Xylose-Based Polyethers and Polyesters Via ADMET Polymerization toward Polyethylene-Like Materials

Abstract

One of the challenges of developing bioderived polymers is to obtain materials with competitive properties. This study investigates the structure-properties relationships of polyesters and polyethers that can be derived from d-xylose through metathesis polymerization, in order to produce bioderived plastic materials that are sourced from sustainable feedstocks and whose properties can compete with those of polyolefins such as polyethylene. Bicyclic diol 1,2-O-isopropylidene-α-d-xylofuranose was coupled with ω-unsaturated fatty acids and alcohols of different chain lengths (C11, C5, C3), and the resulting α,ω-unsaturated esters and ethers polymerized via an acyclic diene metathesis (ADMET) polymerization using a commercial Grubbs second-generation catalyst, obtaining polymers with M n up to 63.0 kg mol–1. Glass transition temperatures (T g) decreased linearly with increasing chain length and were lower for polyethers (−32 to 14 °C) compared to polyesters (−14 to 45 °C). ADMET polymers could be modified postpolymerization by reacting their internal carbon–carbon double bonds. Thiol–ene reaction with methyl thioglycolate lowered the T g while allowing insertion of additional functional groups. Alkene hydrogenation turned the polyester and polyether with C20 hydrocarbon linkers into semicrystalline polymers with T m ≈ 50 °C. The latter, when cast into films, displayed remarkable polyethylene-like properties. Hot-pressed films proved ductile materials (Young modulus E y 60–110 MPa, elongation at break εb 670–1000%, ultimate tensile strength σb 8–10 MPa), while uniaxially oriented films proved very strong yet flexible materials (E y 190–200 MPa, εb 160–350%, σb 43–66 MPa). Gas barrier properties were comparable to those of commercial polyolefins. Polyethers were resistant to hydrolysis, while polyesters depolymerized under alkaline conditions.

Crosslinked xylose-based polyester as a bio-derived and degradable solid polymer electrolyte for Li+-ion conduction

“…Moreover, there is also scope to explore the performance of the polyether analogue of this polyester which has also recently been reported. 71…”

Back to the Future with Biorefineries: Bottom‐Up and Top‐Down Approaches toward Polymers and Monomers

“…[33,106,107] The most promising ones use few, high-yielding steps to get from the sugars to the monomer and only add bio-based functionalities (if any) and thus preserve the inherent renewability of the sugars. From these monomers, a multitude of polymers have been obtained, such as polyesters, [105,108] polycarbonates, [104] and polyethers. [108] One challenge of all these approaches is that they use pure xylose, which is an expensive raw material.…”

“…From these monomers, a multitude of polymers have been obtained, such as polyesters, [105,108] polycarbonates, [104] and polyethers. [108] One challenge of all these approaches is that they use pure xylose, which is an expensive raw material. A more realistic scenario to produce cost-competitive monomers and polymers would be to start from already existing waste xylose streams, such as sugar cane residue.…”

CaO Catalyzed Transesterification of Ethyl 10-Undecenoate as a Model Reaction for Efficient Conversion of Plant Oils and Their Application to Depolymerization of Aliphatic Polyesters

“…On the basis of these results, we thus have an interest in applying the catalyst for conversion of FAEs to fine chemicals including the monomer synthesis of biobased aliphatic polyesters. ,− ,− This is because the conventional monomer synthesis with ethyl (or methyl) 10-undecenoate (derived from castor oil) by transesterification generally requires excess 1,1′-carbonyl diimidazole, p -toluene sulfonic acid, or NaOMe or NEt 3 and 4,4-dimethylaminopyridine, whereas reports for the catalytic transesterification in the presence of Sc­(CF 3 SO 3 ) 3 or Cu/V 2 O 5 were also known. In particular, α,ω-dienes derived from a castor oil derivative, ω-undecenoate containing a terminal olefinic double bond and carboxylate (exemplified as ethyl 10-undecenoate in this study), prepared by transesterification are useful feedstock for the synthesis of biobased linear polyesters via acyclic diene metathesis (ADMET) polymerization and subsequent olefin hydrogenation. ,, This is because ADMET polymerization provides a wide variety of polyesters that are not available by the other methods (like polycondensation), as exemplified in many reports for the synthesis of α,ω-dienes derived from fatty acids and its derivatives. ,,− Therefore, development of a clean, efficient catalytic method has been desired for the synthesis of fine chemicals and monomer synthesis. ,− …”