Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization
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 sh...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Royal Society of Chemistry
2020
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| _version_ | 1797072837564956672 |
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| author | Gregory, GL Sulley, GS Carrodeguas, LP Chen, TTD Santmarti, A Terrill, NJ Lee, K-Y Williams, CK |
| author_facet | Gregory, GL Sulley, GS Carrodeguas, LP Chen, TTD Santmarti, A Terrill, NJ Lee, K-Y Williams, CK |
| author_sort | Gregory, GL |
| collection | OXFORD |
| 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 (fhard = 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 < fhard < 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 (fhard < 0.4 and N > 1300) with linear stress–strain relationships, high ultimate tensile strengths (σb = 1–5 MPa), very high elongations at break (εb = 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 (Td,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. |
| first_indexed | 2024-03-06T23:13:25Z |
| format | Journal article |
| id | oxford-uuid:664afd63-b282-4b4d-8b2e-ecbe02705fa1 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:13:25Z |
| publishDate | 2020 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:664afd63-b282-4b4d-8b2e-ecbe02705fa12022-03-26T18:30:56ZTriblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerizationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:664afd63-b282-4b4d-8b2e-ecbe02705fa1EnglishSymplectic ElementsRoyal Society of Chemistry2020Gregory, GLSulley, GSCarrodeguas, LPChen, TTDSantmarti, ATerrill, NJLee, K-YWilliams, CKThermoplastic 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 (fhard = 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 < fhard < 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 (fhard < 0.4 and N > 1300) with linear stress–strain relationships, high ultimate tensile strengths (σb = 1–5 MPa), very high elongations at break (εb = 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 (Td,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. |
| spellingShingle | Gregory, GL Sulley, GS Carrodeguas, LP Chen, TTD Santmarti, A Terrill, NJ Lee, K-Y Williams, CK Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title | Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title_full | Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title_fullStr | Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title_full_unstemmed | Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title_short | Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization |
| title_sort | triblock polyester thermoplastic elastomers with semi aromatic polymer end blocks by ring opening copolymerization |
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