Manufacture of water-soluble copolymer having vinylamine unit

[Detailed Description of the Invention]

In U.S. Pat. No. 4421 No. 302 specification, the water-soluble polymer of N-vinyl Holm amide containing N-vinyl Holm amide unit and a vinyl amine unit by which partial hydrolysis was carried out is written. This polymer is used as a reinforcement agent of condensation, suspension, and drying speed in M paper. Ethylene is made to copolymerize with N-vinyl Holm amide on U.S. Pat. No. 4255548 item specifications, and the ethylene / vinyl amine copolymer obtained by desorbing all the formyl groups from a copolymer by operation of chloride are written in them. This type of polymer is a flocculant for the fine dispersion substance suspended underwater, for example. It is indicated that polyvinyl amine chloride salt can be used for a U.S. Pat. No. 272140 item specification as an auxiliary agent for paper manufacture. Paper which has high wet strength especially in that case is obtained. Vinyl friend without the tendency to have influence disadvantageous when the subject of the present invention has long storage stability and it is used as an auxiliary agent for paper manufacture for the degree of whiteness of paper : 74 ''''''''''''' t6-'68M4a (t-f;t%a~.) It is. The present invention solves this subject and is (a). It is (b) acetic acid vinyl about 95~10 mol of N - vinyl Holm amide %, Vinyl propionate, 01~C4-An alkyl kana nil ether, N-vinyl pyrrolidone, And it is made to copolymerize with 5~90 mol of ethylenic unsaturated monomer % chosen from the group which comprises the ester of acrylic acid and methacrylic acid, nitril, and amide. Subsequently, it is a process of the water-soluble copolymer which carries out polymerization content of the vinyl amine unit by desorbing 30~100 mol of formyl group %, preferably 70~95-mol % from a copolymer. Used in order that the copolymer obtained by this method may raise the baked strength and wet strength of paper in paper manufacture, a copolymer is [ as opposed to / in that case / dry textiles ] 0. It is added by Stock before paper leaf formation in 1~5% of the weight of quantity, or is given on the surface of paper in the above-mentioned quantity as solution. A thing (being a water-soluble polymer from 95~10 mol of al N - vinyl Holm amide %, and (b) e acid Vinyl, and/or vinyl propionate 5~90-mol %) especially useful for this object, 30~100 mol of formyl group % is desorbed from the unit (a) of a copolymer, and an acetyl group or pro Pionyl machine 30~100-mol % is desorbed from a unit (b). N-vinyl Holm amide (CH2=CH-NH-CHO) can be manufactured, for example by the method of a statement on the West German patent application public notice No. 1224304 specifications. This can be made to copolymerize by the ordinary polymerizing method. Comonomer (b) suitable for this object is an ethylenic unsaturated monomer from the group which comprises the ester of acetic acid vinyl, vinyl propionate, 01~C4-An alkyl kana nil ether and acrylic acid, or methacrylic acid, nitril, and amide. The examples of the An alkyl kana nil ether used are methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, the third class butyl vinyl ether, n-, and isobutyl vinyl ether. (The following are also contained in the monomer of b1 group.) Ester of the acrylic acid and methacrylic acid which are guided from the alcohol which has acryl amide, methacrylamide, acrylics nitril, methacrylic nitril, and 1~18 carbon atoms. Alcohol suitable for manufacture of this ester is methanol and ethanol, for example, They are a grotesque Panol and iso proper tool, n-, Iso-, the third class butyl alcohol, neopentyl alcohol, 2-ethyl Hexanol, n-Octa tool, dodeca Nord, palmityl alcohol, and stearyl alcohol. The compound from the group which comprises the ester guided from the alcohol which has 1~4 carbon atoms preferably is used. Ester manufactured by To be esterified by the molar ratio of 1:1 with acrylic acid or methacrylic acid in divalent 02~C4-alcohol at this ester, For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxy butyl acrylate, and a hydronalium Kishibushi group monomer can be made to copolymerize as a mixture with independent or N-vinyl Holm amide. A copolymer contains 95~10 mol of N-vinyl Holm amide %, preferably 30~40-mol % and one-sort, or several sorts (b) group monomer 5~90-mol %, preferably 40~30-mol % as a copolymerization unit, and the sum total of % in a copolymer is always 100. N-vinyl Holm amide and the following (b) group monomer: Especially the copolymer of acetic acid vinyl, vinyl propionate, C8~C2-An alkyl kana nil ether, and N-vinyl pyrrolidone is important. Monomer (a) and (b) polymerizes using an uncombined radical polymerization initiator, for example, a peroxide, hydroperoxide, a redox catalyst, or the azo compound that decomposes and generates an uncombined radical. A polymerization is preferably performed under normal pressure, decompression, or pressurization in 30~140 degreeC in a solvent or a diluent. The polymer which has a high molecular weight is obtained when polymerizing underwater. This polymerization can be performed in solution with the phase inversion suspension polymerization method as oil Nakamizu type emulsion, for example for manufacture of a water-soluble polymer. For manufacture of an insoluble in water polymer, an underwater oil type emulsion polymerization method and a suspension polymerization method are used. A polymerization initiator is used in 0.1~5.0% of the weight of quantity to an ordinary quantity, for example, a monomer. Especially a useful polymerization initiator is water-soluble azo compound, for example, 2, and 2'-azobis (2-amidinopropane) chloride salt, 4, and 4'-azobis (4'-cyano pentanoic acid). The molecular weight of a copolymer can be affected by use of a polymerization regulation agent and a chain extension agent. The examples of a suitable polymerization regulation agent are alcohol, for example, methanol, ethanol, n-, an iso proper tool, acetone, hydroxy^ammonium salt, chlorinated hydrocarbon and a Thio compound, for example, thioglycolic acid, 2-mercaptoethanol, and Dodecyl mercaptan. The examples of a suitable chain extension agent are a multifunctional monomer, for example, methylene screw acryl amide, Divinyl ethylene urea, Penta erythritol Triallyl ether, and divinylbenzene. A regulation agent and a chain extension agent are used to the monomer used by request in 0.001~10 % of the weight, preferably 0.0.1~5% of the weight of quantity. The polymer which has a low molecular weight can be manufactured also by polymerizing using the polymerization initiator which dissolves in it, for example in an improper tool. When polymerizing in a water medium, pH under polymerization is 4~10, preferably 6~8. The quantity of the diluent or solvent used for a polymerization is chosen so that the solution, suspension, or dispersion liquid of the polymer obtained may have 1~30 % of the weight, preferably 6~30% of the weight of a solid content. By the operation of acid or a base, a formyl group is desorbed from N-vinyl amide by which polymerization content was carried out as a result of this processing, and as the above-mentioned copolymer forms °C and a vinyl amine machine, it denatures. In 20~100 degreeC, desorption of the formyl group from a copolymer can be performed as it is preferably carried out using chloride or sodium hydroxide solution and writes in the U.S. Pat. No. 4421302 item specification. If a formyl group content copolymer is processed with hydrogen chloride or a hydrogen bromide in the absence of water, carbon monoxide will be desorbed from N-formyl group in a copolymer, and an amine machine will arise. N-vinyl Holm amide, acrylics nitril, meta-Krylo nitril, When making acid or a base act on the copolymer of N-vinyl-pyrrolidone Hint 01~C4-An alkyl kana nil ether, Inside of a copolymer (although b1 group monomer hardly receives chemical change, 30~10-mol% preferably of N-vinyl Holm amide and 70~95-mol 6-/, by which polymerization content was carried out are hydrolyzed.) Especially the copolymer of N-vinyl Holm amide and acetic acid vinyl, and/or vinyl propionate is important. For example, if chloride is made to act on this copolymer by 50 degreeC, the acetic acid vinyl or vinyl propionate by which polymerization content was carried out will not be hydrolyzed, but the output into which 30~100-mol% of N-vinyl Holm amide by which polymerization content was carried out was hydrolyzed is obtained. If the copolymer of N-vinyl Holm amide and acetic acid vinyl, or vinyl propionate is processed by 50 degreeC by sodium hydroxide solution, Acetic acid vinyl or vinyl propionate to a formyl group, and the acetyl group or grotesque Bionyl machine by which polymerization content was carried out is desorbed from N-vinyl Holm amide by which polymerization content was carried out, and also when it is any, almost an equivalent amount of bases Desorption. 100~30-mol %, preferably 70~95-mol% by which polymerization content was carried out of N-vinyl Holm amide units are changed per vinyl amine, And the hydrolyzed copolymer which has a value to be based on the Kuikensha method of 50~250, preferably 100~200 is used in order to raise the baked strength and wet strength of paper in paper manufacture. The hydrolyzed copolymer is preferably used as solution and is added by Stock in 0.1~5% of the weight of quantity to dry textiles before paper leaf formation. The copolymer whose 7 Tsuma- (b) are acetic acid vinyl or N-vinyl pyrrolidone is preferably added by Stock during paper manufacture by hydrolyzing 100% of N-vinyl Holm amide, and the wet strength of paper is raised remarkably. Polymer solution can also be given to dry textiles on the surface of paper in 0.1~5 % of the weight, preferably 0.25~1% of the weight of quantity. Solution of a copolymer is effective in manufacture of a copy paper, a print sheet, and packing paper in the paper, the paperboard, and pasteboard of all the publicly known quality, for example. Paper or a paperboard, and pasteboard can be manufactured from much textile materials, for example, may comprise the mixture of sulfite pulp or kraft pulp (bleaching or unbleached), ground pulp, Waste paper, or these textiles. The pH of Stock suspension is 4~9, preferably 6~8. . Preferably, it is added by Stock suspension in 0.25~1% of the weight of quantity to dry textiles before paper leaf formation, and the above-mentioned copolymer raises the baked strength and wet strength of paper to it. The part in the following example and % are related with weight. The value was measured by that of the polymer in 5 and 4 sodium chloride solutions in 25 degreeC at 0 or 5% of the weight of polymer concentration by the 58~64 pages and a 71~74-page statement in 16 shell rose Hemi- (1932) by A, -, and Fikentscher method. K is k-103. Paper leaf was manufactured by the paper machine for high-speed Kouten laboratories. dry Tear length -- DIN53112 -- the 1st page -- humid Tear length -- DIN53112 -- it was measured by the 2nd page. Alkali resistance was measured like measurement of wet strength, however used 1% sodium hydroxide solution instead of water for being impregnated (it is 5 minutes at 50 degreeC) of paper. The degree of whiteness of paper was measured by DIN 53145 using the catoptric light degree meter (Elrepho device). Manufacture of a copolymer: Example 1 In the inside of the churning type pilot container of 21 provided with a thermometer, a condensator, a nitrogen introducing pipe, and two tap funnels, Water 300g, styrene, and molar ratio 1:10 copolymer of a maleic anhydride (this having 1500000-fold weight average molecular weight) >5g which is a form of 30% solution of Na salt, Pirro phosphoric acid sodium 1.5g, acetic acid vinyl 27&, N-vinyl Holm amide 18g and 2, and the mixture from 2-azobis (2,4-dimethylvaleronitrile ") 0.1 g are heated to 65 degreeC. After a polymerization begins, acetic acid vinyl 243g and 2, 2-azobis (2,4-dimethylvaleronitrile) 0.9.9, and N-vinyl Holm amide 1621 are added in 3 hours, and temperature is maintained at 65 degreeC. After adding a monomer, a mixture is maintained at 2 more-hour 75-degreeC, subsequently it dilutes with water 300g, 0.2 g of 2 and 2-azobis isobutyronitrile is added, and a polymerization is continued by 6 more-hour 65~82-degreeC. Subsequently, further 2 and 0.2 g of 2-azobis isobutyronitrile are added, and boil heating of the mixture is carried out. The inside temperature of the highest is set to 98 degreeC in that case. A homogeneous white paste viscous to the altitude of acetic acid vinyl 30% and N-vinyl Holm amide 40% of a copolymer is obtained. Hydrolysis: The above-mentioned copolymer of N-vinyl Holm amide 40% Hint acetic acid Vinyl 30% is inserted in into the flask provided with the stirrer in the form of aqueous suspension 20%, and chloride is dropped 38%. 2-mol chloride is used to 1 mol of N-vinyl Holm amide in a copolymer. Hydrolysis is performed by 30 degreeC in 6 hours, and 90-mol% by which polymerization content was carried out of the 100-mol % and acetic acid [ by which polymerization content was carried out ] vinyl of N-vinyl Holm amide is hydrolyzed. The solution which has the viscosity of 300 mPa5 and 12.2% of solid content by 20 degreeC is obtained, and a value is 100 at that of a copolymer. Example 2 An N-vinyl Holm amide 30% and acetic acid vinyl 4 notes polymer is manufactured using the method of a statement in the Example 1. This copolymer is highly obtained as a viscous white paste. The polymer concentration under paste is 26.2%. Subsequently, after adding 1 mol of 68% chloride to the paste in the flask provided with the stirrer to 1 mol of N-vinyl Holm amide in a copolymer, a mixture is heated by 30 degreeC for 4 hours. 90-mol% of N-vinyl Holm amide by which polymerization content was carried out after this time -- it is admitted that 80-mol% of the acetic acid vinyl by which Hint polymerization content was carried out is hydrolyzed. 17 generated. The viscosity of 9% polymer solution is 3.7. 5 It is 0 mPa5 and a value is 150 at that of a copolymer. Example 1 of use Underwater 0.5% Stock suspension is manufactured from 50% of pine sulfite pulp, and 50% of Donna sulfite pulp. The pH of suspension is Z5 and 30 degrees of the degrees of Beating are SR. This Stock suspension is equally divided into four, and it is processed into the paper leaf which has the amount of 80 g/m20 tsubos on condition of the following, respectively. a) Nothing adds to Stock suspension. b) Add 1% (related with a solid) of solution of resin for neutral humid strengthening of marketing on the basis of a reaction product with the polyamide amine obtained from epichlorohydrin, diethylene triamine, and adipic acid to Stock suspension. This resin is carried out like a statement and Welcoming(ed) by Example 1 of a U.S. Pat. No. 2926116 item specification. C) U.S. Pat. No. 2721 1 It adds to solution of the polyvinyl amine chloride salt (K-value 95) by No. 40 specification. d) Add 1% (related with a solid) of the hydrolyzed copolymer which was obtained by Example 1 to Stock suspension. a) Or the dry Tear length, the humid Tear length, and the degree of whiteness of four sorts of paper leaf obtained by d were investigated. The result is summarized in the 1st table and shown. 1st Table Dry Tear length fence m 2380 2990 2850 3100 humid Tear length fence m 0 720 670 810 unstored papers The members of humid Tear length It is for 5 minutes at 110 degreeC. 0 920 850 Paper stored 940 times Degree of whiteness (% reflectance) 87.0 79.4 Underwater 0.5% Stock suspension is manufactured from 100% of example of 75 *280A use 2 pine sulfite pulp. The pH of suspension is 7.5 and 65 degrees of the degrees of Beating are SR. This Stock suspension is equally divided into four, and it is processed into the paper leaf which has the amount of tsubos of 80 g/m2 on condition of the following, respectively. a) Nothing adds to Stock suspension. b) Add 1% (related with a solid) of solution of resin for neutral humid strengthening of marketing on the basis of a reaction product with the polyamide amine obtained from epichlorohydrin, diethylene triamine, and adipic acid to Stock suspension. This resin is carried out like a statement and manufactured by Example 1 of a U.S. Pat. No. 2926116 item specification. C) 1% (related with a solid) of solution of the polyvinyl amine chloride salt by a U.S. Pat. No. 2721140 item specification is added to Stock suspension (Hydroxylate) -- set pH to six in IJ Umu solution. d) Add 1% (related with a solid) of the hydrolyzed copolymer which was obtained by Example 2 to Stock suspension. a) Or the dry Tear length of four sorts of paper leaf obtained by d, humid Tear length, alkali resistance, and a degree of whiteness are summarized in the 2nd table, and are shown. 2nd Table a) b) c) d) (Present invention) Dry Tear length fence m 4350 4950 5300 5450 alkali-resistance (m) unstored paper Alkali resistance (From) 1%NaOH solution It is 5 minutes at 50'C. 0 840 975 Paper stored for 5 minutes by 1090110"C