Linear polyurethane elastomers are block copolymers which are elastomeric because they are phase separated. The soft block is derived from a hydroxy terminated telechelic polymer, frequently a polyether or polyester of a molecular weight less than 3000 and a glass transition temperature well below room temperature. The hard block, having a Tg above room temperature, consists of a diisocyanate and a diol. Most frequently the diisocyanate is aromatic and the diol is 1,4-butanediol. The elastomers produced are frequently opaque and then yellow in storage due to the presence of the aromatic rings. For applications where transparency and nonyellowing are important, aliphatic diisocyanates are the compounds of choice. One such diisocyanate is methylene bis(4-cyclohexyl-isocyanate), which is conveniently called H12MDI. It is prepared from the same diamine as methylene dianiline diisocyanate (MDI), but the aromatic rings are hydrogenated before phosgenation. The hydrogenation leads to a mixture of three aliphatic diamine isomers. Phosgenation leads to a diisocyanate which is a mixture of the three isomers shown in Figure 1. The isomer content is adjusted by the manufacturer, and the product received is a liquid. Another example of a diisocyanate which is marketed as a mixture is toluene diisocyanate, an 80:20 mixture of the 2,4:2,6 isomers being the most common. The aromatic diisocyanates are planar molecules or bent planar molecules like MDI. The H12MDI is also bent, but does not contain planar rings. Even if polymers from one pure diisocyanate isomer are examined, the cycloaliphatic compounds are much less likely to form highly ordered or crystalline regions in the hard-segment phase due to the greater difficulty in packing correctly. A desire to know the isomer composition of the diisocyanate and what effect the isomer composition has on the properties of the elastomers led to this study. Mixtures of the isomers varying from approximately 10% of the trans-trans isomer up to 95% (t-t) have been prepared and the properties of polyurethanes prepared from them have been studied.
Lewis acid catalysis and nucleophilic carbene catalysis are complementary fundamental concepts to accelerate and control chemical reactions of aldehyde substrates. Their efficient merger has recently been achieved using two separate catalyst species. The present report describes our efforts to develop a cooperative catalyst system which incorporates both features – Lewis acid and nucleophilic NHC – within the same catalyst entity. To generate free carbene moieties under very mild conditions, Ag‐NHC complexes were formed releasing the nucleophilic carbene upon treatment with PPh3. The result is the formation of an enol‐δ‐lactone as new enal dimerization product. Silver is essential for the reactivity mode thus suggesting that it plays a double role in the catalytic event.
Acrylonitrile (ACN) is widely used as monomer in the synthesis of polymers and carbon fibers. Nowadays, its production is based on fossil resources. Herein, an alternative process based on renewable resources is presented. Lactic acid (LA), which can be obtained by fermentation of biomass, was converted to ACN in two steps with an overall selectivity of 57 %. In the first step, a direct amidation of LA in the presence of water was conducted at 230 °C. Zeolites can catalyze the formation of lactamide, and a selectivity of 92 % was reached at 33 % conversion with NH4‐ZSM‐5. In the second step, the dehydration of lactamide to ACN was performed with acetic anhydride, and an ACN selectivity of 62 % was achieved at full conversion.
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