A perspective approach to sustainable routes for non-isocyanate polyurethanes

Cornille, Adrien; Auvergne, Rémi; Figovsky, Oleg; Boutevin, Bernard; Caillol, Sylvain

doi:10.1016/j.eurpolymj.2016.11.027

Cited by 407 publications

(394 citation statements)

References 142 publications

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“…Consequently, there is a need for safer synthetic methods or replacements with less hazardous and fossil‐based chemicals. The most promising method to generate nonisocyanate polyurethanes (NIPUs) is the aminolysis of cyclic carbonates derived from renewable resources . For this purpose, various biobased building blocks of renewable origin such as terpene, vegetable oil, cellulose, and lignin have already been used.…”

Section: Introductionmentioning

confidence: 99%

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

Kühnel¹,

Saake²,

Lehnen

2018

Macro Chemistry & Physics

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Herein, a novel synthesis of a fully renewable lignin‐based building block equipped with cyclic carbonate functionalities is presented. In an efficient two‐step procedure, organosolv lignin from ethanol–water pulping of beech wood is oxyalkylated with glycerol carbonate to insert adjacent hydroxyl groups. The oxyalkylated lignin is then reacted via transesterification with dimethyl carbonate or ethylene carbonate in dimethyl sulfoxide under alkaline conditions producing cyclic carbonate functionalized lignin. This transesterification is studied as a function of time, catalyst type, and catalyst amount using NMR spectroscopy as well as size exclusion chromatography. Transesterification reactions with K2CO3 as catalyst (0.4 eq.) afford lignin‐based cyclic carbonate with almost complete conversion (96%) within 6 h, as analyzed by 31P and 13C NMR spectroscopy. This green building block represents a reactive prepolymer for the synthesis of nonisocyanate polyurethanes.

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Section: Introductionmentioning

confidence: 99%

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

Kühnel¹,

Saake²,

Lehnen

2018

Macro Chemistry & Physics

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“…11 Besides, the synthesis of isocyanates, for methane dipheyl 4,4 0 -diisocyante as example, requires toxic phosgene. reviews [14][15][16][17][18] reported comprehensive studies and summarized the reaction between 5CC and amines. It ts in with the viewpoint of "green chemistry" quite well.…”

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confidence: 99%

Non-isocyanate polyurethane/epoxy hybrid materials with different and controlled architectures prepared from a CO₂-sourced monomer and epoxy via an environmentally-friendly route

Wang

et al. 2017

RSC Adv.

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Polyurethane/epoxy hybrid materials from CO 2 -sourced monomer were prepared via an environmentallyfriendly and non-toxic route, which avioded the use of toxic isocyanate. A series of non-isocyanate polyurethane (NIPU)/epoxy hybrid materials, with different and controlled architectures, were synthesized from CO 2 , polypropylene glycol diglycidyl ether (PPGDGE), amines and diglycidyl ether of bisphenol-A (BADGE). Around 12 wt% CO 2 was incorporated into PPGDGE to form a five-membered cyclic carbonate (5CC-PPGDGE). The complete conversion and selectivity of PPGDGE were obtained.The kinetics of 5CC-PPGDGE was investigated by reacting it with 1,2-ethylenediamine (EDA) at different temperatures. NH 2 -terminated pre-polymers were obtained by reacting 5CC-PPGDGE with various excessive amines. Finally, the hybrid materials were obtained by curing pre-polymers with BADGE. The results showed that a high content of amine with more functional groups led to better mechanical performances than diamine-based hybrid materials. This is the first time that architectures have been controlled by altering the amine ratio and functionality. And these hybrid materials exhibited satisfactory mechanical performances. The DETA-based and TETA-based materials with high amine ratio exhibited a tensile strength of 15.0 MPa and 12.5 MPa, accompanied with elongation at break of 151.3% and 170.9%, respectively. The gel content, glass transition temperature and thermodynamic stability went up first and then declined with the increase of amine ratio, which demonstrated the architectures of hybrid materials ranged from defective to cross-linked and linear structures.

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“…[1][2][3] PUs are usually prepared by reacting polyisocyanates and polyols, and polyisocyanates prepared with diisocyanate are toxic because of their numerous NCO groups and residual isocyanate monomers. [1][2][3] PUs are usually prepared by reacting polyisocyanates and polyols, and polyisocyanates prepared with diisocyanate are toxic because of their numerous NCO groups and residual isocyanate monomers.…”

Section: Introductionmentioning

confidence: 99%

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

Dai

Tang

et al. 2019

J of Applied Polymer Sci

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Cyclic carbonates reacted with diamines or polyamines have been proposed as a greener and safer method to prepare free isocyanate polyurethane coatings. Here, five kinds of bis(cyclic carbonate)s (TDC: toluene bis(cyclic carbonate), MDC: 4,4 0diphenylmethane bis(cyclic carbonate), IPDC: isophorone bis(cyclic carbonate), HMDC: 4,4 0 -methylenebis(cyclohexyl cyclic carbonate), HDC: hexamethylene bis(cyclic carbonate)) were prepared by reacting glycerol carbonate with diisocyanate under atmospheric pressure. Their structures were verified by 1 H-NMR and 13 C-NMR. These difunctional cyclic carbonates were then reacted with several amines to prepare new polyhydroxyurethane (PHU) coatings, and the film properties were tested. It was found that PHUs based on aromatic and alicyclic structures including TDC, MDC, IPDC, and HMDC displayed high hardness but had poor flexibility and impact resistance, whereas PHUs based on aliphatic structures such as HDC exhibited good flexibility and impact resistance and low hardness. When the length of the alkyl groups in the amine curing agents increased, the impact resistance and flexibility of the PHUs increased, but their pencil hardness decreased. PHUs from TDC, MDC, and IPDC had excellent chemical resistance, but the PHUs from HMDC and HDC had less chemical resistance. Some films displayed excellent properties including 4H pencil hardness, 100 cm kg impact resistance, and excellent flexibility. Some PHUs exhibited good thermal stability, with T 5% values all above 242 C.

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A perspective approach to sustainable routes for non-isocyanate polyurethanes

Cited by 407 publications

References 142 publications

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

Non-isocyanate polyurethane/epoxy hybrid materials with different and controlled architectures prepared from a CO₂-sourced monomer and epoxy via an environmentally-friendly route

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

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A perspective approach to sustainable routes for non-isocyanate polyurethanes

Cited by 407 publications

References 142 publications

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

A New Environmentally Friendly Approach to Lignin‐Based Cyclic Carbonates

Non-isocyanate polyurethane/epoxy hybrid materials with different and controlled architectures prepared from a CO2-sourced monomer and epoxy via an environmentally-friendly route

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

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Non-isocyanate polyurethane/epoxy hybrid materials with different and controlled architectures prepared from a CO₂-sourced monomer and epoxy via an environmentally-friendly route