Radical chloride

Reaction of [UOClj] " in nitromethane with phenazine (10) (L) afforded the stable free-radical chloride salt, [LH2 ][C1 ]. The mechanism apparently involved bonding L and H O to the group, followed by... 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

Polymeric vinylidene chloride generally produced by free radical polymerization of CH2 = CCl2. Homopolymers and copolymers are used. A thermoplastic used in moulding, coatings and fibres. The polymers have high thermal stability and low permeability to gases, and are self extinguishing. 

When an aqueous solution of a diazonium salt is added to an alkaline solution of a phenol, coupling occurs with formation of an azo-compound (p. 188). If ho vc cr the ntiueous solution of the diazonium salt, t. . ., />-bromohenzene diazonium chloride, is mixed with an excess of an aromatic hydrocarbon, and aqueous sodium hydroxide then added to the vigorously stirred mixture, the diazotate which is formed, e.g., BrC,H N OH, dissolves in the hydrocarbon and there undergoes decomposition with the formation of nitrogen and two free radicals. The aryl free radical then reacts with the hydrocarbon to give a... 

A similar intramolecular oxidation, but for the methyl groups C-18 and C-19 was introduced by D.H.R. Barton (1979). Axial hydroxyl groups are converted to esters of nitrous or hypochlorous acid and irradiated. Oxyl radicals are liberated and selectively attack the neighboring axial methyl groups. Reactions of the methylene radicals formed with nitrosyl or chlorine radicals yield oximes or chlorides. 

Chlorine atom Methane Hydrogen chloride Methyl radical... 

The resulting free radicals react with chlorine to give the corresponding alkyl chlorides Butyl radical gives only 1 chlorobutane sec butyl radical gives only 2 chlorobutane... 

Hydrogen bromide (but not hydrogen chloride or hydrogen iodide) adds to alkynes by a free radical mechanism when peroxides are present m the reaction mixture As m the free radical addition of hydrogen bromide to alkenes (Section 6 8) a regioselectiv ity opposite to Markovmkov s rule is observed... 

The propagation steps in the formation of benzyl chloride involve benzyl radical as an intermediate... 

In complex cases, the prefixes amino- and imino- may be changed to ammonio- and iminio- and are followed by the name of the molecule representing the most complex group attached to this nitrogen atom and are preceded by the names of the other radicals attached to this nitrogen. Finally the name of the anion is added separately. For example, the name might be 1-trimethylammonio-acridine chloride or 1-acridinyltrimethylammonium chloride. 

Acid Halogenides. For acid halogenides the name is formed from the corresponding acid radical if this has a special name (Sec. 3.1.2.10) for example, NOCl, nitrosyl chloride. In other cases these compounds are named as halogenide oxides with the ligands listed alphabetically for example, BiClO, bismuth chloride oxide VCI2O, vanadium(lV) dichloride oxide. 

For most vinyl polymers, head-to-tail addition is the dominant mode of addition. Variations from this generalization become more common for polymerizations which are carried out at higher temperatures. Head-to-head addition is also somewhat more abundant in the case of halogenated monomers such as vinyl chloride. The preponderance of head-to-tail additions is understood to arise from a combination of resonance and steric effects. In many cases the ionic or free-radical reaction center occurs at the substituted carbon due to the possibility of resonance stabilization or electron delocalization through the substituent group. Head-to-tail attachment is also sterically favored, since the substituent groups on successive repeat units are separated by a methylene... 

A number of methods such as ultrasonics (137), radiation (138), and chemical techniques (139—141), including the use of polymer radicals, polymer ions, and organometaUic initiators, have been used to prepare acrylonitrile block copolymers (142). Block comonomers include styrene, methyl acrylate, methyl methacrylate, vinyl chloride, vinyl acetate, 4-vinylpyridine, acryUc acid, and -butyl isocyanate. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

The chloiine radicals and hydrogen chloride inhibit the reaction in the following manner. 

Oligomeric Vinylphosphonate. A water-soluble oligomer, Fyrol 76 [41222-33-7] is produced by reaction of bis(2-chloroethyl) vinylphosphonate and dimethyl methylphosphonate with elimination of all the chlorine as methyl chloride (127,128). This Hquid, containing 22.5% P, is curable by free-radical initiation, on cotton or other fabrics. Nitrogen components, such as A/-methylolacrylamide or methylolmelamines, are usually included in the finish, which can be durable to multiple launderings (129,130). 

Allyl polymers are made by free-radical polymerization of diaHyl compounds, most frequently diallyl dimethyl ammonium chloride (DADMAC) [7398-69-8] forming a chain containing a five-membered ring (28) poly(DADMAC) [26062-79-3]. 

Compounds containing fluorine and chlorine are also donors to BF3. Aqueous fluoroboric acid and the tetrafluoroborates of metals, nonmetals, and organic radicals represent a large class of compounds in which the fluoride ion is coordinating with trifluoroborane. Representative examples of these compounds are given in Table 5. Coordination compounds of boron trifluoride with the chlorides of sodium, aluminum, iron, copper, 2inc, tin, and lead have been indicated (53) they are probably chlorotrifluoroborates. 

Most chlorofluorocarbons are hydrolytically stable, CCI2F2 being considerably more stable than either CCl F or CHCI2F. Chlorofluoromethanes and ethanes disproportionate in the presence of aluminum chloride. For example, CCl F and CCI2F2 give CCIF and CCl CHCIF2 disproportionates to CHF and CHCl. The carbon—chlorine bond in most chlorofluorocarbons can be homolyticaHy cleaved under photolytic conditions (185—225 nm) to give chlorine radicals. This photochemical decomposition is the basis of the prediction that chlorofluorocarbons that reach the upper atmosphere deplete the earth s ozone shield. 

Copolymers of VF and a wide variety of other monomers have been prepared (6,41—48). The high energy of the propagating vinyl fluoride radical strongly influences the course of these polymerizations. VF incorporates well with other monomers that do not produce stable free radicals, such as ethylene and vinyl acetate, but is sparingly incorporated with more stable radicals such as acrylonitrile [107-13-1] and vinyl chloride. An Alfrey-Price value of 0.010 0.005 and an e value of 0.8 0.2 have been determined (49). The low value of is consistent with titde resonance stability and the e value is suggestive of an electron-rich monomer. 

During the polymeriza tion process the normal head-to-tad free-radical reaction of vinyl chloride deviates from the normal path and results in sites of lower chemical stabiUty or defect sites along some of the polymer chains. These defect sites are small in number and are formed by autoxidation, chain termination, or chain-branching reactions. Heat stabilizer technology has grown from efforts to either chemically prevent or repair these defect sites. Partial stmctures (3—6) are typical of the defect sites found in PVC homopolymers (2—5). 

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