Patent GB-898759-A (GB)
Title: Polymeric quaternary phosphorus compounds and method of preparing same
IPC: D06M13/282
Filed: 1960-02-01
Abstract: The invention comprises dimeric and polymeric phosphonium salts having the following structural configuration in the molecule:- <FORM:0898759/IV (a)/1> wherein R is a substituted or unsubstituted branched or straight chain alkyl radical or a substituted or unsubstituted cycloalkyl radical and X is a chlorine, bromine or iodine atom or a sulphate, phosphate or -O-C(O)-Y radical wherein Y is a C1-C6 alkyl group and wherein n is an integer of at least 2 and when n is 2 the phosphonium salt is a cyclic structure of the following configuration:-  <FORM:0898759/IV (a)/2> (see Group IV(b)) wherein R and X are as defined above.  They may be obtained by reacting a secondary phosphine R2PH with a p  vinyl derivative of the formula CH2=CH-X wherein R is as defined above and X is a Cl, Br or I atom or an -O.C(O).Y radical as defined above in the presence of a free radical initiator which is non-oxidizing to the reactants and then, if desired, when R bears a nitrile substituent hydrolyzing the nitrile to form a carboxyl substituent, and/or when X is -O.C(O)Y treating with an iodide or bromide salt to convert the corresponding compound to the diiodide or dibromide, and also, if desired subjecting the polymer to an anion exchange treatment to convert X to sulphate or phosphate.  The polymer produced may have an average molecular weight of between 5,000 and 10,000.  The temperature for the condensation of the secondary phosphine and the vinyl derivative is preferably from 70 DEG C. to 140 DEG C. and specified free radical initiators are di-t-butylperoxide, 2,21-azodiisobutyronitrile, ultraviolet light and X-ray radiation.  The polymeric phosphonium salts of formula I may also be used as promoters of the condensation reaction.  An inert solvent may also be present.  Specified secondary phosphines for use in the process are bis(2-cyanoethyl)-, bis(2-carboxyethyl)-, bis(2-butoxyethyl)-, dimethyl-, dibutyl-, diisobutyl-, didodecyl-, dicyclohexyl-, bis(2-methoxyethyl)- and bis(2-carbomethoxyethyl)-phosphines.  Secondary phosphines in which the alkyl or cycloalkyl groups are substituted by sulphonic or amido groups may also be used.  The process may be carried out continuously, semi-continuously or batchwise and at atmospheric, sub-atmospheric or super atmospheric pressure.  Examples are given for the production of polymeric dibutyl phosphonium acetate from vinyl acetate and di-n-butyl phosphine.  The products are useful as non-durable antistatic agents for use in textile finishes.ALSO:The invention comprises dimeric or polymeric phosphonium salts having the following structural configuration in the molecule <FORM:0898759/IV (b)/1> wherein R is a substituted or unsubstituted branched or straight chain alkyl radical or a cycloalkyl radical which may be substituted, X is a chlorine, bromine or iodine atom or a sulphate, phosphate or Y.CO.O-radical wherein Y is a C1-C6 alkyl group and n is an integer of at least 2 and when n is 2 the phosphonium salt is a cyclic structure of the configuration <FORM:0898759/IV (b)/2> wherein R and X are as defined above.  They may be obtained by (a) reacting a secondary phosphine of the formula R2PH with a vinyl derivative of the formula CH2=CH-X wherein R is as defined above and X is a Cl, Br, or I atom or an O-C(O)-Y radical wherein Y is C1-C6 alkyl in the presence of a free radical initiator which is non-oxidising to the reactants, and then, if desired, when R bears a nitrile substituent hydrolysing the nitrile to form a carboxyl substituent and/or when X is Y.CO.O- treating with an iodide or bromide to convert the corresponding compound to the diiodide or di bromide, (b) and, if desired, heating the polymer to convert it into a dimer, (c) and also, if desired, subjecting the dimer or the polymer to an anionic exchange treatment to convert X to sulphate or phosphate.  Step (a) of the reaction is preferably carried out at from 70 DEG C. to 140 DEG C. and the straight chain polymer may be converted to the cyclic dimer by heating, preferably at a temperature of at least 160 DEG C. The polymeric compounds of formula I may also be used in reaction (a) as promoters of the reaction. Specified free radical initiators are di-t-butyl peroxides, 2,21-azodiisobutyronitrile, ultraviolet light and X-ray radiation.  An inert solvent may also be present, e.g. acetonitrile, heptane, dioxane, or methyl ethyl ketone.  The alkyl and cycloalkyl groups of the secondary phosphine may be substituted with, e.g. carboxy-, cyano, sulphonic, or amido groups.  Suitable secondary phosphine reactants are bis(2-cyanoethyl)-, bis(2-carboxyethyl)-, bis(2-butoxyethyl)-, dimethyl-, dibutyl-, diisobutyl-, didodecyl-, dicyclohexyl-, bis(2-methoxyethyl)-, and bis(2-carbomethoxyethyl)-phosphines. The process may be carried out continuously, semi-continuously or batchwise and at atmospheric, sub-atmospheric or superatmospheric pressure.  Examples are given for the production of compounds of formula II in which R is CNCH2CH2- and Y is -O.CO.CH3 and Br, respectively, and the conversion of the acetate compound by refluxing with concentrated HCl to form the corresponding compound in which R is HOOC.CH2.CH2-and Y is Cl, and of compounds of formula II in which R is C4H9OCH2CH2 and Y is I, R is C4H9 and Y is CH3CO.O-, R is dodecyl and Y is CH3CO.O-, R is cyclohexyl and Y is I, and R is isobutyl and Y is I.  Examples are also given for the production of polymeric dibutyl phosphonium acetate (see Group IV (a)) and its conversion by heating under nitrogen at 160 DEG C.-165 DEG C. to 1,1,4,4-tetrabutyldiphosphonia cyclohexane diiodide.  The cyclic dimer products may be applied to wool to give lasting protection against insects such as moths and the polymeric products are useful as non-durable antistatic agents for use in textile finishes.