Patent GB-926411-A (GB)
Title: Halogenated organic compounds
IPC: C25D3/10
Filed: 1959-05-13
Abstract: The invention comprises telomeric halosulphates having the general formula Z1(CH2CF2)nO.SO2X, Z1(CF2CF2)nO.SO2X, Z1(CF2CHCl)nO.SO2X or Z1(CF2CFCl)nO.SO2X wherein Z1 is an aryl, R11CX2-or R11CX2CHX-radical, X is chlorine or fluorine, R11 is fluorine, chlorine, bromine, an -O.SO2X radical or an organic group which may contain the substituent -OSO2X, and n is an integer, preferably, from 3-20.  The halosulphates are prepared by reacting the corresponding iodides Z(haloethylene)nI with chloro- or fluoro-sulphonic acid, Z representing an aryl, RCX2- or RCX2CHX-radical, X being chlorine or fluorine and R being fluorine, chlorine, bromine or iodine or an organic radical which may be iodo-substituted.  The preferred iodides are those in which Z is a perfluoro, perchloro, perfluorohydro, perchlorohydro, perfluorochloro or perfluorochlorohydro radical which may also contain iodine. and these compounds may be obtained by telomerization reactions, e.g. from CH2=CF2 and C3F2I or ICF2CF2I, or from CF2=CF2, CF2=CFCl or CF2=CHCl and CF3I or C3H7I.  The halosulphates containing a group -CX2.OSO2X react with compounds containing active hydrogen whereby the said group is replaced by the group -CO.B, B being the residue of an active-hydrogen containing compound BH, specifically water or aqueous alkali yielding carboxylic acids or salts thereof, ammonia or a non-tertiary amine yielding amides, or a thiol yielding thiol esters.  These reactions may be used to prepare condensation polymers (see below).  The esters may be reduced to alcohols and the amides to amines.  The carboxylic acids may be converted into their anhydrides.  The halosulphates containing the group -CHCl.OSO2X may be hydrolysed whereby the said group is converted to the aldehydic group -CHO, the product generally being obtained in the hydrol form from which the free aldehyde is recovered by treatment with P2O5 or H2SO4. In examples: (2) a t telomeric iodide C3F7(CF2.CF.CF3)4(CF2CF2 12 aver.I is prepared by reacting CF2=CF2 with C3F7(CF2CF.CF3)4I at elevated temperature and pressure and the telomeric iodide is reacted with chlorosulphonic acid at 150 DEG C. in a sealed glass vessel; the mixture of chlorosulphates obtained is fractionated to separate chlorosulphates containing the chain (CF2CF2)n wherein n ranges from 9 to 25; (24) a telomeric halosulphate from (2) wherein n=about 11 is refluxed with aq. NaOH yielding  C3F7(CF2CF.CF3)4(CH2CF2) 10CF2COONa; (25) a halosulphate from (2) wherein n=about 9 is reacted with NH3 yielding C3F7(CF2CF.CF3)4(CH2CF2) 8CF2CONH2.  Polyesters, polyamides and polythiol-esters are prepared by reacting polyhydric alcohols, poly-non-tertiary amines and polythiols respectively with halosulphates of the general formula ACX2.OSO2X wherein A is an organic group containing a -CX2SO2X radical, X being fluorine or chlorine; in this reaction the group -CX2SO2X is replaced by a link -CO-B- where B is a residue of an alcohol, amine or thiol, BH. The preferred halosulphates are those having the general formulae Z1(CH2CF2)OSnO2 and Z1(CF2CF2)nOSO2X wherein Z1 is a radical R11CX2- or R11CX2CHX- where R11 is the group -OSO2X or an organic radical containing such a group, and n is an integer.  In examples: (41) a di-chlorosulphate CISO2.O(CF2CF2)3O.SO2Cl is heated at 100 DEG C. with excess of hexamethylene glycol yielding a thermoplastic solid polyester; (42) a dichlorosulphate ClSO2.O(CF2)5O.SO2Cl is similarly reacted with excess trimethylene glycol; (43) the dichlorosulphate of (41) is heated with excess of hexamethylene diamine yielding a solid polyamide.  Mention is made of the use of hexamethylene dithiol yielding polythiol esters containing for example, the repeating unit SCO.(CF2)4CO.S(CH2)5. Other suitable reactants are referred to. Various resins may be plasticized with aldehydes obtained by the hydrolysis of halosulphates having the general formula  A1CX2CHXOSO2X wherein A1 is fluorine, chlorine, hydrogen or an aryl, HCX2-, R11CHX-, R11CX2-, R11CZ1X-, R1CZ12-, R1CZ1H- or Z1CH2-radical, X is chlorine or fluorine, R11 is fluorine, chlorine, bromine, a -O.SO2.X radical or an organic radical, Z1 is an aryl, R11CX2- or R11CX2CHX- radical, R1 is fluorine, chlorine or an organic radical and at least one of A1, Z1 and X (other than X in O.SO2.X) is or contains fluorine (see Group IV(b)).  Aldehydes additional to the above described telomeric aldehydes are mentioned.  Specified resins are homopolymers of CF2=CH2 and CF2=CFCl, polyvinyl chloride, polyvinylidene chloride and fluoride and polymethyl methacrylate.  Ammonium and other salts of perfluorocarboxylic acids obtained by hydrolysis of halosulphates A1CX2OSO2X wherein A1 is a perfluoro radical and X is Cl or F, may be used as dispersing agents in the emulsion polymerization of, for example, CF2=CF2 and CH2=CF2.  Cotton and regenerated cellulose fibres and fabrics are acylated by means of highly halogenated halosulphates within the class defined by the formula A1CX2.OSO2X wherein X is chlorine or fluorine and A1 is fluorine, chlorine, hydrogen or an aryl, HCX2-, R11CHX-, R11CX2-, R11CZ1X-, R1CZ1H-or Z1CH2-radical, Z1, R11 and R1 being as above defined.  The treatment imparts flame and water resistance and when the compounds are highly fluorinated, also imparts resistance to oil and grease spotting. Specification 926,412 is referred to in a disclaimer.ALSO:The invention comprises halogenated halosulphates of the general formula A1CX2O SO2X, D1CXZ1OSO2X or A1CX2CHXOSO2X wherein X is fluorine or chlorine, A1 is fluorine, chlorine, hydrogen or an aryl, HCX2-, R11CHX-, R11CX2-, R11CZ1X-, R1CZ12-, R1CZ1H- or Z1CH2- radical, R11 being fluorine, chlorine, bromine or an organic radical or an -OSO2X group, and R1 being fluorine, chlorine or an organic radical, Z1 is an aryl, R11CX2- or R11CX2CHX- radical, D1 is an organic radical as defined for A1, and where in the compounds D1CXZ1OSO2X, D1 and Z1 may be joined together to form a polyhalogeno alicyclic ring, it being provided that in all three classes of compounds at least one of the symbols A1, D1, Z1 and X (excluding the X of the OSO2X radical) is or contains fluorine.  The halosulphates are prepared by reacting chloro- or fluoro-sulphonic acid, at a temperature at which a halogenated halo sulphate is formed, with halogenated iodides of the general formula ACX2I, DCZXI, or ACX2CHXI wherein A is fluorine, chlorine, hydrogen or an aryl, HCX2-, RCX2-, RCXH-, RCZX-, R1CZ2-, R1CZH- or ZCH2- radical; D is an organic radical as defined for A; X is fluorine or chlorine; Z is an aryl, RCX2- or RCX2CHX- radical; R is fluorine, chlorine, bromine or iodine or an organic radical and R1 is chlorine, fluorine or an organic radical and at least one of A, D, Z and X is or contains fluorine; additionally Z and D may be joined together to form a polyhalogeno-alicyclic ring.  In these reactions the iodine is replaced by the group -OSO2X. There may also be formed as side reaction products chlorides or fluorides by replacement of the iodine by the halogen of the halosulphonic acid.  Organic radicals representable by R and R1 include alkyl, cycloalkyl, alkenyl, aralkyl and heterocyclic radicals, their halogenated analogues and alkoxy, aminoalkyl and thioalkyl groups; nitro, keto, aldo, hydroxy, mercapto, carboxy, nitrile and amido substituents may be present. When R or R1 is aromatic or contains a hydroxy group halosulphonation or halosulphation may occur therein.  The preferred iodides are those in which A, D and Z are perfluoro, perchloro, perfluorochloro, perfluorohydro, perfluorochlorohydro and perchlorohydro aliphatic and cycloaliphatic radicals. Numerous iodides are specified including CF3I, C6H5CF2I, CF2CICF2I, C2F5Cl2I, CF2 = CFCF2CFClI, N NO2CH2CF2CF2I, ICF2CF2CF2I, C7F15CH2CF2I, CF3CHFI, heptafluorocyclobutane iodide, undecafluorocyclohexane iodide and telomeric iodides, for example Z(CF2CF2)nI, Z(CH2CF2)nI, Z(CF2 CFCl)nI, Z(CF2CHCl)nI and especially Y(CH2CF2)nI wherein n is an integer, e.g., from 1 to 20, Z is as above defined and Y is a radical RCX2- or RCX2CHX- wherein R is iodine or an iodine containing organic radical.  The reaction temperature may range from -20 to +300 DEG C.  Elevated pressure may be used and solvents may be present. Typical examples describe the preparation of (1) C3F7OSO2Cl; (2) C3F7(CF2CF.CF3)4 (CF2CF2)12O.SO2Cl, the iodide reactant being obtained by reacting tetrafluoroethylene with C3F7(CF2CF.CF3)4I; (3) CF2ClCF.CF3(CF2CF. CF3)2 (CF2CF2)4O.SO2Cl from th corresponding iodide obtained by reacting CF2 = CF.CF3 with CF2ClCFI.CF3; (4) C2F5(CF2CF2)3O.SO2Cl from the iodide obtained by reacting C2F5I with CF2=CF2; (5) ClSO2O(CF2CF2)3O.SO2Cl from the di-iodide obtained by reacting CF2 = CF2 with ICF2CF2I; (6) ClSO2O(CF2)5OSO2Cl from the di-iodide obtained by reacting CF2I2 with CF2=CF2; (8) C2F5CF.CF3 (CH2CF2)3OSO2Cl from the iodine obtained by reacting CH2=CF2 with C2F5CF(CF3)I; (10) CF3CF2CF2CF2CF(CF3)OSO2Cl from 2-iodo perfluorohexane, which at higher temperatures yields only the 2-chloro perfluorohexane; (11) CF2ClCFClOSO2Cl from the iodide prepared from iodine chloride and CF2=CFCl; (14) CF3CF2CF2OSO2F, purified chromatographically; (15) CF2Cl.CFCl. OSO2F; (16) <FORM:0926411/IV(a)/1> and (17) C3F7(CF2CF.CF3)2OSO2F.  The halosulphates of the formula A1CX2 OSO2X, A1 being as defined above but not fluorine or chlorine, may be hydrolysed to carboxylic acids of the formula A1COOH or salts thereof or be reacted with alcohols, ammonia or amines or thiols to yield respectively the esters, amides, or thioesters of the acids A1COOH.  The hydrolysis proceeds via intermediate formation of an acyl halide which may be isolated in some cases. The acids may be neutralised to form salts or be reacted with P2O5 and/or H2SO4 to form acid anhydrides. The bis-halosulphates yield bis-carboxylic compounds.  The halosulphates may be reacted with mono, di or polyhydric alcohols and mono and poly-amines and