Chlorocarbonates

Manufacture via this process has been completely replaced by chlorination of butadiene (3) (see Chlorocarbons and chlorohydrocarbons, chloroprene ElASTOT RS, synthetic, POLYCm OROPRENE). 

Substitution of fluorine for hydrogen in an organic compound has a profound influence on the compound s chemical and physical properties. Several factors that are characteristic of fluorine and that underHe the observed effects are the large electronegativity of fluorine, its small size, the low degree of polarizabiHty of the carbon—fluorine bond and the weak intermolecular forces. These effects are illustrated by the comparisons of properties of fluorocarbons to chlorocarbons and hydrocarbons in Tables 1 and 2. 

Heterogeneous vapor-phase fluorination of a chlorocarbon or chlorohydrocarbon with HP over a supported metal catalyst is an alternative to the hquid phase process. Salts of chromium, nickel, cobalt or iron on an A1P. support are considered viable catalysts in pellet or fluidized powder form. This process can be used to manufacture CPC-11 and CPC-12, but is hampered by the formation of over-fluorinated by-products with Httle to no commercial value. The most effective appHcation for vapor-phase fluorination is where all the halogens are to be replaced by fluorine, as in manufacture of 3,3,3-trifluoropropene [677-21 ] (14) for use in polyfluorosiHcones. 

Hydrofluorocarbons are also prepared from acetylene or olefins and hydrogen fluoride (3), or from chlorocarbons and anhydrous hydrogen fluoride in the presence of various catalysts (3,15). A commercial synthesis of 1,1-difluoroethane, a CFG alternative and an intermediate to vinyl fluoride, is conducted in the vapor phase over an aluminum fluoride catalyst. 

A variety of processes for synthesizing glycerol from propylene are shown in Figure 1. The first glycerol process, put on stream in 1948, followed the discovery that propylene could be chlorinated in high yields to aHyl chloride [107-05-1] (see Chlorocarbons and chlorohydrocarbons,allylchloride). 

HalogenatedFluids. Chlorocarbons, fluorocarbons, or combinations of the two are used to form lubricating fluids (see Chlorocarbons and CHLOROHYDROCARBONS Fluorine COMPOUNDS, ORGANIC). Generally, these fluids are chemically inert, essentially nonflammable, and often show excellent resistance to solvents. Some have outstanding thermal and oxidation stability, because they are completely unreactive even in Hquid oxygen, and extremely low volatility. 

Halogenation and Hydrohalogenation. Halogens add to the triple bond of acetylene. FeCl catalyzes the addition of CI2 to acetylene to form 1,1,2,2-tetrachloroethane which is an intermediate in the production of the industrial solvents 1,2-dichloroethylene, trichloroethylene, and perchloroethylene (see Chlorocarbons and chlorohydrocarbons). Acetylene can be chlorinated to 1,2-dichloroethylene directiy using FeCl as a catalyst... 

Cmde HCl recovered from production of chlorofluorocarbons by hydrofluorination of chlorocarbons contains unique impurities which can be removed by processes described in References 53—62. CICN—CI2 mixtures generated by reaction of hydrogen cyanide and CI2 during the synthesis of (CICN) can be removed from the by-product HCl, by fractional distillation and recycling (see Cyanides) (59). 

Ethylene Dichlonde and Vinyl Chloride. In the United States, all ethylene dichloride [107-60-2] (EDC) is produced from ethylene, either by chlorination or oxychlorination (oxyhydrochlorination). The oxychlorination process is particularly attractive to manufacturers having a supply of by-product HCl, such as from pyrolysis of EDC to vinyl chloride [75-01-4] monomer (VCM), because this by-product HCl can be fed back to the oxychlorination reactor. EDC consumption follows demand for VCM which consumed about 87% of EDC production in 1989. VCM is, in turn, used in the manufacture of PVC resins. Essentially all HCl generated during VCM production is recycled to produce precursor EDC (see Chlorocarbons and Cm OROHYDROCARBONS ViNYLPOLYAffiRS). 

The role of specific interactions in the plasticization of PVC has been proposed from work on specific interactions of esters in solvents (eg, hydrogenated chlorocarbons) (13), work on blends of polyesters with PVC (14—19), and work on plasticized PVC itself (20—23). Modes of iateraction between the carbonyl functionaHty of the plasticizer ester or polyester were proposed, mostly on the basis of results from Fourier transform infrared spectroscopy (ftir). Shifts in the absorption frequency of the carbonyl group of the plasticizer ester to lower wave number, indicative of a reduction in polarity (ie, some iateraction between this functionaHty and the polymer) have been reported (20—22). Work performed with dibutyl phthalate (22) suggests an optimum concentration at which such iateractions are maximized. Spectral shifts are in the range 3—8 cm . Similar shifts have also been reported in blends of PVC with polyesters (14—20), again showing a concentration dependence of the shift to lower wave number of the ester carbonyl absorption frequency. 

Alkylphenols have been substituted for phenol as chain teaninatois in polycarbonates. In this role, PTBP (14) competes with the diol monomer for reactive chlorocarbonate sites. The ratio of butylphenol to diol controls the molecular weight of the polymer. 

Uses. AEyl chloride is industrially the most important aHyl compound among all the aHyl compounds (see Chlorocarbons and CHLOROHYDROCARBONS, ALLYL CHLORIDE). It is used mosdy as an intermediate compound for producing epichlorohydrin, which is consumed as a raw material for epoxy resins (qv). World production of AC is approximately 700,000 tons per year, the same as that of epichlorohydrin. Epichlorohydrin is produced in two steps reaction of AC with an aqueous chlorine solution to yield dichloropropanol (mixture of 1,3-dichloropropanol and 2,3-dichloropropanol) by chlorohydrination, and then saponification with a calcium hydroxide slurry to yield epichlorohydrin. 

Historical Inhalation Agents. Diethyl ether produces excellent surgical anesthesia, but it is flammable (see Ethers). Chloroform is a nonflammable, sweet smelling, colorless Hquid which provides analgesia at nonanesthetic doses and can provide potent anesthesia at 1% (see Chlorocarbons AND CHLOROHYDROCARBONs). However, a metabohte causes hepatic cell necrosis. Tdlene, a nonflammable colorless Hquid, has a slower onset and recovery and a higher toxicity and chemical reactivity than desirable. Cyclopropane is a colorless gas which has rapid induction (2 —3 min) and recovery characteristics and analgesia is obtained in the range of 3—5% with adequate skeletal muscle relaxation (see Hydrocarbons). The use of cyclopropane has ceased, however, because of its flammabiHty and marked predisposition to cause arrhythmias. 

This aHyhc chloride is a chemical intermediate for various specialty products, but it has no single significant commercial use (see Chlorocarbons and Cm OROHYDROCARBONS, ALLYL Cm ORIDE). 

Reactions 8 and 9 have been used in the large-scale production of carbon tetrachloride since the eady 1900s. As a result of decreased demand for carbon tetrachloride, this process is no longer used in the United States (see Chlorocarbons and chlorohydrocarbons, carbon tetrachloride). 

The reaction of phosgene (carbonic dichloride [75-44-5]) with alcohols gives two classes of compounds, carbonic esters and carbonochloridic esters, commonly referred to as carbonates and chloroformates. The carbonic acid esters (carbonates), R0C(0)0R, are the diesters of carbonic acid [463-79-6]. The carbonochloridic esters, also referred to as chloroformates or chlorocarbonates, C1C(0)0R, are esters of hypothetical chloroformic acid [463-73-0] CICOOH. 

In eadier Hterature carbonochloridic esters are referred to as chloroformates or chlorocarbonates because of the stmctural parallel with formic acid [64-18-6]., chloroformic acid, and carbonic acid. Before 1972, chloroformates were indexed in Chemicaly4bstracts, Eighth Collective Index, under formic acid, chloroesters whereas, in the Ninth Collective Index (Dec. 1990), they are referred to as carbonochloridic acid esters. Table 1 fists the common names of carbonochloridates or chloroformates, the CAS Registry Numbers, and the formulas. 

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