Patent GB-1093603-A (GB)
Title: Polyphosphonium compounds and process therefor
IPC: C08G79/06
Filed: 1966-03-16
Abstract: Polyphosphonium compounds containing the unit <FORM:1093603/C3/1> wherein R and R1 are divalent hydrocarbon groups containing 1 to 18 carbon atoms, each R1 contains one to 18 carbon atoms and is a monovalent hydrocarbon or monohydroxy substituted hydrocarbon group, and two R1 groups on the same phosphorus atom can together form a divalent hydrocarbon group, and wherein R, R1 and R1 may have at least one hydrogen atom replaced by a non-reactive element or functional group, n is an integer of at least 5, Q is an anion and m is the charge of the anion Q may be prepared by reacting at least one diphosphine of the formula <FORM:1093603/C3/2> with an organic dihalide X-R1-X at a temperature between 20 DEG  C. and 400 DEG  C. optionally in the presence of an inert solvent and a metal halide catalyst, followed by an anion exchange reaction if desired.  The group R1 may be alkyl, aryl, aralkyl, alkaryl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl which groups may contain one or more hydroxy groups or the ether or siloxane derivatives of such hydroxy substituted groups. Suitable R and R1 groups are methylene, ethylene, 1,2-propylene, butylene, butenylene, butynylene, 1,3 - cyclopentylene, 1,3 - cyclohexenylene, -C = C-, <FORM:1093603/C3/3> 1,3 - naphthylene, phenylene, biphenylene, terphenylene, tolylene or cumylene, which groups may have one or more hydrogen atoms replaced by non-reactive elements or functional groups.  Suitable inert solvents are anisole, N-methylacetamide, N,N - dimethylacetamide, N,N1 - tetramethylurea, tris - (dimethylamido)-oxophosphoran and hydroxylic solvents such as alkanols and water.  The preferred catalysts are AlCl3, CoCl2, NiCl2, NiBr and Cu2Cl2 and in cases wherein a catalyst is employed, at least a portion of the anions Q are halometalate ions derived from the catalyst.  Anion exchange may occur by dissolving the polymer in a polar solvent and adding to the solution a solid salt or salt solution containing the desired anion. Oxygen should preferably be excluded during the process of the invention.ALSO:Diphosphines of the formula <FORM:1093603/C2/1> wherein R1 represents monovalent hydrocarbon groups or hydroxy-substituted monovalent hydrocarbon groups containing 1 to 18 carbon atoms and R is a divalent hydrocarbon group containing 1 to 18 carbon atoms, may be prepared by the Grignard synthesis and other syntheses employing organo - metallic compounds. Typical compounds prepared are:  <FORM:1093603/C2/2> <FORM:1093603/C2/3> <FORM:1093603/C2/4> <FORM:1093603/C2/5> (C6H5)2PCH = CHP(C6H5)2 (C6H5)2PC6H4P(CH3)2 The compounds of Formula (II) wherein two R1 groups together form an unsaturated divalent hydrocarbon group may also be prepared by reacting two moles of a compound of Formula <FORM:1093603/C2/6> wherein M is an alkali metal, R5 is H or a monovalent hydrocarbon group, and two R5 groups on adjacent carbon atoms can together form a divalent hydrocarbon group with one mole of a compound X-R1-X, wherein R1 is a divalent hydrocarbon group of 1 to 18 carbon atoms and X is a halogen atom, suitably in an inert solven. Typical of such compounds are:  <FORM:1093603/C2/7> <FORM:1093603/C2/8> <FORM:1093603/C2/9> <FORM:1093603/C2/100> The compounds (VII) may be prepared by reacting in a hydrocarbon or a hydrocarbon ether solvent an alkali metal and a compound of formula <FORM:1093603/C2/111> wherein G represents a phenyl, benzyl or allyl group which may be substituted with other monovalent hydrocarbon groups.ALSO:Polyphosphourine compounds containing the unit: <FORM:1093603/B1-B2/1> wherein R and R1 are the same or different divalent hydrocarbon groups containing 1 to 18 carbon atoms, each R1 contains from 1 to 18 carbon atoms and is a monovalent hydrocarbon group which may be monohydroxy substituted or two R1 groups on the same phosphorous atom can together form a divalent hydrocarbon group and wherein R, R1 and R1 may have at least one hydrogen atom replaced by a non-reactive element or functional group, n is an integer of at least 5, Q is an anion and m is the charge of the anion Q may be applied to the surface of fibrous glass cloth, non-fibrous solids, wood and plastics in a thin coating which resist accumulation of static charges or to form a heat resistant self-extinguishing coating.