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), (IV) and (V): 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), (IV) and (V), a flocculating agent and a paper strength increasing agent using the vinylamine copolymer, and a process for producing the vinylamine copolymer.

Description: BACKGROUND OF THE INVENTION This invention relates a novel vinylamine copolymer, a flocculating agent for the treatment of waste water using the vinylamine copolymer and paper strength increasing agent using the vinylamine copolymer in paper making industry, as well as a process for producing the vinylamine copolymer. More particularly, the present invention relates to a vinylamine copolymer having structural units represented by the following formulas (I), (II), (111), (IV) and (V) : wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95 % by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8 % by mole. The invention relates further to a flocculating agent for the treatment of waste water and a paper strength increasing agent using the vinylamine copolymer in papermaking industry, as well as a process for producing the vinylamine copolymer, a flocculating agent using the vinylamine copolymer, a paper strength increasing agent using the vinylamine copolymer and a process for producing the vinylamine copolymer. The novel vinylamine copolymer according to the present invention exhibits excellent effects in the field of application of cationic polymers such as flocculating agents for use in the treatment of waste water, dehydrating agents for organic sludges, drainage aid, retention aid or paper strength increasing agents in papermaking industry. For the preparation of the polyvinylamine, it has been known a method by Hofmann reaction of polyacrylamide and hydrolysis of poly-N-vinylamide. Particularly, the method of hydrolysis of a homopolymer of N-vinylformamide is an excellent method which is capable of synthesizing a polyvinylamine of a high molecular weight with high stability. However, the resultant polymer is extremely hydrophilic and has only an insufficient effect in the case of using is as a flocculating agent for dehydration. For providing a polyvinylamine with a hydrophobic property, there has been known a method of copolymerizing N-vinylformamide and ethylene and then hydrolyzing the resulting product. However, it was difficult to solve the problem by the copolymer of N-vinyl formamide and ethylene, since copolymerizability between N-vinylformamide and ethylene is not favorable and, in addition, it is difficult to obtain a copolymer of a high-molecular weight. The present inventors have previously proposed a method of preparing a flocculating agent with a good dehydrating property by copolymerizing N-vinylamide with acrylonitrile, followed by hydrolysis thereby modifying not less than 10 mol% of nitrile groups into carboxyl groups [refer to Japanese Patent Application Laid Open (KOKAI) No. 59-39399(1984)]. Although the effect was remarkable for N-vinylacetamide copolymer shown in examples, there has been a problem for the N-vinylformamide copolymer in that the dehydrating property is remarkably reduced in the case when not less than 10 mol% of the nitrile groups are modified into carboxyl groups. As a result of a further study, the present inventors have proposed a process for producing a flocculating agent by using a basic hydrolyzate of a copolymer of N-vinylformamide and (metha)acrylonitrile [refer to Japanese Patent Application Laid Open (KOKAI) No. 61-118406(1986)]. However, the proposed hydrolyzate still involves a problem in that most of the nitrile groups are modified into carboxyl groups and, in the case when the content of the nitrile groups in the starting copolymer is high, a water-insoluble polymer is formed or an amphoteric polymer predominantly containing anionic groups is resulted and accordingly, it has been difficult to reduce the water content in the dehydrated sludges in the case of using it as a flocculating agent for dehydration. For overcoming the foregoing drawbacks, as a result of further the present inventors' studies, it has been found that a vinylamine copolymer of a high-molecular weight having a hydrophobic property obtained by partially modifying a vinylformamide copolymer under acidic conditions has an excellent flocculating effect in the treatment of waste water and also has an excellent paper strength increasing effect in the papermaking industry, and the present invention has been attained based on the above finding. SUMMARY OF THE INVENTION In a first aspect of the present invention, there is provided a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III), (IV) and (V) : wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. In a second aspect of the present invention, there is provided a flocculating agent comprising a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III), (IV) and (V) : wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. In a third aspect of the present invention, there is provided a paper strength increasing agent comprising of a vinylamine copolymer having the structural units represented by the following formulas (I), (II), (III), (IV) and (V) : wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (v); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. In a fourth aspect of the present invention, there is provided a drainage aid for papermaking comprising of a vinylamine copolymer having the structural units represented by the following formulas (I) , (II) , (III) , (IV) and (V): wherein x ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 80% by mole. In a fifth aspect of the present invention, there is provided a retention aid for papermaking comprising of a vinylamine copolymer having the structural units represented by the following formulas (I) , (II) , (III) , (IV) and (V): wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar action of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. In a sixth aspect of the present invention, there is provided a process for producing a vinylamine copolymer having the structural units comprising following formulas (I), (II), (III), (IV) and (V): wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural unit (I), (II), (III), and (V): and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. which comprises polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI) CH₂ = 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 to obtain a N-vinylformamide copolymer, and then modifying the formyl and optionally the nitrile groups in the resultant N-vinylformamide polymer under acidic conditions. DETAILED DESCRIPTION OF THE INVENTION The vinylamine copolymer according to the present invention has structural units represented by the formulas (I) , (II) , (III) , (IV) and (V) : (wherein X ⊖ represents an anion or a 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 6.4% by mole based on the total content of the structural units (I), II, (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8% by mole. A preferred structural unit composition for the copolymer according to the present invention 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, and from 0 to 4 mol% of the structural unit (V) in the molar fraction based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV), and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 5% by mole. A particularly preferred structural unit composition 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, and from 0 to 2 mol% of the structural unit (V) in the molar fraction based on the total content of the structural units (I), (II), (III), (IV) and (V), the sum of the molar fractions of said structural units (I) and (II) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80% by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 2.5% by mole. The novel vinylamine copolymer according to the present invention is a water soluble polymer having a reduced viscosity from 0.1 to 10 dl/g, preferably from 0.5 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25°C. The novel vinylamine copolymer according to the present invention can be easily obtained by modifying the formyl and optionally the nitrile groups in an N-vinylformamide copolymer under acidic conditions. The N-vinylformamide copolymer used as the starting material is a copolymer prepared by polymerizing a mixture of N-vinylformamide and a compound represented by the following general formula (VI) CH₂ = CR - CN (VI) (wherein R represents a hydrogen atom or a methyl group), that is, acrylonitrile or methacrylonitrile at a molar ratio from 20 : 80 to 95 : 5, preferably, from 40 : 60 to 95 : 5 and, more preferably, from 40 : 60 to 90 : l0, in the presence of a radical polymerization initiator. It is, preferably, a copolymer of N-vinylformamide and acrylonitrile. As a polymerization method for producing the N-polyvinylamide copolymer, there can be used mass polymerization, solution polymerization or precipitation polymerization using various solvents, and aqueous solution polymerization or the precipitation polymerization which initiates the polymerization by using an aqueous solution of the monomer is preferred. In the case of polymerizing the monomer in the form of an aqueous solution, the monomer concentration, polymerization method and a polymerizing reactor are properly selected in consideration with the molecular weight of an objective polymer and the calorific control from heat of polymerization. The polymerization is conducted, for example, by the following method : (l) a method of polymerizing in a state of a solution with a monomer concentration of from 5 to 20 % by weight and preparing the polymer as a precipitate, (2) a method of polymerizing in a state of a hydrous gel with a monomer concentration of from 20 to 60 % by weight and preparing the polymer as a hydrous gel-like product or precipitate, (3) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60 % by weight in a state of an oil-in-water or water-in-oil type emulsion by using a hydrophobic solvent and an emulsifier, and (4) a method of polymerizing an aqueous solution of the mixture with a monomer concentration of 20 to 60 % by weight in a state of a water-in-oil type dispersion by using a hydrophobic solvent or a dispersion stabilizer. A particularly preferred polymerization method is the precipitation polymerization in water. As the radical polymerization initiator, there can be used any of the ordinary initiators which are commonly used for the polymerization of water-soluble or hydrophilic monomers and azo compounds are preferred for producing a polymer in a high yield. Particularly preferred are water-soluble azo compounds, for example, hydrochlorides and acetates of 2,2′-azobis-2-amidinopropane; sodium salt of 4,4′-azobis-4-cyanovaleric acid; and hydrochlorides and sulfates of azobis-N,N′-dimethylene isobutylamidine. The amount of the polymerization initiator used is usually within a range from 0.01 to 1 % by weight based on the weight of the monomer. Further, the polymerization reaction is usually carried out under an inert gas stream at a temperature from 30 to 100°C. The thus obtained N-vinylformamide copolymer can be modified in the form as it is, a solution, a dispersion or a dilute solution of the polymer or a powder obtained by dehydrating or drying the polymer in the known method, under an acidic condition, whereby a novel polyvinylamine can be obtained. While on the other hand, in the case when the resultant N-vinylformamide copolymer is subjected to basic hydrolysis in water, nitrile groups in the polymer are substantially eliminated. Particularly, in the case when a content of the nitrile group in the polymer is high, it tends to result in an insoluble polymer or form an amphoteric copolymer predominantly containing anionic groups. As the modification method for the N-vinylformamide copolymer, there can be mentioned, for example, (1) a method of hydrolyzing in water under an acidic condition, (2) a method of hydrolyzing in a hydrophilic solvent such as water-containing alcohol, and (3) a method of subjecting to alcohol-addition degradation and modifying formyl groups while separating as an ester of formic acid. As the alcohols in the case of alcohol-addition degradation, those alcohols of 1 to 4 carbon atoms can be mentioned and methanol is preferred. The structural unit (V) may partially be converted into esters depending on the case by the alcohol-addition degradation, but the effect of the copolymer according to the present invention does not substantially change even when it contains not more than 5 mol% of esters. As the modifying agent used in the case of the acidic modification, any of compounds acting strongly acidity can be used and it can exemplify, for example, hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid and alkanesulfonic acid. The amount of the modifying agent used may properly be selected from a range of 0.1 to 2 times to the molar quantity of the formyl groups in the polymer according to the desired rate of modification. The modifying reaction is usually carried out under the condition of from 40 to 100°C, by which a novel vinylamine copolymer containing nitrile groups in the molecules with low carboxyl group content and having preferable water solubility is formed. The vinylamine copolymer according to the present invention exhibits an excellent effect as a cationic flocculating agent for the treatment of waste water for flocculating organic suspensions, a flocculating agent for the dehydration of for example organic sludges. Particularly, it exhibits an excellent effect as a dehydrating fluocculating agent for primary settled raw sludges in the treatment of sewage, sludges produced by the activated sludge treatment of water soluble organic materials, the sludges produced in the aerophobic treatment of water soluble organic materials and mixtures thereof. The novel vinylamine copolymer is used in the same manner as in the method of using the conventional cationic flocculating agent, for example, polymers of dimethylaminoethyl methacrylate. That is, the vinylamine copolymer is used in the form of a 0.1 - 0.5 % by weight aqueous solution, and it is added and mixed in an organic sludge-containing suspention in amount of 20 to 20,000 ppm based on the weight of the suspention. In the case of using the vinylamine copolymer according to the present invention as a flocculating agent, it is preferred that the vinylamine copolymer is a water soluble polymer having a reduced viscosity of 1 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25°C. Since the organic sludges subjected to the flocculating treatment by using the vinylamine copolymer according to the present invention is formed more firm and solid flocks than in the case of using a polymer obtained by modifying a homopolymer of N-vinylformamide, the dehydrating speed is improved, the throughput rate is increased and the water content in the dehydrated sludges is reduced by subjecting to machine dehydration such as compression dehydration or centrifuging vacuum filtration by use of a belt press, screw press or filter press. The vinylamine copolymer according to the present invention can be used also as a cationic water-soluble polymer for papermaking industry and exhibits an excellent effect in use as drainage aid, retention aid and paper strength increasing agents. In the case of using the vinylamine copolymer for these applications, a water-soluble polymer having a reduced viscosity of 0.5 to 10 dl/g measured as a solution thereof prepared by dissolving the copolymer in 1N aqueous sodium chloride solution to a concentration of 0.1 g/dl at a temperature of 25°C. It can be used by any of known papermaking methods. That is, a cationic polymer of an amount equivalent to 0.05 - 2 % by weight based on the dry weight of pulp is added as a 0,1 - 5 wt% aqueous solution to a pulp slurry containing 0,5 - 3 wt% of pulp and then subjected to a papermaking step. Particularly, in the case of using as a paper strength increasing agent, a method of adding to the pulp slurry as an internal additive to the pulp slurry may be used, or it may be coated onto wet or dry web by a roll coater, size press or dipping machine. If necessary, cationic starch, aluminum sulfate and anionic polyacrylamide may be used jointly with the polymer of the present invention. It can be used to any of ground pulp, sulfide pulp, craft pulp and beaten wastepaper with no restriction to the type of the pulps. The cationic polymer is extremely stable in the form of an aqueous solution irrespective of the quality of the solution in which the polymer is dissolved or even if in a diluted aqueous solution. Further, it is stable and does not lose its effect even under the weakly alkaline papermaking conditions when using calcium carbonate as a filler and the additive is excellent under neutral or weakly alkaline papermaking condition. The novel vinylamine copolymer containing nitrile groups in the molecule according to the present invention contributes much to the field of applying flocculating agents and papermaking additives. The present invention will now be described in more details by way of examples but it should be noted that the invention is no way limited to the following examples unless they does not go beyond the gist thereof. Examples (A1 - A10) of Preparation of N-Vinylamine Copolymer Into a 50 ml four-necked flask equipped with a stirrer, a nitrogen introduction tube and a cooling tube, 39.9 g of an aqueous solution containing 4.0 g of a mixture of each of the monomer compositions as shown in Table 1 was charged. After increasing the temperature to 60°C under stirring in a nitrogen gas stream, 0.12 g of 10 wt% aqueous solution of 2,2'-azobis-2-amidinopropane dihydrochloride was added. The resultant mixture was maintained under stirring at 60°C for three hours to obtain a suspension in which a polymer was precipitated in water. The remaining monomer in the water was measured by liquid chromatography to calculate the composition of the polymer. A concentrated hydrochloric acid in the equivalent to the formyl groups in the polymer was added and maintained under stirring at 75°C for 8 hours to hydrolyze the polymer. The solution of the resultant polymer was added in acetone to precipitate the polymer, which was dried in vacuum to obtain a solid polymer (hereinafter referred to as polymer A - J). Each of the compositions of the formed products was determined based on the composition of the copolymer before hydrolysis, colloidal equivalent value of the product, atomic ratio for carbon, nitrogen and chlorine based on the elemental analysis, as well as ¹³C-NMR spectrum shown together with the reduced viscosity of the product. Measurement for the Colloidal Equivalent Amount Solid polymer was dissolved into distilled water to a concentration of 0.1% by weight. After diluting 5,0 g of the aqueous solution by using desalted water into 200 ml and adjusting pH value of the solution to 3 by using a diluted hydrochloric acid, the colloidal equivalent value was determined by the colloidal titration method by using 1/400 N polyvinyl potassium sulfate and using toluidine blue as an indicator. Measurement for the Reduced Viscosity The solid polymer was dissolved in 1N aqueous solution of sodium chloride to a concentration of 0.1 g/dl, and the reduced viscosity at 25°C was measured by using an Ostwald viscometer. Reduced viscosity (dl/g) = (t - t₀)/t₀/0.1 (wherein t₀ represents descending speed of aqueous sodium chloride and t represents descending speed of polymer solution), Example Monomer composition (mol%) VF AN AC A1 90 10 0 A2 75 25 0 A3 60 40 0 A4 60 40 0 A5 50 50 0 A6 40 60 0 A7 40 60 0 A8 50 50 0 A9 50 46.5 3.5 A10 50 45 5 Note : Example Polymer Structural unit of the product (mol%) Reduced viscosity (dl/g) I II III IV V A1 A 75 15 8 2 0 1.9 A2 B 64 11 18 7 0 2.5 A3 C 57 3 25 14 1 3.6 A4 D 30 30 34 6 0 2.0 A5 E 33 17 35 14 1 2.5 A6 F 35 5 30 29 1 3.1 A7 G 17 23 47 11 2 2.5 A8 H 46 4 32 16 2 3.0 A9 I 32 18 33 13 4 2.8 A10 J 31 19 32 12 6 2.9 Note : 0.5 eq of hydrochloric acid was used to the formyl groups in the polymer upon modification in Examples A4 and A7. Modifying reaction was carried out at 95°C in Example A8. X is chlorine ion in the structural unit (I), and R and M are hydrogen atom in the structural units (III) and (V). Comparative Example of preparation of N-Vinylamine Copolymer The procedures are the same as those in Example A5 except for using one equivalent of an aqueous 40 % sodium hydroxide solution to the formyl groups of the N-vinylformamide copolymer instead of concentrated hydrochloric acid in Example 5. The resultant polymer was a slightly soluble amphoteric copolymer not substantially containing the nitrile groups. Examples B1 - B7 and Comparative Example B8 - B10 (Flocculating Property) 100 ml (2.0 % by weight of solid content) of mixed raw sludges obtained from sewage treatment plant of a city were put into a 200 ml - polyethylene beaker and 6 ml of an aqueous 0.2 wt% solution of each of the polymers shown in Table 3 was added thereto. The suspension was agitated by using a stirrer having at its end three rods of 5 mm in diameter and 20 mm in length at a speed of 1000 rpm for 10 sec. The flocculated sludges were charged in a cylinder bottomed with a 60 mesh nylon screen having a diameter of 65 mm and subjected to gravity filtration, and after 10 sec, the amount of the filtrate was measured. Further, a portion of the gravity-filtered sludges was charged in a centrifuging basket having a dish drainer at the bottom and centrifuged at a speed of 3000 rpm for 30 sec for dehydration. The sludges after the dehydration was dried at 110°C for 6 hours and the solid content was measured to calculate the water content in the sludges after centrifuging dehydration. While on the other hand, the sludges are gravity-filtered under the same conditions as described above. The sludges after the filtration were put between polyester filter cloths, which were put between polyvinyl chloride plates provided with draining grooves and dehydrated by a hydraulic press having a piston of 20 mm in diameter under the condition of a piston pressure at 490.5 N/cm² (50 kg/cm²) for 30 sec. The sludges after the dehydration were dried at 110°C for 6 hours and the solid content was measured to calculate the water content in the sludges after the press dehydration. These results are shown collectively in Table 3. Example and Comparative Example Polymer Amount of filtrate 10 sec. after the gravity filtration (ml) Water content of sludges after centrifuging dehydration (wt%) Water content of sludges after press-dehydration (wt%) B1 A 55 78.2 75.4 B2 B 60 78.4 75.2 B3 C 60 78.0 74.6 B4 E 65 77.6 74.6 B5 F 65 77.2 74.4 B6 H 65 77.0 73.8 B7 I 60 78.8 75.6 B8 J 55 81.6 77.8 B9 K 45 83.4 80.5 B10 L not agulated - - Examples C1 - C8 and Comparative Example C9 (Paper Strength Increasing Effect) A 0.6 % LBKP slurry having freeness of 400 ml measured by Canadian Standard was present together with calcium carbonate in an amount of 17 % based on the pulp, and the mixture was put into a 500 ml-beaker. After adding the chemicals shown below in the form of an aqueous solution under stirring, papers of 60 g of basis weight were made by using a TAPPI Standard square type paper machine, pH value upon paper making being 8.5. (Condition of Using Added Chemicals) Concentration of aqueous solution (wt%) Addition amount to pulp dry weight (wt%) Cationic starch 1.0 0.5 Polymers A - G and I 0.5 0.5 Sizing agent (alkyl ketene dimer) 1.0 0.2 Filler retention improving agent 0.1 0.02 For the comparison, paper was made in the same manner without adding any of the polymers A - G and I among the added chemicals. The thus obtained wet paper was dried for three minutes by using a drum drier at 120°C. After allowing to stand the resultant paper under the condition at a temperature of 20°C and relative humidity of 60 %, the specific burst factor and the burst length were measured according to JIS-P 8112 and JIS-P 8113. where S₁ : burst strength n/cm² (9.81 kg/cm²) W : basis weight of test paper (g/m²) S₂ : tensile strength (kg) B : width of the test piece (mm) The results are shown in Table 4. Example Polymer Specific burst factor N/cm² (Kg/cm²) Burst length (Km) C1 A 14.3 (1.46) 2.55 C2 B 14.4 (1.47) 2.54 C3 C 16.0 (1.63) 2.69 C4 D 15.4 (1.57) 2.38 C5 E 13.6 (1.39) 2.44 C6 F 13.6 (1.39) 2.17 C7 G 15.3 (1.38) 2.40 C8 I 13.9 (1.42) 2.38 Comparative Example C9 not added 11.0 (1.12) 1.92 Examples C11 - C18 and Comparative Example C19 (Paper Strength Increasing Effect) 1 % slurry of waste liner board paper having a freeness of 300 ml measured by Canadian Standard was put into a 500 ml-beaker and an aqueous 0.5 wt% solution of each of the polymers A - G was added in an amount of 0.3 % by weight based on the dry weight of the pulp and then the resultant mixture was maintained for one minute. Papers of basis weight of 120 g were made by using a TAPPI Standard square type paper machine. After treating the thus resultant wet paper in the same procedures as in Example C1, the paper strength of the resultant paper was measured. For the comparison, paper was made in the same procedures as above but without adding any of the polymers and the strength of the resultant paper was measured. The results are shown in Table 5. Example Polymer Specific burst factor (Kg/cm² N/cm²) C11 A 24.6 (2.51) C12 B 26.6 (2.71) C13 C 26.7 (2.72) C14 D 26.6 (2.71) C15 E 28.1 (2.86) C16 F 27.7 (2.82) C17 G 26.6 (2.71) C18 I 27.1 (2.76) Comparative Example C19 not added 22.2 (2.26) Examples D1 - D8 and Comparative Example D9(Drainage Aid Effect for Papermaking) One liter of 0.3 % slurry of LBKP having a freeness of 220 ml measured by Canadian Standard was put into a 2 liter-beaker and each of the polymers A - G and I in the form of 0.2 wt%. aqueous solution was added in an amount of 0.2 % by weight based on the dry weight of the pulp under stirring. After stirring the mixture at a speed of 200 rpm for one minute, the freeness of each product was measured by using a Canadian Freeness Tester. For the comparison, an experiment was conducted in the same way without adding any of the polymers. The results are shown in Table 6. Example Polymer Freeness (ml) D1 A 270 D2 B 260 D3 C 300 D4 D 285 D5 E 285 D6 F 255 D7 G 250 D8 I 280 Comparative Example D9 not added 220 Examples E1 - E8 and Comparative Example E9 (Retention Aid Effect for Papermaking) One liter of 0.5 % LBKP slurry having a freeness of 410 ml measured by Canadian Standard was put into a 2 liter-beaker and 30 % by weight of papermaking talc, 0.3 % by weight of reinforcing rosin and 4 % by weight of aluminum sulfate based on the dry weight of the pulp were respectively added under stirring. Further, after adding an aqueous 0.2 wt% solution of each of the polymers A - G and I in an amount of 0.03 % by weight based on the pulp and stirring at a speed of 200 rpm for one minutes, papers of 70 g basis weight were made by the same procedures as in Example C1. The ash content in the thus obtained resultant paper was measured and the results are shown in Table 7. For the comparison, paper was made in the same procedures but without adding any of the polymers. Example Polymer Ash content (%) E1 A 15.7 E2 B 15.6 E3 C 17.1 E4 D 18.0 E5 E 16.7 E6 F 16.5 E7 G 15.7 E8 I 15.5 Comparative Example E9 not added 12.7

Claims: A vinylamine copolymer having structural units represented by the following formulas (I), (II), (III), (IV) and (V): wherein X ⊖ represents an anion or a 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 6,4 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (R) is 20 to 95% by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80 % by mole based on the total content of the structural units (I), (II), (III), (IV), (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III), (IV) and (V) is 0 to 8 % by mole. The 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 copolymere in an aqueous 1N sodium chloride solution to a concentration of 0.1 g/dl at 25°C. The vinylamine copolymer according to claim 1, wherein 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 60 % by mole, the molar fraction of the structural unit (IV) is 0 to 30 % by mole, and the molar fraction of the structural unit (V) is 0 to 4 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II)is 20 to 95 % by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80 % by mole based on the total content of the structural units (I), (II), (III) (IV) and (V); and the molar fraction of said structural unit (V) based on the total content of the structural units (III),(IV) and (V) is 0 to 5 % by mole. The vinylamine copolymer according to claim 1, wherein the molar fraction of the structural unit (I) is 5 to 85 % by mole, the molar fraction of the structural unit (II) is 5 to 60 % by mole, the molar fraction of the structural unit (III) is 10 to 60 % by mole, the molar fraction of the structural unit (IV) is 0 to 30 % by mole. and the molar fraction of the structural unit (V) is 0 to 2 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); the sum of the molar fractions of said structural units (I) and (II) is 20 to 95 % by mole and the sum of the molar fractions of said structural units (III), (IV) and (V) is 5 to 80 % by mole based on the total content of the structural units (I), (II), (III), (IV) and (V); and the molar traction of said structural unit (V) based on the total content of the structural units (III),(IV) and (V) is 0 to 2,5 % by mole. A flocculating agent comprising a vinylamine copolymer according to any of the claims 1 to 4. A paper strength increasing agent comprising a vinylamine copolymer according to any of the claims 1 to 4. A drainage aid for papermaking comprising a vinylamine copolymer according to any of the claims 1 to 4. A retention aid for papermaking comprising a vinylamine copolymer according to any of the claims 1 to 4. A process for producing a vinylamine copolymer according to claim 1, which comprises polymerizing a mixture of N-vinylformamide and a compound of the following general formula (VI): CH₂=CR-CN (VI) (wherein R represents a hydrogen atom or a methyl group) at a molar ratio of from 20 : 80 to 95 : 5 in the presence of a radical polymerization initiator to obtain a N-vinylformamide copolymer and then modifying the formyl and optionally nitrile groups in the resultant N-vinylformamide copolymer under acidic conditions. The process according to claim 9, wherein the radical polymerization initiator is from 0.01 to 1 % by weight based on the monomer. The process according to claim 9, wherein the polymerizing reaction is carried out in an inert gas stream at a temperature from 30 to 100°C. A process according to claim 9, wherein the modification is carried out under acidic conditions by (1) a method of hydrolyzing in water, (2) a method of hydrolyzing in a hydrophilic solvent of water-containing alcohol or (3) a method of subjecting to alcohol-addition degradation, and then modifying while separating the formyl groups as esters of formic acid. The process according to claim 9, wherein the modifying agent is hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid or an alkane sulfonic acid. The process according to claim 9, wherein the modifying agent is used from 0.1 to 2 molar times to the formyl groups in the N-vinylformamide copolymer. The process according to claim 9, wherein the modification is carried out at a temperature from 40°C to 100°C. The process according to claim 9, wherein the radical polymerization initiator is an azo compound.

Inventors: ITAGAKI, TAKAHARU, SATOH, KOHICHI, SAWAYAMA, SHIGERU, SHIRAGA, MITSUAKI
Applicants: MITSUBISHI KASEI CORPORATION
Application year: 1987
Main classification: C08F226
IPC codes: D21H17, C08F220, C02F1, C08F26, C08F8, B01D21, C08F226, C08F20