Chlorine group 13 chlorides

When polyethylene is chlorinated in the presence of sulphur dioxide, sulphonyl chloride as well as chlorine groups may be incorporated into the polymer Figure 10.10). This reaction is used to produce a useful elastomer (Hypalon, see Chapter 11). 

It is well known that the trimeric phosphonitri-lic chloride can be polymerized, at 200-300°C, to poly(dichlorophosphazene) (1), hereafter this polymer will be referred to as chloropolymer. Since this polymer contains hydrolytically-unstable chlorine groups, these groups are usually replaced with various alcohols, phenols, or amines to import the polymer stability. In our laboratories, the substitution is generally with alcohols or phenols. The reaction scheme is shown in Figure 1. 

The chemical stability of PE is comparable to paraffin. It is not affected by mineral acids and alkalis. Nitric acid oxidizes PE and halogens react with it by substitution mechanisms. By chlorination in the presence of sulfur dioxide, chlorine groups and sulfonyl chloride are incorporated and an elastomer is formed. Oxidation of polyethylene which leads to structural changes can occur to a measurable extent at temperatures as low as 50 °C. Under the influence of ultraviolet light the reaction can occur at room temperature. 

In summaiy, depending on polymer type, amino, mercapto, epoxy, or vinyl are the most common functional groups which react with the polymer. Alkoxy or chlorine groups are often used to react with the filler surface, chlorine being less popular because it produces hydrogen chloride, a corrosive material. 

The three chlorine groups in cyanuric chloride have different reactivities which make possible the stepwise introduction of different substituents. At-razine, a veiy important herbicide, is made by reacting cyanuric chloride with monoethyl- and monoisopropylamine ... 

The reaction of an alkylalumlnum compound with titanium tetrachloride produces at room temperatures an almost Instantaneous precipitation of lower valence titanium chloride (B-TiClg) and evolution of gaseous hydrocarbons (36). This process (Reactions 5 and 6) represents a ligand exchange reaction of an alkyl and a chlorine group followed by decomposition of the unstable o-bonded alkyl titanium trichloride. These reactions are typical for numerous Ziegler-type catalysts ... 

Introduction of Chlorine. Thionyl chloride is used to introduce chlorine in place of various groups, OH, SH, NO2, SO3H, hydrogen and oxygen. 

At mixed oxide electrodes, free orbitals of the metals from the platinum group (Pt, Ir, Ru) are able to catalyze direct reactions such as the formation of chlorine. First, chloride is bound to the surface of the electrode oxidation happens in the second step. 

Vinyl chloride, chlorinated Vinyl chloride Single Tg Up to 61.3 or 65.2 % Cl in 1 with dependence on mol% CCI2 groups Carmoin et al. (1977), Lehr (1985, 1986)... 

Excess of halogen forms sulphur trihalides (equation 15). In the case of arylsulphur trichlorides the equilibrium is shifted to the left by increasing the temperature with aliphatic derivatives containing a methylene group linked to sulphur the decomposition of the trichloride may lead to the formation of a-chlorinated sulphenyl chlorides (equation 18). 

Olefin polymers containing only pendent chlorine groups may also be prepared using this procedure. The properties are very similar to those of CSMs in appearance and properties however, the lack of sulfonyl chloride group makes them more difficult to cure and less flexible in compounding techniques. 

At higher chlorine levels, where vicinal chlorine groups may occur, one may also include a term for poly(vinylidine chloride) (Tg = 226°C). The relationship of glass-transition temperature to chlorine content for a CSM with random chlorine substitution is shown in Figure 1. 

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