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Thermoplastic elastomers benefit from high elasticity and straightforward (re)processability; they are widely used across a multitude of sectors. Currently, the majority derive from oil, do not degrade or undergo chemical recycling. Here a new series of ABA triblock polyesters are synthesized and show high-performances as degradable thermoplastic elastomers; their composition is poly(cyclohexene-alt-phthalate)-b-poly(ε-decalactone)-b-poly(cyclohexene-alt-phthalate) {PE-PDL-PE}. The synthesis is accomplished using a zinc(ii)/magnesium(ii) catalyst, in a one-pot procedure where ε-decalactone ring-opening polymerization yielding dihydroxyl telechelic poly(ε-decalatone) (PDL, soft-block) occurs first and, then, addition of phthalic anhydride/cyclohexene oxide ring-opening copolymerization delivers semi-aromatic polyester (PE, hard-block) end-blocks. The block compositions are straightforward to control, from the initial monomer stoichiometry, and conversions are high (85-98%). Two series of polyesters are prepared: (1) TBPE-1 to TBPE-5 feature an equivalent hard-block volume fraction (f hard = 0.4) and variable molar masses 40-100 kg mol-1; (2) TBPE-5 to TBPE-9 feature equivalent molar masses (∼100 kg mol-1) and variable hard-block volume fractions (0.12 < f hard < 0.4). Polymers are characterized using spectroscopies, size-exclusion chromatography (SEC), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). They are amorphous, with two glass transition temperatures (∼-51 °C for PDL; +138 °C for PE), and block phase separation is confirmed using small angle X-ray scattering (SAXS). Tensile mechanical performances reveal thermoplastic elastomers (f hard < 0.4 and N > 1300) with linear stress-strain relationships, high ultimate tensile strengths (σ b = 1-5 MPa), very high elongations at break (ε b = 1000-1900%) and excellent elastic recoveries (98%). There is a wide operating temperature range (-51 to +138 °C), an operable processing temperature range (+100 to +200 °C) and excellent thermal stability (T d,5% ∼ 300 °C). The polymers are stable in aqueous environments, at room temperature, but are hydrolyzed upon gentle heating (60 °C) and treatment with an organic acid (para-toluene sulfonic acid) or a common lipase (Novozyme® 51032). The new block polyesters show significant potential as sustainable thermoplastic elastomers with better properties than well-known styrenic block copolymers or polylactide-derived elastomers. The straightforward synthesis allows for other commercially available and/or bio-derived lactones, epoxides and anhydrides to be developed in the future.

Project description: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 (M n 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.

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Soft, Formstable (Co)Polyester Blend Elastomers.

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