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WO2016047267A1 - Copolymère à base d'acide acrylique ainsi que procédé de fabrication de celui-ci, et agent de traitement de l'eau - Google Patents

Copolymère à base d'acide acrylique ainsi que procédé de fabrication de celui-ci, et agent de traitement de l'eau Download PDF

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Publication number
WO2016047267A1
WO2016047267A1 PCT/JP2015/071561 JP2015071561W WO2016047267A1 WO 2016047267 A1 WO2016047267 A1 WO 2016047267A1 JP 2015071561 W JP2015071561 W JP 2015071561W WO 2016047267 A1 WO2016047267 A1 WO 2016047267A1
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Prior art keywords
acrylic acid
reactor
acid copolymer
structural unit
mass
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English (en)
Japanese (ja)
Inventor
正裕 藤原
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to SG11201702148RA priority Critical patent/SG11201702148RA/en
Priority to CN201580043910.0A priority patent/CN106574021B/zh
Priority to JP2016550010A priority patent/JP6504177B2/ja
Publication of WO2016047267A1 publication Critical patent/WO2016047267A1/fr
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    • 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
    • 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
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers

Definitions

  • the present invention relates to an acrylic acid copolymer (hereinafter, also referred to as “AA / ATBS polymer”) suitable as a main component of a water treatment agent having an excellent effect of suppressing the formation of scale with respect to calcium phosphate, and a method for producing the same.
  • AA / ATBS polymer acrylic acid copolymer
  • an agent for suppressing the formation of scale, precipitation or deposition a structural unit derived from acrylic acid or a salt thereof, 2-acrylamido-2-methylpropanesulfonic acid (“acrylamide-tert”) Copolymers (AA / ATBS polymers) containing structural units derived from “-butylsulfonic acid” or salts thereof are known.
  • acrylamide-tert 2-acrylamido-2-methylpropanesulfonic acid
  • AA / ATBS polymers 2-acrylamido-2-methylpropanesulfonic acid
  • Patent Document 1 discloses an AA / ATBS polymer neutralized to pH 3.5 to 6.0 with sodium hydroxide.
  • Patent Document 2 discloses an AA / ATBS polymer neutralized with sodium hydroxide and calcium hydroxide.
  • Patent Document 3 discloses an AA / ATBS polymer further comprising a structural unit derived from a poorly water-soluble monomer such as phenoxyethyl acrylate.
  • Patent Document 4 discloses an AA / ATBS polymer further containing a structural unit derived from ethoxylated tristyrylphenol methacrylate.
  • the acrylic phosphate copolymer (AA / ATBS polymer) suitable as a main component of the water treatment agent which is not sufficient in terms of the inhibitory effect of calcium phosphate scale and is excellent in the inhibitory effect of scale formation on calcium phosphate and its A manufacturing method and a water treatment agent are desired.
  • the inventor has intensively studied to solve the above problems. As a result, when acrylic acid and sodium 2-acrylamido-2-methylpropanesulfonate were polymerized by the conventional method, a small amount of high molecular weight polymer was produced as a by-product, and this high molecular weight polymer was capable of inhibiting scale formation. The knowledge which became the factor which decreases is obtained. Further, based on such knowledge, the present inventor has found that an AA / ATBS polymer in which the ratio of the high molecular weight polymer is reduced to a specific amount or less exhibits an excellent scale inhibiting ability against calcium phosphate scale. Completed the invention.
  • the present inventor found that the conventional production method changes the sodium concentration in the reaction solution with the progress of the reaction, so that the polymerization cannot be continued under certain conditions. It came to the idea that it is a thing. Based on this idea, it is possible to efficiently produce an AA / ATBS polymer with a very low content of the high molecular weight polymer by carrying out the polymerization while keeping the sodium concentration in the reaction solution at a constant amount. I found that there was.
  • the structural unit (x) is a structural unit derived from a sodium salt of acrylic acid
  • the structural unit (y) is a structural unit derived from a sodium salt of 2-acrylamido-2-methylpropanesulfonic acid.
  • [4] A method for producing an acrylic acid polymer according to any one of [1] to [3] above, A step of polymerizing the monomer while continuously supplying a monomer comprising acrylic acid or a sodium salt thereof and 2-acrylamido-2-methylpropanesulfonic acid or a sodium salt thereof to the reactor; A method for producing an acrylic acid copolymer.
  • [5] A method for producing an acrylic acid copolymer according to any one of [1] to [3] above, Using a production apparatus in which three reactors are connected, in the first reactor, acrylic acid or its sodium salt, and 2-acrylamido-2-methylpropanesulfonic acid or its sodium salt in the presence of a polymerization initiator The monomer is polymerized while continuously supplying the monomer, and then the reaction liquid is transferred from the first reactor to the second reactor connected to the first reactor. In the second reactor, after the polymerization of the monomer contained in the reaction solution is continued, the reaction solution is supplied from the second reactor to the third reaction connected to the second reactor.
  • a method for producing an acrylic acid copolymer wherein the pH of the polymer-containing liquid is adjusted to 9 or less in the third reactor.
  • a water treatment agent comprising the acrylic acid copolymer according to any one of [1] to [3].
  • the acrylic acid copolymer has a weight average molecular weight Mw of 4000 to 20000,
  • the content ratio of the acrylic acid copolymer having a molecular weight of 70,000 or more is 0.05% by mass or less with respect to the total amount of all polymers, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is The water treatment agent according to the above [8], wherein the polydispersity (Mw / Mn) is 3.5 or less.
  • the weight average molecular weight (hereinafter also referred to as “Mw”) and the number average molecular weight (hereinafter also referred to as “Mn”) of the polymer are gel permeation chromatography (hereinafter also referred to as “GPC”). It is a standard sodium polyacrylate conversion value measured by the above.
  • (meth) acryl means acryl and methacryl.
  • the acrylic acid copolymer (AA / ATBS polymer) of the present invention has a more uniform composition, it is suitable as a main component for agents that suppress scale formation, precipitation, or deposition, and as a dispersant for inorganic particles. It is.
  • the content ratio of the two types of structural units (x) and (y) is in a specific range, and substantially consists of an acrylic acid copolymer having a specific range of Mw. It is suitable as a main component of a water treatment agent that has an excellent effect of suppressing formation.
  • the acrylic acid copolymer of the present invention can also be used as a constituent component of a scale formation inhibitor other than calcium phosphate, a dispersant such as inorganic particles, a surfactant, an antistatic agent, and a detergent composition.
  • a dispersant such as inorganic particles
  • a surfactant such as sodium phosphate
  • an antistatic agent such as sodium phosphate
  • the acrylic acid copolymer (AA / ATBS polymer) of the present invention comprises a structural unit (x) derived from acrylic acid or a sodium salt thereof, and 2-acrylamido-2-methylpropanesulfonic acid or a sodium salt thereof. And the content ratio of the structural unit (x) and the structural unit (y) is 35 to 90 mass% and 10 mass%, respectively, when the total of both is 100 mass%.
  • the content ratio of the acrylic acid copolymer having a molecular weight of 70000 or more is 0.30% by mass or less based on the total amount of all the polymers. .
  • the structural unit (x) contained therein is at least one of a structural unit derived from acrylic acid and a structural unit derived from a sodium salt of acrylic acid
  • the structural unit (y ) Is at least one of a structural unit derived from 2-acrylamido-2-methylpropanesulfonic acid and a structural unit derived from the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid.
  • a particularly preferred embodiment is a polymer in which at least one of the structural units (y) has —SO 3 Na.
  • the content ratio of the structural unit (x) and the structural unit (y) constituting the AA / ATBS-based polymer of the present invention is, from the viewpoint of obtaining high calcium phosphate precipitation preventing ability, when the total of both is 100% by mass, They are 35 to 90% by mass and 10 to 65% by mass, respectively, preferably 40 to 80% by mass and 20 to 60% by mass, more preferably 45 to 75% by mass and 25 to 55% by mass.
  • the content ratio is 0.30% by mass or less based on the total amount of all the polymers. , Preferably 0.10% by mass or less, more preferably 0.05% by mass or less.
  • the Mw of the AA / ATBS polymer of the present invention is 2000 to 30000, preferably 4000 to 20000, from the viewpoint of obtaining high calcium phosphate precipitation preventing ability.
  • the polydispersity (Mw / Mn), which is the ratio of Mw to the number average molecular weight Mn, is 3.8 or less, preferably 3.5 or less, more preferably 3.1 or less.
  • the lower limit is usually 2.0.
  • the structure of the AA / ATBS polymer of the present invention is not particularly limited, but is preferably a random copolymer.
  • the AA / ATBS polymer of the present invention is preferably obtained by a continuous polymerization method using a monomer consisting of acrylic acid or a sodium salt thereof and 2-acrylamido-2-methylpropanesulfonic acid or a sodium salt thereof. Can be.
  • a method for producing an AA / ATBS polymer in the present invention includes acrylic acid or a sodium salt thereof and 2-acrylamido-2-methylpropanesulfonic acid or A step of polymerizing the sodium salt monomer while continuously supplying the monomer is provided.
  • a method for producing an AA / ATBS polymer of a particularly preferred embodiment uses a production apparatus in which three reactors are connected, and acrylic acid or acrylic acid in the presence of a polymerization initiator is used in the first reactor.
  • the monomer was polymerized while continuously supplying the sodium salt and a monomer comprising 2-acrylamido-2-methylpropanesulfonic acid or its sodium salt, and then the reaction solution (hereinafter referred to as “reaction solution”).
  • reaction solution hereinafter referred to as “reaction solution”.
  • reaction solution (S2) the reaction solution
  • reaction solution (S2) the reaction solution
  • the polymerization of the monomer, the transfer of the polymer, etc. are continuously advanced, so that the acrylic acid copolymer that is a high molecular weight polymer.
  • a uniform AA / ATBS polymer with a high production rate of an acrylic acid copolymer having an Mw of 2000 to 30000 can be produced while suppressing the by-product formation.
  • an acrylic acid copolymer having a Mw of 2000 to 30000 or a precursor thereof is substantially obtained by polymerization of the monomers continued in the second reactor and the third reactor. Is formed.
  • FIG. 1 shows a schematic diagram of a production apparatus having three reactors.
  • the production apparatus (100) of FIG. 1 includes a first reactor (10) having means for supplying a raw material (15), stirring means, temperature adjusting means, reflux cooling means, discharge means, etc., and raw materials (25).
  • Second reactor (20) having means for supplying, stirring means, temperature adjusting means, reflux cooling means, discharge means, etc., means for supplying pH adjusting agent etc. (35), stirring means, temperature adjusting means, reflux cooling
  • a third reactor (30) provided with means, discharge means and the like.
  • a monomer comprising acrylic acid or a sodium salt thereof and 2-acrylamido-2-methylpropanesulfonic acid or a sodium salt thereof is continuously supplied, and the presence of a polymerization initiator is present.
  • This monomer preferably comprises acrylic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • water is used as a polymerization medium, and a chain transfer agent can be used as necessary.
  • the proportion of acrylic acid constituting the monomer supplied to the first reactor (10) is preferably 35 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 45 to 75% by mass. is there.
  • the concentration of the monomer in the first reactor (10) is preferably 20 to 200% by mass, more preferably 50 to 150% by mass when the polymerization medium is 100% by mass.
  • Supplying the above to the first reactor (10) is preferably employed.
  • polymerization initiator examples include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis ( Isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride , 2, 2 '-Azobis
  • the amount of the polymerization initiator used is preferably 0.2 to 2.0 parts by mass, more preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the monomer.
  • chain transfer agent examples include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid
  • Thiol chain transfer agents such as n-dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.)
  • Sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof sodium hydrogensulfite, potassium hydrogensulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.
  • the monomer polymerization temperature (reaction system temperature) in the first reactor (10) is appropriately selected depending on the type of the polymerization initiator and the like, but is preferably 60 because the polymerization proceeds smoothly. C. to 100.degree. C., more preferably 70.degree. C. to 90.degree.
  • the polymerization of the continuously supplied monomer is completed not in the first reactor (10) but in the second reactor (20) or the third reactor (30).
  • the reaction liquid (S1) obtained in the first reactor (10) and supplied to the second reactor (20) usually contains a polymer, a monomer, a polymerization initiator, and the like.
  • reaction liquid (S2) obtained in the second reactor (20) and supplied to the third reactor (30) in addition to the polymer, a monomer, a polymerization initiator, and the like may be included.
  • the average residence time of the monomer in the first reactor (10) is preferably 30 to 300 minutes, more preferably 50 to 200 minutes.
  • the polymerization performed in the second reactor (20) may be performed only on the monomer contained in the reaction liquid (S1), and if necessary, the supplied single unit. It may be performed together with the mass.
  • a polymerization initiator, a polymerization medium and the like may be accommodated in advance.
  • the temperature of the reaction system in the second reactor (20) is preferably 60 ° C. to 100 ° C., more preferably 70 ° C. to 90 ° C.
  • the polymerization temperature may be the same as or different from the temperature in the first reactor (10).
  • the average residence time of the monomer in the second reactor (20) is preferably 20 to 200 minutes, more preferably 30 to 100 minutes, since the polymerization is completed while forming a uniform polymer.
  • the third reactor (30) polymerization of monomers remaining in the reaction liquid (S2) sent from the second reactor (20), and acrylic acid contained in the reaction liquid (S2) Neutralization of the precursor of the system copolymer is performed. Since the pH of the reaction solution (S2) is usually in the range of 1.0 to 5.0, neutralization usually involves alkali metal hydroxides such as sodium and potassium, chlorides or carbonates; Alkaline earth metal hydroxides such as calcium and magnesium, chlorides or carbonates; ammonia; alkaline aqueous solutions in which alkaline substances such as organic amines such as monoethanolamine, diethanolamine and triethanolamine are dissolved in water are used It is done. The said alkaline substance may be used independently and may be used in combination of 2 or more type. In the third reactor (30), a polymerization medium or the like may be stored in advance.
  • alkali metal hydroxides such as sodium and potassium, chlorides or carbonates
  • Alkaline earth metal hydroxides such as calcium and magnesium, chlorides or carbonates
  • the pH of the polymer-containing liquid in the third reactor (30) is adjusted to 9 or less, preferably in the range of 3.0 to 8.0, with the alkaline aqueous solution.
  • an AA / ATBS polymer-containing liquid substantially consisting of an acrylic acid copolymer having a Mw of 2000 to 30000 and a solid content concentration of preferably 30 to 50% by mass is obtained.
  • the polymerization medium is water, an aqueous polymer solution is obtained.
  • the polymerization reaction can proceed under the condition of a constant sodium concentration. Therefore, a phenomenon such as a change in polymerization rate due to a change in sodium concentration hardly occurs, and as a result, a homogeneous AA / ATBS system having a Mw of 2000 to 30000 is suppressed while suppressing the formation of a high molecular weight polymer having a molecular weight exceeding 70000. A polymer can be obtained.
  • the acrylic acid copolymer of the present invention is a water treatment agent having an excellent effect of suppressing scale formation with respect to calcium phosphate, a scale formation inhibitor other than calcium phosphate, a dispersant such as inorganic particles, a surfactant, an antistatic agent, and a detergent composition. It is suitable as a constituent component.
  • the water treatment agent of the present invention contains the AA / ATBS polymer of the present invention, and is usually a composition further containing water.
  • the kind of AA / ATBS polymer is not particularly limited, and may be one kind or two or more kinds.
  • the content ratio of the AA / ATBS polymer in the water treatment agent of the present invention is preferably 5 to 45% by mass, more preferably 10 to 35% by mass, since the effect as a water treatment agent can be sufficiently obtained. .
  • the water treatment agent of the present invention can suppress other scales such as polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, a (meth) acrylic acid copolymer, a styrene / maleic acid copolymer, etc.
  • Agents, bactericides, anticorrosives, antislime agents, antifoaming agents, and the like are examples of the water treatment agent of the present invention.
  • the water treatment agent of the present invention is suitable for, for example, calcium phosphate that easily adheres to the heat transfer surface of a heat exchanger, piping of cooling water, and the like. Therefore, by using the water treatment agent of the present invention, for example, problems such as a decrease in heat exchange efficiency and blockage of piping in a cooling water system, a boiler water system, a seawater desalination apparatus, and the like can be suppressed.
  • Example 1 (Production by continuous polymerization) The first reactor (10), the second reactor (20), and the third reactor (30) were charged with 2100 g of water and maintained at 75 ° C. Thereafter, while stirring the inside of the first reactor (10), a 60% aqueous solution of acrylic acid (hereinafter also referred to as “60% AA”) was added at 11.0 g / min, sodium 2-acrylamido-2-methylpropanesulfonate.
  • 60% AA 60% aqueous solution of acrylic acid
  • 50% aqueous solution (hereinafter also referred to as “50% ATBSNa”) at 9.0 g / min, sodium persulfate 15% aqueous solution (hereinafter also referred to as “15% NPS”) at 0.5 g / min, hypophosphorous acid Polymerization was carried out by supplying a 30% aqueous solution of sodium acid (hereinafter also referred to as “30% NHP”) at 2.5 g / min. Simultaneously with the supply of these raw materials (15), the reaction liquid in the first reactor (10) is transferred to the second reactor (20) at 23.0 g / min, and the first reactor (10 The amount of liquid in) was 2100 g. The average residence time of the reaction liquid in the first reactor (10) was 90 minutes.
  • the second reactor (20) the supply of the reaction solution from the first reactor (10) has started, and at the same time, the reaction solution in the second reactor (20) was fed at a rate of 23.0 g / min. The solution was transferred to (30).
  • polymerization was continued under stirring, keeping a liquid quantity at 2100g, and the average residence time of the reaction liquid in the 2nd reactor (20) was 90 minutes.
  • the third reactor (30) the supply of the reaction solution (pH 4.0) from the second reactor (20) started, and at the same time, the supply of 48% aqueous solution of water and NaOH, and the third reactor The reaction solution in (30) was discharged and collected.
  • ⁇ GPC measurement conditions> Apparatus: HLC8020 system manufactured by Tosoh Corporation Detection: RI Column: Tosoh G4000PWxl, G3000PWxl and G2500PWxl are connected Eluent: 0.1 M NaCl + phosphate buffer (pH 7) Standard: Polyacrylic acid Na manufactured by Soka Science Co., Ltd.
  • Example 2 (Production by continuous polymerization) The same operation as in Example 1 was performed except that a 30% aqueous solution of sodium hydrogen sulfite (hereinafter also referred to as “30% NaHSO 3 ”) was used instead of 30% NHP, and the solid content concentration was 40%.
  • a pH 7.0 aqueous polymer solution containing the acrylic acid copolymer (E2) was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E2) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 3 (Production by continuous polymerization) Except having changed the usage-amount of 60% AA and 50% ATBSNa, operation similar to Example 1 was performed, and the acrylic acid-type copolymer (E3) whose solid content concentration is 40% is contained, and pH 7.0 is set. A polymer aqueous solution was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E3) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 4 (Production by continuous polymerization) Except having changed the usage-amount of 60% AA and 50% ATBSNa, operation similar to Example 2 was performed, the acrylic acid-type copolymer (E4) whose solid content concentration is 40%, pH 7.0 was included. A polymer aqueous solution was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E4) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 5 (Production by continuous polymerization) Except having changed the usage-amount of 60% AA and 50% ATBSNa, operation similar to Example 1 was performed, and the acrylic acid-type copolymer (E5) whose solid content concentration is 40% is contained, and pH 7.0 is set. A polymer aqueous solution was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E5) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 6 (Production by continuous polymerization) Except having changed the usage-amount of 60% AA and 50% ATBSNa, operation similar to Example 2 was performed, the acrylic acid-type copolymer (E6) whose solid content concentration is 40%, pH 7.0 was included. A polymer aqueous solution was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E6) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 7 (Production by continuous polymerization) Except that the amount of 30% NHP used was changed, the same operation as in Example 1 was performed, and an aqueous polymer solution having a pH of 7.0 containing an acrylic acid copolymer (E7) having a solid content concentration of 40% was obtained. Obtained (see Table 1). Thereafter, the acrylic acid copolymer (E7) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 8 (Production by continuous polymerization) Except for changing the amount of 30% NaHSO 3 used, the same operation as in Example 2 was performed, and an aqueous polymer solution having a pH of 7.0 containing an acrylic acid copolymer (E8) having a solid content concentration of 40%. (See Table 1). Thereafter, the acrylic acid copolymer (E8) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 9 (Production by continuous polymerization) Except that the amount of 30% NHP used was changed, the same operation as in Example 1 was performed, and an aqueous polymer solution having a pH of 7.0 containing an acrylic acid copolymer (E9) having a solid content concentration of 40% was obtained. Obtained (see Table 1). Thereafter, the acrylic acid copolymer (E9) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 10 (Production by continuous polymerization) Except for changing the amount of 30% NaHSO 3 used, the same operation as in Example 2 was performed, and an aqueous polymer solution having a pH of 7.0 containing an acrylic acid copolymer (E10) having a solid content concentration of 40%. (See Table 1). Thereafter, the acrylic acid copolymer (E10) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 11 (Production by continuous polymerization) The same operation as in Example 1 was carried out except that 50% ATBSNa was used in combination with 5.0 g / min and 50% ATBSNa was used in combination with 5.0 g / min instead of 50% ATBSNa alone.
  • Example 12 (Production by continuous polymerization) In place of the single use of 50% ATBSNa, the same operation as in Example 2 was carried out except that 50% ATBSNa was used in combination with 5.0 g / min and 50% ATBSNa was used with 5.0 g / min.
  • a polymer aqueous solution having a pH of 7.0 containing an acrylic acid copolymer (E12) having a partial concentration of 40% was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E12) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 13 (Production by continuous polymerization) Acrylic acid copolymer having a solid content of 40% was carried out in the same manner as in Example 1 except that 50% ATBS was used in place of 50% ATBSNa and the supply rate was 8.0 g / min. A polymer aqueous solution having a pH of 7.0 containing the coalescence (E13) was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E13) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Example 14 (Production by continuous polymerization) Acrylic acid copolymer having a solid content concentration of 40%, except that 50% ATBS is used in place of 50% ATBSNa and the supply amount is 8.0 g / min. A polymer aqueous solution having a pH of 7.0 containing the coalescence (E14) was obtained (see Table 1). Thereafter, the acrylic acid copolymer (E14) was analyzed in the same manner as in Example 1, and the results are also shown in Table 1.
  • Comparative Example 1 (Production by semi-batch polymerization) A reactor equipped with a stirrer and a condenser was charged with 250 g of water and maintained at 75 ° C. Next, a mixed solution of 470 g of 70% AA and 450 g of 50% ATBSNa, 25 g of 15% NPS, and 100 g of a 30% aqueous sodium hypophosphite solution were respectively supplied to the reactor over 3 hours, and polymerization was performed with stirring. . After the supply of the raw materials was completed, the reaction system was aged for 1 hour with stirring while maintaining the reaction system at 75 ° C.
  • Comparative Example 2 (Production by batch polymerization) The same procedure as in Comparative Example 1 was performed except that 30% NaHSO 3 was used instead of 30% NHP, and the acrylic acid-based copolymer (C2) having a solid content concentration of 40% was contained, and the pH was 7.0. An aqueous polymer solution was obtained. Thereafter, the acrylic acid copolymer (C2) was analyzed in the same manner as in Example 1. As a result, Mw was 12000 and Mw / Mn was 3.8. Moreover, the content rate of the acrylic acid type copolymer of molecular weight 70000 or more calculated
  • the suppression rate of the water treatment agent containing the acrylic acid copolymer obtained in Comparative Examples 1 and 2 was 81%.
  • the suppression rate was as high as 90 to 99% (see Table 1).
  • the acrylic acid copolymer of the present invention is a water treatment agent having an excellent effect of suppressing scale formation with respect to calcium phosphate, a scale formation inhibitor other than calcium phosphate, a dispersant such as inorganic particles, a surfactant, an antistatic agent, and a detergent composition. It is suitable as a constituent component.
  • the water treatment agent of the present invention is suitable for, for example, calcium phosphate that easily adheres to the heat transfer surface of a heat exchanger, piping of cooling water, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Le copolymère à base d'acide acrylique de l'invention contient : une unité structurelle (x) dérivée d'un acide acrylique ou d'un sel de sodium de celui-ci ; et une unité structurelle (y) dérivée d'un acide 2-acrylamide-2-méthylpropanesulfonique ou d'un sel de sodium de celui-ci. La proportion des teneurs en unité structurelle (x) et en unité structurelle (y), est comprise respectivement entre 35 et 90% en masse et 10 et 65% en masse, lorsque le total des deux équivaut à 100% en masse. Ce copolymère à base d'acide acrylique présente une masse moléculaire moyenne en poids comprise entre 2000 et 30000, et la proportion de la teneur en copolymère à base d'acide acrylique de masse moléculaire supérieure ou égale à 70000, est inférieure ou égale à 0,30% en masse pour la masse totale de l'ensemble du polymère.
PCT/JP2015/071561 2014-09-22 2015-07-29 Copolymère à base d'acide acrylique ainsi que procédé de fabrication de celui-ci, et agent de traitement de l'eau Ceased WO2016047267A1 (fr)

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SG11201702148RA SG11201702148RA (en) 2014-09-22 2015-07-29 Acrylic acid-based copolymer, method for producing same and water treatment agent
CN201580043910.0A CN106574021B (zh) 2014-09-22 2015-07-29 丙烯酸系共聚物及其制造方法以及水处理剂
JP2016550010A JP6504177B2 (ja) 2014-09-22 2015-07-29 アクリル酸系共重合体の製造方法

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CN114213571A (zh) * 2021-12-17 2022-03-22 科威天使环保科技集团股份有限公司 一种三元共聚物阻垢剂的制备方法
JP7049517B1 (ja) 2021-12-27 2022-04-06 日本パーカライジング株式会社 リン酸亜鉛化成処理用表面調整剤

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