CA2844585A1 - Polymer mixtures as deposit inhibitors in water-bearing systems - Google Patents
Polymer mixtures as deposit inhibitors in water-bearing systems Download PDFInfo
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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
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or 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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- 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
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- 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
Abstract
A polymer mixture in solid or aqueous form, comprising, based on the polymer fraction, (A) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 20 000 g/mol of (a1) 20 to 80% by weight of at least one monomer selected from the group consisting of C2 to C8 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, (a2) 20 to 80% by weight of at least one monoethylenically unsaturated C3 to carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 50 000 g/mol of (b1) 30 to 100% by weight of at least one monoethylenically unsaturated C3 to C8 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups, (b3) 0 to 70% by weight of at least one nonionic monomer of the formula (I) H2C=C(R1)(CH2)x O[R2-O]o-R3 (I), where R1 is hydrogen or methyl, R2 is identical or different, linear or branched, C2-C6 alkylene radicals, which can be arranged in blocks or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a number from 3 to 50.
Description
Polymer mixtures as deposit inhibitors in water-bearing systems Description The invention relates to polymer mixtures as deposit inhibitors for inhibiting the precipitation and sedimentation of calcium salts and magnesium salts in water-bearing systems.
The solubility of most substances in water is restricted. In particular, in industrial water treatment, the prevention of mineral sediments in water-bearing systems is an essential task. Inorganic substances and salts such as calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate and barium sulfate, and calcium phosphate have a low solubility in water. If these dissolved components are concentrated in aqueous systems (thickening), the solubility product is exceeded with the consequence that these substances precipitate out and cause sediments. The solubility of the substances is, in addition, dependent on the temperature and the pH. In particular, many substances such as calcium carbonate, calcium sulfate or magnesium hydroxide exhibit an inverse solubility, i.e. their solubility decreases with increasing temperature. This leads to high process temperatures frequently being the cause of unwanted precipitates and formation of deposits in cooling and boiler feed water systems on heat-exchange surfaces or in pipelines.
Precipitates and sediments of inorganic substances and salts in water-bearing systems may only be removed again with great effort. Each mechanical and chemical cleaning is costly and time-consuming and inescapably leads to production failures.
Not only in cooling and boiler feed water systems are attempts made to prevent the formation of calcium carbonate deposits, calcium sulfate deposits, magnesium hydroxide deposits and other salt deposits. Also in seawater desalination by distillation and by membrane methods such as reverse osmosis or electrodialysis, efforts are made to prevent formation of these solid deposits. In particular in thermal seawater desalination
The solubility of most substances in water is restricted. In particular, in industrial water treatment, the prevention of mineral sediments in water-bearing systems is an essential task. Inorganic substances and salts such as calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate and barium sulfate, and calcium phosphate have a low solubility in water. If these dissolved components are concentrated in aqueous systems (thickening), the solubility product is exceeded with the consequence that these substances precipitate out and cause sediments. The solubility of the substances is, in addition, dependent on the temperature and the pH. In particular, many substances such as calcium carbonate, calcium sulfate or magnesium hydroxide exhibit an inverse solubility, i.e. their solubility decreases with increasing temperature. This leads to high process temperatures frequently being the cause of unwanted precipitates and formation of deposits in cooling and boiler feed water systems on heat-exchange surfaces or in pipelines.
Precipitates and sediments of inorganic substances and salts in water-bearing systems may only be removed again with great effort. Each mechanical and chemical cleaning is costly and time-consuming and inescapably leads to production failures.
Not only in cooling and boiler feed water systems are attempts made to prevent the formation of calcium carbonate deposits, calcium sulfate deposits, magnesium hydroxide deposits and other salt deposits. Also in seawater desalination by distillation and by membrane methods such as reverse osmosis or electrodialysis, efforts are made to prevent formation of these solid deposits. In particular in thermal seawater desalination
2 plants, both effects, namely firstly concentration by evaporation of water, and, secondly, high processing temperatures, play an important role.
The productivity of desalination plants is limited in this case by the upper processing temperature. It is desirable to operate seawater desalination plants at an evaporation temperature as high as possible in order to achieve a process efficiency as high as possible and to minimize the energy required for producing fresh water. For characterization of the process efficiency, the characteristic kWh/m3 of water is used. This characteristic can be minimized by process temperatures as high as possible for the multistage expansion evaporation process and the multiple effect evaporation process.
The maximum process temperature in these processes is limited, primarily, by the deposit formation which increases continuously with increasing temperature. It is known that, in particular, the sedimentation of basic magnesium salts such as magnesium hydroxide (brucite) and magnesium carbonate hydroxide (hydromagnesite), and also calcium carbonate and calcium sulfate play a critical role in thermal desalination plants.
It is known that low-molecular-weight polyacrylic acids and salts thereof produced by means of free-radical polymerization are employed as deposit inhibitors in industrial water treatment and in seawater desalination owing to the dispersant properties, and properties inhibiting crystal growth, thereof. For a good activity, the mean molecular weight (Mw) of these polymers should be <50 000 g/mol. Frequently, polyacrylic acids having Mw <10 000 g/mol are described as particularly effective. A disadvantage of these polymers is their sensitivity to hardness rising with increasing temperature, i.e. the risk that the polymers precipitate as Ca or Mg polyacrylates increases. In addition, the polyacrylic acids have only a very low inhibitory activity against sediments of brucite or hydromagnesite.
In addition, it is known that copolymers comprising sulfonic acid groups act as deposit inhibitors, in particular for avoiding deposits of calcium phosphates and calcium phosphonates. A disadvantage of these polymers is their limited activity for avoiding CaCO3 precipitates.
The productivity of desalination plants is limited in this case by the upper processing temperature. It is desirable to operate seawater desalination plants at an evaporation temperature as high as possible in order to achieve a process efficiency as high as possible and to minimize the energy required for producing fresh water. For characterization of the process efficiency, the characteristic kWh/m3 of water is used. This characteristic can be minimized by process temperatures as high as possible for the multistage expansion evaporation process and the multiple effect evaporation process.
The maximum process temperature in these processes is limited, primarily, by the deposit formation which increases continuously with increasing temperature. It is known that, in particular, the sedimentation of basic magnesium salts such as magnesium hydroxide (brucite) and magnesium carbonate hydroxide (hydromagnesite), and also calcium carbonate and calcium sulfate play a critical role in thermal desalination plants.
It is known that low-molecular-weight polyacrylic acids and salts thereof produced by means of free-radical polymerization are employed as deposit inhibitors in industrial water treatment and in seawater desalination owing to the dispersant properties, and properties inhibiting crystal growth, thereof. For a good activity, the mean molecular weight (Mw) of these polymers should be <50 000 g/mol. Frequently, polyacrylic acids having Mw <10 000 g/mol are described as particularly effective. A disadvantage of these polymers is their sensitivity to hardness rising with increasing temperature, i.e. the risk that the polymers precipitate as Ca or Mg polyacrylates increases. In addition, the polyacrylic acids have only a very low inhibitory activity against sediments of brucite or hydromagnesite.
In addition, it is known that copolymers comprising sulfonic acid groups act as deposit inhibitors, in particular for avoiding deposits of calcium phosphates and calcium phosphonates. A disadvantage of these polymers is their limited activity for avoiding CaCO3 precipitates.
3 In order to compensate for the disadvantages of certain polymers, frequently mixtures of a plurality of different polymers or copolymers are used. In the case of polymer mixtures, a synergistic activity is observed from time to time.
EP 388 836 discloses a mixture of a hydrolyzed polymaleic anhydride and a hydrolyzed copolymer of maleic anhydride and ethylenically unsaturated copolymers having a molecular weight from 400 to 800 g/mol for inhibiting scale sediments in aqueous systems.
.Ethylenically unsaturated comonomers mentioned are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, aconitic acid, itaconic anhydride, ethyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, vinyl acetate, styrene, alpha-methylstyrene, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methyl vinyl ketone, acrolein, ethylene and propylene.
US 2009/0101587 Al discloses a deposit-inhibiting composition comprising a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid and an oligomeric phosphinosuccinic acid.
US 5263541 discloses a mixture of polyvinyl sulfonate and polyacrylic acid as calcium sulfate deposit inhibitor.
DE 41 07 322 describes a composition of a hydrolyzed homopolymer of maleic anhydride having a weight-average molecular weight of 400 to 800 and a carboxyl-comprising acrylic polymer having a molecular weight of 800 to 9500 as deposit inhibitor. Acrylic polymers mentioned are polyacrylic acid and polymethacrylic acid, and also copolymers of acrylic acid or methacrylic acid with a vinyl carboxylate or styrene.
US 4,936,987 describes a mixture of a copolymer of acrylic acid or methacrylic acid and 2-acrylamido-2-methylpropylsulfonic acid or 2-methacrylamido-2-methylpropylsulfonic acid and at least one further component. Further components mentioned are, inter alia, homopolymers of maleic acid or acrylic acid, and also copolymers of acrylamide and acrylate, copolymers of acrylic acid and 2-hydroxypropyl acrylate, or copolymers of maleic acid and sulfonated styrene.
EP 388 836 discloses a mixture of a hydrolyzed polymaleic anhydride and a hydrolyzed copolymer of maleic anhydride and ethylenically unsaturated copolymers having a molecular weight from 400 to 800 g/mol for inhibiting scale sediments in aqueous systems.
.Ethylenically unsaturated comonomers mentioned are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, aconitic acid, itaconic anhydride, ethyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, vinyl acetate, styrene, alpha-methylstyrene, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methyl vinyl ketone, acrolein, ethylene and propylene.
US 2009/0101587 Al discloses a deposit-inhibiting composition comprising a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid and an oligomeric phosphinosuccinic acid.
US 5263541 discloses a mixture of polyvinyl sulfonate and polyacrylic acid as calcium sulfate deposit inhibitor.
DE 41 07 322 describes a composition of a hydrolyzed homopolymer of maleic anhydride having a weight-average molecular weight of 400 to 800 and a carboxyl-comprising acrylic polymer having a molecular weight of 800 to 9500 as deposit inhibitor. Acrylic polymers mentioned are polyacrylic acid and polymethacrylic acid, and also copolymers of acrylic acid or methacrylic acid with a vinyl carboxylate or styrene.
US 4,936,987 describes a mixture of a copolymer of acrylic acid or methacrylic acid and 2-acrylamido-2-methylpropylsulfonic acid or 2-methacrylamido-2-methylpropylsulfonic acid and at least one further component. Further components mentioned are, inter alia, homopolymers of maleic acid or acrylic acid, and also copolymers of acrylamide and acrylate, copolymers of acrylic acid and 2-hydroxypropyl acrylate, or copolymers of maleic acid and sulfonated styrene.
4 JP 06154789 describes a composition of hydrolyzed copolymer of maleic anhydride and isobutene and hydrolyzed copolymer of maleic anhydride and aliphatic diene as deposit inhibitor. The inhibitor acts primarily against silicate and calcium carbonate deposits.
It is an object of the invention to provide compositions having an improved deposit-inhibiting activity which effectively prevent, in particular, precipitation and deposition of calcium carbonate, calcium sulfate and basic magnesium salts in the water-bearing systems.
The object is achieved by a polymer mixture in solid or aqueous form comprising, based on the polymer fraction, (A) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 20 000 g/mol of (al) 20 to 80% by weight of at least one monomer selected from the group consisting of C2 to 08 olefins, ally' alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of Ci to 04 monocarboxylic acids, (a2) 20 to 80%
by weight of at least one monoethylenically unsaturated 03 to 08 carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 50 000 g/mol of (bl) 30 to 100% by weight of at least one monoethylenically unsaturated 03 to C8 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups, (b3) 0 to 70% by weight of one or more nonionic monomers of the formula (I) H2C=C(R1)(CH2),(0[R2-0}0-R3 (I),
It is an object of the invention to provide compositions having an improved deposit-inhibiting activity which effectively prevent, in particular, precipitation and deposition of calcium carbonate, calcium sulfate and basic magnesium salts in the water-bearing systems.
The object is achieved by a polymer mixture in solid or aqueous form comprising, based on the polymer fraction, (A) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 20 000 g/mol of (al) 20 to 80% by weight of at least one monomer selected from the group consisting of C2 to 08 olefins, ally' alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of Ci to 04 monocarboxylic acids, (a2) 20 to 80%
by weight of at least one monoethylenically unsaturated 03 to 08 carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 50 000 g/mol of (bl) 30 to 100% by weight of at least one monoethylenically unsaturated 03 to C8 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups, (b3) 0 to 70% by weight of one or more nonionic monomers of the formula (I) H2C=C(R1)(CH2),(0[R2-0}0-R3 (I),
5 where R1 is hydrogen or methyl, R2 is identical or different, linear or branched, Cr C8 alkylene radicals, which can be arranged in blocks or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a number from 3 to 50.
It has been found that mixtures of the polymers (A) and (B) have a higher activity in the inhibition of sediments of calcium carbonate, calcium sulfate and basic magnesium salts than the same amount of only one of the polymers (A) or (B) alone. One or more different polymers (A) can be mixed with one or more different polymers (B).
The polymer mixture according to the invention comprises 5 to 95% by weight of a water-soluble or water-dispersible polymer (A) of 20 to 80% by weight of at least one monomer (al) selected from the group consisting of C2 to C8 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, and 20 to 80% by weight of at least one monomer (a2) selected from unsaturated C3 to C8 carboxylic acids, anhydrides or salts of same, and also, optionally, 0 to 50% by weight of one or more monomers (a3) comprising sulfonic acid groups.
The polymer mixture comprises 5 to 95% by weight of a water-soluble or water-dispersible polymer (B) of 30 to 100% by weight of at least one monomer (bl) selected from monoethylenically unsaturated C3 to C8 carboxylic acids, anhydrides or salts of same, and also, optionally, 0 to 70% by weight of one or more monomers (b2) comprising sulfonic acid groups.
Suitable C2 to C8 olefins which can be used as monomer (al) are, for example, ethylene, propylene, n-butene, isobutene, 1-pentene, 1-hexene, 1-heptene and diisobutene, preferably isobutene and diisobutene.
It has been found that mixtures of the polymers (A) and (B) have a higher activity in the inhibition of sediments of calcium carbonate, calcium sulfate and basic magnesium salts than the same amount of only one of the polymers (A) or (B) alone. One or more different polymers (A) can be mixed with one or more different polymers (B).
The polymer mixture according to the invention comprises 5 to 95% by weight of a water-soluble or water-dispersible polymer (A) of 20 to 80% by weight of at least one monomer (al) selected from the group consisting of C2 to C8 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, and 20 to 80% by weight of at least one monomer (a2) selected from unsaturated C3 to C8 carboxylic acids, anhydrides or salts of same, and also, optionally, 0 to 50% by weight of one or more monomers (a3) comprising sulfonic acid groups.
The polymer mixture comprises 5 to 95% by weight of a water-soluble or water-dispersible polymer (B) of 30 to 100% by weight of at least one monomer (bl) selected from monoethylenically unsaturated C3 to C8 carboxylic acids, anhydrides or salts of same, and also, optionally, 0 to 70% by weight of one or more monomers (b2) comprising sulfonic acid groups.
Suitable C2 to C8 olefins which can be used as monomer (al) are, for example, ethylene, propylene, n-butene, isobutene, 1-pentene, 1-hexene, 1-heptene and diisobutene, preferably isobutene and diisobutene.
6 Suitable alkyl vinyl ethers which can be used as monomer (al) comprise 1 to 4 carbon atoms in the alkyl chain. Examples are vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether and vinyl isobutyl ether.
Vinyl esters of C1 to C4 monocarboxylic acids which can be used as monomer (al) are, for example, vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate.
Preferred monomers (al) are isobutene, diisobutene, vinyl acetate, vinyl methyl ether allyl alcohol and isoprenol. Particular preference is given to isobutene, diisobutene and isoprenol.
Suitable monoethylenically unsaturated C3-C8 carboxylic acids which can be used as monomer (a2) and (bl) are, for example, acrylic acid, methacrylic acid, ethacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid and also water-soluble salts thereof. If said unsaturated C3-C8 carboxylic acids can form anhydrides, these anhydrides are also suitable as monomer (al), for example maleic anhydride, itaconic anhydride and methacrylic anhydride.
Preferred monoethylenically unsaturated C3-C8 carboxylic acids are acrylic acid, methacrylic acid, maleic acid and fumaric acid and also anhydrides and water-soluble salts thereof. These are preferred both as monomer (a2) and monomer (bl). Water-soluble salts are, in particular, the sodium and potassium salts of the acids.
Monomers comprising sulfonic acid groups (a3) and (b2) are preferably those of the formulae (11a) and (11b) H2C=CH-X-S03H (11a), H2C=C(CH3)-X-S03H (11b), where X is an optionally present spacer group which can be selected from -(CH2),- where n =0 to 4, -C8I-14-, -CH2-0-C6H4-, -C(0)-NH-C(CH3)2-, -C(0)-NH-CH(CH2CH3)-, -C(0)NH-
Vinyl esters of C1 to C4 monocarboxylic acids which can be used as monomer (al) are, for example, vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate.
Preferred monomers (al) are isobutene, diisobutene, vinyl acetate, vinyl methyl ether allyl alcohol and isoprenol. Particular preference is given to isobutene, diisobutene and isoprenol.
Suitable monoethylenically unsaturated C3-C8 carboxylic acids which can be used as monomer (a2) and (bl) are, for example, acrylic acid, methacrylic acid, ethacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid and also water-soluble salts thereof. If said unsaturated C3-C8 carboxylic acids can form anhydrides, these anhydrides are also suitable as monomer (al), for example maleic anhydride, itaconic anhydride and methacrylic anhydride.
Preferred monoethylenically unsaturated C3-C8 carboxylic acids are acrylic acid, methacrylic acid, maleic acid and fumaric acid and also anhydrides and water-soluble salts thereof. These are preferred both as monomer (a2) and monomer (bl). Water-soluble salts are, in particular, the sodium and potassium salts of the acids.
Monomers comprising sulfonic acid groups (a3) and (b2) are preferably those of the formulae (11a) and (11b) H2C=CH-X-S03H (11a), H2C=C(CH3)-X-S03H (11b), where X is an optionally present spacer group which can be selected from -(CH2),- where n =0 to 4, -C8I-14-, -CH2-0-C6H4-, -C(0)-NH-C(CH3)2-, -C(0)-NH-CH(CH2CH3)-, -C(0)NH-
7 CH(CH3)CH2-, -C(0)NH-C(CH3)2CH2-, -C(0)NH-CH2CH(OH)CH2-, -C(0)NH-CH2-, -C(0)NH-CH2CH2- and -C(0)NH-CH2CH2CF12-=
Particularly preferred monomers comprising sulfonic acid groups are in this case 1-acrylamido-1-propanesulfonic acid (X = -C(0)NH-CH(CH2CH3)- in formula 11a), 2-acrylamido-2-propanesulfonic acid (X = -C(0)NH-CH(CH3)CH2- in formula 11a), 2-acrylamido-2-methylpropanesulfonic acid (AMPS, X = -C(0)NH-C(CH3)2CH2- in formula 11a), 2-methacrylamido-2-methylpropanesulfonic acid (X = -C(0)NH-C(CH3)2CH2-in formula 11b), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C(0)NH-CH2CH(OH)CH2- in formula 11b), allylsulfonic acid (X = CH2 in formula Ha), methallylsulfonic acid (X = CH2 in formula 11b), allyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11a), methallyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11b), 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methy1-2-propene-1-sulfonic acid (X =
CH2 in formula 11b), styrenesulfonic acid (X = C6H4 in formula 11a), vinylsulfonic acid (X not present in formula 11a), 3-sulfopropyl acrylate (X = -C(0)0-CH2CH2CH2- in formula Ha), 2-sulfoethyl methacrylate (X = -C(0)0-CH2CH2- in formula 11b), 3-sulfopropyl methacrylate (X = -C(0)0-CH2CH2CH2- in formula 11b), sulfomethacrylamide (X = -C(0)NH- in formula 11b), sulfomethylmethacrylamide (X = -C(0)NH-CH2- in formula 11b), and also salts of said acids. Suitable salts are generally water-soluble salts, preferably the sodium, potassium and ammonium salts of said acids.
Particular preference is given to 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropane-sulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) and methallylsulfonic acid, and also salts of said acids. These are preferred both as monomer (a3) and also (b2).
Very particularly preferred monomers comprising sulfonic acid groups are 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and allylsulfonic acid, and also water-soluble salts thereof, in particular sodium, potassium and ammonium salts thereof. These are preferred both as monomer (a3) and (b2).
Particularly preferred monomers comprising sulfonic acid groups are in this case 1-acrylamido-1-propanesulfonic acid (X = -C(0)NH-CH(CH2CH3)- in formula 11a), 2-acrylamido-2-propanesulfonic acid (X = -C(0)NH-CH(CH3)CH2- in formula 11a), 2-acrylamido-2-methylpropanesulfonic acid (AMPS, X = -C(0)NH-C(CH3)2CH2- in formula 11a), 2-methacrylamido-2-methylpropanesulfonic acid (X = -C(0)NH-C(CH3)2CH2-in formula 11b), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C(0)NH-CH2CH(OH)CH2- in formula 11b), allylsulfonic acid (X = CH2 in formula Ha), methallylsulfonic acid (X = CH2 in formula 11b), allyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11a), methallyloxybenzenesulfonic acid (X = -CH2-0-C6H4- in formula 11b), 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methy1-2-propene-1-sulfonic acid (X =
CH2 in formula 11b), styrenesulfonic acid (X = C6H4 in formula 11a), vinylsulfonic acid (X not present in formula 11a), 3-sulfopropyl acrylate (X = -C(0)0-CH2CH2CH2- in formula Ha), 2-sulfoethyl methacrylate (X = -C(0)0-CH2CH2- in formula 11b), 3-sulfopropyl methacrylate (X = -C(0)0-CH2CH2CH2- in formula 11b), sulfomethacrylamide (X = -C(0)NH- in formula 11b), sulfomethylmethacrylamide (X = -C(0)NH-CH2- in formula 11b), and also salts of said acids. Suitable salts are generally water-soluble salts, preferably the sodium, potassium and ammonium salts of said acids.
Particular preference is given to 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropane-sulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) and methallylsulfonic acid, and also salts of said acids. These are preferred both as monomer (a3) and also (b2).
Very particularly preferred monomers comprising sulfonic acid groups are 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and allylsulfonic acid, and also water-soluble salts thereof, in particular sodium, potassium and ammonium salts thereof. These are preferred both as monomer (a3) and (b2).
8 As component (b3), the copolymer comprises 0 to 70% by weight of at least one nonionic monomer of the formula (I) H2C=C(R1)(CH2),(0[R2-0]0-R3 (I).
where R' is hydrogen or methyl, R2 is identical or different C2-C6 alkylene radicals, which can be linear or branched and arranged in blocks and/or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a natural number from 3 to 50.
The alkylene radicals can also be arranged in blocks and randomly, that is to say in one or more blocks of identical alkylene oxide radicals in blocks and, in addition, randomly in one or more blocks of two or more different alkylene oxide radicals. This is also included by the wording "arranged in blocks or randomly".
Preferred nonionic monomers (b3) are those based on ally' alcohol (R1 = H; x =
1) and isoprenol (R1 = methyl; x = 2).
The nonionic monomer (b3) preferably comprises on average 8 to 40, particularly preferably 10 to 30, especially 10 to 25, alkylene oxide units. The index o in the formula (I) relates to the median number of alkylene oxide units.
Preferred alkylene oxide units R2-0 are ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide, particular preference is given to ethylene oxide and 1,2-propylene oxide.
In a special embodiment, the nonionic monomers (b3) only comprise ethylene oxide units.
In a further special embodiment, the nonionic monomers (b3) comprise ethylene oxide and 1,2-propylene oxide units which can be arranged in blocks or randomly.
Preferably, R3 is hydrogen or methyl.
where R' is hydrogen or methyl, R2 is identical or different C2-C6 alkylene radicals, which can be linear or branched and arranged in blocks and/or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a natural number from 3 to 50.
The alkylene radicals can also be arranged in blocks and randomly, that is to say in one or more blocks of identical alkylene oxide radicals in blocks and, in addition, randomly in one or more blocks of two or more different alkylene oxide radicals. This is also included by the wording "arranged in blocks or randomly".
Preferred nonionic monomers (b3) are those based on ally' alcohol (R1 = H; x =
1) and isoprenol (R1 = methyl; x = 2).
The nonionic monomer (b3) preferably comprises on average 8 to 40, particularly preferably 10 to 30, especially 10 to 25, alkylene oxide units. The index o in the formula (I) relates to the median number of alkylene oxide units.
Preferred alkylene oxide units R2-0 are ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide, particular preference is given to ethylene oxide and 1,2-propylene oxide.
In a special embodiment, the nonionic monomers (b3) only comprise ethylene oxide units.
In a further special embodiment, the nonionic monomers (b3) comprise ethylene oxide and 1,2-propylene oxide units which can be arranged in blocks or randomly.
Preferably, R3 is hydrogen or methyl.
9 Generally, the weight-average molecular weight of the copolymers (A) is 1000 to 20 000 g/mol, preferably 1500 to 15 000 g/mol, and particularly preferably 2000 to 000 g/mol, and in particular 2000 to 8000 g/mol.
5 The molecular weight is determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards.
Generally, the polydispersity index of the polymers (A) Mw/Mr, is 5 3.0, preferably 5 2.5.
5 The molecular weight is determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards.
Generally, the polydispersity index of the polymers (A) Mw/Mr, is 5 3.0, preferably 5 2.5.
10 The polymers (A) are preferably binary copolymers or terpolymers. If they are binary copolymers, they preferably comprise 20 to 60% by weight of monomer (al) and 40 to 80% by weight of monomer (a2), particularly preferably 25 to 50% by weight of monomer (al) and 50 to 75% by weight of monomer (a2).
If they are terpolymers, they preferably comprise 25 to 50% by weight of monomer (al), 30 to 60% by weight of monomer (a2) and 10 to 30% by weight of monomer (a3).
A plurality of different monomers (al) and/or a plurality of different monomers (a2) can also be present in the polymers A. For example, terpolymers and quaterpolymers can comprise only monomers (al) and (a2), preferably in the amounts stated above for binary copolymers.
In a preferred embodiment of the invention, polymer (A) is a copolymer of isobutene and maleic acid, preferably in the quantitative ratios stated above for binary copolymers.
In a further preferred embodiment of the invention, polymer (A) is a copolymer of isoprenol and maleic acid, preferably in the quantitative ratios cited above for binary copolymers.
In a further embodiment of the invention, polymer (A) is a terpolymer of isoprenol, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid, preferably in the quantitative ratios cited above for terpolymers. In a further preferred embodiment, allylsulfonic acid is used instead of 2-acrylamido-2-methylpropanesulfonic acid.
In a further embodiment of the invention, polymer (A) is a terpolymer of isoprenol, maleic acid and acrylic acid, preferably in the quantitative ratios cited above.
The polymers (B) are homopolymers or copolymers. Copolymers can comprise monomers 5 (b1), monomers (b1) and (b2), monomers (b1) and (b3), and monomers (b1), (b2) and (b3). If copolymers of the monomers (b1) and (b2) are concerned, they preferably comprise 50 to 90% by weight of monomers (b1) and 10 to 50% by weight of monomers (b2), particularly preferably 60 to 85% by weight of monomers (b1) and 15 to 40% by weight of monomers (b2).
If copolymers of the monomers (b1) and (b3) are concerned, they preferably comprise 50 to 95% by weight of monomers (b1) and 5 to 50% by weight of monomers (b3), particularly preferably 60 to 90% by weight of monomers (b1) and 10 to 40% by weight of monomers (b3).
If copolymers of the monomers (b1), (b2) and (b3) are concerned, they preferably comprise 30 to 80% by weight of monomers (b1), 10 to 50% by weight of monomers (b2) and 5 to 50% by weight of monomers (b3), particularly preferably 40 to 75% by weight of monomers (b1), 15 to 40% by weight of monomers (b2) and 5 to 40% by weight of monomers (b3). Preference is given to binary copolymers, but they can also be terpolymers.
In a preferred embodiment of the invention, the polymer (B) is an acrylic acid homopolymer.
In a further preferred embodiment of the invention, polymer (B) is a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, preferably in the quantitative ratios cited above.
In a further preferred embodiment of the invention, polymer (B) is a copolymer of acrylic acid and allylsulfonic acid, preferably in the quantitative ratios cited above.
If they are terpolymers, they preferably comprise 25 to 50% by weight of monomer (al), 30 to 60% by weight of monomer (a2) and 10 to 30% by weight of monomer (a3).
A plurality of different monomers (al) and/or a plurality of different monomers (a2) can also be present in the polymers A. For example, terpolymers and quaterpolymers can comprise only monomers (al) and (a2), preferably in the amounts stated above for binary copolymers.
In a preferred embodiment of the invention, polymer (A) is a copolymer of isobutene and maleic acid, preferably in the quantitative ratios stated above for binary copolymers.
In a further preferred embodiment of the invention, polymer (A) is a copolymer of isoprenol and maleic acid, preferably in the quantitative ratios cited above for binary copolymers.
In a further embodiment of the invention, polymer (A) is a terpolymer of isoprenol, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid, preferably in the quantitative ratios cited above for terpolymers. In a further preferred embodiment, allylsulfonic acid is used instead of 2-acrylamido-2-methylpropanesulfonic acid.
In a further embodiment of the invention, polymer (A) is a terpolymer of isoprenol, maleic acid and acrylic acid, preferably in the quantitative ratios cited above.
The polymers (B) are homopolymers or copolymers. Copolymers can comprise monomers 5 (b1), monomers (b1) and (b2), monomers (b1) and (b3), and monomers (b1), (b2) and (b3). If copolymers of the monomers (b1) and (b2) are concerned, they preferably comprise 50 to 90% by weight of monomers (b1) and 10 to 50% by weight of monomers (b2), particularly preferably 60 to 85% by weight of monomers (b1) and 15 to 40% by weight of monomers (b2).
If copolymers of the monomers (b1) and (b3) are concerned, they preferably comprise 50 to 95% by weight of monomers (b1) and 5 to 50% by weight of monomers (b3), particularly preferably 60 to 90% by weight of monomers (b1) and 10 to 40% by weight of monomers (b3).
If copolymers of the monomers (b1), (b2) and (b3) are concerned, they preferably comprise 30 to 80% by weight of monomers (b1), 10 to 50% by weight of monomers (b2) and 5 to 50% by weight of monomers (b3), particularly preferably 40 to 75% by weight of monomers (b1), 15 to 40% by weight of monomers (b2) and 5 to 40% by weight of monomers (b3). Preference is given to binary copolymers, but they can also be terpolymers.
In a preferred embodiment of the invention, the polymer (B) is an acrylic acid homopolymer.
In a further preferred embodiment of the invention, polymer (B) is a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, preferably in the quantitative ratios cited above.
In a further preferred embodiment of the invention, polymer (B) is a copolymer of acrylic acid and allylsulfonic acid, preferably in the quantitative ratios cited above.
11 Generally, the weight-average molecular weight of the polymers (B) is 1000 to 50 000 g/mol, preferably 1000 to 30 000 g/mol and particularly preferably 1500 to 20 000 g/mol, and in particular 1500 to 10 000 g/mol.
The molecular weight is determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards.
Generally, the polydispersity index of the polymers (B) Mw/Mn is 5 2.5, preferably 5 2Ø
The present invention also relates to compositions comprising (A) 3 to 95% by weight of the water-soluble or water-dispersible polymers having a weight-average molecular weight of 1000 to 20 000 g/mol of (al) 20 to 80% by weight of at least one monomer selected from the group consisting of 02 to 08 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, (a2) 20 to 80% by weight of at least one monoethylenically unsaturated C3 to carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 3 to 95% by weight of the water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 g/mol to 50 000 g/mol of (bl) 30 to 100% by weight of at least one monoethylenically unsaturated C3 to 08 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups,
The molecular weight is determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards.
Generally, the polydispersity index of the polymers (B) Mw/Mn is 5 2.5, preferably 5 2Ø
The present invention also relates to compositions comprising (A) 3 to 95% by weight of the water-soluble or water-dispersible polymers having a weight-average molecular weight of 1000 to 20 000 g/mol of (al) 20 to 80% by weight of at least one monomer selected from the group consisting of 02 to 08 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, (a2) 20 to 80% by weight of at least one monoethylenically unsaturated C3 to carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 3 to 95% by weight of the water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 g/mol to 50 000 g/mol of (bl) 30 to 100% by weight of at least one monoethylenically unsaturated C3 to 08 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups,
12 (b3) 0 to 70% by weight of one or more nonionic monomers of the formula (I) H2C=C(R1)(CH2),(0[R2-0]0-R3 (I), where R1 is hydrogen or methyl, R2 is identical or different, linear or branched, Cr 06 alkylene radicals, which can be arranged in blocks or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a number from 3 to 50, (C) 0 to 80% by weight of phosphonates, (D) 0 to 90% by weight of water;
(E) 0 to 50% by weight of additives such as polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors, biocides, complexing agents, surfactants or antifoams.
The weight ratio of polymers (A):(B) is generally from 1:20 to 20:1.
The compositions according to the invention can optionally comprise up to 80%
by weight phosphonates (C). Phosphonates can additionally support the deposit-inhibiting activity of the polymers. In addition, they act as corrosion inhibitors.
Examples of phosphonates are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 2-phos-phonobutane-1,2,4-tricarboxylic acid (PBTC), aminotrimethylenephosphonic acid (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediamine-tetra(methylenephosphonic acid) (EDTMP), and also the water-soluble salts thereof, in particular the sodium, potassium and ammonium salts thereof.
In addition, the compositions according to the invention can comprise up to 90% by weight of water.
(E) 0 to 50% by weight of additives such as polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors, biocides, complexing agents, surfactants or antifoams.
The weight ratio of polymers (A):(B) is generally from 1:20 to 20:1.
The compositions according to the invention can optionally comprise up to 80%
by weight phosphonates (C). Phosphonates can additionally support the deposit-inhibiting activity of the polymers. In addition, they act as corrosion inhibitors.
Examples of phosphonates are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 2-phos-phonobutane-1,2,4-tricarboxylic acid (PBTC), aminotrimethylenephosphonic acid (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediamine-tetra(methylenephosphonic acid) (EDTMP), and also the water-soluble salts thereof, in particular the sodium, potassium and ammonium salts thereof.
In addition, the compositions according to the invention can comprise up to 90% by weight of water.
13 In addition, the formulations can, in addition to the polymer mixtures according to the invention, optionally the phosphonates, and optionally water, according to requirements, also comprise up to 50% by weight of further additives (E) such as polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors such as benzotriazole, tolyltriazole, benzimidazole or ethynyl carbinol alkoxylates, biocides, complexing agents and/or surfactants.
The polymer mixtures of polymers (A) and (B) are generally produced by mixing the respective polymer solutions in stirred systems such as, e.g., in stirred tanks, by pneumatic circulation in containers, by circulation using pumps or by forced flow in pipes.
Internals in the stirred systems, termed flow baffles, can accelerate the mixing operation.
By installing fixed mixing elements in pipelines such as metal sheet lamellae, spirals or rigids, or mixing nozzles, the mixing operation can likewise be accelerated.
The choice of the mixer or the mixing process depends on the respective requirements, in particular the viscosities and shear strengths of the polymer solutions that are to be mixed.
Solid polymer mixtures can be produced by spray drying and spray granulation of the aqueous polymer mixtures or by mixing the solid polymers by means of rotating mixing drums, blade mixers, screw mixers, fluidized-bed mixers or air-shock mixers. The invention relates to both solid polymer mixtures, for example obtained by spray drying or spray granulation, and aqueous polymer mixtures. The water content of aqueous polymer mixtures is generally up to 90% by weight, preferably up to 70% by weight, particularly preferably up to 50% by weight.
The invention also relates to the use of the polymer mixtures and compositions as deposit inhibitors for inhibiting the precipitation and sedimentation of calcium salts and magnesium salts in water-bearing systems. Calcium salts the precipitation of which is inhibited are generally calcium carbonate, calcium sulfate, calcium phosphonates and calcium phosphates, in particular calcium carbonate and calcium sulfate. Magnesium salts the precipitation of which is inhibited are generally basic magnesium salts such as hydromagnesite and brucite.
The polymer mixtures of polymers (A) and (B) are generally produced by mixing the respective polymer solutions in stirred systems such as, e.g., in stirred tanks, by pneumatic circulation in containers, by circulation using pumps or by forced flow in pipes.
Internals in the stirred systems, termed flow baffles, can accelerate the mixing operation.
By installing fixed mixing elements in pipelines such as metal sheet lamellae, spirals or rigids, or mixing nozzles, the mixing operation can likewise be accelerated.
The choice of the mixer or the mixing process depends on the respective requirements, in particular the viscosities and shear strengths of the polymer solutions that are to be mixed.
Solid polymer mixtures can be produced by spray drying and spray granulation of the aqueous polymer mixtures or by mixing the solid polymers by means of rotating mixing drums, blade mixers, screw mixers, fluidized-bed mixers or air-shock mixers. The invention relates to both solid polymer mixtures, for example obtained by spray drying or spray granulation, and aqueous polymer mixtures. The water content of aqueous polymer mixtures is generally up to 90% by weight, preferably up to 70% by weight, particularly preferably up to 50% by weight.
The invention also relates to the use of the polymer mixtures and compositions as deposit inhibitors for inhibiting the precipitation and sedimentation of calcium salts and magnesium salts in water-bearing systems. Calcium salts the precipitation of which is inhibited are generally calcium carbonate, calcium sulfate, calcium phosphonates and calcium phosphates, in particular calcium carbonate and calcium sulfate. Magnesium salts the precipitation of which is inhibited are generally basic magnesium salts such as hydromagnesite and brucite.
14 Water-bearing systems in which the polymer mixtures are preferably employed are seawater desalination plants, brackish water desalination plants, cooling water systems and boiler feed water systems.
Surprisingly, it has also been found that the polymer mixtures according to the invention, owing to their dispersive properties and properties stabilizing Fe(III) ions, are outstandingly suitable for preventing iron-comprising sediments in water-bearing systems.
The invention therefore further relates to the employment of the polymer mixtures and compositions as deposit inhibitors for inhibiting the precipitation and sedimentation of iron-comprising salts and compounds. In particular, sedimentation of iron oxides and iron oxide hydrates (iron hydroxides) are prevented.
Generally, the mixtures according to the invention are added to the water-bearing systems in amounts from 0.1 mg/I to 100 mg/I. The optimum dosage depends on the requirements of the respective application or the operating conditions of the respective process. For instance, in the thermal desalination of seawater, the mixtures are preferably used in concentrations from 0.5 mg/I to 10 mg/I. In industrial cooling circuits or boiler feed water systems, dosages up to 100 mg/I are employed. Frequently, water analyses are carried out in order to determine the proportion of deposit-forming salts and thereby the optimum dosage.
The invention will be described in more detail by the examples hereinafter.
Examples The median molecular weights were determined by means of GPC.
Instrument:
Waters Alliance 2690 with UV-detector (Waters 2487) and RI detector (Waters 2410) Columns: Shodex 0Hpak SB 804HQ and 802.5HQ
(PHM gel, 8 x 300 mm, pH 4.0 to 7.5) Eluent: 0.05 M aqueous ammonium formate/methanol mixture = 80:20 (parts by volume) Flow rate: 0.5 ml/min Temperature: 50 C
5 Injection: 50 to 100 pl Detection: RI and UV
Molecular weights of the polymers were determined relative to polyacrylic acid standards from Varian Inc. The molecular weight distribution curves of the polyacrylic acid standards 10 were determined by light scattering. The masses of the polyacrylic acid standards were 115 000, 47 500, 28 000, 16 000, 7500, 4500, 4100, 2925 and 1250 g/mol.
Polymers 2, 3, 6, 7, 12 and 14 are produced by free-radical polymerization of the monomers in water using sodium peroxodisulfate as initiator and sodium hypophosphite
Surprisingly, it has also been found that the polymer mixtures according to the invention, owing to their dispersive properties and properties stabilizing Fe(III) ions, are outstandingly suitable for preventing iron-comprising sediments in water-bearing systems.
The invention therefore further relates to the employment of the polymer mixtures and compositions as deposit inhibitors for inhibiting the precipitation and sedimentation of iron-comprising salts and compounds. In particular, sedimentation of iron oxides and iron oxide hydrates (iron hydroxides) are prevented.
Generally, the mixtures according to the invention are added to the water-bearing systems in amounts from 0.1 mg/I to 100 mg/I. The optimum dosage depends on the requirements of the respective application or the operating conditions of the respective process. For instance, in the thermal desalination of seawater, the mixtures are preferably used in concentrations from 0.5 mg/I to 10 mg/I. In industrial cooling circuits or boiler feed water systems, dosages up to 100 mg/I are employed. Frequently, water analyses are carried out in order to determine the proportion of deposit-forming salts and thereby the optimum dosage.
The invention will be described in more detail by the examples hereinafter.
Examples The median molecular weights were determined by means of GPC.
Instrument:
Waters Alliance 2690 with UV-detector (Waters 2487) and RI detector (Waters 2410) Columns: Shodex 0Hpak SB 804HQ and 802.5HQ
(PHM gel, 8 x 300 mm, pH 4.0 to 7.5) Eluent: 0.05 M aqueous ammonium formate/methanol mixture = 80:20 (parts by volume) Flow rate: 0.5 ml/min Temperature: 50 C
5 Injection: 50 to 100 pl Detection: RI and UV
Molecular weights of the polymers were determined relative to polyacrylic acid standards from Varian Inc. The molecular weight distribution curves of the polyacrylic acid standards 10 were determined by light scattering. The masses of the polyacrylic acid standards were 115 000, 47 500, 28 000, 16 000, 7500, 4500, 4100, 2925 and 1250 g/mol.
Polymers 2, 3, 6, 7, 12 and 14 are produced by free-radical polymerization of the monomers in water using sodium peroxodisulfate as initiator and sodium hypophosphite
15 (polymers 2 and 7) and sodium bisulfite (polymers 3, 6, 12 and 14) as molecular weight modifier.
Polymers 4, 5, 8, 9 and 13 are produced by free-radical polymerization of the monomers using a redox system of hydrogen peroxide, iron(II) sulfate and sodium hydroxymethanesulfinate as initiator and mercaptoethanol as chain-transfer agent.
Polymers 1, 10 and 11 are produced by free-radical polymerization of maleic anhydride with the respective comonomers in o-xylene or toluene using t-butyl perpivalate as initiator.
Following the polymerization, a solvent exchange and hydrolysis of the anhydride ring are performed.
The aqueous polymer solutions are adjusted in each case to pH 7.5 (using sodium hydroxide solution) and a solids content of 40.0% by weight.
Polymers 1,4, 5, 8, 9, 10 and 11 are polymers (A) in accordance with the abovementioned definition.
Polymers 4, 5, 8, 9 and 13 are produced by free-radical polymerization of the monomers using a redox system of hydrogen peroxide, iron(II) sulfate and sodium hydroxymethanesulfinate as initiator and mercaptoethanol as chain-transfer agent.
Polymers 1, 10 and 11 are produced by free-radical polymerization of maleic anhydride with the respective comonomers in o-xylene or toluene using t-butyl perpivalate as initiator.
Following the polymerization, a solvent exchange and hydrolysis of the anhydride ring are performed.
The aqueous polymer solutions are adjusted in each case to pH 7.5 (using sodium hydroxide solution) and a solids content of 40.0% by weight.
Polymers 1,4, 5, 8, 9, 10 and 11 are polymers (A) in accordance with the abovementioned definition.
16 Polymers 2, 3, 6, 7, 12, 13 and 14 are polymers (B) in accordance with the abovementioned definition.
Polymer 1: Copolymer of maleic acid and isobutene (weight ratio 70:30), Na salt, Mw 4000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 2: Copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight ratio 75:25), Na salt, Mw 7000 g/mol, aqueous solution, pH 7.5, solids content:
40.0% by weight Polymer 3: Copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight ratio 75:25), Na salt, M, 8000 g/mol, aqueous solution, pH 7.5, solids content:
40.0% by weight Polymer 4: Copolymer of maleic acid and isoprenol (weight ratio 65:35), Na salt, Mw 4000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 5: Copolymer of maleic acid and isoprenol (weight ratio 60:40), Na salt, Mw 7500 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 6: Polyacrylic acid, Na salt, Mw 1200 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 7: Polyacrylic acid, Na salt, Mw 3500 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 8: Copolymer of maleic acid, isoprenol and 2-acrylamido-2-methylpropane-sulfonic acid (weight ratio 40:40:20), Na salt, Mw 7000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 9: Copolymer of maleic acid, isoprenol and acrylic acid (weight ratio 35:40:25), Na salt, Mw 3800 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight
Polymer 1: Copolymer of maleic acid and isobutene (weight ratio 70:30), Na salt, Mw 4000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 2: Copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight ratio 75:25), Na salt, Mw 7000 g/mol, aqueous solution, pH 7.5, solids content:
40.0% by weight Polymer 3: Copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (weight ratio 75:25), Na salt, M, 8000 g/mol, aqueous solution, pH 7.5, solids content:
40.0% by weight Polymer 4: Copolymer of maleic acid and isoprenol (weight ratio 65:35), Na salt, Mw 4000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 5: Copolymer of maleic acid and isoprenol (weight ratio 60:40), Na salt, Mw 7500 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 6: Polyacrylic acid, Na salt, Mw 1200 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 7: Polyacrylic acid, Na salt, Mw 3500 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 8: Copolymer of maleic acid, isoprenol and 2-acrylamido-2-methylpropane-sulfonic acid (weight ratio 40:40:20), Na salt, Mw 7000 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight Polymer 9: Copolymer of maleic acid, isoprenol and acrylic acid (weight ratio 35:40:25), Na salt, Mw 3800 g/mol, aqueous solution, pH 7.5, solids content: 40.0% by weight
17 Polymer 10: Copolymer of maleic acid and methyl vinyl ether (weight ratio 70:30), Na salt, Mw 9500 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 11: Copolymer of maleic acid and vinyl acetate (weight ratio 60:40), Na salt, Mw 6500 g/mol, aqueous solution, pH 7.5, solids content 40.0% by weight Polymer 12: Copolymer of acrylic acid and allylsulfonic acid (weight ratio 80:20), Na salt, Mw 5100, aqueous solution, solids content 40.0% by weight Polymer 13: Copolymer of acrylic acid and isoprenol polyethylene glycol of the formula CH2=C(CH3)CH2CH2-(E0)113-H (weight ratio 90:10), Na salt, Mw 6200 g/mol, aqueous solution, solids content 40.0% by weight Polymer 14: Terpolymer of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and allyl alcohol alkoxylate of the formula CH2=CHCH20-(E0)16-H (weight ratio 55:30:15), Na salt, Mw 8500 g/mol, aqueous solution, solids content 40.0% by weight The polymer mixtures are produced by mixing the 40% strength by weight polymer solutions. The amounts of solution are chosen in such a manner that a mixture of the desired polymer composition results. A mixture having a 50:50 composition has identical quantitative fractions (in % by weight) of the polymers used.
18 Use as deposit inhibitor Examples 1 to 3 Calcium carbonate inhibition test A solution of NaHCO3, Mg2SO4, CaCl2 and polymer is shaken for 2 h at 70 C in the water bath. After filtering the still-warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined complexometrically or by means of a Ca2+-selective electrode and the CaCO3 inhibition is determined by comparison of before/after in % in accordance with formula I hereinafter:
Ca2+ 215 mg/I
mg2+ 43 mg/I
HCO3- 1220 mg/I
Na + 460 mg/I
ci 380 mg/I
S042- 170 mg/I
Polymer mixture (100% strength) 3 mg/I
Temperature 70 C
Time 2 hours pH 8.0-8.5
Ca2+ 215 mg/I
mg2+ 43 mg/I
HCO3- 1220 mg/I
Na + 460 mg/I
ci 380 mg/I
S042- 170 mg/I
Polymer mixture (100% strength) 3 mg/I
Temperature 70 C
Time 2 hours pH 8.0-8.5
19 Formula I:
CaCO3 inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca 2+) blank value after 24 h x100 Table 1 Mixture Inhibition composition in '% [ok]
by weight Example 1 Polymer 4 58.4 Polymer 7 80.7 Mixture 4/7 50:50 83.4 Mixture 4/7 35:65 86.8 Example 2 Polymer 1 46.0 Polymer 3 64.8 Polymer 6 68.5 Mixture 1/3/6 30:30:40 72.0 Example 3 Polymer 1 46.0 Polymer 13 66.7 Mixture 1/13 25:75 73.2 Examples 4 to 7 Calcium sulfate inhibition test A solution of NaCl, Na2SO4, CaCl2 and polymer was shaken for 24 h at 70 C in the water bath. After filtration of the still-warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined complexometrically or by means of a Ca2+-selective electrode and the CaS0.4 inhibition in % determined by before/after comparison in accordance with formula ll hereinafter:
5 Ca 2+ 2940 mg/I
S042- 7200 mg/I
Na + 6400 mg/I
Cl- 9700 mg/I
Polymer mixture (100% strength) 10 mg/I
10 Temperature 70 C
Time 24 hours pH 8.0-8.5 Formula II:
CaSO4 inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca 2+) blank value after 24 h x 100 Table 2 Mixture Inhibition composition in % [A]
by weight Example 4 Polymer 5 51.9 Polymer 6 91.0 Mixture 5/6 50:50 93.7 Example 5 Polymer 7 68.9 Polymer 11 47.7 Mixture 7/11 70:30 72.3 Example 6 Polymer 4 58.4 Polymer 12 78.9 Mixture 4/12 25:75 81.3 Example 7 Polymer 4 58.4 Polymer 14 57.8 Mixture 4/14 50:50 66.0 Examples 8 to 10 Experiments on inhibiting basic Mg salt sediments (DSL method) The deposit-inhibiting activity of the polymers according to the invention is carried out using a modified version of the "Differential Scale Loop (DSL)" instrument from PSL
Systemtechnik. This is a "tube blocking system" as a fully automated laboratory system for studying precipitates and deposits of salts in pipelines and water pipes. In this instrument, in a modified mode of operation, a magnesium chloride solution A is mixed together with a sodium hydrogencarbonate solution B which comprises the polymer under test at a temperature of 120 C and a specific pressure of 2 bar at a mixing point in the volumetric ratio 1:1 and pumped at a constant flow rate through a test capillary of stainless steel at constant temperature. In this case, the differential pressure between mixing point (starter capillary) and capillary end is determined. A rise of the differential pressure indicates deposit formation within the capillary due to basic magnesium salts (hydromagnesite, brucite). The time measured up to a pressure rise of a defined height (0.1 bar) is a measure of the deposit-inhibiting activity of the polymer used.
The specific experimental conditions are:
Solution A: 100 mM MgCl2 Solution B: 200 mM NaHCO3 Concentration of the polymer after mixing A and B: 10 mg/I
Capillary length: 2.5 m Capillary diameter: 0.88 mm Capillary material: stainless steel Temperature: 120 C
Total flow rate: 5m1/min System pressure: 2 bar Pressure rise threshold: 0.1 bar Table 3: Time taken to pressurize by 0.1 bar (mean value from four measurements) Mixture composition Inhibition in % by weight [min]
Example 8 Polymer 1 18.5 Polymer 3 23.9 Mixture 1/3 50:50 28.0 Example 9 Polymer 2 23.5 Polymer 8 24.9 Mixture 2/8 40:60 30.3 Example 10 Polymer 6 8.2 Polymer 9 20.0 Polymer 10 17.7 Mixture 6/9/10 20:50:30 22.5
CaCO3 inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca 2+) blank value after 24 h x100 Table 1 Mixture Inhibition composition in '% [ok]
by weight Example 1 Polymer 4 58.4 Polymer 7 80.7 Mixture 4/7 50:50 83.4 Mixture 4/7 35:65 86.8 Example 2 Polymer 1 46.0 Polymer 3 64.8 Polymer 6 68.5 Mixture 1/3/6 30:30:40 72.0 Example 3 Polymer 1 46.0 Polymer 13 66.7 Mixture 1/13 25:75 73.2 Examples 4 to 7 Calcium sulfate inhibition test A solution of NaCl, Na2SO4, CaCl2 and polymer was shaken for 24 h at 70 C in the water bath. After filtration of the still-warm solution through a 0.45 pm Milex filter, the Ca content of the filtrate is determined complexometrically or by means of a Ca2+-selective electrode and the CaS0.4 inhibition in % determined by before/after comparison in accordance with formula ll hereinafter:
5 Ca 2+ 2940 mg/I
S042- 7200 mg/I
Na + 6400 mg/I
Cl- 9700 mg/I
Polymer mixture (100% strength) 10 mg/I
10 Temperature 70 C
Time 24 hours pH 8.0-8.5 Formula II:
CaSO4 inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24 h/mg (Ca2+) zero value ¨ mg (Ca 2+) blank value after 24 h x 100 Table 2 Mixture Inhibition composition in % [A]
by weight Example 4 Polymer 5 51.9 Polymer 6 91.0 Mixture 5/6 50:50 93.7 Example 5 Polymer 7 68.9 Polymer 11 47.7 Mixture 7/11 70:30 72.3 Example 6 Polymer 4 58.4 Polymer 12 78.9 Mixture 4/12 25:75 81.3 Example 7 Polymer 4 58.4 Polymer 14 57.8 Mixture 4/14 50:50 66.0 Examples 8 to 10 Experiments on inhibiting basic Mg salt sediments (DSL method) The deposit-inhibiting activity of the polymers according to the invention is carried out using a modified version of the "Differential Scale Loop (DSL)" instrument from PSL
Systemtechnik. This is a "tube blocking system" as a fully automated laboratory system for studying precipitates and deposits of salts in pipelines and water pipes. In this instrument, in a modified mode of operation, a magnesium chloride solution A is mixed together with a sodium hydrogencarbonate solution B which comprises the polymer under test at a temperature of 120 C and a specific pressure of 2 bar at a mixing point in the volumetric ratio 1:1 and pumped at a constant flow rate through a test capillary of stainless steel at constant temperature. In this case, the differential pressure between mixing point (starter capillary) and capillary end is determined. A rise of the differential pressure indicates deposit formation within the capillary due to basic magnesium salts (hydromagnesite, brucite). The time measured up to a pressure rise of a defined height (0.1 bar) is a measure of the deposit-inhibiting activity of the polymer used.
The specific experimental conditions are:
Solution A: 100 mM MgCl2 Solution B: 200 mM NaHCO3 Concentration of the polymer after mixing A and B: 10 mg/I
Capillary length: 2.5 m Capillary diameter: 0.88 mm Capillary material: stainless steel Temperature: 120 C
Total flow rate: 5m1/min System pressure: 2 bar Pressure rise threshold: 0.1 bar Table 3: Time taken to pressurize by 0.1 bar (mean value from four measurements) Mixture composition Inhibition in % by weight [min]
Example 8 Polymer 1 18.5 Polymer 3 23.9 Mixture 1/3 50:50 28.0 Example 9 Polymer 2 23.5 Polymer 8 24.9 Mixture 2/8 40:60 30.3 Example 10 Polymer 6 8.2 Polymer 9 20.0 Polymer 10 17.7 Mixture 6/9/10 20:50:30 22.5
Claims (23)
1. A polymer mixture in solid or aqueous form, comprising, based on the polymer fraction, (A) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 20 000 g/mol determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards, of (al) 20 to 80% by weight of at least one monomer selected from the group consisting of C2 to C8 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, (a2) 20 to 80% by weight of at least one monoethylenically unsaturated C3 to C8 carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 5 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 50 000 g/mol determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards, of (b1) 30 to 100% by weight of at least one monoethylenically unsaturated C3 to C8 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups, (b3) 0 to 70% by weight of one or more nonionic monomers of the formula (I) H2C=C(R1)(CH2)x O[R2-O]o-R3 (I), where R1 is hydrogen or methyl, R2 is identical or different, linear or branched, C2-C6 alkylene radicals, which can be arranged in blocks or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a number from 3 to 50.
2. The polymer mixture according to claim 1, characterized in that monomers (a1) are selected from the group consisting of isobutene, diisobutene, vinyl acetate, vinyl methyl ether, allyl alcohol and isoprenol
3 The polymer mixture according to claim 1 or 2, wherein monomer (a2) or (b1) is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, mesaconic acid and itaconic acid, anhydrides thereof and water-soluble salts thereof.
4. The polymer mixture according to any one of claims 1 to 3, wherein monomer (a3) or (b2) is selected from the group consisting of 1-acrylamidopropanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid (ALS) and methallylsulfonic acid and the water-soluble salts thereof.
The polymer mixture according to any one of claims 1 to 4, wherein the polymer (A) is a copolymer of 20 to 60% by weight of monomer (a1) and 40 to 80% by weight of monomer (a2).
6 The polymer mixture according to any one of claims 1 to 5, wherein the polymer (A) is a copolymer of isobutene and maleic acid
7. The polymer mixture according to any one of claims 1 to 5, wherein the polymer (A) is a copolymer of isoprenol and maleic acid.
8. The polymer mixture according to any one of claims 1 to 4, wherein the polymer (A) is a terpolymer of 25 to 50% by weight of monomer (al), 30 to 60% by weight of monomer (a2) and 10 to 30% by weight of monomer (a3).
9. The polymer mixture according to any one of claims 1 to 4 and 8, wherein the polymer (A) is a terpolymer of isoprenol, maleic acid and 2-acrylamido-2-methyl-propanesulfonic acid or a terpolymer of isoprenol, maleic acid and allylsulfonic acid.
10. The polymer mixture according to any one of claims 1 to 4 and 8, wherein the polymer (A) is a terpolymer of isoprenol, maleic acid and acrylic acid.
11. The polymer mixture according to any one of claims 1 to 10, wherein polymer (B) is a homopolymer of a monoethylenically unsaturated C3 tO C8 carboxylic acid, an anhydride or salt of same.
12. The polymer mixture according to claim 11, wherein polymer (B) is an acrylic acid homopolymer.
13. The polymer mixture according to any one of claims 1 to 10, wherein polymer (B) is a copolymer of 50 to 90% by weight of monomer (b1) and 10 to 50% by weight of monomer (b2).
14. The polymer mixture according to any one of claims 1 to 10, wherein polymer (B) is a copolymer of 50 to 95% by weight of monomer (b1) and 5 to 50% by weight of monomer (b3).
15. The polymer mixture according to any one of claims 1 to 10, wherein polymer (B) is a copolymer of 30 to 80% by weight of monomer (b1), 10 to 50% by weight of monomer (b2) and 5 to 50% by weight of monomer (b3).
16. The polymer mixture according to either claim 14 or 15, wherein monomer (b3) is that based on allyl alcohol (R1 = H; x = 1) or isoprenol (R1 = methyl; x = 2).
17. The polymer mixture according to any one of claims 1 to 10 and 13, wherein polymer (B) is a copolymer of acrylic acid and 2-acrylamido-2-methyl-propanesulfonic acid.
18. The polymer mixture according to any one of claims 1 to 10 and 13, wherein polymer (B) is a copolymer of acrylic acid and allylsulfonic acid.
19. A composition comprising (A) 3 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 20 000 g/mol determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards, of (a1) 20 to 80% by weight of at least one monomer selected from the group consisting of C2 to C8 olefins, allyl alcohol, isoprenol, C1 to C4 alkyl vinyl ethers and vinyl esters of C1 to C4 monocarboxylic acids, (a2) 20 to 80% by weight of at least one monoethylenically unsaturated C3 to C8 carboxylic acid, an anhydride or salt of same, (a3) 0 to 50% by weight of one or more monomers comprising sulfonic acid groups, (B) 3 to 95% by weight of a water-soluble or water-dispersible polymer having a weight-average molecular weight of 1000 to 50 000 g/mol determined by means of gel-permeation chromatography in comparison with polyacrylic acid standards, of (b1) 30 to 100% by weight of at least one monoethylenically unsaturated C3 to C8 carboxylic acid, an anhydride or salt of same, (b2) 0 to 70% by weight of one or more monomers comprising sulfonic acid groups, (b3) 0 to 70% by weight of one or more nonionic monomers of the formula (I) H2C=C(R1)(CH2)x O[R2-O]o-R3 (I), where R1 is hydrogen or methyl, R2 is identical or different, linear or branched, C2-C6 alkylene radicals, which can be arranged in blocks or randomly, and R3 is hydrogen or a straight-chain or branched C1-C4 alkyl radical, x is 0, 1 or 2, and o is a number from 3 to 50, (C) 0 to 80% by weight of phosphonates, (D) 0 to 90% by weight of water;
(E) 0 to 50% by weight of additives such as polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors, biocides, complexing agents, surfactants or antifoams.
(E) 0 to 50% by weight of additives such as polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors, biocides, complexing agents, surfactants or antifoams.
20. The use of polymer mixtures according to any one of claims 1 to 18 or of compositions according to claim 19 as deposit inhibitors in water-bearing systems.
21. The use according to claim 20 for inhibiting the precipitation and sedimentation of calcium salts and magnesium salts.
22. The use according to claim 21 for inhibiting the precipitation and sedimentation of calcium carbonate, calcium sulfate and basic magnesium salts.
23. The use according to any one of claims 20 to 22 in seawater desalination plants, brackish water desalination plants, cooling water systems and boiler feed water systems.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11177163 | 2011-08-10 | ||
| EP11177163.0 | 2011-08-10 | ||
| PCT/EP2012/065308 WO2013020937A1 (en) | 2011-08-10 | 2012-08-06 | Polymer blends as coating inhibitors in water-carrying systems |
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| CA2844585A1 true CA2844585A1 (en) | 2013-02-14 |
| CA2844585C CA2844585C (en) | 2019-09-17 |
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| EP (1) | EP2742008B1 (en) |
| JP (1) | JP2014527561A (en) |
| KR (1) | KR20140058555A (en) |
| CN (1) | CN103874663B (en) |
| AU (1) | AU2012293673B2 (en) |
| BR (1) | BR112014003040B1 (en) |
| CA (1) | CA2844585C (en) |
| CL (1) | CL2014000334A1 (en) |
| ES (1) | ES2561455T3 (en) |
| IL (1) | IL230884B (en) |
| MA (1) | MA35338B1 (en) |
| MX (1) | MX365529B (en) |
| RU (1) | RU2608409C2 (en) |
| TN (1) | TN2014000054A1 (en) |
| WO (1) | WO2013020937A1 (en) |
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| US9127235B2 (en) * | 2013-10-09 | 2015-09-08 | Ecolab Usa Inc. | Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control |
| US9635852B2 (en) | 2013-12-23 | 2017-05-02 | Dow Global Technologies Llc | Pymetrozine suspension concentrates and its preparation method |
| CN104710023B (en) * | 2015-02-15 | 2017-03-29 | 天津正达科技有限责任公司 | The preparation method of the special dirt dispersion agent of circularly-cooling sea water |
| JP6631147B2 (en) * | 2015-10-14 | 2020-01-15 | 栗田工業株式会社 | Boiler feed water treatment apparatus and boiler operating method |
| EP3370839A1 (en) | 2015-11-06 | 2018-09-12 | Basf Se | Processes for the separation of water from aqueous systems |
| US20190071610A1 (en) * | 2016-03-18 | 2019-03-07 | General Electric Company | Methods and compositions for prevention of fouling in caustic towers |
| TWI655157B (en) * | 2017-12-06 | 2019-04-01 | 中國鋼鐵股份有限公司 | Preparation for high temperature tolerance type of phosphate to inhabit corrosion and scaling and method for using the same |
| RU2702542C1 (en) * | 2019-07-02 | 2019-10-08 | Открытое акционерное общество "Всероссийский дважды ордена Трудового Красного Знамени теплотехнический научно-исследовательский институт" (ОАО "ВТИ") | Inhibitor of corrosion and scale formation for use in systems of reverse cooling of power plants or other industrial enterprises |
| CN112138873B (en) * | 2020-09-16 | 2021-05-18 | 东北大学 | Application of selective inhibitor EDTMPS in flotation and desilication of magnesite |
| CN112438254B (en) * | 2020-12-04 | 2022-06-03 | 中化化工科学技术研究总院有限公司 | Pesticide dispersing auxiliary and pesticide composition containing same |
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| US4936987A (en) | 1983-03-07 | 1990-06-26 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
| US4640793A (en) * | 1984-02-14 | 1987-02-03 | Calgon Corporation | Synergistic scale and corrosion inhibiting admixtures containing carboxylic acid/sulfonic acid polymers |
| NZ213578A (en) * | 1984-11-09 | 1988-04-29 | Calgon Corp | Inhibiting corrosion and scale deposition in aqueous systems by adding water soluble polymers |
| JP2592803B2 (en) * | 1985-06-26 | 1997-03-19 | ロ−ム アンド ハ−ス コンパニ− | Stabilization of aqueous systems |
| US4698161A (en) * | 1985-06-27 | 1987-10-06 | Pony Industries, Inc. | Polymer blend for dispersion of particulate materials in aqueous systems |
| US4925568A (en) * | 1986-08-15 | 1990-05-15 | Calgon Corporation | Polyacrylate blends as boiler scale inhibitors |
| JPS6490097A (en) * | 1987-09-30 | 1989-04-05 | Kurita Water Ind Ltd | Scaling inhibitor |
| CA1340659C (en) * | 1987-12-18 | 1999-07-20 | Edward Samuel Beardwood | Anti-scale and corrosion inhibitor |
| JPH01299699A (en) * | 1988-05-30 | 1989-12-04 | Hakutou Kagaku Kk | Non-phosphorus water treating agent for preventing corrosion and scale of metals in water system |
| GB8906413D0 (en) * | 1989-03-21 | 1989-05-04 | Ciba Geigy Ag | Composition for treating water or aqueous systems |
| JPH0360798A (en) * | 1989-07-26 | 1991-03-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Scale inhibitor for magnesium hydroxide |
| US5263541A (en) | 1989-11-01 | 1993-11-23 | Barthorpe Richard T | Inhibition of scale growth utilizing a dual polymer composition |
| GB9005440D0 (en) | 1990-03-10 | 1990-05-09 | Ciba Geigy Ag | Composition |
| CA2042341C (en) * | 1990-05-23 | 2001-06-12 | Judy H. Bardsley | Silica scale inhibition |
| US5080801A (en) * | 1991-04-03 | 1992-01-14 | Nalco Chemical Company | Mixed polymers for preventing scale caused by mineral processing water |
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2012
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- 2014-02-06 TN TNP2014000054A patent/TN2014000054A1/en unknown
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- 2014-02-10 CL CL2014000334A patent/CL2014000334A1/en unknown
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| CA2844585C (en) | 2019-09-17 |
| RU2608409C2 (en) | 2017-01-18 |
| CN103874663B (en) | 2016-04-20 |
| EP2742008B1 (en) | 2015-11-18 |
| CN103874663A (en) | 2014-06-18 |
| JP2014527561A (en) | 2014-10-16 |
| CL2014000334A1 (en) | 2014-08-01 |
| MX2014001534A (en) | 2014-02-27 |
| BR112014003040A2 (en) | 2017-03-21 |
| TN2014000054A1 (en) | 2015-07-01 |
| IL230884B (en) | 2019-12-31 |
| BR112014003040B1 (en) | 2020-11-17 |
| MA35338B1 (en) | 2014-08-01 |
| RU2014108707A (en) | 2015-09-20 |
| IL230884A0 (en) | 2014-03-31 |
| AU2012293673A1 (en) | 2014-03-06 |
| MX365529B (en) | 2019-06-06 |
| EP2742008A1 (en) | 2014-06-18 |
| WO2013020937A1 (en) | 2013-02-14 |
| ES2561455T3 (en) | 2016-02-26 |
| KR20140058555A (en) | 2014-05-14 |
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