Vinylamine copolymer, flocculating agent and paper strength increasing agent using the same, as well as process for producing the same

Abstract

Disclosed herein is a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III)[,] and (IV) [and (VI)]: 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 (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)] (IV) is 0 to 8% by mole which is based on the total content of the structural units (III)[,] and (IV), [and (V),] a flocculating agent and a paper strength increasing agent using the vinylamine copolymer, and a process for producing the vinylamine copolymer.

What is claimed is: 
     
       1. A process for producing a vinylamine copolymer having the structural units comprising following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR10## 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 (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, and the molar fraction of the structural unit (V).]. is 0 to 8% by mole based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., which comprises polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI)   CH.sub.2 ═CR--CN                                       (VI)     (wherein R represents a hydrogen atom or a methyl group) at a molar ratio from 20:80 to 95:5 in the presence of a radical polymerization initiator, and then modifying formyl groups in the resultant polymer under an acidic condition.   
     
     
       2. A process for producing a vinylamine copolymer having the structural units comprising the following formulas (I), (II), (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).].: ##STR11## wherein X⊖ represents an anion, 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 (II) 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).]. (.Iadd.IV) .Iaddend.is 0 to 8% by mole based on the total content of the structural units (III).[.,.]. .Iadd.and .Iaddend.(IV) .[.and (V).]., which comprise polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI):   CH.sub.2 ═CR--CN                                       (VI)     wherein R represent a hydrogen atom or a methyl group) at a molar ratio from 20:80 to 95:5 in the presence of a radical polymerization initiator to obtain an N-vinylformamide copolymer, and then modifying the thus obtained N-vinylformamide copolymer under an acidic condition in the presence of a modifying agent to obtain the vinylamine copolymer defined above.   
     
     
       3. A process according to claim 2, wherein the radical polymerization initiator is from 0.01 to 1% by weight based on the monomer. 
     
     
       4. A process according to claim 2, wherein the polymerizing reaction is carried out in an inert gas stream at a temperature from 30 to 100° C. 
     
     
       5. A process according to claim 2, wherein the modification is carried out under an acidic condition by (1) a method of hydrolyzing in water, (2) a method of hydrolyzing in a hydrophilic solvent of a water-containing alcohol or (3) a method of subjecting to alcohol-addition degration and then modifying while separating the formyl groups as esters of formic acid. 
     
     
       6. A process according to claim 2, wherein the modifying agent is hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid or alkane sulfonic acid. 
     
     
       7. A process according to claim 2, wherein the modifying agent is from 0.1 to 2 molar times to the formyl group in the polymer. 
     
     
       8. A process according to claim 2, wherein the modification is carried out at a temperature from 40° C. to 100° C. 
     
     
       9. A process according to claim 2, wherein the radical polymerization initiator is an azo compound. .Iadd.10. A process for producing a vinylamine copolymer, said process comprising: polymerizing, in the presence of a radical polymerization initiator, a mixture of (i)N-vinylformamide and (ii) a compound of the following general formula:   CH.sub.2 ═CR--CN       wherein R represents a hydrogen atom or a methyl group at a molar ratio from 20:80 to 95:5 and   
     
     
       hydrolyzing the resultant polymer. .Iadd.11.  A process for producing a vinylamine copolymer, said process comprising: polymerizing, in the presence of a radical polymerization initiator, a mixture of (i)N-vinylformamide and (ii) a compound of the following general formula:   CH.sub.2 ═CR--CN       wherein R represents a hydrogen atom or a methyl group at a molar ratio from 20:80 to 95:5 and   hydrolyzing the resultant polymer under acid conditions to modify formyl groups. .Iaddend.