Polyquaternary flocculants

Abstract

Polyquaternary flocculants of average molecular weight, in excess of 10,000 are prepared by reacting a secondary amine with an epihalohydrin or diepoxide for use in flocculation of aqueous systems where ordinary cationic flocculants cannot be used.

What is claimed:  .[.1. A water-dispersible polyquaternary polymer of essentially linear structure consisting essentially of the difunctional reaction product of a lower dialkylamine and a difunctional epoxy compound selected from the group consisting of epihalohydrins, diepoxides, percursors of epihalohydrins and diepoxides which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of ##EQU10## wherein R and R 2  are individually selected from the group consisting of alkyl of 1 to 3 carbon atoms; E is a residue obtained from said epoxy compound; the total amounts of reactants being substantially equimolar, the combination of which is such as to provide a polyquaternary compound which as a 37% aqueous solution, by weight, based on the cationic portion of said polyquaternary compound has a viscosity at 25° C. of at least 100 centistokes; and X -  represents an ion forming the anionic 
     
        portion of said polyquaternary..]. 2.  The polymer of claim .[.1.]. .Iadd.21 .Iaddend.wherein said E is the residue obtained from 
     
     
        epichlorohydrin. 3.  The polymer of claim 2 wherein both R and R 2  are methyl groups.  .[.4. A water-dispersible polyquaternary polymer consisting essentially of the reaction product of a lower dialkylamine, a polyfunctional amine, and a difunctional epoxy compound selected from the group consisting of epihalohydrins, diepoxides, percusors of epihalohydrins and diepoxides which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of the structures ##EQU11## as the cationic portion, and X -  as the anionic portion wherein R and R 2  are individually selected from the group consisting of alkyls of 1 to 3 carbon atoms; E is a residue obtained from said epoxy compound; A is a residue obtained after at least bifunctional epoxy reaction from a polyfunctional amine selected from the group consisting of ammonia; primary amines; alkylene diamines of 2 to 6 carbon atoms; polyalkylenepolyamines of the structure ##EQU12## wherein y represents an integer of about 1 to 5, R 3  is an alkylene radical of about 2 to 6 carbon atoms, and R 4  is selected from the group consisting of hydrogen, alkyl of about 1 to 3 carbon atoms, and ω-aminoalkyl of about 2 to 6 carbon atoms; a polyglycolamine of a structure such as: ##EQU13## wherein a is an integer of about 1 to 5; piperazine; heteroaromatic diamines of the structure ##SPC7## wherein q is zero or an integer of about 1 to 3; and aromatic diamines of the structure ##SPC8##   wherein p and q are individually zero or an integer of about 1 to 3; X -  is an anion forming the anionic portion of said polyquaternary compound; the amount of said polyfunctional amine being up to about 15 mole percent of the total moles of said dialkylamine and said polyfunctional amine, the amount of said E is from at least that amount which is equimolar to the molar quantities of said amines up to the full functional equivalency of said amines, so as to provide a polyquaternary compound which as a 37% aqueous solution based on the cationic portion of said polyquaternary compound has a viscosity at 25° C. of at least 10 centistokes; and the amount of said ion present is such as to satisfy anion requirements of the cationic portion of said polyquaternary   
     
     
        compound..]. .[.5.  The polymer of claim 4 wherein said polyamine is ethylenediamine and the amount thereof is between about 3 and 6 mole percent of the total amount of amines in the reaction..]. .[.6. The polymer of claim 4 wherein said E is the residue obtained after bifunctional amine reaction from epichlorohydrin..]. .[.7. The polymer of claim 4 wherein said A is the residue obtained after at least bifunctional epoxy reaction from still bottoms resulting from purification of hexamethylenediamine..]. .[.8. The polymer of claim 4 wherein said E is the residue obtained after bifunctional amine reaction from 
     
     
        1,4-butanediol-diglycidyl ether..]. 9.  The polymer of claim .[.1.]. .Iadd.21 .Iaddend.wherein said viscosity is 235 centistokes. .[.10. The polymer of claim 4 wherein said viscosity is 800 centistokes..]. .[.11. The polymer of claim 4 wherein said A is the residue obtained after at least bifunctional epoxy reaction from still bottoms resulting from purification of ethylenediamine..]. .[.12. A process for preparing a polyquaternary compound from a secondary amine selected from dialkylamines wherein the alkyl groups are individually selected from those containing about 1 to 3 carbon atoms and an epoxy compound selected from the group consisting of epihalohydrins, diepoxides, precursors for epihalohydrins and diepoxides which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to about 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70° C., the total amounts of said reactants employed being substantially equimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70° C. for a time period sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25° C. of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus 
     
     
        formed..]. 13.  The process of claim .[.12.]. .Iadd.29 .Iaddend.wherein 
     
     
        said reactants are diamethylamine and epichlorohydrin.  14.  The process 
     
     
        of claim 13 wherein said viscosity is 235 centistokes. 15.  The process of 13 wherein the amount of water is about 18%, by weight, based on the total weight of reactants and water.  .[.16. A process for preparing a polyquaternary compound from a first reactant selected from the group consisting of dialkylamines wherein the alkyl groups are individually selected from those containing 1 to 3 carbon atoms; a second reactant selected from the group consisting of ammonia, primary amines, alkylenediamines of about 2 to 6 carbon atoms, polyamines of the structure: ##EQU14## wherein y represents an integer of about 1 to 5, R 3  is an alkylene of about 2 to 6 carbon atoms, and R 4  is selected from the group consisting of hydrogen, alkyl of about 1 to 3 carbon atoms, and ω-aminoalkyls of about 2 to 6 carbon atoms, piperazine, heteroaromatic diamines of the structure ##SPC9## wherein q is zero or an integer of about 1 to 3, and aromatic diamines of the structure ##SPC10##   wherein p and q are individually zero or an integer of about 1 to 3; and a third reactant selected from the group consisting of epihalohydrins, diepoxides, precursors which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof, the molar quantity of said second reactant being up to 15% of the total molar quantity of said first and said second reactants, and the molar quantity of said third reactant, being an amount which ranges from substantially equimolar to the total molar quantity of amines employed to substantially equal to the total functionality requirements of the amines: which process comprises (a) forming an aqueous reaction mixture of said reactants while maintaining the reaction mixture at a temperature in the range of about 20° C. to about 100° C., the amount of water in said mixture being from about 10% to 55%, by weight, based on the total weight of reactants and water; (b) maintaining said reaction mixture at a temperature in the range of about 50 to 100° C. until a polyquaternary compound is obtained which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary compound has a viscosity of at least 10 centistokes; and   
     
     
        thereafter recovering said polyquaternary compound..]. .[.17.  The process of claim 16 wherein in step (a) the amount of said third reactant added is substantially equal to the total molar amounts of amines employed..]. .[.18. The process of claim 17 wherein subsequent to step (b) and prior to recovery of said polyquaternary compound, an added amount of said third reactant is added and the reaction mixture maintained at a temperature in the range of 50 to 100° C. until a polyquaternary compound is again obtained which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary compound has a viscosity at 25° C. of at least 10 centistokes..]. .[.19. The process of claim 18 wherein step (a) both the first and second reactants are in the aqueous reaction mixture and said third reactant is added thereto..]. .[.20. The process of claim 18 wherein said first reactant is present in said aqueous reaction mixture, said third reactant is added thereto at a rate which maintains the temperature in the range of 50 to 70° C. and upon completion of addition of said third reactant reaction is allowed to proceed at a temperature in the range of 50 to 70° C. until from about 50% to about 80% of the reaction potential of said first and said third reactants has been achieved and then adding said second reactant to the reactant mixture thus formed..]. .Iadd.21. A water-dispersible polyquaternary polymer of essentially linear structure consisting essentially of the difunctional reaction product of dimethylamine and a difunctional epoxy compound selected from the group consisting of epihalohydrins and precursors for epihalohydrins which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of ##EQU15## wherein E is a residue obtained from said epoxy compound; the total amounts of reactants being substantially equimolar, the combination of which is such as to provide a polyquaternary compound which as a 37% aqueous solution, by weight, based on the cationic portion of said polyquaternary compound has a viscosity at 25°C. of at least 100 centistokes; and X -  represents an ion forming the anionic portion of 
     
     
        said polyquaternary..Iaddend. .Iadd.22.  The polymer of claim 21 wherein said viscosity is 250 centistokes..Iaddend..Iadd. 23. The polymer of claim 21 wherein said viscosity is at least 200 centistokes..Iaddend..Iadd. 24. The polymer of claim 23 wherein the lower dialkylamine is dimethylamine and the difunctional epoxy compound is epichlorohydrin..Iaddend..Iadd. 25. The polymer of claim 21 wherein said viscosity is 100 centistokes..Iaddend. .Iadd.26. The polymers of claim 25 wherein the lower dialkylamine is dimethylamine and the difunctional epoxy compound is epichlorohydrin..Iaddend. .Iadd.27. A water-dispersible polyquaternary polymer of essentially linear structure consisting essentially of the difunctional reaction product of a lower dialkylamine and a difunctional epoxy compound selected from the group consisting of diepoxides and precursors of diepoxides which under alkaline conditions are readily converted into the corresponding epoxy compounds, and mixtures thereof, said polyquaternary polymer containing repeating units of ##EQU16## wherein R and R 2  are individually selected from the group consisting of alkyl of 1 to 3 carbon atoms; E is a residue obtained from said epoxy compound; the total amounts of reactants being substantially equimolar, the combination of which is such as to provide a polyquaternary compound which as a 37% aqueous solution, by weight, based on the cationic portion of said polyquaternary compound has a viscosity at 25°C. of at least 100 centistokes; and X -  represents an ion forming the anionic 
     
     
        portion of said polyquaternary..Iaddend. .Iadd.28.  A process for preparing a polyquaternary compound from a secondary amine selected from dialkylamines wherein the alkyl groups are individually selected from those containing about 1 to 3 carbon atoms and an epoxy compound selected from the group consisting of diepoxides and precursors for diepoxides which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70°C., the total amounts of said reactants employed being substantially eqimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70°C. for a time sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25°C. of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus formed..Iaddend..Iadd.29. A process for preparing a polyquaternary compound from dimethylamine and an epoxy compound selected from the group consisting of epihalohydrins and precursors for epihalohydrins which under alkaline conditions are readily converted into corresponding epoxy compounds, and mixtures thereof; which process comprises the steps of (1) preparing an aqueous reaction mixture of one of said reactants, the amount of water therein being from about 10% to about 55%, by weight, based on the total weight of reactants and water; (2) adding the other of said reactants to the reaction mixture at a rate which maintains the reaction mixture at a temperature in the range of about 20 to 70°C., the total amounts of said reactants employed being substantially equimolar; (3) heating the reaction mixture at a temperature in the range of about 40 to 70°C. for a time period sufficient to obtain a polyquaternary compound which as a 37% aqueous solution, by weight, based on the total weight of the cationic portion of said polyquaternary has a viscosity at 25°C. of at least 100 centipoises; and thereafter recovering the polyquaternary compound thus formed..Iaddend.