Bio-derived polymers for coating applications: comparing poly(limonene carbonate) and poly(cyclohexadiene carbonate)

Stößer, Tim; Li, Chengjiao; Unruangsri, Junjuda; Saini, Prabhjot; Sablong, RJ Rafaël; Meier, Michael A. R.; Williams, Charlotte K.; Koning, CE Cor

doi:10.1039/c7py01223c

Cited by 86 publications

(61 citation statements)

References 65 publications

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“…Williams et al studied the cross‐linking of limonene oxide based polycarbonates via thiol‐ene reaction and compared them with the cyclohexadiene oxide based pendants. The materials were evaluated for coating applications, and show good solvent and scratch resistance . Coates and co‐workers used this promising monomer to obtain crystalline polycarbonates .…”

Section: Cyclohexene Oxide Derivatives and Other Alicyclic Epoxide Momentioning

confidence: 99%

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Scharfenberg

Hilf

Frey

2018

Adv Funct Materials

163

109

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Aliphatic polycarbonates synthesized from carbon dioxide (CO 2 ) and epoxides are resource-saving, highly biocompatible and biodegradable polymers. Since the discovery of the copolymerization of epoxides and CO 2 in 1969 by Inoue et al., this has become an important and useful technology for the large-scale utilization of CO 2 in chemical synthesis, employing mainly propylene oxide, and cyclohexene oxide (CHO). Only in recent years, functionalized polycarbonates have become an emerging topic with a broad scope of potential applications. This review summarizes synthetic routes and properties of numerous functionalized polycarbonates synthesized from CO 2 and functional epoxide monomers. Implications for new materials and possible applications, for instance for pharmaceutical purposes and membranes are reviewed. Besides polycarbonates based on oxirane and CHO derivatives, particular emphasis is placed on the manifold synthetic approaches and postpolymerization modifications of glycidyl ether based polycarbonates. Not only functionalized linear polycarbonates are presented but also a variety of novel polycarbonate architectures, e.g., star and hyperbranched polymers.

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Section: Cyclohexene Oxide Derivatives and Other Alicyclic Epoxide Momentioning

confidence: 99%

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Scharfenberg

Hilf

Frey

2018

Adv Funct Materials

163

109

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“…The presence of dual alkene functionality in limonene makes it a versatile monomer that has been used in the synthesis of thermoplastic polymers and in coating applications. [93] Epoxidation of the endocyclic alkene to limonene oxide (LO) followed by ring opening copolymerisation with CO 2 affords polylimonene carbonate (PLimC) with a T g similar to that of polycarbonates but with higher thermal and scratch resistance property (scheme 22). [94] Scheme 22.Synthesis of limonene based polycarbonates with antimicrobial properties (PLimC-NQ) or those similar to rubber (PLimC-B3MP).…”

Section: Monoterpenes As Highly Functionalized Monomersmentioning

confidence: 99%

Chemo-enzymatic routes towards the synthesis of bio-based monomers and polymers

Ahmed

Leferink

Scrutton

2019

Molecular Catalysis

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Scheme 7. Kinetic resolution of aromatic mandelic acid derivatives. Enantioselective hydrolysis of α-hydroxynitriles using nitrilases offer a facile approach to chiral hydroxy acids with theoretical yields of 100% in a dynamic kinetic resolution (DKR) process. Robertson et. al. identified 137 nitrilases after screening 651 environmental samples of which 44 were found to be (R) and 4 were (S)-selective on mandelonitrile. [36] Further investigation revealed nitrilase I and II to be proficient in the DKR of arylnitriles (rac-14 and 15) towards the synthesis of a panel of mandelic acid (R)-14 and phenyllactic acid derivatives (S)-15.[37] Scheme 8.Chemo-enzymatic DKR of α-hydroxynitriles towards the production of aromatic hydroxy acids. Dehydrogenases provide an alternative route to hydroxy acids via the asymmetric reduction of the pro-chiral ketone in α-keto esters. Fusion proteins consisting of glutathione Stransferase N-terminally linked to putative dehydrogenases from S. cerevisiae (Ypr1p and Gre1p) were used to reduce ethyl 2-oxo-4-phenylbutanoate to the corresponding alcohol with high enaniopurity.[38] Further systematic investigation by the same group on 18 reductases fused with GST showed activity towards α-and β-keto esters. [39] Five enzymes encoded from the yeast gene YDLI24w, YAL060w, YGL157w, YDR541c and YGL151w displayed excellent enantioselectivity across all three α-keto esters, affording the corresponding alcohol in >99% ee. Xu and co-workers engineered a highly stereoselective D-lactate dehydrogenase (D-LDH) towards a panel of aliphatic and aromatic αketoesters.[40] The Y52L mutant of D-LDH showed enhanced activity compared to the wildtype across the whole substrate panel (scheme 9). Scheme 9. Panel of α-keto acids using engineered D-lactate dehydrogenase (D-LDH). Values in brackets show % change in specific activity between wt and Y52L mutant.

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“…Although very attractive, this protocol still requires a combination of catalysts and the use of a solvent to reach relatively low molar masses (around 30 kg/mol). In the context of green chemistry, some recent investigations were devoted to the copolymerization and terpolymerisation of CO2 with biobased epoxides precursors [64][65][66]. Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

Grondin

Aupetit

Tassaing

2019

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We report a rational investigation of the selective synthesis of poly(cyclohexene carbonate) from CO 2 and cyclohexene oxide by using commercially available Lewis acids with nontoxic metal centers. After a preliminary screening, we focused on the use of zinc salts, and the effect of the pressure, the temperature, the catalyst loading, and the presence of cocatalyst or a solvent on the reaction yields, selectivity, and molar masses was evaluated for selected catalytic platforms. Thus, we found that ZnTosylate in catalytic amounts under solvent-and cocatalyst-free conditions enables the selective synthesis of poly(cyclohexene carbonate) with a molecular weight of about 62.1 kg/mol with about 70% yields at 343 K and 4 MPa. To the best of our knowledge, this is a rare example of high molar mass polycyclohexene carbonates that are moreover obtained under solvent-and cocatalyst-free conditions. The high selectivity of ZnTos towards the formation of poly(cyclohexene carbonate) was interpreted, thanks to in situ FTIR spectroscopy and DFT calculations, as resulting from its ability to coactivate CO 2 . Abstract:We report a rational investigation of the selective synthesis of poly(cyclohexene carbonate) from CO2 and cyclohexene oxide by using commercially available Lewis acids with nontoxic metal centers. After a preliminary screening, we focused on the use of zinc salts, and the effect of the pressure, the temperature, the catalyst loading, and the presence of cocatalyst or a solvent on the reaction yields, selectivity, and molar masses was evaluated for selected catalytic platforms. Thus, we found that ZnTosylate in catalytic amounts under solvent-and cocatalyst-free conditions enables the selective synthesis of poly(cyclohexene carbonate) with a molecular weight of about 62.1 kg/mol with about 70% yields at 343 K and 4 MPa. To the best of our knowledge, this is a rare example of high molar mass polycyclohexene carbonates that are moreover obtained under solvent-and cocatalyst-free conditions. The high selectivity of ZnTos towards the formation of poly(cyclohexene carbonate) was interpreted, thanks to in situ FTIR spectroscopy and DFT calculations, as resulting from its ability to coactivate CO2.

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Bio-derived polymers for coating applications: comparing poly(limonene carbonate) and poly(cyclohexadiene carbonate)

Abstract: Two fully bio-based polycarbonates, poly(limonene carbonate) and poly(cylcohexadiene carbonate), were post-functionalized via thiol–ene reactions and tested as future coating materials.

Cited by 86 publications

References 65 publications

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Chemo-enzymatic routes towards the synthesis of bio-based monomers and polymers

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

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