JP2002138115A - Method of producing allylether polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a water-soluble polymer suitable for use as an additive to a non-phosphorus or low-phosphorus descaling agent having excellent anti-gelling property, hard to cause precipitation, and capable of suppressing generation of scale even when used with zinc-based or condensed phosphoric acid-based anti-corrosion agents, for example. SOLUTION: This method of producing an allylether polymer comprises polymerization of a monomer component in which allylether monomer is indispensable, where the allylether monomer is expressed by formula (1), and the monomer component comprises a compound expressed by formula (2) at a content of 500 ppm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an allyl ether polymer. More specifically, the present invention relates to a method for producing an allyl ether-based polymer preferably used as an aqueous additive. Here, the water-based additive is, specifically, various water-based treatment agents, cleaning agents, water treatment agents, fiber treatment agents,
Scale inhibitors, detergent builders and the like.

[0002]

2. Description of the Related Art Scale inhibitors are used in boilers, condensers,
It is used for water treatment agents such as heat exchangers and gas washing towers.

[0003] Heat transfer surfaces of boilers, condensers, heat exchangers, etc., packing surfaces of gas cleaning towers and pipes, etc., include cations such as calcium and magnesium present in makeup water, cooling water, and trapped water. In addition to anions such as carbonate ions, bicarbonate ions, sulfite ions, and sulfate ions, zinc ions and phosphate ions due to the anticorrosive agent are precipitated, and scale is easily generated. This phenomenon is particularly remarkable in a system using a refrigerant having a high Ca concentration and a high pH, that is, a so-called brine.

Such adhesion of scale not only increases operating costs due to a decrease in heat transfer effect and an increase in flow resistance, but also indicates an indication caused by adhesion of scale to sensors of various instruments such as a thermometer and a pH meter. This causes abnormal values and delays in response speed. Further, continuation of normal operation becomes difficult due to local corrosion and the like. Since the attached scale is hard and cannot be easily peeled, the cost required for stopping the operation, removing the scale, and the like also increases.

Therefore, conventionally, lignin compounds, phosphorus compounds, poly (meth) acrylates, and the like have been used as scale inhibitors for the purpose of preventing such scale adhesion.

However, lignin compounds have a problem that the quality is not constant. In addition, phosphorus-based compounds, including those added as corrosion inhibitors as described above,
When the hydrolyzed phosphate ions are highly concentrated, they become scale components. Moreover, if the scale component composed of phosphate ions is further contained in the blow water and released into a closed water system such as a lake or inland sea outside the system, it causes serious pollution such as blue-green algae and red tide. Poly (meth) acrylate has been highly evaluated among these conventionally used scale inhibitors.
It is easy to generate phosphorus and other scales.

In order to solve the above problems, the present inventors include (meth) acrylic acid monomers and allyl ether monomers as excellent scale inhibitors having no or low phosphorus. A scale inhibitor consisting of a copolymer derived from a monomer component (Japanese Patent Publication No. 62-59640) was presented.

However, as a result of further studies by the present inventors to provide a higher performance scale inhibitor, even such a polymeric scale inhibitor has low gelation resistance. In this case, it was found that it was easily insolubilized in the boiler water system and the cooling water system, and had poor performance as a scale inhibitor.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and its main object is to reduce the scale even when used in combination with a corrosion inhibitor such as a zinc or condensed phosphoric acid. An object of the present invention is to provide a phosphorus-free or low-phosphorus scale inhibitor which is excellent in gelation resistance and hardly causes precipitation while controlling generation thereof, and a polymer suitable as a raw material thereof. Another object of the present invention is to provide a copolymer which can be applied to an aqueous additive in a field where physical properties corresponding to gelation resistance are desired.

[0010]

Means for Solving the Problems The present inventors diligently studied to achieve the above object. As a result, the specific allyl ether-based monomer represented by the following general formula (1) as an essential component is used as the allyl ether-based monomer, and the monomer component at the time of polymerization is contained as an impurity as described below. It has been found that it is important that the content of the compound represented by the general formula (2) is not more than a specific amount in solving the problem.

More specifically, the polymer has a structural unit derived from the specific allyl ether-based monomer, and the polymer contains a dioxolane compound having an alkyl group and a halogenated alkyl group as substituents. If the amount is less than or equal to the specified amount, the polymer may contain various water-based additives (eg, treating agents, detergents, water treating agents, fiber treating agents, detergent builders, etc.).
It was also found that it had physical properties suitable for.

The present inventors presumed that various impurities contained in the monomer components used in the polymerization will affect the physical properties of the polymer obtained by the polymerization in the course of the above-mentioned studies, Paying attention to the raw material for producing the allyl ether monomer of the general formula (1), which is an essential component in the body component, the amount of the specific compound in the raw material affects the physical properties of the polymer; And, I have found that the compound is specifically a dioxolane compound having a substituent as shown by the following general formula (2).

The method for producing an allyl ether polymer according to the present invention is a method for producing an allyl ether polymer in which a monomer component having an allyl ether monomer as an essential component is polymerized. The system monomer is an allyl ether system monomer represented by the following general formula (1), and a monomer component having a content of the compound represented by the following general formula (2) of 500 ppm or less is used. It is characterized by the following. General formula (1):

[0014]

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<Where p represents an integer of 1 to 4;
And r each independently represent an integer of 0 or 1 to 100; R ² and R ³ each independently represent an alkylene group having 2 to 4 carbon atoms; Y and Z each independently represent a hydroxyl group; An alkoxyl group, a monovalent phosphate group (however,
A monovalent metal, a divalent metal, a salt of an ammonium group or an organic amine group or a mono- or di-ester of an alkyl group having 1 to 4 carbon atoms or a monovalent sulfonic acid group (including 1
Or a salt of a divalent metal, an ammonium salt or an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms), or Y and Z are bonded to each other to form 2 Which represents a divalent phosphoric acid group or a divalent sulfonic acid group> General formula (2):

[0016]

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(Where R ⁴ is an alkylene group having 2-4 carbon atoms, R ⁵ is an alkyl group having 1-5 carbon atoms, and X represents halogen).

More specifically, the compound represented by the general formula (2) may be, for example, an impurity contained in a raw material used for producing the allyl ether-based monomer (I). is there. Further, it may be an impurity produced by a side reaction during the production of the allyl ether-based monomer (I).

In the method for producing an allyl ether-based polymer of the present invention, the content of the compound represented by the general formula (2) is set to 500 ppm or less, so that the compound is obtained by polymerization according to the method of the present invention. The polymer has excellent gelation resistance and can be prevented from being insolubilized in, for example, a boiler water system or a cooling water system.

Further, when used in combination with an anticorrosive such as a zinc-based or condensed phosphoric-acid-based agent, the formation of scale can be controlled by suppressing the precipitation of zinc ions or phosphate ions, and no phosphorus-based compound is contained. Accordingly, it is possible to obtain a polymer having no phosphorus or low phosphorus and having excellent low-pollution properties and useful for scale prevention.

Similarly, the polymer obtained by polymerization according to the method of the present invention may be any of various polymers having physical properties such as gelation resistance.
It is most suitable as a polymer having various physical properties (detergency, dispersibility of pigment, clay, etc.) desired as an aqueous additive.
Therefore, the allyl ether-based polymer of the present invention is most suitable as various water-based additives.

The polymer obtained by polymerization according to the method of the present invention is a water-soluble polymer having excellent various physical properties and usable for various aqueous additives.

In the method for producing an allyl ether polymer according to the present invention, the amount of the monomer component used is set to 100% by weight, and the allyl ether monomer of the general formula (1) is used in an amount of 1: 1.
It is preferable to copolymerize a monomer component containing 0 to 95.0% by weight. More specifically, 1.0 to 95.0% by weight of an allyl ether monomer (I) of the general formula (1) and 99.0 to 5.0% by weight of a (meth) acrylic acid monomer (II) % And a monomer component composed of 0 to 70% by weight of the other monomer (III) copolymerizable with these monomers, in a proportion that the total amount of each of the components is 100% by weight. Is preferred.

The polymer obtained in a preferred embodiment of the method of the present invention contains a structural unit derived from an allyl ether-based monomer as shown in the following general formula (3) in an amount of from 0.5 to 0.5. Having 80 mol% and the general formula (3):

[0025]

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Wherein p represents an integer of 1 to 4, and q
And r each independently represent an integer of 0 or 1 to 100; R ² and R ³ each independently represent an alkylene group having 2 to 4 carbon atoms; Y and Z each independently represent a hydroxyl group; An alkoxyl group, a monovalent phosphate group (however,
A monovalent metal, a divalent metal, a salt of an ammonium group or an organic amine group or a mono- or di-ester of an alkyl group having 1 to 4 carbon atoms or a monovalent sulfonic acid group (including 1
Or a salt of a divalent metal, an ammonium salt or an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms), or Y and Z are bonded to each other to form 2 Represents a divalent phosphoric acid group or a divalent sulfonic acid group> and a general formula (4) represented by the following general formula (4):

[0027]

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(In the above, R ¹ represents ^{1 to} 12 carbon atoms.
Wherein M is a metal salt. The polymer has 20 to 99.5 mol% of a structural unit derived from a (meth) acrylic acid-based monomer in the polymer. A polymer,
The following general formula (2),

[0029]

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Wherein R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms, and X represents halogen.
m or less.

By adopting these constitutions, more specifically, by using this water-soluble polymer as a scale inhibitor, which is one application of the water-based additive, it has higher gelation resistance. Since it can be a polymer, insolubilization can be minimized in a boiler system and a cooling water system, scale prevention with higher performance can be realized.

When used in combination with a corrosion inhibitor such as a zinc-based or condensed phosphoric-acid-based agent, the formation of scale can be controlled by suppressing the precipitation of zinc ions and phosphate ions, and since phosphorus-based compounds are not contained, It can be a phosphorus-free or low-phosphorus polymer excellent in low pollution and useful for scale prevention. Further, a polymer having excellent gelation resistance and not being insolubilized in a boiler water system or a cooling water system can be obtained.

According to the above configuration, even when used in combination with a corrosion inhibitor such as a zinc-based or condensed phosphoric-acid-based agent, the formation of scale can be controlled by suppressing the precipitation of zinc ions and phosphate ions, and the phosphorus-based agent can be used. Since it does not contain a compound, it can be a phosphorus-free or low-phosphorus scale inhibitor excellent in low pollution. Further, it is possible to obtain a high-performance scale inhibitor having excellent gelation resistance and not being insolubilized in a boiler water system or a cooling water system.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be described in detail below.

The allyl ether monomer (I) represented by the above general formula (1) used in the present invention includes, for example,
3-allyloxypropane-1,2-diol, 3-allyloxypropane-1,2-diol phosphate, 3-
Allyloxypropane-1,2-diol sulfonate,
3-allyloxy-1,2-di (poly) oxyethylene ether propane, 3-allyloxy-1,2-di (poly)
Oxyethylene ether propane, 3-allyloxy-
1,2-di (poly) oxyethylene ether propane phosphate, 3-allyloxy-1,2-di (poly) oxyethylene ether propane sulfonate, 3-allyloxy-1,2-di (poly) oxypropylene ether propane, -Allyloxy-1,2-di (poly) oxypropylene ether propane phosphate, 3-allyloxy-1,2-di (poly) oxypropylene ether propane sulfonate, 6-allyloxyhexane-1,2,2
3,4,5-pentaol, 6-allyloxyhexane-
1,2,3,4,5-pentaol phosphate, 6-
Allyloxyhexane-1,2,3,4,5-pentaolsulfonate, 6-allyloxy-1,2,3,4,5
Penta (poly) oxyethylene ether hexane, 6
-Allyloxy-1,2,3,4,5-penta (poly) oxypropylene ether hexane, 3-allyloxy-2
-Hydroxypropanesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts of these exemplified compounds, or phosphoric acid esters or sulfate esters of the exemplified compounds and their monovalent metal salts, Valent metal salt, ammonium salt or organic amine salt; 3-allyloxy-2- (poly) oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or phosphorus of these compounds Acid esters or sulfates and their monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts; 3-allyloxy-2- (poly) oxypropylenepropanesulfonic acid and its monovalent metal salts, divalent metal salts , Ammonium salts or organic amine salts, or phosphates or sulfates of these compounds Ether and monovalent metal salts thereof, divalent metal salts, ammonium salts or organic amine salts; and the like. Among these allyl ether monomers, those having p of 1 in the general formula (1) are easily available industrially and are advantageous.

The monomer component used in the present invention contains at least one of the above-mentioned allyl ether monomers (I),
When the content of the compound represented by the following general formula (2) is 500 p
pm or less. The following general formula (2):

[0037]

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(Where R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms, and X represents a halogen). And a dioxolane compound having a halogenated alkyl group.

The substitution position of the substituent is not particularly limited.
Further, the kind of the halogen element is not limited. R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms, and X is a halogen element. The halogen element is not particularly limited as long as it is a halogen element. Specifically, it is a halogen element selected from fluorine, chlorine, bromine, and iodine, and more specifically, chlorine.

Among the compounds, particularly representative compounds are
The alkyl group represented by R ⁵ is an ethyl group, and <X—R ⁴ —
The dioxolane compound wherein the alkyl halide group represented by> is a chloromethyl group. More specifically, 2-
Alkyl-4-halogenated alkyl dioxolane. More specifically, it is 2-ethyl-4-chloromethyldioxolan.

The compound of the above general formula (2) is derived from a raw material for producing an glycidyl compound, such as an allyl glycidyl ether, which is an epoxy compound used for producing the allyl ether monomer used in the present invention. so,
It is derived from an epoxy compound and an alkyl aldehyde having a halogen element as a substituent. Specifically, the raw material for the production of allyl glycidyl ether, epihalohydrin epichlorohydrin and by-produced from propyl aldehyde contained in the raw material, thereby,
As a result, a halogenated alkyl group and a dioxolane compound having an alkyl group as a substituent represented by the general formula (2) are produced. The position where the substituent on the dioxolane structure enters is not particularly limited. The above dioxolane compounds having different substitution positions may be produced depending on reaction conditions, production conditions, and the like. In terms of the reaction mechanism, more specifically, it is a 2-alkyl-4-halogenated alkyldioxolane having a substituent at the 2-position and 4-position.

In the present invention, attention has been paid to the generated impurity amount. Then, if predetermined production conditions are set so that the amount becomes a certain amount or less, that is, glycidyl compound which is a raw material used in producing an allyl ether-based monomer and has a small content of this impurity is glycidyl compound. By adopting a compound, and also in terms of production conditions, by adopting production conditions such that generation of this impurity is reduced,
Preferably, a specific allyl ether-based monomer that can be used in the present invention can be obtained.

Then, the allyl ether monomer is
For example, it has been found that it is an optimum raw material for a water-soluble polymer. Specifically, when the water-soluble polymer is used for a scale inhibitor, the content of the compound represented by the general formula (2) is added to the important physical property such as gelation resistance of the polymer. It has been found that it particularly affects, and the range of the preferable content in the polymer is specified.

When the amount of the compound represented by the general formula (2) among the impurities contained in the raw material for producing the allyl ether monomer (I) is more than 500 ppm, the allyl ether obtained by the production is preferably used. Many impurities are present in the system monomer and the allyl ether monomer composition. Then, the polymer represented by the general formula (2) is contained in a polymer obtained by polymerizing the allyl ether-based monomer or the allyl ether-based monomer composition as a monomer component. Become. And its content in the polymer,
When the amount exceeds the predetermined amount, the gelation resistance, which is a physical property of the polymer, is low, and the polymer is easily insoluble in a boiler water system and a cooling water system.

If the content of the compound represented by the general formula (2) among the impurities contained in the raw material of the allyl ether-based monomer (I) is less than 0.1 ppm, it becomes a measurement limit of analysis. Therefore, in order to obtain excellent performance as a scale inhibitor, the content of the compound represented by the general formula (2) mixed or generated in the raw material of the allyl ether-based monomer (I) is included. The amount is preferably in the range of 0.1 to 500 ppm, and desirably in the range of 0.1 to 300 ppm in order to become a raw material suitable as a higher performance scale inhibitor. More preferably, 1-2
It is within the range of 00 ppm.

The allyl ether-based monomer (I) is, for example, a compound in which the allyl ether-based monomer (I) is 3-allyloxypropane-1,2-diol (3-allyloxy-1,2).
-Dihydroxypropane) can be obtained, for example, by reacting allyl glycidyl ether with water. In this case, in the general formula (1),
This is the case where r = 0, Z = OH, q = 0, and Y = OH.

When the allyl ether monomer is 3-allyloxy-2-hydroxypropanesulfonic acid, the allyl ether monomer is obtained, for example, by reacting allyl glycidyl ether with sodium hydrogen sulfite. Obtainable. In this case, in the general formula (1), r = 0, Z = SO ₃ Na (H), q
= 0, Y = OH.

More preferably, in the embodiment of the present invention, the content of the compound of the general formula (2) is 500 ppm.
Hereinafter, specifically, the content is 0.1 to 500 ppm
It is necessary to use an allyl glycidyl ether within the range as a raw material.

In other words, when producing an allyl ether monomer represented by the general formula (1), the epoxy compound as a raw material to be used is used as an impurity contained therein, as an impurity contained in the general formula (2). It is preferable to select an epoxy compound in which the content of the compound represented by the formula is in the range of 0.1 to 500 ppm. Such a method of evaluating and selecting a raw material is one of the preferred embodiments in the production form of the allyl ether-based monomer used in the present invention. In other words, focusing on a raw material having a small amount of a specific compound, selecting the raw material, and producing a water-soluble polymer having physical properties such as excellent gelation resistance, etc. It is valid. This selection method is very effective as one index of a raw material selection method or a preferable raw material evaluation method when producing a polymer suitable for various uses.

Specific examples of the allyl ether-based monomer used in the present invention include the following general formula (1):
This is an allyl ether-based monomer shown when p = 1. This structure is shown below as general formula (5). General formula (5):

[0051]

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More specifically, the polymer of the present invention is a polymer obtained by polymerizing a monomer component containing at least the monomer component represented by the general formula (5). And a polymer having at least a structural unit represented by the following general formula (6).

More specifically, the structure represented by the general formula (6) is a structure derived from the monomer component represented by the general formula (5). General formula (6):

[0054]

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In the formula, q and r each independently represent 0 or an integer of 1 to 100, R ² and R ³ each independently represent an alkylene group having 2 to 4 carbon atoms, Y and Z
Are each independently a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a monovalent phosphate group (however, a salt of a monovalent metal, a divalent metal, an ammonium group or an organic amine group, or a salt having 1 to 4 carbon atoms)
Or a mono or diester of an alkyl group of
A monovalent sulfonic acid group (including a salt of a monovalent metal, a divalent metal, an ammonium salt or an organic amine group, or an ester of an alkyl group having 1 to 4 carbon atoms), or Y
And Z are bonded to each other and represent a divalent phosphate group or a divalent sulfonic acid group as a whole. In the embodiment of the present invention, the specific polymer described above is also Similarly, the content of the specific compound represented by the general formula (2) is preferably in the range of 0.1 to 500 ppm. Within this range, the polymer exhibits good physical properties such as gelation resistance.

In the present invention, specifically, the content of the compound represented by the general formula (2) is 0.1 to 500 pp.
An allyl ether-based monomer synthesized by reacting water with a glycidyl compound having a range of m is a preferred embodiment in the present invention. More specifically, the glycidyl compound is allyl glycidyl ether, and the compound formed by reacting with water is 3-allyloxypropane-
The case of 1,2-diol (3-allyloxy-1,2-dihydroxypropane) is a preferred embodiment of the present invention.

Similarly, an allyl ether monomer synthesized by reacting sodium hydrogen sulfite with a glycidyl compound having a content of the compound represented by the general formula (2) in the range of 0.1 to 500 ppm. Is a preferred form in the present invention. More specifically, a preferred embodiment of the present invention is where the glycidyl compound is allyl glycidyl ether and the compound formed by reaction with sodium bisulfite is 3-allyloxy-2-hydroxypropanesulfonic acid.

The above-mentioned gelation resistance is a numerical value that evaluates the ease of precipitation of a polymer in the presence of calcium ions, and is used as an index indicating the performance of the scale inhibitor of the present invention. The gelation resistance can be determined by a gelation resistance test described below. The smaller the gelation resistance value, the better the gelation property and the higher the performance when used as a scale inhibitor.

The (meth) acrylic acid monomer (II) which can be used as a monomer component in the present invention is represented by the following general formula (7):
It is a structure shown by.

[0060]

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(Wherein, R ¹ represents hydrogen or a methyl group, M represents hydrogen, a monovalent metal, a divalent metal, an ammonium group or an organic amine group) The above (meth) acrylic acid-based monomer (II)
For example, acrylic acid, sodium acrylate, potassium acrylate, lithium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, potassium methacrylate, lithium methacrylate, ammonium methacrylate and the like can be mentioned. These may be structures of various metal salts such as a sodium salt.

Further, other monomers optionally used in the present invention, that is, the above-mentioned allyl ether monomer (I) and (meth) acrylic acid monomer (II)
The amount of the other monomer (III) that can be copolymerized with is not particularly limited. For example, when good water solubility and good gelation resistance are desired as a water-soluble polymer, the total of the monomer components used, ie, allyl ether monomer (I), (meth) acrylic acid The total amount of the system monomer (II) and other copolymerizable monomer (III) is 100
% By weight, other copolymerizable monomers (II
I) is used in an amount up to 70% by weight. That is, 0-7
It is used in the range of 0% by weight. More preferably, 0-5
The range is 0% by weight. More preferably, it is in the range of 0 to 25% by weight.

Examples of the other copolymerizable monomer (III) include styrene, p-methylstyrene, α-methylstyrene, vinyl acetate, vinyl pyrrolidone, methyl vinyl ether, ethyl vinyl ether,
(Meth) allyl alcohol, isoprenol, isoprene, butadiene, (meth) acrylonitrile, (meth)
Acrylamide, N, N-dimethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) ) Acrylate, diethylaminoethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, Phenoxy polyethylene glycol (meth) acrylate, naphthoxy polyethylene glycol (meth) acrylate There is maleic acid, fumaric acid,
Itaconic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts of these acids, such as vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, and (meth) allylbenzene Sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, sulfoethyl (meth) acrylate, 2-methyl-1,3-butadiene-1-sulfonic acid, 2-hydroxy-3- (meth) acrylamidopropanesulfone Examples thereof include acids, isoamylsulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts of these acids. These other monomers (III) may be used alone,
Two or more of them may be used as a mixture. In order to make the polymer of the present invention a more preferable polymer as a water-soluble polymer, a water-soluble monomer may be selected from the monomers listed above. In addition, when improving the chelating power, detergency and dispersibility of a metal, it may be preferable to use an unsaturated dibasic acid such as maleic acid or fumaric acid in combination.

The amounts of the above-mentioned allyl ether monomer (I), (meth) acrylic acid monomer (II) and other copolymerizable monomer (III) are as follows. (I) 1.0 to 95.0% by weight, (meth) acrylic acid-based monomer (II) 5 to 99.0% by weight and copolymerizable monomer (III) 0 to 70% by weight Range (provided that the total amount thereof is 100% by weight). In order for the polymer obtained in the present invention to have good physical properties as a scale inhibitor, allyl ether-based monomer (I), (meth) acrylic acid-based monomer (II) and monomer (III) ) Is preferably within the above range.

Allyl ether monomers (I), (meth)
In order to obtain a copolymer from a monomer component composed of the acrylic acid monomer (II) and the monomer (III), a conventionally known polymerization method can be used. For example, water, organic solvents,
Alternatively, polymerization in a solvent such as a mixed solvent of a water-soluble organic solvent and water can be exemplified. At this time, for polymerization in an aqueous solvent, a persulfate, hydrogen peroxide, an organic peroxide, an azo-based initiator or the like is used as a polymerization initiator, and an accelerator such as sodium hydrogen sulfite or ascorbic acid is used in combination. can do. For polymerization in a mixed solvent of a water-soluble organic solvent and water, any of the above-mentioned various polymerization initiators or a combination of a polymerization initiator and an accelerator can be appropriately selected and used.

The copolymer thus obtained can be used as it is as a scale inhibitor, but if necessary, it can be further neutralized with an alkaline substance. Such alkaline substances include hydroxides, chlorides and carbonates of monovalent and divalent metals; ammonia;
Organic amines and the like can be mentioned.

As a scale inhibitor containing a polymer obtained by the method of the present invention, the polymer alone is sufficiently effective, but may be used in combination with other additives used in the art. it can. For example, a phosphorus-free water treatment composition can be obtained in combination with a phosphorus-free anticorrosive such as molybdenum. If necessary, it can be used in combination with a slime inhibitor or a chelating agent.

The scale inhibitor containing the polymer obtained by the method of the present invention can be used in the same manner as a normal scale inhibitor, for example, by metering injection or intermittent injection so that the concentration in the circulating water becomes constant. It can be used, and its addition amount is generally 1 to 50 ppm, and a sufficient effect is recognized.

In the above description, the case of a scale inhibitor is shown as an example of the water-based additive. However, the allyl ether-based monomer and the monomer composition of the present invention have a small amount of specific impurities.
It is also useful as a monomer component for polymerization of a water-soluble polymer that requires similar physical properties, and similar properties-improving effects can be expected for polymers for various uses, specifically, water-soluble polymers. The water-soluble polymer described above has properties such as gelation resistance in detergent builders, calcium ion dispersibility, detergency and bleaching performance in fiber treatment agents, and dispersibility in various other dispersants (eg, pigment dispersants). , Good physical properties can be expected.

[0070]

EXAMPLES The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. “%” In Examples and Comparative Examples indicates “% by weight”. The following examples,
Each polymer obtained in the comparative example (hereinafter, “water-soluble copolymer”
) And the scale inhibition rate of a scale inhibitor using the water-soluble copolymer as a main component were evaluated by the following methods.

[1] Gelation resistance test Demineralized water, boric acid-sodium borate, and calcium chloride aqueous solution were added to a 500 ml tall beaker in this order.
= 8.5, the polymer concentration was 100 ppm in terms of solid content,
900ppm of calcium concentration in terms of calcium carbonate
The test solution was adjusted to 500 g so that After leaving this test solution in a thermostat at 90 ° C. for 1 hour, stirring,
The sample was placed in a 5 cm quartz cell, and the absorbance (a) at a UV wavelength of 380 nm was measured. A test solution prepared by removing calcium chloride from the above test solution was prepared as a blank, and the absorbance (b) was measured by the same operation, and the gelation degree was determined from the following equation. The greater the degree of gelation, the more easily the copolymer and calcium ions combine to form a gel, indicating that the performance is poor when used as a scale inhibitor. Gelation degree = (a)-(b) [2] Calcium carbonate scale inhibition test 70 g of demineralized water in a glass bottle with a capacity of 225 ml that can be sealed.
And a 0.735% aqueous solution of calcium chloride dihydrate 10
g, and the water-soluble copolymer (1) obtained in Examples 1 to 5,
0.00 of each of (2), (3), (4), and (5)
10 g of a 1, 0.005, 0.01% aqueous solution (1 ppm, 5 ppm or 10 p
pm) mixed. 0.42% sodium bicarbonate
An aqueous solution (10 g) was added and mixed, and the pH was adjusted to 8.5 with an aqueous sodium hydroxide solution. The obtained calcium carbonate 5
A glass bottle of a supersaturated aqueous solution of 00 ppm is sealed and
For 18 hours. Then, after cooling, the precipitate was filtered through a 0.1 μm membrane filter, and the filtrate was subjected to JI
Analysis was performed according to SK0101, and the scale inhibition rate was determined according to the following equation.

The water-soluble copolymer (1) obtained in Examples 1 to 5
The above method was repeated, except that the water-soluble copolymers (6) and (7) obtained in Comparative Examples 1 and 2 were used instead of (5). The test was repeated by repeating the above method except that no water-soluble copolymer was added.

The scale suppression rate can be calculated by the following equation.

Inhibition rate (%) = 100 × (CB) / (AB) A: Ca concentration before heating treatment (= 500 ppm: in terms of calcium carbonate) B: Filtrate after test without scale inhibitor Ca concentration (= 190 ppm: in terms of calcium carbonate) C: Ca concentration in the filtrate after the scale inhibitor addition test.

[3] Method of Measuring Polymer Molecular Weight The weight average molecular weight was measured by the following method GPC (gel permeation chromatography): Column: GF-7MHQ (manufactured by Showa Denko) Mobile phase: disodium hydrogen phosphate 12 Hydrate to 34.
5 g and 46.2 sodium dihydrogen phosphate dihydrate
g, pure water is added to all (special grade reagent) to make the total amount 500
0 g aqueous solution. -Detector: UV 214 nm (Model 481, manufactured by Nippon Waters)-Flow rate: 0.5 ml / min-Temperature: 35 ° C-Calibration curve: Sodium polyacrylate standard sample (manufactured by Sowa Kagaku)

Example 1 235 g of demineralized water was charged into a 2 L 4-necked flask equipped with a reflux condenser and a dropping device, and the (meth) acrylic acid-based monomer was added to the demineralized water while stirring at the boiling point. 530 g of a 35% aqueous solution of sodium acrylate as monomer (II), 163.0 g of a 40% aqueous solution of 3-allyloxy-1,2-dihydroxypropane as allyl ether monomer (I), and as a polymerization initiator 74.5 g of a 15% aqueous solution of sodium persulfate was added dropwise over 2 hours. After completion of the dropwise addition, the boiling point was maintained for 30 minutes to complete the polymerization, and a pale yellow transparent water-soluble copolymer (1) was obtained.

A 40% aqueous solution of 3-allyloxy-1,2-dihydroxypropane was synthesized by reacting allyl glycidyl ether with pure water. Of the raw materials used for synthesizing the 3-allyloxy-1,2-dihydroxypropane aqueous solution,
In the allyl glycidyl ether, the content of impurities, 2-ethyl-4-chloromethyldioxolane, was 80 p.
pm.

The weight-average molecular weight of the water-soluble copolymer (1) measured by gel permeation chromatography was 4,600. The gelation resistance of the water-soluble copolymer (1) was evaluated by the gelation resistance test.

Example 2 211.0 g of demineralized water was charged into the same four-neck flask as used in Example 1, and the allyl ether monomer (I) was added to the demineralized water while stirring at the boiling point. 239.8 g of a 30% aqueous solution of sodium 3-allyloxy-2-hydroxypropanesulfonate as))
Then, 472.7 g of a 35% aqueous solution of sodium acrylate as a (meth) acrylic acid monomer (II) and 72 g of a 15% aqueous solution of sodium persulfate as a polymerization initiator were added dropwise over 2 hours. After completion of the dropwise addition, the boiling point was maintained for 30 minutes to complete the polymerization, and a pale yellow transparent water-soluble copolymer (2) was obtained.

A 30% aqueous solution of sodium 3-allyloxy-2-hydroxypropanesulfonate was obtained by reacting an allyl glycidyl ether with an aqueous solution of sodium hydrogen sulfite.

Among the raw materials used in the synthesis of sodium 3-allyloxy-2-hydroxypropanesulfonate, the content of 2-ethyl-4-chloromethyldioxolane as an impurity was 20 ppm in allyl glycidyl ether.
Met. The weight average molecular weight measured by gel permeation chromatography was 4,900. The water-soluble copolymer (2) thus obtained was subjected to the same gelation resistance test as in Example 1.

Example 3 Among the raw materials used for the synthesis of sodium 3-allyloxy-2-hydroxypropanesulfonate, 2-ethyl-4 in allyl glycidyl ether was used.
A water-soluble copolymer (3) was obtained in exactly the same manner as in Example 2 except that the one having a content of -chloromethyldioxolane of 80 ppm was used. The weight average molecular weight was 5,000 as measured by gel permeation chromatography. The water-soluble copolymer (3) obtained as described above was subjected to the same gelation resistance test as in Example 1.

Example 4 Of the raw materials used for the synthesis of sodium 3-allyloxy-2-hydroxypropanesulfonate, 2-ethyl-4 in allyl glycidyl ether was used.
A water-soluble copolymer (4) was obtained in exactly the same manner as in Example 2 except that the one having a content of -chloromethyldioxolane of 160 ppm was used. The weight average molecular weight was 5,000 as measured by gel permeation chromatography. The water-soluble copolymer (4) obtained as described above was subjected to the same gelation resistance test as in Example 1.

Example 5 Among the raw materials used for the synthesis of sodium 3-allyloxy-2-hydroxypropanesulfonate, 2-ethyl-4 in allyl glycidyl ether was used.
A water-soluble copolymer (5) was obtained in exactly the same manner as in Example 2 except that the one having a content of -chloromethyldioxolane of 400 ppm was used. The weight average molecular weight was 5,300 as measured by gel permeation chromatography. The water-soluble copolymer (5) thus obtained was subjected to the same gelation resistance test as in Example 1.

Comparative Example 1 Among the raw materials used for the synthesis of a 40% aqueous solution of 3-allyloxy-1,2-dihydroxypropane, allyl glycidyl ether was an impurity.
-Ethyl-4-chloromethyldioxolane content is 8
The one of 00 ppm was used. Except that, in the same manner as in Example 1, a water-soluble copolymer (6) was obtained. The polymerization average molecular weight was 4,600.

Comparative Example 2 Among the raw materials used for the synthesis of sodium 3-allyloxy-2-hydroxypropanesulfonate, which is a 30% aqueous solution, allyl glycidyl ether was 2-ethyl-4-chloromethyl as an impurity. A dioxolane having a content of 800 ppm was used. Otherwise in the same manner as in Example 2, the water-soluble copolymer (7)
I got The weight average molecular weight was 4,800.

As described above, a gelation resistance test similar to that of Example 1 was performed on the water-soluble copolymer (6) obtained in Comparative Example 1 and the water-soluble copolymer (7) obtained in Comparative Example 2. . Table 1 shows the above results. In the table, <degree of gelation> is an item of gelation resistance.

[0088]

[Table 1]

As is evident from Table 1, those having a content of 800 ppm of 2-ethyl-4-chloromethyldioxolan mixed as an impurity into the allyl glycidyl ether, which is the raw material of the allyl ether monomer (I), were used. In the case of Comparative Examples 1 and 2, it was found that a polymer having a high gelation degree was obtained and the gelation resistance was poor. On the other hand, the water-soluble copolymers (1) to (5) obtained in the present example have better gelation resistance than the water-soluble copolymers (6) and (7) obtained in the comparative example. I understood.

[0090]

The polymer obtained by the method of the present invention is
Boiler water system, cooling water system, etc.
This has the effect of not being insolubilized in various water systems. Also, when used in combination with an anticorrosive such as a zinc-based or condensed phosphoric acid-based one, the generation of scale can be controlled by suppressing the precipitation of zinc ions and phosphate ions, and since it does not contain a phosphorus-based compound, A polymer useful for prevention of scale, which is excellent in phosphorus or low phosphorus and has low pollution properties, can be obtained.

The polymer obtained by the method of the present invention is useful as the same kind of water-based additive in applications such as water-based treatment agents, detergents, water treatment agents, fiber treatment agents, detergent builders, and various dispersants. It is a polymer.

Therefore, even when used in combination with a corrosion inhibitor such as a zinc-based or condensed phosphoric acid-based agent, the formation of scale can be controlled by suppressing the precipitation of zinc ions and phosphate ions, and no phosphorus-based compound is contained. Therefore, it is possible to obtain a phosphorus-free or low-phosphorus polymer excellent in low pollution and useful for scale prevention. Further, a polymer having excellent gelation resistance and not being insolubilized in a boiler water system or a cooling water system can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 230/02 C08F 230/02 290/06 290/06 C11D 3/37 C11D 3/37 F term (reference) 4H003 EB28 FA04 FA07 FA37 4J027 AC02 AC07 BA02 BA04 BA06 CB01 CB02 CC02 CD00 4J100 AB02R AB03R AB04R AB07R AD03R AE03R AE04R AE18P AG04R AJ02Q AJ08R AJ09R AK03Q AK08Q AK18R AL03R AL04R AL08R AL09R AM02R AM15R AM21R AP01R AQ08R AS02R AS03R AS06R BA02R BA03P BA03R BA05R BA06R BA08P BA08R BA31R BA55P BA56P BA56R BA64P BA65P BC43R BC49R CA04 CA05 DA38 JA00 JA11 JA15 JA18 JA57

Claims (4)

[Claims] 1. A method for producing an allyl ether polymer in which a monomer component having an allyl ether monomer as an essential component is polymerized, wherein the allyl ether monomer is represented by the following general formula (1): Characterized by using an allyl ether-based monomer having a content of a compound represented by the following general formula (2) of 500 ppm or less as the monomer component: Production method. General formula (1): Wherein p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R ² and R
³ independently represents an alkylene group having 2 to 4 carbon atoms; Y and Z each independently represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a monovalent phosphate group (however, a monovalent metal, 2
A salt of a valent metal, an ammonium group or an organic amine group or a mono- or diester of an alkyl group having 1 to 4 carbon atoms or a monovalent sulfonic acid group (however, a monovalent metal, a divalent metal, an ammonium salt or an organic amine) Group, or an ester of an alkyl group having 1 to 4 carbon atoms),
Alternatively, Y and Z are bonded to each other and represent a divalent phosphate group or a divalent sulfonic acid group as a whole.> General formula (2): (However, R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms, and X represents halogen) 2. The allyl ether-based polymer according to claim 1, wherein the compound represented by the general formula (2) is contained in a raw material for producing the allyl ether-based monomer. Manufacturing method. 3. The method according to claim 1, wherein the monomer component is 1.0 to 95.0% by weight of the allyl ether monomer (I) and 99.0 to 5.0 (meth) acrylic acid monomer (II). 0% by weight and other monomers (III) copolymerizable with these monomers
3. The method for producing an allyl ether-based polymer according to claim 1, which is a monomer component comprising 0 to 70% by weight. 4. The method for producing an allyl ether polymer according to claim 1, wherein said allyl ether polymer is contained in an aqueous additive.