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DREAM POLYMERS FUNDED PROJECTS claim to be able to synthesise alternating polymethylene carbonate polyols from tertiary amines and an aqueous formaldehyde solution or a suspen- sion of polymeric paraformaldehyde in organic solvents with dry ice as the CO2 source. At temperatures from 120 °C to 175 °C, reaction times ranging from 12 hours to 5 days were required to achieve the maximum yield of 39% of product. The details published about the structures of the co-oligomers produced and the synthetic routes need to be re-examined and assessed. Furthermore, the space-time yields achieved are inadequate for industrial applications. The physical properties and the chemical stability of the prod- ucts are only partially described in the publications. The ‘Dream Polymers’ project therefore aimed to develop a process that would enable polymeth- ylene carbonate polyols to be produced with space-time yields suitable for industrial applications. Formaldehyde Formaldehyde is available as a monomeric gas in industrial quantities and its properties are well established in the scientific literature.3,4,5 However, because of its very high propensity to undergo polymerisation, monomeric formalde- hyde is difficult to store and transport and is generally only available locally. In the laboratory environment, formaldehyde is commonly used either in the form of an aqueous solution, or the linear polymer paraformaldehyde or the trimer trioxane. Paraformaldehyde is a short-chain polymer of formaldehyde. Paraformaldehyde depolymerises to form monomeric formaldehyde in the presence of water or acids or when heated. Trioxane represents the least reac- tive form of formaldehyde. High temperatures (150–200 °C) are needed for the thermal dissociation into formaldehyde. If aqueous formaldehyde solutions or paraformaldehyde are to be used in chemical reactions certain require- ments need to be met, e.g. water and/or methanol-tolerance, suitable condi- tions for the depolymerisation of paraformaldehyde, suppression of undesir- able side reactions, etc. 1.9.2 Project description The research project was concerned with the chemical conversion of CO2 using formaldehyde in order to provide access to polymethylene carbonate polyols synthesised completely from molecular building blocks that have themselves been generated either directly or indirectly from CO2. Low mole- cular weight variants of these newly synthesised substances were tested for their suitability to be processed into polyurethanes, while the high molecular weight species were studied as polyoxymethylene (POM) thermoplastics. The project was split into five work packages to be carried out by the respect- ive project partners. Work Package 1 (WP1) ‘Primary Materials’ described the 75PDF Image | Chemical Processes and Use of CO2
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