Patent GB-1102903-A (GB)
Title: Fluoro alkyl-containing compounds and water- and oil-repellent compositions containing them
IPC: C07C51/41
Filed: 1965-02-19
Abstract: The invention comprises homopolymers and copolymers of compounds of the formulae Rt(CH2)m1OCO(CH2)p1CR1 =CH2 Rt(CH2)mCOO(CH2)p2CH=CH2 and RtCONH(CH2)rOCO(CH2)p1CR1 =CH2 wherein Rt is (CF3)2CF(CF2)n-, R1 is H or CH3, n is 2-20, m is 0-20, m1 is 1-20, p1 is 0-20, p2 is 1-20 and r is 2-10.  The copolymers may be copolymers of at least two of said unsaturated compounds or copolymers of at least one of said unsaturated compounds in an amount of at least 25% by weight and a polymerizable ethylenic monomer.  The invention also comprises a polyester prepared by esterifying 30 to 100% of the hydroxyl groups in a polyvinyl alcohol, having an average polymerization degree of 300 to 1000 and a saponification value of 70-100%, with an acid halide Rt(CH2)mCOX, where X is -F, -Cl, -Br or -I and Rt, n and m are as defined above.  The above compositions may be dissolved or suspended in dispersion media, e.g., acetone, ether or C2Cl3F3.ALSO:The invention comprises compounds of the general formulae Rf(CH2)mCOX Rf(CH2)m1OCOCH2X Rf(CH2)m1OCO-NHR-NCO Rf(CH2)m1OCO(CH2)p1 -CR1 = CH2 Rf(CH2)mCOO(CH2)p2-CH = CH2 [Rf(CH2)m1-O-]q-T -X3- q [Rf(CH2)m1-NH-]q-T -X3- q Rf-CONH(CH2)rOCOCH2X Rf-CONH(CH2)rOCO-NHR-NCO Rf-CONH(CH2)rOCO(CH2)p1 -CR1 = CH2 <FORM:1102903/C2/1> [Rf-CONH(CH2)rO-]q-T -X3- q [Rf-CONH(CH2)rNH-]q-T-X3- q\t and Fe, Zr, Al and Cr salts of compounds of the formula Rf(CH2)mCOOH; in the above formulae Rf is (CF3)2CF(CF2)n-, R is selected from <PICT:1102903/C2/1> <PICT:1102903/C2/2> and -(CH2)k-, R1 is H or CH3 Y is C1- 3 alkyl, X is F, Cl, Br or I, T is the 1,3,5-triazin-2,4,6-triyl radical, k is 2-20, n is 2-20, m is 0-20, m1 is 1-20, p1 is 0-20, p2 is 1-20, q is 1 or 2, and r is 2-10.  The compounds are prepared by conventional general processes from corresponding starting materials of the formulae Rf(CH2)m1OH . . . . (1) Rf(CH2)mCOOH . . . (2) RfCONH(CH2)rOH . . (3) RfCONH(CH2)rNH2 . . (4) and Rf(CH2)m1NH2 . . . (5) The starting materials of Formula (1) above are prepared by the reaction of a compound RfI with CH2 = CH(CH2)m2-2OH or CH2 = CH(CH2)m2-2OCOR11 where m2 is 3-20 and R11 is C1- 3 alkyl, to give products of the formula RfCH2CHI(CH2)m2-2OH or RfCH2CHI(CH2)m2-2OCOR11 respectively, which products are then, respectively, reduced or reduced and hydrolysed. The compounds of Formula (2) above are prepared by reacting Rf I with CH2 = CH(CH2)m2-2COOH or CH2 = CH(CH2)m2-2COOR11 to give, respectively, RfCH2CHI(CH2)m2-2COOH or RfCH2CHI(CH2)m2-2COOR11 which are then, respectively, reduced or reduced and hydrolysed. The compounds of Formula (3) above are prepared by reaction of RfCOOH with H2N(CH2)rOH.  The compounds of Formulae (4) and (5) above are obtained from compounds of Formulae (3) and (1), respectively, by reaction with ammonia water.  The compounds RfI where n is even are prepared from (CF3)2CFI and CF2 = CF2.  The compound RfI where n is 4 may be reacted with ethylene to give RfCH2CH2I which is dehydroiodinated to RfCH = CH2 and the latter oxidized to RfCOOH.ALSO:Articles are rendered oil- and water-repellent by impregnating with compositions comprising at least one fluoroalkyl-containing compound dissolved or suspended in at least one liquid medium, said fluoralkyl-containing compound being present in the composition in an amount of at least 0.1 gram/100 ml. of said liquid medium and being selected from Groups A, B, C-1 and C-2 below. Group A consists of compounds of the formul  <FORM:1102903/D1-D2/1> and {RtCONH(CH2)2NH-}a -T-X3-a where Rt is (CF3)2CF-(CF2)n-, R is selected from <FORM:1102903/D1-D2/2> and -(CH2)k-, R1 is H or CH3, T is the 1,3,5-triazin-2,4, or 6-triyl radical, X is F, Cl, Br or I, Y is C1-3 alkyl, k is 2-10, n is 2-20, m is 0-20, m1 is 1-20, p1 is 0-20, p2 is 1-20, q is 1 or 2 and r is 2-10.  Group B consists of the Fe, Zr, Al and Cr salts of acids of the formula Rt(CH2)mCOOH where the symbols Rt and m have the same significance as in Group A alone. Group C2 consists of polyesters prepared by branched-chain fluoralkylcontaining unsaturated compounds, copolymers of at least two of said compounds, and copolymers of at least one of said compounds in at least 25% by weight with an ethylenic polymerisable substance, the said unsaturated compound being of formula Rt(CH2)m1 OCO(CH2)p1 CR1=CH2 Rt(CH2)mCOO(CH2)p2CH=CH2 or RtCONH(CH2)r OCO(CH2)p1 CR1=CH2 where Rt, R1, m, m1, p1, p2 and r are as defined alone.  Group C2 consists of polyesters prepared by esterfying 30-100% of the hydroxyl groups of a polyvinyl alcohol, having an average polymerization degree of 300-1,000 and a saponification value of 70-100%, with a compound Rt(CH2)m COX where Rt, m and X are as defined above.