Polymerization polycarbonates

Keywords Carbon dioxide and epoxides copolymerization Group 13 metal catalysts Group 3 metal catalysts Lactide polymerization Polycarbonate Polylactide... 

FIGURE 23.5 Membrane materials (a, b) organic polymeric polycarbonate and (c) inorganic ceramic, (a and b From personal archive.)... 

Enoue et al. in 1968, first prepared highly polymeric polycarbonate by polymerization of epoxy with zinc compounds such as Et2Zn as the catalysts [96-100]. The polymer is stable up to 180 C [96], Polycarbonate of epoxide with carbon dioxide has been industrially produced from PAC Polymer Company [96]. Since the polycarbonates are biodegradable polymers, they have been investigated as release sustaining materials for drugs [101]. 

Hagenaars AC, Pesce JJ, Bailly C, Wolf BA (2001) Characterization of melt-polymerized polycarbonate preparative fractionation, branching distribution and simulation. Polymer 42 7653-7661... 

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. 

Cychc carbonates are prepared in satisfactory quaUty for anionic polymerization by catalyzed transesterification of neopentyl glycol with diaryl carbonates, followed by tempering and depolymerization. Neopentyl carbonate (5,5-dimethyl-1,3-dioxan-2-one) (6) prepared in this manner has high purity (99.5%) and can be anionically polymerized to polycarbonates with mol wt of 35,000 (39). 

An important direct use of phosgene is in the preparation of polymers. Polycarbonate is the most significant and commercially valuable material (see Polycarbonates). However, the use of phosgene has been described for other polymer systems, eg, fiber-forming polymeric polyketones and polyureas (90,91). 

Transesterification. There has been renewed interest in the transesterification process for preparation of polycarbonate because of the desire to transition technology to environmentally friendly processes. The transesterification process utilizes no solvent during polymerization, producing neat polymer direcdy and thus chlorinated solvents may be entirely eliminated. General Electric operates a polycarbonate plant in Chiba, Japan which produces BPA polycarbonate via this melt process. 

An analogue of the transesterification process has also been demonstrated, in which the diacetate of BPA is transesterified with dimethyl carbonate, producing polycarbonate and methyl acetate (33). Removal of the methyl acetate from the equihbrium drives the reaction to completion. Methanol carbonylation, transesterification using phenol to diphenyl carbonate, and polymerization using BPA is commercially viable. The GE plant is the first to produce polycarbonate via a solventiess and phosgene-free process. 

Polymerization by Transimidization Reaction. Exchange polymerization via equihbrium reactions is commonly practiced for the preparation of polyesters and polycarbonates. The two-step transimidization polymerization of polyimides was described in an early patent (65). The reaction of pyromellitic diimide with diamines in dipolar solvents resulted in poly(amic amide)s that were thermally converted to the polyimides. High molecular weight polyimides were obtained by employing a more reactive bisimide system (66). The intermediate poly(amic ethylcarboamide) was converted to the polyimide at 240°C. 

Monofunctional, cyclohexylamine is used as a polyamide polymerization chain terminator to control polymer molecular weight. 3,3,5-Trimethylcyclohexylamines ate usehil fuel additives, corrosion inhibitors, and biocides (50). Dicyclohexylamine has direct uses as a solvent for cephalosporin antibiotic production, as a corrosion inhibitor, and as a fuel oil additive, in addition to serving as an organic intermediate. Cycloahphatic tertiary amines are used as urethane catalysts (72). Dimethylcyclohexylarnine (DMCHA) is marketed by Air Products as POLYCAT 8 for pour-in-place rigid insulating foam. Methyldicyclohexylamine is POLYCAT 12 used for flexible slabstock and molded foam. DM CHA is also sold as a fuel oil additive, which acts as an antioxidant. StericaHy hindered secondary cycloahphatic amines, specifically dicyclohexylamine, effectively catalyze polycarbonate polymerization (73). 

When the catalyst is triethylamine, the yield is nearly 100% cycHc oligomers but if pyridine is used, the polymer is nearly 100% linear. A basic catalyst in the second step, such as lithium stearate or an organic titanate [bis-(acetylacetonato)diisopropoxytitanium], produces a polycarbonate with a molecular weight of 250,000—300,000 when polymerized at 300°C for 30 min. A fiber glass composite has been prepared using this basic procedure (39). 

Acrylic Resins. The first synthetic polymer denture material, used throughout much of the 20th century, was based on the discovery of vulcanised mbber in 1839. Other polymers explored for denture and other dental uses have included ceUuloid, phenolformaldehyde resins, and vinyl chloride copolymers. Polystyrene, polycarbonates, polyurethanes, and acryHc resins have also been used for dental polymers. Because of the unique combination of properties, eg, aesthetics and ease of fabrication, acryHc resins based on methyl methacrylate and its polymer and/or copolymers have received the most attention since their introduction in 1937. However, deficiencies include excessive polymerization shrinkage and poor abrasion resistance. Polymers used in dental appHcation should have minimal dimensional changes during and subsequent to polymerization exceUent chemical, physical, and color stabiHty processabiHty and biocompatibiHty and the abiHty to blend with contiguous tissues. 

Bisphenol A Polycarbonate Resins. These resins are manufactured by interfacial polymerization (84,85). A small amount of resin is produced by melt-polymerization of bisphenol with diphenyl carbonate in Russia and the People s RepubHc of China. Melt technology continues to be developmental in Japan and the West, but no commercial activities have started-up to date, although some were active in the late 1960s. No reports of solvent-based PC manufacture have been received. 

While polymeric surfaces with relatively high surface energies (e.g. polyimides, ABS, polycarbonate, polyamides) can be adhered to readily without surface treatment, low surface energy polymers such as olefins, silicones, and fluoropolymers require surface treatments to increase the surface energy. Various oxidation techniques (such as flame, corona, plasma treatment, or chromic acid etching) allow strong bonds to be obtained to such polymers. 

Just as many small-molecule materials, polymers also form glasses [4]. Actually, most polymeric materials of everyday use are made of polymer glasses, polystyrene (PS) cups or compact discs made of polycarbonates, for instance. In many respects polymer glasses are very similar to small-molecule glasses, and there is nothing special about them. However, on the other hand, the special aspects of polymer materials allow specific studies beyond characteristic studies on small-molecule glasses. 

In multiphase polymeric systems, the properties of the end products do not solely depend on the properties of the pure components, but other various parameters also have a great impact (Fig. 1). In order to emphasize these factors, the following systems are taken into consideration (I) elastomer toughened styrene system, (2) elastomer toughened polycarbonate blends, and (3) direct reactive blend processing. 

Though less prevalent than addition polymerization, condensation polymerization produces important polymers such as polyesters, polyamides (nylons), polycarbonates, polyurethanes, and phenol-formaldehyde resins (Chapter 12). 

Membranes used for the pressure driven separation processes, microfiltration (MF), ultrafiltration (UF) and reverse osmosis (RO), as well as those used for dialysis, are most commonly made of polymeric materials. Initially most such membranes were cellulosic in nature. These ate now being replaced by polyamide, polysulphone, polycarbonate and several other advanced polymers. These synthetic polymers have improved chemical stability and better resistance to microbial degradation. Membranes have most commonly been produced by a form of phase inversion known as immersion precipitation.11 This process has four main steps ... 

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-... 

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