Polycarbonates carbonic ester polymers

Aliphatic polycarbonates have few characteristics which make them potentially valuable materials but study of various aromatic polycarbonates is instructive even if not of immediate commercial significance. Although bisphenol A polycarbonates still show the best all-round properties other carbonic ester polymers have been prepared which are outstandingly good in one or two specific properties. For example, some materials have better heat resistance, some have better resistance to hydrolysis, some have greater solvent resistance whilst others are less permeable to gases. 

By reaction of polyhydroxy compounds with a carbonic acid derivative, a series of related polymers may be produced with carbonate (—0 C0 0—) linkages, the polymers being referred to as polycarbonates. Carbonic acid, C0(0H)2, itself does not exist in the free state but by means of ester exchange Figure 20.1) (1) and phosgenation techniques (II) it is possible to produce useful products. 

Particularly noteworthy are the tyrosine-derived polycarbonates (27), a family of polymers based on alkyl esters of desaminotyrosyl-tyrosine. The lead polymer in this family is poly[desaminotyrosyl-tyrosine ethyl ester (DTE) carbonate], a polymer derived from desaminotyrosyl-tyrosine ethyl ester. Other polymers in this series of tyrosine-derived polycarbonates are poly[desaminotyrosyl-tyrosine butyl ester (DTB) carbonate], poly[desaminotyrosyl-tyrosine hexyl ester (DTH) carbonate], and poly [desaminotyrosyl-tyrosine octyl ester (DTO) carbonate], where the letters B, H, and O indicate the presence of butyl, hexyl, or octyl ester pendent chains, respectively. 

Polycarbonates and Polyurethanes The chemistry of carbonic acid derivatives is particularly important because two large classes of polymers are bonded by linkages containing these functional groups the polycarbonates and the polyurethanes. Polycarbonates are polymers bonded by the carbonate ester linkage, and polyurethanes are polymers bonded by the carbamate ester linkage. Lexan polycarbonate is a strong, clear polymer used in bulletproof windows and crash helmets. The diol used to make Lexan is a phenol called bisphenol A, a common intermediate in polyester and polyurethane synthesis. 

Transesterification of diphenyl carbonate and bisphenol A. The final step in the nonphosgenation process for polycarbonates is the reaction of bisphenol A (BPA) and the carbonate ester, diphenyl carbonate (DPC). Research has focused on the transesterification melt process because it has the advantage over the conventional interfacial process of allowing the reaction of the diphenyl carbonate and bisphenol A to take place completely in the liquid phase. The disadvantage of this approach is that elevated temperatures are needed to ensure that unreacted DPC and BPA are completely volatilized from the product. Only a lower molecular weight (30,000-50,000) polymer can be made in this way. Typical molecular weights for polycarbonate produced by phosgenation in the interfacial pro-... 

High molecular weight, lightstabUizir compounds for imparting improved resistance to ultraviolet radiation to polycarbonate-based polymers are prepared by interfacial condensation of phosgene or its derivatives or carbonate esters with bisphenol derivatives [270]. 

Theoretically, the formation of polycarbonate by ester interchange between bisphenol A and diphenyl carbonate, as shown above, requires equimolar quantities of reagents. However, if equimolar quantities are used the polymer is liable to be discoloured. The reason for this lies in the thermal instability of bisphenol A. In the presence of alkali at temperatures above 150°C, bisphenol A decomposes into p-isopropenyl phenol and phenol ... 

Nearly all of the polymers produced by step-growth polymerization contain heteroatoms and/or aromatic rings in the backbone. One exception is polymers produced from acyclic diene metathesis (ADMET) polymerization.22 Hydrocarbon polymers with carbon-carbon double bonds are readily produced using ADMET polymerization techniques. Polyesters, polycarbonates, polyamides, and polyurethanes can be produced from aliphatic monomers with appropriate functional groups (Fig. 1.1). In these aliphatic polymers, the concentration of the linking groups (ester, carbonate, amide, or urethane) in the backbone greatly influences the physical properties. 

Whereas the tensile strength was not a sensitive function of the monomer structure, the tensile modulus (Young s Modulus) was clearly related to the monomer structure. This is expected since the tensile modulus is a measure of the polymer s resistance to deformation and is related to the "stiffness" of a polymeric material. The highest tensile modulus (22,000 kg/cm2,2.2 GPa) was measured for poly(BPA iminocarbonate). Replacement of BPA by Dat-Tyr-Hex reduced the tensile modulus significantly. This observation can possibly be attributed to the presence of the long hexyl ester pendent chain in Dat-Tyr-Hex. Generally, the polyiminocarbonates were somewhat "stiffer" than the corresponding polycarbonates. Thus, the tensile moduli of poly(Dat-Tyr-Hex iminocarbonate) and poly(Dat-Tyr-Hex carbonate) were 16,300 kg/cm2 (1.6 GPa) and 13,900 kg/cm2 (1.3 GPa) respectively. 

A similiar comparison can be made between permeability data of polyesters and polycarbonates containing "polyester-like" monomers. For example, polycarbonates 26 and 27, which contain predominantly bisphenols which are structurally similiar to the repeat unit (circled) of an alkyl terephthalate polymer (PBT), possess essentially the same low permeability as that polyester (Table V). Furthermore, there has been a recent announcement (3 ) that aliphatic polycarbonates, such as polypropylene and polyethylenecarbonate, are being developed as potential gas barrier materials. In summary these results suggest that the relative low permeabilities of commercial polyesters and high permeabilities of commerical polycarbonates are not a direct consequence of the ester or carbonate links, but are due instead to the structure of the monomers they are prepared from, i.e., the aliphatic diol and aromatic bisphenol, respectively. 

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