The Reaction Injection Molding (RIM) technology has made it possible to master the fast reaction of di‐ and polyamines with di‐ and polyisocyanates, leading to the preferred polyurea structure. Telechelics with amino end groups are gaining increased interest for the manufacture of polyurethane‐polyurea materials by this technology. They make it possible to substitute all urethane groups in the elastomers with urea groups. The telechelics which are considered are amine‐terminated polyethers (ATPE) and polyesters based on the typical soft‐segment forming polycondensation polymers which are widely used in polyurethane chemistry.
Isocyanate‐terminated prepolymers of toluene diisocyanate and polyether polyols can be hydrolyzed in aqueous alkaline media via the carbamate intermediate to the amineterminated prepolymers. The reactivity of these aromatic ATPEs was ideally fit for the RIM process. ATPEs by the hydrolysis process are somewhat limited if products with low viscosities are required. In the reaction of chloro‐nitrobenzenes with polyether polyols followed by the hydrogenation of the nitro groups of the terminal phenoxy moieties, we found a path for the synthesis of low viscosity aromatic ATPEs. Capping of polyether polyols with acetoacetate groups and subsequent reaction of the acetoacetylated polyethers with amines, leads to polyethers with terminal imine or enamine groups, which are derivates of aminocrotonic acid. We determined that this approach is a universal method for the synthesis of a large variety of aromatic as well as aliphatic ATPEs with low viscosities. Trifluoroacetic acid turned out to be the ideal catalyst for the reaction of the acetoacetylated polyethers with aromatic diamines, one amino group forming the imine link, the second one remaining intact and providing the desired reactivity towards isocyanates. Aliphatic diamines do not require a catalyst for this reaction. They lead to aminocrotonates with aliphatic amino groups that have high reactivity towards isocyanates, which is to be expected from aliphatic amines. The reaction of the chloroformates of polyether polyols with diamines can also be used to synthesize a variety of ATPEs. We recently developed an approach to low viscosity ATPEs having secondary amino end groups. The hydroxyl groups of the polyether polyols are converted to chloride or methanesulfonyl. The polyethers terminated with these leaving‐groups are reacted with primary aliphatic or aromatic amines to give the secondary ATPEs in very good yields.
Nanoscale metal oxide particles have been synthesized by using a novel method which combines laser vaporization of metal targets with controlled condensation in a diffusion cloud chamber. The following oxides have been synthesized: ZnO, SiO2, Fe2O3, Bi2O3, PdO, NiO, AgO, TeO, Sb2O3, TiO2, ZrO2, A12O3, CuO, In203, SnO2, V2O5 and MgO. With this method, the size of the particles can be conveniently controlled by careful control of the degree of supersaturation which is accomplished by adjusting the temperature gradient, total pressure, and partial pressure of the metal vapor generated by laser vaporization in a diffusion cloud chamber. The microscale structures of the SiO2 and A1203 particles exhibit interesting web-like matrices with a significant volume of vacancies. These materials may have special applications in catalysis and as reinforcing agents for liquid polymers.
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