Patent GB-1114782-A (GB)
Title: Production of fluoroethylene derivatives
IPC: C07C17/275
Filed: 1965-05-07
Abstract: 1:1 Adducts (with respect to the ethylenic or acetylenic bond) are obtained by reacting an ethylenically or acetylenically unsaturated organic silicon compound containing at least one hydrogen atom, with an iodofluoroalkane having at least one -CF2CF2- group which is an a -iodoperfluoroalkane, a -iodoperfluorochloroalkane, a  - iodo - o  - hydroperfluoroalkane, a  - diodo - o  - hydroperfluorochloroalkane, a - iodo - o  - haloperfluoroalkane (the halogen being Cl, Br or I) or an a -iodo-o -haloperfluorochloroalkane (the halogen being Br or I), at a temperature above 170 DEG  C., a pressure below 5 atmospheres and residence time below 2 hours.  In examples: (7) C10F21I is reacted with CH2 = CHSiCl3. The product is dissolved in methanol or ethylene glycol and the solution is hydrogenated or treated with NaHSO3 to give C10F21CH2CH2Si(OR)3, where R is CH3 or HOCH2CH2.  R may also be derived from triethyleneglycol. (14) C10F21I is reacted with CH2 = CHSiCl2.CH3, the product dissolved in tetrahydrofuran and treated successively with concentrated aqueous ammonia and zinc turnings to obtain a fluoroalkylsilazane.  An iodine-free product is obtained by extracting the silazane with CHCl:CCl2, adding ammonia and expelling the CHCl:CCl2 while hot by ammonia steam.  (15) C10F21I is reacted with CH2 = CHCH2SiCl3 and the product treated as in (14). (16) C10F21I is reacted with CH2=CHSiCl (CH3)2 and the product dissolved in tetrahydrofuran and treated successively with ammonia solution, zinc turnings and HCl gas to give C10F21CH2CH2SiCl(CH3)2, which can be hydrogenated with LiAlH4 to give the corresponding hydrogen silane, which can itself be added to unsaturated organic compounds, e.g. with methyl acrylate to give C10F21CH2CH2Si(CH3)2 C2H4COOCH3.  Other unsaturated silicon compounds for reaction with the iodofluoroalkanes are listed.  Trichlorosilane, methyldichlorosilane and methyl hydrogen polysiloxane can add to the double bond of perfluorooctyl cyclohex-1-ene.ALSO:The compounds C7F15CH2CH2I, PhC2H4C8F17 and <FORM:1114782/C4-C5/1> are of use as lubricants.ALSO:Perfluorocaprylic acid C7F15COOH is obtained by electro-fluorination of C3H7CF2CH2CH2COOH.ALSO:1:1-Adducts (with respect to the ethylenic or acetylenic bond) are obtained by reacting an ethylenically or acetylenically unsaturated organic compound containing at least one hydrogen atom, with an iodofluoroalkane having at least one -CF2CF2- group which is an a -iodoperfluoroalkane, a -iodoperfluorochloroalkane, a -iodo-o -hydroperfluoroalkane, a  iodo - o  -hydroperfluorochloroalkane, a  - iodo - o  -haloperfluoroalkane (the halogen being Cl, Br or I) or an a  - iodo - o -haloperfluorochloroalkane (the halogen being Br or I), at a temperature above 170 DEG  C., a pressure below 5 atmospheres and residence time below 2 hours.  Secondary reactions may involve loss of iodine or hydrogen iodide, and may be completed after the reaction by catalytic hydrogenation or treatment with a base.  In examples, ethylene is reacted with C4F9I, C6F13I, C7F15I, C8F17I and C10F21 to give RfCH2Ch2I; and with I(CF2)6I to give ICH2CH2(CF2)6CH2CH2I and some I(CF2)6CH2CH2I; acetylene and H(CF2)8I give ICH: CH(CF2)8H; CH2: CCl2 and Cl(CF2)6I give Cl(CF2)6CH2CCl2I, which can be saponified to Cl(CF2)6CH2COOH; 1-octene and C8F17I after reaction and treatment with Zn and HCl give C8H17 C8F17; as in the previous example, cyclohexene and C8F17I give perfluorooctylcyclohexane or the initial product treated with NaOH gives perfluorooctylcyclohex-1-ene, which can add Br2; butadiene and C8F17I give C8F17CH2CH: CHCH2I, which with Na acetate, Na malonic ester or Na acetylacetone gives the expected product with elimination of NaI; allyl chloride and C8F17I after reaction and treatment with NaOH give C8F17CH: CHCH2Cl, in which by reaction with NaBr or NaI the Cl can be replaced by Br or I, or which by hydrolysis gives the alcohol; styrene and C8F17I after reaction and treatment with Na/Hg give PhCH2CH2C8F17, which can be sulphonated or sulphochlorinated; and allylbenzene and C8F17I after reaction and treatment with Na/Hg give PhC3H6C8F17, which can be sulphonated. Other reactants are specified, including organo-tin compounds.  In addition, propene and ICF2-CF2I after reaction and hydrogenation gives ICF2CF2CH2CH2CH3, which on reaction with acrylonitrile and hydrogenation gives C3H7CF2CF2CH2CH2CN, which can be saponified to the free acid.ALSO:The 1:1 adducts of perfluroalkyl iodides with unsaturated compounds or their further reaction products (see Divisions C2 and C3) are used for impregnating textiles and other materials for dirt -, oil - and water-repellency.  Thus (1) C10F21CH2CH2SiCl3 can be used for textiles and paper, and a solution in CCl4 can be used for impregnating a textile fabric by dipping or spraying; textiles, leather, paper and cellulose regenerates can be impregnated by treatment with a solution of C10F21CH2CH2Si (OR)3, where ROH is methanol, ethylene glycol or triethylene glycol, in CHCl : CCl2; (2) the adduct from C10F21I and CH2 = CHSiCl2-CH3, dissolved in tetrahydrofuran and treated successively with concentrated aqueous ammonia and zinc turnings, gives an aqueous solution suitable for impregnating textiles; or the fluoroalkylsilazane can be extracted with CHCl:CCl2 and this solution washed with concentrated aqueous ammonia and then diluted and used for impregnating textiles; or an iodine-free product is obtained by expelling the CHCl : CCl2 from the hot suspension with the NH4OH by ammonia steam, and the resulting aqueous solution can be used for impregnating textiles, paper and leather (e.g. cotton); (3) the adduct from C10F21I and CH2 = CHCH2 SiCl3 can be treated as in (2) and the products similarly used.  It is also stated that a spray which is a solution, in Freons (Trade Mark) or chlorinated hydrocarbons, of a wax or oil containing such adducts may be used for impregnation of textiles.