Polycarbonate precursors

Cycloaddition and transesterification reactions to give polycarbonate precursors (174)... 

Srivastava, R. Srinivas, D. Ratnasamy, P. Synthesis of Polycarbonate Precursors over Titanosihcate Molecular sieves. Catal. Lett. 2003, 91, 133-137. 

Organic solvents are most commonly used, and encapsulating polymers include ethylcellu-lose, NC, polvvinylidene chloride, polystyrene, polycarbonate, polymethylmethacrylate, polyvinyl acetate and others. Inter facial polymerization produces a polymer such as nylon at the interface between layered solns of two precursor materials such as (in the case of a nylon) a diamine and a diacid (Refs 3 11). If the particle or drop-... 

Aluminum porphyrins with alkoxide, carboxylate, or enolate can also activate CO2, some catalytically. For example, Al(TPP)OMe (prepared from Al(TPP)Et with methanol) can bring about the catalytic formation of cyclic carbonate or polycarbonate from CO2 and epoxide [Eq. (6)], ° - and Al(TPP)OAc catalyzes the formation of carbamic esters from CO2, dialkylamines, and epoxide. Neither of the reactions requires activation by visible light, in contrast to the reactions involving the alkylaluminum precursors. Another key difference is that the ethyl group in Al(TPP)Et remains in the propionate product after CO2 insertion, whereas the methoxide or acetate precursors in the other reactions do not, indicating that quite different mechanisms are possibly operating in these processes. Most of this chemistry has been followed via spectroscopic (IR and H NMR) observation of the aluminum porphyrin species, and by organic product analysis, and relatively little is known about the details of the CO2 activation steps. 

Polycarbonates, both aliphatic and aromatic, have been prepared by the ring opening polymerization of cyclic monomers or oligomers [22], Cyclic monomeric precursors are more common in aliphatic polycarbonates, but because of steric reasons aromatic polycarbonates can only be prepared from cyclic oligomers. Both cationic and anionic initiators have been examined and anionic initiators appear to be more efficient. 

Mercuric-5-nitrotetrazole [Structure (2.13)] was prepared according to the methods reported by Gilligan et al. [14] and Redman and Spear [15]. Thus, 5-aminotetrazole was treated with sodium nitrite and copper sulfate to obtain Cu(NT)2HNT-4H20 (where NT nitrotetrazole). The copper salt was subsequently converted to the ethylene diamine complex MNT was then obtained by treating the complex with mercuric nitrate in HN03 medium. The precursors and final product were air dried. The synthesis of these compounds is carried out in a fume hood behind a protective polycarbonate shield in a stainless steel reaction vessel. 

Oligocyclic monomers are useful precursors to high-molar-mass polycarbonates (Brunelle et al., 1994 Otaige, 1997), because they have a low... 

Among the emerging pollutants of industrial origin, Bisphenol A [2,2 bis(4-hydroxydiphenyl)pro-pane] (BPA) has special relevance since it was one of the first chemicals discovered to mimic estrogens as endocrine disrupters.147 This compound was first reported by Dianin in 1891.1411 BPA is produced in large quantities worldwide, mainly for the preparation of polycarbonates, epoxy resins, and unsaturated polyester-styrene resins.149 The final products are used in many ways, such as coatings on cans, powder paints, additives in thermal paper, in dental composite fillings, and even as antioxidants in plasticizers or polymerization inhibitors in polyvinyl chloride (PVC). To a minor extent, BPA is also used as precursor for flame retardants such as tetrabromobisphenol A or tetrabromobisphenol-S-bis(2,3-dibromopropyl) ether.150 This substance can enter the environment... 

The most commonly used hard templates are anodic aluminum oxide (AAO) and track-etched polycarbonate membranes, both of which are porous structured and commercially available. The pore size and thickness of the membranes can be well controlled, which then determine the dimension of the products templated by them. The pores in the AAO films prepared electrochemically from aluminum metals form a regular hexagonal array, with diameters of 200 nm commercially available. Smaller pore diameters down to 5 nm have also been reported (Martin 1995). Without external influences, capillary force is the main driving force for the Ti-precursor species to enter the pores of the templates. When the pore size is very small, electrochemical techniques have been employed to enhance the mass transfer into the nanopores (Limmer et al. 2002). 

This experimental investigation focuses on the preparation of polycrystalline magnesium oxide nanorods via capillary-driven infiltration of a precursor solution into the cylindrical pores of a track-etched polycarbonate membrane followed by thennal decomposition procedure. The nanomaterial was fully characterized by SEM, EDX,... 

Of specific potential are several processes which presently experience (or even surpass) the pilot-plant stage vinyl acetate from syngas, precursors of polymers such as polycarbonate and polyurethanes via reductive or oxidative carbonylation, methyl mediacrylates and adipic acid through alternative routes, polypropene and COCs (cf. Section 4.1.14) by means of metallocenes (cf. Section 2.3.1.5) - new routes have been opened in all these cases. The last-named example emphasizes in an almost classical way the principle of tailor-making novel, optimized, homogeneous catalysts. Chapter 3 should again be consulted for details. 

The sol-gel method is a low temperature synthesis route for complex oxides [42]. It can be used to make complex functional oxide nanowires inside the pores of templates. In addition to the sol-gel method precursor-based solution deposition routes can also be used for nanostructure formation [43]. In both cases a postdeposition high temperature anneal (>500-600 °C) is needed to form the required stoichiometric phase. Due to the requirement of a high temperature anneal, alumina templates are used as the polycarbonate membranes decompose at a much lower temperature. For chemical solution deposition the membrane is dipped directly into the precursor solution. For sol-gel growth generally the required sol is prepared and the template is put into the sol for a required period (e.g. 0.5-1 h). After removing the membrane from the sol it is dried and then annealed at higher temperature before the required phase is formed. A schematic of the sol-gel route is shown in Figure 21.10. 

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