Polycarbonate Formation

An important industrial reaction and one of the earliest applications of phase transfer catalysis by quaternary ammonium salts is the synthesis of polycarbonates [13]. Typically, 2,2-(4,4 -dihydroxydiphenyl)propane(bisphenol A) is dissolved in concentrated aqueous sodium hydroxide and exposed to a dichloromethane solution of phosgene. Salts such as benzyltriethylammonium chloride or tertiary amines catalyze the condensation polymerization [13—18]. The two phase polymerization is formulated in equation 6.6. 

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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... 

Note that the essential step of polycarbonate formation involves the reaction sequence shown below ... 

Cr(tpp)Cl], linked to Argogel chloride beads see Section 4.6.5.2.10 catalyst for polycarbonate formation 505,1006... 

Studies on the mechanism of interfacial polycarbonate formation are complicated by its interfacial nature, involving four phases. In addition, effects such... 

Polycarbonate formation, using these oligomeric polyformal mixtures in combination with BPA (and phenol as a chain stopper) was carried out using a two-phased phosgenation procedure to give the block copolyformal-carbonates 16. 

Self-catalyzed esterification is often too slow to be of practical use, especially because hydroxyl-terminated polymers are either sought or are a consequence of the process (aromatic polyesterifications are carried out with a large excess of hydroxyls at the beginning of the process, because of the low solubility of the diadd), and strong protic acids are not advisable, as they would catalyze polymer hydrolysis if allowed to remain with the polymer. Even volatile catalysts such as methanesul-fonic acid are avoided. Therefore, metallic salts are currently used as catalysts, both for esterification and alcoholysis. Strong bases, such as lithium hydroxide, can also be used, but for alcoholysis only (as in polycarbonate formation). 

Scheme 3.7. Overall stoichiometry of bisphenol A polycarbonate formation.

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

Within the scope of thermoelectric nanostructures, Sima et al. [161] prepared nanorod (fibril) and microtube (tubule) arrays of PbSei. , Tej by potentiostatic electrodeposition from nitric acid solutions of Pb(N03)2, H2Se03, and Te02, using a 30 fim thick polycarbonate track-etch membrane, with pores 100-2,000 nm in diameter, as template (Cu supported). After electrodeposition the polymer membrane was dissolved in CH2CI2. Solid rods were obtained in membranes with small pores, and hollow tubes in those with large pores. The formation of microtubes rather than nanorods in the larger pores was attributed to the higher deposition current. 

The in vitro system we have been using to study the transepithelial transport is cultured Madin-Darby canine kidney (MDCK) epithelial cells (11). When cultured on microporous polycarbonate filters (Transwell, Costar, Cambridge, MA), MDCK cells will develop into monolayers mimicking the mucosal epithelium (11). When these cells reach confluence, tight junctions will be established between the cells, and free diffusion of solutes across the cell monolayer will be markedly inhibited. Tight junction formation can be monitored by measuring the transepithelial electrical resistance (TEER) across the cell monolayers. In Figure 1, MDCK cells were seeded at 2 X 104 cells per well in Transwells (0.4 p pore size) as described previously. TEER and 14C-sucrose transport were measured daily. To determine 14C-sucrose... 

The most desirable property of polycarbonates is their high ductility on impact, relative to other engineering polymers in the unmodified state. There is no consensus on the mechanism of ductility researchers continue to explore this behavior through molecular dynamics studies of chain segment motion during the formation of crazes and propagation of the failure. 

Boronic acids (69 and 70) (Fig. 45) with more than one boronic acid functionality are known to form a polymer system on thermolysis through the elimination of water.93 Specifically, they form a boroxine (a boron ring system) glass that could lead to high char formation on burning. Tour and co-workers have reported the synthesis of several aromatic boronic acids and the preparation of their blends with acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) resins. When the materials were tested for bum resistance using the UL-94 flame test, the bum times for the ABS samples were found to exceed 5 minutes, thereby showing unusual resistance to consumption by fire.94... 

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