JPH1180288A - Hydrophilic graft polymer-containing composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic graft polymer-containing composition excellent in properties such as dispersibility and anti-gelation properties and easy in handling and its use. SOLUTION: A hydrophilic graft polymer-containing composition comprises a hydrophilic graft polymer obtained by the graft polymerization of a monoethylenically unsaturated monomer containing an unsaturated carboxylic acid-based monomer as the essential component on to a polyether compound and a polyether compound as the essential components and, optionally, an unsaturated carboxylic acid-based polymer obtained by the polymerization of a monoethylenically unsaturated monomer alone. In this instance, the mutual ratio of the hydrophilic graft polymer, the polyether compound and the unsaturated carboxylic acid-based polymer is such that the hydrophilic graft polymer is 60-98 wt.%; the polyether compound is 2-40 wt.%; and the unsaturated carboxylic acid-based polymer is 0-5 wt.%. A scale inhibitor contains this hydrophilic graft polymer-containing composition as the essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition containing a hydrophilic graft polymer and its use.

[0002]

2. Description of the Related Art A hydrophilic graft polymer obtained by graft-polymerizing an unsaturated carboxylic acid monomer such as (meth) acrylic acid to a polyether compound, a polyether compound as a raw material thereof, and a by-product thereof. A composition containing an unsaturated carboxylic acid-based polymer, which is a product of
-71710, JP-A-59-62614 and JP-A-7-53645.
The compositions disclosed in these documents are said to be used for various uses such as detergent builders and dispersants for organic particles and inorganic particles.

[0003]

However, all of the above-mentioned known compositions have low dispersibility and low gelation resistance, and when used in the above-mentioned applications, the desired performance cannot be sufficiently obtained. was there. Its viscosity was high and it was difficult to handle. On the other hand, in order to increase the efficiency of use of water resources, water having a high concentration of calcium carbonate or the like is used as circulating water, and in recent years, a high scale-inhibiting effect has been demanded for a scale inhibitor. The known composition is also used as a scale inhibitor,
Its anti-scaling ability was low and did not satisfy recent high anti-scaling standards.

Accordingly, an object of the present invention is to provide a hydrophilic graft polymer-containing composition which is excellent in physical properties such as dispersing ability and gelation resistance, is easy to handle, and has a high scale preventing ability. To provide an agent.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have adjusted the mutual proportion of the hydrophilic graft polymer, polyether compound and unsaturated carboxylic acid polymer. By doing so, the physical properties of the composition are improved, and it is found that the composition is easy to handle.
The present invention has been reached.

That is, the composition containing a hydrophilic graft polymer according to the present invention is obtained by graft-polymerizing a monoethylenically unsaturated monomer containing an unsaturated carboxylic acid monomer as an essential component to a polyether compound. A composition comprising a hydrophilic graft polymer and a polyether compound as essential components, and may further include an unsaturated carboxylic acid-based polymer obtained by polymerizing only the monoethylenically unsaturated monomer. The relative proportion of the hydrophilic graft polymer, polyether compound and unsaturated carboxylic acid polymer is 60 to 98% by weight of the hydrophilic graft polymer, 2 to 40% by weight of the polyether compound, and 0 to 5% by weight.

The scale inhibitor according to the present invention contains the above-mentioned composition containing a hydrophilic graft polymer as an essential component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the following, first, a polyether compound and a monoethylenically unsaturated monomer will be described, followed by a description of a hydrophilic graft polymer and an unsaturated carboxylic acid-based polymer. The configuration of the entirety of the graft-polymer-containing composition and the scale inhibitor will be described. Although the polyether compound itself is an essential component constituting the hydrophilic graft polymer-containing composition according to the present invention,
It is also a raw material for obtaining another essential component, a hydrophilic graft polymer. The monoethylenically unsaturated monomer is a raw material for obtaining the hydrophilic graft polymer, and is blended as necessary to constitute the hydrophilic graft polymer-containing composition of the present invention. It is also a raw material for obtaining an unsaturated carboxylic acid polymer. [Polyether compound] The polyether compound used in the present invention is a component that lowers the viscosity and makes the composition easier to handle. This polyether compound is a compound having 30 mol% or more (preferably 50 mol% or more) of the repeating units represented by the following general formula. The polyether compound contains ethylene oxide and / or propylene oxide as an essential component, and optionally forms a cyclic ether further containing another alkylene oxide by a known method or the like in the presence of a compound to be reacted as a polymerization initiation point. Obtained by polymerization.

-RCH-CH ₂ -O- (where R is at least one of a hydrogen atom and a methyl group and may be present in one molecule) Used for obtaining a polyether compound. Other alkylene oxides include, for example, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monoxide, styrene oxide,
1-diphenylethylene oxide, epifluorohydrin, epichlorohydrin, epicubromodrine, glycidol, butyl glycidyl ether, hexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether , Ethylene glycol diglycidyl ether, bisphenyl A diglycidyl ether, methacryl chloride epoxide, cyclohexene oxide, dihydronaphthalene oxide,
Examples thereof include vinylcyclohexene monoxide, oxetane, tetrahydrofuran, and 1,4-epoxycyclohexane, and one or more of these are used. Other copolymerizable alkylene oxides have a total of 7
It must be less than 0 mol%. When it is 70 mol% or more, the hydrophilicity decreases.

The compound to be reacted is a compound that serves as a starting point of polymerization of the cyclic ether, and there is no particular limitation on its type, molecular weight and the like. Examples of the compound to be reacted include water; hydrogen; oxygen; carbon dioxide; alcohol; hydrogen halide; ammonia;
Carboxylic acids; acid halides; lactones; aldehydes;
Benzene and the like can be mentioned.
Used over seeds. Among them, at least one selected from water, alcohol and amine is preferable as the compound to be reacted.

Examples of the alcohol include primary aliphatic alcohols having 1 to 22 carbon atoms, such as methanol, ethanol, n-propanol and n-butanol; phenol, iso-propylphenol, octylphenol, tert-butylphenol, nonylphenol and the like.
Aromatic alcohols such as naphthol; secondary alcohols having 3 to 18 carbon atoms such as iso-propyl alcohol and alcohols obtained by oxidizing n-paraffin; tertiary alcohols such as tert-butanol; ethylene glycol, diethylene glycol, propanediol And diols such as butanediol and propylene glycol; triols such as glycerin and trimethylolpropane; and polyols such as sorbitol. These may be used alone or in combination of two or more.

Examples of the amine include aniline, naphthylamine, ethylenediamine, dodecylamine and the like, and one or more of these are used. There is no particular limitation on the reaction mode of the polymerization of the cyclic ether, and there are no particular restrictions on hydroxides of alkali metals, strong alkalis such as alcoholates, anionic polymerization using an alkylamine or the like as a base catalyst, halides of metals and metalloids, mineral acids And cationic polymerization using acetic acid or the like as a catalyst, or coordination polymerization using a combination of alkoxides of metals such as aluminum, iron and zinc, alkaline earth compounds, Lewis acids and the like.

The polyether compound may be a derivative derived from the polyether obtained by the above polymerization.
Examples of such a derivative include a terminal group converter obtained by converting a terminal functional group of a polyether, and a reaction between a polyether and a crosslinking agent having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group and a halogen group. And a crosslinked product obtained by the reaction. As the terminal group converter, at least one terminal hydroxyl group of the above polyether is converted to a fatty acid having 2 to 22 carbon atoms such as acetic acid and acetic anhydride and dicarboxylic acids such as acid anhydride, succinic acid, succinic anhydride and adipic acid. Those esterified with an acid are preferred.

The weight average molecular weight of the polyether compound is
100,000 or less, preferably 80,000 or less,
More preferably, it is 50,000 or less. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 2
00 or more. When the weight average molecular weight exceeds 100,000, the viscosity becomes high, so that handling becomes difficult. On the other hand, when the weight-average molecular weight is less than 200, the compatibility is reduced, so that the composition is phase-separated and the scale preventing ability may be reduced.

[0015] The number of repeating units in the polyether compound is not particularly limited, and is preferably 2 or more, more preferably 3 or more in the polyether compound.
It is preferable that at least one of R in the repeating unit is a hydrogen atom. [Monoethylenically unsaturated monomer] The monoethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer as an essential component, and may contain another unsaturated copolymerizable with the unsaturated carboxylic acid-based monomer. It may further contain a saturated monomer.

The unsaturated carboxylic acid monomer is an ethylenically unsaturated carboxylic acid and / or an ester which forms a carboxylic acid by hydrolysis. Examples of ethylenically unsaturated carboxylic acids include (meth) acrylic acid;
Maleic acid; fumaric acid; maleic anhydride and the like, and one or more of these are used. When the unsaturated carboxylic acid monomer contains (meth) acrylic acid and at least one selected from maleic acid, fumaric acid and maleic anhydride as essential components, the acid value and the dispersibility are increased, and the scale is increased. It is preferable because the prevention ability is improved. It is further preferable that the unsaturated carboxylic acid monomer contains acrylic acid and at least one of maleic acid and maleic anhydride as essential components.

The ester which forms a carboxylic acid by hydrolysis is not particularly limited as long as it is an ester of the above-mentioned ethylenically unsaturated carboxylic acid, and examples thereof include monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate and the like. Esters of maleic acid;
Esters of fumaric acid such as monomethyl fumarate, dimethyl fumarate, monoethyl fumarate and diethyl fumarate;
Methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth)
Esters of (meth) acrylic acid such as hydroxypropyl acrylate; aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 2-
Examples thereof include sulfoalkyl (meth) acrylates such as sulfoethyl (meth) acrylate, and one or more of these are used. When polymerizing using the above ester to produce a hydrophilic graft polymer or unsaturated carboxylic acid polymer, a step of hydrolyzing a part or all of the ester group to convert it into a carboxyl group after polymerization is necessary. Becomes Therefore, it is preferable that the unsaturated carboxylic acid-based monomer is composed only of the ethylenically unsaturated carboxylic acid from the viewpoint that this conversion step is unnecessary.

The other unsaturated monomer copolymerizable with the unsaturated carboxylic acid monomer is not particularly limited as long as it is a monomer other than the unsaturated carboxylic acid monomer. Meta)
Amide group-containing monomers such as acrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; and styrene and styrene sulfonic acid. Aromatic vinyl monomers; trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; silicon-containing vinyl monomers such as γ- (methacryloyloxypropyl) trimethoxysilane Monomers: maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide,
Maleimide derivatives such as stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; vinyl monomers containing nitrile groups such as (meth) acrylonitrile;
Aldehyde group-containing vinyl monomers such as (meth) acrolein; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, vinylsulfonic acid, hydroxyallyloxypropanesulfonic acid, 2-hydroxy-3-butenesulfone Sulfonic acid group-containing monomers such as acid and 2-hydroxy-3-allyloxy-1-propanesulfonic acid; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol: vinyl Other functional group-containing monomers such as pyrrolidone can be exemplified, and one or more of these are used.

The proportion of the unsaturated carboxylic acid monomer in the monoethylenically unsaturated monomer is not particularly limited. However, in order to increase the acid value and the dispersing ability and to improve the scale preventing ability,
It is preferably at least 60% by weight, more preferably at least 65% by weight, most preferably at least 70% by weight. (Hydrophilic graft polymer) The hydrophilic graft polymer used in the present invention is a component that enhances physical properties such as dispersibility and gelation resistance, and imparts a scale-preventing ability. A polymer obtained by graft polymerization of an unsaturated monomer. The hydrophilic graft polymer is composed of a polyether portion derived from a polyether compound, and a graft chain portion derived from polymerization of the monoethylenically unsaturated monomer and derived from the monoethylenically unsaturated monomer. ing.

The weight ratio of the polyether portion and the graft chain portion (polyether portion / graft chain portion) is not particularly limited, but is preferably 10 / 90-80.
/ 20, more preferably 20/80 to 80/20, and most preferably 30/70 to 70/30 from the viewpoint of enhancing the scale prevention ability. The weight ratio is 10 /
If it is less than 90, the gelation resistance will decrease, and the viscosity will increase, making it difficult to handle, and the scale preventing ability tends to decrease. On the other hand, if the weight ratio is larger than 80/20, the dispersibility may be reduced.

The weight average molecular weight of the hydrophilic graft polymer is from 500 to 200,000, preferably 1,000.
-100,000, more preferably 1500-8000
0. If the weight average molecular weight is less than 500, the dispersing ability may decrease. On the other hand, when the weight average molecular weight is 20
If it exceeds 0000, the dispersing ability and the gelation resistance will decrease, and the viscosity will increase, making it difficult to handle, and the scale preventing ability may decrease.

The method for producing the hydrophilic graft polymer used in the present invention is a method for graft-polymerizing the above monoethylenically unsaturated monomer to the above polyether compound.
There is no particular limitation, and examples thereof include a method of graft-polymerizing the monoethylenically unsaturated monomer to the polyether compound in the presence of an organic peroxide.

The organic peroxide is used as a polymerization initiator for graft polymerization. Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide,
Ketone peroxides such as acetylacetone peroxide; tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-
2,5-dihydroperoxide, 1,1,3,3-
Tetramethylbutyl hydroperoxide, 2- (4
Hydroperoxides such as -methylcyclohexyl) -propane hydroperoxide; di-tert-
Butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (tert-butylperoxy) p-diisopropylbenzene, α, α′-bis (tert-butylperoxy) p-isopropyl Hexin, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3; tert-butylperoxyacetate, tert
-Butylperoxylaurate, tert-butylperoxybenzoate, di-tert-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyisopropylcarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxybivalate, tert-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert
-Butylperoxy-3,5,5-trimethylcyclohexanoate, tert-butylperoxybenzoate, tert-butylperoxymaleic acid, cumylperoxyoctoate, tert-hexylperoxybivalate, tert-hexylperoxy Peroxyesters such as neohexanoate and cumylperoxyneohexanoate; n-butyl-4,4-bis (te
rt-butylperoxy) valate, 2,2-bis (tert-butylperoxy) butane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis ( tert-butylperoxy) cyclohexane, 2,2-bis (tert
Peroxyketals such as -butylperoxy) octane; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylcyclohexanoyl peroxide, succi Nick acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-
Diacyl peroxides such as toluyl peroxide; di-isopropylperoxydicarbonate, di-
2-ethylhexyl peroxydicarbonate, di-n
-Propylperoxydicarbonate, bis- (4-t
tert-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, di (3
-Methyl-3-methoxybutyl) peroxydicarbonates such as peroxydicarbonate and di-allylperoxydicarbonate; and other organic peroxides such as acetylcyclohexylsulfonyl peroxide and tert-butylperoxyallylcarbonate. These may be used alone or in combination of two or more.

The amount of the organic peroxide used is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, based on the monoethylenically unsaturated monomer. is there. If it is less than 0.1% by weight, the graft ratio to the polyether compound tends to decrease. On the other hand, 3
If it exceeds 0% by weight, the organic peroxide is expensive,
It is not economically preferable. The organic peroxide is preferably added simultaneously with the ethylenically unsaturated monomer simultaneously and separately without previously mixing with the polyether compound, but may be added to the polyether compound in advance, It may be added to the monoethylenically unsaturated monomer.

An organic peroxide decomposition catalyst or a reducing compound may be used together with the organic peroxide. Examples of organic peroxide decomposition catalysts include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Carboxylic acids such as formic acid, acetic acid, propionic acid, lacnic acid, isoleic acid, and benzoic acid, esters and metal salts thereof; pyridine, indole,
Heterocyclic amines such as imidazole and carbazole and derivatives thereof and the like can be mentioned.
Used over seeds.

Examples of the reducing compound include organometallic compounds such as ferrocene; metals such as iron, copper, nickel, cobalt and manganese such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate and manganese naphthenate; Inorganic compounds capable of generating ions; inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, and perchloric acid; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxylate, benzene Sulfinic acid and its substituted products, sulfur-containing compounds such as homologues of cyclic sulfinic acids such as paratoluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid,
Mercapto compounds such as thiopropionic acid, sodium sulfopropyl α-thiopropionate and sodium sulfoethyl ester α-thiopropionate; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine, and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde And aldehydes such as n-butyraldehyde, isobutyraldehyde and isovalerian aldehyde; ascorbic acid; and one or more of these are used. The graft polymerization may be performed in the presence of an acidic substance together with the organic peroxide. The acidic substance has a function of improving the graft ratio of the monoethylenically unsaturated monomer to the polyether compound, increasing the dispersibility of the obtained hydrophilic graft polymer, and improving the scale prevention ability. The acidic substance is not particularly limited as long as it is an acidic substance, but at least one selected from organic sulfonic acid compounds, inorganic acids, and phosphoric acid compounds is preferable.

Examples of the organic sulfonic acid compound include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and octanesulfonic acid;
Aromatic sulfonic acids such as benzenesulfonic acid, benzenedisulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; chlorobenzenesulfonic acid, 1-naphthylamine-4-sulfonic acid (naphthionic acid), dobiasic acid, peric acid, gamma acid (γ-acid) ), Aromatic acids having a nuclear substituent such as jaeic acid (J acid), koch acid, metanilic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, etc., and one or more of these can be used. Is done.

Examples of the inorganic acid include hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chlorous acid, hypochlorous acid, periodic acid, sulfuric acid, fuming sulfuric acid, and sulfurous acid. , Nitric acid, fuming nitric acid, manganic acid, permanganic acid, chromic acid, dichromic acid, etc., and one or more of these are used. Examples of the phosphoric acid compound include phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid,
Metaphosphoric acid, pyrophosphoric acid, methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, octyl phosphate,
Dodecyl phosphate, stearyl phosphate, phenyl phosphate,
Dimethyl phosphate, diethyl phosphate, dipropyl phosphate,
Examples thereof include dibutyl phosphate, dioctyl phosphate, didodecyl phosphate, distearyl phosphate, diphenyl phosphate, and the like. One or more of these are used.

The amount of the acidic substance used is not particularly limited.
0.05 to 20 based on the polyether compound
%, More preferably 0.1 to 15% by weight.
If the amount of the acidic substance is less than 0.05% by weight, a large amount of unreacted polyether compound remains, and the graft ratio of the monoethylenically unsaturated monomer tends to decrease. On the other hand, when the use amount of the acidic substance exceeds 20% by weight, the effect corresponding to the added amount may not be exhibited. The acidic substance may be added to the polyether compound in advance, or may be added to the monoethylenically unsaturated monomer.

The graft polymerization is preferably carried out substantially without solvent, but a solvent of not more than 20% by weight of the whole reaction system may be used. If the amount exceeds 20% by weight of the entire reaction system, the graft ratio of the monoethylenically unsaturated monomer may decrease. When the viscosity of the reaction system is high, it is sometimes preferable to use a small amount of solvent when adding the solvent. The solvent may be distilled off after the addition.

The above-mentioned solvent is not particularly limited, but one having a chain transfer constant of the monomer used as small as possible to the solvent or one having a boiling point of 80 ° C. or higher which can be used in the reaction under normal pressure. Are preferred. Examples of such a solvent include alcohols such as iso-butyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. Diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; acetic acid compounds such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetate esters of ethylene glycol monoalkyl ether, acetate esters of propylene glycol monoalkyl ether, etc. These may be used alone or in combination of two or more.
Examples of the alkyl group in the alcohols and diethers include a methyl group, an ethyl group, a propyl group, and a butyl group.

The temperature of the graft polymerization is preferably 80 ° C. or higher, more preferably 90 to 160 ° C. If the temperature is lower than 80 ° C., the graft polymerization does not easily proceed, and the graft ratio of the monoethylenically unsaturated monomer tends to decrease. On the other hand, if the temperature exceeds 160 ° C., thermal decomposition of the polyether compound and the obtained hydrophilic graft polymer may occur.

At the time of graft polymerization, it is preferable to initially or partially charge the polyether compound. As the monoethylenically unsaturated monomer, for example, at least one monomer (A) selected from the group consisting of maleic acid, fumaric acid, and maleic anhydride and (meth) acrylic acid are used in combination to form a polyether. When graft-polymerizing a compound, at least half of the monomer (A) and an acidic substance are mixed in advance with a polyether compound, heated to 80 ° C. or higher, and the remaining monoethylenic non-ethylated compound is added to the heated mixture. It is preferable to separately add a saturated monomer and an organic peroxide to carry out graft polymerization. According to this method, the molecular weight of the obtained hydrophilic graft polymer can be easily adjusted.

The method for producing the hydrophilic graft polymer is not limited to the above method. (Unsaturated carboxylic acid-based polymer) The unsaturated carboxylic acid-based polymer used in the present invention is not an essential component constituting the composition of the present invention, but increases the acid value and increases the polyvalent metal ion chelating ability. Can be applied to objects. The unsaturated carboxylic acid-based polymer is a polymer obtained by polymerizing only the monoethylenically unsaturated monomer described in detail above.

The weight average molecular weight of the unsaturated carboxylic acid polymer is preferably from 500 to 200,000, more preferably from 1,000 to 100,000. If the weight average molecular weight is less than 500, the dispersing ability may decrease. On the other hand, if the weight average molecular weight exceeds 200,000, the composition becomes turbid and the appearance deteriorates, and the viscosity becomes high, so that the handling may be difficult. Further, the scale preventing ability and the dispersing ability tend to decrease.

The acid value of the unsaturated carboxylic acid polymer is preferably from 200 to 1200 mgKOH / g, more preferably from 300 to 1000 mgKOH / g. When the acid value is less than 200 mgKOH / g, the acid value and dispersibility of the composition tend to decrease. On the other hand, when the acid value is 12
If it exceeds 00 mgKOH / g, the compatibility of the unsaturated carboxylic acid-based polymer with the hydrophilic graft polymer and the polyether compound may be reduced, and the composition may not be uniform and may be phase-separated. is there.

The unsaturated carboxylic acid polymer is, for example,
The product obtained by radical polymerization of the above monoethylenically unsaturated monomer in the presence of an initiator may be used, but the monoethylenically unsaturated monomer is grafted to a polyether compound in the presence of an organic peroxide. At the time of polymerization, it may be obtained as a by-product. In addition, when an unsaturated carboxylic acid-based polymer is obtained by radical polymerization or graft polymerization, monoethylenically unsaturated monomers, polyether compounds, specific examples of organic peroxides, and preferable examples thereof, and The polymerization conditions and the like are the same as those described in the section of the hydrophilic graft polymer. [Hydrophilic graft polymer-containing composition and use thereof] The hydrophilic graft polymer-containing composition according to the present invention contains a hydrophilic graft polymer and a polyether compound as essential components, and contains an unsaturated carboxylic acid-based polymer. May be further contained, and if necessary, other components described later can be contained.

The mixing ratio of the hydrophilic graft polymer is 60 to 98% by weight, preferably 65 to 98% by weight of the total of the three (hydrophilic graft polymer, polyether compound and unsaturated carboxylic acid polymer). , More preferably 70
~ 98% by weight. When the compounding ratio of the hydrophilic graft polymer is less than 60% by weight of the total of the three, the dispersing ability is reduced and the scale preventing ability is reduced. On the other hand, 98
If the content is more than 10% by weight, the viscosity increases and the handling becomes difficult.

The mixing ratio of the polyether compound is 2 to 40% by weight of the total of the three, preferably 2 to 35% by weight.
More preferably, it is 2 to 30% by weight. When the compounding ratio of the polyether compound is less than 2% by weight of the total of the three,
The viscosity increases, making it difficult to handle. On the other hand, if it exceeds 40% by weight of the total of the three, the dispersibility will be reduced. The compounding ratio of the unsaturated carboxylic acid polymer is 0 to 5% by weight of the total of the three.
And preferably 0 to 4% by weight, more preferably 0 to 4% by weight.
3% by weight. The compounding ratio of the hydrophilic graft polymer is 3
When the content exceeds 5% by weight of the total, the composition becomes turbid and the appearance becomes poor, and the viscosity becomes high, so that it becomes difficult to handle. Also,
The scale prevention ability may be reduced.

The composition containing a hydrophilic graft polymer according to the present invention may contain other components. Other components include proteases, enzymes such as (alkali) lipase and (alkali) cellulase; anionic surfactants,
Surfactants such as nonionic surfactants, cationic surfactants and amphoteric surfactants; alkali builders such as silicates, carbonates and sulfates; diglycolic acid, oxycarboxylates, EDTA (ethylenediaminetetraacetic acid) ), DTPA
(Diethylenetriamine hexaacetic acid) Chelate builder such as citric acid; low molecular weight polymer having carboxyl group; anti-redeposition agent; fluorescent agent; bleaching agent; perfume; dispersant; organic sulfonic acid; inorganic polyphosphate; phosphonic acid; ,
Metal salts such as manganese; anticorrosives; slime control agents; chelating agents; algaecides; preservatives;
Cleaning agents; oxygen scavengers; sludge dispersants; carryover inhibitors; bases and the like. These other components may be used alone or in combination of two or more. The mixing ratio is not particularly limited.

Examples of the anionic surfactant include an alkyl benzene sulfonate, an alkyl or alkenyl ether sulfate, an alkyl or alkenyl sulfate, an α-olefin sulfonate, an α-sulfofatty acid or ester salt, an alkane sulfonate, Or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate,
Examples thereof include an amino acid type surfactant, an N-acyl amino acid type surfactant, an alkyl or alkenyl phosphate or a salt thereof.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide,
Fatty acid glycerin monoester, alkylamine oxide and the like can be mentioned.

Examples of the cationic surfactant include a quaternary ammonium salt. Examples of the amphoteric surfactant include a carboxyl-type or sulfobetaine-type amphoteric surfactant. Examples of the base include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and lithium hydroxide; sodium carbonate, calcium carbonate,
Carbonates of alkali metals and alkaline earth metals such as lithium carbonate; amines such as ammonia, monoethanolamine, diethanolamine and triethanolamine; and the like, and one or more of these are used.

The method for producing the hydrophilic graft polymer-containing composition according to the present invention is not particularly limited, and examples thereof include the following. The above components are prepared in advance and mixed while adjusting the mixing ratio so as to satisfy the above range to produce a composition. When the mixing ratio of each component in the reaction mixture obtained by the production method described in the section of the hydrophilic graft polymer satisfies the above range, the reaction mixture is used as it is as a composition.

The above components are further added to the reaction mixture obtained by the production method described in the section of the hydrophilic graft polymer, and the composition ratio is adjusted to satisfy the above range to produce a composition. I do. The hydrophilic graft polymer-containing composition according to the present invention has high physical properties such as a dispersing ability and a gel-resistant substance, has excellent scale preventing ability, and has a low viscosity for easy handling. Builders, fiber treatment agents, pigment dispersants, organic and inorganic solid particle dispersants, papermaking aids, cement additives, CWM dispersants, foaming agents, foam enhancers, compatibilizers, solubilizers, rust inhibitors , Emulsifiers, dyeing auxiliaries and the like.

The scale inhibitor according to the present invention comprises the above hydrophilic graft polymer-containing composition as an essential component, and strongly disperses water-insoluble inorganic particles such as calcium carbonate.
Prevent scale from occurring. This scale inhibitor contains a hydrophilic graft polymer and a polyether compound as essential components, and may further contain an unsaturated carboxylic acid-based polymer, and may contain the above-mentioned other components as necessary.

The weight average molecular weight of the hydrophilic graft polymer contained in the scale inhibitor is, as described above, 500 to 500.
There is no particular limitation as long as it is 200,000, but when the upper limit is 50,000, the scale prevention ability is improved,
preferable. The upper limit of the weight average molecular weight of the hydrophilic graft polymer is more preferably 20,000, and most preferably 10,000.

The weight average molecular weight of the polyether compound contained in the scale inhibitor is 10,000 as described above.
There is no particular limitation as long as it is 0 or less, but if it is 20,000 or less, the viscosity decreases and the handling becomes easy, so that it is preferable. The upper limit of the weight average molecular weight of the polyether compound is
More preferably, it is 5000. The scale inhibitor is
When the gelation resistance of the hydrophilic graft polymer is high, the ability to prevent scale is further improved. Examples of the hydrophilic graft polymer having high gelation resistance include a hydrophilic graft polymer containing a sulfonic acid group and / or a hydroxyl group. For example, hydroxyalkyl (meth) acrylates and And a monoethylenically unsaturated monomer such as a sulfonic acid group-containing monomer.

The scale inhibitor may contain other components other than the hydrophilic graft polymer. As the other components, for example, acrylic acid / 3-allyloxy-
1,2-propanediol copolymer, acrylic acid / 2-
Allyloxy-1,2-propanediol copolymer, acrylic acid / 2-hydroxy-3-allyloxy-1-propanesulfonic acid copolymer, acrylic acid / maleic acid copolymer, acrylic acid / allyl alcohol copolymer, Acrylic acid / hydroxy methacrylate copolymer, maleic acid /
Ethylene sulfonic acid copolymer, maleic acid / styrene copolymer, maleic acid / pentene copolymer, maleic acid /
Carboxyl group-containing low molecular weights such as allyl alcohol copolymer, maleic acid / ethylene copolymer, maleic acid / butadiene copolymer, acrylic acid polymer, maleic acid polymer, aspartic acid polymer, and glyoxylic acid polymer Polymer; organic sulfonic acid; inorganic polyphosphate such as sodium tripolyphosphate, sodium hexametaphosphate; phosphonic acid such as nitrilotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid; zinc, chromium Anticorrosives; antiseptic agents; antiseptics; antibacterial agents; slime control agents; ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyiminodisuccinic acid (HIDS) Iminodisuccinic acid (IDS),
Chelating agents such as citric acid; cleaning agents; oxygen scavengers; sludge dispersants; and carryover inhibitors.
These other components may be used alone or in combination of two or more. The amount is not particularly limited.

The scale inhibitor according to the present invention may be added as it is to a water system such as a cooling water system, a boiler water system, a seawater desalination apparatus, a pulp dissolving pot, a black liquor concentrating pot, or an oil field. 1 to 100 ppm.
When the scale inhibitor contains components other than the above-mentioned hydrophilic graft polymer, they can be added separately. Scale inhibitor according to the present invention, calcium carbonate, calcium phosphate, zinc hydroxide, barium sulfate, calcium sulfate, calcium sulfite, calcium silicate, magnesium silicate, magnesium hydroxide, zinc phosphate, basic zinc carbonate, silica, It can be used to prevent and remove scales such as iron.

[0051]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. -Example 1-Phenoxy polyethylene glycol having a weight average molecular weight of 530 (obtained by adding an average of 10 moles of ethylene oxide to phenol) to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser. ) 100 parts by weight and 51.8 parts by weight of maleic acid were charged, and the charged substance was heated under a nitrogen stream to form a solution.
The temperature was raised to 36 ° C. Next, the temperature of the solution was increased to 135 to 13
While maintaining the temperature at 7 ° C., 48.2 parts by weight of acrylic acid and 90% of perbutyl C (tert-butylcumyl peroxide 90%) were added.
(Manufactured by Nippon Oil & Fats Co., Ltd.) 10 parts by weight separately and continuously over 1 hour. Then one
Stirring of the reaction mixture was continued for a period of time to obtain a hydrophilic graft polymer-containing composition. When the viscosity of this composition was measured using a B-type viscometer, it was 12000 cps (100 ° C.).
Met.

The obtained composition was neutralized with sodium hydroxide to convert the carboxyl group contained in the composition into its sodium salt, and the composition was heated and evaporated to dryness. The dried product was extracted with dichloromethane using a Soxhlet, and the components contained in the extract were analyzed by GPC and NMR, and it was confirmed that this component was phenoxy polyethylene glycol (polyether compound) as a raw material.

Next, the residue after the extraction was separated by hydrophobic chromatography, and it was separated into two. Each fraction was analyzed by GPC and NMR. From the analysis results, one of the two fractions is a hydrophilic graft polymer (weight average molecular weight 4960) composed of a polyether portion and a graft chain portion obtained by graft copolymerization of maleic acid and acrylic acid. I understand. The ratio of the polyether portion to the graft chain portion (polyether portion / graft chain portion) was 39.8 / 60.2. The other of the two fractions, from the analysis results,
It was found to be an unsaturated carboxylic acid polymer (weight average molecular weight 1240) in which maleic acid and acrylic acid were copolymerized.

The mutual proportion of the hydrophilic graft polymer, polyether compound and unsaturated carboxylic acid polymer contained in the obtained composition was 83% by weight of the total of the three. , The polyether compound is 16% by weight,
The unsaturated carboxylic acid polymer was 1% by weight. The obtained composition was subjected to the following scale prevention performance test, dispersibility test and gelation resistance test. As a result, the scale inhibition rate was 98%, the dispersibility was 790 ppm, and the gelation resistance was 5 ppm. [Scale prevention performance test] Hydrophilic graft polymer-containing composition 1 mg / l, calcium chloride 278 mg /, prepared using NaOH aqueous solution and / or HCl aqueous solution
1 (calcium: 100 mg / l) and sodium hydrogencarbonate 210 mg / l, pH 8.5 test solution 1
00 ml into a container, the container is sealed and
It was left for 0 hours. After standing, the test solution was filtered through a 0.45 μm membrane filter, and the filtrate was titrated with EDTA.
The calcium in the filtrate was quantified, and the quantified value was expressed as C (mg /
l). Calcium was quantified in the same manner as above for the test solution containing no hydrophilic graft polymer-containing composition, and the quantified value was defined as B (mg / l). B and C were substituted into the following equation to calculate the scale suppression rate.

Scale inhibition rate (%) = (CB) / (1)
00-B) × 100 [Dispersion ability test] 50 m of hydrophilic graft polymer-containing composition
g was added to a 100 ml color tube with a stopcock (2.5 cm inside diameter), and water was further added to make a total of 100 ml. Then, an aqueous solution of sodium hydroxide was dropped into the color tube, and the content of the color tube was adjusted to pH8. Adjusted to .5. 2 g of manganese dioxide powder (Wako Pure Chemical Reagent (for chemistry) dried at 120 ° C. for 3 hours) was further added to the colorimetric tube, and the colorimetric tube was shaken up and down 100 times and then allowed to stand for 4 hours. 15 from bottom of colorimetric tube
From a height of 1 cm, 1 ml of the test solution was collected with a whole pipette, and the concentration of manganese dioxide contained in the test solution was quantified by the permanganate method. The higher the concentration of manganese dioxide, the higher the dispersing power. [Gelling resistance test] 1000 ml of a test liquid having a pH 8.5 and a hydrophilic graft polymer-containing composition concentration of 5 mg / l and a calcium chloride concentration of 223 mg / l (Politz)
sch buffer) was prepared. This test solution was added at 60 ° C for 2 hours.
The mixture was allowed to stand for 0 hour, and filtered with a 1 μm membrane filter. The composition concentration in the filtrate was quantified using a calibration curve prepared in advance by a TOC measuring device. The higher the composition concentration, the higher the gelation resistance. Example 2 170 parts by weight of methoxypolyethylene glycol having a weight average molecular weight of 5000 and maleic acid 1 were placed in a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser.
2.3 parts by weight were charged, and the charged material was heated to form a solution under a nitrogen stream, and the solution was heated to 130 ° C. with stirring.
Next, while maintaining the temperature of the solution at 129 to 132 ° C., 17.8 parts by weight of acrylic acid and perhexa V (n-butyl-
2.7 parts by weight of 90% 4,4-bis (tert-butylperoxy) octane (manufactured by NOF Corporation) was added dropwise to the above solution over 20 minutes. Thereafter, the stirring of the reaction mixture was continued for 1 hour to obtain a hydrophilic graft polymer-containing composition. When the viscosity of this composition was measured using a B-type viscometer, it was 14000 cps (100 ° C.).

When the obtained composition was analyzed in the same manner as in Example 1, methoxypolyethylene glycol (polyether compound) having a weight average molecular weight of 5000 was obtained.
A hydrophilic graft polymer (weight average molecular weight: 20,000) comprising a polyether portion, a graft chain portion in which maleic acid and acrylic acid are graft-copolymerized, and an unsaturated carboxylic acid copolymer in which maleic acid and acrylic acid are copolymerized. It was found that the polymer contained a polymer (weight average molecular weight: 1800). The ratio of polyether portion / graft chain portion in this hydrophilic graft polymer was 79/21.

The mutual proportion of the hydrophilic graft polymer, the polyether compound and the unsaturated carboxylic acid polymer contained in the obtained composition was 72% by weight in the total of the three. , The polyether compound is 27% by weight,
The unsaturated carboxylic acid polymer was 1% by weight. The obtained composition was subjected to a scale prevention performance test, a dispersibility test, and a gelation resistance test in the same manner as in Example 1. As a result, the scale inhibition rate was 80%, the dispersibility was 510 ppm,
The gelation resistance was 5 ppm.

Comparative Example 1 A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 100 parts by weight of polyethylene glycol having a weight average molecular weight of 200,000 and 20 parts by weight of water. Below, the charge was heated to form a solution, and the solution was heated to 100 ° C. with stirring. Next, 52 parts by weight of acrylic acid and perbutyl O (tert-butylperoxy-2-
Contains 97% ethyl hexanate, manufactured by NOF Corporation
2.6 parts by weight were added dropwise to the solution. Then 120 ° C
The heating of the reaction mixture was continued for 2 hours to obtain a comparative composition. An attempt was made to measure the viscosity of this comparative composition using a B-type viscometer, but the viscosity was too high to measure.

When the obtained comparative composition was analyzed in the same manner as in Example 1, a polyethylene glycol (polyether compound) having a weight average molecular weight of 210,000, a polyether portion, and a graft chain obtained by graft polymerization of acrylic acid were obtained. It was found that a hydrophilic graft polymer (weight average molecular weight: 280,000) consisting of a portion and an unsaturated carboxylic acid polymer obtained by polymerization of acrylic acid (weight average molecular weight: 13,500) were included. The ratio of polyether portion / graft chain portion in this hydrophilic graft polymer was 50/50.

The relative proportion of the hydrophilic graft polymer, the polyether compound and the unsaturated carboxylic acid polymer contained in the obtained comparative composition was 46 weight% of the total of the three. %, The polyether compound was 43% by weight, and the unsaturated carboxylic acid polymer was 11% by weight.
When a scale prevention performance test, a dispersibility test and a gelation resistance test were performed on the obtained comparative composition in the same manner as in Example 1, the scale inhibition rate was 13% and the dispersibility was 13
The gelation resistance was 0 ppm and the gelation resistance was 1 ppm.

Comparative Example 2 200 parts by weight of methoxypolyethylene glycol having a weight-average molecular weight of 480 was charged into a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser.
The charge is heated to form a solution, and the solution is stirred under 128
The temperature was raised to ° C. Next, while maintaining the temperature at 128 to 131 ° C., 21 parts by weight of acrylic acid and 90% of perhexa V (n-butyl-4,4-bis (tert-butylperoxy) octane are contained, manufactured by NOF Corporation) 1.9 parts by weight were added dropwise to the above solution over 30 minutes. After that, stirring of the reaction mixture was continued for 1 hour to obtain a comparative composition. It was 3000 cps (100 degreeC) when the viscosity of this comparative composition was measured using the Brookfield viscometer.

When the obtained comparative composition was analyzed in the same manner as in Example 1, methoxypolyethylene glycol (polyether compound) having a weight average molecular weight of 500 was obtained.
And a hydrophilic graft polymer (weight average molecular weight 3900) comprising a polyether portion and a graft chain portion obtained by graft polymerization of acrylic acid, and an unsaturated carboxylic acid polymer obtained by polymerization of acrylic acid (weight average molecular weight 3500) And was found to be included. The ratio of polyether portion / graft chain portion in this hydrophilic graft polymer was 83/17.

The relative proportion of the hydrophilic graft polymer, the polyether compound and the unsaturated carboxylic acid polymer contained in the obtained comparative composition was 54 weight% of the total of the three. %, The polyether compound was 45% by weight, and the unsaturated carboxylic acid polymer was 1% by weight. When a scale prevention performance test, a dispersibility test and a gelation resistance test were performed on the obtained comparative composition in the same manner as in Example 1, the scale inhibition rate was 24% and the dispersibility was 290.
ppm, and the gelation resistance was 5 ppm.

[0064]

The composition containing a hydrophilic graft polymer according to the present invention is excellent in physical properties such as dispersibility and gelation resistance,
Easy handling due to low viscosity. The scale inhibitor according to the present invention has a high scale preventing ability and is effective in preventing and removing scale such as calcium carbonate.

Claims (6)

[Claims] A hydrophilic graft polymer obtained by graft-polymerizing a monoethylenically unsaturated monomer containing an unsaturated carboxylic acid monomer as an essential component onto a polyether compound, and a polyether compound as an essential component The composition may further include an unsaturated carboxylic acid-based polymer obtained by polymerizing only the monoethylenically unsaturated monomer. In the composition, the hydrophilic graft polymer, the polyether compound and the unsaturated The mutual proportion of the carboxylic acid-based polymer is 60 to 98% by weight of the hydrophilic graft polymer, 2 to 40% by weight of the polyether compound, and 0 to 5% by weight of the unsaturated carboxylic acid-based polymer.
A composition containing a hydrophilic graft polymer, characterized in that: 2. The hydrophilic graft polymer has a weight average molecular weight of 500 to 200,000, the polyether compound has a weight average molecular weight of 100,000 or less, and a polyether portion and a graft chain portion in the hydrophilic graft polymer. The hydrophilic graft polymer-containing composition according to claim 1, wherein the mutual weight ratio is polyether portion / graft chain portion = 10/90 to 80/20. 3. The hydrophilic graft polymer-containing composition according to claim 1, wherein the monoethylenically unsaturated monomer comprises only an unsaturated carboxylic acid monomer. 4. The method according to claim 1, wherein the unsaturated carboxylic acid monomer contains (meth) acrylic acid and at least one selected from maleic acid, fumaric acid and maleic anhydride as essential components. 3. The composition containing a hydrophilic graft polymer according to any one of the above items 3. 5. A composition comprising the hydrophilic graft polymer-containing composition according to any one of claims 1 to 4 as an essential component.
Scale inhibitor. 6. The scale inhibitor according to claim 5, wherein the weight average molecular weight of the hydrophilic graft polymer is 500 to 50,000, and the weight average molecular weight of the polyether compound is 20,000 or less.