JP2007246785A - Water-soluble polymer, method for producing the same, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble polymer, which has excellent properties such as re-contamination preventing property and heavy metal ion chelating ability in addition to excellent storage stability, because of its suppressed aging in terms of viscosity and is useful in various applications; a method for producing the water-soluble polymer; and its use. <P>SOLUTION: The water-soluble polymer has a structural unit represented by general formula (1) and has a carbon-carbon double bond amount of 2% or less as calculated by the formula using<SP>1</SP>H-NMR measurements: integration of 5-7 ppm peak ×100/peak integration of 3.0-3.8 ppm, wherein R<SP>1</SP>is a hydrogen atom or a methyl group, R<SP>2</SP>is a hydrogen atom, a methyl group, -CH<SB>2</SB>COOM, or -CH<SB>2</SB>OH, R<SP>3</SP>is a divalent group, X is -NH-, -NR<SP>4</SP>-, or -S-, and M is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a water-soluble polymer, a production method thereof, and an application thereof. More specifically, the present invention relates to a water-soluble polymer containing a water-soluble group such as a carboxyl group and an amino group useful for various uses, a production method thereof, and a use thereof.

A polymer having a carboxyl group, an amino group or the like becomes water-soluble due to these groups, and exhibits various properties. Examples of applications of such water-soluble polymers include detergent compositions, fiber treatment agents, dispersants, flocculants, scale inhibitors, chelating agents, bleaching aids, pH adjusters, water treatment agents, peroxides. A stabilizer etc. can be mentioned. Especially in applications of detergent compositions and fiber treatment agents, calcium ion scavenging ability, clay (mud particle) dispersibility, iron and copper heavy metal ion scavenging ability, iron ion deposition prevention ability, copper ion hydrogen peroxide stabilization ability Therefore, a water-soluble polymer that can improve these characteristics is required. In other technical fields in which a water-soluble copolymer is used, improvement in basic performance such as processing capability is demanded.

As a conventional water-soluble polymer, a water-soluble polymer having a specific structural unit having an amide bond and a carboxyl group in the main chain and having a weight average molecular weight of 500 to 100,000 (for example, see Patent Document 1). ) And a water-soluble polymer having an amine value of 3.0 mmol / g or more (for example, see Patent Document 2). Preferred examples of these water-soluble polymers include amide monomers derived from maleic anhydride and polyalkylene polyamine, and water-soluble polymers obtained by Michael addition polymerization thereof.
These water-soluble polymers are excellent in performance such as anti-recontamination ability and heavy metal ion chelating ability when used as, for example, detergent compositions, fiber treatment agents, water treatment agents, and various fields in which water-soluble polymers are used. However, there is room for improvement in terms of improving handling performance and excellent storage stability during storage of products. That is, in a water-soluble polymer having excellent properties such as anti-recontamination ability and heavy metal ion chelating ability, if storage stability can be improved, it is excellent in both performance and quality in various useful applications. Therefore, such a water-soluble polymer is required.
JP 2000-319385 A (page 2-4) JP 2003-292617 A (second page)

The present invention has been made in view of the above situation, and has excellent properties such as anti-recontamination ability and heavy metal ion chelating ability, is excellent in storage stability, and is useful in various applications, An object of the present invention is to provide a manufacturing method and use thereof.

The present inventor has made various studies on water-soluble polymers that can be used in various applications such as detergent compositions, fiber treatment agents, water treatment agents, etc., and has a specific structure having an amide bond and a carboxyl group in the main chain. It was noted that the water-soluble polymer having units has properties as an amphoteric polymer and can exhibit excellent properties such as recontamination prevention ability and heavy metal ion chelating ability. The water-soluble polymer can be produced, for example, by Michael addition polymerization of an amide monomer. And if the amount of carbon-carbon double bonds remaining in the water-soluble polymer is below a specific value, the unreacted carbon-carbon double bonds remaining at the polymer ends and the like will be sufficiently reduced, and during storage It was found that the Michael addition reaction that proceeds gradually is sufficiently suppressed, so that the increase in the molecular weight of the polymer over time is sufficiently suppressed. In addition, since the change in molecular weight over time is sufficiently suppressed, the viscosity of the polymer does not change and the performance of the polymer is maintained, and handling can be facilitated even after long-term storage. As a result, they have come up with the idea that the above problems can be solved brilliantly. Furthermore, it has also been found that the present invention can be suitably applied to various uses such as a cleaning agent, a water treatment agent or a dispersing agent, and the present invention has been achieved.

In conventional water-soluble polymers, the viscosity changes over time during storage of the product, resulting in a phenomenon that the viscosity rises, and has an improvement in that so-called storage stability can be improved and maintained. Was. Storage stability is an important product quality for products such as detergent compositions. In the present invention, it was found that a water-soluble polymer having excellent storage stability can be obtained by suppressing the change in viscosity over time.

That is, the present invention is a water-soluble polymer having a structural unit represented by the following general formula (1) and / or (2), wherein the water-soluble polymer is represented by the following formula in ¹ H-NMR measurement;

It is a water-soluble polymer whose carbon-carbon double bond amount calculated by is 2% or less.

In formula, R < ¹ > is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a hydrogen atom, a methyl group, —CH ₂ COOM or —CH ₂ OH. R ³ is the same or different and represents a divalent group having 2 to 16 carbon atoms. X is the same or different and represents —NH—, —NR ⁴ — or —S—. R ⁴ is the same or different and represents a methyl group, an ethyl group, —CH ₂ COOM or —CH ₂ CH ₂ OH. M is the same or different and represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom.

The present invention is also a method for producing the water-soluble polymer, wherein the production method comprises a step of reacting a compound to be added to a carbon-carbon double bond during or after the polymerization. It is also a manufacturing method.
The present invention is also a cleaning agent, water treatment agent or dispersant containing the water-soluble polymer.
The present invention is described in detail below.

The water-soluble polymer of the present invention has a structural unit represented by the general formula (1) and / or (2). In the above general formulas (1) and (2), R ³ is the same or different, and the following general formulas (3) to (8);

(In the formula, p is an integer of 2 to 6. q is an integer of 1 to 6. r is an integer of 1 to 4. M is the same or different, and the general formula (1 It is the same as M in the above). It is preferably one or more compounds selected from the group consisting of: Incidentally, when ^{R 3} is the general formula (3), since p is 2 to 6, ^{R 3} will be satisfied from 2 to 16 carbon atoms.
In the general formula (5), R ^{5 s} are the same or different and are represented by the following general formula (9) or (10);

(Wherein, M is the same or different and is the same as M in the general formula (1)).

In the general formula (1), it is preferable that at least one of R ¹ and R ² is a hydrogen atom. Among these, (i) R ¹ and R ² are hydrogen atoms, R ³ is a divalent group having 2 to 10 carbon atoms, and —X— is —NH—. A polymer, (ii) a water-soluble polymer having a structural unit in which R ¹ and R ² are hydrogen atoms, and —R ³ —X— is — (CH ₂ CH ₂ NH) _n — (n is 1 to 1 And (iii) a water-soluble polymer having a structural unit in which R ¹ and R ² are hydrogen atoms, and —R ³ —X— is — (CH ₂ ) _m —NH— (m Represents an integer of 2 to 6.), (iv) R ¹ and R ² are hydrogen atoms, and —R ³ —X— is —CH ₂ CH ₂ N (CH ₂ CH ₂ NH ₂ ) CH ₂ CH. A water-soluble polymer having a structural unit of ₂ NH—, (v) R ¹ and R ² are hydrogen atoms, and —R ³ —X— is —CH (CO OM) (CH ₂ ) ₄ NH— a water-soluble polymer having a structural unit, (vi) R ¹ and R ² are hydrogen atoms, and —R ³ —X— is —CH (COOM) CH ₂ S—. (Vii) a water-soluble polymer having a structural unit in which R ¹ and R ² are hydrogen atoms, and —R ³ —X— is —CH ₂ CH ₂ S—. More preferred.

Among the above (i) to (vii), the form (i) is more preferable. Thus, it is a water-soluble polymer having the structural unit represented by the general formula (1) and / or (2), and the water-soluble polymer is calculated by the above formula in ¹ H-NMR measurement. A water-soluble polymer having a carbon-carbon double bond amount of 2% or less is also a preferred embodiment of the present invention.
In this form, in the above formula, R ¹ and R ² represent a hydrogen atom. R ³ is the same or different and represents a divalent group having 2 to 10 carbon atoms. X represents -NH-. M is the same or different and represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom.
In the above (ii), a water-soluble polymer having —CH ₂ CH ₂ NH— in which n is 1 as a structural unit, —R ³ —X— in which n is 3 is — (CH ₂ CH ₂ NH ) A water-soluble polymer having _3- as a structural unit is preferable.

The water-soluble polymer may have both of the structural units represented by the general formulas (1) and (2), or may have only one of them. When the water-soluble polymer has both of the structural units, the ratio of the structural units is as follows: the structural unit represented by the general formula (1) / the structural unit represented by the general formula (2) is 99 / It is preferable that it is 1-1 / 99.

The water-soluble polymer structure of the present invention may contain other components as long as it contains the structural unit represented by the general formula (1) and / or (2) as an essential component.
As said other component, the amide-type monomer which does not have -COOM in General formula (11) and (12), etc. are mentioned.
The proportion of the structural unit represented by the general formula (1) and / or (2) is 80 to 100% in a molar ratio in the water-soluble polymer, and preferably 90 to 100% in a molar ratio. More preferably, the molar ratio is 100%.

The water-soluble polymer preferably has a weight average molecular weight of 500 to 100,000. More preferably, it is 500-50000, More preferably, it is 500-20000, Especially preferably, it is 1000-20000, Most preferably, it is 1400-15000.
The viscosity of the water-soluble polymer is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, and still more preferably 1000 mPa · s or less.

The water-soluble polymer of the present invention has a structural unit represented by the above general formula (1) and / or (2), and is calculated using the above formula (1) by ¹ H-NMR measurement. The amount of carbon-carbon double bonds is 2% or less. By setting the carbon-carbon double bond amount to 2% or less, the double bond of the polymer present in the water-soluble polymer may be further subjected to an addition reaction with the (particularly terminal) amino group contained in the polymer, It is possible to sufficiently reduce the reaction of double bonds between polymers, and to sufficiently increase the molecular weight of the water-soluble polymer due to these reactions. An increase in the viscosity of the coalescence over time can be suppressed, and the water-soluble polymer can be stably stored for a long time.

The amount of carbon-carbon double bonds in the water-soluble polymer is more preferably 1% or less, still more preferably 0.5% or less, and most preferably not substantially contained.
In the above formula (1), hydrogen atoms bonded to carbon atoms having a carbon-carbon double bond are attributed to a peak of 5 to 7 ppm, and hydrogen atoms bonded to carbon adjacent to the carbonyl group are 3.0 to 3. It is attributed to a peak of 8 ppm. Therefore, in the present invention, the values obtained by integrating the peaks are used as indicators of the carbon-carbon double bond amount and the carbon-carbon atom single bond amount, respectively.
When R ¹ and R ² are not hydrogen atoms, the amount of carbon-carbon double bonds can be analyzed by a bromine addition method.

The amount of the carbon-carbon double bond was measured under the following ¹ H-NMR measurement conditions.
Apparatus: Varian's unity plus-400
Solvent: Heavy water internal standard substance: Sodium 3- (trimethylsilyl) -1-propanesulfonate (DSS) (DSS added to heavy water at a ratio of 0.1%)
Measurement was performed using a 45 ° pulse, a pulse delay time of 20 seconds, an integration count of 16 times, and a temperature of room temperature.

The present invention is also a water-soluble polymer having a structural unit represented by the general formula (1) and / or (2), wherein the water-soluble polymer is a monomer containing an amide monomer. It is obtained by polymerizing components, and is also a water-soluble polymer in which the amount of carbon-carbon double bonds derived from the α, β-unsaturated carbonyl group of the amide monomer is 2% or less. The form of such a water-soluble polymer is also one aspect of the present invention.
The form in which the amount of carbon-carbon double bonds derived from the α, β-unsaturated carbonyl group of the amide monomer is 2% or less is the carbon-carbon double bond required in the ¹ H-NMR measurement described above. It is also a preferred form of a water-soluble polymer whose amount is 2% or less. That is, the form in which the amount of carbon-carbon double bonds determined in ¹ H-NMR measurement is 2% or less, and the amount of carbon-carbon double bonds derived from the α, β-unsaturated carbonyl group of the amide monomer. Is combined with the form in which 2% or less, the amount of carbon-carbon double bonds determined in ¹ H-NMR measurement is changed to the carbon-carbon double derived from the α, β-unsaturated carbonyl group of the amide monomer. A preferred embodiment of the present invention is a water-soluble polymer having a binding amount of 2% or less.

The amide monomer may be any compound that has an α, β-unsaturated carbonyl group and an amide group and can be Michael-added. Preferred forms thereof include the following general formulas (11) and (12 ).

^Wherein, R 1 ^{to R} 3, X and M are the same or different and each is the same as ^R 1 ^{to R} 3, X and M in the general formula (1) to (10). Moreover, as a suitable example of these R < ¹ > -R < ³ >, X, and M, it is the same as that of the above-mentioned.

In the water-soluble polymer, the amount of carbon-carbon double bond derived from α, β-unsaturated carbonyl group is 2% or less means that it is derived from α, β-unsaturated carbonyl group of amide monomer. It means that the amount of carbon-carbon double bonds remaining in the water-soluble polymer is 2% or less with respect to the carbon-carbon single bond. In other words, the amount of carbon-carbon double bonds (mole) remaining in the water-soluble polymer derived from the α, β-unsaturated carbonyl group of the amide monomer is determined by the α, β-unsaturation of the amide monomer. This means that the value obtained by dividing the carbon-carbon double bond of the saturated carbonyl group by the amount (mol) of the carbon-carbon bond (single bond) is 2% or less.

When a water-soluble polymer is prepared from an amide monomer by Michael addition polymerization, as the amide monomer is polymerized, the carbon-carbon double bond of the α, β-unsaturated carbonyl group becomes a carbon-carbon bond ( The monomer constitutes a structural unit of the polymer, but the carbon-carbon double bond of the α, β-unsaturated carbonyl group remains at the end of the polymer. Become. If such a carbon-carbon double bond remains in the water-soluble polymer, an α, β-unsaturated carbonyl group and a site that can be added thereto exist, so that the polymer can be used as a product. Even during storage, Michael addition gradually proceeds, the molecular weight of the polymer increases over time, handling properties may decrease due to increased viscosity, and the properties of water-soluble polymers may be affected. There is.

In the above embodiment of the present invention, the amount of carbon-carbon double bonds derived from α, β-unsaturated carbonyl groups is 2% or less, thereby preventing recontamination, iron ion deposition, copper ion peroxidation. It has excellent characteristics such as hydrogen stabilization ability and heavy metal ion chelating ability, and the change in viscosity with time is suppressed, handling performance during product storage is improved, and storage stability can be improved. In addition, it can be a water-soluble polymer useful in various applications such as detergent compositions, fiber treatment agents, water treatment agents, and peroxide stabilizers. That is, the molecular weight increases due to the addition reaction of the polymer double bonds remaining after the polymerization to the amino group contained in the polymer (especially the terminal) or the reaction between the double bonds between the polymers. By reacting with this double bond and a highly reactive compound (specific examples will be described later), the ratio of double bonds in the polymer is kept constant (2%) or less, It has been found that the change with time of the polymer can be suppressed.
A preferable range of the amount of carbon-carbon double bonds derived from the α, β-unsaturated carbonyl group is preferably 2% or less. More preferably, it is 1% or less, More preferably, it is 0.5% or less, Most preferably, it is not containing substantially.

The amount of carbon-carbon double bonds in the water-soluble polymer can be calculated using ¹ H-NMR measurement or, in some cases, other methods. ^{In 1} H-NMR measurement, it is determined from a signal derived from a carbon-carbon single bond and a signal derived from a carbon-carbon double bond derived from an α, β-unsaturated carbonyl group. When signals derived from other functional groups or the like overlap, the integral value derived from the signal is subtracted.

The water-soluble polymer may have a carboxyl group bonded to the polymer main chain and an amide group in the polymer main chain, and further have at least one functional group selected from an amino group and a thioether group. For this reason, it works effectively to capture calcium ions and heavy metal ions, and has excellent ability to prevent iron ion deposition, clay dispersibility, and copper ion hydrogen peroxide stabilization, and adsorbs to fabrics etc. Can be improved, and excellent performance can be exhibited in various applications.

The amine value, clay dispersibility, iron ion deposition preventing ability, copper ion hydrogen peroxide stabilizing ability and calcium ion scavenging ability of the water-soluble polymer are preferably within the following ranges. By setting it as such a range, the function of a water-soluble polymer will fully be exhibited, and it can be used effectively in various uses, such as a cleaning agent, a water treatment agent, or a dispersing agent. The amine value of the water-soluble polymer is preferably 3.0 mmol / g or more. Thus, the water-soluble polymer having an amine value of 3.0 mmol / g or more is also a preferred embodiment of the present invention. More preferably, it is 4.0 mmol / g or more, More preferably, it is 5.0 mmol / g or more.
The water dispersibility of the water-soluble polymer is preferably 20% or more. If the clay dispersibility is less than 20%, particularly when used as a cleaning agent, the cleaning effect may not be sufficiently exhibited. More preferably, it is 30% or more, and further preferably 40% or more.

The ability of the water-soluble polymer to prevent deposition of iron ions is preferably 30% or more. If the ability to prevent the deposition of iron ions is less than 30%, the cleaning effect may not be sufficiently exhibited when used as a cleaning agent. More preferably, it is 40% or more, More preferably, it is 50% or more. The water-soluble polymer preferably has a copper ion hydrogen peroxide stabilization ability of 20% or more. More preferably, it is 30% or more, still more preferably 45% or more, and particularly preferably 60% or more. The calcium ion scavenging ability of the water-soluble polymer is preferably 20 mgCaCO ₃ / g or more. When the calcium ion scavenging ability is less than 20 mg CaCO ₃ / g, when used as a cleaning agent, the cleaning effect may not be sufficiently exhibited. More preferably, it is not 25mgCaCO ₃ / g or more, further preferably 30mgCaCO ₃ / g or more.
If the amine value, clay dispersibility, iron ion deposition prevention ability, copper ion hydrogen peroxide stabilization ability and calcium ion scavenging ability index (setting range) of the water-soluble polymer are within the above ranges, Although the function of the coalescence can be sufficiently exhibited, it is preferable to form a water-soluble polymer that satisfies the preferred ranges of these various indicators in combination.

The present invention is also a method for producing the water-soluble polymer, wherein the production method comprises a step of reacting a compound to be added to a carbon-carbon double bond during or after the polymerization. It is also a manufacturing method.
The method for producing the water-soluble polymer includes a step of reacting a compound to be added to a carbon-carbon double bond during or after the polymerization, and exhibits the effects of the present invention. Although it is not particularly limited as long as it is a method for obtaining a water-soluble polymer, it is preferable to obtain a water-soluble polymer by the following method.

The method for producing the water-soluble polymer includes (1) a step of obtaining the amide monomer by an amidation reaction, (2) a step of Michael addition polymerization of the amide monomer, and (3) Michael. It is preferable to include a step of reacting a compound added to the carbon-carbon double bond during or after the addition polymerization.
In the step (1), the amide monomer represented by the general formulas (11) and (12) is preferably obtained, for example, by an amidation reaction between an acid anhydride or ester and an amine compound. It is.
As said acid anhydride, following General formula (13);

(Wherein, ^{R 1} and ^{R 2,} the general formula (1) the same. ^{R 1} and ^{R 2} in) an acid anhydride represented by can be preferably used. Among these, acid anhydrides such as maleic anhydride and citraconic anhydride are preferable. Particularly preferred is maleic anhydride.
As the ester, maleic acids such as monomethyl maleate, dimethyl maleate, monoethyl maleate and diethyl maleate are suitable.
Examples of the amine compound include the following general formula (14);

(In the formula, R ³ and X are the same as R ³ and X in the general formula (1)). More preferably, when X is —NH— or NR ⁴ —, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (2-aminoethyl) amine, Lysine, arginine, cystine and the like, and when X is —S—, cysteine, cysteamine, aminoethyl mercaptoethylethylamine and the like. More preferred are ethylenediamine, diethylenetriamine, and triethylenetetramine.

As the amidation reaction, (i) an acid anhydride (preferably in a powder form) is gradually added to an amine compound in an aqueous solvent (preferably in water) with stirring. A method of amidation, (ii) a method of amidating an acid anhydride and an amine compound or a hydrolyzate of an acid anhydride and an amine compound in an inert organic solvent such as toluene or xylene by a conventionally known method, (iii) A method of amidating a monoester of an acid anhydride and an amine compound by a conventionally known transesterification reaction in an inert organic solvent such as toluene or xylene can be suitably used. Among these, the method (i) is preferable. According to the method (i), since it can be synthesized with an aqueous solvent, a removal step required when an organic solvent is used is unnecessary, and synthesis at a high concentration is possible, which is economically excellent. You can do it. Moreover, it is preferable in the case where the polymerization in the next step is carried out with an aqueous solvent (preferably water), and is an excellent method from the viewpoint of safety and environment.

The solvent used in the method (i) is preferably water or an aqueous solvent. Such an aqueous solvent is preferably an aqueous solvent in which an organic solvent that can be mixed with water is appropriately added in an amount of 10% or less in order to improve the solubility of the amine. Examples of the organic solvent that can be mixed with water include lower alcohols such as methanol, ethanol and isopropyl alcohol; amides such as dimethylformamide; ethers such as diethyl ether and dioxane; and the like. Can be appropriately selected and used.
The reaction temperature of the amidation reaction is preferably 50 ° C. or lower. When it exceeds 50 ° C., there is a possibility that a simple hydrolysis reaction of an acid anhydride may proceed rather than an amidation reaction. More preferably, it is 40 degrees C or less, More preferably, it is 30 degrees C or less. In addition, in the amidation reaction, it is preferable that the acid anhydride is substantially continuously added over 10 minutes or more, and after all the acid anhydride is added, aging is further performed for 10 minutes or more.

In the amidation reaction, an acid may be generated as the reaction proceeds, and the amine compound may be neutralized to reduce the reaction rate. In such a case, it is preferable to add a basic compound such as an alkali metal hydroxide such as sodium hydroxide in an amount corresponding to the neutralized amine.

In the preferred method for producing the water-soluble polymer of the present invention, the step (2) includes a monomer component containing the amide monomer represented by the general formula (11) and / or (12). A method of Michael addition polymerization is preferred. Among them, it is preferable to perform Michael addition polymerization of an amide monomer synthesized from maleic anhydride and a polyalkylene polyamine (ethylenediamine, diethylenetriamine, etc.). In addition, the obtained amphoteric polymer having a carbon-carbon double bond amount of a certain amount or less is one of the preferred water-soluble polymers of the present invention.

The molecular weight of the amide monomer is preferably 100 to 1000, more preferably 150 to 800, and still more preferably 180 to 500.
As said monomer component, another monomer may be included as needed. The other monomer is not particularly limited as long as it is a monomer capable of Michael addition polymerization with the amide monomer represented by the general formulas (11) and (12). In the general formulas (11) and (12), an amide monomer having no —COOM may be used.
When the other monomer is used, the amount of the other monomer used is preferably less than 20 mol% with respect to 100 mol% of the monomer component, and more preferably less than 10 mol%. preferable.
In the method for producing the water-soluble polymer, after obtaining an amide monomer by the amidation reaction, the obtained amide monomer may be once isolated and subjected to Michael addition polymerization. After the amidation reaction, Michael addition polymerization may be performed subsequently.

The polymerization method for performing the Michael addition polymerization in the present invention is preferably solution polymerization, and in this case, either stirring or standing may be used. As the solvent for the solution polymerization, the aqueous solvent exemplified in the amidation reaction can be suitably used. A catalyst for performing the above solution polymerization is basically unnecessary, but a catalyst that does not adversely affect the polymerization can be used as necessary.
Although the monomer concentration at the time of performing the solution polymerization is not particularly limited, it is preferably 10% or more, more preferably 20% or more. Further, the pH of the polymerization solution is not particularly limited, and can be set appropriately depending on the solubility of the monomer. In the Michael addition polymerization, the higher the pH, the higher the polymerizability. Therefore, it is preferably 7 or more, more preferably 10 or more.
The polymerization temperature when performing the above solution polymerization is preferably 20 to 100 ° C., and more preferably 80 ° C. or less in order to prevent cleavage of the amide bond. The polymerization time is not particularly limited, and the polymerization pressure may be normal pressure (atmospheric pressure), pressurization, or reduced pressure.

In the preferred method for producing the water-soluble polymer of the present invention, the step (3) is preferably a step of reacting a compound added to a carbon-carbon double bond during or after the polymerization. By adding a specific compound to the carbon-carbon double bond, the amount of the carbon-carbon double bond in the water-soluble polymer can be sufficiently reduced, and the factor causing the Michael addition reaction is reduced. It is possible to obtain a water-soluble polymer excellent in temporal stability in which increase is suppressed and viscosity increase and performance deterioration are sufficiently suppressed.
The reaction for adding the carbon-carbon double bond can be performed during or after the polymerization of the monomer component including the amide monomer.
The reaction conditions for the addition reaction are not particularly limited, but it is preferably performed at a temperature of room temperature to about 80 ° C. for 10 minutes to 24 hours.

The compound added to the carbon-carbon double bond is preferably at least one selected from the group consisting of amines, thiols, sulfites, and bisulfites.
As the amines, ethylamine, propylamine, butylamine, and ethanolamine are preferable. As the thiols, ethanethiol, propanethiol, butanethiol, mercaptoethanol, mercaptopropionic acid and salts and esters thereof are preferable. As the sulfites, sodium sulfite and potassium sulfite are preferable. As the bisulfites, sodium bisulfite (SBS) and potassium bisulfite are preferable.
Among these, SBS is preferable as the compound added to the carbon-carbon double bond.
The step (3) is preferably a step of reacting bisulfite, thiol, amine, or the like with the amphoteric polymer obtained by Michael addition polymerization of the amide monomer. A method for producing a polymer having a bond amount of a certain amount or less can be suitably used as the production method of the present invention.

The method for adding to the carbon-carbon double bond is not limited to the above. For example, the Michael addition reaction described in JP-A-10-212302, JP-A-5-78412, or JP-A-2001-200011 It may be a method comprising adding a mixture of the described (a) surfactant and (b) a compound that can be added beyond the vinyl carbon-carbon bond.
In the above Michael addition reaction, one or more mono- and / or polyfunctional nucleophilic compounds are reacted, and a compound having an SH group is suitable as the nucleophilic compound. For example, mercaptoethanol, 1, 2-bis- (2-mercaptoethoxy) -ethane and mixtures thereof, sodium bisulfite, sodium hydrogen sulfite, pentaerythritol-tetrakis- (2-mercapto-acetate) and mixtures thereof are preferred.

The surfactant (a) includes methoxy-terminated ethylene oxide, adduct of siloxane, 4 to 24 mol ethylene oxide adduct of C ₁₂ -C ₁₄ fatty alcohol, and an alkali metal salt of fatty acid sulfate containing 10 to 30 carbon atoms. Ethylene oxide / propylene oxide adducts of glycols or glycerin, or mixtures thereof, phenol or substituted phenols or ethylene oxide adducts of ethylene oxide and / or propylene oxide oligomers, fatty acids or fatty acid salts containing 10 to 30 carbon atoms, A single surfactant or a mixture of surfactants selected from the group consisting of alkali metal salts of fatty acids containing 10 to 30 carbon atoms, sodium or potassium salt of stearic acid and / or lauric acid is preferred.

Examples of the compound (b) that can be added beyond the vinyl carbon-carbon bond include a. Alkali metal sulfite b. Alkali metal hydrogen sulfite c. Alkyl or aryl or substituted alkyl or arylsulfinic acid, or a salt thereof d. Alkali metal salt of thiosulfate e. Hypophosphorous acid and its salts f. It is preferably one or more compounds selected from the group consisting of sulfur-containing amino acids and salts thereof and mixtures thereof.

The present invention is also a cleaning agent, a water treatment agent or a dispersant containing the water-soluble polymer.
The water-soluble polymer of the present invention can be used for various applications, and more specifically, organic chelating agents, scale inhibitors, flocculants, detergent builders, bleaching aids, masking agents, fibers It can be used as a treatment agent, an additive for paper / pulp, a semiconductor cleaner, a photographic agent, a soil modifier, a pH adjuster, a cleaner, an additive, a skin care agent, and the like. For example, in various cleaning applications, it can be used for cars, baths, clothing, tableware, body use, toothpaste, and is suitable for cleaning and removing dirt adhered to hard surfaces such as glass, plastic and metal. It is used. As a cleaning method, methods such as immersion cleaning, spray cleaning, circulation cleaning, brush cleaning, and spray cleaning can be used.

The cleaning agent, water treatment agent or dispersing agent of the present invention only needs to contain the water-soluble polymer as an essential component, and may further contain a surfactant. The blending amount of the water-soluble polymer in the cleaning agent, water treatment agent or dispersant is preferably 0.1 to 20% by weight. More preferably, it is 0.5 to 15% by weight. The surfactant content is preferably 5 to 70% by weight. More preferably, it is 20 to 60% by weight. As the surfactant, at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant can be preferably used.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, saturated or Unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof are preferred.
Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester, Alkylamine oxide is preferred.
Examples of the amphoteric surfactant include carboxy type or sulfobetaine type amphoteric surfactants, and the cationic surfactant is preferably a quaternary ammonium salt.

The said cleaning agent etc. may contain the enzyme as needed. As the enzyme, protease, lipase, cellulase and the like can be used. In particular, protease, alkaline lipase and alkaline cellulase having high activity in the alkaline washing liquid are preferable. The enzyme content is preferably 0.01 to 5% by weight. Outside this range, the balance with the surfactant is lost, and the cleaning power cannot be improved. Moreover, you may contain the component and zeolite normally used for cleaning agents, such as a well-known alkali builder, chelate builder, anti-redeposition agent, a fluorescent agent, a bleaching agent, and a fragrance | flavor as needed. As the alkali builder, silicate, carbonate, sulfate and the like can be used. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), citric acid or the like can be used as necessary.

The cleaning agent of the present invention is excellent in re-contamination prevention ability, and at the same time, is excellent in capturing heavy metal ions such as iron ions present in the cleaning liquid, and in clay dispersibility. It is valid. Further, the cleaning agent of the present invention can be used for powder detergents, liquid detergents or gel detergents.

The present invention further relates to a method for preserving and / or transporting the water-soluble polymer, wherein the method for preserving and / or transporting is carried out at a concentration of 30 to 70% by mass and a temperature of 0 to 50 ° C. It is also a transportation method. Since the water-soluble polymer of the present invention can be suitably stored and / or transported at such a concentration and temperature, it can be suitably used for various applications such as a cleaning agent, a water treatment agent or a dispersing agent.
The concentration is 30 to 70% by mass. When the content is lower than 30% by mass, the transportation becomes large. When the content is higher than 70% by mass, the viscosity becomes high, and the handling of the aqueous solution may be complicated. Preferably, it is 35-65 mass%, More preferably, it is 40-60 mass%.
The temperature is 0 to 50 ° C. If it is lower than 0 ° C, the aqueous solution may be frozen, and if it is higher than 50 ° C, the polymer may be decomposed. Preferably, it is 10-45 degreeC, More preferably, it is 15-40 degreeC.

The water-soluble polymer of the present invention is a water-soluble polymer having the above-described constitution and useful for various applications, and can make the polymer sufficiently stable.

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 weight” and “%” means “mass%”.

The weight average molecular weight of the polymers obtained in the examples was measured as follows.
<Weight average molecular weight>
It measured by the gel permeation chromatography (GPC) analysis of the following conditions.
Device: Hitachi L-7000 Series Detector: RI
Column: SB-G + SB-804HQ + SB-803HQ + SB-802.5HQ manufactured by SHODEX
Column temperature: 40 ° C
Calibration curve: “POLYETHYLENE OXIDE STANDARD” manufactured by GL Sciences Inc.
GPC software: “BORWIN” manufactured by JASCO
Eluent: 0.5M acetic acid + 0.5M sodium acetate Flow rate: 0.8ml / min

Example 1 and Comparative Example 1
118 g of ion-exchanged water was charged in a 0.5-liter glass separable flask equipped with a reflux condenser and a stirrer, and 60 g of ethylenediamine was added. Thereafter, 98 g of maleic anhydride pulverized in a mortar was gradually added while being kept at 15 ° C. or lower by cooling with ice under stirring. After completion of the addition, the mixture was reacted for 30 minutes or longer, and then gradually neutralized by gradually adding 84 g of a 48% aqueous sodium hydroxide solution to obtain an aqueous solution of maleic acid-ethylenediamineamide monomer. This aqueous solution was stirred at 80 ° C. for 4 hours to obtain a water-soluble polymer 1 having a solid content of 50% and a final neutralization degree of 100%. Next, 40 g of this polymer aqueous solution was subdivided into glass screw bottles having a capacity of 50 ml, and 0.57 g, 1.71 g, and 2.86 g of 35% sodium hydrogen sulfite (SBS) aqueous solution were added to this. 1, 3 and 5% by mass) were added and stirred with a magnetic stirrer at room temperature to reduce the remaining carbon-carbon double bonds derived from α, β-unsaturated carbonyl groups, respectively. Polymers 1A, 1B, and 1C were used, and the polymer to which SBS was not added was called polymer 1D.

After each aqueous solution of polymers 1A, 1B, 1C and 1D was purified by dialysis as described below, ¹ H-NMR of each polymer obtained by drying under reduced pressure was measured, and the amount of carbon-carbon double bonds was calculated. , 0.8%, 0.2%, 0.1% and 2.2%, respectively. ¹ H-NMR measurement is performed immediately after polymerization (within 24 hours after polymerization), and the measurement date is taken as 0 day, and the polymers 1A (□), 1B (■), 1C (◯) and 1D (♦) are The change in weight average molecular weight when stored at 25 ° C. in a sealed container is shown in FIG.
(Dialysis method)
A dialysis membrane (Dialysis membrane 36; manufactured by Wako Pure Chemical Industries, Ltd.) cut to a length of 30 cm was washed with ion-exchanged water, and 8 g of an aqueous polymer solution was added and sealed. This dialysis tube was immersed in 1000 g of ion exchange water in a 1 L beaker. After 2 hours, the ion exchange water in the beaker was replaced, and dialysis was further performed for 2 hours. The dialysis membrane was taken out from the beaker and the outside of the dialysis membrane was washed away with ion-exchanged water. Then, the contents of the dialysis membrane were taken out to obtain a polymer aqueous solution after dialysis.

Example 2 and Comparative Example 2
130.7 g of ion-exchanged water was charged in a 0.5-liter glass separable flask equipped with a reflux condenser and a stirrer, and 87.2 g of hexamethylenediamine was added. Thereafter, 73.5 g of maleic anhydride pulverized in a mortar was gradually added while being kept at 15 ° C. or lower by cooling with ice under stirring. After completion of the addition, the mixture was allowed to react for 30 minutes or more, and then 62.5 g of a 48% sodium hydroxide aqueous solution was gradually added to neutralize to obtain an aqueous solution of maleic acid-hexamethylenediamine monoamide monomer. This aqueous solution was stirred at 80 ° C. for 4 hours to obtain a water-soluble polymer 2 having a solid content of 50% and a final neutralization degree of 100%. Furthermore, addition reaction by SBS was performed in the same manner as in Example 1 to obtain polymers 2A (□), 2B (■), 2C (◯), and 2D (♦).
In the same manner as in Example 1, the polymers 2A, 2B, 2C and 2D were purified by dialysis and ¹ H-NMR measurement was performed, and the amount of carbon-carbon double bonds was calculated. They were 4%, 0.2%, and 2.8%. These changes in weight average molecular weight when stored in the same manner as in Example 1 are shown in FIG.

Example 3 and Comparative Example 3
A glass separable flask having a capacity of 1 liter equipped with a reflux condenser and a stirrer was charged with 245.9 g of ion-exchanged water, and 175.5 g of triethylenetetramine was added. Thereafter, 117.6 g of maleic anhydride pulverized in a mortar was gradually added while maintaining the temperature at 15 ° C. or lower by cooling with ice. After completion of the addition, the mixture was reacted for 30 minutes or more, and then neutralized by gradually adding 100 g of a 48% aqueous sodium hydroxide solution to obtain an aqueous solution of maleic acid-triethylenetetramine monoamide monomer. This aqueous solution was stirred at 80 ° C. for 1 hour to obtain a water-soluble polymer 3 having a solid content of 50% and a final neutralization degree of 100%. Next, 40 g of this polymer aqueous solution was divided into a glass screw mouth bottle with a capacity of 50 ml, and 2 g of 35% sodium bisulfite (SBS) aqueous solution (3.5% by mass with respect to polymer 3) was added thereto. Stirring with a magnetic stirrer at room temperature to reduce the remaining α, β-unsaturated carbonyl group-derived carbon-carbon double bonds is referred to as Polymer 3A, and SBS is not added. 3B.
Purification of polymers 3A and 3B by dialysis and ¹ H-NMR measurement were performed in the same manner as in Example 1, and the amount of carbon-carbon double bonds was calculated to be 0.4% and 3.2%, respectively. It was. Changes in the weight average molecular weights of the polymers 3A (■) and 3B (♦) when stored in the same manner as in Example 1 are shown in FIG.

1-3, compared with the polymers 1D, 2D and 3B of the comparative examples, the polymers 1A to 1C, 2A to 2C and 3A of the examples suppressed the change with time of the weight average molecular weight and were stable in storage. It is a polymer with excellent properties.
In the above-described Examples and Comparative Examples, a polymer of maleic acid and ethylenediamine, a polymer of maleic acid and hexamethylenediamine, and a polymer of maleic acid and triethylenetetramine are used as the water-soluble polymer. In the case of the water-soluble polymer having the structural unit represented by (1) and / or (2), the mechanism for suppressing the change with time of the weight average molecular weight is the same. Therefore, if the amount of carbon-carbon double bonds calculated by the above formula is 2% or less, it can be said that the advantageous effects of the present invention are surely exhibited. At least in the case of a polymer of maleic acid and ethylenediamine, a polymer of maleic acid and hexamethylenediamine, and a polymer of maleic acid and triethylenetetramine, the advantageous effects of the present invention are sufficiently obtained in the above-described examples and comparative examples. This proves the technical significance of the present invention.

FIG. 1 is a graph showing the change with time of the weight average molecular weight of the polymers 1A to 1D. FIG. 2 is a graph showing the change with time of the weight average molecular weight of the polymers 2A to 2D. FIG. 3 is a graph showing the change with time of the weight average molecular weights of the polymers 3A and 3B.

Claims (6)

A water-soluble polymer having a structural unit represented by the following general formula (1) and / or (2),
The water-soluble polymer has the following formula in ¹ H-NMR measurement:

A water-soluble polymer, wherein the carbon-carbon double bond amount calculated by the formula (1) is 2% or less.

In formula, R < ¹ > is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a hydrogen atom, a methyl group, —CH ₂ COOM or —CH ₂ OH. R ³ is the same or different and represents a divalent group having 2 to 16 carbon atoms. X is the same or different and represents —NH—, —NR ⁴ — or —S—. R ⁴ is the same or different and represents a methyl group, an ethyl group, —CH ₂ COOM or —CH ₂ CH ₂ OH. M is the same or different and represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. The water-soluble polymer according to claim 1, wherein the water-soluble polymer has an amine value of 3.0 mmol / g or more. A method for producing the water-soluble polymer according to claim 1, comprising:
The production method comprises a step of reacting a compound to be added to a carbon-carbon double bond during or after polymerization. The water-soluble compound according to claim 3, wherein the compound added to the carbon-carbon double bond is at least one selected from the group consisting of amines, thiols, sulfites, and bisulfites. A method for producing a polymer. A cleaning agent, a water treatment agent or a dispersing agent comprising the water-soluble polymer according to claim 1. A method for storing and / or transporting the water-soluble polymer according to claim 1 or 2,
The storage and / or transporting method is carried out at a concentration of 30 to 70% by mass and a temperature of 0 to 50 ° C.

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