CN1112377C - Polymer dispersion, method of manufacturing same, and use of same - Google Patents

Polymer dispersion, method of manufacturing same, and use of same Download PDF

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Publication number
CN1112377C
CN1112377C CN97120209A CN97120209A CN1112377C CN 1112377 C CN1112377 C CN 1112377C CN 97120209 A CN97120209 A CN 97120209A CN 97120209 A CN97120209 A CN 97120209A CN 1112377 C CN1112377 C CN 1112377C
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water
methyl
polymeric dispersions
polymkeric substance
total
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CN1187494A (en
Inventor
田中胜利
佐藤一行
宫原庸
中村智法
越路祐一
的场干之
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Hymo Corp
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Hymo Corp
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Priority claimed from JP30749696A external-priority patent/JP3260288B2/en
Priority claimed from JP2829897A external-priority patent/JPH10212320A/en
Priority claimed from JP14603897A external-priority patent/JP4030075B2/en
Priority claimed from JP15312497A external-priority patent/JP3260297B2/en
Application filed by Hymo Corp filed Critical Hymo Corp
Publication of CN1187494A publication Critical patent/CN1187494A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

To obtain a polymer dispersion having a low viscosity, a good workability, and an excellent storage stability by polymerizing a monomer component contg. (meth)acrylic acid in an aq. salt soln. in the presence of a cationic water-soluble polymer.The monomer component contg. (meth)acrylic acid comprises 15-100mol% acrylic acid and 0-85mol% acrylamide. The cationic water-soluble polymer is, e.g. a dimethyldiallylammonium chloride (co)polymer. The wt. ratio of the monomer component to the cationic water-soluble polymer is (100:1)-(10:1). A chloride, sulfate, or nitrate of an alkali metal (e.g. Na or K) or ammonium is used as the salt for forming the aq. salt soln. The concn. of the salt is from 5wt.% to the saturation concn. In a papermaking process, the aq. soln. is mixed into a paper material and then a water-diluted polymer dispersion is added to the material.

Description

Polymeric dispersions, its production method and uses thereof
The present invention relates to a kind of method of production anionic polymer dispersion and the purposes of this dispersion, relate more specifically to the production method of dispersion of the fine particle of (methyl) vinylformic acid (being total to) polymkeric substance, this method has prevented to condense, the purposes that also relates to resulting dispersions with low viscosity simultaneously, this dispersion in use can dilute with water, also dilute with water has not saved the operation of a step trouble simultaneously, as has neutralized.
The clear 62-20511 of Japanese Patent Application Publication discloses a kind of in the presence of as a kind of polymer dielectric of dispersion agent, makes monomer polymerization obtain the method for water soluble polymer dispersions in the aqueous solution of salt (this solution dissolved monomer and not lysigenous polymkeric substance).In this method, requiring the ionic charge of polymer dielectric and used monomeric ionic charge is same type.
On the other hand, the clear 60-185900 of Japanese Patent Application Publication discloses a kind of method that obtains fine polymer dispersion of particles body by polymeric acrylic acid and acrylamide in the aqueous solution of salt (this solution dissolved monomer and not lysigenous polymkeric substance).This method does not need to exist simultaneously any polymer dielectric just can obtain fine particle.The fine polymer particle of gained is water-fast herein, if neutralize this dispersion, then dissolves in a kind of solvent.That is to say that this is the technology of a kind of difference and the clear 62-20511 of Japanese Patent Application Publication.Yet fine particle has accumulative character and curing and condenses into bean curd shape (bean curd shape) in the acrylate copolymer-acrylamide copolymer dispersion that obtains with described method when leaving standstill, thereby makes this method practical at all.Because this point, the industrial application of described dispersion becomes impossible.
General objects of the present invention provides the method for dispersion of the fine particle of a kind of production (methyl) vinylformic acid (being total to) polymkeric substance, this method has prevented to condense, a kind of purposes of dispersions with low viscosity also is provided simultaneously, this dispersion in use can dilute with water, also dilute with water not, saved the operation of a step trouble simultaneously, as neutralization etc.
The present inventor finds, has low viscosity, the fine polymer dispersion of particles body that well adds 1 property and superior storage stability can be by in the presence of the polymer dielectric that is used as dispersed retention agent (dispersibilityretaining agent), polymerization comprises that (methyl) acrylic acid water-soluble monomer produces in the aqueous solution of salt, wherein the aqueous solution dissolves described monomer and not lysigenous polymkeric substance, thereby the contriver has formulated the present invention.
An object of the present invention is in the aqueous solution of salt, in the presence of the dispersed retention agent of the polymer dielectric that comprises the aqueous solution that is dissolved in described salt, comprise the method for the polymeric dispersions of (methyl) acrylic acid water-soluble monomer production (methyl) vinylformic acid (being total to) polymkeric substance by polymerization, wherein
(1) concentration of (methyl) vinylformic acid (being total to) polymkeric substance is 5wt.% at least in the described polymeric dispersions,
(2) median size of (methyl) vinylformic acid (being total to) polymer particle is 1～100 μ m in the described polymeric dispersions,
(3) viscosity with production described polymeric dispersions after month of harsh output is 10～3000cp,
Can identify polymer particle when (4) amplifying 400 times of observations with microscope when 10 times of described polymer dispersed body and function distilled water dilutings and with diluent, and
(5) when by add alkali with the pH regulator of described diluent to 7.0 the time, described polymer particle dissolving forms the aqueous solution.
Another object of the present invention provides a kind of production and has the method that comprises (methyl) acrylic acid polymeric dispersions that will polymeric water-soluble monomer component, and the water-soluble monomer of described production method is (methyl) vinylformic acid of 15～100mol% and the acrylamide of 0～85mol%.
Another object of the present invention provides a kind of method of producing polymeric dispersions, dispersed retention agent in the wherein said production method is selected from by chlorination dimethyldiallylammonium (being total to) polymkeric substance, acrylamide-2-methyl propane sulfonic acid (being total to) polymkeric substance, and composition thereof the group formed.
Another object of the present invention provides a kind of method of producing polymeric dispersions, will comprise that the weight ratio of (methyl) acrylic acid water-soluble monomer and dispersed retention agent is 100: 1～10: 1 by polymeric in the wherein said production method.
The dispersion of a kind of (methyl) vinylformic acid (being total to) polymkeric substance in the aqueous solution of salt that a further object of the invention provides, wherein
(1) concentration of (methyl) vinylformic acid (being total to) polymkeric substance is 5wt.% at least in the described polymeric dispersions,
(2) median size of (methyl) vinylformic acid (being total to) polymer particle is 1～100 μ m in the described polymeric dispersions,
(3) viscosity with the described polymeric dispersions of production after one month of harsh output is 10～3000cp,
Can identify polymer particle when (4) amplifying 400 times of observations with microscope when 10 times of described polymer dispersed body and function distilled water dilutings and with diluent, and
(5) when by add alkali with the pH regulator of described diluent to 7.0 the time, described polymer particle dissolving forms the aqueous solution.
A further object of the invention provides a kind of papermaking process, comprise with cellulose pulp and fillers dispersed in water with the preparation pulp slurry, the pH that keeps slurries simultaneously is in 6.5～10 scopes, form the scraps of paper, dry to make paper, described method also comprises in described pulp slurry and adds cationic polymers, shears described pulp slurry, and adds the described poly-of dilute with water before forming the described scraps of paper. the compound dispersion.
A further object of the invention provides the method that a kind of improvement contains the soil of steam, comprise containing adding and mix the described polymeric dispersions that contains 0.1～5kg polymkeric substance in the described soil of 20～400% water, fill possible soil thereby preparation has toward every 1m3.
Also have a purpose to provide a kind of method that prevents splitting in addition, comprise that described polymeric dispersions with dilute with water is sprayed on the surface of base-material (web) as the anti-stripper of interlayer, multilayer base-material surperficial stacked of the anti-stripper of interlayer, compacting and dry these layers then will be stained with on the surface.
Another one purpose of the present invention provides a kind of method of the solid suspension that flocculates, and comprises adding and mix the described polymeric dispersions that is in undiluted state or dilute with water state in solid suspension.
Among the present invention, comprise (methyl) acrylic acid will the polymeric monomer comprise 15～100mol% from by vinylformic acid, the monomer of choosing in the group that methacrylic acid and composition thereof is formed, with 0～85% non-ionic monomer of from the group of forming by following material, choosing: acrylamide, vinyl cyanide, (methyl) methyl acrylate, (methyl) Hydroxyethyl acrylate, vinyl ロ methyl ether, vinyl-acetic ester and composition thereof.
The multipolymer of wherein preferred (methyl) vinylformic acid and acrylamide.In addition, use that further to comprise terpolymer of acrylonitrile also be ideal.
Used dispersed retention agent is to have in dispersion to form the polymer dielectric that the back keeps dispersiveness to work among the present invention.This polymer dielectric can be cationic, also can be anionic.
The electrolytical example of cationic polymers as dispersed retention agent has in the present invention: the salt of (methyl) propenoic acid dialkyl ammonium alkyl ester or (being total to) polymkeric substance of level Four product, (being total to) polymkeric substance of the salt of dialkyl amino alkyl (methyl) acrylamide or (being total to) polymkeric substance of level Four product and dialkyldiallyl ammonium salt.
The salt of (methyl) propenoic acid dialkyl aminoalkyl ester or the example of level Four product have: hydrochlorinate (methyl) vinylformic acid dimethylaminoethyl ester, propylene dichloride acyl-oxygen ethyl trimethyl ammonium etc.Equally, the example of the salt of dialkyl aminoalkyl (methyl) acrylamide or level Four product has the hydrochloride or the methylate of dimethylaminopropyl (methyl) acrylamide.An example of dialkyldiallyl ammonium salt is the chlorination dimethyldiallylammonium.
Equally, the electrolytical example of anionic water-soluble polymer has: (being total to) polymkeric substance that the monomer of choosing from the group of being made up of following material by polymerization obtains: styrene sulfonic acid or its salt, vinyl sulfonic acid or its salt, acrylamide-2-methyl propane sulfonic acid or its salt etc.
Above-mentioned polymer dielectric can be to have the multipolymer of at least a ion monomer or the multipolymer of all right right and wrong ion monomer such as acrylamide.
Most preferred cationic polymers ionogen as dispersed retention agent of the present invention is chlorination dimethyldiallylammonium (a being total to) polymkeric substance, and most preferred anionic polymer ionogen is acrylamide-2-methyl propane sulfonic acid (being total to) polymkeric substance.
Comprise (methyl) acrylic acid will the polymeric monomer and the weight ratio of dispersed retention agent be preferably 100: 1～10: 1.If the amount of dispersed retention agent very little, dispersion condenses into bean curd shape in time.On the contrary, if the amount of dispersed retention agent is excessive, its effect is because of meaningless being restricted economically.
The example that is used for the salt of the salifiable aqueous solution of shape of the present invention has: an alkali metal salt such as sodium salt, sylvite etc. and ammonium salt such as ammonium chloride, ammonium sulfate, ammonium nitrate etc.The concentration of salt that is used for the aqueous solution of above-mentioned salt be required 5wt.% to saturation concentration, but the pH that requires the concentration of salt and dispersion dissolves used monomer but not in the scope of lysigenous polymkeric substance at the aqueous solution of salt.On the other hand, the dispersed retention agent that comprises the coexistence of polymer dielectric must be dissolved in the aqueous solution of described salt.
(methyl) of the present invention vinylformic acid (being total to) polymeric dispersions and as the polymer dielectric of dispersed retention agent can be respectively by under the atmosphere that does not have oxygen at nitrogen in water-bearing media dissolved monomer, and by adding water-soluble azo type initiators for polymerization, as chlorination 2,2 '-azo two (2-amidine propanes) or use the water soluble oxidized reductive polymerization initiator free yl polymerizating monomer of ammonium persulphate and sodium bisulfite to prepare simultaneously.
The temperature of paradigmatic system can be chosen arbitrarily in 0～100 ℃ of scope according to the character of used polymerization starter.For regulating the molecular weight of resulting polymkeric substance, can add chain transfer agents, as Virahol or mercaptan and can select for use as conventional radical polymerization is any.When preparation (methyl) vinylformic acid (being total to) polymeric dispersions, must stir with circumferential speed to eliminate the deposition of fine polymer particle greater than 1m/min.Unless the content escape, stirring velocity does not have the upper limit, thereby can select any agitation condition for use.Normally work as the polymer dielectric of dispersed retention agent, but from the angle of homogenizing product, polymerization of the present invention is preferably under agitation finished by static polymerization in the aqueous solution.
The concentration of polymkeric substance is higher or be at least 5wt% in the dispersion of the present invention, normally is that 5wt% is to about 40wt%.
Dispersion of the present invention contain high density formation polymkeric substance but the viscosity of dispersion is lower because polymkeric substance is dispersed in the dispersion medium with fine particle in stable conditionly, thereby its viscosity is lower usually or between 10～3000cp.Therefore, it is characterized in that polymeric dispersions is easy to flow and is easy to and handles.
Polymer particle in the dispersion of the present invention can identify when amplifying 400 times with opticmicroscope at undiluted state with under with the state of 10 times of distilled water dilutings.At this moment, the median size of polymer particle is generally 1～100 μ m, preferred 2～30 μ m, more preferably 2～20 μ m.When the median size of polymer particle surpassed 100 μ m, particle was tending towards being easy to deposition thereby has reduced sedimentation Stability, thereby needed for a long time with complete dissolve polymer when using.On the contrary, dispersion of the present invention has good sedimentation Stability, even thereby under normal temps, store electricity any trouble take place never, as the particle generation bulk that bonds mutually.Simultaneously, its solvability in water is also very good during use.
Molecular weight to the polymkeric substance in the dispersion of the present invention has no particular limits.Consider to add to be used for flocculation and to handle mud, add as chemical substance and be used for flocculation and dehydration and add as chemical substance and to be used for paper-making process, more preferably higher molecular weight as chemical substance.In this case, desirable molecular weight is greater than 100 ten thousand.If dispersion of the present invention is to describe with soltion viscosity, when polymkeric substance be dissolved in (viscosity is measured with the Brookfield viscometer at 25 ℃) in the aqueous solution of salt of 2wt% ammonium sulfate, when its concentration reaches 0.5wt%, usually between 5～200cp.Equally, even after storing one month, the viscosity of dispersion of the present invention is almost without any variation.
When dispersion of the present invention was diluted to 10 times, polymer particle can identify with microscope, when in solution, add alkali with the pH regulator of dispersion to 7.0 the time, described polymer particle dissolving forms the aqueous solution.That is to say that dispersion of the present invention can be said to the dispersion of the fine particle that is water-insoluble polymer.
In the papermaking process that uses dispersion of the present invention, in pulp slurry, add cationic polymers, mix as the aqueous solution of cationic starch or cationic polyacrylamide or their mixture and with it, in water, regulate its pH to 6.5～10 behind plain paper pulp of loosen collagen fibre and the filler, apply shearing force, add the polymeric dispersions of dilute with water of the present invention then.That is to say, the invention is characterized in not have to use to comprise the polymer of monomers that contains (methyl) acrylate.(methyl) vinylformic acid (being total to) polymkeric substance is difficult to dissolving, even and when molecular weight is high, also have low viscosity, thereby do not need violent stirring with this polymer dispersed and be mixed in the paper making raw material.
At this moment, add the amount of cationic polymers preferably at 0.1～2wt%/paper making raw material sosoloid (SS).When using cationic starch, its cationization ratio is preferably 1～7mol%.
The pH of the pulp slurry that the present invention is used is 6.5～10, thereby this is used for making neutralized paper.In this pH value scope, the disassociation of (methyl) vinylformic acid (being total to) polymkeric substance and (methyl) acrylate (be total to) polymkeric substance, by with the synergy of the cationic polymers that adds at back, along with the viscosity increase, poly-in having produced, can improve retention and freeness (freeness).
The amount of (methyl) vinylformic acid (being total to) polymkeric substance that can effectively improve retention and freeness that is added is 0.002～0.05wt%/paper making raw material SS, more preferably 0.005～0.02wt%.If add-on very little, to improving retention and freeness does not have effect; If add-on is too much, paper is scared, and the paper quality of being produced degenerates.
When polymeric dispersions of the present invention is used as the soil improvement agent of aqueous soil, use with undiluted state as raw-material polymeric dispersions usually; That is to say, toward the 1m that contains 20～400% water 3Soil in sneak into the polymeric dispersions that contains 0.1～5kg polymkeric substance, fill possible soil thereby can prepare to have.In the time of necessary, can add and mix an amount of cement and/or lime.With regard to lime, can use white lime or unslaked lime.Wish that the weight ratio of polymer content and cement and/or lime is 1: 1～1: 500 in the polymeric dispersions this moment.Compare with traditional powdery polymer, the polymeric dispersions that will add is easier to add and mix in the present invention, and, as advantages more of the present invention, can or not supervene the smell that resembles latex by oil pollution.
In anti-splitting method according to the present invention, the polymeric dispersions of dilute with water of the present invention sticks to the base-material surface as anti-splitting agent by spraying; With with the mutual stacked mode in described surface, scribble the base-material of anti-splitting agent on the compacting multiple-level surface, dry then.At this moment, should be higher than 4.0, preferably not be higher than 3.5 by the pH of water-reducible polymeric dispersions, thus the not disassociation of most (methyl) acrylic acid groups.The concentration of polymkeric substance is preferably 0.1～1.5wt% in the solution of dilute with water, and its viscosity is preferably 1～50cp.The amount of institute's adhered polymer is preferably 0.1～1.5wt%/paper pulp solid content.Equally in the method for the invention, can use traditional anti-splitting agent simultaneously, as starch, treated starch, casein, polygalactomannan etc.
In the method for the invention, do not have as traditional possibility of preventing the corruption change of splitting agent such as starch, do not have the worry that is difficult to spray because of the viscosity that increases yet.
In flucculation process of the present invention, polymeric dispersions of the present invention adds and mixes as polymeric flocculant to solidify suspended substance at undiluted state or dilute with water state, at this moment, the pH value of the solution of polymeric dispersions or its dilute with water preferably is not more than 4.0, more preferably no more than 3.5.In the method for the invention, only the method adding flocculation agent by direct or simple dilution may be an advantage, thereby the dissolving of having saved trouble is operated.
Embodiment
(preparation embodiment-1)
Be equipped with agitator, in the reactor of nitrogen ventpipe and temperature regulator, the sodium chloride aqueous solution that adds 79 parts of 20wt%, with 20 parts have the monomer that consists of 35mol% vinylformic acid and 65mol% acrylamide, (CPS Co. makes, trade(brand)name: Age Flock WT40HV) be dissolved in wherein with 1 part of poly dimethyl allyl ammonium muriate as dispersed retention agent.Then, add the hydrochlorinate 2 of amount of monomer 500ppm, 1% aqueous solution of 2 '-azo two (2-amidine propane) is as polymerization starter.Under agitation in 53 ℃ of polymerizations of carrying out 10 hours, thereby obtain being dispersed with in the aqueous solution of salt the polymeric dispersions (pH3) of 10～20 μ m fine particles.With this dispersion called after " sample-1 ".The viscosity of described polymeric dispersions is not higher than 500cp, with 20 times of deionized water dilutions, can identify fine particle at microscopically, and polymkeric substance is water-fast in itself.In described dispersion, sneak into aqueous sodium carbonate with pH regulator to 7 with dispersion, polymer dissolution then, its molecular weight is according to the characteristic viscosity measuring based on the described aqueous solution.
(preparation embodiment-2)
Carry out and preparation embodiment-1 identical operations, only be to use the monomer of the acrylamide of the vinylformic acid that contains 55mol% and 45mol%, thereby obtain the water-insoluble polymer dispersion.With this dispersion called after " sample-2 ".
(preparation embodiment-3)
Carry out and preparation embodiment-1 identical operations, only be to use the monomer of the acrylamide of the vinylformic acid that contains 90mol% and 10mol%, thereby obtain the water-insoluble polymer dispersion.With this dispersion called after " sample-3 ".
(preparation embodiment-4)
Carry out identical operations, only be to use acrylamide-2-methyl propane sulfonic acid sodium homopolymer (limiting viscosity is 1dl/g) as dispersed retention agent, thereby obtain the water-insoluble polymer dispersion with preparation embodiment-1.With this dispersion called after " sample-4 ".
(comparative preparation embodiment-1)
Carry out identical operations, just do not use any dispersed retention agent, thereby obtain the water-insoluble polymer dispersion with preparation embodiment-1.With this dispersion called after " comparative sample-1 ".Comparative sample-1 begins to lose its flowability after remaining static 1 hour, and after coagulation became bean curd shape in 5 hours, thus the state that causes condensing and can't use.Therefore, comparative sample-1 can not be known as dispersion.
(comparative preparation embodiment-2)
Carry out identical operations, just do not use any dispersed retention agent, thereby obtain the water-insoluble polymer dispersion with preparation embodiment-2.With this dispersion called after " comparative sample-2 ".Comparative sample-2 begins to lose its flowability after remaining static 1 hour, and after coagulation became bean curd shape in 5 hours, thus the state that causes condensing and can't use.Therefore, comparative sample-2 can not be known as dispersion.
(comparative preparation embodiment-3)
Carry out identical operations, just do not use any dispersed retention agent, thereby obtain the water-insoluble polymer dispersion with preparation embodiment-3.With this dispersion called after " comparative sample-3 ".Comparative sample-3 begins to lose its flowability after remaining static 1 hour, 5 hours after coagulations become bean curd shape, thus the state that causes condensing and can't use.Therefore, comparative sample-3 can not be known as dispersion.
(comparative preparation embodiment-4)
80 parts of deionized waters and 20 parts are had the monomer that consists of 35mol% sodium acrylate and 65mol% acrylamide packs into and scribbles in the reactor of Teflon.After feeding nitrogen, add the hydrochlorinate 2 of amount of monomer 100ppm, 1% aqueous solution of 2 '-azo two (2-amidine propane) is as polymerization starter.Under static state carry out polymerization in 10 hours in 48 ℃, thereby obtain a kind of polymkeric substance of gel state.With the resulting gel of forcing machine roughening (roughen), be pressed into fine powder with the throughcirculation dryer drying and with grinding mill.These fine particle called afters " comparative sample-4 " with water-soluble polymers.
The feature of the polymkeric substance of sample-1～comparative sample-4 is shown in table 1
(table 1)
Sequence number The sample name The ratio of monomer component (mol%) The type of dispersed retention agent Molecular weight (1,000,000) Performance after 1 day
NaAAc HAAc AAm
1 Sample-1 0 35 65 PDDAC 4.5 ○
2 Sample-2 0 55 45 PDDAC 4.5 ○
3 Sample-3 0 90 10 PDDAC 4.5 ○
4 Sample-4 0 35 65 PAMPS 4.5 ○
5 Comparative sample-1 0 35 65 - 4.5 ×
6 Comparative sample-2 0 55 45 - 4.5 ×
7 Comparative sample-3 0 90 10 - 4.5 ×
8 Comparative sample-4 35 0 65 - 4.5 □
NaAAc: sodium acrylate
HAAc: vinylformic acid
Aam: acrylamide
PDDAC: chlorination poly dimethyl allyl ammonium
PAMPS: polyacrylamide-2-methyl propane sulfonic acid sodium
Zero: good flowability
*: cohesion
: fine powder
(synthesizing of cationic starch)
(Mollin ChemicalCo. makes as the starch cationic agent with chlorination 3-chloro-2-Hydroxyproyl Trimethyl ammonium, trade(brand)name: COPA-60S) under alkaline condition, (use sodium hydroxide) and prepare the described raw starch of table 2, promptly obtain and to be used for the cationic starch of embodiment.The composition of every kind of cationic starch is shown in Table 2.
(table 2)
Sequence number The sample name Cationization percentage ratio Starting material
1 CS-1 5mol％ Tapioca (flour)
2 CS-2 2mol％ Tapioca (flour)
3 CS-3 5mol％ W-Gum
4 CS-4 2mol％ W-Gum
(system paper test-1)
With britt type dynamic shock tester (dynamic jar tester) test filler retention and total retention, the results are shown in the table 3.The paper material that is used to test is a 900ppm lime carbonate, on the high mountain range of 300ppm, and 4000ppm paper pulp, the fair average quality paper of pH8.1 and 300ml CSF.In the test process, in britt type dynamic shock tester, add the 500ml paper material, begin to stir, add the 0.1wt% aqueous solution of the described cationic starch of table 2 with 1500rpm.After 30 minutes, add the 0.1wt% aqueous solution of the dilute with water of the described polymeric dispersions of table 1.In addition, after 30 minutes, open the cock of extracting the plain boiled water sample, flow out the plain boiled water that passes through 150 order silk screens.Discard the plain boiled water in preceding 10 seconds, 30 minutes plain boiled water is measured as sample thereafter.By total retention and filler retention 600 ℃ of ashing measure sample.The amount of the chemical substance that is added is every part of added amount of paper material sosoloid.
(table 3)
Cationic starch Vinylformic acid (being total to) polymkeric substance Filler retention (%) Total retention (%)
The sample name Add-on (ppm) The sample name Add-on (ppm)
Embodiment 1 CS-1 10000 Sample-1 250 64.0 85.0
Embodiment 2 CS-2 10000 Sample-2 250 64.0 85.0
Embodiment 3 CS-3 10000 Sample-3 250 64.0 85.0
Embodiment 4 CS-4 10000 Sample-4 250 63.5 83.0
Embodiment 5 CS-1 3000 Sample-1 250 59.5 76.0
The comparative example 1 CS-1 10000 Do not add 0 45.5 67.5
The comparative example 2 CS-2 10000 Do not add 0 42.5 67.2
The comparative example 3 CS-3 10000 Do not add 0 43.5 67.0
(system paper test-2)
With britt type dynamic shock tester test filler retention and total retention, the results are shown in the table 4.The paper material that is used to test is a 900ppm lime carbonate, 300ppm kaolin, 4000ppm paper pulp, the fair average quality paper of pH8.1 and 300ml CSF.In the test process, in britt type dynamic shock tester, add the 500ml paper material, begin to stir with 1500rpm, (HYMO CO. makes the road, trade(brand)name: 0.1wt% aqueous solution HYMOLOCNR12ML) to add nitrile-acrylamide-acrylic acid acyl-oxygen ethyl trimethyl ammonium muriate multipolymer.After 30 minutes, open the cock of extracting the plain boiled water sample, flow out the plain boiled water that passes through 150 order silk screens.Discard the plain boiled water in preceding 10 seconds, 30 minutes plain boiled water is measured as sample thereafter.By total retention and filler retention 600 ℃ of ashing measure sample.Add chemical substance amount be every part of added amount of paper material SS part, HYMOLOCNR12ML b referred to as preceding rank polymkeric substance (prestage polymer), the polymkeric substance shown in the table 1 b referred to as back rank polymkeric substance (poststage polymer).
(table 4)
Preceding rank polymkeric substance Back rank polymkeric substance Filler retention (%) Total retention (%)
Add-on (ppm) The sample name Add-on (ppm)
Embodiment 6 250 Sample-1 150 64.5 85.0
Embodiment 7 250 Sample-2 150 64.6 85.0
Embodiment 8 250 Sample-3 150 64.5 85.0
Embodiment 9 250 Sample-4 150 64.0 84.5
The comparative example 4 250 Do not add 0 43.5 67.0
The comparative example 5 300 Do not add 0 44.5 67.7
The comparative example 6 350 Do not add 0 45.5 68.2
(evaluation)
By papermaking process of the present invention, can improve the retention of the cellulose fiber peacekeeping filler in the paper-making process.Low viscous high-molecular-weight propylene acid (being total to) polymkeric substance that can flocculate effectively can reach described purpose under the works fine condition by using, thereby produces high economic benefit.
(test of aqueous soil)
Cohesive soil with moisture 156% is packed into from an end of mixing roll that twin shaft packer (puddle) is housed, and every kind of sample and unslaked lime add and mix and discharge to improve the soil from the other end with pump or feeder successively.The amount of the chemical substance that is added is with the every 1m of kilogram number 3Aqueous soil is shown in table 5.As specimen, the soil of getting part improvement is as sample, determines the shape of improving the soil and the soil strict seal is distributed to prevent water part that by estimating slaking is 6 days then.According to JIS A 1210 (tamping the method for measurement by tamping), be placed in the mould that internal diameter is 15cm by three layers improving the soil, every layer of hammer ram with 4.5kg distinguished tamping 92 times, described improving the soil tamped measurement.Then, prepare water logging and the test of expanding according to JIS A 1211 (CBR measuring method), soil immersed in the tank 4 days and measured swell increment.The immersion amount and the swell increment of the sample of the preferred embodiments of the invention all are not higher than 1%.
And, remove the water that from tank, takes out, the measurement of being scheduled to after 15 minutes, load-injection (load-penetration) curve is determined in test according to CBR, the load when measuring injection 2.5mm, injection intensity just.Test result is shown in Table 5.
(table 5)
Polymkeric substance Add-on (the kg/m of unslaked lime 3) Injection intensity (kg) The state of improving the soil
The sample name Add-on (kg/m 3)
Embodiment 10 Sample-1 1.4 0 27.3 ○
Embodiment 11 Sample-2 0.7 50 57.2 ○
Embodiment 12 Sample-3 0.7 50 55.4 ○
Embodiment 13 Sample-4 0.7 50 56.7 ○
The comparative example 7 Comparative sample-4 0.7 50 - ×
The comparative example 8 Comparative sample-4 1.4 50 - ×
Zero: have the granular of rustle
*: soft and can't mix
(evaluation)
Contain the method for the soil of big water gaging by improvement of the present invention, the soil after the improvement has low viscosity and excellent kneading performance, is easy to mix with machine, soil is granular and rustle is arranged, can be reused for filling, prevent environmental damage, thereby go a long way community greatly.
(anti-splitting test)
Old corrugated cardboard is adjusted to Canadian standard 400ml with the making beating of Niagara type hollander and with its freeness, preparation paper pulp.The liquid adhesive of adding 2% in described paper pulp adds 0.9% commercially available negatively charged ion paper toughener in paper pulp, stir and mix.Resulting pulp slurry is diluted to 0.5%; To prepare every dry weight be 100g/m to the paper trier by hand 2Moisture content be that 86% l Water Paper A and moisture content are 96% l Water Paper B.With polymer concentration is 0.5%, and the diluent that amount of polymers is shown in the anti-splitting agent of table 6 (amount of polymers/paper pulp solid content) is being sprayed to by nozzle on the one side of l Water Paper A under 2 normal atmosphere from nozzle.Then, l Water Paper B on stacked on the coatingsurface of l Water Paper A; Place it between two shields and pressurize and drying, promptly obtain dry combination board with the test rolling press.Regulate the moisture of this combination board, and measure its T-stripping strength (gram/inch) according to J-TAPPI paper pulp method of testing No.19-77.The results are shown in table 6.
(anti-splitting test Comparative Examples)
The polymer concentration that will be used for application examples is that the solution of the dilute with water of 0.5% anti-splitting agent is adjusted to pH7.0 with sodium hydroxide, and as aqueous polymers solution, other operations are with above-mentioned identical.The results are shown in table 6.
(table 6)
Polymkeric substance The pH of the solution of dilute with water T-stripping strength (gram/inch) The spraying shape
The sample name Add-on (%)
Embodiment 14 Sample-1 0.3 2.7 402 Vaporific
Embodiment 15 Sample-2 0.3 2.7 400 Vaporific
Embodiment 16 Sample-3 0.3 2.7 398 Vaporific
Embodiment 17 Sample-4 0.3 2.7 400 Vaporific
The comparative example 9 Sample-1 0.3 7.0 125 Big drop
The comparative example 10 Sample-2 0.3 7.0 136 Big drop
The comparative example 11 Sample-3 0.3 7.0 126 Big drop
The comparative example 12 Sample-4 0.3 7.0 134 Big drop
(evaluation)
According to anti-splitting method of the present invention, described solution with dilute with water of low viscosity and good workability can easily spray and can plug nozzle or because spraying difficulty and inhomogeneous adhesion, thereby the combination board with high anti-splitting effect is provided
(flocculation test 1)
In the flocculation steel basin, under to the situation of precise volumes pump exit side pressurization toward water as 10 times of volumes of adding dispersion original solution in the muddy water of the waste water of washing aggregate, at the same time with precise volumes pump supply sample-1 original solution, in 1 second the residence time, in pipeline, to carry out dilute with water.Under mixing and condition of stirring, finish flocculation treatment.Deposit and separate with thickening material, obtain good deposition.
Adopt and use the same method, finish flocculation treatment with the solution of 10 times of sample-4 starting material dilutions, deposition is good.In contrast to this, comparative sample-1 does not have flowability, is impossible with precise volumes pump supply original solution therefore.
(flocculation test 2)
In a flocculation treatment, alumina is handled with caustic soda, and the impurity (being commonly referred to red mud) in the solution (sodium aluminate is dissolved) is flocculated and deposits, and adds as raw-material sample-3 and with the precise volumes pump delivery to handle in the flocculation steel basin.Then, in settler, carry out solid-liquid separation, observe good separation performance.In contrast to this, comparative sample-3 does not have flowability, is impossible with precise volumes pump supply original solution therefore.
(evaluation)
In solid flucculation process of the present invention, do not need the needed large-scale dissolution equipment of conventional powdery polymeric flocculant.When using the water-in-oil-type polymeric flocculant, also can not bring oil to system--the water pollutant.According to the present invention, the polymer flocculant dispersion by the dispersed retention agent manufacturing of common use all is stable in a very long time, thereby for example, starting material can directly be supplied with the precise volumes pump.Thereby slave unit aspect and processibility aspect, the economic worth of the product that the present invention obtains is high.
Though the present embodiment preferred of the present invention has been described above, it should be understood that the present invention is not limited to this, those skilled in the art can carry out variations and modifications and not break away from the scope of the present invention that proposes in the following claim.

Claims (11)

  1. One kind in the aqueous solution of salt, in the presence of the dispersed retention agent of the polymer dielectric that comprises the aqueous solution that is dissolved in described salt, comprise the method for the polymeric dispersions of (methyl) acrylic acid water-soluble monomer manufacturing (methyl) vinylformic acid (being total to) polymkeric substance by polymerization, wherein
    (1) concentration of (methyl) vinylformic acid (being total to) polymkeric substance is 5wt.% at least in the described polymeric dispersions,
    (2) median size of (methyl) vinylformic acid (being total to) polymer particle is 1～100 μ m in the described polymeric dispersions,
    (3) viscosity with the described polymeric dispersions of production after one month of harsh output is 10～3000cp,
    Can identify polymer particle when (4) amplifying 400 times of observations with microscope when 10 times of described polymer dispersed body and function distilled water dilutings and with diluent, and
    (5) when by add alkali with the pH regulator of described diluent to 7.0 the time, described polymer particle dissolving forms the aqueous solution.
  2. 2. the method for production polymeric dispersions as claimed in claim 1 wherein, comprises (methyl) acrylic acid acrylamide that consists of 15～100mol% vinylformic acid and 0～85mol% that will the polymeric water-soluble monomer.
  3. 3. the method for production polymeric dispersions as claimed in claim 1 or 2, wherein, dispersed retention agent is selected from by chlorination dimethyldiallylammonium (being total to) polymkeric substance, acrylamide-2-methyl propane sulfonic acid (being total to) polymkeric substance, and composition thereof the group formed.
  4. 4. the method for production polymeric dispersions as claimed in claim 1 or 2 wherein, will comprise that the weight ratio of (methyl) acrylic acid water-soluble monomer and dispersed retention agent is 100: 1～10: 1 by polymeric.
  5. 5. the method for production polymeric dispersions as claimed in claim 3 wherein will comprise that the weight ratio of (methyl) acrylic acid water-soluble monomer and dispersed retention agent is 100: 1～10: 1 by polymeric.
  6. 6. the dispersion of (methyl) vinylformic acid (being total to) polymkeric substance in the aqueous solution of salt, wherein
    1) concentration of (methyl) vinylformic acid (being total to) polymkeric substance is 5wt.% at least in the described polymeric dispersions,
    (2) median size of (methyl) vinylformic acid (being total to) polymer particle is 1～100 μ m in the described polymeric dispersions,
    (3) viscosity with the described polymeric dispersions of production after one month of harsh output is 10～3000cp,
    Can identify polymer particle when (4) amplifying 400 times of observations with microscope when 10 times of described polymer dispersed body and function distilled water dilutings and with diluent, and
    (5) when by add alkali with the pH regulator of described diluent to 7.0 the time, described polymer particle dissolving forms the aqueous solution.
  7. 7. papermaking process, comprise with cellulose pulp and fillers dispersed in water with the preparation pulp slurry, the pH that keeps slurries simultaneously is in 6.5～10 scopes, form the scraps of paper by pulp slurry, dry to make paper, described method also comprises in described pulp slurry and adds cationic polymers, shears described pulp slurry, adds the polymeric dispersions according to the dilute with water of claim 6 then before forming the scraps of paper.
  8. 8. papermaking process as claimed in claim 7, wherein cationic polymers is selected from by cationic starch, the group that cationic polyacrylamide and composition thereof is formed.
  9. 9. an improvement contains the method for the soil of steam, comprises toward 1m 3Contain in the described soil of 20～400% water and mix the polymeric dispersions that contains 0.1～5kg polymkeric substance, have with preparation and fill possible soil according to claim 6.
  10. 10. method that prevents splitting, comprise that the polymeric dispersions according to claim 6 with dilute with water is sprayed on the surface of base-material as the anti-stripper of interlayer, the surface that is stained with the multilayer base-material of the anti-stripper of interlayer on the surface is piled up, then compacting and dry these layers.
  11. 11. the method for the solid suspension that flocculates comprises adding and mix the polymeric dispersions according to claim 6 that is in undiluted state or dilute with water state in solid suspension.
CN97120209A 1996-11-05 1997-11-05 Polymer dispersion, method of manufacturing same, and use of same Expired - Fee Related CN1112377C (en)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
JP30749696A JP3260288B2 (en) 1996-11-05 1996-11-05 Papermaking method
JP307496/1996 1996-11-05
JP307496/96 1996-11-05
JP028298/97 1997-01-29
JP028298/1997 1997-01-29
JP2829897A JPH10212320A (en) 1997-01-29 1997-01-29 Production of anionic water-soluble polymer dispersion, anionic water-soluble polymer dispersion, and its use
JP146038/97 1997-05-21
JP14603897A JP4030075B2 (en) 1997-05-21 1997-05-21 Hydrous soil improving agent and hydrous soil improving method
JP146038/1997 1997-05-21
JP15312497A JP3260297B2 (en) 1997-05-28 1997-05-28 Delamination inhibitor and delamination prevention method
JP153124/1997 1997-05-28
JP153124/97 1997-05-28
JP183188/1997 1997-06-25
JP18318897 1997-06-25
JP183188/97 1997-06-25

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ATE520723T1 (en) * 2006-12-11 2011-09-15 Basf Se METHOD FOR LOWERING THE VISCOSITY OF AQUEOUS POLYMER DISPERSIONS OF WATER-SOLUBLE POLYMERS
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Citations (2)

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DE3939034A1 (en) * 1989-11-25 1991-05-29 Henkel Kgaa PRODUCTION OF STABLE POLYMER DISPERSIONS BY MEANS OF AMPHOTER POLYMERS AS STABILIZERS
DE4200715A1 (en) * 1992-01-14 1993-07-15 Bayer Ag Vinyl polymer DISPERSIONS

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CA1267483A (en) * 1984-11-19 1990-04-03 Hisao Takeda Process for the production of a water-soluble polymer dispersion
US5084506A (en) * 1987-12-03 1992-01-28 Ppg Industries, Inc. Stable nonaqueous microparticle dispersions prepared from aminoplast resins
US4783502A (en) * 1987-12-03 1988-11-08 Ppg Industries, Inc. Stable nonaqueous polyurethane microparticle dispersion
US5708071A (en) * 1994-12-15 1998-01-13 Hymo Corporation Aqueous dispersion of an amphoteric water-soluble polymer, a method of manufacturing the same, and a treating agent comprising the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3939034A1 (en) * 1989-11-25 1991-05-29 Henkel Kgaa PRODUCTION OF STABLE POLYMER DISPERSIONS BY MEANS OF AMPHOTER POLYMERS AS STABILIZERS
DE4200715A1 (en) * 1992-01-14 1993-07-15 Bayer Ag Vinyl polymer DISPERSIONS

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