Patent GB-1069051-A (GB)
Title: Photographic silver halide emulsions
IPC: G03C1/10
Filed: 1963-06-11
Abstract: Polyoxyalkylene compounds having the for mula <F\1> wherein Z represents = N - or ­ N+R1X-in which R1 represents an alkyl group having 1-20 carbon atoms and X- is an acid anion; A1, A2 and A3 each represent -R5-[OR6]xOH, wherein x is an integer, R6 is ethylene or 1,2-propylene and R5 is the same as R6 or is -alkylene <FORM:1069051/C2/1> and when the R6 group has 3 carbon atoms, Z is ­ N+R1X-; B represents a C1-20 alkyl group or an aryl group or is the same as A1, A2 or A3; p is 2-10; or a compound of the formula <FORM:1069051/C2/2> where Z is as above and n is an integer such that the average value is 8-100 or a compound of the formula <FORM:1069051/C2/3> where R is C1- 20 alkyl group; R7 is -CH2-CH2-or <FORM:1069051/C2/4> q and q1 each represent an integer such that 4q + q1 has an average value of 6-100; Y is a hydroxyl group, a methane sulphonate group or <FORM:1069051/C2/5> where R2, R3 and R4 are C1- 4 alkyl and X- is an acid anion and when R7 is 1,2-propylene group Y is other than an hydroxyl group, are made by condensing the appropriate amine, amino alcohol, amino acid or polyhydroxy amide with ethylene or 1,2-propylene oxide or with a polyethylene- or polypropylene-glycol. Specified values of B and R1 are methyl, ethyl, propyl, butyl, heptyl, octyl, decyl, dodecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and phytyl. Suitable values of X- are chloride, bromide, methyl sulphonate, ethyl sulphonate, propyl sulphonate, butyl sulphonate and p-toluene- and benzene sulphonate.  Preferred products are those containing 6-100 alkylene oxide units per molecule and those derived from ethylenediamine, ethylenediamine tetraacetic acid, an alkylaminopropylamine -N,N1,N1-trisacetic acid, an alkylaminopropylamine, 1-dimethylamino - 3,6,9 - trimethyl - 3,6,9 - triazaundecanol and N-methylgluconamine.  The reaction with alkylene oxides may be effected in the presence of a catalyst, e.g. Lewis-acids, tertiary amines, acids and inorganic bases.  The reaction with polyalkylene glycols is carried out using an acid catalyst and removing the water liberated as an azeotrope, e.g. with p-xylene. Compounds of the formulae I and II where Z is ­ N+R1 X- are made by quaternizing the tertiary amine, e.g. with methyl p-toluene sulphonate. Compounds of the Formula III in which Y is a methane sulphonate group are made by reacting the hydroxy compound with methyl sulphonyl chloride.  The compounds of the Formula III is which Y is quaternary nitrogen or pyridinium are made by reacting the appropriate tertiary base with the methane sulphonate esters or with the halohydrin compounds obtained by condensing the compounds in which Y is -OH with epihalohydrins; pyridine is the preferred tertiary base.  The examples relate to polyoxyalkylene derivatives of the compounds specified above.ALSO:Compounds having the formula <FORM:1069051/C3/1> wherein Z represents =N- or ­N(+)R1X(-) in which R1 represents an alkyl group having 1-20 carbon atoms and X(-) is an acid anion; A1, A2 and A3 each represent -R5-[OR6]xOH, wherein x is an integer, R6 is ethylene or 1,2-propylene and R5 is the same as R6 or is <FORM:1069051/C3/2> and when the R6 group has 3 carbon atoms, Z is ­N(+)R1X(-); B represents a C1- 20 alkyl group or an aryl group or is the same as A1, A2 or A3; p is 2-10; or a compound of the formula <FORM:1069051/C3/3> where Z is as above and n is an integer such that the average value is 8-100 or a compound of the formula <FORM:1069051/C3/4> where R is C1- 20 alkyl group; R7 is -CH2-CH2-or <FORM:1069051/C3/5> q and q1 each represent an integer such that 4q + q1 has an average value of 6-100; Y is a hydroxyl group, a methane sulphonate group or <FORM:1069051/C3/6> where R2, R3 and R4 are C1- 4 alkyl and X(-) is an acid anion and when R7 is 1,2-propylene group Y is other than a hydroxyl group, are made by condensing the appropriate amine, amino alcohol, amino acid or polyhydroxyamide with ethylene or 1,2-propylene oxide or with a polyethylene- or polypropylene-glycol.  Specified values of B and R1 are methyl, ethyl, propyl, butyl, heptyl, octyl, decyl, dodecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and phytyl. Suitable values of X(-) are chloride, bromide, methyl sulphonate, ethyl sulphonate, propyl sulphonate, butyl sulphonate and p-toluene- and benzene sulphonate. Preferred products are those containing 6-100 alkylene oxide units per molecule and those derived from ethylenediamine, ethylenediamine tetraacetic acid, an alkylaminopropylamine - N,N1,N1 - trisacetic acid, an alkylaminopropylamine, 1-dimethylamino - 3,6,9 - trimethyl - 3,6,9 - triazaundecanol and N-methylgluconamine.  The reaction with alkylene oxides may be effected in the presence of a catalyst, e.g. Lewis-acids, tertiary amines, acids and inorganic bases.  The reaction with polyalkylene glycols is carried out using an acid catalyst and removing the water liberated as an azeotrope, e.g. with p-xylene.  Compounds of the Formula I and II, where Z is­N(+)R1X(-) are made by quaternizing the tertiary amine, e.g. with methyl p-toluene sulphonate. Compounds of the Formula III in which Y is a methane sulphonate group are made by reacting the hydroxy compound with methyl sulphonyl chloride.  The compounds of the Formula III in which Y is quaternary nitrogen or pyridinium are made by reacting the appropriate tertiary base with the methane sulphonate esters or with the halohydrin compounds obtained by condensing the compounds in which Y is -OH with epihalohydrins; pyridine is the preferred tertiary base.  The examples relate to polyoxyalkylene derivatives of the compounds specified above.