Vinylamine copolymer flocculating agent etc.

Abstract

[Disclosed herein is a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III), (IV) and (V): <IMAGE> [I] <IMAGE> [II] <IMAGE> [III] <IMAGE>nion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M(+)represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer and the molar fraction of the structural unit (V) is 0 to 8% by mole which is based on the total content of the structural units (III), (IV) and (V), a flocculating agent and a paper strength increasing agent using the vinylamine copolymer, and a process for producing the vinylamine copolymer.] Disclosed herein is a vinylamine copolymer comprising structural units represented by the following formulas: <IMAGE> (A) <IMAGE> (B) <IMAGE> (C) <IMAGE> (D) wherein X(-) represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M(+) represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D), wherein the total of the molar fractions of all structural units of the vinylamine copolymer is equal to 100%.

What is claimed is: 
     
       1. A vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR11## wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]. and the total of the molar fractions of the structural units .[.I-V is equal to 100%.]. .Iadd.I-III is at least 60%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer.Iaddend..   
     
     
       2. A vinylamine copolymer according to claim 1, wherein the reduced viscosity of the vinylamine copolymer is from 0.1 to 10 dl/g measured as a solution thereof prepared by dissolving said copolymer in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25° C. 
     
     
       3. A vinylamine copolymer according to claim 1, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]. 
     
     
       4. A vinylamine copolymer according to claim 3, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mol % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       5. A flocculating agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and (IV) .[.and (V).].: ##STR12## wherein X.sup.⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and the total of the molar fractions of the structural units .[.I-V is equal to 100.]. .Iadd.I-III is at least 60%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer.Iaddend..   
     
     
       6. A flocculating agent according to claim 5, wherein the reduced viscosity of the vinylamine copolymer is from 0.1 to 10 dl/g measured as a solution thereof prepared by dissolving said copolymer in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25° C. 
     
     
       7. A flocculating agent according to claim 5, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       8. A flocculating agent according to claim 7, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mol % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       9. A paper strength increasing agent comprising of a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR13## wherein X.sup.⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and the total of the molar fractions of the structural units .[.I-V is equal to 100%.]. .Iadd.I-III is at least 60%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer.Iaddend..   
     
     
       10. A paper strength increasing agent according to claim 9, wherein the reduced viscosity of the vinylamine copolymer is from 0.1 to 10 dl/g measured as a solution thereof prepared by dissolving said copolymer in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25° C. 
     
     
       11. A paper strength increasing agent according to claim 9, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 80 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 40 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 8 mol % of the structural unit .[.(V).]. .Iadd.(IV .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       12. A paper strength increasing agent according to claim 11, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mol % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III.[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       13. A drainage aid for papermaking comprising of a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR14## wherein X.sup.⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and the total of the molar fractions of the structural units .[.I-V is equal to 100%.]. .Iadd.I-III is at least 60%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer.Iaddend..   
     
     
       14. A drainage aid according to claim 13, wherein the reduced viscosity of the vinylamine copolymer is from 0.1 to 10 dl/g measured as a solution thereof prepared by dissolving said copolymer in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25° C. 
     
     
       15. A drainage aid according to claim 13, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 80 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 40 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 8 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       16. A drainage aid according to claim 15, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mol % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       17. A retention aid for papermaking comprising of a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (VO.].: ##STR15## wherein X.sup.⊖ represents an anion or hydroxyl ion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of the structural unit (IV) .[.is 0 to 40% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (V).]. is 0 to 20% by mole which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., and the total of the molar fractions of the structural units .[.I-V is equal to 100%.]. .Iadd.I-III is at least 60%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer. .Iaddend.   
     
     
       18. A retention aid according to claim 17, wherein the reduced viscosity of the vinylamine copolymer is from 0.1 to 10 dl/g measured as a solution thereof prepared by dissolving said copolymer in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25° C. 
     
     
       19. A retention aid according to claim 17, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 2 to 85 mol % of the structural unit (II) in the molar fraction, from 5 to 80 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 40 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 8 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction which is based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].. 
     
     
       20. A retention aid according to claim 19, wherein the composition of said vinylamine copolymer is from 5 to 85 mol % of the structural unit (I) in the molar fraction, from 5 to 60 mol % of the structural unit (II) in the molar fraction, from 10 to 60 mol % of the structural unit (III) in the molar fraction, .[.from 0 to 30 mol % of the structural unit (IV) in the molar fraction,.]. all of said molar fractions being based on the vinylamine copolymer, and from 0 to 2.5 mol % of the structural unit .[.(V).]. .Iadd.(IV) .Iaddend.in the molar fraction based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (IV).].. .Iadd.21. A vinylamine copolymer comprising structural units represented by the following formulas: ##STR16##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D); wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and hydrolyzing the resultant polymer.   
     
     
        .Iadd.22.  A flocculating agent comprising a vinylamine copolymer comprising structural units represented by the following formulas: ##STR17##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D); wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   
     
     
       hydrolyzing the resultant polymer.  .Iadd.23.  A paper strength increasing agent comprising a vinylamine copolymer comprising structural units represented by the following formulas: ##STR18##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D); wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   
     
     
       hydrolyzing the resultant polymer.  .Iadd.24.  A drainage aid for papermaking comprising a vinylamine copolymer comprising structural units represented by the following formulas: ##STR19##.Iaddend. wherein X.sup.⊕ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊖ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D); wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   
     
     
       hydrolyzing the resultant polymer.  .Iadd.25.  A retention aid for papermaking comprising a vinylamine copolymer comprising structural units represented by the following formulas: ##STR20##.Iaddend. X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer, and the molar fraction of the structural unit (D) is 0 to 20% by mole which is based on the total content of the structural units (C) and (D) ; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   
     
     
       hydrolyzing the resultant polymer.  .Iadd.26.  A vinylamine copolymer prepared by: polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile, at a molar ratio of 20:80 to 95:5, respectively; and   hydrolyzing the resultant polymer. .Iaddend. .Iadd.27. A vinylamine copolymer comprising structural units represented by the following formulas: ##STR21##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer;   wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   
     
     
       hydrolyzing the resultant polymer.  .Iadd.28.  A vinylamine coplymer prepared by polymerizing a mixture comprising (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile, at a molar ratio of 20:80 to 95:5, respectively, in the presence of a radical polymerization initiator and hydrolyzing the resulting polymer under acidic conditions. .Iaddend. .Iadd.29. A vinylamine copolymer prepared by polymerizing a mixture comprising (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile, at a molar ratio of 20:80 to 95:5, respectively, in the presence of a radical polymerization initiator and hydrolyzing the resulting polymer under acidic conditions until at least part of formyl unit is hydrolyzed to amino unit. .Iaddend. .Iadd.30. A vinylamine copolymer comprising structural units represented by the following formulas: ##STR22##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (A) is 5 to 85% by mole, the molar fraction of the structural unit (B) is 2 to 85% by mole, the molar fraction of the structural unit (C) is 5 to 80% by mole, all of said molar fractions being based on the vinylamine copolymer; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile, at a molar ratio of 20:80 to 95:5, respectively; and   
     
     
       hydrolyzing the resultant polymer under acidic conditions.  .Iadd.31.  A vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III) and (IV): ##STR23##.Iaddend. wherein X.sup.⊖ represents an anion, R represents a hydrogen atom or a methyl group, M.sup.⊕ represents a hydrogen ion or a monovalent cation, in which the molar fraction of the structural unit (I) is 5 to 85% by mole, the molar fraction of the structural unit (II) is 2 to 85% by mole, the molar fraction of the structural unit (III) is 5 to 80% by mole, the molar fraction of hte structural unit (IV) is 0 to 20% by mole which is based on the total content of the structural units (III) and (IV) and the total of the molar fractions of the structual units I-III is at least 40%; wherein the vinylamine copolymer is prepared by:   polymerizing, in the presence of a radical polymerization initiator, a mixture consisting essentially of (1) N-vinylformamide and (2) acrylonitrile or methacrylonitrile and   hydrolyzing the resultant polymer.