Classifications

• • 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
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
  • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
  • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/14—Monomers containing only one unsaturated aliphatic radical
• • 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
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the present invention relates to a polycarboxylic acid copolymer. More specifically, the present invention relates to a polycarboxylic acid copolymer useful as a water treatment agent, etc.
• Polycarboxylic acid copolymers are water-soluble polymers that are widely used in various fields. Among them, low molecular weight ones have excellent chelating ability and dispersing performance, and are preferably used for various applications such as dispersants for inorganic pigments and metal ions, detergent builders, and water treatment agents such as anticorrosives and scale inhibitors. For example, in cooling water systems, boiler water systems, seawater desalination plants, pulp dissolving pots, black liquor concentration pots, etc., deposits (scale) such as calcium carbonate, zinc phosphate, calcium phosphate, zinc hydroxide, magnesium silicate, etc. adhere to the inner walls, which can cause operational problems such as reduced thermal efficiency and localized corrosion. Polycarboxylic acid copolymers are used as anticorrosives and scale inhibitors to suppress or remove the scale.
• Patent Document 1 discloses a silica scale inhibitor containing a (meth)acrylic acid-based copolymer, which is a copolymer containing structural units derived from (meth)acrylic acid (salt) and structural units derived from a monomer containing a sulfonic acid (salt) group, and which is characterized in that the structural units derived from the monomer containing a sulfonic acid (salt) group are 11 mol% or more relative to 100 mol% of the structures derived from all monomers, the copolymer has a sulfonic acid (salt) group at at least one main chain end, and has a weight average molecular weight of 20000 or more.
• Patent Document 2 discloses a silica scale inhibitor characterized in that it is obtained by adding an oxidizing agent to polyethylene glycol.
• Patent Document 3 discloses a silica scale inhibitor containing a (meth)acrylic acid-based copolymer that is a copolymer containing structural units derived from (meth)acrylic acid (salt) and structural units derived from a monomer containing a sulfonic acid (salt) group, and that is characterized in that the structural units derived from the monomer containing a sulfonic acid (salt) group are 11 mol% or more relative to 100 mol% of the structures derived from all monomers, and that has a weight average molecular weight of 9,200 or less.
• Patent Document 4 discloses a water-soluble copolymer that is characterized in that it is formed by polymerizing 45 to 95% by weight of a monomer containing a polyalkylene oxide group and 55 to 5% by weight of a monomer containing a sulfonic acid group.
• the present invention was made in consideration of the above-mentioned current situation, and aims to provide a copolymer that can suppress the precipitation of both magnesium silicate and silica polymer.
• the inventors conducted various studies on polycarboxylic acid copolymers and found that a copolymer having structural units derived from an unsaturated carboxylic acid monomer, a sulfonic acid group-containing monomer, a polyalkylene glycol monomer, and a hydrophobic monomer can suppress the precipitation of both magnesium silicate and silica polymer. They came to the conclusion that the above-mentioned problems could be solved perfectly, and thus arrived at the present invention.
• a polymerizable composition comprising a structural unit (a) derived from an unsaturated carboxylic acid monomer (A), a structural unit (b) derived from a sulfonic acid group-containing monomer (B), and a polymerizable compound represented by the following formula (1); (wherein R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom or a methyl group; R 4 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; (R 5 O) are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms; n is the average number of moles of oxyalkylene groups added and is a number from 1 to 300; x1 is a number from 0 to 4; and y1 is 0 or 1), comprising a structural unit (c) derived from a polyalkylene glycol monomer (C) and a structural formula (1);
• m is the average number of moles of oxyalkylene groups (-O-R 9 -) added and represents a number from 0 to 5.
• R 10 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R 11 and R 12 are the same or different and represent an alkyl group having 1 to 18 carbon atoms, with the proviso that the total carbon number of R 11 and R 12 is 4 or more.
• the polycarboxylic acid copolymer according to any one of [1] to [7] above which may have a structural unit (e) derived from a monomer (E) other than the unsaturated carboxylic acid monomer (A), the sulfonic acid group-containing monomer (B), the polyalkylene glycol monomer (C) and the hydrophobic monomer (D), and the proportion of the structural unit (e) is 0 to 30 mass% relative to 100 mass% of all structural units.
• a water treatment agent comprising a polycarboxylic acid copolymer, the polycarboxylic acid copolymer comprising a structural unit (a) derived from an unsaturated carboxylic acid monomer (A), a structural unit (b) derived from a sulfonic acid group-containing monomer (B), and a copolymer represented by the following formula (1);
• R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom or a methyl group.
• R 4 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
• R 5 O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms.
• n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 300.
• x1 is a number from 0 to 4.
• y1 is 0 or 1.
• a water treatment agent having a structural unit (c) derived from a polyalkylene glycol monomer (C) represented by the following formula, and a structural unit (d) derived from a hydrophobic monomer (D).
• the polycarboxylic acid copolymer of the present invention has the above-mentioned composition and can suppress the precipitation of both magnesium silicate and silica polymer, making it suitable for use in water treatment agents, etc.
• the polycarboxylic acid copolymer of the present invention (hereinafter also referred to as the copolymer of the present invention) has a structural unit (a) derived from an unsaturated carboxylic acid monomer (A), a structural unit (b) derived from a sulfonic acid group-containing monomer (B), a structural unit (c) derived from a polyalkylene glycol monomer (C) represented by the following formula (1), and a structural unit (d) derived from a hydrophobic monomer (D).
• the polycarboxylic acid copolymer has carboxyl group or its salt, polyoxyalkylene group and hydrophobic group, which mainly contributes to the suppression of silicate precipitation, and the polyoxyalkylene group mainly contributes to the suppression of silicate precipitation.
• the polycarboxylic acid copolymer has carboxyl group or its salt, and sulfonic acid group or its salt, which improves the solubility and hardness resistance of the polymer, and therefore it is considered that the effect of suppressing silicate precipitation and the effect of suppressing silicate precipitation can be fully exerted.
• the structural unit derived from a monomer is not limited to one formed by polymerizing a monomer, and may be one formed by a reaction other than a polymerization reaction.
• the content of the structural unit (a) is not particularly limited, but is preferably 15 to 95% by mass relative to 100% by mass of all structural units. It is more preferably 30 to 80% by mass, even more preferably 40 to 70% by mass, and particularly preferably 50 to 60% by mass.
• the content of the structural unit (b) is not particularly limited, but is preferably 0.1 to 40% by mass relative to 100% by mass of all structural units. More preferably, it is 0.5 to 30% by mass, even more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass.
• the content of the structural unit (c) is not particularly limited, but is preferably 5 to 80% by mass relative to 100% by mass of all structural units. It is more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.
• the content of the structural unit (d) is not particularly limited, but is preferably 0.1 to 20% by mass relative to 100% by mass of all structural units. More preferably, it is 0.5 to 15% by mass, even more preferably 2 to 12% by mass, and particularly preferably 5 to 9% by mass.
• the balance of each structural unit is favorable, resulting in superior ability to inhibit the precipitation of silicate and silica polymer.
• the copolymer may have a structural unit (e) derived from a monomer (E) other than the unsaturated carboxylic acid monomer (A), the sulfonic acid group-containing monomer (B), the polyalkylene glycol monomer (C), and the hydrophobic monomer (D).
• the proportion of the structural unit (e) in the copolymer is preferably 0 to 30% by mass relative to 100% by mass of all structural units. It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, particularly preferably 0 to 5% by mass, and most preferably 0% by mass.
• the copolymer preferably has a weight average molecular weight of 10,000 to 200,000. This provides a superior ability to inhibit precipitation of magnesium silicate and silica polymer.
• the weight average molecular weight is more preferably 15,000 to 100,000, further preferably 30,000 to 85,000, and particularly preferably 40,000 to 75,000. In one embodiment, the weight average molecular weight is also preferably 50,000 to 170,000.
• the weight average molecular weight can be measured by the method described in the Examples.
• the unsaturated carboxylic acid monomer (A) is not particularly limited as long as it has a carboxyl group or a salt thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), and may be a monomer represented by the following formula (6):
• R 13 , R 14 , and R 15 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, -(CH 2 ) p1 COOM 2 (-(CH 2 ) p1 COOM 2 may form an anhydride with -COOM 1 or another -(CH 2 ) p1 COOM 2 ), -(CH 2 ) p2 (CO) q1 -O-R 16 , or -(CH 2 ) p3 CONR 17 R 18.
• p1, p2, and p3 are the same or different and represent an integer of 0 to 2, and q1 represents 0 or 1.
• M 1 and M 2 are the same or different and represent a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, a quaternary ammonium group, or an organic amine group.
• R 16 , R 17 and R 18 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
• the number of carbon atoms in the alkyl group having 1 to 10 carbon atoms in the above R 13 , R 14 , and R 15 is preferably 1 to 8, and more preferably 1 to 4.
• the alkyl group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. It is preferable that at least one of the above R 13 , R 14 , and R 15 is a hydrogen atom, and more preferably at least two of them are hydrogen atoms.
• Examples of the hydrocarbon group having 1 to 30 carbon atoms in R 16 , R 17 , and R 18 include an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
• the monovalent metal atoms in M1 and M2 include, for example, alkali metal atoms such as lithium, sodium, and potassium.
• the divalent metal atoms include, for example, alkaline earth metal atoms such as calcium and magnesium.
• the trivalent metal atoms include, for example, aluminum and iron.
• the organic amine group includes, for example, alkanolamine groups such as ethanolamine group, diethanolamine group, and triethanolamine group, and triethylamine group.
• the above M1 and M2 are preferably hydrogen atoms or alkali metal atoms.
• unsaturated carboxylic acid monomer (A) include the following unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers.
• unsaturated monocarboxylic acid monomers include (meth)acrylic acid, crotonic acid, isocrotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, ⁇ -hydroxyacrylic acid, and the like; their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; half esters of the following unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms or glycols having 2 to 4 carbon atoms; and half amides of unsaturated dicarboxylic acid monomers and amines having 1 to 22 carbon atoms.
• Examples of the alcohols having 1 to 22 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, and icosanol.
• glycols having 2 to 4 carbon atoms examples include ethylene glycol, propylene glycol, and diethylene glycol.
• Examples of the amines having 1 to 22 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, dodecylamine, etc.
• the unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule, and examples thereof include maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, and their anhydrides.
• the unsaturated carboxylic acid monomer (A) is preferably (meth)acrylic acid (salt), maleic acid (salt) or maleic anhydride, more preferably (meth)acrylic acid (salt) from the viewpoint of improving the polymerizability.
• the sulfonic acid group-containing monomer (B) is not particularly limited as long as it has a sulfonic acid group or a salt thereof and an ethylenically unsaturated hydrocarbon group.
• Examples of the sulfonic acid group-containing monomer (B) include 3-(meth)allyloxy-2-hydroxypropanesulfonic acid, 2-(meth)allyloxyethylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid, ⁇ -methyl-p-styrenesulfonic acid, vinylsulfonic acid, vinylsulfamic acid, (meth)allyl sulfonic acid, isoprene sulfonic acid, 4-(allyloxy)benzenesulfonic acid, and the like.
• sulfonic acid examples include 1-methyl-2-propene-1-sulfonic acid, 1,1-dimethyl-2-propene-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-butene-3-sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-((meth)acryloyloxy)ethanesulfonic acid, 2-(meth)allyloxyethylenesulfonic acid, and salts thereof.
• the salt is not particularly limited, and examples thereof include the same salts as those represented by M1 and M2 in formula (6) above.
• the sulfonic acid group-containing monomer (B) is preferably 2-acrylamido-1-methylpropanesulfonic acid or a salt thereof, or a monomer represented by the following formula (7);
• R 19 represents a hydrogen atom or a methyl group
• R 20 represents a CH 2 group, a CH 2 CH 2 group, or a direct bond
• X 2 and Y 2 each independently represent a hydroxyl group or -SO 3 M 3
• M 3 represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group (with the proviso that at least one of X 2 and Y 2 represents -SO 3 M 3 ).
• R 19 in the above formula (7) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• R20 in the above formula (7) represents a CH2 group, a CH2CH2 group or a direct bond, and is preferably a CH2 group.
• X 2 and Y 2 each independently represent a hydroxyl group or -SO 3 M 3 , and at least one of X 2 and Y 2 represents -SO 3 M 3. In order to more fully exert the effects of the present invention, it is preferable that only one of X 2 and Y 2 is -SO 3 M 3 .
• M3 represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.
• M 3 is a metal atom, an ammonium group or an organic amine group
• --SO 3 M 3 represents a metal salt, an ammonium salt or an organic amine salt of a sulfonic acid.
• the metal atom and organic amine group in M3 may be the same as those in M1 and M2 .
• M3 is preferably a hydrogen atom, an alkali metal atom, or an ammonium group, more preferably a hydrogen atom, sodium, or potassium, and further preferably a hydrogen atom or sodium.
• the sulfonic acid group-containing monomer (B) is more preferably a monomer represented by the above formula (7), and even more preferably 3-(meth)allyloxy-2-hydroxypropanesulfonic acid or a salt thereof.
• the monomer represented by the above formula (7) has a hydroxyl group in its structure, and contributes to improving the solubility of the polymer after polymerization, particularly for polymers with large molecular weights.
• the polyalkylene glycol monomer (C) is represented by the following formula (1);
• R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom or a methyl group;
• R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms;
• R 5 O are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms;
• n represents the average number of moles of oxyalkylene groups added and is a number from 10 to 200;
• x1 represents a number from 0 to 4; and
• y1 represents 0 or 1.
• R 1 to R 3 are the same or different and each represents a hydrogen atom or a methyl group.
• R 1 and R 2 are hydrogen atoms
• R 3 is a hydrogen atom or a methyl group. More preferably, R 1 and R 2 are hydrogen atoms, and R 3 is a methyl group.
• R 4 in the above formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. It is preferably a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, more preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, even more preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and most preferably a hydrogen atom.
• Hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, i-propyl, sec-butyl, i-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 2- Aliphatic alkyl groups such as methylbutyl group, i-amyl group, ne
• cyclopropyl cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, cyclooctyl, cyclohexylpropyl, cyclododecyl, norbornyl (C7), adamantyl (C10), cyclopentylethyl, and other alicyclic alkyl groups; vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, and octadecenyl groups.
• icosenyl group and other alkenyl groups
• ethynyl group 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, icosenyl group, and other alkynyl groups
• R 5 O may be the same or different” and represent an oxyalkylene group having 2 to 18 carbon atoms, which means that the n oxyalkylene groups of R 5 O present in the polyalkylene glycol may all be the same or different.
• the oxyalkylene group preferably has 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms.
• the oxyalkylene group represented by R 5 O is an alkylene oxide adduct, and examples of such alkylene oxides include alkylene oxides having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, styrene oxide, etc. More preferred are alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and even more preferred are ethylene oxide and propylene oxide.
• the polyalkylene glycol is an adduct of any two or more kinds of alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form of random addition, block addition, alternating addition, etc.
• the oxyalkylene group in the polyalkylene glycol has an oxyethylene group as an essential component, more preferably 50 mol % or more of the oxyethylene group, and even more preferably 90 mol % or more of the oxyethylene group.
• n represents the average number of moles of oxyalkylene groups added, and is 1 to 300. n is preferably 5 to 200, more preferably 8 to 100, even more preferably 10 to 85, even more preferably 20 to 70, and particularly preferably 40 to 60.
• x1 represents a number from 0 to 4, and y1 represents 0 or 1.
• x1 is preferably 1 to 4.
• y1 is preferably 0. Since the monomer (A) in which y1 is 0 is inexpensive, the copolymer of the present invention can be produced at low cost.
• x1 is preferably 1 to 4, more preferably 1 or 2, and further preferably 2.
• R3 is preferably a methyl group.
• x1 is preferably 0. In this case, R3 is more preferably a hydrogen atom or a methyl group.
• polyalkylene glycol monomer (A) examples include (poly)alkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate and alkoxy (poly)alkylene glycol (meth)acrylates whose ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 2-methyl-2-buten-1-ol, 3-allyloxy-1,2-propanediol, and other unsaturated alcohols having 2 to 8 carbon atoms, with 1 to 300 moles of alkylene oxide added thereto, and compounds whose ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms.
• (poly)alkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate and alkoxy (poly)alkylene glyco
• compounds whose ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms and compounds whose ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms are preferred. More preferably, it is a compound in which 1 to 300 moles of alkylene oxide are added to an unsaturated alcohol having 2 to 8 carbon atoms, and even more preferably, it is a compound in which an alkylene oxide is added to (meth)allyl alcohol or 3-methyl-3-buten-1-ol.
• the hydrophobic monomer (D) may be any hydrophobic monomer, but is preferably a monomer having an ethylenically unsaturated group and a hydrocarbon group having 4 to 18 carbon atoms which may have a heteroatom.
• the hydrocarbon group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, even more preferably 4 to 6 carbon atoms, and particularly preferably 4 to 5 carbon atoms.
• the hydrocarbon group may have a heteroatom such as a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom or a halogen atom, and a carbon atom or a hydrogen atom constituting the hydrocarbon group may be substituted with a heteroatom, or it may have a substituent having a heteroatom.
• the substituent having a hetero atom is not particularly limited, but examples thereof include a hydroxyl group, an ether group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, an amino group, and a phosphoric acid group.
• the hydrophobic monomer (D) is more preferably a monomer represented by the following formula (2).
• R 6 , R 7 and R 8 are the same or different and each represents a hydrogen atom or a methyl group; x2 represents a number from 0 to 4; y2 represents 0 or 1; and Z represents a hydrocarbon group having 4 to 18 carbon atoms or a group represented by the following formula (3).
• X 1 and Y 1 represent a hydroxyl group or a group represented by the following formula (4) or (5), and one of X 1 and Y 1 is a hydroxyl group and the other is a group represented by the following formula (4) or (5).
• R 9 is the same or different and represents an alkylene group having 2 to 4 carbon atoms.
• m is the average number of moles of oxyalkylene groups (-O-R 9 -) added and represents a number from 0 to 5.
• R 10 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
• R 11 and R 12 are the same or different and represent an alkyl group having 1 to 18 carbon atoms, with the proviso that the total carbon number of R 11 and R 12 is 4 or more.
• x2 represents a number from 0 to 4, and y2 represents 0 or 1.
• Z when Z is a hydrocarbon group having 4 to 18 carbon atoms, it is preferable that x2 is 0 and y2 is 1.
• x2 when Z is a group represented by the above formula (3), x2 is preferably 1 to 4, more preferably 1 or 2, and y2 is preferably 0.
• R 6 to R 8 are the same or different and each represents a hydrogen atom or a methyl group.
• R 6 and R 7 are hydrogen atoms
• R 8 is a hydrogen atom or a methyl group. More preferably, R 6 to R 8 are hydrogen atoms.
• Z is a hydrocarbon group having 4 to 18 carbon atoms or a group represented by the above formula (3).
• the hydrocarbon group for Z preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, further preferably 4 to 6 carbon atoms, and particularly preferably 4 to 5 carbon atoms.
• the hydrocarbon group for Z is not particularly limited so long as it has 4 or more carbon atoms, and examples of the hydrocarbon group include an aliphatic alkyl group, an alicyclic alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Specific examples of these include those described above for R4 in formula (1).
• the hydrocarbon group represented by Z is preferably an aliphatic alkyl group or an alicyclic alkyl group.
• An aliphatic alkyl group is more preferred, and an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, or a hexyl group is even more preferred.
• X 1 and Y 1 are a hydroxyl group or a group represented by the above formula (4) or (5).
• one of X 1 and Y 1 is a hydroxyl group and the other is a group represented by the above formula (4).
• R 9 may be the same or different and represents an alkylene group having 2 to 4 carbon atoms.
• the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group.
• an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group, is preferred.
• the alkylene group one or more types can be used.
• m is the average number of moles of oxyalkylene groups (-O-R 9 -) added, and represents a number from 0 to 5.
• m is preferably 0 to 4, more preferably 0 to 3, even more preferably 0 to 2, particularly preferably 0 to 1, and most preferably 0.
• R 10 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms.
• the number of carbon atoms in R 10 is preferably 2 to 12, more preferably 3 to 8, further preferably 4 to 6, and particularly preferably 4 or 5.
• Specific examples of the alkyl group for R 10 include those mentioned for R 4 in the above formula (1).
• R 11 and R 12 are the same or different and are alkyl groups having 1 to 18 carbon atoms, and the total number of carbon atoms of R 11 and R 12 is 4 or more.
• the total number of carbon atoms of R 11 and R 12 is preferably 4 to 18, and more preferably 6 to 12.
• Specific examples of the alkyl group for R 11 and R 12 include those mentioned for R 4 in the above formula (1), with preferred examples being ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl and hexyl groups.
• the monomer represented by the above formula (2) include alkyl (meth)acrylates having an alkyl group with 4 to 18 carbon atoms, such as butyl (meth)acrylate and pentyl (meth)acrylate; and reaction products of a compound having a carbon-carbon double bond and an epoxy ring, such as (meth)allyl glycidyl ether and vinyl glycidyl ether, with an alcohol having 4 to 18 carbon atoms and/or an amine compound having an alkyl group with 1 to 18 carbon atoms.
• a reaction product of (meth)allyl glycidyl ether and an alcohol having 4 to 18 carbon atoms is preferred.
• Examples of the alcohol having 4 to 18 carbon atoms include butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, and dodecyl alcohol (lauryl alcohol).
• Examples of the amine compound having an alkyl group having 1 to 18 carbon atoms include di-n-isopropylamine, di-n-butylamine, and the like.
• the method for preparing the monomer represented by formula (2) above is not particularly limited, and any appropriate method can be used.
• a simple method for preparing the monomer is to react the hydroxyl group and/or amino group of an amine compound having an alcohol with 4 to 18 carbon atoms and/or an alkyl group with 1 to 18 carbon atoms with the epoxy ring of a compound having a carbon-carbon double bond and an epoxy ring.
• the reaction may be carried out without a catalyst, or in the presence of an acidic catalyst such as boron trifluoride or a basic catalyst such as sodium hydroxide or potassium hydroxide.
• the copolymer of the present invention may have a structural unit (e) derived from a monomer (E) other than the monomers (A) to (D).
• Other monomers (E) are not particularly limited as long as they can be copolymerized with the monomers (A) to (D), and examples thereof include N-vinyl lactam monomers such as N-vinylpyrrolidone; (meth)acrylic acid esters having an alkyl group having 1 to 3 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acid esters such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl acrylate
• the polycarboxylic acid copolymer of the present invention can be produced by polymerizing monomer components, specific and preferred examples of which are as described above.
• the content of each monomer component relative to 100% by mass of the total monomer components can be determined based on the ratio of the structural units (a) to (e) relative to 100% by mass of all structural units described above.
• a chain transfer agent can be used to adjust the molecular weight of the resulting polymer.
• chain transfer agents include thiol-based chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; secondary alcohols such as isopropyl alcohol; and hydrophilic chain transfer agents such as lower oxides and salts of phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (sodium sulfite, sodium hydrogen sulfite, sodium dithionite, sodium metabisulfite, etc.).
• Thiol-based chain transfer agents are preferred.
• the amount of the chain transfer agent used may be set appropriately, but is preferably 0.1 mol or more, more preferably 0.25 mol or more, and even more preferably 0.5 mol or more, relative to 100 mol of the total amount of the monomer components, and is preferably 10 mol or less, more preferably 7 mol or less, and even more preferably 5 mol or less.
• the above polymerization reaction can be carried out by a method such as solution polymerization or bulk polymerization, using a radical polymerization initiator as necessary.
• Solution polymerization can be carried out batchwise or continuously, or a combination of both.
• the solvent used in this case include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; and cyclic ether compounds such as tetrahydrofuran and dioxane.
• polymerization by the aqueous solution polymerization method is preferable.
• a water-soluble polymerization initiator for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azoamidine compounds such as 2,2'-azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2'-azobis-2-(2-imidazolin-2-yl)propane hydrochloride, and water-soluble azo-based initiators such as azonitrile compounds such as 2-carbamoylazoisobutyronitrile are used, and in this case, accelerators such as alkali metal sulfites such as sodium hydrogensulfite, metabisulfites, sodium hypophosphite, Fe(II) salts such as Mohr's salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiour
• a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate
• a promoter such as hydrogen peroxide and L-ascorbic acid (salt)
• a combination of hydrogen peroxide and L-ascorbic acid (salt) is more preferred.
• These radical polymerization initiators and accelerators may be used alone or in combination of two or more kinds.
• radical polymerization initiators When solution polymerization is carried out using a lower alcohol, an aromatic or aliphatic hydrocarbon, an ester compound, or a ketone compound as a solvent, or when bulk polymerization is carried out, peroxides such as benzoyl peroxide, lauroyl peroxide, and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; and azo compounds such as azobisisobutyronitrile are used as radical polymerization initiators.
• accelerators such as amine compounds can also be used in combination.
• the above-mentioned various radical polymerization initiators or combinations of radical polymerization initiators and accelerators can be appropriately selected and used.
• the amount of the radical polymerization initiator used is preferably 0.001 mol or more, more preferably 0.01 mol or more, even more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more, per 100 mol of the total amount of the monomer components, and is preferably 20 mol or less, even more preferably 10 mol or less, particularly preferably 5 mol or less, and most preferably 3 mol or less.
• polymerization conditions such as polymerization temperature are appropriately determined depending on the polymerization method, solvent, polymerization initiator, and chain transfer agent used, but the polymerization temperature is preferably 0°C or higher and 110°C or lower. It is more preferably 30°C or higher, and even more preferably 50°C or higher. It is also more preferably 100°C or lower, and even more preferably 80°C or lower.
• the method of feeding each monomer component into the reaction vessel is not particularly limited, and examples of the method include feeding the entire amount into the reaction vessel at once at the beginning; feeding the entire amount into the reaction vessel in portions or continuously; feeding a portion into the reaction vessel at the beginning and feeding the remainder into the reaction vessel in portions or continuously.
• the feeding rate of each monomer into the reaction vessel may be changed continuously or stepwise during the reaction to change the feeding weight ratio of each monomer per unit time continuously or stepwise, thereby synthesizing two or more copolymers with different monomer ratios simultaneously during the polymerization reaction.
• the radical polymerization initiator may be charged into the reaction vessel from the beginning, or may be added dropwise to the reaction vessel, or these may be combined depending on the purpose.
• the polycarboxylic acid copolymer of the present invention can be used as a water treatment agent (scaling inhibitor, anticorrosive agent, etc.), a fiber treatment agent, a dispersant, a bleach stabilizer, a metal ion sequestering agent, a thickener, various binders, an emulsifier, a skin care agent or a hair care agent, etc.
• a water treatment agent scaling inhibitor, anticorrosive agent, etc.
• the water treatment agent is useful for preventing scale formation in cooling water circulation systems, boiler water circulation systems, seawater desalination plants, reverse osmosis membrane treatment plants, pulp digesters, black liquor concentration plants, and the like.
• a silica scale inhibitor containing the polycarboxylic acid copolymer of the present invention is also one embodiment of the present invention.
• the water treatment agent may contain any suitable water-soluble polymer as long as the polymer does not affect the performance and effect of the water treatment agent.
• Detectors Refractive index (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2998) Eluent: 137.79 g of sodium dihydrogen phosphate dihydrate and 316.31 g of disodium hydrogen phosphate dodecahydrate were dissolved in a mixed solvent of 17,209.9 g of water and 1,536 g of acetonitrile.
• RI Refractive index
• PDA multi-wavelength visible ultraviolet
• borate buffer solution 7.420 g of boric acid, 1.753 g of sodium chloride, and 19.069 g of sodium borate decahydrate were mixed with ion-exchanged water to make a total of 1,000 g.
• Preparation of magnesium aqueous solution Ion-exchanged water was added to 8.115 g of magnesium sulfate heptahydrate to make a total of 1000 g.
• Preparation of an aqueous silica solution 2.129 g of sodium metasilicate nonahydrate was mixed with ion-exchanged water to make a total of 150 g.
• the amounts of ion-exchanged water and the aqueous polymer solution added were adjusted so that the total amount did not change.
• the polymer concentration was evaluated by changing it in increments of 5 ppm, and the amount of addition capable of maintaining the SiO2 concentration at 200 ppm or more was defined as the minimum amount of addition required for inhibiting silica scale.
• Example 1 (1) Synthesis of Monomer 370.0 parts of n-butyl alcohol and 4.3 parts of sodium hydroxide were charged into a glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), and a reflux condenser, and the temperature was raised to 60°C while stirring. Next, 57.0 parts of allyl glycidyl ether (hereinafter also referred to as "AGE”) was added over 30 minutes, and then the reaction was allowed to proceed for 5 hours. This solution was transferred to an eggplant flask and the solvent was removed using a rotary evaporator.
• AGE allyl glycidyl ether
• the dropping was carried out continuously at a constant speed, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes. After the dropwise addition of the mixed liquid 2 was completed, the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining the polymer (1) of the present disclosure.
• Example 2 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 96.9 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 3.1 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (101.1 parts), 50% AMPS (41.9 parts), IPN-50 (70.0 parts), monomer (1) (10.0 parts), and water (9.5 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.3 parts), 2-mercaptopropionic acid (2.5 parts), and water (47.2 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (2) of the present disclosure.
• Example 3 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 97.9 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 2.1 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (67.4 parts), 50% AMPS (28.0 parts), IPN-50 (110.0 parts), monomer (1) (10.0 parts), and water (34.7 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.2 parts), 2-mercaptopropionic acid (2.9 parts), and water (46.9 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (3) of the present disclosure.
• Example 4 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 97.9 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 2.1 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (67.4 parts), 50% AMPS (28.0 parts), IPN-50 (110.0 parts), monomer (1) (10.0 parts), and water (34.7 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.2 parts), 2-mercaptopropionic acid (1.7 parts), and water (48.1 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (4) of the present disclosure.
• Example 5 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 95.8 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 4.2 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (144.0 parts), 50% AMPS (17.7 parts), IPN-50 (32.0 parts), monomer (1) (16.0 parts), and water (40.3 parts), and mixed solution 2, which was a mixture of L-ascorbic acid (0.4 parts), 2-mercaptopropionic acid (2.5 parts), and water (47.1 parts), were simultaneously dropped from separate nozzles.
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (5) of the present disclosure.
• Example 6 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.3 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 2.7 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (77.4 parts), 50% AMPS (115.5 parts), IPN-50 (39.6 parts), monomer (1) (10.8 parts), and water (36.7 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.2 parts), 2-mercaptopropionic acid (2.1 parts), and water (27.7 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (6) of the present disclosure.
• Example 7 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 96.9 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60 ° C. under a nitrogen atmosphere, 3.1 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (101.1 parts), 50% AMPS (41.9 parts), IPN-50 (70.0 parts), monomer (1) (10.0 parts), and water (27.0 parts), and mixed solution 2, which was a mixture of L-ascorbic acid (0.3 parts), 2-mercaptopropionic acid (1.7 parts), and water (48.0 parts), were simultaneously dropped from separate nozzles.
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining the polymer (7) of the present disclosure.
• Example 8 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.2 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60° C. under a nitrogen atmosphere, 2.8 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• the dropwise addition was carried out continuously at a constant rate, and the entire amount of mixed liquid 1 was dropped over 150 minutes, and the entire amount of mixed liquid 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining polymer (8) of the present disclosure.
• Example 9 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.2 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60°C under a nitrogen atmosphere, 2.8 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (90.0 parts), 40% HAPS (50.0 parts), IPN-50 (63.0 parts), monomer (1) (9.0 parts), and water (68.0 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.2 parts), 2-mercaptopropionic acid (1.5 parts), and water (28.3 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining the polymer (9) of the present disclosure.
• Example 10 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.2 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60°C under a nitrogen atmosphere, 2.8 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (90.0 parts), 40% HAPS (50.0 parts), IPN-50 (63.0 parts), monomer (1) (9.0 parts), and water (68.0 parts), and mixed solution 2, which was a mixture of L-ascorbic acid (0.2 parts), 2-mercaptopropionic acid (1.3 parts), and water (28.5 parts), were simultaneously dropped from separate nozzles.
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (10) of the present disclosure.
• Example 11 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.1 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60°C under a nitrogen atmosphere, 2.9 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (99.0 parts), 40% HAPS (10.0 parts), IPN-50 (63.0 parts), monomer (1) (14.4 parts), and water (93.6 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.3 parts), 2-mercaptopropionic acid (1.4 parts), and water (28.3 parts)
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (11) of the present disclosure.
• Example 12 A glass reaction vessel equipped with a thermometer, a stirrer (paddle blade), a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 87.2 parts of water, and the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 60°C under a nitrogen atmosphere, 2.8 parts of 35% hydrogen peroxide solution was added to the reaction vessel.
• mixed solution 1 which was a mixture of AA (90.0 parts), 40% HAPS (25.0 parts), IPN-50 (54.0 parts), monomer (1) (27.0 parts), and water (84.0 parts), and mixed solution 2, which was a mixture of L-ascorbic acid (0.3 parts), 2-mercaptopropionic acid (1.4 parts), and water (28.4 parts), were simultaneously dropped from separate nozzles.
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a polymer (12) of the present disclosure.
• mixed solution 1 which was a mixture of AA (144.0 parts), 40% HAPS (75.0 parts), monomer (1) (9.0 parts), and water (52.0 parts), and mixed solution 2, which was a mixture of L-ascorbic acid (0.4 parts), 2-mercaptopropionic acid (3.5 parts), and water (26.1 parts), were simultaneously dropped from separate nozzles.
• the dropping was performed continuously at a constant rate, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a comparative polymer (1) of the present disclosure.
• mixed solution 1 which was a mixture of AA (21.1 parts) and water (100.0 parts)
• mixed solution 2 which was a mixture of L-ascorbic acid (0.1 parts), 2-mercaptopropionic acid (1.0 parts), and water (29.0 parts)
• the dropping was performed continuously at a constant speed, and the entire amount of mixed solution 1 was dropped over 150 minutes and mixed solution 2 was dropped over 210 minutes.
• the reaction vessel was maintained at 60° C. for an additional 60 minutes to complete the polymerization reaction, thereby obtaining a comparative polymer (2) of the present disclosure.

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