Polycarbonates from biorenewable diols via carbonate metathesis polymerization

Vanderhenst, Rob; Miller, Stephen A.

doi:10.1680/gmat.12.00022

Cited by 36 publications

(30 citation statements)

References 39 publications

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“…152 Starting from 1,10-decanediol, a molecule readily available from sebacic acid by simple reduction, Miller and Vanderhenst described two distinct routes to aliphatic polycarbonates. 153 In a first approach, an α,ω-bis-carbonate was synthesized from the reaction of the diol with either methylchloroformate or dimethyl carbonate. This monomer was then polymerized by carbonate interchange reactions in the melt in the presence of various catalysts yielding polycarbonates with molecular weight in the range of 8-50 kg mol −1 .…”

Section: Scheme 28mentioning

confidence: 99%

Structure–properties relationship of fatty acid-based thermoplastics as synthetic polymer mimics

et al. 2013

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Section: Scheme 28mentioning

confidence: 99%

Structure–properties relationship of fatty acid-based thermoplastics as synthetic polymer mimics

et al. 2013

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“…In order to provide sufficient access to long-chain polyacetals (PA-18, PA-19, PA-23) and polycarbonates (PC-18, PC-19, PC-23), we established a one-pot synthesis directly from the corresponding diols as the starting material (Scheme 1). Essentially, this follows the procedures for shorter chain (C 5 to C 12 ) analogs, 17,25,26 slightly adapting reaction conditions to the different melting points and solubilities of the long-chain linear α,ω-diols (Scheme 1).…”

Section: Synthesis Of Long-chain Polyacetals and Polycarbonatesmentioning

confidence: 99%

Physical properties and hydrolytic degradability of polyethylene-like polyacetals and polycarbonates

2014

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Long-chain polyacetals and polycarbonates were prepared by polycondensation of α,ω-diols (C 18 , C 19 , C 23 ) derived from fatty acids as a renewable feedstock with diethoxymethane and dimethyl carbonate, respectively, in one step. Studies of hydrolytic degradation of the solid polymers show a much higher stability compared to their shorter-chain counterparts. Long-chain polyacetals were found to degrade slowly under acidic conditions, while the long-chain polycarbonates also degraded in a basic environment. To rationalize the impact of acetal and carbonate groups on the thermal and crystalline properties of polyacetals and polycarbonates, additional model polymers with a further reduced and systematically varied functional group density were generated by ADMET copolymerization of the unfunctionalized undeca-1,10-diene with bis(undec-10-en-1-yloxy)methane or di(undec-10-en-1-yl) carbonate, respectively, followed by exhaustive hydrogenation. Long-chain polycarbonates possess polyethylene-like solid state structures. By comparison to polyesters, a given density of carbonate groups in the polymer chain reduces melting and crystallization temperatures significantly more strongly. By contrast, long-chain polyacetals possess more complex non-uniform crystal structures, and only adopt a polyethylene-like structure at very low densities of acetal groups. Also, acetal groups more strongly impact melting and crystallization temperatures vs. carbonates. † Electronic supplementary information (ESI) available: Details on synthetic procedures and degradation studies, characterization methods and DSC, IR and WAXD data for long-chain polyacetals (PA-18, PA-19, PA-23) and polycarbonates (PC-18, PC-19, PC-23) as well as for randomly long-spaced polyacetals (PA-50.0H to PA-0.0H) and polycarbonates (PC-50.0H to PC-0.0H) are given. See

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“…K 2 CO 3 is a renewable green basic catalyst prepared from CO 2 and KOH. It has been successfully used for polycarbonate synthesis . Moreover, as far as we know, K 2 CO 3 has never been used to prepare polyurethanes by the transurethanization approach.…”

Section: Introductionmentioning

confidence: 99%

“…It has been successfully used for polycarbonate synthesis. 26 Moreover, as far as we know, K 2 CO 3 has never been used to prepare polyurethanes by the transurethanization approach. Furthermore, since only few diisocyanates are used in industry to prepare the broad range of polyurethane materials, the number of new polyurethane materials can be considerably increased through replacing diisocyanates with DMC and diamines.…”

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confidence: 99%

Synthesis and properties of renewable nonisocyanate polyurethanes (NIPUs) from dimethylcarbonate

Duval

Kébir

Charvet

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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Novel fully renewable AA-BB type nonisocyanate polyurethanes (NIPUs) were synthesized using the transurethanization approach. Dicarbamate monomers were prepared by the reaction of a diamine with an excess of dimethylcarbonate (DMC), in presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst. Then, the dicarbamate was reacted with a diol to afford the polymer, in presence of TBD or K 2 CO 3 as catalyst. Several renewable diamines and diols were tested. The two steps were conducted under neat conditions. The obtained Polym. Chem. 2015, 00, 000-000

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Polycarbonates from biorenewable diols via carbonate metathesis polymerization

Cited by 36 publications

References 39 publications

Structure–properties relationship of fatty acid-based thermoplastics as synthetic polymer mimics

Structure–properties relationship of fatty acid-based thermoplastics as synthetic polymer mimics

Physical properties and hydrolytic degradability of polyethylene-like polyacetals and polycarbonates

Synthesis and properties of renewable nonisocyanate polyurethanes (NIPUs) from dimethylcarbonate

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