Isocyanate- and Phosgene-Free Routes to Polyfunctional Cyclic Carbonates and Green Polyurethanes by Fixation of Carbon Dioxide

• Published in: Macromolecular rapid communications. Vol. 35; no. 14; pp. 1238 - 1254
• Main Authors: Blattmann, Hannes, Fleischer, Maria, Bähr, Moritz, Mülhaupt, Rolf
• Format: Journal Article
• Language: English
• Published: Weinheim Blackwell Publishing Ltd 01.07.2014; Wiley
• Subjects: Applied sciences; Architecture; Biocompatibility; Biocompatible Materials - chemical synthesis; Biocompatible Materials - chemistry; Carbon dioxide; Carbon Dioxide - chemistry; carbon dioxide fixation; Carbonates; Coatings; cyclic carbonate; Epoxy Compounds - chemistry; Exact sciences and technology; Fixation; functional polymers; green chemistry; Green Chemistry Technology; Isocyanates - chemistry; Organic polymers; Phosgene - chemistry; Physicochemistry of polymers; Polycarboxylate Cement - chemical synthesis; Polycarboxylate Cement - chemistry; Polycondensation; Polymerization; Polyols; polyurethane; Polyurethane resins; Polyurethanes - chemical synthesis; Polyurethanes - chemistry; Preparation, kinetics, thermodynamics, mechanism and catalysts; cyclic carbonate; State of the art; Organic carbonate; Oxygen heterocycle; functional polymers; Polyaddition; Functional polymer; carbon dioxide fixation; Alcohol polymer; Diamine; Preparation; Polyurethane; Green chemistry; polyurethane; green chemistry
• ISSN: 1022-1336; 1521-3927; 1521-3927
• DOI: 10.1002/marc.201400209

The catalytic chemical fixation of carbon dioxide by carbonation of oxiranes, oxetanes, and polyols represents a very versatile green chemistry route to environmentally benign di‐ and polyfunctional cyclic carbonates as intermediates for the formation of non‐isocyanate poly­urethane (NIPU). Two synthetic pathways lead to NIPU thermoplastics and thermosets: i) polycondensation of diacarbamates or acyclic dicarbonates with diols or diamines, respectively, and ii) polyaddition by ring‐opening polymerization of di‐ and polyfunctional cyclic carbonates with di‐ and polyamines. The absence of hazardous and highly moisture‐sensitive isocyanates as intermediates eliminates the need for special safety precautions, drying and handling procedures. Incorporated into polymer backbones and side chains, carbonate groups enable facile tailoring of a great variety of urethane‐functional polymers. As compared with conventional polyurethanes, ring‐opening polymerization of polyfunctional cyclic carbonates affords polyhydroxyurethanes with unconventional architectures including NIPUs containing carbohydrate segments. NIPU/epoxy hybrid coatings can be applied on wet surfaces and exhibit improved adhesion, thermal stability and wear resistance. Combining chemical with biological carbon dioxide fixation affords 100% bio‐based NIPUs derived from plant oils, terpenes, carbohydrates, and bio polyols. Biocompatible and biodegradable NIPU as well as NIPU biocomposites hold great promise for biomedical applications. Exploiting carbon dioxide as feedstock for polyfunctional cyclic carbonates affords a versatile molecular tool box for producing linear and cross‐linked non‐isocyanate polyurethanes (NIPUs) with unconventional architectures. This green route to NIPUs holds great promise with respect to tailoring coatings, adhesives, sealants, foams as well as bio‐based polyurethanes, and biocompatible and bio‐functional NIPUs for biomedical applications.