CN104203842A - Method for treating cooling water system - Google Patents

Method for treating cooling water system Download PDF

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Publication number
CN104203842A
CN104203842A CN201380017931.6A CN201380017931A CN104203842A CN 104203842 A CN104203842 A CN 104203842A CN 201380017931 A CN201380017931 A CN 201380017931A CN 104203842 A CN104203842 A CN 104203842A
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CN
China
Prior art keywords
methyl
acid
salt
monomer
polymerization
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CN201380017931.6A
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Chinese (zh)
Inventor
西田育子
藤田和久
村野靖
中野真人
佐野友纪
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Kurita Water Industries Ltd
Nippon Shokubai Co Ltd
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Kurita Water Industries Ltd
Nippon Shokubai Co Ltd
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Publication of CN104203842A publication Critical patent/CN104203842A/en
Pending legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F25/00—Component parts of trickle coolers
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F25/00—Component parts of trickle coolers
    • F28F2025/005—Liquid collection; Liquid treatment; Liquid recirculation; Addition of make-up liquid

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A method for treating a cooling water system which has a calcium hardness of 300 mg/L or higher in terms of CaCO3 amount and a concentration of chloride ions and/or sulfate ions of 1,000 mg/L or higher, the method comprising adding a treating agent containing a (meth)acrylic acid-based copolymer to the cooling water system, wherein the (meth)acrylic acid-based copolymer comprises structural units (a) derived from a (meth)acrylic acid monomer (A) and structural units (b) derived from a specific (meth)allyl ether monomer (B), the contents of the structural units (a) and the structural units (b) being 80-90 mol% and 10-20 mol%, respectively, per 100 mol% all the monomer-derived structural units, and the (meth)acrylic acid-based copolymer has a sulfonic acid group or a salt thereof as at least one of the terminals of the backbone thereof.

Description

The treatment process of cooling water system
Technical field
The present invention relates to a kind for the treatment of process of cooling water system, be specifically related to adhere on a kind of heat-transfer surface that prevents pipe arrangement or heat exchanger in the high cooling water system of calcium hardness or deposit calcium and be dirt and the heat transfer obstruction, the flow that produce decline, the treatment process of the cooling water system of metallic corrosion.
Background technology
In open cycle cooling water system, in the heat-transfer surface that contacts with water, pipe arrangement, can there is dirt and hinder.In addition, consider and while implementing highly enriched running, the salt of dissolving is concentrated, the salt of formation insoluble, and dirt from saving resource, the viewpoint of saving energy.The dirt generating in heat exchange department can cause the obstruction of conducting heat, and the dirt that is attached to pipe arrangement can cause that flow declines.In addition, know at present, the dirt of generation comes off and in the time of system internal recycle, can block pumps, pipe arrangement, heat exchange department, and follow obstruction, and the dirt meeting in pipe arrangement, heat exchange department is promoted etc.
As generated dirt kind, can exemplify: charcoal acid calcium, calcium sulfate, calcium sulfite, calcium phosphate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium hydroxide, zinc phosphate, zinc hydroxide, zinc subcarbonate etc.
In order to prevent the generation of such dirt, can use dirt preventing agent.As this dirt preventing agent, conventionally can use: the inorganic polyphosphoric acid types such as Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP; The phosphonic acid based of hydroxy ethylene diphosphonic acid or phosphinylidyne butane tricarboxylic acid etc.; Toxilic acid, vinylformic acid, methylene-succinic acid etc. are containing carboxyl material; And as required, by the sulfonic vinyl monomer that has of itself and vinyl sulfonic acid, allyl sulphonic acid, 2-methacryloyl amido-2-methyl propane sulfonic acid etc., or, the multipolymer that the nonionic vinyl monomer of acrylamide etc. combines.
In addition, be arranged at the metal parts of open cycle cooling water system, for example, the heat exchanger of carbon steel, copper or copper alloy system, reactor, pipe arrangement, by being corroded with contacting of water coolant, therefore, conventionally implementing by medicament and add the anti-corrosive treatment of carrying out.
As this medicament, normally the phosphorus compound of orthophosphoric acid salt, hexametaphosphate, hydroxy ethylene phosphonate, phosphoryl butane tricarboxylic acid's salt etc. is added in water coolant.Also there is independent interpolation or merge and add as the heavy metallic salt of zinc salt or dichromate etc.
In recent years, be subject to the trend of global reduction carrying capacity of environment and efficent use of resources, recycle-water (processing again water) has been increased for the water coolant of supplementary feed.Recycle-water, has calcium hardness, phosphorus concentration, chloride ion, feature that sulfate ion concentration is high.This recycle-water calcium hardness is high, therefore, as the problem when the supplementary feed by this recycle-water, can exemplify, even add above-mentioned dirt preventing agent and can not prevent the generation of dirt.Therefore, for the salt that reduces water coolant concentrates, need to increase the amount of discharge water (blow water), but be difficult to water saving.
Another problem is, the acceleration of the metallic corrosion of the high and cooling water system that causes of chloride ion, sulfate ion concentration.Therefore, problem when supplementary feed using recycle-water as water coolant is, in dirt composition concentration and the high water quality of corrosive ion concentration, prevents dirt and protection against corrosion simultaneously.
From prevent dirt viewpoint consider time, have the acid of injecting sulfuric acid etc. and the method that reduces the pH of water coolant, still, the method is added acid, make therefrom further to increase as the chloride ion of corrosive ion or the concentration of sulfate ion, therefore actual being suitable in aspect has difficulties.
Disclose and a kind ofly removed the calcium hardness in supplementary feed by water softener, and adjusted the method (patent documentation 1) of total alkalinity and pH, still, because need to regenerate continually water softener, therefore actual being suitable in aspect has difficulties.
In addition, as the reason that cannot bring into play the effect of dirt preventing agent in the high water system of calcium hardness, in patent documentation 2, exemplify the gelation reaction of polymkeric substance and calcium, and illustrated because polymkeric substance loses molten sustainability and precipitate, therefore become and cannot prevent dirt.As its countermeasure, propose one and on main chain end, there is sulfonic (methyl) acrylic acid polymer, thus, can improve resistance to gellifying property, and also can bring into play excellent dirt preventing effectiveness in the water system of high calcium concn.
By this technology, in the high water quality of calcium hardness, also can prevent dirt, still, even and used normally used anti-corrosive treatment, in the cooling water system using the recycle-water high concentration of corrosive ion as supplementary feed, may not obtain sufficient anticorrosion ability.And even improve the concentration of anticorrosive agent in order to improve Corrosion Protection, because anticorrosive agent self becomes phosphoric acid salt or zinc hydroxide etc., therefore dirt, in fact cannot obtain effect.
Prior art document
Patent documentation
Patent documentation 1: No. 3928182 communique of Japanese Patent
Patent documentation 2: No. 3650724 communique of Japanese Patent
Summary of the invention
The problem that invention will solve
The present invention In view of the foregoing completes, its object is to provide a kind for the treatment of process of cooling water system, the treatment process of this cooling water system is in dirt composition and the high water quality of corrosive ion concentration for supplementary feed by recycle-water (processing again water), prevent calcium in pipe arrangement or heat exchanger be adhering to of dirt and prevent from conducting heat hinder, the obstruction of degradation under flow, and prevent the corrosion of metal of pipe arrangement or heat exchanger etc.
Solve the method for problem
The inventor etc. concentrate one's attention on research result in order to reach aforementioned object, find, by the treatment agent forming as follows being made an addition to the high cooling water system of concentration of calcium hardness and chloride ion or sulfate ion, can reach aforementioned object, thereby complete the present invention.This treatment agent is to contain (methyl) acrylic copolymer to form, this (methyl) acrylic copolymer contains from the structural unit (a) of specific (methyl) acrylic monomer with specific ratio and is the structural unit (b) of monomer from specific (methyl) allyl ethers, and at least one of main chain end is sulfonic group or sulfonic group salt.
That is, the invention provides a kind for the treatment of process of cooling water system, its in calcium hardness with CaCO 3count that 300mg/L is above, chloride ion and/or sulfate ion concentration is in cooling water system more than 1000mg/L, add and contain the treatment agent that (methyl) acrylic copolymer forms, wherein,
Aforementioned (methyl) acrylic copolymer, (methyl) allyl ethers that has the structural unit (a) of (methyl) acrylic monomer (A) representing from following general formula (1), represent from following general formula (2) is the structural unit (b) of monomer (B)
And in all from 100 % by mole of the structural units of monomer, the content of structural unit (a) is that 80～90 % by mole, the content of structural unit (b) are 10～20 % by mole,
And aforementioned (methyl) acrylic copolymer, is sulfonic group or sulfonic group salt at least one of main chain end.
In general formula (1), R 1represent hydrogen atom or methyl, X represents hydrogen atom, atoms metal, ammonium or organic amino group;
In general formula (2), R 2represent hydrogen atom or methyl, Y and Z represent respectively hydroxyl, sulfonic group or their salt independently, and at least one in Y and Z represents sulfonic group or sulfonic group salt.
The effect of invention
A kind for the treatment of process of cooling water system can be provided according to the present invention, it is in dirt composition and the high water quality of corrosive ion concentration for supplementary feed by recycle-water (processing again water), prevent calcium be dirt be attached to pipe arrangement or heat exchanger and prevent from conducting heat hinder, the obstruction of degradation under flow, and prevent the corrosion of metal of pipe arrangement or heat exchanger etc.
Embodiment
The treatment process of cooling water system of the present invention, is characterized in that, has calcium hardness with CaCO 3count that 300mg/L is above, chloride ion and/or sulfate ion concentration is in the cooling water system of water quality more than 1000mg/L, the treatment agent that contains (methyl) acrylic copolymer with specific structure by interpolation, the dirt that can prevent cooling water system hinders, and can suppress corrosion of metal.
(methyl) acrylic copolymer:
(methyl) acrylic copolymer that the treatment agent using in the treatment process of cooling water system of the present invention contains is, the structural unit (a) that contains (methyl) acrylic monomer (A) representing from following general formula (1) and, be the multipolymer of the structural unit (b) of monomer (B) from (methyl) allyl ethers of following general formula (2) expression.
In general formula (1), R 1represent hydrogen atom or methyl, X represents hydrogen atom, atoms metal, ammonium or organic amino group;
In general formula (2), R 2represent hydrogen atom or methyl, Y and Z represent respectively hydroxyl, sulfonic group or their salt independently, and at least one in Y and Z represents sulfonic group or sulfonic group salt.
Said structure unit (a), structural unit (b), particularly, refer to the structural unit representing with following general formula (3), (4) respectively.
In general formula, R 1and X is identical with aforementioned formula (1).
In general formula, R 2, Y and Z identical with aforementioned formula (2).
((methyl) acrylic monomer (A))
Should (methyl) acrylic monomer (A) represent with aforementioned formula (1), wherein, as the specific examples of the atoms metal of the X in general formula (1), can exemplify: lithium, sodium, potassium etc.; As the specific examples of organic amino group, can exemplify: monoethanolamine, diethanolamine, trolamine etc.
As the specific examples of this (methyl) acrylic monomer (A), can exemplify: vinylformic acid, methacrylic acid and their salt are (for example, sodium salt, sylvite, ammonium salt etc.), wherein, particularly preferably vinylformic acid, sodium acrylate, methacrylic acid.These can use separately one or be used in combination two or more.
In addition, aforementioned " (methyl) acrylic acid series " refers to, acrylic acid series and metha crylic both.Other similar terms are also identical.
((methyl) allyl ethers is monomer (B))
Should (methyl) allyl ethers be that monomer (B) represents with aforementioned formula (2), wherein, in general formula (2), among the sulfonic group of Y and Z or sulfonic group salt, as the specific examples of metal-salt, can exemplify: the salt such as sodium, potassium, lithium, as the specific examples of the salt of organic amino group, can exemplify: monoethanolamine, diethanolamine, trolamine etc.
Be the specific examples of monomer (B) as aforementioned (methyl) allyl ethers, can exemplify: 3-(methyl) allyloxy-2-hydroxyl-1-propanesulfonic acid and salt thereof, 3-(methyl) allyloxy-1-hydroxyl-2-propanesulfonic acid and salt thereof, wherein, 3-(methyl) allyloxy-2-hydroxyl-1-propanesulfonate particularly preferably.These can use separately one or be used in combination two or more.
In addition, aforementioned " (methyl) allyl ethers system " refers to, allyl ethers system and methallyl ethers system (methallyl ether system) etc. both.Other similar terms are also identical.
< mol ratio >
Should (methyl) acrylic copolymer be, contain from the structural unit (a) of (methyl) acrylic monomer (A) and, be the multipolymer of the structural unit (b) of monomer (B) from (methyl) allyl ethers, in all from 100 % by mole of the structural units of monomer, the content of structural unit (a) is that 80～90 % by mole, the content of structural unit (b) are the ratios of 10～20 % by mole.When the content of structural unit (a) exceedes 90 % by mole, become too strong with the affinity of calcium, in the time being applicable to the high water system of calcium hardness, polymkeric substance generation gelation and easy precipitation becomes and cannot bring into play performance; While being less than 80 % by mole, the ratio of giving etch-proof carboxyl is little, and Corrosion Protection reduces.
< molecular weight >
Be somebody's turn to do preferably 1000～40000 left and right of weight-average molecular weight of (methyl) acrylic copolymer.The weight-average molecular weight of being somebody's turn to do (methyl) acrylic copolymer exceedes at 40000 o'clock, and resistance to gellifying property reduces; Be less than at 1000 o'clock, dirt prevents from reducing.In addition weight-average molecular weight that, should (methyl) acrylic copolymer more preferably 5000～38000.
In addition, above-mentioned weight-average molecular weight is the sour value converting of standard polypropylene of measuring by gel permeation chromatography (GPC method).
(other monomers (C))
Be somebody's turn to do (methyl) acrylic copolymer, at least there is aforementioned structure unit (a) and aforementioned structure unit (b) according to aforementioned ratio, but, in addition to these, also can contain from can be the structural unit (c) of other monomers (C) of monomer (B) copolymerization with (methyl) acrylic monomer (A) or (methyl) allyl ethers.Now, the ratio of structural unit (c) is, with respect to all from 100 % by mole of the structural units of monomer, preferably below 10 % by mole, further preferably below 5 % by mole.
As other monomers (C), can exemplify: 2-acrylamide-2-methyl propane sulfonic, (methyl) allyl sulphonic acid, vinyl sulfonic acid, styrene sulfonic acid, methacrylic acid 2-sulfonic acid ethyl ester (2-ス Le ホ エ チ Le メ タ Network リ レ ー ト) etc. containing sulfonic unsaturated monomer and their salt; The N-vinyl monomer of NVP, N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-METHYLFORMAMIDE, N-vinyl-methylacetamide, N-vinyl oxazolidone etc.; The nitrogenous nonionic unsaturated monomer of (methyl) acrylamide, N,N-DMAA, NIPA etc.; 3-(methyl) allyloxy-1, the hydroxyl unsaturated monomer of 2-dihydroxypropane, (methyl) vinyl carbinol, isoprene alcohol (イ ソ プ レ ノ ー Le) etc.; 3-(methyl) allyloxy-1, in 2-dihydroxypropane with the unsaturated monomer containing polyoxyethylene groups with the compound of the degree additional ring oxidative ethane of 1～100 mole of left and right etc. in the compound (3-(methyl) allyloxy-1,2-bis-(gathering) oxygen Vinyl Ether propane) of the degree additional ring oxidative ethane of 1～200 mole of left and right, (methyl) vinyl carbinol; (methyl) acrylate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Hydroxyethyl acrylate etc.; The unsaturated dicarboxylic acid monomer of methylene-succinic acid etc.; The unsaturated aromatic monomer of vinylbenzene etc. etc.
These monomers (C) can use separately one or be used in combination two or more.
(preparation method)
As the preparation method of this (methyl) acrylic copolymer, can exemplify: will contain aforementioned monomer (A), (B) and the monomer mixture of the monomer (C) that uses as required (below, sometimes be only called " monomer mixture "), under the existence of polymerization starter, make the method for its polymerization.
< polymerization starter >
As polymerization starter, can use known initiator.For example, hydrogen peroxide, the persulphate of Sodium Persulfate, Potassium Persulphate, ammonium persulphate etc., dimethyl-2, 2 '-azo two (2 Methylpropionic acid ester), 2, 2 '-azo two (isopropyl cyanide), 2, 2 '-azo two (2-methylbutyronitrile), 2, 2 '-azo two (2, 4-methyl pentane nitrile), 2, two (4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), 2, two (isopropylformic acid) dimethyl esters of 2 '-azo, 4, 4 '-azo two (4-cyanovaleric acid), 2, two (the 2-methyl-prop amidine) dihydrochlorides of 2 '-azo, 2, two [N-(2-propyloic)-2-methyl-prop amidine] the n hydrates of 2 '-azo, 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides of 2 '-azo, 2, two [2-(2-tetrahydroglyoxaline-2-yl) propane] the dithionate dihydrates of 2 '-azo, 1, the azo based compound of 1 '-azo two (hexanaphthene-1-nitrile) etc., the organo-peroxide of benzoyl peroxide, lauroyl peroxide, peroxyacetic acid, ditertiary butyl peroxide, hydrogen phosphide cumene etc. etc. is suitable.In these polymerization starters, when the viewpoint of the resistance to gelation of the polymkeric substance obtaining from raising is considered, preferably use persulphate described later.
The usage quantity of this polymerization starter, as long as the amount of copolymerization that can trigger monomer mixture, is not particularly limited it, but except following special situation about recording, with respect to 1 mole of monomer mixture, and preferably below 15g, further preferred 1～12g.
< chain-transfer agent >
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, as required, not producing for polymerization in the scope of baneful influence, can use chain-transfer agent as the molecular weight regulator of polymkeric substance.
As chain-transfer agent, can exemplify particularly: the sulfydryl tethers transfer agent of mercaptoethanol, thioglycerin, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, dimercaptosuccinic acid, Thiovanic acid monooctyl ester, 3-thiohydracrylic acid monooctyl ester, mistabrom, N-dodecyl mercaptans, spicy thioalcohol, Thiovanic acid butyl ester etc.; The halogenide of tetracol phenixin, methylene dichloride, methenyl bromide, bromo trichloromethane (Bromotrichloromethane) etc.; The secondary alcohol of Virahol, glycerine etc.; Phosphorous acid, Hypophosporous Acid, 50 and their salt (sodium hypophosphite, potassium hypophosphite etc.) or, sulfurous acid, heavy sulfurous acid, SODIUM HYDROSULPHITE, the heavy sulfurous acid of methyl and their salt (is sometimes referred to as " heavy sulfurous acid (salt) class " below.For example, Sodium Metabisulphate 65, potassium acid sulfite, V-Brite B, potassium hyposulfite, methyl Sodium Metabisulphate 65, methyl potassium acid sulfite etc.) etc. lower oxyde and salt etc. thereof.Above-mentioned chain-transfer agent can use separately one or be used in combination two or more.
By using this chain-transfer agent, can suppress prepared multipolymer and reach the phenomenon that required above polymer quantizes, can effectively prepare low-molecular-weight multipolymer.Wherein, in copolymerization of the present invention, preferably use heavy sulfurous acid (salt) class.Thus, can on the main chain end of obtained multipolymer, effectively introduce sulfonic group, and can improve resistance to gelation.In addition, as chain-transfer agent, by using heavy sulfurous acid (salt) class, can improve the tone of multipolymer (composition), therefore preferred.
The addition of chain-transfer agent, as long as making the amount of monomer mixture polymerization preferably, does not limit it, but except following special situation about recording, with respect to 1 mole of monomer mixture, and preferably 1～20g, further preferred 2～15g.
< initiator is >
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, as initiator system (combination of polymerization starter and chain-transfer agent), more than one uses of difference in preferably combination persulphate and heavy sulfurous acid (salt) class.Thus, can on main polymer chain end, effectively introduce sulfonic group, obtain also having the low-molecular-weight water-soluble polymers of excellent resistance to gelation beyond excellent dispersive ability, sequestering power, thereby can effectively embody action effect of the present invention.By in initiator system, beyond persulphate, add heavy sulfurous acid (salt) class, can suppress obtained polymkeric substance becomes the phenomenon that required above polymer quantizes, and can effectively prepare thus low-molecular-weight polymkeric substance.
As above-mentioned persulphate, can exemplify particularly: Sodium Persulfate, Potassium Persulphate and ammonium persulphate etc.
In addition, heavy sulfurous acid of the present invention (salt) class is as mentioned above, wherein, and preferably Sodium Metabisulphate 65, potassium acid sulfite, ammonium bisulfite 56to 70.
Aforementioned persulphate and heavy sulfurous acid (salt) class the interpolation ratio of used time are, with respect to persulphate 1 mass parts, preferably 0.1～5 mass parts of heavy sulfurous acid (salt) class, further preferred 0.2～3 mass parts, is more preferably in the scope of 0.2～2 mass parts.With respect to persulphate 1 mass parts, when heavy sulfurous acid (salt) class is less than 0.1 mass parts, the tendency that the effect that exists heavy sulfurous acid (salt) to play dies down.Therefore the tendency that, exist the sulfonic introduction volume of the end of polymkeric substance to reduce, the resistance to gelation of multipolymer reduces.In addition, the tendency that also exists the weight-average molecular weight of (methyl) acrylic copolymer to uprise.On the other hand, with respect to persulphate 1 mass parts, when heavy sulfurous acid (salt) class exceedes 5 mass parts, cannot more obtain under the state of the effect that heavy sulfurous acid (salt) class produces along with adding ratio, exist heavy sulfurous acid (salt) class in polymerization reaction system to supply with the tendency of (being invalidly consumed) superfluously.Therefore, superfluous heavy sulfurous acid (salt) class is decomposed in polymerization reaction system, and the sulphurous acid gas (SO of volume occurs 2gas).In addition the tendency that, also exists the performance of the impurity generating in (methyl) acrylic copolymer of volume, (methyl) acrylic copolymer obtaining to reduce.In addition, the tendency that the impurity while existing low temperature to keep is easily separated out.
Addition while using aforementioned persulphate and heavy sulfurous acid (salt) class, with respect to 1 mole of monomer mixture, preferably 2～the 20g of total amount of persulphate and heavy sulfurous acid (salt) class, further preferred 2～15g, be more preferably 3～10g, be further more preferably 4～9g.When the addition of aforementioned persulphate and heavy sulfurous acid (salt) class is less than 2g, the tendency that exists the molecular weight of the polymkeric substance obtaining to increase.In addition the tendency that, also exists the sulfonic group of introducing in the end of (methyl) acrylic copolymer obtaining to reduce.On the other hand, when addition is greater than 20g, along with addition cannot more obtain persulphate and weigh the effect of sulfurous acid (salt) class, on the contrary, there is the tendency of the purity drop of (methyl) acrylic copolymer obtaining.
The form that aforementioned persulphate can be being dissolved in solvent described later, be preferably dissolved in the solution (preferred aqueous solutions) of the persulphate of water is added.Concentration while use as this persulfate solution (preferred aqueous solutions) is, preferably 1～35 quality %, and further preferred 5～35 quality %, are more preferably 10～30 quality %.Wherein, when the concentration of persulfate solution is less than 1 quality %, the concentration of goods reduces, and carries and take care of to become loaded down with trivial details.On the one hand, when the concentration of persulfate solution is greater than 35 quality %, processes and become difficulty.
The form that aforementioned heavy sulfurous acid (salt) class can be being dissolved in solvent described later, be preferably dissolved in the solution (preferred aqueous solutions) of heavy sulfurous acid (salt) class of water is added.Concentration while use as this heavy sulfurous acid (salt) class solution (preferred aqueous solutions) is, preferably 10～42 quality %, and further preferred 20～42 quality %, are more preferably 32～42 quality %.Wherein, when the concentration of heavy sulfurous acid (salt) class solution is less than 10 quality %, the concentration of goods reduces, and carries and take care of to become loaded down with trivial details.On the one hand, when the concentration of heavy sulfurous acid (salt) class solution exceedes 42 quality %, process and become difficulty.
Other additive > of <
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, other additives beyond initiator, the chain-transfer agent of the polymerization reaction system when can be used in aqueous solution polymerization aforementioned monomer mixture, can in the scope that does not affect action effect of the present invention, add in right amount suitable additive, for example, can add in right amount heavy metal concentration conditioning agent, pH adjusting agent etc.
For aforementioned heavy metal concentration conditioning agent, be not particularly limited, for example, can utilize polyvalent metal compounds or monomer.Particularly, can exemplify: vanadium oxytrichloride, vanadium trichloride, oxalic acid vanadyl (vanadyl oxalate), vanadylic sulfate, vanadic anhydride, ammonium meta-vanadate, ammonium sulfate six water Vanadosulfuric acids (ammonium hypovanadous sulfate:(NH 4) 2sO 4vSO 46H 2o), ten sulfate dihydrate ammonium vanadium (ammonium vanadous sulfate:(NH 4) V (SO 4) 212H 2o), venus crystals (II), copper (II), cupric bromide (II), etheric acid copper (II) (Copper (II) ア セ チ Le ア セ テ ー ト), the high cuprammonium of chlorination (ammonium cupric chloride), cupric ammonium chloride (ammonium copper chloride), copper carbonate, cupric chloride (II), Cuprocitrol (II), Tubercuprose (II), copper hydroxide (II), cupric nitrate, copper naphthenate, cupric oleate (II), toxilic acid copper, cupric phosphate, copper sulfate (II), cuprous chloride, cupric cyanide (I), cupric iodide, cupric oxide (I), cupric thiocyanide, etheric acid iron (iron acetylacetate), ferric ammonium citrate, ammonium ferric oxalate (ammonium ferric oxalate), ferric ammonium sulfate, ferric ammonium sulfate (ammonium ferric sulfate), ironic citrate, ferrous fumarate, toxilic acid iron, iron lactate, ferric nitrate, pentacarbonyl iron, high ferric phosphate, the water-soluble polyvalent metal salt of tetra-sodium high ferro etc., the polyvalent metal oxides of Vanadium Pentoxide in FLAKES, cupric oxide (II), iron protoxide, oxidation high ferro etc., the polyvalent metal sulfide of iron sulphide (III), iron sulphide (II), cupric sulfide etc., copper powder, iron powder etc.
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, the concentration of heavy metal ion of (methyl) acrylic copolymer preferably obtaining is 0.05～10ppm, therefore, preferably add in right amount as required aforementioned heavy metal concentration conditioning agent.
< polymer solvent >
Be somebody's turn to do in the preparation of (methyl) acrylic copolymer, generally polymerization aforementioned monomer mixture in solvent, still, now for the solvent of polymerization reaction system, the solvent of the water-based of preferably water, ethanol, ethylene glycol, glycerine, polyethylene glycols etc., particularly preferably water.These can use separately one or be used in combination two or more.In addition, in order to improve the solvability of aforementioned monomer mixture in solvent, can suitable interpolation organic solvent in the polymerization for each monomer does not produce the scope of baneful influence.
As aforementioned organic solvent, particularly, from the lower alcohol of methyl alcohol, ethanol etc.; The amides of dimethyl formamide etc.; In the ethers of diethyl ether, dioxan etc. etc., suitablely select one or more uses.
The usage quantity of aforementioned solvents, with respect to monomer mixture total amount, preferably 40～200 quality %, further preferred 45～180 quality %, are more preferably the scope of 50～150 quality %.When the usage quantity of this solvent is less than 40 quality %, molecular weight uprises.On the one hand, when the usage quantity of this solvent exceedes 200 quality %, the concentration step-down of prepared (methyl) acrylic copolymer, according to circumstances needs to remove solvent.In addition, the major part of this solvent or total amount, put in advance reaction vessel at the polymerization initial stage, but, for example, can be in polymerization a part for solvent be suitably added separately to (dripping) in reaction system, also can be dissolved in advance the form of solvent with monomer mixture composition, initiator composition, other additive, coexist in polymerization and suitably add (dripping) in reaction system with these compositions one.
< polymerization temperature >
For the polymerization temperature of aforementioned monomer mixture, be not particularly limited.While consideration from effectively preparing the viewpoint of polymkeric substance, polymerization temperature is preferably more than 50 DEG C, further preferably more than 70 DEG C, or preferably below 99 DEG C, further preferably below 95 DEG C.When polymerization temperature is less than 50 DEG C, beyond the rising of molecular weight, impurity increase, the polymerization time needing is long, and therefore, productivity reduces.Therefore and preferred on the one hand, polymerization temperature is 99 DEG C when following, and the heavy sulfurous acid (salt) can suppress to use heavy sulfurous acid (salt) as initiator system time decomposes and produces the phenomenon of the sulphurous acid gas of volume.Herein, polymerization temperature refers to the reaction soln temperature in reaction system.
Especially, start the method (room temperature starts method) of polymerization from room temperature, for example, each batch to carry out in the situation of polymerization (180 minutes treatment processs) for 180 minutes, 70 minutes with interior, preferably 0～50 minute, further preferably reach design temperature (in the scope of above-mentioned polymerization temperature in 0～30 minute, but preferably 70～90 DEG C, further preferred 80～90 DEG C of degree).Then, preferred polymeric maintains this design temperature till stopping.While exceeding above-mentioned scope, (methyl) acrylic copolymer obtaining may become polymer and quantize heating-up time.In addition, be the example of 180 minutes although exemplified polymerization time, when the treatment process of polymerization time is different, preferably with reference to this example, being same as the ratio of heating-up time with respect to polymerization time, set the heating-up time.
(pressure of reaction system, reaction environment)
When aforementioned monomer polymerization of mixtures, for the pressure in reaction system, be not particularly limited, under normal pressure (normal atmosphere), decompression under, under the inferior any pressure that pressurizes, all can implement reaction.Preferably, while using heavy sulfurous acid (salt) as initiator system, the sulphurous acid gas when preventing that polymerization from carrying out emit and realize lower molecular weight, can under condition of normal pressure, implement to react, or, in capping system and under the condition of pressurization, implement reaction.In addition, when the lower enforcement of normal pressure (normal atmosphere) polymerization, there is no need to arrange pressurizing device or reliever, and there is no need to use reaction vessel or the pipe arrangement of withstand voltage system.Therefore, while consideration from the viewpoint of preparation cost, preferably normal pressure (normal atmosphere).,, according to the application target of obtained (methyl) acrylic copolymer, set best pressure condition.
Environment in reaction system can be the state of air ambient, can be also inert environment.For example, preferably before starting, polymerization will in system, replace to the non-active gas of nitrogen etc.Thus, can prevent that environmental gas in reaction system (for example, oxygen etc.) is dissolved in liquid phase plays a role as stopper.Its result, can prevent initiator (persulphate etc.) inactivation and reduce, and can further become lower molecular weight.
(degree of neutralization in polymerization)
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, the polyreaction of aforementioned monomer mixture is preferably carried out under acidic conditions.By reacting under acidic conditions, can suppress the viscosity rise of the aqueous solution of polymerization reaction system, and can prepare preferably low-molecular-weight (methyl) acrylic copolymer.And, compare in the past, can under the condition of high density, carry out polyreaction, therefore can significantly improve preparation efficiency.Particularly, when the degree of neutralization in polymerization is set to low 0～25 % by mole, can improves synergistically aforementioned amount of initiator and reduce the effect producing, can improve especially the reduction effect of impurity.In addition, the pH of the reaction soln in preferred polymeric at 25 DEG C is adjusted into 1～6.By carry out polyreaction under this acidic conditions, the mode that can complete with high density and a step is implemented polymerization, therefore, can omit enrichment process.Thus, productivity significantly improves, and can suppress the rising of preparation cost.
In above-mentioned acidic conditions, the reaction soln in polymerization is at the pH of 25 DEG C preferably 1～6, and further preferably 1～5, be more preferably 1～4.This pH is less than in 1 situation, for example, while using heavy sulfurous acid (salt) as initiator system, may cause the generation of sulphurous acid gas and the corrosion of device.On the one hand, pH exceedes in 6 situation, while using heavy sulfurous acid (salt) class, reduces the efficiency of heavy sulfurous acid (salt) class as initiator system, increases molecular weight.
As the pH adjusting agent of the pH for regulating reaction soln, can exemplify: the alkali-metal oxyhydroxide of sodium hydroxide, potassium hydroxide etc.; The oxyhydroxide of the alkaline-earth metal of calcium hydroxide, magnesium hydroxide etc.; The organic amine salt of ammonia, monoethanolamine, trolamine etc. etc.These can use separately one or be used in combination two or more.Wherein, the preferably alkali-metal oxyhydroxide of sodium hydroxide, potassium hydroxide etc., further preferred sodium hydroxide.In this specification sheets, sometimes above-mentioned substance is only called " pH adjusting agent " or " neutralizing agent ".
Preferably 0～25 % by mole of degree of neutralization in polymerization,, is more preferably in the scope of 2～10 % by mole by further preferably 1～15 % by mole.Degree of neutralization in polymerization in corresponding scope time, can carry out copolymerization best, can reduce impurity, and can prepare the good polymkeric substance of resistance to gelation.In addition, the viscosity of the aqueous solution of polymerization reaction system can not rise, and can prepare preferably low-molecular-weight polymkeric substance.And, compare in the past, can under the condition of high density, carry out polyreaction, therefore can significantly improve preparation efficiency.
On the one hand, when the degree of neutralization in polymerization exceedes 25 % by mole, there is the situation that chain transfer efficiency reduces, molecular weight rises of heavy sulfurous acid (salt) class to occur.In addition,, along with the carrying out of polymerization, it is remarkable that the rising of the viscosity of the aqueous solution of polymerization reaction system becomes.Its result, the molecular weight of the polymkeric substance obtaining increase to required more than, thereby cannot obtain low-molecular-weight polymkeric substance.In addition, sometimes cannot give full play to above-mentioned degree of neutralization and reduce the effect producing, and be difficult to significantly reduce impurity.
For neutralization method, be not particularly limited.For example, can the part using (methyl) acrylic acid salt of (methyl) sodium acrylate etc. as raw material use, also can be used as the alkali-metal oxyhydroxide etc. that neutralizing agent uses sodium hydroxide etc., in polymerization, neutralize, also can be used together these.In addition, in and time the interpolation form of neutralizing agent, can be solid, can be also the aqueous solution that is dissolved in suitable solvent, is preferably dissolved in water.
Use the concentration of aqueous solution when aqueous solution, preferably 10～60 quality %, further preferred 20～55 quality %, are more preferably 30～50 quality %.When this concentration of aqueous solution is less than 10 quality %, the density loss of goods, carries and keeping becomes loaded down with trivial details, while exceeding 60 quality %, may separate out, and viscosity also uprises, and therefore liquor charging becomes loaded down with trivial details.
(adding conditional of raw material)
When polymerization, preferably aforementioned monomer mixture, initiator, chain-transfer agent and other additive, be dissolved in advance suitable solvent (the preferably solvent of the same race with the solvent of being used by the liquid that drips), as monomer mixture solution, initiator solution and chain-transfer agent solution and other additive solution, with respect to (water-based) solvent (being adjusted to if desired specified temperature) joining in reaction vessel, when drip the drop time of regulation continuously, carry out polymerization respectively.Further, for a part for the solvent of water-based, also can be different from the solvent that the initial stage that the container joining in advance in reaction system forms adds, after it, drip separately.But, be not defined in this preparation method.
For example, about the method for dripping, can drip continuously, also can intermittently drip in the mode being subdivided into several times.Can add one or more of monomer of a part or total amount the initial stage.In addition, the speed of dripping (amount of dripping) of one or more of monomer, when normal till the beginning of dripping extremely stops, (always) drips in the mode of certain (a certain amount of), or can change in time the speed (amount of dripping) of dripping according to polymerization temperature etc.In addition, can not make whole compositions that drips carry out identical dripping, can stagger time opening or termination time according to each composition that drips, or, also can shorten drop time or extend drop time.
While using heavy sulfurous acid (salt) class as initiator system, the molecular weight at polymerization initial stage is large for final molecular weight impact.Therefore, in order to reduce initial stage molecular weight, preferably from polymerization, preferably 60 minutes with interior, further preferably 30 minutes with interior, be more preferably in 10 minutes, add (dripping) heavy sulfurous acid (salt) class or its solution 5～20 quality %.Particularly, as described later, the situation that starts polymerization from room temperature is effective.
In addition, dripping in composition when polymerization, use in the situation of heavy sulfurous acid (salt) class as initiator system, for the drop time of heavy sulfurous acid (salt) class or its solution, with respect to the termination of dripping of monomer (A), (B), preferably drip stop accelerate 1～30 minute, further preferably 1～20 minute, be more preferably 1～15 minute.Thus, heavy sulfurous acid (salt) the class amount after polymerization stops can be reduced, the generation of sulphurous acid gas or the formation of impurity that this heavy sulfurous acid (salt) class causes can be effectively and efficiently suppressed.Therefore,, after polymerization stops, the sulphurous acid gas of gas phase portion is dissolved in liquid phase and can significantly reduces impurity.Polymerization is when after stopping, heavy sulfurous acid (salt) class is residual, can cause generating impurity and impurity when the performance of polymkeric substance reduces or low temperature keeps such as separates out at the phenomenon.Therefore the initiator system of containing heavy sulfurous acid (salt) class when, preferred polymeric finishes is consumed and not residual.
Wherein, with respect to dripping the termination time of monomer (A), (B), the termination time of dripping of heavy sulfurous acid (salt) class (solution), while only accelerating to be less than 1 minute, exists polymerization to stop the residual situation of rear heavy sulfurous acid (salt) class.As such situation, comprise: the dripping of heavy sulfurous acid (salt) class or its solution stops and monomer (A), dripping of (B) stop the situation of while; The Stopping Phase that drips of heavy sulfurous acid (salt) class (solution) stops slow situation for dripping of monomer (A), (B).Now, there is the tendency that is difficult to effectively and suppresses efficiently the generation of sulphurous acid gas or the formation of impurity, exist residual initiator to produce the situation of baneful influence for the thermostability of obtained polymkeric substance.On the one hand, the termination time of dripping of heavy sulfurous acid (salt) class or its solution, while being greater than in advance 30 minutes with respect to the termination time of dripping of monomer (A), (B), before polymerization stops, heavy sulfurous acid (salt) class was consumed.Therefore the tendency that, exists molecular weight to increase.In addition, in polymerization, the speed of dripping of drip velocity ratio monomer (A), (B) of heavy sulfurous acid (salt) class is fast, and the volume of dripping in the short period of time, therefore the tendency that, exists impurity or sulphurous acid gas volume to occur during this drips.
In addition, dripping in composition when polymerization, use in the situation of heavy sulfurous acid (salt) class as initiator system, dripping the termination time of persulphate (solution), with respect to dripping the termination time of monomer (A), (B), preferably postpone 1～30 minute, further preferably 1～25 minute, be more preferably 1～20 minute.Thus, can reduce polymerization and stop rear residual monomer component amount, can significantly reduce the impurity that residual monomer causes.
Wherein, the termination time of dripping of persulphate (solution) only postponed while being less than 1 minute with respect to the termination time of dripping of monomer (A), (B), exist polymerization to stop after the residual situation of monomer component.As such situation, comprise: the dripping of persulphate (solution) stops and dripping of monomer (A), (B) stops the situation of while; The Stopping Phase that drips of persulphate (solution) stops fast situation for dripping of monomer (A), (B).Now, exist and be difficult to effectively and the tendency of the formation of inhibition of impurities efficiently.On the one hand, the termination time of dripping of persulphate (solution) postponed while being greater than 30 minutes with respect to the termination time of dripping of monomer (A), (B), may polymerization stop rear residual persulfate or its resolvent, and form impurity.
(polymerization time)
When polymerization, reducing polymerization temperature and use in the situation of heavy sulfurous acid (salt) as initiator system, suppressing the generation of sulphurous acid gas, and prevent the formation of impurity, is also more important.For this reason, total drop time when preferred polymeric, reach 150～600 minutes, further preferably 160～450 minutes, be more preferably 180～300 minutes.
Total drop time is while being less than 150 minutes, the tendency that exists the effect producing as persulfate solution and heavy sulfurous acid (salt) solution of the interpolation of initiator system to reduce, therefore, there is following tendency: for obtained (methyl) acrylic copolymer, the amount containing sulfenyl of the sulfonic group of introducing in main chain end etc. reduces.Its result, the tendency that exists the weight-average molecular weight of this polymkeric substance to uprise.
In addition,, may there is the superfluous situation about existing of heavy sulfurous acid (salt) in the mode of dripping between short-term in reaction system.Therefore, so superfluous heavy sulfurous acid (salt) decomposes and sulphurous acid gas occurs, and outside being discharged into and being, or, form impurity.But, by implement polymerization temperature and amount of initiator in low specified range, can improve above-mentioned situation.
On the one hand, total drop time, while exceeding 600 minutes,, because the generation of sulphurous acid gas is suppressed, therefore,, still, there is productivity reduction, the limited situation of use in the better performances of the polymkeric substance obtaining.Refer to this total drop time, start the time of having dripped up to the last composition that drips (being not limited to a kind of composition) from dripping of the initial composition that drips (being not limited to a kind of composition).
(the polymer/solid constituent concentration of monomer)
Solid component concentration in the aqueous solution in the time that dripping of the total amount of aforementioned monomer, polymerization starter and chain-transfer agent stops (, the polymer/solid constituent concentration of monomer), preferably 35 quality % above, further preferably 40～70 quality %, be more preferably 45～65 quality %.Solid component concentration when polyreaction stops is that 35 quality % are when above, the mode that can complete with high density and a step is implemented polymerization, therefore, can effectively obtain low-molecular-weight (methyl) acrylic copolymer, for example, can omit enrichment process.Therefore, can significantly improve this preparation efficiency, productivity, and suppress preparation cost.
Wherein, if while improving the solid component concentration in polymerization reaction system, have tendency as follows: along with the carrying out of polyreaction, the rising of the viscosity of reaction soln becomes significantly, the weight-average molecular weight of the polymkeric substance obtaining also significantly improves.But, by carrying out polyreaction in acidic side (pH of 25 DEG C is 1～6, and the degree of neutralization of carboxylic acid is 0～25 % by mole of scope), can suppress the viscosity rise along with the reaction soln of the carrying out of polyreaction.Therefore, even carry out polyreaction under the condition of high density, also can obtain low-molecular-weight polymkeric substance, can significantly improve the preparation efficiency of polymkeric substance.
(curing step)
In preparation method that should (methyl) acrylic copolymer, after the interpolation of whole use raw materials stops, also can improve the percent polymerization etc. of monomer as object, set curing step.Normally 1～120 minute curing time, preferably 5～90 minutes, further preferably 10～60 minutes.Curing time, while being less than 1 minute, may cause following situation: along with slaking is insufficient, monomer component is residual, forms the impurity that residual monomer causes, causes performance reduction etc.On the one hand, while being greater than 120 minutes, may there is polymers soln painted in the curing time.
In curing step, the temperature of preferred polymers soln is same as above-mentioned polymerization temperature scope.Therefore, this temperature can remain certain temperature (preferably, the temperature in the time dripping termination), also can in slaking, change in time temperature.
(operation after polymerization)
Be somebody's turn to do in the preparation method of (methyl) acrylic copolymer, preferably under acidic conditions as above, carry out polymerization.Therefore, for the degree of neutralization (the final degree of neutralization of carboxylic acid) of the carboxylic acid of obtained (methyl) acrylic copolymer, after polymerization stops, can as required, be set in the scope of regulation as the suitable alkaline components of the suitable interpolation of aftertreatment.As aforementioned alkaline components, can exemplify: the alkali-metal oxyhydroxide of sodium hydroxide, potassium hydroxide etc.; The oxyhydroxide of the alkaline-earth metal of calcium hydroxide, magnesium hydroxide etc.; The organic amine of ammonia, monoethanolamine, diethanolamine, trolamine etc. etc.
Also different according to the different final degree of neutralization of use, therefore it is not particularly limited.
The final degree of neutralization of carboxylic acid while particularly use as acid polymkeric substance, preferably 0～75 % by mole, further preferably 0～70 % by mole.The final degree of neutralization of carboxylic acid while use as neutral or alkaline polymkeric substance, preferably 75～100 % by mole, further preferably 85～99 % by mole.In addition, when the final degree of neutralization while use as neutral or alkaline polymkeric substance exceedes 99 % by mole, may make aqueous solutions of polymers painted.
In addition, not neutralizing while still use with acidity, is acid in reaction system, therefore, has the situation of the virose sulphurous acid gas of residual tool in reaction system and in environment.Now, preferably add the superoxide of hydrogen peroxide etc. to decompose, or, import (blowing out) air or nitrogen and discharge.
In addition, the preparation method of being somebody's turn to do (methyl) acrylic copolymer can be batch, can be also continous way.
As above (methyl) acrylic copolymer obtaining, brings and prevents that the dirt of cooling water system from hindering and suppressing the effect of corrosion of metal.Be still not clear for its mechanism, but think: from the carboxyl of the structural unit (a) of (methyl) acrylic monomer (A), strong with the affinity of the calcium ion as dirt composition, by adsorbing and hinder growth on the vegetative point of crystallization.In addition, the known material that contains carboxyl has Corrosion Protection, by structural unit (a) being set as to certain above % by mole, can make dirt prevent from bringing into play with anticorrosion ability simultaneously.
But, in order to prevent gelation, for with the interaction of calcium ion little, be the structural unit (b) of monomer (B) from high (methyl) allyl ethers of solvability, need to set certain above mole number, meanwhile, need to improve resistance to gellifying property using main chain end as sulfonic group.
Then, describe for the treatment process of cooling water system of the present invention.
The treatment process > of < cooling water system
In the treatment process of cooling water system of the present invention, the treatment agent of aforesaid by containing (methyl) acrylic copolymer makes an addition to the cooling water system with following water quality, prevents that thus the dirt of cooling water system from hindering, and suppresses corrosion of metal.
(methyl) acrylic copolymer is as described above, but, particularly preferably by from be selected from vinylformic acid (AA), methacrylic acid (MAA) and sodium acrylate (SA) one or more (methyl) acrylic monomer (A) structural unit (a) and, the multipolymer that forms from the structural unit (b) of 3-allyloxy-2-hydroxyl-1-propanesulfonate (HAPS).More specifically, be the multipolymer of AA/HAPS, MAA/HAPS, AA/SA/HAPS, AA/MAA/HAPS etc.
In addition, the operating condition when being suitable for treatment process of the present invention, is not particularly limited.
(water quality of cooling water system)
The treatment process of cooling water system of the present invention, is applicable to have calcium hardness with CaCO 3count that 300mg/L is above, chloride ion and/or sulfate ion concentration is the cooling water system of water quality more than 1000mg/L.
For making an addition to dirt preventing agent/anticorrosive agent this cooling water system, that formed by aforesaid (methyl) acrylic copolymer (below, also be called " copolymer systems dirt preventing agent/anticorrosive agent ") addition means, be not particularly limited, can make an addition to the position that will prevent burn into dirt, or in before this position etc.
In addition, be not particularly limited for its addition, can be according to the suitable selection of water quality of the cooling water system adding, but, the concentration of this copolymer systems dirt preventing agent/anticorrosive agent, conventionally add in the mode that reaches 0.01～100mg/L, preferably add in the mode that reaches 2～50mg/L.
As required, this copolymer systems dirt preventing agent/anticorrosive agent, can and use with other dirt preventing agent or anticorrosive agent, foundry loam control agent.
(the also anticorrosive agent of use)
As can and the anticorrosive agent of use; can exemplify: for example, the phosphonic acids of hydroxy ethylene diphosphonic acid or phosphoryl butane tricarboxylic acid, ethylenediamine tetramethylene phosphonic acid, nitrilo trimethylammonium phosphonic acids (nitrilotrimethyl phosphonic acid) etc., orthophosphoric acid salt, polymeric phosphate, phosphoric acid ester, zinc salt, nickel salt, molybdenum salt, tungsten salt, oxygen yl carboxylic acid salt, triazole species, amine etc.
(the also dirt preventing agent of use)
As can and the dirt preventing agent of use; can exemplify: for example, the phosphonic acids of hydroxy ethylene diphosphonic acid or phosphoryl butane tricarboxylic acid, ethylenediamine tetramethylene phosphonic acid, nitrilo trimethylammonium phosphonic acids (nitrilotrimethyl phosphonic acid) etc., orthophosphoric acid salt, polymeric phosphate, polymaleic acid, polyacrylic acid, maleic acid, toxilic acid/vinylformic acid, toxilic acid/iso-butylene, toxilic acid/sulfonic acid, vinylformic acid/sulfonic acid, vinylformic acid/containing the multipolymer of the monomer of nonionic base, vinylformic acid/sulfonic acid/containing the ter-polymers of the monomer of nonionic base etc.
As the sulfonic acid in aforementioned dirt preventing agent, can exemplify: for example, vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxy-propanesulfonic acid, 2-acrylamide-2-methyl propane sulfonic, 2-methacryloyl amido-2-methyl propane sulfonic acid, methacrylic acid 4-sulphur butyl, allyloxy Phenylsulfonic acid, methylallyl oxygen base Phenylsulfonic acid and their metal-salt etc.
In addition, as in aforementioned dirt preventing agent containing nonionic base monomer, can exemplify: for example, list (methyl) acrylate of (gather) ethene/propylene oxide of alkylamide (C1～C5 alkylamide), hydroxyethyl meth acrylate (hydroxyethyl methacrylate), additional mole number 1～30, pair add the mono vinyl ether ethene/propylene oxide etc. of mole number 1～30.
(the also foundry loam control agent of use)
As can and the foundry loam control agent of use, can contain: for example, the quaternary ammonium salt of alkyl dimethyl benzyl ammonium chloride etc., chloromethyl three thiazolines, chlormethylisothiazo,ine, methyl isothiazoline, or ethylamino isopropylamino methyl is disliked triazine (ethylaminoisopropylaminomethylthiatriazine: エ チ Le ア ミ ノ イ ソ プ ロ ピ Le ア ミ ノ メ チ Le チ ア ト リ ア ジ Application), hypochlorous acid, hypobromous acid, the mixture of hypochlorous acid and thionamic acid (acid of ス Le ホ Off ァ ミ Application) etc., enzyme, Kill microbial inoculum, tinting material, spices, water-miscible organic solvent, and defoamer etc.
For aforesaid dirt preventing agent, anticorrosive agent, foundry loam control agent, can use separately respectively one or be used in combination two or more.
Embodiment
, by embodiment, the present invention is described in further detail below, still, the present invention is not defined in these examples.
In addition, by following method carry out non-corrosibility test, calcium phosphate dirt is separated out inhibition test, and, carry out mensuration and the sulfonic confirmation having or not of end of molecular weight by following method.
(1) non-corrosibility test
Be that 50mm × 30mm × 1mm, surface-area are 0.31dm for size 2soft steel (JISG3141SPSS-SB) carry out #400 grinding, and with the test film after toluene degreasing as sample, and quality measurement, using this quality quality before test.
In 5000ml plastic containers (Port リ container), add the water dechlorinating for the wooden raised path between farm fields water in open country, the amount of the water of this dechlorination is the amount that deducts each reagent addition from 5000ml, add afterwards after sodium bicarbonate aqueous solution, sodium silicate aqueous solution, polymers soln, magnesium sulfate solution, sodium chloride aqueous solution, phosphoric acid solution, calcium chloride water, aqueous sodium persulfate solution, zinc sulfate solution, regulate pH by a small amount of aqueous sodium hydroxide solution and aqueous sulfuric acid, thereby as test water.The test water of about 1000ml is transferred to 1000ml beaker and is placed in temperature the thermostatic bath that remains on the corrosion testing apparatus of 40 DEG C, and afore-mentioned test sheet is screwed in turning axle and floods, and is rotated with 170 revolutions (rpm).By the raffinate of test water, flow into continuously in 1000ml beaker with the speed of 0.8ml/ minute (min) by roller pump.
Start three days to take out test film from dip test sheet, the corrosion product adhering to the clean test film surface removal of pickling, measures the quality after dry, using this amount quality after test.Afterwards, based on the quality change of test film, calculate corrosion speed (mdd) by following formula, and evaluate Corrosion Protection.
Corrosion speed (the mdd)=rear quality (mg) of quality (mg)-test/{ surface-area (dm of test film before test 2) × test number of days (my god)
Corrosion speed is less than the ◎ that is labeled as of 10mdd; 10mdd above and be less than 20mdd be labeled as zero; 20mdd is above and be less than the △ that is labeled as of 30mdd; More than 30mdd being labeled as ×.Condition of water quality is shown in Table 1.
(2) calcium phosphate dirt is separated out inhibition test
In 500ml conical beaker, add ultrapure water, the amount of this ultrapure water is the amount that deducts each reagent addition from 500ml, add afterwards after sodium bicarbonate aqueous solution, sodium silicate aqueous solution, polymers soln, magnesium sulfate solution, sodium chloride aqueous solution, phosphoric acid solution, calcium chloride water, aqueous sodium persulfate solution, regulate pH by a small amount of aqueous sodium hydroxide solution and aqueous sulfuric acid, after clogging, in the thermostatic bath of 60 DEG C, leave standstill 20 hours.Afterwards, the phosphoric acid concentration of filtrate of the filter paper filtering of 0.1 μ m for measuring, calculates the recall rate of phosphoric acid based on following formula.
Phosphoric acid recall rate (%)=(phosphoric acid concentration before the phosphoric acid concentration/test after test) × 100
The recall rate of phosphoric acid more than 90% is labeled as ◎; More than 80% and be less than 90% be labeled as zero; More than 50% and be less than 80% the △ that is labeled as; Be less than 50% be labeled as ×.Condition of water quality is shown in Table 1.
Table 1
Recycle-water A: suppose the water quality of recycle-water as supplementary feed
Recycle-water B: suppose the water quality of recycle-water as supplementary feed
(3) molecular weight
Weight-average molecular weight, is to use gel permeation chromatography (TOSOH Co., Ltd (TOSOH CORPORATION) system " HLC-8320GPC "), measures with following condition.
Detect instrument: RI
Post: the Shodex Asahipak processed GF-310-HQ of Showa Denko K. K, GF-710-HQ, GF-1G
Elutriant: 0.1N aqueous sodium acetate solution
Flow velocity: 0.5ml/ minute
Column temperature: 40 DEG C
Typical curve: polyacrylic acid standard substance (POLYACRYLIC ACID STANDARD) (wound and science Co., Ltd. system)
(4) end sulfonic group
The multipolymer that is 1 by pH regulator (aqueous solution), after reduced pressure at room temperature distilled water, uses heavy water as solvent, carry out 1whether HNMR measures, confirm to exist from the peak of the 2.7ppm that imports sulfonic group material on main polymer chain end.
Embodiment 1～8 and comparative example 1～9
Polymkeric substance in the polymers soln using in embodiment 1～8 and comparative example 1～9, it is respectively the monomer of the ratio shown in Aggregation Table 2 and the table 3 and multipolymer that obtains illustrates respectively the situation whether weight-average molecular weight and end sulfonic group exist in table 2 and table 3.
In addition, in table 2 and table 3, show respectively and use this multipolymer to carry out the corrosion speed (mdd) of the result of Corrosion Protection evaluation test and carry out the phosphoric acid recall rate (%) of the result of calcium phosphate dirt inhibition test.
Table 2
AA: vinylformic acid
HAPS:3-allyloxy-2-hydroxyl-1-propanesulfonate
Table 3
AA: vinylformic acid
MA: toxilic acid
HAPS:3-allyloxy-2-hydroxyl-1-propanesulfonate
Based on table 2 and table 3, according to the calcium phosphate inhibition test of carrying out in the water quality of hypothesis recycle-water supply, relatively when phosphoric acid recall rate, their order is, comparative example 4,5 < comparative example 1-3, comparative example 6,7 < embodiment, comparative example 8,9.Known from its result: to have the polymkeric substance from the structural unit of vinylformic acid (AA) and 3-allyloxy-2-hydroxyl-1-propanesulfonate (HAPS), main chain end has in the severe water quality that sulfonic embodiment, comparative example 8,9 are supplementary feed at hypothesis recycle-water, demonstrates excellent dirt preventing effectiveness.Its reason is thought, by the sulfonic importing of main chain end, is difficult to the gelation of generation and Ca ion.
From its result, comparative example 1～5 is not because have sulfonic group, and therefore, calcium phosphate dirt preventing effectiveness is poor.From its result, although the structural unit that comparative example 6,7 has from HAPS,, because do not have sulfonic group in main chain end, therefore, in the water quality that is supplementary feed at hypothesis recycle-water, dirt preventing effectiveness is poor.Think equally, comparative example 1～7 is not because have sulfonic group in main chain end, therefore, occurs and the gelation of Ca ion, and dirt preventing effectiveness is poorer than embodiment, comparative example 8,9.
According to Corrosion Protection evaluation test, relatively when corrosion speed, their order is, comparative example 8,9 > comparative example 6,7 > comparative example 1-5 > embodiment.From its result, the anticorrosion ability of embodiment, comparative example 1-5 that carboxyl is many is high.Its reason is thought, when carboxyl is many, is easily adsorbed in erosional surface, therefore, can suppress the carrying out of corrosion.
From its result, comparative example 8,9 demonstrates the excellent dirt preventing effectiveness identical with embodiment, and still, Corrosion Protection is poorer than embodiment.From its result, when the ratio of sulfonic acid exceedes 20 % by mole, anticorrosion ability reduces, and in the water quality of hypothesis recycle-water, cannot suppress corrosion, cannot obtain dirt preventing effectiveness and anticorrosion ability simultaneously.
From the above results, in the water quality that is supplementary feed at hypothesis recycle-water, the ratio on the main chain end of polymkeric substance with AA, HAPS with sulfonic group and HAPS is the polymkeric substance of 10～20 % by mole, demonstrates excellent dirt preventing effectiveness and anticorrosion ability.
Industrial applicibility
The treatment process of cooling water system of the present invention, dirt composition and the high water quality of corrosive ion at recycle-water (processing again water) for supplementary feed, can prevent calcium be dirt be attached to pipe arrangement or heat exchanger and prevent from conducting heat hinder, the obstruction of degradation under flow, and can prevent the corrosion of metal of pipe arrangement or heat exchanger etc.

Claims (2)

1. a treatment process for cooling water system, its in calcium hardness with CaCO 3count that 300mg/L is above, chloride ion and/or sulfate ion concentration is in cooling water system more than 1000mg/L, add and contain the treatment agent that (methyl) acrylic copolymer forms, wherein,
Aforementioned (methyl) acrylic copolymer, (methyl) allyl ethers that has the structural unit (a) of (methyl) acrylic monomer (A) representing from following general formula (1), represent from following general formula (2) is the structural unit (b) of monomer (B)
And in all from 100 % by mole of the structural units of monomer, the content of structural unit (a) is that 80～90 % by mole, the content of structural unit (b) are 10～20 % by mole,
And aforementioned (methyl) acrylic copolymer, is sulfonic group or sulfonic group salt at least one of main chain end,
In general formula (1), R 1represent hydrogen atom or methyl, X represents hydrogen atom, atoms metal, ammonium or organic amino group;
In general formula (2), R 2represent hydrogen atom or methyl, Y and Z represent respectively hydroxyl, sulfonic group or their salt independently, and at least one in Y and Z represents sulfonic group or sulfonic group salt.
2. the treatment process of cooling water system as claimed in claim 1, wherein, (methyl) acrylic copolymer, be by from be selected from vinylformic acid, methacrylic acid and sodium acrylate one or more (methyl) acrylic monomer (A) structural unit (a) and form from the structural unit (b) of 3-(methyl) allyloxy-2-hydroxyl-1-propanesulfonate.
CN201380017931.6A 2012-03-30 2013-03-29 Method for treating cooling water system Pending CN104203842A (en)

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