Polycarbonates complexes

In the case of polar polymers the situation is more complex, since there are a large number of dipoles attached to one chain. These dipoles may either be attached to the main chain (as with poly(vinyl chloride), polyesters and polycarbonates) or the polar groups may not be directly attached to the main chain and the dipoles may, to some extent, rotate independently of it, e.g. as with poly(methyl methacrylate). 

A variety of synthetic polymers, including polycarbonate resins, substituted olefins, and polyelectrolyte complexes, are employed as ultrafiltration membranes. Many of these membranes can be handled dry, have superior organic solvent resistance, and are less sensitive to temperature and pH than cellulose acetate, which is widely used in RO systems. 

The pace of development has increased with the commercialization of more engineering plastics and high performance plastics that were developed for load-bearing applications, functional products, and products with tailored property distributions. Polycarbonate compact discs, for example, are molded into a very simple shape, but upon characterization reveal a distribution of highly complex optical properties requiring extremely tight dimension and tolerance controls (3,223). 

Oxidative carbonylation generates a number of important compounds and materials such as ureas, carbamates, 2-oxazolidinones, and aromatic polycarbonates. The [CuX(IPr)] complexes 38-X (X = Cl, Br, I) were tested as catalysts for the oxidative carbonylation of amino alcohols by Xia and co-workers [43]. Complex 38-1 is the first catalyst to selectively prepare ureas, carbamates, and 2-oxazolidinones without any additives. The important findings were the identity of the counterion and that the presence of the NHC ligand influenced the conversions. 2-Oxazohdinones were formed from primary amino alcohols in 86-96% yield. Complex 38-1 also catalysed the oxidative carbonylation of primary amines to ureas and carbamates. n-Propylamine, n-butylamine, and t-butylamine were transformed into the... 

Unfortunately, it turns out that the good agreement between simulation and experiment is to some extent fortuituous - attempts aimed at reproducing differences between different polycarbonates (such as TMC-PC and BPA-PC) were less successful [186]. It is clear that the complexity of the chemical structure (Fig. 5.1) makes it very difficult to pin down the precise reasons for the successes and failures of the mapping procedure for this polymer. 

Nelissen [157] has adopted a standard approach for the determination of FRs in polyester compounds (Figure 3.26). The analysis is complicated by spectral interferences of PET/PBT and by the complexity of FR structures, notably DBDPO, Saytex BT 93 W (ethylene-bis-tetrabromophthalimide), PDBS 80, Pyrochek 68PB, Saytex HP7010, Saytex 8010, FR1808, FR 1025, F 2400, BC 52 and BC 58 (brominated polycarbonate oligomers). 

Ito and co-workers observed the formation of zinc bound alkyl carbonates on reaction of carbon dioxide with tetraaza macrocycle zinc complexes in alcohol solvents.456 This reversible reaction was studied by NMR and IR, and proceeds by initial attack of a metal-bound alkoxide species. The metal-bound alkyl carbonate species can be converted into dialkyl carbonate. Spectroscopic studies suggested that some complexes showed monodentate alkyl carbonates, and varying the macrocycle gave a bidentate or bridging carbonate. Darensbourg isolated arylcarbonate compounds from zinc alkoxides as a by-product from work on polycarbonate formation catalysis.343... 

The formation of relatively ill-defined catalysts for epoxide/C02 copolymerization catalysts, arising from the treatment of ZnO with acid anhydrides or monoesters of dicarboxylic acids, has been described in a patent disclosure.968 Employing the perfluoroalkyl ester acid (342) renders the catalyst soluble in supercritical C02.969 At 110°C and 2,000 psi this catalyst mixture performs similarly to the zinc bisphenolates, producing a 96 4 ratio of polycarbonate polyether linkages, with a turnover of 440 g polymer/g [Zn] and a broad polydispersity (Mw/Mn>4). Related aluminum complexes have also been studied and (343) was found to be particularly active. However, selectivity is poor, with a ratio of 1 3.6 polycarbonate polyether.970... 

Equations 1 to 3 show some of fixation reactions of carbon dioxide. Equations la and lb present coupling reactions of CO2 with diene, triene, and alkyne affording lactone and similar molecules [2], in a process catalyzed by low valent transition metal compounds such as nickel(O) and palladium(O) complexes. Another interesting CO2 fixation reaction is copolymerization of CO2 and epoxide yielding polycarbonate (equation 2). This reaction is catalyzed by aluminum porphyrin and zinc diphenoxide [3],... 

Various properties (3,4,5,15,16,18-32) as well as the morphology ( L iJL, 19.,23 33) of such copolymers were investigated in great detail. Synthesis of these block copolymers, while complex, is potentially not costly since materials and methods used in the manufacturing of polysiloxanes and polycarbonates can be used. 

Carbon dioxide is one of the most abundant carbon resources on earth. It reacts with an epoxide to give either a cyclic carbonate or a polycarbonate depending on the substrates and reaction conditions. Kinetic resolution of racemic propylene oxide is reported in the formation of both cyclic carbonate and polycarbonate. The fe ei value defined as ln[l-(conversion)(l+%ee)]/ln[l-(conversion)(l% ee)] reached 6.4 or 5.6 by using a Co(OTs)-salen complex with tetrabutylammonium chloride under neat propylene oxide or using a combination of a Co-salen complex and a chiral DMAP derivative in dichloromethane, respectively. 

Co(OAr)-salen complex [Ar = 2,4-(N02)2CeH3] with tetrabutylammonium chloride under neat propylene oxide, quite similar to the conditions for the cyclic carbonate synthesis, give polycarbonate with fe ei of 3.5. ° Without any additives, the use of Co(OAc)-salen provides the polycaronate with fe ei of 2.8. ... 

It is also possible to desymmetiize a meso epoxide in the alternating copolymerization. Thus, asymmetric alternating copolymerization of cyclohexene oxide with CO2 catalyzed by a dimeric zinc complex provides a polycarbonate in which the diol unit is optically active with 80% ee. (See Scheme 4.24.)... 

Salen Metal Complexes as Catalysts for the Synthesis of Polycarbonates from Cyclic Ethers and Carbon Dioxide... 

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