Compositions of inorganic-organic alloy with highly charged nitrogen content polymers and their manufacture

Abstract

Inorganic-organic alloy polymer adduct .Iadd.or organic blends polymer .Iaddend.compositions for waste water treatment, having the formula: A.B.sup.+.C.D.sup.+ wherein A is from 0% to 98% by weight of the total alloy composition, and is selected from the group comprising: polyhydroxyaluminumchloride, hydroxyaluminumchloride, polyhydroxyaluminumagnesiumchloride, .[.polyhydroxyaluminumagnesium sulfate,.]. polyhydroxyaluminumagnesiumsulfate, hydroxyaluminumsulfate, polyhydroxyaluminumzincoxidechloride, polyhydroxyaluminumchlorosulfate, polyhydroxymagnesiumchlorosulfate, polyaluminumferricchloride, polyaluminumferrouschloride, polyaluminumcholridesulfate, polyhydroxyaluminumchloridesilicate, .[.and.]. polyhydroxyaluminumsodiumsulfophosphate; .Iadd.and aluminum salts; where A vary from 0% to 100% B + is from .[.2% to 98%.]. .Iadd.0 to 100% .Iaddend.by weight of the total alloy composition, and is selected from the group comprising polymers or resins made from guanidine, dicyandiamide, or cyanoguanidine compounds, copolymerized with cationic charges, multiple organic cationic charges, protonized agents, alkylamines, alkanolamines, alkyl, or hydroxyalkylguanidine, or any mixture thereof; C is from .[.0 to 95%.]. .Iadd.0% to 100% .Iaddend.by weight of the total alloy composition, and is an aqueous solution of cationic resin mixed with a reagent selected from polyalkylamines, polyethylenepolyamines, N-substituted ethyleneimines, polyquaternary compound, 1,3-bisquaternaryammonium compound, and polyquaternaryalkylamines; .[.and.]. .Iadd.melamine-formaldehyde protonized or quaternized or their blends.Iaddend.. D + is from .[.0% to 95%.]. .Iadd.0% to 100% .Iaddend.by weight of the total alloy composition, and is selected from the group comprising aqueous solutions of the quaternary ammonium compounds .Iadd.like PDADMAC, or cationic (co)polyacrylamide, or their (co)polymers.Iaddend., .[.and their ethylenically unsaturated (co)polymerizable compounds,.]. POLYDADMAC melamine formaldehyde alloy, Manich type, (co)polyacrylamidemelamineformaldehyde alloy polymers, incorporated therein .Iadd.and provided that at least one of A, B + , C, D + is positive.Iaddend.. Methods for making the compounds are also disclosed.

What is claimed is: 
     
       1. Water-soluble inorganic-organic alloy polymer adduct composition for purification of potable water, acid rain water, paper mill effluent, industrial waste water, industrial waste liquids, solids and semiliquids, water-borne waste and paint, said composition having the formula:   A.B.sup.+.C.D.sup.+     wherein   A=[Me m   II  Me n   III  (OH) p  (SO 4 ) y  (Aci)(2m+3n)-p-2y] r , where r=0 to 98% .Iadd.and 2m+3n>2y+p.Iaddend.;   .[.B=.]. .Iadd.B +  =.Iaddend. ##STR29##  where x=2 to 98%; C=(PAM) z  (PAM-PAD) t+z  ;   D=(PQAM) w  ;   Me m   II  is selected from the divalent cation group comprising Mg, Zn, Ca, and Fe 2+  ;   m=0 to 5;   Me n   III  is a tri-or more valent metal selected from the group comprising Fe, Al, and Al-Zr complexes;   n=1 to 20;   Aci is selected from the monovalent anionic group comprising Cl - , Br - , I - , and NO 3  ;   PAM=polyamine;   PAD=polyamide;   PQAM=polyquaternized polymer;   p=0 to 75;   y=0 to 15   z=0 to 95% percent by weight of polyamine;   t=0 to 95% percent by weight of polyamide;   w=0 to 98% percent by weight of polyquaternized polymer; and   R 1  =bridge cationic or multiple organic cationic charge or mixture thereof .Iadd.which can vary from 0 to 80% by weight R 2  alkyl phosphonic esters and/or amine derivatives, phosphonium cationic charge groups, such as tetrakis (hydroxymethyl)-phosphonium halide, hydroxide, oxalate, acetate, sulfate, phosphate, tri-hydroxymethyl-phosphonium or halide derivatives, or tetramethylhalide phosphonium halide derivatives, the halo-group being chlorine, bromine, or iodine, phosphorous acid and its esters or salts, H 3  PO 4  and its salts, such as sodium dihydrogen phosphate, which can vary from 0 to 80% by weight.     
     
     
       2. A composition according to claim 1 wherein A is selected from the group .[.comprising:.]. .Iadd.consisting:.Iaddend. Al m  (OH) n  X 3m-n-2k  (SO 4 ) k  ; Al 1-x  Fe x   II  Fe y   III  (OH) 3+2y-2  (Hal) z  ;   Al m  (OH) x  (SO 4 ) y  (H 2  PO 4 ) z  ; Me n  (OH) m  X 3n-m  ; regular chloride, sulfate, phosphate, nitrate, or acetate salts of aluminum, iron, titanium, vanadium, zirconium, chromium, antimony, or a mixture thereof.   
     
     
       3. A composition according to claim 1 wherein B +  is selected from the group .[.comprising.]. .Iadd.consisting .Iaddend.polymers or resins made from guanidine, dicyandiamide, or cyanoguanidine compounds, copolymerized with cationic charges, multiple organic cationic charges, protonized agents, alkylamines, alkanolamines, alkyl, or hydroxyalkylguanidine, or any mixture thereof. 
     
     
       4. A composition according to claim 2, wherein D +  (PQAM) is selected from the group .[.comprising.]. .Iadd.consisting .Iaddend.aqueous solutions of the quaternary ammonium compounds and their ethylenically unsaturated and their (co)polymerizable compounds. 
     
     
       5. Water-soluble inorganic-organic alloy polymer adduct composition for purification of potable water, acid rain water, paper mill effluent, industrial waste water, industrial waste liquids, solids and semiliquids, water-borne waste and paint, said composition having the formula:   A.B.sup.+.C.D.sup.+     wherein   A=5 to 95% by weight of polyhydroxyaluminumchloride inorganic adducts polymer;   B +  =0 to 95% by weight of polymers of copolymerized dicyandiamide;   C=0 to 95% by weight of polyalkylamines, and 0 to 95% by weight of a mixture of polyalkylamine and an aqueous solution of cationic resin; and   D +  =0 to 95% by weight of an aqueous solution of a quaternary ammonium compound.   
     
     
       6. Water-soluble inorganic-organic alloy polymer adduct composition for purification of potable water, acid rain water, paper mill effluent, industrial waste water, industrial waste liquids, solids and semiliquids, water-borne waste and paint, said composition having the formula:   A.B.sup.+.C.D.sup.+     wherein   A=0 to 98% by weight of polyhydroxyaluminummagnesiumchloride inorganic adducts polymer;   B +  =0 to 95% by weight of polymers of copolymerized dicyandiamide;   C=5 to 95% by weight of polyalkylamines, and 0 to 95% by weight of a mixture of polyalkylamine and an aqueous solution of cationic resin; and   D +  =0 to 95% by weight of an aqueous solution of a quaternary ammonium compound.   
     
     
       7. Water-soluble inorganic-organic alloy polymer adduct composition for purification of potable water, acid rain water, paper mill effluent, industrial waste water, industrial waste liquids, solids and semiliquids, water-borne waste and paint, said composition having the formula:   A.B.sup.+.C.D.sup.+     wherein   A==5 to 95% by weight of polyhydroxyaluminummagnesium sulfate inorganic adducts polymer;   B +  =0 to 95% by weight of polymers of copolymerized dicyandiamide;   C=0 to 95% by weight of polyalkylamines, and 0 to 95% by weight of a mixture of polyalkylamine and an aqueous solution of cationic resin; and   D +  =0 to 95% by weight of an aqueous solution of a quaternary ammonium compound.   
     
     
       8. Water-soluble inorganic-organic alloy polymer adduct composition for purification of potable water, acid rain water, paper mill effluent, .[.inductrial.]. .Iadd.industrial .Iaddend.waste water, industrial waste liquids, solids and semiliquids, water-borne waste and paint, said composition having the formula: wherein   A=5 to 95% by weight of polyhydroxyaluminumchlorosulfate inorganic adducts polymer;   B +  =0 to 70% by weight of polymers of copolymerized dicyandiamide;   C=0 to 95% by weight of polyalkylamines, and 0 to 95% by weight of a mixture of polyalkylamine and an aqueous solution of cationic resin; and   D +  =0 to 95% by weight of an aqueous solution of a quaternary ammonium compound. .Iadd.9. Water-soluble inorganic-organic, or organic adduct, or blend polymers composition for purification of potable water, acid rain water, pulp and paper mill streams or waste water, industrial water streams or waste water liquids, semiliquids or solids, for removal of suspended matters, leather or textile industries stream or waste water, water-borne spray paint or water wash spray booth, wherein said composition having formula:   A.B.sup.+.C.D.sup.+     which correspond to the formula ##STR30## with the proviso that the resulting polymer adduct or blend composition contains at least two of the four components recited in the formula A.B + .C.D +  and that at least two of the r,x,z,t+z,w are positive numerical value,   where:     r=0 to 98% percent by weight;   Me m   II  is a divalent cation group selected from Mg, Ca, Zn, Fe 2+  and,   m=0 to 5;   Me n   III  is a tri-or more valent metal, preferably Al, Fe, or Al-Zr complex, and   n=1 to 20;   Aci is selected from the monovalent anion group of (a)Cl - , (b)Br - , I - , (d)NO 3   - , (e) CH 3  COO - , and (f) a mixture of these selected Aci is Cl -  ;   PAM, PAD and PQAM stand for water soluble polyamine, polyamide and polyquaternized or cationic polymers;   p=0 to 75;   y=0 to 15;   2m+3n>2y+p   x=0 to 98% by weight in compositions;   z=percentage by weight of the water soluble polyamine in the alloy composition, which can vary from 0 to 95%;   t=percentage by weight of the water soluble polyamide, which can vary from 0 to 95%;   t+z=percentage by weight of a water soluble mixture of polyamine-polyamide, which can vary in compositions in percentage from 0% to 95% by weight; z>t   w=percentage by weight of the water soluble quaternary ammonium polymer, polydiallyldimethyl ammonium chloride (PDADMAC), or water soluble cationic polyacrylamide and its copolymers, or allyltrialkylammonium polymer or its cationic or nonionic copolymer, nonionic polyacrylamide, or their copolymers or organic alloy or blends, which can vary in percentage from 0 to 98% by weight;   R 1  - refers to hydrogen, bridge cationic or multiple organic cationic charges, which can vary from 0% to 80% by weight   R 2  - refers to hydrogen, alkyl phosphonic esters or amine derivatives, dialkyl hydrogen phosphite, phosphorous acid and its esters or salts, H 3  PO 4  acid or its salts like sodium dihydrogen phosphate, phosphonium cationic charge groups, comprising tetrakis (hydroxymethyl)-phosphonium halide, hydroxide, oxalate, acetate, sulfate, phosphate, tri-hydroxymethyl-phosphonium or halide derivatives, or tetramethylhalide phosphonium halide derivatives, the halo-group being chlorine, bromine, or iodine, which may vary from 0 to 80% by weight. .Iaddend. .Iadd.10. The composition of claim 9 wherein the components present are A and B +  in a weight percent ratio of A:B +  of (1- 99):(99- 1)..Iaddend. .Iadd.11. The composition of claim 10 wherein the ratio of A to B +  is (1-20):(80-99). .Iaddend. .Iadd.12. The composition of claim 11 wherein the ratio of A to B +  is (50-96):(3-39). .Iaddend. .Iadd.13. The composition of claim 9 wherein the components present are B +  and D +  in a weight percent ratio of B +  :D +  of (83-99):(1-17). .Iaddend. .Iadd.14. The composition of claim 9 wherein the components present are A and C in a weight present ratio of A:C of (2-93):(7-98). .Iaddend. .Iadd.15. The composition of claim 14 wherein the ratio of A:C is (93.5:1.5) or (6.5:98.5). .Iaddend. .Iadd.16. The composition of claim 9 wherein the components present are A and D +  in a weight percent ratio of A:D +  of (49-99):(1.0-51). .Iaddend. .Iadd.17. The composition of claim 16 wherein the ratio of A:D +  is (49-56):(44-51). .Iaddend. .Iadd.18. The composition of claim 9 wherein the components present are B +  and C in a weight percent ratio of B +  :C of 95:3.5. .Iaddend. .Iadd.19. The composition of claim 9 wherein the components present are A,B +  and C in a weight percent ratio of A:B +  :C of (1-5):(20-94):(4-79). .Iaddend. .Iadd.20. The composition of claim 19 wherein the ratio of A:B +  :C is (2-5):(52-94):(4-43). .Iaddend. .Iadd.21. The composition of claim 19 wherein the ratio of A:B +  :C is (1:5):(20-52):(43-79). .Iaddend. .Iadd.22. The composition of claim 9 wherein the components present are A,B + ,D +  in a weight percent ratio of A:B +  :D +  (10-14):(3-84):(2-87). .Iaddend. .Iadd.23. The composition of claim 22 wherein the ratio of A:B +  :D +  is 10:3:87. .Iaddend. .Iadd.24. The composition of claim 22 wherein the ratio of A:B +  :D +  is 14:84:2. .Iaddend. .Iadd.25. The composition of claim 9 wherein the components present are B + ,C and D +  in a weight percent ratio of B +  :C:D +  of 96:3:1. .Iaddend. .Iadd.26. The composition according to claim 9 wherein A is selected from the group consisting of I(a) through I(f)   I(a): [Me m   I  Me n   II  (OH) p  (SO 4 ) y  (Aci).sub.(2m+3n)-p-2y ]   wherein:   Me m   II  is a divalent cation group from Mg,Zn,Ca,Fe 2+  and m=0 to 5;   Me n   III  is a tri- or more valent metal, selected from Al,Fe or Al-Zr complexes, and = 1 to 20;   Aci is selected from a monovalent anion group consisting of (a) Cl - , (b) Br - , (c) I - , (d) NO 3   - , (e) CH 3  COO -  or (f) a mixture of two or more of foregoing.   I(b): Al m  (OH) n  X 3m-n-2k  (SO 4 ) k     wherein: X is sodium, potassium, chlorine   k,m,n, are positive numbers.     I(c): Al 1-x  Fe x   III   F  e y   II  ()H) 3+2y-z  (Hal) z     wherein: Hal=chlorine,bromine,iodine,or a mixture thereof;   (x+y)/(1-x)=about 0.2 to 1.5,   z<3+2y, and   (3+2y-2)/(3+2y)=about 0.24 to 0.67;     I(d): Al m  (OH) n  (SO 4 ) y  (H 2  PO 4 ) z  with the proviso that the sum of x+2y+2 is 3; m and x are positive integers; and y and z are 0 or positive integers.   I(e): Me n  (OH) m  X 3n-m     wherein: m,n are positive integers   Me n   III  is a tri- or more valent metal, and   X is Cl - , Ch 3  COO - , or NO 3   -  ;     I(f): regular salts of aluminum,iron,titanium,vanadium,chromium, antimonium, comprising chloride,sulfate,phosphate,nitrate, acetate or mixture thereof. .Iaddend. .Iadd.27. The composition of the claim 9 wherein A is selected from the following group of inorganic adduct polymers:   1. Polyhydroxyaluminumchloride; Al 4  (OH) 9  (Cl) 3 , or Al 8  (OH) 2  1, or Al 11  (OH) 30  (Cl) 3       2. Hydroxyaluminumchloride: Al 2  (OH) 5  Cl as chlorhydrol TR-50, Astrigen TR-50.   3. Polyhydroxyaluminum magnesiumchloride; Al 3  Mg(OH) 9  (Cl) 2     4. Polyhydroxyaluminumcalciumchloride: Al 7  Ca 0 .04 (OH) 17 .01)Cl) 4  ;     5. Polyhydroxyaluminum magnesiumsulfate: Al 4  Mg(OH) 4  (SO 4 ) 3 .5     6. Hydroxyaluminum sulfate: Al 2  (OH) 4  (SO 4 );   7. Oxialuminum sulfate: Al 2  O(SO 4 ) 2     8. Polyhydroxyaluminumzincoxidechloride: Al 3  (OH) 3  ZnO(OH)(Cl) 2       9. Polyhydroxyaluminum and/or magnesiumchlorosulfate: Al 4  (OH) 6  (Cl) 4  (SO 4 );   Al 4  Mg(OH) 6  (Cl) 4  (SO 4 ) 2  ; or   Al 3  Mg(OH) 6  (Cl) 3  (SO 4 );     10. Polyaluminumferric and/or ferrous chloride: Al 2  Fe 2  (OH) 3 .32 (Cl) 6 .68   AlFe 0 .25 I I  Fe 0 .25III (O) (H) 2 .12 (Cl) 2 .12 ;     11. Polyaluminumchloridesulfate; and   12. Polyhydroxyaluminumchloro silicate;   13. Aluminumzirconium(penta or tetra)chlorohydrate Al 8  Zr(OH) 22  (Cl) 5  or Al 4  Zr(OH) 12  (Cl) 4 . .Iaddend. .Iadd.28. Inorganic-organic or organic alloy polymer adduct composition for purification of potable water, industrial water streams or waste water treatment, or water-borne spray paint booth or water wash spray booth, paint booth waste water said composition having formula:   A.B.sup.+ C.D.sub.+     with the proviso that resulting polymer alloy or blend contain at least two of the four components recited and provided that at least one of the components present is A or B +  or D + , wherein:       A is from 0% to 98% by weight of the total alloy composition, and is selected from the group comprising: polyhydroxyaluminumchloride,hydroxyaluminumchloride,polyhydroxyaluminum magnesiumchloride,polyhydroxyaluminum magnesiumsulfate, hydroxyaluminumsulfate,oxialuminumsulfate, polyhydroxyaluminumzincoxidechloride, polyhydroxyaluminumchlorosulfate, polyaluminumferric chloride, polyaluminumferrouschloride, polyaluminumchloridesulfate, polyhydroxyaluminumsilicate, and polyhydroxyaluminumsodium sulfophosphate;   B +  is from 0 to 98% by weight of the total alloy composition, and is selected from the group comprising polymer or resin made from guanidine,dicyandiamide, or cyanoguanidine copolymerized with cationic charges monomer or multiple organic cationic charges,protonized agents,alkyl amine,alkanol amine, alkyl or hydroxyalkylguanidine, or mixture thereof,   C is from 0 to 95% by weight of the total alloy composition, and is an aqueous solution of cationic resin selected from polyalkyl amine, polyamine, polyethylenepolyamine,N-substituted ethyleneimines,polyquaternaryamine,1,3-bisquaternaryammonium amine,water soluble colloidal cationic melamine-formaldehyde or melamine-urea-formaldehyde resins,and   D +  is from 0% to 95% by weight of total alloy or blend composition,and is selected from the group of aqueous solution of the quaternary ammonium polymer comprising polydiallyldimethyl ammonium chloride(PDADMAC), water soluble cationic polyacrylamide and its copolymers,POLYDADMAC- melamine-formaldehyde alloy,Manich type (co)polyacrylamide- melamine-formaldehyde alloy or blend polymers incorporated therein. .Iaddend. .Iadd.29. The composition of claim 9 wherein the component B +  is selected from the guanidine compounds and resin guanidine resin or polymer cationic charged guanidine or cyanoguanidine of formula B(1) through B(7). .Iaddend. .Iadd.30. The composition of claim 9 wherein the component C is selected from water soluble cationic polyamine, alkyl polyamine, polyamine-polyamide,water soluble cationic colloidal melamine-formaldehyde or melamine-urea-formaldehyde resins. .Iaddend. .Iadd.31. The composition of claim 9 wherein the component D +  is selected from aqueous solution of quaternary ammonium compound,water soluble cationic polyacrylamide and its copolymers,POLYDADMAC, POLYDADMAC-melamine-formaldehyde alloy,Manich type (co)polyacrylamide-melamine-formaldehyde alloy polymers, polyacrylamide,(co)polymers of hydrochloride of N,N-diglycine- polydiallylamine,or mixture thereof. .Iaddend.