CN102206302B - Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent - Google Patents
Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent Download PDFInfo
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- CN102206302B CN102206302B CN201110084440.6A CN201110084440A CN102206302B CN 102206302 B CN102206302 B CN 102206302B CN 201110084440 A CN201110084440 A CN 201110084440A CN 102206302 B CN102206302 B CN 102206302B
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Abstract
The invention provides a water-soluble polymer dispersion liquid, a paper strength agent, a papermaking filter aid and a papermaking retention agent, which may not impair the paper quality and can maintain high filteration rate and enhance paper strength. The water-soluble polymer dispersion liquid, in a saline solution, of which the salt concentration is higher than 10 weight % and lower than a saturation concentration and at the presence of a polymeric dispersant (B), is a dispersion liquid obtained by dispersion polymerization of the free radical polymeric components (a) of at least cationic free radical polymeric monomers (a1), anionic free radical polymeric monomers (a2) and (methyl) acrylamide (a4). In a water diluted dispersion liquid where the total content of the component (A) and the component (B) of the dispersion liquid is 0.2 wt.%, the minimal turbidity of the diluted dispersion liquid ranges from 10NTU to 500NTU, when the pH value is 5-8.
Description
Technical field
The present invention relates to water-soluble polymer dispersion, paper power toughener, paper grade (stock) flocculating aids (Filter water-based upwards drug) and retention aid for paper making (step stays upwards drug).
Background technology
Paper is used to various uses, noticeable as recycling resource.But, if carry out recirculation, in papermaking, when from dewatering of pulp as raw material, water cannot be deviate from, produce the problems such as paper pulp retention reduction.Therefore, in order to be deviate from by water from paper pulp, improve retention, thus improve the production efficiency of paper, use drainage agent, retention aid or paper power toughener at present.
As the method solving drainability, problem that retention is low, be currently suggested in salt brine solution, use and the dispersion of water-soluble polymer diffuse-aggregate in salt brine solution is used as retention aid, flocculating aids (patent documentation 1 and patent documentation 2).According to the method, drainability and retention can be improved, but when using the dispersion liquid obtained by the method, there is the problem of the undercapacity of gained paper.
In addition, as paper power toughener, widely use in aqueous by the acrylamide family macromolecule that acrylamide and other polymerizable monomer copolymerization obtain at present, the applicant it is also proposed various use acrylic amides high molecular paper power toughener (see such as patent documentation 3 and patent documentation 4 etc.).But, by paper recycling is reused, as paper pulp generation staple fibre and the deterioration of paper material, in addition, the concentration of the inorganics in papermaking systems or impurity rises, and is given that paper power effect still exists drainability, retention is difficult to the problems such as raising by these paper power tougheners.
Prior art document
Patent documentation
Patent documentation 1: JP 61-123610 publication
Patent documentation 2: JP 62-020511 publication
Patent documentation 3: specially permit No. 3109194 publication
Patent documentation 4: specially permit No. 3487059 publication
Summary of the invention
The object of this invention is to provide and a kind ofly the quality of institute's paper can not be made disorderly and the water-soluble polymer dispersion of higher drainability and paper power, paper power toughener, paper grade (stock) flocculating aids and retention aid for paper making can be maintained.
The present inventor is in order to solve above-mentioned problem, carry out meticulous research, find: under the existence of macromolecule dispersing agent, the dispersion polymerization of specific free radical polymerization monomer composition is made to obtain dispersion liquid, the turbidity that the dilution dispersion liquid of above-mentioned dispersion liquid shows within the scope of specific pH is produce muddiness such in certain limit, disperse the water-soluble polymer dispersion obtained the quality of paper can not be made disorderly and higher drainability and paper power can be maintained thus, thus complete the present invention.
That is, the present invention relates to:
A kind of water-soluble polymer dispersion, described dispersion liquid is in the salt brine solution of less than more than 10 % by weight to saturation concentration in salt concn, under the existence of macromolecule dispersing agent (B), the dispersion liquid of the water-soluble polymers (A) at least making radical polymerization composition (a) dispersion polymerization containing radical cation polymerizable monomer (a1), radical anion polymerizable monomer (a2) and (methyl) acrylamide (a4) obtain; When the total content of above-mentioned (A) composition in described dispersion liquid and above-mentioned (B) composition being diluted to the dilution dispersion liquid of 0.2 % by weight with water, the minimum value of the turbidity of described dilution dispersion liquid under pH 5-8 is more than 10NTU, and maximum value is less than 500NTU; Paper power toughener containing above-mentioned water-soluble polymer dispersion, paper grade (stock) flocculating aids and the retention aid for paper making containing above-mentioned water-soluble polymer dispersion.
By water-soluble polymer dispersion of the present invention is used as paper power toughener, quality can not be made disorderly, paper power can be given to paper.In addition, by adding water-soluble polymer dispersion of the present invention, due to the retention of mineral filler or the paper pulp as paper material can be improved, retention aid for paper making can also be used as.In addition, by adding water-soluble polymer dispersion of the present invention, due to drainability during copy paper can be improved, paper grade (stock) flocculating aids can also be used as.
Embodiment
Water-soluble polymer dispersion of the present invention is in the salt brine solution of less than more than 10 % by weight to saturation concentration in salt concn, (following at macromolecule dispersing agent (B), be called (B) composition) existence under, the dispersion liquid of the water-soluble polymers (A) (hereinafter referred to as (A) composition) that radical polymerization composition (a) dispersion polymerization is obtained.
(following as radical polymerization composition (a), be called (a) composition), at least (following containing radical cation polymerizable monomer (a1), be called (a1) composition), radical anion polymerizable monomer (a2) is (following, be called (a2) composition) and (methyl) acrylamide (a4) (hereinafter referred to as (a4) composition).
As (a1) composition, as long as have at least 1 Cationic functional groups as amino or quaternary ammonium group, have the material of 1 free-radical polymerised functional group, just there is no particular limitation, can use known material.Specifically, enumerate such as (methyl) vinylformic acid-N, N-dimethylaminoethyl, (methyl) vinylformic acid-N, N-lignocaine ethyl ester, N, (methyl) propylene Monomer of acyls etc. containing quaternary ammonium salt that (methyl) propylene Monomer of acyls containing tertiary amino such as N-dimethylamino-propyl (methyl) acrylamide, N, N-diethylin propyl group (methyl) acrylamide, the salt that should contain (methyl) propylene Monomer of acyls of tertiary amino, (methyl) the propylene Monomer of acyls that should contain tertiary amino and quaternizing agent are obtained by reacting.Salt can be the inorganic acid salt such as hydrochloride, vitriol, also can be the organic acid salts such as acetate.In addition, as quaternizing agent, methyl chloride, benzyl chloride, methyl-sulfate, epoxy chloropropane etc. are enumerated.These (a1) compositions can be used alone a kind, also can be used in combination by two or more.Wherein, (methyl) vinylformic acid-N, the polymer hydrophobicity that the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl obtains is higher, and its solvability in salt brine solution is low, is preferred at that point.
As (a2) composition, as long as have at least 1 anionic property functional group, have the material of 1 free-radical polymerised functional group, just there is no particular limitation, can use known material.Specifically, the monomer containing carboxyl such as such as (methyl) vinylformic acid, fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride etc. is enumerated; (first generation) allyl sulphonic acids etc. are containing sulfonic monomer; The monomer etc. containing phosphate such as 2-methyl-2-vinylformic acid-2-(phosphono oxygen base) ethyl ester (リ Application acid 2-メ タ Network リ ロ ィ Le ォ キ シ ェ チ Le), vinyl phosphonate.In addition, these materials also can form the salt of basic metal class or amine etc.These materials can be used alone a kind, also can be used in combination by two or more.Wherein, because methylene-succinic acid can improve compendency and the dewatering of water-soluble polymer dispersion, be therefore preferred.
In addition, in (a) composition, as required, cross-linkable monomer (a3) (hereinafter referred to as (a3) composition) can also be used.By using (a3) composition, when adding in copy paper system, the density of polymkeric substance can be improved, having and easily improving water filtering performance and the such advantage of retention performance.
As (a3) composition, as long as have the material of at least 2 free-radical polymerised functional groups, just there is no particular limitation, can use known material.Specifically, polyfunctional group (methyl) acrylic amides such as such as methylene-bisacrylamide are enumerated; The diacrylate classes such as hexanediyl ester, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, six glycol diacrylates, tripropylene glycol diacrylate, dicyclopentenyl diacrylate (ジ シ Network ロ ペ Application タ ニ Le ジ ァ Network リ レ mono-ト); As Viscoat 295, the pentaerythritol triacrylate, 1 of polyfunctional group vinyl monomer with more than 3 vinyl, 3,5-triacryl six hydrogen-1,3,5-triazines, three propenyl isocyanuric acid esters, three propenyl amine, tetramethylol methane tetraacrylate etc.; The aromatic multi-vinyl based compounds etc. such as Vinylstyrene.These materials can be used alone a kind, also can be used in combination by two or more.Wherein, the copolymerizable of methylene-bisacrylamide or 1,3,5-triacryl, six hydrogen-1,3,5-triazines and (a1) composition, (a2)-(a4) composition etc. is high, is preferred in this.
In addition, in (a) composition, except (a1) composition, (a2) composition and (a4) composition, the free radical polymerization monomer (a5) (hereinafter referred to as (a5) composition) with 1 free-radical polymerised functional group can also be used.As (a5) composition, specifically, N-substituted acrylamide class, aromatic vinyl monomer, alkyl (methyl) esters of acrylic acid, vinyl carboxylates class, vinyl cyanide, vinyl alcohol etc. are enumerated.As N-substituted acrylamide class, as long as the material beyond (a1) composition, just there is no particular limitation, can use known material.Specifically, enumerate N, N-DMAA, N, the simple function group N-substituted acrylamide classes such as N-diethyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide.As aromatic vinyl monomer, be set forth in Monofunctional monomers's class in vinylbenzene, alpha-methyl styrene, Vinyl toluene equimolecular with aromatic nucleus.In addition, as alkyl (methyl) esters of acrylic acid, enumerate the monofunctional monomer classes such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate.As vinyl carboxylates class, enumerate vinyl-acetic ester, propionate etc.These materials can be used alone a kind, also can be used in combination by two or more.Wherein, N,N-DMAA is high with the copolymerizable as (a4) composition of the essential component of (A) composition, is preferred.
In addition, to the usage quantity of each composition, there is no particular limitation, usually, (a1) composition uses about 3-40 % by mole, (a2) composition uses about 1-20 % by mole, (a3) composition uses about 0-1 % by mole, (a4) composition uses about 20-96 % by mole, preferably (a1) composition uses 6-20 % by mole, (a2) composition uses 3-20 % by mole, (a3) composition uses 0.001-0.01 % by mole, and (a4) composition uses 20-90.999 % by mole.In addition, when using (a5) composition, its usage quantity is generally less than about 1 % by mole, is preferably less than 0.5 % by mole.
As (B) composition used in the present invention, (following with radical cation polymerizable monomer (b1), be called (b1) composition) be requisite monomer component, be polymerized the composition obtained, as long as can be dissolved in salt brine solution, just there is no particular limitation.Usually can be only by the homopolymerization of (b1) composition, or by (b1) composition and described later to have sulfonic free radical polymerization monomer (b2) (following, be called (b2) composition), cross-linkable monomer (b3) is (following, be called (b3) composition) and any one of the composition that obtains of the monomer component copolymerization such as (methyl) acrylamide (b4) (hereinafter referred to as (b4) composition).
As (b1) composition, the monomer identical with spendable (a1) composition when preparing (A) composition can be used.In addition, as (b1) composition, use acrylyl oxy-ethyl-trimethyl salmiac (ァ Network リ ロ ィ Le ォ キ シ ェ チ Le ト リ メ チ Le ァ Application モ ニ ゥ system Network ロ リ De), easily positively charged ion amount when forming polymkeric substance is adjusted to the value of expectation, keep polymkeric substance to the solvability of salt brine solution, improving dispersing property, is preferred in this.As the usage quantity of (b1) composition, usually, from the view point of guaranteeing (A) composition dispersiveness, more than 30 % by mole are preferably.
As (b2) composition, as long as have at least 1 sulfonic group, and have monomer and/or its salt of 1 free-radical polymerised functional group, just there is no particular limitation, can use known material.Specifically, can enumerate allyl sulphonic acid, sodium allyl sulfonate, methallyl sulfonic acid, sodium methallyl sulfonate, methallyl sulfonic acid ammonium etc. has allylic containing sulfonic unsaturated monomer, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic etc.Wherein, as (b2) composition, if use (first generation) sodium allyl sulfonate, then can improve the copolymerizable with (methyl) acrylamide, easily producing the transfer (chain tra nsfer) of free radical, is preferred.In addition, when stating (b3) composition after a procedure, by also using (b2) composition, then can easily adjust molecular weight and crosslinking structure, be preferred in this.
As (b3) composition, the monomer identical with (a3) composition used when preparing (A) composition can be used.In addition, as (b3) composition, preferred methylene-bisacrylamide or 1,3,5-triacryl, six hydrogen-1,3,5-triazines.
(B) composition used in the present invention can also containing (b4) composition as polymeric composition.By using (b4) composition, thus there is the dispersing property that can not lose (B) composition, the advantage that easily viscosity can be adjusted to expected value.From guaranteeing dispersed viewpoint, the usage quantity of (b4) composition preferably uses in the scope being no more than about 69.999 % by mole.
As (B) composition, from the viewpoint improving (A) composition dispersiveness, preferably there is branched structure.There is (B) composition of branched structure, by and obtain as polymeric composition with above-mentioned (b3) composition.As the usage quantity of (b1) composition with (b3) composition, (b1) composition is about 30-99.99 % by mole, and (b3) composition is about 0.001-1 % by mole.By making the usage quantity of each composition within the scope of this, thus forming suitable branched structure, when disperseing (A) composition, can uniform particle be obtained.
In addition, when using (b3), from the view point of preventing the gelation by excessive being cross-linked in (B) composition, easily adjusting viscosity, preferably also with (b2) composition.As the usage quantity of (b2) composition, be generally (mol ratio) about the 0.5-500 times amount of (b3) composition usage quantity.
In addition, as the polymeric composition of (B) composition, as required, the free radical polymerization monomer (b5) (hereinafter referred to as (b5) composition) beyond (b1) composition-(b4) composition can also be contained.As (b5) composition, the monomer identical with spendable (a5) composition when preparing (A) composition or the monomer containing carboxyl such as (methyl) vinylformic acid, fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride can be used.These materials can be used alone a kind, also can be used in combination by two or more.Wherein, N,N-DMAA is high with the copolymerizable of (b1)-(b4) composition, is preferred.If (b5) usage quantity of composition is more than 1 % by mole, then copolyreaction reduces, and therefore, the usage quantity of (b5) composition is preferably less than 1 % by mole, in the scope more preferably below 0.5 % by mole.
By using known method, above-mentioned polymeric composition can be carried out radical polymerization and obtaining (B) composition.As radical polymerization, there is no particular limitation.(B) composition weight-average molecular weight obtained thus is generally about 10,000-200 ten thousand, when nonvolatile component is adjusted to 20 % by weight, is preferably 1000-20000mPas at the solution viscosity of 25 DEG C.By making the solution viscosity of (B) composition within the scope of this, easily can improve the dispersiveness of water-soluble polymer dispersion, product viscosity being adjusted to the value of expectation, on this aspect of raising product storage stability, also can obtain more excellent product.Due to same viewpoint, the scope of above-mentioned solution viscosity is preferably in the scope of 3000-20000mPas.
Under the existence of (B) composition, by known method, (a) composition is carried out radical polymerization acquisition (A) composition.(A) weight-average molecular weight of composition is generally about 1,000,000-2,000 ten thousand, is preferably about 3,000,000-1,000 ten thousand.In addition, wherein so-called weight-average molecular weight is by gel permeation chromatography, the value of the Weight-average molecular flow measurement obtained with polyethylene oxide scaled value.
In addition, (A) composition can also comprise the multiple polymers obtained by different (a) composition polymerization of multiple composition.Can enumerate such as water-soluble polymers (A1) and water-soluble polymers (A2) mixing wait and prepare (A) composition, described water-soluble polymers (A1) is that radical polymerization composition (a) being (a1)/(a2) >=2 by (a1) composition and the mol ratio [(a1)/(a2)] of (a2) composition obtains through being polymerized, and described water-soluble polymers (A2) is that (a) composition being 2 > (a1)/(a2) >=1 by (a1) composition and the mol ratio [(a1)/(a2)] of (a2) composition obtains through being polymerized.The drainability of the water-soluble polymers obtained thus and paper power effect etc. can be adjusted to higher degree.
To the usage quantity of (B) composition, there is no particular limitation, in order to the dispersion liquid of the aftermentioned expectation of stable acquisition is (when to be diluted to 0.2 % by weight and to form dilution dispersion liquid by the total content of above-mentioned (A) composition in dispersion liquid and (B) composition with water, the minimum value of the turbidity of this dilution dispersion liquid under pH 5-8 is more than 10NTU, maximum value is less than 500NTU), usually, relative to 100 weight parts radical polymerization composition (a), preferably use (B) composition about 1-10 weight part.
As in salt concn be less than more than 10 % by weight to saturation concentration salt brine solution in, under the existence of (B) composition, by diffuse-aggregate for (a) composition method, as long as undertaken by known method.Usually according to carrying out as follows: add radical polymerization initiator in the aqueous solution being mixed with the salt of specified amount, (a) composition, (B) composition, water etc., be uniformly mixed liquid and carry out radical polymerization.Polymerization temperature is different according to the kind of polymerization starter, usually in the scope of 0-80 DEG C, as long as can play the temperature of selected polymerization starter function.
As polymerization starter, can use azo, peroxide, redox class any one.As azo-initiator, can 2 be enumerated, 2 '-azo two (amidine propane) hydrochloride (2,2 '-ァ ゾ PVC ス (ァ ミ ジ ノ プ ロ パ Application) Salt Suan salt), 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-base) propane] hydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) etc.In addition, as the example of redox class, the combination of ammonium peroxydisulfate and S-WAT, sodium bisulfite, Trimethylamine 99, Tetramethyl Ethylene Diamine etc. can be enumerated.As the example of superoxide, ammonium peroxydisulfate or Potassium Persulfate, hydrogen peroxide, Benzoyl Peroxide (ベ Application ゾ ィ Le ペ Le ォ キ サ ィ De), lauroyl peroxide (ラ ゥ ロ ィ Le ペ Le ォ キ サ ィ De) etc. can be enumerated.
The salt used during polymerization all can be contained in mixed solution at when filling with substance, also can add stage by stage in the course of the polymerization process.In addition, as long as polyreaction is carried out in salt concn more than 10 % by weight, just can add further after polymerisation.
In addition, as the salt used when preparing salt brine solution, as long as (A) composition can not be dissolved, just having no particular limits, usually can enumerate the inorganic salt such as vitriol, phosphoric acid salt.Specifically, such as ammonium sulfate, sodium sulfate, magnesium sulfate, Tai-Ace S 150, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate etc. can be enumerated.Wherein, effect is separated out, preferably sulfuric acid ammonium from the view point of the solubleness in water and polymkeric substance.
The water-soluble polymer dispersion obtained thus has following feature: namely, when above-mentioned (A) composition in dispersion liquid being diluted to the dilution dispersion liquid of 0.2 % by weight with the total content of (B) composition with water, the minimum value of the turbidity of this dilution dispersion liquid under pH 5-8 is more than 10NTU, and maximum value is less than 500NTU.
In addition, so-called turbidity in the present invention is muddy degree, by using ANALITE turbidometer 160 type (manufacture of McVan society), measuring and utilizes the scattered light of 180 of the infrared light of 900nm degree and obtain.Wherein, the determination object of turbidity of the present invention is not the turbidity of the dispersion liquid self that dispersion polymerization obtains, but so that the total content of above-mentioned (A) composition and (B) composition is diluted to the 0.2 % by weight dilution dispersion liquid obtained for object.In addition, in the present invention, specific turbidity is limited to the situation of the pH adjustment of dilution dispersion liquid in the scope of 5-8.As the concrete measuring method of turbidity of the present invention, as long as with water (being preferably deionized water) dilution, above-mentioned (A) composition in dispersion liquid is made to be 0.2 % by weight with the total content of (B) composition, obtained dilution dispersion liquid, then alkali or acid is added, change the pH of dilution dispersion liquid, and measure turbidity in time, the minimum value of the turbidity that the pH obtaining dilution dispersion liquid goes out shown by this dilution dispersion liquid in the scope of 5-8 and maximum value.As the alkali used in adjustment pH, there is no particular limitation, can enumerate sodium hydroxide, potassium hydroxide; As acid, sulfuric acid, hydrochloric acid, nitric acid etc. can be enumerated, from the view point of the easy trickle adjustment pH when turbidity measurement, use the aqueous solution of about 1 % by weight.In addition, the mensuration temperature of pH is about 25 DEG C.
When the minimum value of the above-mentioned turbidity of the dilution dispersion liquid of water-soluble polymer dispersion is less than 10NTU, produce the problem that cannot obtain the target drainability of water-soluble polymer dispersion.On the other hand, when the maximum value of the above-mentioned turbidity of the dilution dispersion liquid of water-soluble polymer dispersion is more than 500NTU, when using water-soluble polymer dispersion, such as when being diluted to proper concn and using, or when using with other reagent mix, can precipitation be produced, in this condition, there is the possibility that cannot give full play to the script performance such as paper delivery power reinforced effects or drainability raising effect.In addition, for the mechanism of the state of water-soluble polymers composition and the relation of effect of the present invention that present above-mentioned turbidity, not yet fully understand, but in this condition, supposition is due to multiple interpolymer interaction, forms ionic complex.
In addition, at when filling with substance, can also, not containing whole (a) composition in mixed solution, add stage by stage to be polymerized in dispersion polymerization.Thus, the water-soluble polymer dispersion with above-mentioned feature can more easily be obtained.
In addition, the median size of gained water-soluble polymer dispersion is generally 0.1 μm about-150 μm.By making median size within the scope of this, thus the permanent stability of gained dispersion liquid can be more excellent.From the same viewpoint, preferred median size is 0.1 μm-100 μm.(A) content of composition is generally 10-40 % by weight, and the viscosity of the water-soluble polymer dispersion at 25 DEG C is preferably 100-20000mPas.By the content of (A) composition and viscosity being adjusted within the scope of this, the precipitation etc. of particle in water-soluble polymer dispersion can be suppressed, improving the stability of dispersion state.
In order to water-soluble polymer dispersion of the present invention being used as paper power toughener, drainability rising agent and retention aid, the weight-average molecular weight of usual water-soluble polymer dispersion (mixture of (A) composition and (B) composition) is preferably more than 3,000,000, in addition, preferably with water etc., the total content of (A) composition and (B) composition is diluted to 0.01-1 about % by weight.
No matter be machine-made paper or paperboard, all can use aqueous polymer dispersion liquid of the present invention, in addition, other additive for papermaking (sizing agents can also be used simultaneously; Or known paper power toughener; Organic and inorganic water insoluble microparticle aggegation auxiliary agent).
Embodiment
Below, by enumerating embodiment and comparative example carries out more specific description to the present invention, but the present invention is by the restriction of these embodiments.
The manufacture method of (Production Example 1) macromolecule dispersing agent
In five mouthfuls of separating flasks (separable flask) of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, add 80 % by weight aqueous solution 250g (the weight 200g of pure compound), the 529g ion exchanged water of acrylyl oxy-ethyl-trimethyl salmiac, be heated to 65 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 5 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, are under agitation polymerized.Make temperature increase by self-heating, at 80 DEG C, carry out polyreaction 1 hour, thus obtain macromolecule dispersing agent.
After nonvolatile component being adjusted to 20 % by weight, adjustment temperature to 25 DEG C, uses PVC ス メ ト ロ Application (Vismetron) viscometer (sesame Pu シ ス テ system (strain) manufacture) to measure the viscosity of gained macromolecule dispersing agent.(following, viscosity is the value measured with same method.)
The manufacture method of (Production Example 2) macromolecule dispersing agent
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, add 80 % by weight aqueous solution 249.99g (the weight 199.992g of pure compound of acrylyl oxy-ethyl-trimethyl salmiac; 99.995 % by mole), 0.008g (0.005 % by mole) methylene-bisacrylamide, 529.7g ion exchanged water, be heated to 50 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 1.5 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, are under agitation polymerized.Make temperature increase by self-heating, at 80 DEG C, carry out polyreaction 1 hour, thus obtain macromolecule dispersing agent.
The manufacture method of (Production Example 3) macromolecule dispersing agent
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, add 80 % by weight aqueous solution 215.63g (the weight 172.5g of pure compound of acrylyl oxy-ethyl-trimethyl salmiac; 69.85 % by mole), 0.1966g (0.1 % by mole) methylene-bisacrylamide, 0.1g (0.05 % by mole) sodium methallyl sulfonate, 27.2g (30 % by mole) acrylamide, 536.47g ion exchanged water, be heated to 60 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, are under agitation polymerized.Make temperature increase by self-heating, at 80 DEG C, carry out polyreaction 1 hour, thus obtain macromolecule dispersing agent.
Table 1
In table, the numeral of (b 1)-(b4) is % by mole, and viscosity represents the measured value at 25 DEG C, for the record of each compound (monomer etc.) ellipsis, represents following compound.
DMAEA-Q: acrylyl oxy-ethyl-trimethyl salmiac
MBAA: methylene-bisacrylamide
SMAS: sodium methallyl sulfonate
AM: acrylamide
The manufacture method of (embodiment 1) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1049.25g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 101.73g (the weight 81.384g of pure compound of 282.17g (85 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 9 % by mole), 36.45g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 2) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1017.95g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 215.15g (79 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 29.9g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 3) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261.01g (82 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 34.95g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 4) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1049.25g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 2.Add 80 % by weight aqueous solution 101.73g (the weight 81.384g of pure compound of 282.17g (85 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 9 % by mole), 36.45g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 5) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1017.95g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 2.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 215.15g (79 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 29.9g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 6) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 2.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261.01g (82 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 34.95g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 7) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1049.25g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 101.73g (the weight 81.384g of pure compound of 282.17g (85 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 9 % by mole), 36.45g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 8) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1017.95g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 215.15g (79 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 29.9g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 9) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261.01g (82 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 34.95g (6 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 10) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1049.25g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 101.73g (the weight 81.384g of pure compound of 282.16g (84.998 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 9 % by mole), 36.45g (6 % by mole) methylene-succinic acid, 0.0144g (0.002 % by mole) methylene-bisacrylamide, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 11) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1017.95g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 215.14g (78.998 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 29.9g (6 % by mole) methylene-succinic acid, 0.0118g (0.002 % by mole) methylene-bisacrylamide, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 12) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261g (81.998 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 34.95g (6 % by mole) methylene-succinic acid, 0.0138g (0.002 % by mole) methylene-bisacrylamide, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 13) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that the dispersion liquid of water-soluble polymers embodiment 1 obtained obtains with embodiment 2 mixes with weight ratio 1: 1.
The manufacture method of (embodiment 14) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that the dispersion liquid of water-soluble polymers embodiment 7 obtained obtains with embodiment 8 mixes with weight ratio 1: 1.
The manufacture method of (embodiment 15) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that the dispersion liquid of water-soluble polymers embodiment 10 obtained obtains with embodiment 11 mixes with weight ratio 1: 1.
The manufacture method of (embodiment 16) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261.01g (82 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 17.47g (3 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, after 3 hours, add 17.47g (3 % by mole) methylene-succinic acid, under agitation be polymerized 21 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (embodiment 17) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1043.59g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 2.Add 80 % by weight aqueous solution 130.05g (the weight 104.04g of pure compound of 261.01g (82 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), 17.47g (3 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, after 3 hours, add 17.47g (3 % by mole) methylene-succinic acid, under agitation be polymerized 21 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 1) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1042.52g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 135.42g (the weight 108.336g of pure compound of 291.66g (88 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 2) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1042.52g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 135.42g (the weight 108.336g of pure compound of 291.66g (88 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 12 % by mole), be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 3) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1037.14g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 270.13g (84.998 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 0.0138g (0.002 % by mole) methylene-bisacrylamide, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 4) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1037.14g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 75 % by weight aqueous solution 206.6g (the weight 154.95g of pure compound of benzyl chloride quaternary ammonium salt of 270.13g (84.998 % by mole) acrylamide, vinylformic acid-N, N-dimethylaminoethyl wherein; 15 % by mole), 0.0138g (0.002 % by mole) methylene-bisacrylamide, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 5) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1039.52g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 150.42g (the weight 120.336g of pure compound of 215g (73 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 15 % by mole), 64.67g (12 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 6) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1039.52g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 150.42g (the weight 120.336g of pure compound of 215g (73 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 15 % by mole), 64.67g (12 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 7) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1041.73g ion exchanged water, dissolve the macromolecule dispersing agent, the 400g ammonium sulfate that there is no branched structure that obtain in 110g Production Example 1.Add 80 % by weight aqueous solution 139.35g (the weight 111.48g of pure compound of 163.71g (60 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 15 % by mole), 124.81g (25 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
The manufacture method of (comparative example 8) water-soluble polymer dispersion
In five mouthfuls of separating flasks of 2 liters with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe, in 1041.73g ion exchanged water, dissolve the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in 110g Production Example 3.Add 80 % by weight aqueous solution 139.35g (the weight 111.48g of pure compound of 163.71g (60 % by mole) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac wherein; 15 % by mole), 124.81g (25 % by mole) methylene-succinic acid, be heated to 30 DEG C and use nitrogen replacement.Add 20g wherein as 2 of polymerization starter, 2 % by weight aqueous solution of 2 '-azo two (2-amidine propane) hydrochloride, be under agitation polymerized 24 hours, obtain the dispersion liquid of the water-soluble polymers be dispersed in salt brine solution.Measure median size and the viscosity of gained dispersion liquid, then with water, the total content of (A) composition in dispersion liquid and (B) composition is diluted to 0.2 % by weight, then measure the turbidity of dilution dispersion liquid.Result illustrates in table 2.
For the water-soluble polymer dispersion obtained by embodiment and comparative example, measure median size, viscosity, result is shown in table 2 and table 3.In addition, each measuring method is as described below.
(median size)
Carry out with the observation by light microscope mean value of any 100 discrete particles (in the measuring microscope visual field).
(viscosity)
Use Type B viscosity, according to JIS K7117-1, the viscosity at measuring 25 DEG C.
(turbidity)
With deionized water, the total content of (A) composition in dispersion liquid and above-mentioned (B) composition is diluted to 0.2 % by weight, instill the aqueous sodium hydroxide solution of 1 % by weight, the pH of dilution dispersion liquid is made to change to 8 from the pH demonstrated (25 DEG C), be changed in the process of 8 at its pH by 5, measure minimum value and the maximum value of the turbidity gone out shown by dilution dispersion liquid, obtain the scope of turbidity.
Table 2
Numeral in table is % by mole, and viscosity represents measured value when nonvolatile component being adjusted to 20 % by weight at 25 DEG C.
In addition, for the record of compound (monomer etc.) ellipsis each in table 2, following compound is represented.
DMAEA-Q: acrylyl oxy-ethyl-trimethyl salmiac
DMAEA-BQ: the benzyl chloride quaternary ammonium salt of vinylformic acid-N, N-dimethylaminoethyl
IA: methylene-succinic acid
MBAA: methylene-bisacrylamide
AM: acrylamide
Evaluation method:
(evaluation Example 1-17 and comparative evaluation example 1-4)
Corrugation waste paper Niagara formula hollander is carried out beating, is adjusted to Canadian Standard Freeness (C.S.F) 300ml, obtains the paper material that solid component concentration is 1.0 % by weight.Then, add the Tai-Ace S 150 relative to paper material solids component 1.0 % by weight, preparation pH is the paper pulp of 7.0.Subsequently, with tap water, the water-soluble polymer dispersion obtained in embodiment 1-17 and comparative example 1-8 being diluted to solids component ((A)+(B)) concentration is 0.05 % by weight, prepares the diluent of water-soluble polymer dispersion.Then, with the amount relative to paper material solids component in paper pulp 0.05 % by weight, in paper pulp, add the diluent of water-soluble polymer dispersion, by patting-tabletting machine (tap sheet machine) dehydration, at 5kg/cm
2lower extruding carries out copy paper in 2 minutes, obtains being quantitatively 150g/m
2paper.Then, by the rotary-type drying machine of paper that obtains at 105 DEG C dry 4 minutes, 23 DEG C, damping 24 hours under the condition of 50%R.H., then measure than pop strength and quality coefficient of variation.Simultaneously, 500ml being added the paper pulp after mentioned reagent adds in Britt Jar (40 order), the agitator with turbine impellers is used to stir (2000rpm), and take out 100ml filtered water in chamber from below, after No. 2 filter paper suction strainers, at 110 DEG C, drying 60 minutes, measures dried quality, obtains overall retention (OPR).In addition, the drainage amount of each paper pulp after adding mentioned reagent is also measured.
In addition, drainage amount measures according to JIS P8121, measure according to JIS P8131 than pop strength, quality coefficient of variation, by by the light (whiteness (brightness)) input personal images treatment system Hyper-700 (OBS manufacture) through gained paper, carries out statistical study to whiteness distribution and measures.In addition, the numerical value of quality coefficient of variation is less, represents that quality is better.
Water-soluble polymer dispersion solids component in each evaluation Example illustrates in table 3 relative to the adding rate of paper material solids component and the measurement result of projects.
Table 3
Claims (9)
1. a water-soluble polymer dispersion, described dispersion liquid is in the salt brine solution of less than more than 10 % by weight to saturation concentration in salt concn, under the existence of macromolecule dispersing agent (B), the dispersion liquid of the water-soluble polymers (A) at least making radical polymerization composition (a) dispersion polymerization containing 3-40 % by mole of radical cation polymerizable monomer (a1), 1-20 % by mole radical anion polymerizable monomer (a2), 0-1 % by mole cross-linkable monomer (a3) and 20-96 % by mole of (methyl) acrylamide (a4) obtain; When the total content of above-mentioned (A) composition in described dispersion liquid and above-mentioned (B) composition being diluted to the dilution dispersion liquid of 0.2 % by weight with water, the minimum value of the turbidity of described dilution dispersion liquid under pH 5-8 is more than 10NTU, maximum value is less than 500NTU, wherein, as described water-soluble polymers (A), at least containing following 2 kinds of water-soluble polymerss:
By radical cation polymerizable monomer (a1) and the mol ratio [(a1)/(a2)] of radical anion polymerizable monomer (a2) be (a1)/(radical polymerization composition (a) of a2)≤2 is through being polymerized the water-soluble polymers (A1) obtained; And
By the mol ratio [(a1)/(a2)] of radical cation polymerizable monomer (a1) and radical anion polymerizable monomer (a2) for 2> (a1)/(radical polymerization composition (a) of a2)≤1 is through being polymerized the water-soluble polymers (A2) obtained.
2. water-soluble polymer dispersion as claimed in claim 1, wherein, described macromolecule dispersing agent (B) as polymeric composition, has branched structure containing radical cation polymerizable monomer (b1).
3. water-soluble polymer dispersion as claimed in claim 2, wherein, described macromolecule dispersing agent (B) containing the cross-linkable monomer (b3) of 0.001-1 % by mole as polymeric composition.
4. the water-soluble polymer dispersion as described in any one of claim 1-3, wherein, relative to 100 weight parts radical polymerization composition (a), the usage quantity of described macromolecule dispersing agent (B) is 1-10 weight part.
5. the water-soluble polymer dispersion as described in any one of claim 1-3, wherein, the median size of described water-soluble polymers (A) is 0.1 μm-150 μm.
6. the water-soluble polymer dispersion as described in any one of claim 1-3, wherein, the content of described water-soluble polymers (A) is 10-40 % by weight, and the viscosity of the described water-soluble polymer dispersion at 25 DEG C is 100-20000mPas.
7. containing, for example the paper power toughener of the water-soluble polymer dispersion described in any one of claim 1-6.
8. containing, for example the paper grade (stock) flocculating aids of the water-soluble polymer dispersion described in any one of claim 1-6.
9. containing, for example the retention aid for paper making of the water-soluble polymer dispersion described in any one of claim 1-6.
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| CN101608047A (en) * | 2008-06-19 | 2009-12-23 | 荒川化学工业株式会社 | Water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and retention aid for paper making |
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