JP5765903B2 - Sulfonic acid group-containing monomer and method for producing the same - Google Patents

Description

  The present invention relates to a sulfonic acid group-containing monomer and a method for producing the same.

Conventionally, sulfonic acid group-containing polymers have been used in a wide range of fields such as water treatment agents, detergent builders, detergent compositions, dispersants, and cleaning agents.
For example, Patent Document 1 discloses that a polyalkylene glycol polymer having a sulfonic acid group exhibits high performance in aqueous applications such as a dispersant and a detergent builder.

In recent years, as consumers have become more aware of the environment, washing, such as using the remaining hot water from a bath for washing, has become established for the purpose of saving water. As a result, dirt components contained in the remaining hot water of the bath adhere to fibers during washing, and hard water components are concentrated due to reheating of the bath. The ability to capture metal ions such as calcium ions and magnesium ions in water that cause the deterioration of gel and the ability to gel is further demanded for polymers. In addition, liquid detergents whose demand is currently increasing are concentrated liquid detergents having a surfactant content of 50% or more, so that detergent additives are suitable for blending into such concentrated liquid detergents. Therefore, there is a need for a detergent additive that is more compatible with a surfactant than before.
However, it cannot be said that the conventional sulfonic acid group-containing polymer can sufficiently satisfy recent strict requirements regarding the performance of such aqueous applications, and responds to such new needs. There has been room for further improvement in the polymer that can be suitably used as a detergent additive exhibiting higher performance.

JP 2008-303347 A

  The present invention has been made in view of the above-described situation. For example, in detergent applications, a novel sulfonic acid that can be used as a raw material for a sulfonic acid group-containing polymer that exhibits excellent calcium ion scavenging ability and gelation resistance. It aims at providing a group containing monomer and its manufacturing method.

  In order to achieve the above-mentioned object, the present inventors have examined sulfonic acid group-containing monomers as raw materials for various sulfonic acid group-containing polymers / copolymers. As a result, it has been found that a polymer using a specific sulfonic acid group-containing monomer as a raw material exhibits excellent gelation resistance and calcium ion scavenging ability at the time of washing, and it is conceived that the above problems can be solved brilliantly. The present invention has been achieved.

  That is, the present invention is a sulfonic acid group-containing monomer represented by the following general formula (1).

In the general formula (1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and Y ₁ is the same or different, Represents an alkylene group having a number of 2 to 20, n represents an average number of added moles of an oxyalkylene group (—Y ₁ —O—), represents a number of ₁ to 300, and M ₁ represents a hydrogen atom or a monovalent cation. Represents.

  Another aspect of the present invention provides a method for producing a sulfonic acid group-containing monomer. The production method of the present invention comprises (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the following general formula (2), an epihalohydrin, and an alkali compound (step A), and (ii) step A. It is a manufacturing method of the sulfonic acid group containing monomer including the process (process B) which makes the obtained reaction material and a sulfurous compound react.

In the general formula (2), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and Y ₁ is the same or different, It represents an alkylene group having 2 to 20, n represents an average addition mole number of the oxyalkylene group _(-Y 1 -O-), represents the number of 1 to 300.

  Another production method of the present invention includes (i) a step (step C) of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2) and an epihalohydrin in the presence of a catalyst (ii) ) A sulfonic acid group comprising a step (step D) of reacting the reaction product obtained in step C with an alkali compound, and (iii) a step of reacting the reaction product obtained in step D with a sulfite compound (step B). It is a manufacturing method of a containing monomer.

  Another production method of the present invention includes (i) a step (step C) of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2) and an epihalohydrin in the presence of a catalyst (ii) ) A process for producing a sulfonic acid group-containing monomer, which comprises reacting the reaction product obtained in Step C with a sulfurous acid compound (Step E).

  Another production method of the present invention comprises (i) a step of reacting the polyalkylene glycol chain-containing monomer represented by the general formula (2) with oxirane methanesulfonic acid (salt) (step F), It is a manufacturing method of the sulfonic acid group containing monomer to contain.

  The sulfone group-containing monomer of the present invention has excellent copolymerizability with various nonionic monomers, cationic monomers and anionic monomers. The polymer obtained from the sulfonic acid group-containing monomer of the present invention exhibits excellent gelation resistance and calcium ion scavenging ability during washing due to the structure derived from the sulfonic acid group-containing monomer of the present invention. To do.

2 is a ¹ H-NMR chart of the monomer (1) obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.
[Sulphonic acid group-containing monomer of the present invention]
The sulfonic acid group-containing monomer of the present invention has a structure represented by the following general formula (1).

In the general formula (1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and Y ₁ is the same or different, Represents an alkylene group having a number of 2 to 20, n represents an average number of added moles of an oxyalkylene group (—Y ₁ —O—), represents a number of ₁ to 300, and M ₁ represents a hydrogen atom or a monovalent cation. Represents.

In the general formula (1), and when _{R 1} is a single _{bond, H 2 C = C (R} 0) of the above general formula (1) -R 1 in _{-O-, H 2 C = C (} R ₀ ) -O-means. That _{H 2 C = C (R 0} ) -R 1 - is, _{R 0} is CH _3, methallyl group when _{R 1} is a CH ₂ group, _{R 0} is CH _{3, R 1} is _CH 2 CH ₂ group Is an isoprenyl group, R ₀ is a CH ₃ group, R ₁ is a single bond, an isopropenyl group, R ₀ is a hydrogen atom, R ₁ is a CH ₂ group, an allyl group, R ₀ is a hydrogen atom, R _{When 1} is a CH ₂ CH ₂ group, it means a butenyl group, R ₀ is a hydrogen atom, and when R ₁ is a single bond, it means a vinyl group.

In the above general formula (1), Y ₁ is the same or different and is an alkylene group having 2 to 20 carbon atoms. However, since the polymerizability of the sulfonic acid group-containing monomer of the present invention is improved, Y 1 ₁ is preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms. Specifically, an alkylene group having 2 to 4 carbon atoms such as an ethylene group, a propylene group, or a butylene group is preferable, and an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group is particularly preferable. The alkylene group may be one type or two or more types, but in the case of two or more types, the structure of —Y ₁ —O— may be a block shape, which may be randomly continuous or alternately continuous. It may be continuous.

In the general formula (1), that n represents an average addition mole number of the oxyalkylene group (-Y 1 _-O-), but the number of 1 to 300, can introduce more polyalkylene glycol chains in the polymer From the viewpoint, n is preferably 2 or more, more preferably 5 or more, and still more preferably 10 or more. Further, from the viewpoint of improving the polymerizability of the monomer of the present invention, n is preferably 200 or less, more preferably 100 or less, and even more preferably 50 or less.

In the general formula (1), M ₁ represents a hydrogen atom or a monovalent cation. Examples of the monovalent cation include alkali metal ions such as sodium, potassium and lithium, ammonium ions, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetrabutylammonium salt, and sodium, potassium and lithium. Alkali metal ions such as sodium ions are preferable, and sodium ions are particularly preferable.

  By polymerizing the sulfonic acid group-containing monomer of the present invention, the resulting sulfonic acid group-containing polymer has a structure derived from the sulfonic acid group-containing monomer of the present invention. The structure derived from the sulfonic acid group-containing monomer is a structure in which the carbon-carbon double bond of the sulfonic acid group-containing monomer of the present invention is a single bond, and can be represented by the following general formula (3).

In the general formula (3), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and Y ₁ is the same or different, Represents an alkylene group having a number of 2 to 20, n represents an average number of added moles of an oxyalkylene group (—Y ₁ —O—), represents a number of ₁ to 300, and M ₁ represents a hydrogen atom or a monovalent cation. Represents.

The group having a carbon-carbon double bond for polymerization of the sulfonic acid group-containing monomer of the present invention, that is, H ₂ C═C (R ₀ ) —R ₁ — is an isoprenyl group, a methallyl group, an allyl group, a vinyl group. Is preferred. From the viewpoint of polymerizability, an isoprenyl group and a methallyl group are particularly preferable.

[Method for producing sulfonic acid group-containing monomer of the present invention]
Although the said sulfonic acid group containing monomer may be manufactured with the applicable well-known manufacturing method, it is preferable to manufacture with the method of the following manufacturing method (1)-(4). According to this method, the sulfonic acid group-containing monomer of the present invention can be produced with a high yield.

  That is, a preferred production method (1) of the sulfonic acid group-containing monomer of the present invention is a reaction of (i) a polyalkylene glycol chain-containing monomer represented by the general formula (2), an epihalohydrin, and an alkali compound. This is a method for producing a sulfonic acid group-containing monomer comprising a step (step A) of reacting, and (ii) a step of reacting the reaction product obtained in step A with a sulfite compound (step B).

  A preferred method (2) for producing a sulfonic acid group-containing monomer of the present invention is a step of (i) reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2) with an epihalohydrin in the presence of a catalyst. (Step C), (ii) a step of reacting the reactant obtained in Step C with an alkali compound (Step D), and (iii) a step of reacting the reactant obtained in Step D with a sulfite compound (Step B), a method for producing a sulfonic acid group-containing monomer.

  A preferred method (3) for producing a sulfonic acid group-containing monomer of the present invention is a step of (i) reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2) with an epihalohydrin in the presence of a catalyst. A process for producing a sulfonic acid group-containing monomer comprising (Step C) and (ii) a step (Step E) of reacting the reaction product obtained in Step C with a sulfite compound.

  The preferred production method (4) of the sulfonic acid group-containing monomer of the present invention comprises (i) a reaction between the polyalkylene glycol chain-containing monomer represented by the general formula (2) and oxirane methanesulfonic acid (salt). This is a method for producing a sulfonic acid group-containing monomer including a step (step F).

In the polyalkylene glycol chain-containing monomer represented by the general formula (2) in the production methods (1) to (4), preferred embodiments of R ₀ , R ₁ and Y ₁ are the general formula (1). The same as the preferred embodiments of R ₀ , R ₁ and Y ₁ in
The polyalkylene glycol chain-containing monomer represented by the general formula (2) is a known method for converting an alkylene oxide into an alkylene glycol monovinyl ether, (meth) allyl alcohol, isoprenol or an alcohol having an alkylene oxide addition structure thereof. What was manufactured by adding by this can be used, and since the purity of a monomer can be made high, it is preferable.

  The epihalohydrin in the production methods (1) to (3) has a structure represented by the following general formula (4).

In the above general formula (4), X ₁ represents a halogen atom. Specific examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is preferable because it is industrially inexpensive.

  In the production methods (1) to (3), the sulfurous acid compound is preferably sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof. The sulfurous acid compound can be used as an acid (that is, sulfurous acid or the like is used), but it is preferably used as a salt from the viewpoint of handling and from the viewpoint of improving the yield. As the salt, sodium, potassium, lithium, ammonium, quaternary ammonium salt and the like are preferable. Examples of the sulfite compound include lower oxides such as sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, and salts thereof. Among them, sodium hydrogen sulfite and sodium metabisulfite are particularly preferable because they are industrially inexpensive.

  The oxirane methanesulfonic acid (salt) in the production method (4) has a structure represented by the following general formula (5).

In the general formula (5), M ₁ represents a hydrogen atom or a monovalent cation. Preferred embodiments of M ₁ are the same as the preferred embodiment M ₁ in the general formula (1). Specific examples of the oxirane methane sulfonic acid (salt) include oxirane methane sulfonic acid, sodium oxirane methane sulfonate, potassium oxirane methane sulfonate, ammonium oxirane methane sulfonate, and tetrabutyl ammonium oxirane methane sulfonate.

  That is, the production methods (1) to (4) are represented by the following reaction formulas.

<Reaction conditions for production method (1)>
(Reaction conditions for step A)
In the method (1) for producing a sulfonic acid group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2), an epihalohydrin, and an alkali compound ( Step A) is an essential step.
The reaction of Step A is performed in the presence of an alkali compound and, if necessary, a phase transfer catalyst and / or a solvent. Although it does not specifically limit as an alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable. The amount of the alkali compound used is the molar ratio of the polyalkylene glycol chain-containing monomer represented by the general formula (2) to the hydroxyl group (in terms of hydroxyl value), and usually (hydroxyl group) / (alkali compound) = 15/1. Is 1/15, preferably 5/1 to 1/5, and more preferably 3/1 to 1/3. You may use an alkaline compound in the state of aqueous solution. In this case, the reaction may be performed while removing water (including water produced as a by-product with the progress of the reaction). The type of phase transfer catalyst is not particularly limited, but tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium chloride, octyltrimethyl Ammonium chloride, cetyltrimethylammonium chloride, trimethylammonium chloride, triethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetraoctylammonium bromide, benzyltrimethylammonium bromide, benzyltri Quaternary ammonium salts such as tillammonium bromide, octyltrimethylammonium bromide, cetyltrimethylammonium bromide, trimethylammonium bromide, triethylammonium bromide; phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide; 15-crown-5, 18- And crown ethers such as crown-6. When a phase transfer catalyst is used, the amount used is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (2). ) / (Phase transfer catalyst) = 1 / 0.0001 to 1 / 0.3, preferably 1 / 0.001 to 1 / 0.2, more preferably 1 / 0.005 to 1/0. .1. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

  The amount of epihalohydrin used in the reaction of Step A is a molar ratio of the polyalkylene glycol chain-containing monomer represented by the above general formula (2) to the hydroxyl group (in terms of hydroxyl value), usually (hydroxyl group) / ( Epihalohydrin) = 1/1 to 1/15, preferably 1/1 to 1/10, more preferably 1/1 to 1/5. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.

  The reaction in Step A is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but can also be carried out in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (2), Preferably it is 0.00. It is the range of 01-3 times mass.

  The reaction of step A may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (2), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

(Reaction conditions for step B)
In the method (1) for producing a sulfonic acid group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step A with a sulfite compound (step B) is an essential step.
The reaction of Step B is performed in the presence of a solvent as necessary. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process A, Preferably it is the range of 0.01-3 times mass.

  The amount of the sulfite compound used is a molar ratio with respect to the number of moles of the glycidyl group of the reaction product obtained in Step A, usually (glycidyl group) / (sulfite compound) = 2/1 to 1/2. Yes, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4 / 1 to 1 / 1.4. The sulfite compound may be used in the form of an aqueous solution.

  The reaction in Step B is performed by adjusting the pH as necessary. The pH may be adjusted before or during the reaction, and it is preferable to add an alkaline compound. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, and amines.

  When a catalyst is used in the above step A, the reaction may be performed as it is under the remaining catalyst. The reaction of step B may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reaction product obtained in Step A, which is a raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

  Step A is a so-called slurry reaction and can be carried out in a reaction apparatus having a general stirring apparatus. For example, using a stirred tank reactor, any of batch, semi-batch, and continuous tank reactors can be used. After the reaction in step A, it is preferable to carry out step B after carrying out steps such as desalting and removal of excess epihalohydrin. The desalting step can be carried out by sedimentation separation, centrifugation, filtration, washing or the like, and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed, and it is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in order to obtain a sufficient separation rate. Excess epihalohydrin can be easily removed by distillation, evaporation or the like. The reaction of step B may be performed in batch or continuously, and can be performed, for example, in any apparatus of a tank type or a tube type reactor.

<Reaction conditions for production method (2)>
(Reaction conditions for step C)
In the method (2) for producing a sulfonic acid group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the general formula (2) with an epihalohydrin in the presence of a catalyst ( Process C) is an essential process.
The reaction in Step C may be an acid or a base as a catalyst, but an acid is preferred. The acid may be Lewis acid or Bronsted acid, but Lewis acid is preferred. As a Lewis acid, what is generally called a Lewis acid can be used. For example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, titanium tetrachloride, magnesium chloride. And antimony pentachloride. The amount used is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (2), and usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.1, preferably 1 / 0.0005 to 1 / 0.05, and more preferably 1 / 0.001 to 1 / 0.03. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

  The amount of epihalohydrin used in the reaction of Step C is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (2). ) / (Epihalohydrin) = 1/1 to 1/30, preferably 1/1 to 1/10, more preferably 1/1 to 1/5. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.

  The reaction in Step C is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (2), Preferably it is 0.00. It is the range of 01-3 times mass.

  The reaction of step C may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (2), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

(Reaction conditions for step D)
In the method (2) for producing a sulfonic acid group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step C with an alkali compound (step D) is an essential step.
The reaction in Step D is performed in the presence of an alkali compound and, if necessary, a solvent. Although it does not specifically limit as an alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable. The amount of alkali compound used is usually a (halogen group) / (alkali compound) = 1/1 to 1/100 in terms of molar ratio to the number of moles of halogen groups in the reaction product obtained in Step C, preferably Is 1/1 to 1/50, more preferably 1/1 to 1/20. You may use an alkaline compound in the state of aqueous solution. The reaction in Step D can be performed in the presence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, It is the range of 0.01-100 times mass normally with respect to the reaction material obtained at the process C, Preferably it is the range of 0.1-50 times mass. The reaction in step D may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (2), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

In the production method (2) of the sulfonic acid group-containing monomer of the present invention, (iii) the step of reacting the reaction product obtained in step D with the sulfite compound (step B) is an essential step. Preferred conditions for step B are as described above (reaction conditions for step B). After the reaction of step C and step D, step B is carried out after steps such as desalting and removal of excess epihalohydrin are performed. Is preferred. The desalting step can be carried out by sedimentation separation, centrifugation, filtration, washing, etc., and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed. It is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in that a sufficient separation rate can be obtained. Excess epihalohydrin can be easily removed by distillation, evaporation operation, and the like. The reaction of step C and step D may be performed in batch or continuously, and can be performed in any of a tank type reactor and a tubular reactor, for example. Preferred embodiments of step B are as described above.

<Reaction conditions for production method (3)>
In the method (3) for producing a sulfonic acid group-containing monomer of the present invention, (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the above general formula (2) with an epihalohydrin in the presence of a catalyst ( Process C) is an essential process. Preferred conditions for step C are as described above (reaction conditions for step C).

(Reaction conditions for step E)
In the production method (3) of the sulfonic acid group-containing monomer of the present invention, (ii) the step of reacting the reaction product obtained in step C with the sulfite compound (step E) is an essential step.
The reaction of step E is performed in the presence of a solvent as necessary. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, water; alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone Can be mentioned. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, it is the range of 0.005-5 times mass normally with respect to the reaction material obtained at the process C, Preferably it is the range of 0.01-3 times mass.

The amount of the sulfite compound used is a molar ratio with respect to the number of moles of the halogen group in the reaction product obtained in Step C. Usually, (halogen group) / (sulfur compound) = 2/1 to 1/2. Yes, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4 / 1 to 1 / 1.4. The sulfite compound may be used in the form of an aqueous solution.
Reaction of the process E is performed by adjusting pH as needed. The pH may be adjusted before or during the reaction, and it is preferable to add an alkaline compound. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, and amines.
When a catalyst is used in the above step C, the reaction may be performed as it is under the remaining catalyst. The reaction of step E may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of the fluidity of the reaction product obtained in Step A, which is a raw material, the reaction is preferably performed at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

A preferred embodiment of step C is as described above. The reaction in the step E may be performed in a batch or continuously. For example, the reaction can be performed in either a tank-type reactor or a tubular reactor. After the reaction in step E, it is preferable to perform a step such as desalting. The desalting step can be carried out by sedimentation separation, centrifugation, filtration, washing, etc., and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed. It is preferable to carry out at a temperature of 15 ° C. to 100 ° C. in that a sufficient separation rate can be obtained.
<Reaction conditions for production method (4)>
(Reaction conditions for step F)
In the method (4) for producing a sulfonic acid group-containing monomer of the present invention, (i) the polyalkylene glycol chain-containing monomer represented by the general formula (2) is reacted with oxirane methanesulfonic acid (salt). The process (process F) is an essential process.
The reaction in Step F is performed in the presence of a catalyst as necessary. Examples of the catalyst used in the reaction include alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate; tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium. Chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, octyltrimethylammonium chloride, cetyltrimethylammonium chloride, trimethylammonium chloride, triethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetra Octylua Moniumuburomido, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, octyl trimethyl ammonium bromide, it can be cetyltrimethylammonium bromide, trimethylammonium bromide, etc. quaternary ammonium salts such as triethylammonium bromide exemplified. The amount used is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (2), and usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.3, preferably 1 / 0.001 to 1 / 0.2, and more preferably 1 / 0.005 to 1 / 0.1. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained.

  The reaction in step F is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction. For example, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; acetone, Mention may be made of ketones such as methyl ethyl ketone; and chlorinated hydrocarbons such as dichloromethane and dichloroethane. These may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is the range of 0.005-5 times mass with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (2), Preferably it is 0.00. It is the range of 01-3 times mass.

  As usage-amount of the oxirane methanesulfonic acid (salt) used for reaction of the process F, it is molar ratio with respect to the hydroxyl group (hydroxyl value conversion) of the polyalkylene glycol chain containing monomer represented by the said General formula (2). Usually, (hydroxyl group) / (oxirane methanesulfonic acid (salt)) = 5/1 to 1/5, preferably 3/1 to 1/3, more preferably 1.5 / 1 to 1. /1.5.

  The reaction in step F may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (2), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

The reaction in the step F may be performed in a batch or continuously. For example, the reaction can be performed in any apparatus of a tank type and a tube type reactor.
Although the sulfonic acid group-containing monomer of the present invention can be produced by the above method, a purification step may be provided as necessary. A purification step by extraction or washing is preferable in that the amount of the crosslinking component that causes gelation during polymerization can be reduced.

  Among the production methods (1) to (4), the production methods (1) to (3) are preferable because the raw materials and the catalyst are inexpensive and simple in terms of production. Among these, the production method (1) is particularly preferable because generation of a crosslinking component that causes gelation during polymerization can be suppressed.

  The polymer (or polymer composition) obtained from the sulfonic acid group-containing monomer of the present invention can be used in various applications such as a water treatment agent, a detergent builder, a detergent composition, a dispersant, and a cleaning agent.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

  The polyalkylene glycol chain-containing monomer and the reaction intermediate were quantified by liquid chromatography. Further, the weight average molecular weight, gelation resistance and calcium ion scavenging ability of the polymer were measured according to the following methods.

<Quantification of sulfonic acid group-containing monomer and reaction intermediate>
The reaction intermediate and the ethylene oxide adduct of isoprenol were quantified by liquid chromatography under the following conditions.
Measuring device: Hitachi High-Technologies Co., Ltd. Column: Shiseido Co., Ltd. CAPCELL PAK C18 MGII 4.6 mmΦ × 250 mm 5 μm
Temperature: 40.0 ° C
Eluent: 0.1 wt% formic acid / acetonitrile = 6/4 (volume ratio)
Flow rate: 1.0 mL / min
Detector: RI, UV (detection wavelength 210 nm).

<Measurement conditions of weight average molecular weight>
Device: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 mL / min.
Calibration curve: Soka Kagaku Co., Ltd. Polyacrylic acid standard eluent: 0.1N sodium acetate aqueous solution <Measurement of solid content>
In an oven heated to 130 ° C., the polymer of the present invention (1.0 g of the polymer composition of the present invention plus 1.0 g of water) was allowed to stand for 1 hour for drying treatment. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.

<Measurement method of gelation resistance>
To a 500 mL tall beaker, add deionized water, boric acid-sodium borate pH buffer, 1% aqueous solution of copolymer, calcium chloride solution in this order, pH 8.5, copolymer 100 mg solids / L, calcium hardness 120 mg CaCO ₃ / 500 mL of L test solution was prepared. The tall beaker was sealed with a polyethylene film and left in a constant temperature water bath at 90 ° C. for 1 hour. Then, the turbidity of the test solution generated by the gel formed by the combination of the copolymer and calcium ions is detected by measuring the absorbance in a quartz cell with a UV wavelength of 380 nm and 50 mm, and the resulting absorbance value makes the gel resistant. Noh was evaluated. It shows that gel-proof ability is excellent, so that a value is small.

<Calcium ion scavenging ability>
Prepare 50 g of 0.01 mol / L, 0.001 mol / L, and 0.0001 mol / L aqueous solutions using calcium chloride dihydrate as the calcium ion standard solution for the calibration curve, and use 1.0% NaOH aqueous solution. Adjust the pH to 9.9 to 10.2, add 1 mL of 4 mol / L potassium chloride aqueous solution (hereinafter abbreviated as 4M-KCl aqueous solution), and further stir well using a magnetic stirrer. A sample solution was prepared. In addition, as a test calcium ion standard solution, a required amount (50 g per sample) of a 0.001 mol / L aqueous solution was similarly prepared using calcium chloride dihydrate.
Next, 10 mg of the test sample ((co) polymer) was weighed in a 100 mL beaker in terms of solid content, added with 50 g of the above test calcium ion standard solution, and sufficiently stirred using a magnetic stirrer. The (co) polymer used as a test sample was medium in a 48% aqueous sodium hydroxide solution (hereinafter also referred to as “48% NaOH”) so that pH = 7.5 when the solid content was 40% by weight. The sum was used. Next, as with the calibration curve sample, the pH was adjusted to 9.9 to 10.2 with 1.0% aqueous sodium hydroxide solution, and 1 mL of 4M-KCl aqueous solution was added to prepare a test sample solution. .
The calibration curve sample solution and the test sample solution thus prepared were measured using a titration device COM-1700 manufactured by Hiranuma Sangyo Co., Ltd., with an Orion 9720BNWP Sure-Flow calcium composite electrode manufactured by Thermo Fisher Scientific Co., Ltd. went.

<Example 1>
In a 1 L four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 400 g of an ethylene oxide average 10-mole adduct of isoprenol (hereinafter also referred to as “IPN10”, hydroxyl value 106.5 (mgKOH / g)), epichlorohydrin 351 7 g and 48% NaOH 94.9 g were charged, and the mixture was allowed to react for 6 hours while maintaining at 50 ° C. After the reaction, the generated salt is removed, and then the epichlorohydrin and water are removed from the remaining organic layer to contain an intermediate (A) (a compound having a structure where n is an average of 10 in the following general formula (6)). 451.2g of reaction liquid was obtained. As a result of analysis by liquid chromatography, 324.9 g of intermediate (A) and 64.1 g of IPN10 were contained.
Next, while introducing nitrogen into a 1 L SUS separable flask equipped with a stirrer, thermometer, nitrogen inlet pipe and cooling trap at the nitrogen outlet, pure water 129.5 g, 48% NaOH 6.0 g, 40 50.0 g of% sodium bisulfite (hereinafter also referred to as “40% SBS”) was charged, and the temperature was raised to 63 ° C. while stirring to prepare a reaction system. Next, 140.0 g of the reaction solution containing the intermediate (A) was continuously added dropwise at a constant rate over 120 minutes to the reaction system maintained at 63 ° C. with stirring. Thus, 325.5 g of a solution of the monomer (1) (a compound having a structure where n is an average of 10 in the following general formula (7)) was obtained. As a result of analysis by ¹ H-NMR as shown in FIG. 1, formation of the monomer (1) was confirmed. Furthermore, it was confirmed by analysis by liquid chromatography that the intermediate (A) was completely consumed.

<Polymerization Example 1>
In a 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade), 25.0 g of pure water, 45.1 g of maleic anhydride (hereinafter also referred to as “MA”), 48% NaOH 60. 5 g was charged and the temperature was raised to the boiling point while stirring to obtain a polymerization reaction system. Next, 222.3 g of the monomer (1) solution, 80% aqueous acrylic acid solution (hereinafter also referred to as “80% AA”) in a polymerization reaction system maintained at the boiling point reflux state with stirring. 41. 4 g, 15% sodium persulfate (hereinafter also referred to as “15% NaPS”) 16.3 g, 35% hydrogen peroxide (hereinafter also referred to as “35% H ₂ O ₂ ”) 2.9 g are separately provided. It was dripped from the nozzle. Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for the monomer (1) solution, 80% AA and 15% NaPS, and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous solution of the polymer (1) was obtained. The weight average molecular weight of the polymer (1) was 48,000.

<Polymerization example 2>
A 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 25.0 g of pure water, 45.1 g of MA, 222.3 g of the monomer (1) solution, and 60.5 g of 48% NaOH. While charging and stirring, the temperature was raised to the boiling point to obtain a polymerization reaction system. Next, 41.4 g of 80% AA, 16.3 g of 15% NaPS, and 2.9 g of 35% H ₂ O ₂ were dropped from separate nozzles into the polymerization reaction system maintained at the boiling point reflux state with stirring. Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for 80% AA and 15% NaPS and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous solution of the polymer (2) was obtained.

<Polymerization Example 3>
Into a 2.5 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged 100.0 g of pure water, and the temperature was raised to 90 ° C. while stirring to obtain a polymerization reaction system. Next, 653.7 g of a solution of the monomer (1), 513.0 g of 80% AA, 23.8 g of 48% NaOH, 160.0 g of 15% NaPS, 40% in a polymerization reaction system maintained at 90 ° C. with stirring. 60.0 g of SBS was added dropwise from separate nozzles. The dropping time of each solution was 180 minutes for the monomer (1) solution, 80% AA and 48% NaOH, 210 minutes for 15% NaPS, and 170 minutes for 40% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 15% NaPS, the polymerization reaction solution was kept (ripened) at 90 ° C. for 30 minutes to complete the polymerization. After the completion of the polymerization, the polymerization reaction liquid was stirred and allowed to cool, and 427.5 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize. In this way, an aqueous solution of the polymer (3) was obtained.

<Comparative polymerization example 1>
A 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 25.0 g of pure water, 45.1 g of MA, and 60.5 g of 48% NaOH, and the temperature was raised to the boiling point while stirring. A polymerization reaction system was used. Next, 222.3 g of 30% IPN10 aqueous solution, 41.4 g of 80% AA, 16.3 g of 15% NaPS, and 2.9 g of 35% H ₂ O ₂ were respectively added to the polymerization reaction system maintained at the boiling point reflux state with stirring. Dropped from separate nozzles. Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for 30% IPN 10, 80% AA and 15% NaPS, and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous solution of the comparative polymer (1) was obtained.

<Example 2>
The polymers (1) and comparative polymers (1) obtained in Example (1) and Comparative Example (1) were evaluated for gelation resistance and calcium ion scavenging ability according to the above methods. The results are summarized in Table 1.

As is apparent from Table 1, the polymer in the present invention has significantly superior gelation resistance while having the same calcium scavenging ability as compared with the conventional comparative polymer. It became clear that the sulfonic acid group-containing monomer of the present invention can be preferably used as a raw material for these polymers.
In the above examples, examples in which the reaction was carried out using specific compounds are shown. However, the mechanism of action of the sulfonic acid group-containing polymer obtained from the sulfonic acid group-containing monomer of the present invention is all Therefore, from the results of the above-described embodiments, the present invention can be applied in various technical forms of the present invention and in various forms disclosed in the present specification, and advantageous effects can be exhibited. It can be said.

Claims (4)

A sulfonic acid group-containing monomer represented by the following general formula (1).

In the general formula (1), R ₀ represents a C H ₃ group, R ₁ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ₁ is the same or different and has 2 to 4 carbon atoms. Represents an alkylene group, n represents the average number of added moles of the oxyalkylene group (—Y ₁ —O—), represents a number of 5 to 50 , and M ₁ represents a hydrogen atom or a monovalent cation. (I) a step (step A) of reacting a polyethylene glycol chain-containing monomer represented by the following general formula (2), an epihalohydrin, and an alkali compound;
(Ii) a step of reacting the reaction product obtained in the step (i) with a sulfite compound (step B), and a method for producing a sulfonic acid group-containing monomer ,
The method for producing a sulfonic acid group-containing monomer, wherein the sulfurous acid compound is any one of sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfurous acid, and salts thereof.

In the general formula (2), R ₀ represents a C H ₃ group, R ₁ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ₁ is the same or different and has 2 to 4 carbon atoms. It represents an alkylene group, n represents an average addition mole number of the oxyalkylene group _(-Y 1 -O-), represents a number of 5 to 50. And (i) the following general formula (2) represented by polyalkylene glycol chain-containing monomer comprising the steps of the epihalohydrin are reacted under the presence of a catalyst (step C),
(Ii) a step (step D) of reacting the reaction product obtained in step C with an alkali compound;
(Iii) a method for producing a sulfonic acid group-containing monomer comprising a step (step B) of reacting the reaction product obtained in step D with a sulfite compound ,
The method for producing a sulfonic acid group-containing monomer, wherein the sulfurous acid compound is any one of sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfurous acid, and salts thereof.

In the general formula (2), R ₀ represents a C H ₃ group, R ₁ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ₁ is the same or different and has 2 to 4 carbon atoms. It represents an alkylene group, n represents an average addition mole number of the oxyalkylene group _(-Y 1 -O-), represents a number of 5 to 50. And (i) the following general formula (2) represented by polyalkylene glycol chain-containing monomer comprising the steps of the epihalohydrin are reacted under the presence of a catalyst (step C),
(Ii) a method for producing a sulfonic acid group-containing monomer comprising a step (step E) of reacting the reaction product obtained in step C with a sulfurous acid compound ,
The method for producing a sulfonic acid group-containing monomer, wherein the sulfurous acid compound is any one of sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfurous acid, and salts thereof.

In the general formula (2), R ₀ represents a C H ₃ group, R ₁ represents a CH ₂ group or a CH ₂ CH ₂ group, and Y ₁ is the same or different and has 2 to 4 carbon atoms. It represents an alkylene group, n represents an average addition mole number of the oxyalkylene group _(-Y 1 -O-), represents a number of 5 to 50.

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