Chlorosulfonating agent

Chlorosulfonated polyolefins are prepared by interaction of the base resin with chlorine and either sulfur dioxide (18) or sulfiiryl chloride in the presence of a radical initiator (19). Sulfuryl chloride may be used alone as a chlorosulfonating agent, but must be accompanied by a catalytic amount of pyridine or other organic base. It has been proposed that the fimction of the organic base is to catalyze decomposition of the sulfuryl chloride molecule to form SO2 and CI2. However, the chlorosulfonation rate with base-catalyzed sulfuryl chloride is 5-10 times faster than that with gaseous chlorine and sulfur dioxide. So it is possible that the mechanism is more complex. In the latter case, the ratio of sulfonyl chloride to chlorine substituted onto the polymer backbone is, to some extent, a function of the amount of organic base added. The reaction temperature (lower reaction temperatures that result in higher sulfur utilities) also affects it (19). 

The chlorination reaction and the chlorosulfonation reaction are usually carried out simultaneously in homogeneous solution, but may be carried out in stages that is, the resin may be partially chlorinated with elemental chlorine and then chlorosulfonated to the desired composition with a chlorosulfonating agent (20). 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

Carbohydrates. Carbohydrates (240—244) of any form are easily sulfated in the presence of solvent, using sulfating reagents such as SO —pyridine, SO —triethjlamine, SO.—trimethyl amine, or chlorosulfonic acid—pyridine. As an example, starch (qv) is sulfated using SO.—trimethyl amine at 0 to 5°C in aqueous media (16). Sulfated carbohydrate products find some use in industry as thickening agents. 

Because phenoHc compounds are easily sulfonated, their sulfation must be accompHshed with mil der sulfating agents, eg, complexes of sulfur thoxide or chlorosulfonic acid with trimethyl amine, dimethylform amide, pyhdine, or dim ethyl a n i1 in e, in anhydrous or aqueous medium below 100°C (86-89). 

A solution of sulfur trioxide [7446-11-9] dissolved in chlorosulfonic acid [7990-94-5] CISO H, has been used as a smoke (U.S. designation FS) but it is not a U.S. standard agent (see Chlorosulfuric acid Sulfuric acid and sulfur trioxide). When FS is atomized in air, the sulfur trioxide evaporates from the small droplets and reacts with atmospheric moisture to form sulfuric acid vapor. This vapor condenses into minute droplets that form a dense white cloud. FS produces its effect almost instantaneously upon mechanical atomization into the atmosphere, except at very low temperatures. At such temperatures, the small amount of moisture normally present in the atmosphere, requires that FS be thermally generated with the addition of steam to be effective. FS can be used as a fill for artillery and mortar shells and bombs and can be effectively dispersed from low performance aircraft spray tanks. FS is both corrosive and toxic in the presence of moisture, which imposes limitations on its storage, handling, and use. 

A related agent, g1 icetanile sodium (42), is made b / a variant of this process. Methyl phenyl acetate is reacted with chlorosulfonic acid to give 38, which itself readily reacts with aminopyrimidine derivative 39 to give sulfonamide Saponification to acid 4 is followed by conversion to the acid chloride and amide formation with 5-chloro-2-methoxyaniline to complete the synthesis of the hypoglycemic agent glicetanile (42). ... 

Si, and stannic tetrachloride. An effective smoke agent, whether it be mechanically dispersed from an aircraft spray tank or vaporized thermally, is a mixt of S trioxide and chlorosulfonic acid (FS smoke agent) which upon hydrolysis forms sulfuric and hydrochloric acid dispersions. Of course, all such formulations are highly corrosive, and, if not outright toxic, then conducive to pulmonary edema... 

Further auxiliary agents for the production of anionic surfactants are the sulfation and sulfonation agents oleum, chlorosulfonic acid, C1-S02-0H, air-S03 mixtures, air-S02 mixtures, sultones (especially 1,3-propanesultone (CH2—CH2—CH2—SO2), and isethionic acid (2-hydroxyethanesulfonic O-------------------1... 

When two polymers interact or react with each other, they are likely to provide a compatible, even a miscible, blend. Epoxidized natural rubber (ENR) interacts with chloro-sulfonated polyethylene (Hypalon) and polyvinyl chloride (PVC) forming partially miscible and miscible blends, respectively, due to the reaction between chlorosulfonic acid group and chlorine with epoxy group of ENR. Chiu et al. have studied the blends of chlorinated polyethylene (CR) with ENR at blend ratios of 75 25, 50 50, and 25 75, as well as pure rubbers using sulfur (Sg), 2-mercapto-benzothiazole, and 2-benzothiazole disulfide as vulcanizing agents [32]. They have studied Mooney viscosity, scorch... 

Tibric acid (10), interestingly, has the m-carboxysulfonamido functionality but its activity is expressed, instead, as suppression of serum triglyceride levels. In its reported preparation, chloro-sulfonic acid treatment converts 2-chlorobenzoic acid to chlorosulfonate 9, which readily forms the hypolipidemic agent tibric acid (10) on reaction with... 

Suitable agents are chlorosulfonic acid, monohydrate, or concentrated sulfuric acid. Other methods include cyclization of phenylthioglycolic acid chlorides, which is afforded by Friedel-Crafts reaction with aluminum chloride, possibly in the presence of sulfuric acid/sodium chloride. The acid chloride is obtained from phenylthioglycolic acid with thionyl chloride or phosphorus trichloride. 

For products requiring high-quality sulfates, chlorosulfonic acid is an excellent corrosive agent that generates hydrochloric acid as a byproduct. A process flow diagram is shown in Figure 13. The effluent washouts are minimal. 

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