Patent GB-1123379-A (GB)
Title: Fluorocarbon esters and polymers thereof
IPC: D06M15/277
Filed: 1965-12-23
Abstract: The invention comprises homo- and copolymers of unsaturated fluorinated esters of the formula <FORM:1123379/C3/1> wherein Rf is a C3- 21 straight chain or branche chain perfluoroalkyl radical, R is a C1- 18 alkyl radical, R1 is hydrogen or a methyl group and m is 0 or 1-10, p is 0 or 1-10 when m is 0, and p is 0 when m is 1-10, and n is 0 or 1-10. Many ethylenically unsaturated comonomers are specified, including acrylic compounds, vinyl and allyl esters, styrene compounds, halogenated vinyl and vinylidene compounds, vinylalkyl ketones, acrylamides, dienes and the fluorinated unsaturated esters Rf(CH3)zOOC.CR1 = CH2 and RfCH = CH(CH2)zOOC.CR1 = CH2, where z is 1-10. The polymers can be made by bulk-, solution-, suspension- or, preferably, emulsion-polymerization methods using free radical catalysts, U.V. or ionizing radiation or heat to initiate the reaction.  Suitable catalysts and dispersants, for emulsion polymerization, are specified.  Each example describes homopolymers and copolymers and their use as water- and oil-repellent agents (see Divisions C4, D1 and F4).ALSO:Aerosols comprise a propellant and an organic solvent solution of a homopolymer or copolymer of an unsaturated fluorinated ester of the formula <FORM:1123379/C4-C5/1> wherein Rf is a C3-21 straight or branched chain perfluoroalkyl group, R is a C1-18 alkyl group, R1 is hydrogen or a methyl group and m is 0 or 1-10, p is 0 or 1-10 when m is 0, or p is 0 when m is 1-10, and n is 0 or 1-10. Specified propellants are dichlorodifluoromethane, monofluorotrichloromethane and dichlorotetrafluoroethane. Examples 8 and 11 describe the preparation of aerosols.ALSO:The invention comprises compounds of the formula <FORM:1123379/C2/1> wherein Rf is a C3- 21 straight- or branch-chained perfluoroalkyl group, R is a C1- 18 alkyl group, R1 is hydrogen or a methyl group, m is 0 or 1-10, p is 0 when m is 1-10, or p is 1-10 when m is 0 and n is 0 or 1-10.  The esters can be prepared by a number of methods: (1) by condensing a halogen derivative RfCH2CHX(CH2)m1OH, where X is halogen other than F and m1 is 1-10, with a salt RCOOM, where M is an alkali metal or Ag, to give an hydroxy ester RfCH2CH(OH).(CH2)m1OOCR, which is then reacted with an acid derivative CH2 = CR1(CH2)nCOY, where Y is halogen, -OH or -O-C1- 5 alkyl, to give the product <FORM:1123379/C2/2> (2) by reacting RfCH2CHX(CH2)p1 with CH2 = CR1(CH2)nCOY, where p1 is 1-10, to give <FORM:1123379/C2/3> which is condensed with RCOOM to the product <FORM:1123379/C2/4> (3) by condensing RfCH2CHX(CH2)p1OH with CH2 = CR1(CH2)nCOOM to give <FORM:1123379/C2/5> which is reacted with RCOY to give the product obtained in process (2); (4) by reacting RfCH2CHX(CH2)m1OH with RCOY to give RfCH2CHX(CH2)m1OOCR which is condensed with CH2 = CR1(CH2)nCOOM to give the product obtained in process (1); (5) by reacting CH2 = CH(CH2)mOOCR with a halide RfX to give RfCH2CHX(CH2)mOOCR which is condensed with CH2 = CR1(CH2)nCOOM to give the product <FORM:1123379/C2/6> (6) by reacting CH2 = CH(CH2)mOOCR with a sulphonyl halide RfSO2X to give RfCH2CHX(CH2)mOOCR which is converted to the required product as in process (5).  The fluorinated esters may be polymerized to products having oil- and water-repellent properties (see Divisions C3, C4, D1, F4, B2).  Numerous examples are provided.  The starting alcohols RfCH2CHX(CH2)m1OH are made by reacting a halide RfX or a sulphonyl halide RfSO2X with CH2 = CH(CH2)m1OH.ALSO:Rigid and flexible substrates are rendered oil- and water-repellent by coating with a composition comprising a homopolymer or copolymer of a fluorinated diester of the formula:-  <FORM:1123379/B1-B2/1> where Rf is a C3-21 perfluoroalkyl group, R1 is hydrogen or a methyl group, R is a C1-18 alkyl group, m is 0 or 1-10, p is 0 or 1-10 when m is 0 or p is 0 when m is 1-10, and n is 0 or 1-10, said copolymer containing at least 25% by wt. of the diester monomer.  The compositions may take the form of aqueous emulsions, organic solvent solutions or aerosols and can be applied by painting, dipping or spraying.  The coated materials may be dried and cured at elevated temperatures. Specified substrates include fabrics, fibre boards, felts, leather, glass wood. Examples describe the treatment of fabrics. In addition, Examples 8 and 11 describe coating a refrigerator ice-cube tray and fibre board.ALSO:Fibrous and porous materials are rendered water- and oil repellent by treatment with homopolymers or copolymers of unsaturated fluorinated esters of the formula <FORM:1123379/D1-D2/1> wherein Rf is a C3-21 straight or branched chain perfluoroalkyl group, R is a C1-18 alkyl group, R1 is hydrogen or a methyl group; and m is O or 1-10, p is O or 1-10 when m is O or p is O when m is 1-10, and n is O or 1-10, copolymers containing at least 25% wt. of the fluorinated ester monomer.  The compositions may take the form of aqueous emulsions, organic solvent solutions or aerosols and can be applied by painting, dipping or spraying at room or elevated temperatures to woven or knitted fabrics, felts or fibre boards made of natural or synthetic fibres, or to paper, leather or wood. The treatment may be combined or followed by a soaping process and may include the application of other known repellents, e.g. p  pyridinium salts, in a one- or two-step process.  Examples describe the treatment of cotton, wool, nylon and asbestos cloths, umbrella cloth, filter paper, kraft paper and fibre board. Soaping and dry-cleaning after-treatments are also described.