| 摘要 |
Organic sulphates or sulphonated organic compounds are prepared by forming a complex of sulphur trioxide with an organic ester of an oxy-acid of phosphorus and then contacting the complex with an organic compound which is sulphonatable or sulphatable by the complex e.g. olefinic compounds, aromatic hydrocarbons, organic compounds containing active hydrogen and organo metallic compounds. The complex may be formed by contacting the ester with SO3 itself as with chlorsuylphonic acid or oleum. The ester may be a phosphite, phosphinite, phosphinate, phosphate, phosphonate, phosphonite, pyrophosphate or metaphosphate, and numerous alkyl, aryl and aralkyl and partial phosphate, phosphite, metaphosphate and pyrophosphate esters are mentioned, some bearing chloro-, nitro- or sulpho-substituents. The complex is generally prepared using one or more moles of sulphur trioxide per phosphorus atom in the ester or a temperature of -20 DEG to 100 DEG C. in the presence or absence of an inert solvent. Sulphatable organic compounds containing active hydrogen include primary, secondary and tertiary alcohols including methyl, lauryl, benzyl and furfuryl alcohols; polyhydric alcohols including glycol, glycerol and sugars; phenols e.g. resorcinol; non-tertiary amines e.g., dimethylamine, aniline, benzidine, ethyl glycinate, pyrrole and benzotriazole; amides including acetamide, urea, phthalimide and benzene sulphonamide; enolic compounds e.g., ethyl aceto acetate, reductase and ascorbic acid; oximes e.g. dimethyl glyoxime and heptaldoxime; hydrazones e.g. phenyl hydrazone and semicarbazones. Such compounds may be sulphated using one or more moles of SO3, in complexed form, per active hydrogen atom in the compound. Sulphonatable olefins include those of the general formulae R1RC=CH2 and CH2=CR. CR1=CH2 wherein R and R1 represent hydrogen or alone or together form cyclic or acyclic aliphatic groups having up to 18 carbons, e.g., ethylene, butadiene and vinyl cyclohexane. Sulphonatable aromatic compounds specified include chloro- and bromobenzenes, isodurene, phenanthrene, naphthalene sulphonic acid, nonyl benzene, abietic acid, anisole, dimethyl aniline, vanillin and lignin. The sulphonation of olefines is preferably effected with complexes containing 1 mol of SO3 per phosphorus atom. Desirably, sufficient of the complex is used to introduce two SO3 groups into each double bond yielding a cyclic intermediate which on hydrolysis yields a hydroxy sulphonic acid. Sulphonation of the aromatic nucleus requires complexes containing more than one mole of SO3 therein. Accordingly a 1:1-SO3/triethyl phosphate complex selectively sulphonates the vinyl group of styrene. Sulphonation of the aromatic nucleus may be effected with the appropriate complex together with excess SO3 if desired. The sulphations and sulphonations are generally effected at from about-20 DEG C. to 100 DEG C. and inert solvents may be present. The organo metallic compounds which may be reacted with the complexes, are those of a C2-30 acyclic or cyclic, saturated or unsaturated, hydrocarbon radical, which may be substituted by halogen or alkoxy, with an alkali metal, beryllium, magnesium, an alkaline earth metal, boron, aluminium, silicon, germanium, tin, lead or a metal having an atomic number of from 21 to 29. The complex used is suitably one containing 1-3 moles of SO3. The reaction may be effected at -100 DEG to +100 DEG C. and yields a sulphonic acid R SO3 H where R corresponds to the organic component of the organo metallic reactant. Disulphonic acids may be obtained using a di-metallo organic reactant. In examples: (1) lauryl alcohol is sulphated using a complex obtained by adding SO3 to a solution of triethyl phosphate in dichloroethane, the product being obtained as the sodium salt; the C16 alcohol CH3. (CH2)7CH (CH2OH). (CH2)5CH3 and octyl alcohol are similarly sulphated; lauryl alcohol is also sulphated using a complex formed from (5) SO3 and tetrabutyl pyrophosphate, (6) chlorsulphonic acid and dipropyl hydrogen phosphate or (7) SO3 and dimethyl phosphite; (14) octadecene-1 is sulphated as in (1); (16) ethyl benzene is sulphonated using a complex formed from triethyl phosphite and chloro sulphonic acid, or (17) from dimethyl hydrogen phosphite or (18) tetrabutyl pyrophosphate and SO3; (19) dodecyl sulphonic acid is prepared by reacting tridodecyl aluminium with an SO3-triethyl phosphate complex in dichloroethane and (20) phenyl ethane sulphonic acid is similarly prepared from tri-styryl aluminium. There is also described the sulphonation of polymeric material including protein, cellulose, starch and polyvinyl alcohol and polystyrene compounds (see Division C3). Specification 368,812 is referred to. ALSO: Organic polymeric material, e.g. cellulose, starch, other carbohydrates, alginates, polyacrylamide, polyvinyl alcohol, and polymers and copolymers of alkenyl-aromatic compounds are sulphated or sulphonated by means of a preformed complex of SO3 and an organic ester of an oxy-acid of phosphorus. The complex may be prepared by reacting SO3, oleum or chlorosulphonic acid with an organic phosphate, phosphite, metaphosphate, pyrophosphate, phosphinite, phosphinate, phosphonite or phosphonate. The complexes generally contain at least one mole of SO3 per phosphorus atom; more than one mole of SO3, should be present if it is desired to sulphonate an aromatic nucleus. The reactions may be effected at -20 DEG to +100 DEG C. in the presenc if desired of an inert solvent. The polymeric alkenyl aromatic compounds to be sulphonated may comprise the recurring unit -CR1 (C6H4R2). CH2- wherein R1 is alkyl, aryl, aralkyl, halogen or hydrogen and R2 is alkyl, aryl, aralkyl, hydrogen or any substituent having a Hammett Sigma value of -1.50 to +1.50 and which is less readily sulphonated than the aromatic nucleus; for example, polystyrene, polyvinyl toluene, styreneacrylonitrile copolymer, vinyl toluene-acrylonitrile copolymer, styrene-vinyl tolueneacrylonitrile terpolymer, styrene-isobutylene copolymer, a-methyl styrene-acrylonitrile-ethyl methacrylate terpolymer, styrene-SO2 copolymer, styrene and/or vinyl toluenemaleic anhydride copolymer, styrene and/or vinyl toluene-ethyl methacrylate copolymer, styrene-ethyl acrylate copolymer and styrene-butadiene copolymer. These polymers may be converted into water-soluble sulphonated polymers if sufficient sulphonating complex is used to sulphonate a majority for example 60-70% of the aryl groups therein. This sulphonation is preferably effected in dichloroethane solution whereupon the sulphonated polymer precipitates out; it may be dissolved in an alcohol, e.g. methanol and alkali added to form a solution of the alkali salt of the polymer. Examples describe the sulphonation of polystyrene, polyvinyl toluene and a styrene-isobutylene copolymer with a preformed complex of 2-7 moles SO3 to one mole of triethyl phosphate yielding water soluble sulphonated polymers free from cross-linking. Specification 368,812 is referred to. |
