Copolymers of carbonates

Copolymers of carbon monoxide, carbon dioxide, sulfur dioxide or carbon disulfide are frequently formed in combination with oxiranes, thiiranes or aziridines. Copolymerization of carbon monoxide and ethylenimine was carried out under radiation and the formation of 3-nylon was observed238. ... 

Alternating copolymers of ethylene with olefins containing double bonds in the cis configuration, like ds-2-butene, cyclopentene, cycloheptene,115 and norbomene,116 have been described. Recently also copolymers of carbon monoxide with styrene and styrene derivatives, having syndiotactic117 and isotactic118 configurations, have been synthesized and characterized. 

The copolymers of carbon monoxide with olefins are of considerable importance from several different standpoints. These include the low price and ready availability of carbon monoxide, the enhanced photodegradability of the copolymers, and their easy chemical conversion to other classes of functionalized polymers. This review summarizes the chemistry involved in the synthesis, characterization, degradation and the derivatization of the copolymers. In addition, work on the spectral characterization of the copolymers have been cited. 

Scheme 8.22 Prevailing structure of copolymers of carbon monoxide with allenes.

Moldability of aryl polyesters have also been improved by the use of polybutylene terephthalate (PET) instead of PET or by the use of blends of PET and PET. PET under the trade name of Celanex, Valox, Gafite and Versel is being produced at an annual rate of 25 thousand tons. Copolymers of carbonate and aryl esters, acrylics and aryl esters, and imide and aryl esters as well as physical blends of polyesters and other polymers are available. These aryl polyesters are being used for bicycle wheels, springs, and blow molded containers. The properties of typical aryl polyesters are as follows ... 

COPO Copolymer of carbon monoxide with polyolefins (ethylene or propylene)... 

Wong, P. K. Copolymers of carbon monoxide. European Patent 0384517 B1 (Shell Internationale Research Maatschappij B.V.), January 18,1995. 

Swierenga and co-workers [79,80] in two articles described in detail their development of the calibration model used for PET measurements. Van Wijk et al. [72] summarized from their work that Raman spectroscopy can be used for determining the dye uptake or measuring one or more structural parameters or mechanical properties of polymeric fibers. Based on the results of their work, the authors stated that Raman spectroscopy was useful for studying melt-spinning thermoplastics, such as polyester, polyamide, polyolefins, and alternating copolymers of carbon monoxide and olefins so-called polyketones and, in addition, for polymers which are spun from solution such as cellulose, aromatic polyamides, polyketones, aromatic polyesters, and polyolefins. 

Belov GP, Novikova EV. Polyketones as alternating copolymers of carbon monoxide. Russ Chem Rev 2004 73 267-92. 

Although aliphatic polycarbonates have been produced, the term polycarbonate usually refers to the bisphenol A esters and copolymers of carbonic acid. Bisphenol A polycarbonate has been made by transesterifying diphenyl carbonate with bisphenol A, but most now is manufactured by interfacial polymerization of bisphenol A with phosgene. 

As part of the research described in Fig. 7.5, Winston and Wichacheewaf measured the percentages of carbon and chlorine in copolymers of styrene (molecule 1) and 1-chloro-l,3-butadiene (molecule 2) prepared from various feedstocks. A portion of their data is given below ... 

Two of the perfluoropolyether fluid stmctures yet to be commercialized are interesting. The first stmcture is a strictly alternating copolymer of ethylene oxide and methylene oxide, which has the longest Hquid range of any molecule containing carbon (40). The second stmcture is the perfluoromethylene oxide polyether which has low temperature Hquid properties down to —120° C ... 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

The synthesis of copolymers of olefins with carbon monoxide (eq. 3) or ketones (eq. 4) leads to backbone or side-chain carbonyl functionaUty,... 

Other patents include copolymers of vinyl ketones with acrylates, methacrylates, and styrene (53) an ethylene—carbon monoxide (1—7 wt %) blend... 

In order to achieve the desired fiber properties, the two monomers were copolymerized so the final product was a block copolymer of the ABA type, where A was pure polyglycoHde and B, a random copolymer of mostly poly (trimethylene carbonate). The selected composition was about 30—40% poly (trimethylene carbonate). This suture reportedly has exceUent flexibiHty and superior in vivo tensile strength retention compared to polyglycoHde. It has been absorbed without adverse reaction ia about seven months (43). MetaboHsm studies show that the route of excretion for the trimethylene carbonate moiety is somewhat different from the glycolate moiety. Most of the glycolate is excreted by urine whereas most of the carbonate is excreted by expired CO2 and uriae. 

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

Polyester C rbon te Copolymers. Polyester carbonate resins have molecular stmctures composed of iso- and terephthalate units in conjunction with the standard bisphenol A PC moieties. 

In the 1960s materials became available which are said to have been obtained by chlorination at lower temperatures. In one process the reaction is carried out photochemically in aqueous dispersion in the presence of a swelling agent such as chloroform. At low temperatures and in the presence of excess chlorine the halogen adds to the carbon atom that does not already have an attached chlorine. The product is therefore effectively identical with a hypothetical copolymer of vinyl chloride and symmetrical dichloroethylene. An increase in the amount of post-chlorination increases the melt viscosity and the transition temperature. Typical commercial materials have a chlorine content of about 66-67% (c.f. 56.8% for PVC) with a Tg of about 110% (c.f. approx. 80°C for PVC). 

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