JP6752177B2 - Composition containing sulfonic acid group-containing ether compound and method for producing the same - Google Patents

Description

The present invention relates to a sulfonic acid group-containing ether compound-containing composition and a method for producing the same. More specifically, the present invention relates to a sulfonic acid group-containing ether compound-containing composition useful for various uses, such as a water treatment agent, a detergent builder, and a dispersant, and a method for producing the same.

The sulfonic acid group-containing ether compound having an unsaturated double bond, a sulfonic acid (salt) group and an ether bond is a polymer used in water treatment agents, detergent builders, detergent compositions, dispersants, cleaning agents and the like. It is a compound useful as a raw material, and sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (hereinafter, also referred to as “HAPS”) is known as a typical compound.

Such a sulfonic acid group-containing ether compound includes a production method in which a specific ether compound such as allylglycidyl ether and a sulfite aqueous solution are added dropwise to alkaline water whose pH is adjusted to 10 or more, and a sulfonic acid group-containing ether compound. The composition is disclosed (see, for example, Patent Document 1).
In addition, a sulfonic acid group-containing ether compound including a step of adjusting the pH to 5.5 or more using an alkaline substance and a step of adding a specific ether compound such as allyl glycidyl ether to a reactor in which the sulfite compound is present. A production method and a composition containing a sulfonic acid group-containing ether compound are disclosed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2011-213615 International Publication No. 2010/030024

As described above, methods for producing a sulfonic acid group-containing ether compound and a composition containing a sulfonic acid group-containing ether compound have been conventionally reported, but no description is given regarding long-term storage of the sulfonic acid group-containing ether compound. Not. The present inventor has found a new problem that the color tone changes when the sulfonic acid group-containing ether compound-containing composition is stored for a long period of time. When a composition containing a sulfonic acid group-containing ether compound having a changed color tone is used as a raw material for a polymer, the color tone of the obtained polymer deteriorates, which is not desirable. Therefore, it is necessary to improve the color stability of the sulfonic acid group-containing ether compound-containing composition when stored for a long period of time.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a sulfonic acid group-containing ether compound-containing composition and a method for producing the same, which have excellent color tone stability even when stored for a long period of time.

As a result of various studies on means for solving the above problems, the present inventor has made at least one compound selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds with respect to sulfonic acid group-containing ether compounds. When the composition contains the above in a predetermined ratio, the color change of the sulfonic acid group-containing ether compound is suppressed, and the sulfonic acid group-containing ether compound-containing composition has excellent color stability even when stored for a long period of time. I found that. The present inventor has further found a suitable method for producing a sulfonic acid group-containing ether compound-containing composition having excellent color stability, and has conceived that the above problems can be solved brilliantly, and reached the present invention. It was done.

That is, the present invention provides the following general formula (1);

(In the formula, ^{R 1,} .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ groups, .X representing H or CH ₃ group, Y represents a hydroxyl group or a sulfonic acid (salt) groups, One of X and Y represents a hydroxyl group, and the other represents a sulfonic acid (salt) group.) From a sulfonic acid group-containing ether compound, a sulfur-containing compound, a phosphorus-containing compound, and a nitrogen-containing compound. The content of at least one compound selected from the group consisting of the sulfur-containing compound, the phosphorus-containing compound and the nitrogen-containing compound includes at least one compound selected from the group consisting of sulfonic acid group-containing ether compounds. It is a sulfonic acid group-containing ether compound-containing composition characterized by being 2.3 to 19 mol% with respect to 100 mol%.
The present invention also has the following general formula (1);

(In the formula, ^{R 1,} .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ groups, .X representing H or CH ₃ group, Y represents a hydroxyl group or a sulfonic acid (salt) groups, One of X and Y represents a hydroxyl group, and the other represents a sulfonic acid (salt) group.) From a sulfonic acid group-containing ether compound, a sulfur-containing compound, a phosphorus-containing compound, and a nitrogen-containing compound. A method for producing a composition containing at least one compound selected from the above group.
The above manufacturing method is described in the following general formula (2);

(In the formula, R ¹ represents a single bond, CH ₂ groups or CH ₂ CH ₂ groups. R ² represents H or CH ₃ groups.) Sulfonic acid (salt) and / or weight. At least one selected from the group consisting of a sulfur-containing compound, a phosphorus-containing compound and a nitrogen-containing compound in the composition containing the sulfonic acid group-containing ether compound obtained by the step of reacting with sulfite (salt) and the above reaction step. A method for producing a sulfonic acid group-containing ether compound-containing composition, which comprises a step of adjusting the amount of the seed compound to 2.3 to 19 mol% with respect to 100 mol% of the sulfonic acid group-containing ether compound. But also.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Sulfonic acid group-containing ether compound-containing composition>
The sulfonic acid group-containing ether compound-containing composition of the present invention comprises at least one compound selected from the group consisting of a sulfur-containing compound, a phosphorus-containing compound and a nitrogen-containing compound (hereinafter, also referred to as "color inhibitor"). It is characterized in that it contains 2.3 to 19 mol% with respect to 100 mol% of the sulfonic acid group-containing ether compound represented by the general formula (1).
Coloring of a sulfonic acid group-containing ether compound-containing composition is considered to occur due to an oxidation reaction of impurities contained in the composition, and is at least one selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds. It is presumed that the antioxidant action of the compound in the above suppresses the oxidation reaction of impurities, thereby suppressing the coloring of the composition.
When the sulfonic acid group-containing ether compound-containing composition of the present invention contains two or more compounds corresponding to the color-suppressing substance, the total amount of the two or more compounds is the sulfone represented by the above general formula (1). It is 2.3 to 19 mol% with respect to 100 mol% of the acid group-containing ether compound.

Examples of the sulfur-containing compound include sodium sulfite and sodium hyposulfite. Further, a sulfur-containing reducing agent, a sulfur-containing antioxidant and the like can be mentioned. Sodium sulfite and sodium hyposulfite are preferable in consideration of solubility in water and reactivity to allyl glycidyl ether.

Examples of the phosphorus-containing compound include sodium phosphite, sodium hypophosphite and the like. In addition, phosphorus-containing reducing agents, phosphorus-containing antioxidants and the like can be mentioned. Sodium phosphite and sodium hypophosphite are preferable in consideration of solubility in water and reactivity to allyl glycidyl ether.

Examples of the nitrogen-containing compound include sodium nitrite and sodium nitrite. Further, a nitrogen-containing reducing agent, a nitrogen-containing antioxidant and the like can be mentioned. Sodium nitrite and sodium hyponitrite are preferable in consideration of solubility in water and reactivity to allyl glycidyl ether.

The color-suppressing substance contained in the sulfonic acid group-containing ether compound-containing composition of the present invention may be at least one compound selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds, and is not particularly limited. However, a sulfur-containing compound is preferable, and sulfite (salt) and / or sulfite (sulfite) is more preferable.

Examples of the salt of sulfite (salt) and / or heavy sulfite (salt) include metal salts, ammonium salts, organic amine salts, and more specifically, alkali metals such as sodium salts and potassium salts. Salts; alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts, barium salts; salts such as aluminum salts and iron salts; ammonium salts; alkanolamines such as monoethanolamine salts, diethanolamine salts and triethanolamine salts Salts; alkylamine salts such as monoethylamine salts, diethylamine salts, triethylamine salts; polyamine salts such as ethylenediamine salts and triethylenediamine salts can be mentioned.

In the sulfonic acid group-containing ether compound-containing composition of the present invention, the content of at least one compound selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds is represented by the above general formula (1). It is characterized in that it is 2.3 to 19 mol% with respect to 100 mol% of the sulfonic acid group-containing ether compound. By containing the color-inhibiting substance in such a ratio, the effect of suppressing the coloration of the sulfonic acid group-containing ether compound-containing composition can be satisfactorily exhibited. The content of the color inhibitor with respect to 100 mol% of the sulfonic acid group-containing ether compound represented by the general formula (1) is preferably 2.3 mol% or more, more preferably 3.3 mol% or more, still more preferably 3. It is 5.5 mol% or more, most preferably 4.0 mol% or more, preferably 17 mol% or less, more preferably 15 mol% or less, still more preferably 13 mol% or less, and most preferably 10 mol% or less.
The content of at least one compound selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds in the sulfonic acid group-containing ether compound-containing composition can be measured using redox titration. ..

The sulfonic acid group-containing ether compound-containing composition of the present invention (hereinafter, also referred to as “the composition of the present invention”) requires a compound represented by the above general formula (1) (sulfonic acid group-containing ether compound). ..
In the above sulfonic acid group-containing ether compound, the sulfonic acid (salt) group means a group represented by -SO ₃ Z (Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). .. The metal atom is preferably an alkali metal such as sodium or potassium; an alkaline earth metal such as magnesium, calcium, strontium or barium; aluminum, iron or the like is preferable, and the organic amine group is a monoethanolamine group or a diethanolamine group. Alkanolamine groups such as triethanolamine groups; alkylamine groups such as monoethylamine groups, diethylamine groups and triethylamine groups; polyamine groups such as ethylenediamine groups and triethylenediamine groups are preferable. The sulfonic acid (salt) group is more preferably a sulfonic acid group, a lithium sulfonic acid group, a potassium sulfonate group, a sodium sulfonate group, an ammonium sulfonate group, or a quaternary amine group of sulfonic acid.

In the general formula (1), R ¹ and R ² tend to improve the scale prevention ability of the obtained polymer when the sulfonic acid group-containing ether compound-containing composition is used as a raw material of the polymer. since, ^{R 1} in the general formula (1) is a CH ₂ group or _CH 2 CH ₂ group, ^{R 2} is preferably H or CH ₃ group. The sulfonic acid group-containing ether compound is more preferably sodium 3- (meth) allyloxy-2-hydroxy-1-propanesulfonate.
The sulfonic acid group-containing ether compound-containing composition of the present invention contains 20 to 80% by mass of the compound represented by the above general formula (1) with respect to 100% by mass of the sulfonic acid group-containing ether compound-containing composition of the present invention. Is preferable. If the concentration of the compound represented by the general formula (1) is too high, impurities are precipitated or precipitated, and if the concentration is too low, the polymerization concentration becomes low when used as a raw material for a polymer. There is a possibility that the polymerization reaction will not proceed easily, but if the compound represented by the general formula (1) is contained at the above concentration, the occurrence of such a problem can be sufficiently suppressed. It is more preferably 30 to 60% by mass, still more preferably 35 to 50% by mass.

The sulfonic acid group-containing ether compound-containing composition of the present invention may contain a solvent such as water, a by-product, or the like, in addition to the compound represented by the general formula (1) and the color-suppressing substance.
The compound represented by the following general formula (3) is a compound that is likely to be by-produced when the compound represented by the above general formula (1) is produced, and is contained in the above-mentioned sulfonic acid group-containing ether compound-containing composition. The content ratio of the compound represented by the following general formula (3) is appropriately less than 10 mol% with respect to 100 mol% of the compound represented by the above general formula (1). When such a sulfonic acid group-containing ether compound-containing composition is used as a polymer raw material, it becomes possible to obtain a polymer having particularly excellent scale prevention ability (scale suppression ability). From the viewpoint of the performance of such a polymer and the polymerizable property of the sulfonic acid group-containing ether compound, it is appropriate that the content ratio of the compound represented by the following general formula (3) is less than 10 mol%. It is preferably less than 5 mol%, more preferably less than 3 mol%.

(In the general formula (3), ^{R 1} represents, .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ group represents H or CH ₃ group.)

The sulfonic acid group-containing ether compound-containing composition of the present invention may contain impurities other than the compound represented by the above general formula (3), but impurities other than the compound represented by the above general formula (3). It is appropriate that the content of the compound is less than 10 mol% with respect to 100 mol% of the compound represented by the above general formula (1). More preferably, it is less than 5 mol%.

Examples of the solvent contained in the sulfonic acid group-containing ether compound-containing composition of the present invention include water and polar solvents, such as lower alcohols such as methanol and ethanol, acetone, dimethyl sulfoxide, dimethyl formamide, and dioxane. Be done. One or more of these can be used. Of these, water is preferred.

When the sulfonic acid group-containing ether compound-containing composition of the present invention contains a solvent, the content of the solvent is preferably 20 to 80% by mass with respect to 100% by mass of the sulfonic acid group-containing ether compound-containing composition. More preferably, it is 40 to 70% by mass. More preferably, it is 50 to 65% by mass.

<Method for producing sulfonic acid group-containing ether compound-containing composition>
The method for producing a sulfonic acid group-containing ether compound-containing composition of the present invention includes a step of reacting a compound represented by the general formula (2) with a sulfite compound (hereinafter, also referred to as a “reaction step”) and a reaction step. The step of adjusting the amount of the color-suppressing substance in the sulfonic acid group-containing ether compound-containing composition obtained in the above step to 2.3 to 19 mol% with respect to 100 mol% of the sulfonic acid group-containing ether compound (hereinafter, "coloring"). Also referred to as a "suppressing substance concentration adjusting step"). Further, as long as the action and effect of the present invention are not impaired, other steps as performed by a usual production method may be further included.

The above reaction step is not particularly limited as long as the compound represented by the general formula (2) is reacted with the sulfurous acid compound, but the step of adjusting the pH of the reaction system to 5.5 or more using an alkaline substance (hereinafter, "" Also referred to as "pH adjustment step") and a step of adding the compound represented by the above general formula (2) to a reactor in which sulfurous acid (salt) and / or sulfite (salt) is present (hereinafter, also referred to as "addition step"). It is preferable to include (referred to as). When the compound represented by the above general formula (2) is added to a reactor in which a sulfurous acid compound is present, if the pH is low, it is discharged to the outside of the system as sulfurous acid gas, and the yield of the obtained sulfonic acid group-containing ether compound decreases. It is considered that.

In the above pH adjustment step, examples of the alkaline substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide; ammonia; amines and the like. It is preferable to adjust the pH using seeds or two or more kinds.

As the sulfurous acid compound, sulfite, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof are suitable. The sulfurous acid compound can be used as an acid (that is, sulfurous acid or the like is used), but it is preferable to add it as a salt from the viewpoint of handling and from the viewpoint of improving the yield. That is, the sulfite compound is preferably a salt, more preferably at least one salt selected from the group consisting of sulfite, hydrogen sulfite, bisulfite and metabisulfite. Among them, lower oxides such as sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, and salts thereof are preferable. From the viewpoint of economic efficiency or improvement in yield, hydrogen sulfite and metabisulfite are more preferable, and sodium bisulfite and sodium metabisulfite are more preferable.
The salt is the same as the above-mentioned salt of sulfite (salt) and / or sodium bisulfite (salt).

The amount of the sulfurous acid compound used is preferably 0.9 mol or more and 1.3 mol or less in terms of stoichiometry with respect to 1 mol of the compound represented by the general formula (1). “Stoichiometrically” means, for example, when sodium hydrogen sulfite is used as the sulfite compound, 1 mol reacts with 1 mol of the compound represented by the above general formula (2). 9 mol or more and 1.3 mol or less are preferable, and in the case of sodium metabisulfite, 1/2 mol reacts with 1 mol of the compound represented by the above general formula (2), so that the amount is 1/2 mol. It means that 0.45 mol or more and 0.65 mol or less are preferable. If the stoichiometric amount is less than 0.9 mol, the unreacted compound represented by the general formula (2) may increase, or a large amount of by-products may be produced as a by-product. Further, if it exceeds 1.3 mol, there is a possibility that the amount of by-products derived from the sulfite compound increases. The amount of the sulfite compound used is more preferably 0.95 mol or more, still more preferably 0.97 or more, in terms of stoichiometric amount, relative to 1 mol of the compound represented by the general formula (2). .. Further, the stoichiometric amount is more preferably 1.2 mol or less, still more preferably 1.1 mol or less.

It is preferable that a part or all of the total amount of the sulfurous acid compound used is added (initially charged) to the reactor before the start of the reaction. For example, assuming that the total amount used is 100 mol%, it is preferable to initially charge 50 mol% or more of the total amount, more preferably 80 mol% or more, still more preferably 100 mol% (that is, the total amount is initially charged). It is to be. Further, instead of the initial charge, for example, before adding 50 mol% out of 100 mol% of the total amount of the compound represented by the general formula (2) at the very early stage of the reaction (the very early stage after the start of the reaction). It is also preferable to add 80 mol% or more of the total amount of the sulfite compound used in 100 mol%, and more preferably 100 mol% (total amount).

In the addition step, the compound represented by the general formula (2) is added to the reactor in which the sulfite compound is present. As a result, side reactions can be suppressed and the yield of the sulfonic acid group-containing ether compound can be improved.
A part of the total amount of the compound represented by the general formula (2) may be initially charged, but from the viewpoint of improving the yield of the sulfonic acid group-containing ether compound, the total amount used. It is preferable to add 60 mol% or more of 100 mol% to the reactor after the start of the reaction. More preferably 80 mol% or more, still more preferably 100 mol%, that is, the entire amount is added to the reactor after the start of the reaction. In addition, "after the start of the reaction" means at the same time as the start of the reaction or after the start of the reaction.

In the preparation of the raw material in the above reaction step, the preparation operation is usually performed while flowing nitrogen gas for the purpose of preventing oxidative deterioration of the vinyl group existing in the raw material due to oxygen in the air, but after the preparation of the alkaline substance is completed, further The time for introducing nitrogen is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 15 minutes or longer, and most preferably 25 minutes or longer. Further, it is preferred that less than 60 minutes, the reactor volume, if over several 10 m ^3, not limited thereto, there may be cases up to several days. It is preferable to maintain the nitrogen introduction for a time within the above range and then stop the nitrogen introduction. By introducing nitrogen by such a method, it is possible to sufficiently suppress the oxidative deterioration of the raw material. On the other hand, when sulfite (salt) or bisulfite (salt) is used as a color-suppressing substance, there is a possibility that these may flow out as highly toxic sulfite gas when the nitrogen introduction time is long. When the time is within the above range, the occurrence of such a defect is sufficiently suppressed, and the effect of suppressing the coloring of the obtained sulfonic acid group-containing ether compound-containing composition can be sufficiently obtained. Furthermore, wasteful nitrogen gas can be reduced and costs can be reduced.

In the above reaction step, the synthesis reaction may be carried out while flowing nitrogen gas for the purpose of preventing oxidative deterioration due to oxygen in the air of the vinyl group existing in the raw material and for the purpose of preventing the invasion of oxygen gas from outside the reaction system. is there.
The nitrogen gas flow rate is usually the space (volume) above the reactor and the nitrogen gas flow rate (volume / hour), and is in the unit of SV (space velocity) [hr ^-1 ], which does not depend on the size of the reactor. It can be represented.
On the other hand, the SV value of nitrogen gas when the dropping operation of a raw material such as allyl glycidyl ether in the above reaction step is performed is not particularly limited as long as it is 24 [hr- ¹ ] or less, but the preferable SV value of nitrogen gas is It is 2.4 [hr ^-1 ] or less. More preferably, it is 0.24 [hr- ¹ ] or less. More preferably, it is 0.024 [hr- ¹ ] or less. Most preferably, the flow of nitrogen gas is 0.0 [hr- ¹ ]. When the SV value of nitrogen gas in the reaction step is larger than the above range, sulfurous acid (salt) or bisulfite (salt) as a color-suppressing substance flows out as sulfite gas to the outside of the reaction system, which is not preferable.

In the above production method, the reaction is usually carried out in a solvent. The solvent is not particularly limited, but at least a solvent containing water (a water-only solvent or a mixed solvent containing water and an organic solvent) is preferable. More preferably, water is 50% by mass or more, more preferably 70% by mass or more, and most preferably 100% by mass, that is, water alone solvent in 100% by mass of the total amount of the solvent. The solid content concentration at the time of the reaction (solid content concentration at the end of the reaction) is preferably 20% by mass or more and 80% by mass or less.

The reaction is also preferably carried out at a reaction temperature of 30 ° C. or higher and lower than 80 ° C. If it is lower than 80 ° C., the production of by-products can be reduced, and if it is 30 ° C. or higher, the yield of the target sulfonic acid group-containing ether compound tends to be improved. More preferably, it is 50 ° C. or higher and lower than 75 ° C., and even more preferably 58 ° C. or higher and lower than 68 ° C.
It is most preferable that all the reaction steps in the production method of the present invention are carried out in the above reaction temperature range, but in the time zone of 30% or more of 100% of the total reaction step time, in the above reaction temperature range. It is a preferable form if the reaction is carried out, and more preferably 50% or more.

The method for producing a sulfonic acid group-containing ether compound-containing composition of the present invention is selected from the group consisting of sulfur-containing compounds, phosphorus-containing compounds and nitrogen-containing compounds in the compound-containing composition represented by the above general formula (1). Including a step of adjusting the amount of at least one compound to 2.3 to 19 mol% with respect to 100 mol% of the sulfonic acid group-containing ether compound (hereinafter, also referred to as “color inhibitor concentration adjusting step”). .. By including this step, the color stability when the composition containing the sulfonic acid group-containing ether compound is stored for a long period of time is improved. The sulfur-containing compound, the phosphorus-containing compound, and the nitrogen-containing compound may be used alone or in combination of two or more.

In the above-mentioned color-suppressing substance concentration adjusting step, the following forms A and B are used for adjusting the color-suppressing substance concentration in the sulfonic acid group-containing ether compound-containing composition, and these may be used in combination. The following form A is a form in which the coloring inhibitor is added in the reaction step and the concentration of the coloring inhibitor after the reaction step is within the above range. In this case, the color inhibitory substance in the reaction step so that the total concentration of the sulfur-containing compound, the phosphorus-containing compound and the nitrogen-containing compound in the sulfonic acid group-containing ether compound-containing composition obtained after the reaction step is within the above range. The amount of the compound is adjusted and added, and the reaction step and the color inhibitor concentration adjusting step are performed at the same time.
Form A: A form in which the total concentration of the sulfur-containing compound, the phosphorus-containing compound and the nitrogen-containing compound in the sulfonic acid group-containing ether compound-containing composition obtained after the above reaction step is within the above range.
Form B: In the sulfonic acid group-containing ether compound-containing composition by adding a sulfur-containing compound, a phosphorus-containing compound and a nitrogen-containing compound to the sulfonic acid group-containing ether compound-containing composition obtained after the reaction step. A form in which the total concentration of the above-mentioned color-suppressing substances is adjusted to the above-mentioned range.

The sulfur-containing compound, phosphorus-containing compound and nitrogen-containing compound are not particularly limited, and the same compounds as those contained in the above-mentioned sulfonic acid group-containing ether compound-containing composition of the present invention can be used.

The preferred range of the color inhibitory substance concentration in the sulfonic acid group-containing ether compound-containing composition adjusted by the color inhibitory substance concentration adjusting step is the color inhibitory substance concentration in the sulfonic acid group-containing ether compound-containing composition of the present invention described above. It is the same as the preferable range of. Further, the preferable compound as the color-suppressing substance is also the same as the compound having a preferable color-suppressing substance concentration in the above-mentioned sulfonic acid group-containing ether compound-containing composition of the present invention.
The concentration of the color-suppressing substance in the compound-containing composition represented by the general formula (1) is affected by the amount of the alkaline substance added in the reaction step. For example, sulfite (salt) or sodium bisulfite (as a color-suppressing substance) When (salt) is used, when the amount of the alkaline substance added is small, the concentrations of sulfite (sulfite) and bisulfite (salt) in the composition are low. This is because the pH of the composition is low when the amount of alkaline substance added is small, so when sulfite (salt) or bisulfite (salt) is used as the color inhibitor, these are expelled as sulfite gas. It is considered that this is because the residual sulfurous acid (salt) and bisulfite (salt) concentrations decrease.

In the compound represented by the general formula (2), R ¹ represents a single bond, CH ₂ groups or CH ₂ CH ₂ groups, and among these, CH ₂ groups are preferable. That is, the compound represented by the general formula (2) is preferably a compound in which R ¹ in the general formula (2) has _two CH groups. When R ¹ has _two CH groups, it is possible to further improve the anti-scale ability in a polymer obtained by polymerizing a sulfonic acid group-containing ether compound obtained by using the compound as a raw material. From the viewpoint of further improving the scale prevention ability of the polymer, (meth) allyl glycidyl ether is particularly preferable as the compound represented by the above general formula (2).

As described above, the sulfonic acid group-containing ether compound-containing composition of the present invention is a composition having excellent color stability in which coloring is suppressed even after long-term storage. Such an effect is exhibited by containing at least one compound selected from the group consisting of a sulfur-containing compound, a phosphorus-containing compound and a nitrogen-containing compound in a predetermined ratio with respect to the sulfonic acid group-containing ether compound. Will be. Such a method for stabilizing the sulfonic acid group-containing ether compound, that is, the following general formula (1);

(In the formula, ^{R 1,} .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ groups, .X representing H or CH ₃ group, Y represents a hydroxyl group or a sulfonic acid (salt) groups, One of X and Y represents a hydroxyl group, and the other represents a sulfonic acid (salt) group.) With respect to 100 mol% of the sulfonic acid group-containing ether compound, the sulfur-containing compound and the phosphorus-containing compound. And a method for stabilizing a sulfonic acid group-containing ether compound containing 2.3 to 19 mol% of at least one compound selected from the group consisting of nitrogen-containing compounds is also one of the present inventions. A method for preserving a sulfonic acid group-containing ether compound using a method for stabilizing a sulfonic acid group-containing ether compound is also one of the present inventions.
The preferred form of the method for stabilizing the sulfonic acid group-containing ether compound of the present invention and the method for storing the sulfonic acid group-containing ether compound is the same as the preferred form of the sulfonic acid group-containing ether compound-containing composition of the present invention described above.

The sulfonic acid group-containing ether compound-containing composition of the present invention has the above-mentioned structure, and can suppress coloring and maintain the color tone even when stored for a long period of time. When the sulfonic acid group-containing ether compound-containing composition is used as a raw material for the polymer, the color tone of the polymer is not adversely affected. In addition, the degree of freedom in the blending amount as a raw material of the polymer is increased, and a larger amount of sulfonic acid group-containing ether compound-containing composition can be introduced, so that the hardness water resistance of the polymer is improved. Therefore, the sulfonic acid group-containing ether compound-containing composition is a useful composition as a raw material for a polymer used in a water treatment agent, a detergent builder, a detergent composition, a dispersant, a cleaning agent, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass %".

<Method for quantifying acrylic acid (salt) and 3-allyloxy-2-hydroxy-1-propanesulfonic acid (salt)>
Acrylic acid (salt) was quantified by using high performance chromatography under the following conditions.
Measuring device: Hitachi, Ltd. L-7000 series detector: Hitachi, Ltd. UV detector L-7400
Column: Showa Denko SHODEX RSpak DE-413L
Temperature: 40.0 ° C
Eluent: 0.1% aqueous phosphoric acid solution Flow rate: 1.0 mL / min.
<Method for quantifying allyl glycidyl ether and 3-allyloxy-1,2-propanediol>
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd. (5 μm φ4.6 mm × 250 mm)
Temperature: 40.0 ° C
Eluent: 10 mmol / L disodium hydrogen phosphate / 12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 mL/min
Detector: RI

<Method for quantifying hydrogen peroxide concentration>
The hydrogen peroxide concentration of the 0.1% hydrogen peroxide solution was measured according to the following procedure. Weigh 1.0 g of potassium iodide into a 100 mL beaker, add 70 g of pure water, and stir with a magnetic stirrer. To this, under stirring, 15 mL of 18N sulfuric acid is added with a whole pipette, and then 0.1% hydrogen peroxide solution is further added until the color turns brown (Zg), and the mixture is stirred for 2 minutes. Add 1 mL of 1% starch to this with a whole pipette under stirring, and confirm that the solution turns dark brown. Immediately after confirming the discoloration, titrate with a 0.1 M sodium thiosulfate aqueous solution using an automatic titrator (COM-1700 manufactured by Hiranuma Sangyo Co., Ltd.) under stirring, and the point where the color disappears is defined as the end point (AmL). Separately, as a blank, the one to which 0.1% hydrogen peroxide solution is not added is also titrated to determine the end point (BmL). The hydrogen peroxide concentration is calculated by inputting each measured value into the following formula.
Hydrogen peroxide concentration (%) = (AB) x 0.17 x (factor of 0.1 M sodium thiosulfate aqueous solution) / Z

<Method for quantifying sulfite (salt) and heavy sulfite (salt)>
The measurement of sulfite (salt) and sulfite (salt) concentrations in the sulfonic acid group-containing ether compound-containing composition is contained in the composition by adding hydrogen peroxide as an oxidizing agent in excess to the composition. After decomposing all of the sulfite (sulfite) and sulfite (sulfite), the concentration of residual hydrogen peroxide is calculated by oxidation-reduction titration using sodium thiosulfate as a reducing agent. The measurement was performed according to the following procedure.
A sufficient amount of 0.1% hydrogen peroxide solution is prepared, and the accurate concentration (S%) is calculated according to the above <Measurement of hydrogen peroxide concentration>. In a 50 mL screw tube, 3.0 g of a sulfonic acid group-containing ether compound-containing composition adjusted to a solid content of 40% (correct weight is Xg) and 15 g of 0.1% hydrogen peroxide solution (correct weight is Yg). Weigh and stir with a magnetic stirrer for 10 minutes to make solution C. Weigh 1.0 g of potassium iodide into a 100 mL beaker, add 70 g of pure water, and stir with a magnetic stirrer. To this beaker, add 15 mL of 18N sulfuric acid with a whole pipette under stirring, add Solution C until it turns brown (Zg), and stir for 2 minutes. Further, under stirring, add 1 mL of 1% starch with a whole pipette, and confirm that the solution turns dark brown. Immediately after confirming the discoloration, titrate with a 0.1 M sodium thiosulfate aqueous solution using an automatic titrator (COM-1700 manufactured by Hiranuma Sangyo Co., Ltd.) under stirring, and the point where the color disappears is defined as the end point (AmL). Separately, as a blank, the end point (BmL) of the sample to which the solution C is not added is determined. By inputting each measured value into the following formula, the sulfite (salt) and bisulfite (salt) concentrations are calculated. However, F indicates a factor of 0.1 M aqueous sodium thiosulfate solution.
Sulfite (salt), bisulfite (salt) concentration (ppm) = 30600 × (X + Y) / {X × (S × Y / (X + Y) −0.17 × F × (AB) / Z)}
The constants 30600 and 0.17 in the above formula are derived in consideration of the unit conversion of the molecular weight and concentration of the compound used in the measurement.

<Example 1>
161.9 g of deionized water and 76.3 g of 48% sodium hydroxide aqueous solution were charged into a SUS reaction vessel equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, while introducing nitrogen. After the preparation of the 48% aqueous sodium hydroxide solution was completed, the introduction of nitrogen was further maintained for 30 minutes, and then the introduction of nitrogen was stopped (SV value of nitrogen gas: 0.0 [hr- ¹ ]). To this, 549.0 g of a 35% aqueous sodium hydrogen sulfite solution was added. The liquid temperature was raised to 63 ° C., and 212.9 g of allyl glycidyl ether was added dropwise over 225 minutes. After completion of dropping the allyl glycidyl ether, the temperature of the reaction solution was maintained at 63 ° C. for 30 minutes. (The sulfonic acid group-containing ether compound-containing composition of the present invention thus obtained is referred to as "sulfonic acid group-containing ether compound-containing composition (1)").
In the sulfonic acid group-containing ether compound-containing composition (1), the yield of sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (allyl glycidyl ether base) was 94.9%. The total abundance of sulfite (salt) and sodium bisulfite (salt) contained in the sulfonic acid group-containing ether compound-containing composition (1) is sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (acid type). Conversion) It was 6.2 mol% with respect to 100 mol%.

<Comparative example 1>
161.9 g of deionized water and 76.3 g of 48% sodium hydroxide aqueous solution were charged into a SUS reaction vessel equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, while introducing nitrogen. 549.0 g of a 35% aqueous sodium hydrogen sulfite solution was added thereto. The liquid temperature was raised to 63 ° C., and 212.9 g of allyl glycidyl ether was added dropwise over 225 minutes. After completion of dropping the allyl glycidyl ether, the temperature of the reaction solution was maintained at 63 ° C. for 30 minutes.
Then, while maintaining the temperature of the reaction solution at 63 ° C., 5.1 g of 35% hydrogen peroxide solution was added and maintained for 300 minutes (the sulfonic acid group-containing ether compound-containing composition of the present invention thus obtained). Is referred to as a "sulfonic acid group-containing ether compound-containing composition (2)").
In the sulfonic acid group-containing ether compound-containing composition (2), the yield of sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (allyl glycidyl ether base) was 94.9%. The total abundance of sulfite (sulfite) and sodium bisulfite (salt) contained in the sulfonic acid group-containing ether compound-containing composition (2) is sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (acid type). Conversion) It was 0 mol% with respect to 100 mol%.

<Comparative example 2>
While introducing nitrogen into a SUS reaction vessel equipped with a thermometer, a stirrer, a nitrogen inflow pipe and a cooling trap at the nitrogen outlet, 232 g of ion-exchanged water and 2 g of sodium hydroxide were initially charged. The liquid temperature was raised to 83 ° C., and 200 g of allyl glycidyl ether and 520 g of a 35% sodium bisulfite aqueous solution were added dropwise over 120 minutes. Then, the reaction was completed by maintaining the temperature of the reaction solution at 83 ° C. for 1 hour. The yield (allyl glycidyl ether base) of sodium 3-allyloxy-2-hydroxypropanesulfonate (the sulfonic acid group-containing ether compound of the present invention) was 94.5%. The total abundance of sulfite (salt) and sodium bisulfite (salt) contained in the sulfonic acid group-containing ether compound-containing composition (3) is sodium 3-allyloxy-2-hydroxy-1-propanesulfonate (acid type conversion). It was 2.2 mol% with respect to 100 mol%.

<Measurement method of color tone>
As a method for measuring the color tone (APHA), the L, a, and b values were measured under the following conditions, and APHA was calculated from Equations 1 and 2.
Equipment: Nippon Denshoku Industries Co., Ltd. spectroscopic difference meter SE2000
Equation 1 W = 100-{(100-L) ² + a ² + b ² } ^0.5
Equation 2 APHA = -34.9 x W + 3490

<Evaluation of storage stability>
The sulfonic acid group-containing ether compound-containing composition synthesized in Example 1 and Comparative Example 1 was placed in a 100 mL screw tube, covered, and allowed to stand in an oven at 40 ° C. for 3 months, and the color tone before and after the standing was measured. .. The results are shown in Table 1.

Claims (6)

The following general formula (1);

(In the formula, ^{R 1,} .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ groups, .X representing H or CH ₃ group, Y represents a hydroxyl group or a sulfonic acid (salt) groups, One of X and Y represents a hydroxyl group, and the other represents a sulfonic acid (salt) group), which is a method for preserving a sulfonic acid group-containing ether compound.
The storage method includes a step of adjusting the pH of the reaction system to 5.5 or higher using an alkaline substance, and the following general formula (2):

(In the formula, R ¹ represents a single bond, CH ₂ groups or CH ₂ CH ₂ groups. R ² represents H or CH ₃ groups.) Sulfonic acid (salt) and / or weight. In the composition containing the sulfonic acid group-containing ether compound obtained by performing the reaction step with sulfite (salt), the nitrogen gas flow rate in the raw material dropping operation in the reaction step is adjusted to 0.24 hr ^-1 or less. As a result, in the composition containing the sulfonic acid group-containing ether compound, a total of 3.5 to 19 mol% of sulfite (salt) and / or heavy sulfite (salt) is contained with respect to 100 mol% of the sulfonic acid group-containing ether compound. A method for preserving a sulfonic acid group-containing ether compound. The nitrogen gas flow rate in the raw material dropping operation in the reaction step is 0.024 hr. ^-1 The method for storing a sulfonic acid group-containing ether compound according to claim 1, which comprises the following adjustment. The nitrogen gas flow rate in the raw material dropping operation in the reaction step is 0.0 hr. ^-1 The method for preserving a sulfonic acid group-containing ether compound according to claim 1. The following general formula (1);

(In the formula, ^{R 1,} .R ² represents a single bond, CH ₂ groups or _CH 2 CH ₂ groups, .X representing H or CH ₃ group, Y represents a hydroxyl group or a sulfonic acid (salt) groups, One of X and Y represents a hydroxyl group, and the other represents a sulfonic acid (salt) group), which is a method for stabilizing a sulfonic acid group-containing ether compound.
The stabilization method includes a step of adjusting the pH of the reaction system to 5.5 or more using an alkaline substance, and the following general formula (2):

(In the formula, R ¹ represents a single bond, CH ₂ groups or CH ₂ CH ₂ groups. R ² represents H or CH ₃ groups.) Sulfonic acid (salt) and / or weight. In the composition containing the sulfonic acid group-containing ether compound obtained by performing the reaction step with sulfite (salt), the nitrogen gas flow rate in the raw material dropping operation in the reaction step is adjusted to 0.24 hr ^-1 or less. Thereby, the sulfonic acid group-containing ether compound is characterized in that a total of 3.5 to 19 mol% of sulfite (salt) and / or barbisulfate (salt) is contained in 100 mol% of the sulfonic acid group-containing ether compound. How to stabilize. The nitrogen gas flow rate in the raw material dropping operation in the reaction step is 0.024 hr. ^-1 The method for stabilizing a sulfonic acid group-containing ether compound according to claim 4, which comprises the following adjustment. The nitrogen gas flow rate in the raw material dropping operation in the reaction step is 0.0 hr. ^-1 The method for stabilizing a sulfonic acid group-containing ether compound according to claim 4, wherein the method is characterized by the above.