CN102206302A - 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
- Publication number
- CN102206302A CN102206302A CN2011100844406A CN201110084440A CN102206302A CN 102206302 A CN102206302 A CN 102206302A CN 2011100844406 A CN2011100844406 A CN 2011100844406A CN 201110084440 A CN201110084440 A CN 201110084440A CN 102206302 A CN102206302 A CN 102206302A
- Authority
- CN
- China
- Prior art keywords
- water
- composition
- dispersion liquid
- soluble polymer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
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, the paper grade (stock) flocculating aids (Filter water-based drug that makes progress) and retention aid for paper making (step is stayed upwards drug).
Background technology
Paper is used to various uses, as recycling resource and noticeable.But, if carry out recirculation, in papermaking,, water can't be deviate from from the time as the dewatering of pulp of raw material, produce problems such as paper pulp retention reduction.Therefore, in order from paper pulp, water to be deviate from, improve retention, thereby improve the production efficiency of paper, use drainage agent, retention aid or paper power toughener at present.
Method as solving drainability, problem that retention is low has proposed at present in salt brine solution, use will be in salt brine solution the dispersion of diffuse-aggregate water-soluble polymer as retention aid, flocculating aids (patent documentation 1 and patent documentation 2).According to this method, can improve drainability and retention, but under the situation of using the dispersion liquid that obtains by this method, have the problem of the undercapacity of gained paper.
In addition, as paper power toughener, be widely used in the aqueous solution acrylamide family macromolecule that acrylamide and other polymerizable monomer copolymerization are obtained at present, the applicant has also proposed the high molecular paper power of various use acrylic amides toughener (referring to for example patent documentation 3 and patent documentation 4 etc.).Yet, by being utilized again, paper reuses, as the paper pulp generation staple fibreization and the deterioration of paper material, in addition, the inorganics in the papermaking systems or the concentration of impurity rise, and give paper power effect by these paper power tougheners and still exist drainability, retention to be difficult to problems such as raising.
The prior art document
Patent documentation
Patent documentation 1: the spy opens clear 61-123610 communique
Patent documentation 2: the spy opens clear 62-020511 communique
Patent documentation 3: specially permit communique No. 3109194
Patent documentation 4: specially permit communique No. 3487059
Summary of the invention
The purpose of this invention is to provide and a kind ofly can not make the quality disorder of institute's paper and can keep higher drainability and the water-soluble polymer dispersion of paper power, paper power toughener, paper grade (stock) flocculating aids and retention aid for paper making.
The inventor is in order to solve above-mentioned problem, carried out meticulous research, find: in the presence of macromolecule dispersing agent, make specific free radical polymerization monomer composition dispersion polymerization obtain dispersion liquid, the turbidity that the dilution dispersion liquid of above-mentioned dispersion liquid shows in specific pH scope is for producing such muddiness in the certain limit, the water-soluble polymer dispersion that disperses thus to obtain can not make the quality disorder of paper and can keep higher drainability and paper power, thereby finishes the present invention.
That is, the present invention relates to:
A kind of water-soluble polymer dispersion, described dispersion liquid be more than salt concn is 10 weight % to the salt brine solution below the saturation concentration, in the presence of macromolecule dispersing agent (B), make the dispersion liquid of the water-soluble polymers (A) that radical polymerization composition (a) dispersion polymerization that contains radical cation polymerizable monomer (a1), radical anion polymerizable monomer (a2) and (methyl) acrylamide (a4) obtains at least; The total content of above-mentioned (A) composition in the described dispersion liquid and above-mentioned (B) composition is diluted under the situation of dilution dispersion liquid of 0.2 weight % at water, the minimum value of the turbidity of described dilution dispersion liquid under pH 5-8 is more than the 10NTU, the not enough 500NTU of maximum value; Contain paper power toughener, the paper grade (stock) flocculating aids of above-mentioned water-soluble polymer dispersion and contain the retention aid for paper making of above-mentioned water-soluble polymer dispersion.
By water-soluble polymer dispersion of the present invention is used as paper power toughener, can not make the quality disorder, can give paper power to paper.In addition, by adding water-soluble polymer dispersion of the present invention, owing to can improve mineral filler or, can also be used as retention aid for paper making as the retention of the paper pulp of paper material.In addition, by adding water-soluble polymer dispersion of the present invention,, can also be used as the paper grade (stock) flocculating aids owing to can improve the drainability when copying paper.
Embodiment
Water-soluble polymer dispersion of the present invention be more than salt concn is 10 weight % to the salt brine solution below the saturation concentration, macromolecule dispersing agent (B) (below, be called (B) composition) existence under, make the dispersion liquid of the water-soluble polymers (A) that radical polymerization composition (a) dispersion polymerization obtains (below, be called (A) composition).
As radical polymerization composition (a) (below, be called (a) composition), at least contain radical cation polymerizable monomer (a1) (below, be called (a1) composition), radical anion polymerizable monomer (a2) (below, be called (a2) composition) and (methyl) acrylamide (a4) (below, be called (a4) composition).
As (a1) composition, so long as have at least 1 as amino or quaternary ammonium group Cationic functional groups, have the material of 1 free-radical polymerised functional group, just there is no particular limitation, can use known material.Specifically, enumerate for example (methyl) vinylformic acid-N, N-dimethylaminoethyl, (methyl) vinylformic acid-N, N-lignocaine ethyl ester, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-diethylin propyl group (methyl) acrylamide etc. contain (methyl) acryloyl class monomer, this monomeric salt of (methyl) acryloyl class that contains uncle's amino, this (methyl) acryloyl class monomer that contains uncle's amino of uncle's amino and (methyl) acryloyl class monomer that contains quaternary ammonium salt that the quaternizing agent reaction obtains etc.Salt can be inorganic acid salts such as hydrochloride, vitriol, also can be organic acid salts such as acetate.In addition, as quaternizing agent, enumerate methyl chloride, benzyl chloride, methyl-sulfate, epoxy chloropropane etc.These (a1) compositions can use a kind separately, also can use mixing more than 2 kinds.Wherein, (methyl) vinylformic acid-N, the polymer hydrophobic 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, so 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, for example enumerate the monomer that (methyl) vinylformic acid, fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride etc. contain carboxyl; (first generation) allyl sulphonic acid etc. contains sulfonic monomer; 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 etc. contain the monomer of phosphate etc.In addition, these materials also can form the salt of basic metal class or amine etc.These materials can use a kind separately, also can use mixing more than 2 kinds.Wherein, because methylene-succinic acid can improve the compendency and the dewatering of water-soluble polymer dispersion, be preferred therefore.
In addition, in (a) composition, as required, can also use cross-linkable monomer (a3) (below, be called (a3) composition).By using (a3) composition, when in copying the paper system, adding, can improve the density of polymkeric substance, have easy raising water filtering performance and the such advantage of retention performance.
As (a3) composition, so 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, enumerate for example polyfunctional group (methyl) acrylic amide such as methylene-bisacrylamide; Hexanediyl ester, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, six glycol diacrylates, tripropylene glycol diacrylate, dicyclopentenyl diacrylate diacrylate classes such as (ジ シ Network ロ ペ Application タ ニ Le ジ ァ Network リ レ one ト); Viscoat 295, pentaerythritol triacrylate, 1 as polyfunctional group vinyl monomer with 3 above vinyl, 3,5-triacryl six hydrogen-1,3,5-triazines, three propenyl isocyanuric acid esters, three propenyl amine, tetramethylol methane tetraacrylate etc.; The many vinyl compounds of aromatic series such as Vinylstyrene etc.These materials can use a kind separately, also can use mixing more than 2 kinds.Wherein, methylene-bisacrylamide or 1,3,5-triacryl six hydrogen-1,3,5-triazines and the copolymerization height that (a1) composition, (a2)-(a4) become to grade are preferred in this.
In addition, in (a) composition,, can also use free radical polymerization monomer (a5) with 1 free-radical polymerised functional group (below, be called (a5) composition) except (a1) composition, (a2) composition with (a4) the composition.As (a5) composition, specifically, enumerate N-substituted acrylamide class, aromatic vinyl monomer, alkyl (methyl) esters of acrylic acid, vinyl carboxylates class, vinyl cyanide, vinyl alcohol etc.As N-substituted acrylamide class, so long as (a1) material beyond the composition, just there is no particular limitation, can use known material.Specifically, enumerate N, N-DMAA, N, N-diethyl (methyl) acrylamide, N, simple function group N-substituted acrylamide classes such as 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 the simple function group monomer class that has aromatic nucleus in vinylbenzene, alpha-methyl styrene, the Vinyl toluene equimolecular.In addition, as alkyl (methyl) esters of acrylic acid, enumerate monofunctional monomer classes such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate.As the vinyl carboxylates class, enumerate vinyl-acetic ester, propionate etc.These materials can use a kind separately, also can use mixing more than 2 kinds.Wherein, the copolymerization height of (a4) composition of the necessary composition of N,N-DMAA and conduct (A) composition is preferred.
In addition, there is no particular limitation to the usage quantity of each composition, usually, (a1) composition uses about 3-40 mole %, and (a2) composition uses about 1-20 mole %, (a3) composition uses about 0-1 mole %, (a4) composition uses about 20-96 mole %, and preferred (a1) composition uses 6-20 mole %, and (a2) composition uses 3-20 mole %, (a3) composition uses 0.001-0.01 mole %, and (a4) composition uses 20-90.999 mole %.In addition, under the situation of using (a5) composition, its usage quantity is preferably 0.5 mole below the % below being generally about 1 mole of %.
As (B) composition that uses among the present invention, be to be requisite monomer component with radical cation polymerizable monomer (b1) (below, be called (b1) composition), the composition that polymerization obtains, as long as can be dissolved in the salt brine solution, just there is no particular limitation.Usually can be only with the homopolymerization of (b1) composition, or with (b1) composition and described later have sulfonic free radical polymerization monomer (b2) (below, be called (b2) composition), cross-linkable monomer (b3) (below, be called (b3) composition) and any of the composition that obtains of monomer component copolymerization such as (methyl) acrylamide (b4) (below, be called (b4) composition).
As (b1) composition, can use the identical monomer of spendable (a1) composition when preparing (A) composition.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), positively charged ion amount in the time of easily will forming polymkeric substance is adjusted into the value of expectation, keep the solvability of polymkeric substance to salt brine solution, improving dispersing property, is preferred in this.As the usage quantity of (b1) composition, usually,, be preferably 30 moles more than the % from guaranteeing the viewpoint of (A) composition dispersiveness.
As (b2) composition, so 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. and have allylic sulfonic unsaturated monomer, vinyl sulfonic acid, styrene sulfonic acid, the 2-acrylamide-2-methyl propane sulfonic acid etc. of containing.Wherein, as (b2) composition, if use (first generation) sodium allyl sulfonate, then can improve the copolymerization with (methyl) acrylamide, be easy to generate the transfer (chain transfer) of free radical, be preferred.In addition, under the situation of using aftermentioned (b3) composition, with (b2) composition, then can easily adjust molecular weight and crosslinking structure by also, be preferred in this.
As (b3) composition, can use the identical monomer of (a3) composition that uses when preparing (A) composition.In addition, as (b3) composition, preferred methylene-bisacrylamide or 1,3,5-triacryl six hydrogen-1,3,5-triazines.
(B) composition that uses among the present invention can also contain (b4) composition as the polymerization composition.By use (b4) composition, thereby have the dispersing property that can not lose (B) composition, the advantage that can easily viscosity be adjusted into expected value.From guaranteeing dispersed viewpoint, (b4) usage quantity of composition is preferably used in being no more than 69.999 moles of scopes about %.
As (B) composition,, preferably has branched structure from improving the viewpoint of (A) composition dispersiveness.(B) composition with branched structure is by also obtaining as the polymerization composition with above-mentioned (b3) composition.As (b1) composition and (b3) usage quantity of composition, (b1) composition is about 30-99.99 mole %, and (b3) composition is about 0.001-1 mole %.Usage quantity by making each composition in this scope, thereby form suitable branched structure, when disperseing (A) composition, can obtain homogeneous granules.
In addition, using under the situation of (b3), from prevent (B) composition by excessive crosslinked and gelation, can easily adjust the viewpoint of viscosity, preferred and with (b2) composition.Usage quantity as (b2) composition is about the 0.5-500 that is generally (b3) composition usage quantity doubly measures (mol ratio).
In addition, as the polymerization composition of (B) composition, as required, can also contain the free radical polymerization monomer (b5) (hereinafter referred to as (b5) composition) beyond the composition of (b1) composition-(b4).As (b5) composition, can use spendable (a5) composition is identical when preparing (A) composition monomer or (methyl) vinylformic acid, fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride etc. to contain the monomer of carboxyl.These materials can use a kind separately, also can use mixing more than 2 kinds.Wherein, the N,N-DMAA and (b1)-(b4) the copolymerization height of composition are preferred.If (b5) usage quantity of composition surpasses 1 mole of %, then copolyreaction reduction, therefore, (b5) usage quantity of composition is preferably 1 mole below the %, more preferably in 0.5 mole of scope below the %.
Can above-mentioned polymerization composition be carried out radical polymerization obtain (B) composition by using known method.As radical polymerization, there is no particular limitation.(B) composition weight-average molecular weight that obtains thus is generally about 10,000-2,000,000, nonvolatile component being adjusted under the situation of 20 weight %, is preferably 1000-20000mPas at 25 ℃ solution viscosities.Solution viscosity by making (B) composition can easily improve the dispersiveness of water-soluble polymer dispersion in this scope, product viscosity is adjusted to the value of expectation, improving on this aspect of product storage stability, also can obtain more excellent product.Because same viewpoint, the scope of above-mentioned solution viscosity is preferably in the scope of 3000-20000mPas.
In the presence of (B) composition, with known method (a) composition is carried out radical polymerization and obtain (A) composition.(A) weight-average molecular weight of composition is generally 1,000,000-2000 about ten thousand, is preferably about 3,000,000-10,000,000.In addition, wherein so-called weight-average molecular weight is by gel permeation chromatography, the value that the weight-average molecular weight that obtains with the polyethylene oxide scaled value is measured.
In addition, (A) composition can also comprise the multiple polymers that obtains by different (a) composition polymerization of a plurality of compositions.Can enumerate for example water-soluble polymers (A1) and water-soluble polymers (A2) mixing etc. and (A) composition of preparation, described water-soluble polymers (A1) is that (a1) composition and (a2) mol ratio of composition [(a1)/(a2)] the radical polymerization composition (a) for (a1)/(a2) 〉=2 are obtained through polymerization, and described water-soluble polymers (A2) is to be that (a) composition of 2＞(a1)/(a2) 〉=1 obtains through polymerization with (a1) composition and (a2) mol ratio of composition [(a1)/(a2)].The drainability of the water-soluble polymers that obtains thus and paper power effect etc. can be adjusted into higher degree.
There is no particular limitation to the usage quantity of (B) composition, for the stable dispersion liquid that obtains the aftermentioned expectation (water with above-mentioned (A) composition in the dispersion liquid and (B) total content of composition be diluted under the situation that 0.2 weight % forms the dilution dispersion liquid, the minimum value of the turbidity of this dilution dispersion liquid under pH 5-8 is more than the 10NTU, the not enough 500NTU of maximum value), usually, with respect to 100 weight part radical polymerization compositions (a), preferably use (B) composition about the 1-10 weight part.
As in salt concn be more than the 10 weight % to the salt brine solution below the saturation concentration, in the presence of (B) composition, with the diffuse-aggregate method of (a) composition, as long as by known method.Usually carry out according to following: in the aqueous solution of the salt that has mixed specified amount, (a) composition, (B) composition, water etc., add radical polymerization initiator, mix liquid and carry out radical polymerization.Polymerization temperature is different according to the kind of polymerization starter, in 0-80 ℃ scope, gets final product so long as can bring into play the temperature of selected polymerization starter function usually.
As polymerization starter, can use any of azo class, peroxide, redox class.As azo-initiator, can enumerate 2,2 '-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-yl) propane] hydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) etc.In addition, as the example of redox class, can enumerate the combination of ammonium peroxydisulfate and S-WAT, sodium bisulfite, Trimethylamine 99, Tetramethyl Ethylene Diamine etc.As the example of superoxide, can enumerate ammonium peroxydisulfate or Potassium Persulfate, hydrogen peroxide, Benzoyl Peroxide (ベ Application ゾ ィ Le ペ Le ォ キ サ ィ De), peroxide lauroyl (ラ ゥ ロ ィ Le ペ Le ォ キ サ ィ De) etc.
The salt that uses during polymerization can all be contained in the mixed solution at when filling with substance, also can add stage by stage in polymerization process.In addition, as long as polyreaction is carried out more than salt concn 10 weight %, just can after polymerization, further add.
In addition,, only otherwise can dissolve (A) composition, just have no particular limits, can enumerate inorganic salt such as vitriol, phosphoric acid salt usually as the salt that uses during salt brine solution in preparation.Specifically, can enumerate for example ammonium sulfate, sodium sulfate, sal epsom, Tai-Ace S 150, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate etc.Wherein, separate out the viewpoint of effect, preferably sulfuric acid ammonium from the solubleness water and polymkeric substance.
The water-soluble polymer dispersion that obtains thus has following feature: promptly, water with above-mentioned (A) composition in the dispersion liquid and (B) total content of composition be diluted under the situation of dilution dispersion liquid of 0.2 weight %, the minimum value of the turbidity of this dilution dispersion liquid under pH 5-8 is more than the 10NTU, the not enough 500NTU of maximum value.
In addition, so-called turbidity among the present invention is muddy degree, obtains by 180 scattered lights of spending that use ANALITE turbidometer 160 types (manufacturing of McVan society), measure the infrared light that utilizes 900nm.Wherein, the determination object of turbidity of the present invention is not the turbidity of the dispersion liquid self that obtains of dispersion polymerization, but with above-mentioned (A) composition and (B) total content of composition to be diluted to the dilution dispersion liquid that 0.2 weight % obtains be object.In addition, specific turbidity is limited to the situation that the pH of dilution dispersion liquid is adjusted at the scope of 5-8 among the present invention.Concrete measuring method as turbidity of the present invention, as long as water (being preferably deionized water) dilution, make in the dispersion liquid above-mentioned (A) composition and (B) total content of composition be 0.2 weight %, make the dilution dispersion liquid, add alkali or acid then, change the pH of dilution dispersion liquid, and measure turbidity in time, minimum value and the maximum value of obtaining the shown turbidity that goes out of pH this dilution dispersion liquid in the scope of 5-8 of dilution dispersion liquid get final product.As adjusting the alkali that uses among the pH, there is no particular limitation, can enumerate sodium hydroxide, potassium hydroxide; As acid, can enumerate sulfuric acid, hydrochloric acid, nitric acid etc., from the viewpoint of easy trickle adjustment pH when the turbidity measurement, use the aqueous solution about 1 weight % to get final product.In addition, the mensuration temperature of pH is about 25 ℃.
Under the situation of the not enough 10NTU of minimum value of the above-mentioned turbidity of the dilution dispersion liquid of water-soluble polymer dispersion, generation can't obtain the problem of the target drainability of water-soluble polymer dispersion.On the other hand, under the maximum value of the above-mentioned turbidity of the dilution dispersion liquid of water-soluble polymer dispersion is situation more than the 500NTU, when using water-soluble polymer dispersion, for example under the situation that is diluted to the proper concn use, or under the situation about using with other reagent mix, can produce precipitation, under this state, existence can't be given full play to the possibility of performance originally such as paper delivery power reinforced effects or drainability raising effect.In addition, the mechanism for the relation of the state of the water-soluble polymers composition that presents above-mentioned turbidity and effect of the present invention do not fully understand as yet, but under this state, supposition is because a plurality of interpolymer interactions form ionic complex.
In addition,, can also in mixed solution, not contain all (a) compositions, in dispersion polymerization, add stage by stage to carry out polymerization at when filling with substance.Thus, can more easily obtain to have the water-soluble polymer dispersion of above-mentioned feature.
In addition, the median size of gained water-soluble polymer dispersion is generally about 0.1 μ m-150 μ m.By making median size in this scope, thereby the permanent stability of gained dispersion liquid can be excellent more.From same viewpoint, preferred median size is 0.1 μ m-100 μ m.(A) content of composition is generally 10-40 weight %, and the viscosity of the water-soluble polymer dispersion under 25 ℃ is preferably 100-20000mPas.Be adjusted in this scope by content and viscosity, can suppress in the water-soluble polymer dispersion particulate precipitation etc., improve the stability of dispersion state (A) composition.
For water-soluble polymer dispersion of the present invention being used as paper power toughener, drainability rising agent and retention aid, usually the weight-average molecular weight of water-soluble polymer dispersion ((A) composition and (B) mixture of ingredients) is preferably more than 3,000,000, in addition, preferred water etc. will (A) composition be diluted to about 0.01-1 weight % with (B) total content of composition.
No matter be machine-made paper or paperboard, all can use aqueous polymer dispersion liquid of the present invention, in addition, can also use other additive for papermaking (sizing agents simultaneously; Or known paper power toughener; Organic and inorganic water insoluble microparticle aggegation auxiliary agent).
Embodiment
Below, by enumerating embodiment and comparative example the present invention is carried out more specific description, but the present invention is not subjected to the qualification of these embodiment.
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, the 80 weight % aqueous solution 250g (the weight 200g of pure compound), the 529g ion exchanged water that add acrylyl oxy-ethyl-trimethyl salmiac are heated to 65 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 5 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, under agitation carry out polymerization.By self-heating temperature is risen, under 80 ℃, carried out polyreaction 1 hour, thereby obtain macromolecule dispersing agent.
After nonvolatile component transferred to 20 weight %, adjust temperature to 25 ℃, use PVC ス メ ト ロ Application (Vismetron) viscometer (sesame Pu シ ス テ system (strain) manufacturing) that the viscosity of gained macromolecule dispersing agent is measured.(below, viscosity is to use the value of measuring with quadrat method.)
The manufacture method of (Production Example 2) macromolecule dispersing agent
In five mouthfuls of separating flasks of 2 liters, add 80 weight % aqueous solution 249.99g (the weight 199.992g of pure compound of acrylyl oxy-ethyl-trimethyl salmiac with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe; 99.995 mole %), 0.008g (0.005 mole of %) methylene-bisacrylamide, 529.7g ion exchanged water, be heated to 50 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 1.5 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation.By self-heating temperature is risen, under 80 ℃, carried out polyreaction 1 hour, thereby obtain macromolecule dispersing agent.
The manufacture method of (Production Example 3) macromolecule dispersing agent
In five mouthfuls of separating flasks of 2 liters, add 80 weight % aqueous solution 215.63g (the weight 172.5g of pure compound of acrylyl oxy-ethyl-trimethyl salmiac with agitator, thermometer, reflux cooling pipe, nitrogen ingress pipe; 69.85 mole %), 0.1966g (0.1 mole of %) methylene-bisacrylamide, 0.1g (0.05 mole of %) sodium methallyl sulfonate, 27.2g (30 moles of %) acrylamide, 536.47g ion exchanged water, be heated to 60 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation.By self-heating temperature is risen, under 80 ℃, carried out polyreaction 1 hour, thereby obtain macromolecule dispersing agent.
Table 1
In the table, the numeral of (b 1)-(b4) is mole %, and viscosity is represented the measured value under 25 ℃, 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 the 1049.25g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 101.73g (the weight 81.384g of pure compound that wherein add 282.17g (85 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 9 moles of %), 36.45g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1017.95g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To wherein adding 215.15g (79 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 29.9g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261.01g (82 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 34.95g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1049.25g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 2.To 80 weight % aqueous solution 101.73g (the weight 81.384g of pure compound that wherein add 282.17g (85 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 9 moles of %), 36.45g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1017.95g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 2.To wherein adding 215.15g (79 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 29.9g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the dilution dispersion liquid then.The result is shown in the 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 2.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261.01g (82 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 34.95g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1049.25g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 101.73g (the weight 81.384g of pure compound that wherein add 282.17g (85 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 9 moles of %), 36.45g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1017.95g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To wherein adding 215.15g (79 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 29.9g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261.01g (82 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 34.95g (6 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1049.25g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 101.73g (the weight 81.384g of pure compound that wherein add 282.16g (84.998 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 9 moles of %), 36.45g (6 moles of %) methylene-succinic acid, 0.0144g (0.002 mole of %) methylene-bisacrylamide, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1017.95g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To wherein adding 215.14g (78.998 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 29.9g (6 moles of %) methylene-succinic acid, 0.0118g (0.002 mole of %) methylene-bisacrylamide, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261g (81.998 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 34.95g (6 moles of %) methylene-succinic acid, 0.0138g (0.002 mole of %) methylene-bisacrylamide, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the table 2.
The manufacture method of (embodiment 13) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that embodiment 1 is obtained mixes with weight ratio with the dispersion liquid of the water-soluble polymers that embodiment 2 obtains at 1: 1.
The manufacture method of (embodiment 14) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that embodiment 7 is obtained mixes with weight ratio with the dispersion liquid of the water-soluble polymers that embodiment 8 obtains at 1: 1.
The manufacture method of (embodiment 15) water-soluble polymer dispersion
The dispersion liquid of the water-soluble polymers that embodiment 10 is obtained mixes with weight ratio with the dispersion liquid of the water-soluble polymers that embodiment 11 obtains at 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261.01g (82 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 17.47g (3 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein adding 20g as 2 of polymerization starter, 2 '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, after 3 hours, add 17.47g (3 moles of %) methylene-succinic acid, polymerization under agitation 21 hours, acquisition is dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1043.59g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 2.To 80 weight % aqueous solution 130.05g (the weight 104.04g of pure compound that wherein add 261.01g (82 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), 17.47g (3 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein adding 20g as 2 of polymerization starter, 2 '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, after 3 hours, add 17.47g (3 moles of %) methylene-succinic acid, polymerization under agitation 21 hours, acquisition is dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1042.52g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 135.42g (the weight 108.336g of pure compound that wherein add 291.66g (88 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1042.52g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 135.42g (the weight 108.336g of pure compound that wherein add 291.66g (88 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 12 moles of %), be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1037.14g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To wherein adding 270.13g (84.998 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 0.0138g (0.002 mole of %) methylene-bisacrylamide, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1037.14g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To wherein adding 270.13g (84.998 moles of %) acrylamide, vinylformic acid-N, 75 weight % aqueous solution 206.6g (the weight 154.95g of pure compound of the benzyl chloride quaternary ammonium salt of N-dimethylaminoethyl; 15 moles of %), 0.0138g (0.002 mole of %) methylene-bisacrylamide, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1039.52g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 150.42g (the weight 120.336g of pure compound that wherein add 215g (73 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 15 moles of %), 64.67g (12 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1039.52g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 150.42g (the weight 120.336g of pure compound that wherein add 215g (73 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 15 moles of %), 64.67g (12 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1041.73g ion exchanged water, the macromolecule dispersing agent that does not have branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 1.To 80 weight % aqueous solution 139.35g (the weight 111.48g of pure compound that wherein add 163.71g (60 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 15 moles of %), 124.81g (25 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the 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 the 1041.73g ion exchanged water, the macromolecule dispersing agent with branched structure, the 400g ammonium sulfate that obtain in the dissolving 110g Production Example 3.To 80 weight % aqueous solution 139.35g (the weight 111.48g of pure compound that wherein add 163.71g (60 moles of %) acrylamide, acrylyl oxy-ethyl-trimethyl salmiac; 15 moles of %), 124.81g (25 moles of %) methylene-succinic acid, be heated to 30 ℃ and use nitrogen replacement.To wherein add 20g as 2,2 of polymerization starter '-the 2 weight % aqueous solution of azo two (2-amidine propane) hydrochloride, polymerization under agitation 24 hours obtains to be dispersed in the dispersion liquid of the water-soluble polymers in the salt brine solution.Measure the median size and the viscosity of gained dispersion liquid, again water with (A) composition in the dispersion liquid and (B) total content of composition be diluted to 0.2 weight %, measure the turbidity of dilution dispersion liquid then.The result is shown in the table 2.
For the water-soluble polymer dispersion that obtains by embodiment and comparative example, measure median size, viscosity, the result is shown in table 2 and the table 3.In addition, each measuring method is as described below.
(median size)
Carry out with 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 under measuring 25 ℃.
(turbidity)
With deionized water the total content of (A) composition in the dispersion liquid and above-mentioned (B) composition is diluted to 0.2 weight %, splash into the aqueous sodium hydroxide solution of 1 weight %, make the pH of dilution dispersion liquid change to 8 from the pH (25 ℃) that demonstrates, be changed in 8 the process by 5 at its pH, measure the minimum value and the maximum value of the shown turbidity that goes out of dilution dispersion liquid, obtain the scope of turbidity.
Table 2
Numeral in the table is a mole %, the measured value when viscosity represents that nonvolatile component is adjusted to 20 weight % under 25 ℃.
In addition, for the record of each compound (monomer etc.) ellipsis in the table 2, represent following compound.
DMAEA-Q: acrylyl oxy-ethyl-trimethyl salmiac
DMAEA-BQ: vinylformic acid-N, the benzyl chloride quaternary ammonium salt of 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 is carried out beating with Niagara formula hollander, be adjusted into Canadian Standard Freeness (C.S.F) 300ml, obtain the paper material that solid component concentration is 1.0 weight %.Then, add the Tai-Ace S 150 with respect to paper material solids component 1.0 weight %, preparation pH is 7.0 paper pulp.Subsequently, with tap water the water-soluble polymer dispersion that obtains among embodiment 1-17 and the comparative example 1-8 being diluted to solids component ((A)+(B)) concentration is 0.05 weight %, the diluent of preparation water-soluble polymer dispersion.Then,, in paper pulp, add the diluent of water-soluble polymer dispersion, by patting-tabletting machine (tap sheet machine) dehydration, at 5kg/cm with amount with respect to paper material solids component 0.05 weight % in the paper pulp
2Under push and copied paper in 2 minutes, obtain quantitatively being 150g/m
2Paper.Then, with the paper that obtains with rotary-type drying machine 105 ℃ dry 4 minutes down, damping is 24 hours under 23 ℃, the condition of 50%R.H., measures then than pop strength and quality coefficient of variation.Simultaneously, the paper pulp that 500ml is added after the mentioned reagent adds among the Britt Jar (40 order), the agitator that use has turbine impellers stirs (2000rpm), and from the chamber of below, take out the 100ml filtered water, by behind No. 2 filter paper suction strainers, drying is 60 minutes under 110 ℃, measures dried quality, obtains whole retention (OPR).In addition, also measure to add the drainage amount of each paper pulp after the mentioned reagent.
In addition, the drainage amount is measured according to JIS P8121, measure according to JIS P8131 than pop strength, the quality coefficient of variation will be by importing personal images treatment system Hyper-700 (OBS manufacturing) through the light (whiteness (brightness)) of gained paper, and distribution is carried out statistical study and measured to whiteness.In addition, the numerical value of quality coefficient of variation is more little, and the expression quality is good more.
Water-soluble polymer dispersion solids component in each evaluation Example with respect to the measurement result of the adding rate of paper material solids component and projects shown in the table 3.
Table 3
Claims (11)
1. water-soluble polymer dispersion, described dispersion liquid be more than salt concn is 10 weight % to the salt brine solution below the saturation concentration, in the presence of macromolecule dispersing agent (B), make the dispersion liquid of the water-soluble polymers (A) that radical polymerization composition (a) dispersion polymerization that contains radical cation polymerizable monomer (a1), radical anion polymerizable monomer (a2) and (methyl) acrylamide (a4) obtains at least; The total content of above-mentioned (A) composition in the described dispersion liquid and above-mentioned (B) composition is diluted under the situation of dilution dispersion liquid of 0.2 weight % at water, the minimum value of the turbidity of described dilution dispersion liquid under pH 5-8 is more than the 10NTU, the not enough 500NTU of maximum value.
2. water-soluble polymer dispersion as claimed in claim 1, wherein, described macromolecule dispersing agent (B) contains radical cation polymerizable monomer (b1) as the polymerization composition, has branched structure.
3. water-soluble polymer dispersion as claimed in claim 2, wherein, described macromolecule dispersing agent (B) contains the cross-linkable monomer (b3) of 0.001-1 mole % as the polymerization composition.
4. as each described water-soluble polymer dispersion of claim 1-3, wherein, with respect to 100 weight part radical polymerization compositions (a), the usage quantity of described macromolecule dispersing agent (B) is the 1-10 weight part.
5. as each described water-soluble polymer dispersion of claim 1-4, wherein, described radical polymerization composition (a) contains 3-40 mole % radical cation polymerizable monomer (a1), 1-20 mole % radical anion polymerizable monomer (a2), 0-1 mole % cross-linkable monomer (a3) and 20-96 mole % (methyl) acrylamide (a4).
6. as each described water-soluble polymer dispersion of claim 1-5, wherein, the median size of described water-soluble polymers (A) is 0.1 μ m-1501 μ m.
7. as each described water-soluble polymer dispersion of claim 1-6, wherein, the content of described water-soluble polymers (A) is 10-40 weight %, and the viscosity of the described water-soluble polymer dispersion under 25 ℃ is 100-20000mPas.
8. as each described water-soluble polymer dispersion of claim 1-7, wherein,, contain following 2 kinds of water-soluble polymerss at least as described water-soluble polymers (A):
The water-soluble polymers (A1) that the mol ratio [(a1)/(a2)] of radical cation polymerizable monomer (a1) and radical anion polymerizable monomer (a2) is obtained through polymerization for the radical polymerization composition (a) of (a1)/(a2) 〉=2; And
With the mol ratio [(a1)/(a2)] of radical cation polymerizable monomer (a1) and radical anion polymerizable monomer (a2) is the water-soluble polymers (A2) that 2＞(a1)/(a2) 〉=1 radical polymerization composition (a) obtains through polymerization.
9. contain paper power toughener just like each described water-soluble polymer dispersion of claim 1-8.
10. contain paper grade (stock) flocculating aids just like each described water-soluble polymer dispersion of claim 1-8.
11. contain retention aid for paper making just like each described water-soluble polymer dispersion of claim 1-8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010081160 | 2010-03-31 | ||
| JP2010-081160 | 2010-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102206302A true CN102206302A (en) | 2011-10-05 |
| CN102206302B CN102206302B (en) | 2014-12-24 |
Family
ID=44695389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110084440.6A Active CN102206302B (en) | 2010-03-31 | 2011-03-31 | Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5709043B2 (en) |
| CN (1) | CN102206302B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772567A (en) * | 2014-01-15 | 2014-05-07 | 刘水平 | Preparation method and application of aqueous polymer polyamide in paper-making |
| CN104343052A (en) * | 2013-08-08 | 2015-02-11 | 荒川化学工业株式会社 | Paper strength improver and paper obtained by using the paper strength improver |
| CN108221475A (en) * | 2017-12-14 | 2018-06-29 | 定远县权达新能源科技有限公司 | A kind of modified pulp toughener |
| CN110318292A (en) * | 2018-03-28 | 2019-10-11 | 荒川化学工业株式会社 | The manufacturing method of surface paper power reinforcing agent, coating liquid, paper |
| CN114026287A (en) * | 2019-08-02 | 2022-02-08 | 荒川化学工业株式会社 | Powdery paper strength agent, paper strength agent solution, and paper |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5847657B2 (en) * | 2012-06-11 | 2016-01-27 | Ｍｔアクアポリマー株式会社 | Yield improver for papermaking and papermaking method using the same |
| CN105121591B (en) | 2013-01-31 | 2018-09-18 | 艺康美国股份有限公司 | Mobility for improving oil recovery controls polymer |
| US20140262090A1 (en) * | 2013-03-14 | 2014-09-18 | Ecolab Usa Inc. | Methods for Increasing Retention and Drainage in Papermaking Processes |
| US10442980B2 (en) | 2014-07-29 | 2019-10-15 | Ecolab Usa Inc. | Polymer emulsions for use in crude oil recovery |
| EP3420047B1 (en) | 2016-02-23 | 2023-01-11 | Ecolab USA Inc. | Hydrazide crosslinked polymer emulsions for use in crude oil recovery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126771A (en) * | 2005-11-02 | 2007-05-24 | Arakawa Chem Ind Co Ltd | Method for making paper |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002227095A (en) * | 2001-01-30 | 2002-08-14 | Hymo Corp | Paper strengthening agent and paper strengthening method |
| JP2004044011A (en) * | 2002-07-11 | 2004-02-12 | Hymo Corp | Method for using water-soluble polymer dispersion |
| JP2006182816A (en) * | 2004-12-27 | 2006-07-13 | Hymo Corp | Crosslinked water-soluble polymer dispersion liquid and paper making method using the same |
| JP4942415B2 (en) * | 2006-07-28 | 2012-05-30 | ハイモ株式会社 | Paper making method |
-
2011
- 2011-03-24 JP JP2011066655A patent/JP5709043B2/en active Active
- 2011-03-31 CN CN201110084440.6A patent/CN102206302B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007126771A (en) * | 2005-11-02 | 2007-05-24 | Arakawa Chem Ind Co Ltd | Method for making paper |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104343052A (en) * | 2013-08-08 | 2015-02-11 | 荒川化学工业株式会社 | Paper strength improver and paper obtained by using the paper strength improver |
| CN103772567A (en) * | 2014-01-15 | 2014-05-07 | 刘水平 | Preparation method and application of aqueous polymer polyamide in paper-making |
| CN103772567B (en) * | 2014-01-15 | 2016-02-03 | 刘水平 | A kind of preparation method of waterborne polymeric polymeric amide and the application in papermaking thereof |
| CN108221475A (en) * | 2017-12-14 | 2018-06-29 | 定远县权达新能源科技有限公司 | A kind of modified pulp toughener |
| CN110318292A (en) * | 2018-03-28 | 2019-10-11 | 荒川化学工业株式会社 | The manufacturing method of surface paper power reinforcing agent, coating liquid, paper |
| CN110318292B (en) * | 2018-03-28 | 2022-10-21 | 荒川化学工业株式会社 | Surface paper strength enhancer, coating liquid, and method for producing paper |
| CN114026287A (en) * | 2019-08-02 | 2022-02-08 | 荒川化学工业株式会社 | Powdery paper strength agent, paper strength agent solution, and paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5709043B2 (en) | 2015-04-30 |
| JP2011226042A (en) | 2011-11-10 |
| CN102206302B (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102206302B (en) | Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent | |
| JP5366301B2 (en) | Powdered ionic water-soluble polymer and use thereof | |
| CN1954021B (en) | Anionic water-in-water polymer dispersion, method for the production thereof and its use | |
| CN101608047B (en) | Water-soluble polymer dispersion liquid, paper strengthening agent, drainability improving agent and retention agent for making paper | |
| CN109153749A (en) | Polymer, the manufacturing method of polymer and high polymer coagulant | |
| CN102153697B (en) | Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent | |
| CN1754022A (en) | Anionic functional promoter and charge control agent with improved wet to dry tensile strength ratio | |
| CN100453573C (en) | Positive ion organic high polymer coagulant and preparation method thereof | |
| US7220339B2 (en) | Process for preparing a polymer dispersion | |
| CN109082931A (en) | A kind of paper grade (stock) retention aid and filtering aid reinforcing agent | |
| CN103772603A (en) | Preparation method and application of cross-linked polyacrylamide with high molecular weight and narrow distribution | |
| CN1307206C (en) | Process for preparing a polymer dispersion | |
| JP3871322B2 (en) | How to use water-soluble polymer dispersion | |
| JP4873691B2 (en) | Calcium carbonate dispersion and preparation method thereof | |
| CN104428375A (en) | Use of comb polymer for preparing suspension containing calcium carbonate and having reduced temperature sensitivity | |
| US20220306510A1 (en) | Polymeric structure and its uses | |
| JP2004044011A (en) | Method for using water-soluble polymer dispersion | |
| ES2960380T3 (en) | Method for producing polymer solutions | |
| CN117813429A (en) | N-vinyllactam-containing polymers for papermaking | |
| US20100216962A1 (en) | Method for neutralizing a water-soluble acrylic polymer by at least one monovalent agent and at least one divalent agent, and polymers obtained | |
| JP2008280654A (en) | Paper additive, method for producing the same, and paper containing the same | |
| JP2012229311A (en) | Water-soluble polymer dispersion, paper strength additive, filtration improvement agent for papermaking, and retention aid for papermaking | |
| JPH1160879A (en) | Water-base dispersion composition of water-soluble polymer and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |