JP3230255B2 - Dispersant for aluminum compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dispersant for aluminum compounds. More specifically, the present invention relates to a dispersant that imparts dispersibility and dispersion stability of an aluminum compound when producing an aqueous slurry of a high-concentration aluminum compound.

[0002]

2. Description of the Related Art Aluminum compounds such as aluminum hydroxide and aluminum oxide are widely used in various fields such as papermaking, paints and fine ceramics in the form of an aqueous slurry dispersed in water. An aqueous slurry of an aluminum compound is also used as a high quality product raw material.
In addition, it is required to be uniformly dispersed in water from the viewpoint of handling. In particular, it is necessary that even a high-concentration slurry has low viscosity and excellent viscosity stability over time. For example, among aluminum compounds, when applying aluminum hydroxide as a white pigment to paper or the like, in order to increase the efficiency of the drying process after coating, to reduce the water content as much as possible, that is, high concentration and low viscosity Preferably, it is an aqueous slurry. Further, an aqueous slurry having excellent dispersibility and dispersion stability has been demanded from the viewpoints of coating workability and coating film properties. In addition, in terms of transportation and storage, in order to reduce costs, an aqueous slurry having a high concentration and a low viscosity, and at the same time, having excellent dispersion stability that does not settle in the transportation and storage tanks and form a hard cake is required. It has been. Therefore, it has been expected to provide a dispersant that can be used to prepare a high-concentration aqueous slurry having excellent dispersibility and dispersion stability with a small amount of addition.

Further, in recent years, demand for aluminum compounds having a small particle diameter (1 μm or less) has been increased with the improvement in quality of products, and the amount of aluminum compounds used has been increasing. However, the smaller the particle size, the worse the dispersibility and dispersion stability, and thus a better dispersant is required.

Conventionally, dispersants for this purpose include inorganic phosphates such as condensed phosphates such as pyrophosphate and hexametaphosphate, as well as zinc salts and silicates. On the other hand, as an organic dispersant, a polyacrylate or a water-soluble salt of an α-olefin-maleic anhydride copolymer (for example, JP-A-60-9)
No. 9334) and the like.

[0005]

However, among these dispersants, the inorganic dispersants have a problem in dispersion stability of the obtained aqueous slurry and require a large amount of addition. As a result, there were serious drawbacks such as an increase in cost and a decrease in performance of the coating film. Organic dispersants have relatively better performance than the above-mentioned inorganic dispersants, but are not satisfactory. In particular, when it is used for dispersing a particulate aluminum compound having an average particle diameter of 1 μ or less, both dispersibility and dispersion stability have room for improvement.

Accordingly, an object of the present invention is to provide a dispersant for an aluminum compound which can obtain a low viscosity even in a high-concentration slurry with a small amount of addition and has excellent dispersion stability.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a dispersant for an aluminum compound comprising a water-soluble salt of a hydrolyzate of a copolymer of maleic anhydride and an aliphatic conjugated diene.

[0008] The aliphatic conjugated diene constituting the copolymer of the present invention is, for example, an aliphatic conjugated diene having 4 to 12 carbon atoms, preferably 4 to 7 carbon atoms, and more preferably 4 to 5 carbon atoms. Specifically, 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,3-dimethyl-
Examples thereof include 1,3-butadiene, 2-ethyl-1,3-butadiene, and 1,3-heptadiene. In particular,
1,3-butadiene and isoprene are preferred because they have high reactivity with maleic anhydride, are easily available industrially, and are inexpensive. The copolymer of the present invention may contain one kind of these aliphatic conjugated diene units, or may contain two or more kinds thereof.

The copolymer of the present invention has a maleic anhydride unit content of 30 to 90 mol%, preferably 40 to 80 mol%.
In order to obtain an excellent dispersing effect, it is appropriate to set the molar percentage, more preferably 45 to 75 molar%. In addition, the content of the maleic anhydride unit in the copolymer can be determined by using a CHN elemental analysis method or an NMR spectrum method.

Further, the weight average molecular weight of the copolymer is 10
It is suitable that it is 0.000 to 50,000, preferably 2,000 to 30,000, since it exhibits an excellent dispersing effect. Here, the weight average molecular weight can be determined by measurement by gel permeation chromatography (GPC).

The dispersant of the present invention contains a water-soluble salt of a hydrolyzate of the above-described copolymer of maleic anhydride and an aliphatic conjugated diene. The hydrolyzate of the copolymer is usually a complete hydrolyzate, but may be a partial hydrolyzate as long as it is water-soluble.

Further, the copolymer of the present invention comprises sodium,
Salts of alkali metals such as potassium, alkaline earth metals such as calcium and barium, or basic substances such as ammonia and alkylamine. Among them, a sodium salt or an ammonium salt is preferable.

The method for producing the dispersant of the present invention will be described below.

The copolymer used in the dispersant of the present invention can be obtained by subjecting maleic anhydride and an aliphatic conjugated diene to a radical copolymerization reaction in a solvent in the presence of a radical generator.

In the polymerization, the aliphatic conjugated diene is preferably added continuously to a mixture of maleic anhydride and a solvent. This is because if the aliphatic conjugated diene is previously charged together with maleic anhydride and the reaction solvent, the Diels-Alder reaction proceeds during the temperature increase or at the beginning of the polymerization reaction, and the yield may decrease. By continuously supplying the aliphatic conjugated diene, the polymerization reaction can be prioritized over the Diels-Alder reaction. The radical generator may be added in advance to a mixture of maleic anhydride and the reaction solvent, or may be added continuously as in the case of the aliphatic conjugated diene.

Examples of the solvent include hydrocarbons such as benzene, toluene, xylene and cyclohexane; ketones such as acetone, cyclohexanone and methyl ethyl ketone; esters such as ethyl acetate and isopropyl acetate; ethers such as dibutyl ether, tetrahydrofuran and dioxane; Alternatively, dimethylsulfoxide, dimethylformamide, gamma-butyrolactone and the like can be used. These solvents can be classified into those in which maleic anhydride is dissolved but the copolymer is insoluble, and those in which both maleic anhydride and the copolymer are soluble. With the former type of solvent, the polymerization proceeds as a precipitation polymerization or a suspension polymerization in the presence of a suitable dispersant. On the other hand, when the latter type of solvent is used, it proceeds as solution polymerization. Solvents such as amines and alcohols are not suitable for reacting with maleic anhydride or the resulting copolymer.

Among the above-mentioned solvents, aromatic hydrocarbon solvents are preferred from the viewpoints of production and process. The aromatic hydrocarbon solvent is a poor solvent for the present copolymer, and after completion of the reaction, the copolymer precipitates and is obtained as a precipitate. Therefore, there is an advantage that most of the solvent can be easily separated by removing the supernatant solution after completion of the polymerization reaction, and further, unreacted maleic acid and by-products can be removed at the same time. Further, when producing a hydrolyzate of the copolymer, there is also an advantage that a small amount of solvent remaining in the system can be easily removed as an azeotropic mixture with water.

The amount of the solvent used is not particularly limited. However,
From the viewpoint of controlling local and rapid reaction, for example, 50 to 150 parts by weight with respect to 100 parts by weight of maleic anhydride.
It is appropriate to use 0 parts by weight of the solvent.

In the present method, the feed rates of the aliphatic conjugated diene and the radical generator are not particularly limited. However,
When an aromatic hydrocarbon is used as the solvent, it is preferable that the feed rate of the aliphatic conjugated diene satisfies the following conditions from the viewpoint of suppressing the Diels-Alder reaction and suppressing the formation of an insoluble three-dimensional polymer. .

Y> 280X + 80 and X ≧ 0.07 where Y represents the reaction temperature (° C.) and X is the feed rate of the aliphatic conjugated diene (total moles of conjugated diene / total moles of maleic anhydride / Conjugated diene supply time (hour)).

The aliphatic conjugated diene can be supplied uniformly during the polymerization reaction, or the supply rate can be increased or decreased for controlling the reaction.

On the other hand, when the radical generator is continuously supplied, the supply rate of the radical generator is not particularly limited. However, it is preferable that radicals are generated in accordance with the supply of the aliphatic conjugated diene, and it is preferable to supply all the radical generators in substantially the same time as the supply time of the conjugated diene. Further, the radical generator can be supplied evenly during the polymerization reaction, or the supply rate can be increased or decreased for controlling the reaction.

The radical generator used in the present method is determined in consideration of its half-life. It is preferable to use a radical generator having a half-life of 1 hour or less in the reaction temperature range. If the half-life is too long, the amount of radicals generated per unit time will decrease, and the Diels-Alder reaction will proceed from the polymerization reaction, leading to a decrease in yield, and it will be necessary to increase the amount of the radical generator used. Absent.

At a reaction temperature range of 90 ° C. or higher,
Examples of the radical generator having a half life of 1 hour or less include t-butylperoxy (2-ethylhexanoate),
peroxyesters such as t-butylperoxybenzoate; dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide;
Peroxy ketals such as bis (t-butylperoxy) -3,3,5-trimethylcyclohexane can be mentioned.

The amount of the radical generator used is, for example, 0.05 to 15% by weight, preferably 0.5 to 10% by weight, based on maleic anhydride. If the amount is too small, the polymerization reaction will not proceed effectively, and if it is too large, the molecular weight will be too low, and it is not preferable from an economic viewpoint.

The amounts of the maleic anhydride and the aliphatic conjugated diene can be appropriately adjusted depending on the maleic anhydride units and the aliphatic conjugated diene units of the copolymer.

The aliphatic conjugated diene and the radical generator are:
It can be supplied as such or as a mixture with a solvent.
However, it is preferable to supply a mixture with a solvent from the viewpoint of suppressing a local rapid reaction. The mixing ratio (weight ratio) with the solvent is 5 to 500 parts by weight of the solvent and 100 parts by weight of the aliphatic conjugated diene,
It is appropriate to use 500 to 5000 parts by weight of the solvent with respect to parts by weight.

The reaction temperature is preferably 90 ° C. or higher. If the temperature is lower than this temperature, the average molecular weight of the copolymer becomes too high than a desired value, or three-dimensional cross-linking easily occurs, and the copolymer cannot be used as a water-soluble copolymer. On the other hand, the upper limit of the reaction temperature is not particularly limited, but is preferably lower than 180 ° C. in order to obtain the desired average molecular weight of the copolymer. In consideration of the average molecular weight of the copolymer and the reaction time, the reaction temperature is more preferably in the range of 100 to 160 ° C.

Since the polymerization reaction is almost completed after the addition of the aliphatic conjugated diene and the radical generator, the polymerization reaction may be terminated when the addition is completed. However, in order to completely consume the unreacted monomer and radical generator, it is preferable to continue the polymerization reaction for a certain period of time, for example, about 30 minutes to 2 hours.

After the completion of the reaction, the copolymer precipitated in the precipitation or suspension polymerization is recovered by filtration or decantation of the supernatant. If necessary, it can be further washed with a poor solvent. On the other hand, in solution polymerization, a copolymer is precipitated by adding a reaction solution to a large amount of a poor solvent, and the copolymer is recovered by filtration separation or decantation of a supernatant.

The copolymer thus recovered is heated under reflux for a certain period of time together with water, or is subjected to steam distillation by introducing steam to distill off the residual solvent and hydrolyze to form an aqueous solution. Can be. However, from an economical and industrial point of view, it is desirable to carry out hydrolysis using water vapor to obtain an aqueous solution.

Further, the aqueous solution of the hydrolyzate of the copolymer is neutralized with a basic substance to finally form a water-soluble salt. At this time, it is preferable that the aqueous solution be in a neutral to weakly alkaline region. Further, the concentration is preferably 10 to 60% by weight as a solid content. The basic substance is not particularly limited, and examples thereof include basic substances such as alkali metal compounds, alkaline earth metal compounds, ammonia, and alkylamines. As the alkali metal compound and the alkaline earth metal compound,
Sodium hydroxide, potassium hydroxide, magnesium hydroxide, and alkylamines such as methylamine, ethylamine, aniline, cyclohexylamine, monoethanolamine, and ethylenediamine can be used. Of these, sodium hydroxide or ammonia is preferred. In addition, it is also possible to coexist the above-mentioned basic substance at the time of hydrolysis, to carry out the hydrolysis, and to obtain a water-soluble salt of the copolymer.

The addition amount of the dispersant of the present invention is 0.05 to 5% by weight, preferably 0.1
An excellent dispersing effect is exhibited in the range of 2% by weight.

The dispersant of the present invention can be used for aluminum compounds such as aluminum hydroxide and aluminum oxide. Particularly, the dispersant has excellent dispersibility and dispersibility with respect to fine-particle aluminum hydroxide as compared with conventional dispersants. Stability can be imparted.

In producing an aqueous slurry of an aluminum compound using the dispersant of the present invention, other inorganic or organic pigments, latexes and emulsions can be added. In some cases, other dispersants or surfactants can be used in combination.

[0036]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Production Example 1 An autoclave was charged with 30 parts by weight of maleic anhydride and 47 parts by weight of toluene, and heated to 115 ° C. in a nitrogen atmosphere. A mixture of 1.5 parts by weight of di-t-butyl peroxide and 40 parts by weight of toluene and a mixture of 8.3 parts by weight of 1,3-butadiene and 33 parts by weight of toluene were separately added thereto over 4 hours. did. Thereafter, the mixture was aged at 115 ° C. for 1 hour to complete the reaction. After cooling, the supernatant solvent was removed, followed by washing and drying to obtain 20 parts by weight of a copolymer.
Next, hydrolysis is performed with an aqueous sodium hydroxide solution, and the pH is adjusted.
Was adjusted to 9 to obtain a copolymer aqueous solution having a solid concentration of 30% by weight. Production Example 2 100 parts by weight of maleic anhydride and 271 parts by weight of toluene were charged into an autoclave and heated to 150 ° C. in a nitrogen atmosphere. To this, a mixed solution of 5 parts by weight of di-t-butyl peroxide and 99 parts by weight of toluene and a mixed solution of 55.1 parts by weight of 1,3-butadiene and 30 parts by weight of toluene were separately added over 4 hours. Then, at 150 ° C, 1
After aging for a period of time, the reaction was terminated. After cooling, the supernatant solvent was removed, washed and dried to obtain 107 parts by weight of a copolymer. Next, hydrolysis is carried out with an aqueous sodium hydroxide solution,
The pH was adjusted to 9 to obtain a copolymer aqueous solution having a solid content of 30% by weight. Production Example 3 100 parts by weight of maleic anhydride and cyclohexanone 309
Charge the autoclave to 100 parts by weight in a nitrogen atmosphere.
Heated to ° C. 5 parts by weight of t-butyl peroxy (2-ethylhexanoate) and 86 parts of cyclohexanone
Parts by weight of a mixed solution and a mixed solution of 55.1 parts by weight of 1,3-butadiene and 5 parts by weight of cyclohexanone were separately added over 2 hours. Thereafter, the reaction was aged at 100 ° C. for 1 hour to terminate the reaction. After cooling, the reaction solution was poured into an excess of toluene, and the copolymer was precipitated and separated by filtration.
After washing and drying, 113 parts by weight of a copolymer were obtained. Next, hydrolysis was carried out with an aqueous sodium hydroxide solution, the pH was adjusted to 9, and a copolymer aqueous solution having a solid content concentration of 30% by weight was obtained. Production Example 4 100 parts by weight of maleic anhydride and 366 parts by weight of toluene were charged into an autoclave and heated to 120 ° C. in a nitrogen atmosphere. This is followed by t-butyl peroxybenzoate 10
A mixture of parts by weight, 48.6 parts by weight of isoprene and 34 parts by weight of toluene was added over 2 hours. Then 120
The reaction was completed by aging at 1 ° C. for 1 hour. After cooling, the supernatant solvent was removed, washed and dried to obtain 101 parts by weight of a copolymer. Next, hydrolysis was carried out with an aqueous sodium hydroxide solution, the pH was adjusted to 9, and a copolymer aqueous solution having a solid content concentration of 30% by weight was obtained. Production Example 5 100 parts by weight of maleic anhydride and 274 of cyclohexanone
Charge the autoclave to 100 parts by weight in a nitrogen atmosphere.
Heated to ° C. 5 parts by weight of t-butylperoxy (2-ethylhexanoate) and 10 parts of cyclohexanone
A mixture of 9 parts by weight, a mixture of 69.5 parts by weight of isoprene and a mixture of 17 parts by weight of toluene were separately added over 2 hours. Thereafter, the reaction was aged at 100 ° C. for 1 hour to terminate the reaction. After cooling, the reaction solution was poured into an excess of toluene to precipitate the copolymer, which was separated by filtration, washed and dried to obtain 102 parts by weight of the copolymer. Next, hydrolysis is carried out with an aqueous sodium hydroxide solution to adjust the pH to 9, and
An aqueous copolymer solution having a solid content of 30% by weight was obtained. Production Example 6 An autoclave was charged with 25 parts by weight of maleic anhydride and 40 parts by weight of toluene, and heated to 150 ° C. in a nitrogen atmosphere. 13. A mixture of 0.25 parts by weight of di-t-butyl peroxide and 33 parts by weight of toluene and isobutene.
A mixture of 3 parts by weight and 27 parts by weight of toluene were separately added over 4 hours. Thereafter, the mixture was aged at 150 ° C. for 1 hour to terminate the reaction. After cooling, the supernatant solvent was removed, washed and dried to obtain 38 parts by weight of a copolymer. Next, hydrolysis was carried out with an aqueous sodium hydroxide solution, the pH was adjusted to 9, and a copolymer aqueous solution having a solid content concentration of 30% by weight was obtained. Production Example 7 An autoclave was charged with 100 parts by weight of maleic anhydride and 310 parts by weight of toluene, and heated to 130 ° C in a nitrogen atmosphere. A mixture of 1 part by weight of di-t-butyl peroxide and 83 parts by weight of toluene and 57.1 parts of isobutene were added thereto.
Parts by weight of a mixed solution of 7 parts by weight of toluene and 4 parts by weight of toluene separately.
Added over time. Thereafter, the reaction was aged at 130 ° C. for 1 hour to terminate the reaction. After cooling, remove the supernatant solvent,
After washing and drying, 155 parts by weight of a copolymer was obtained. Next, hydrolysis was carried out with an aqueous sodium hydroxide solution, the pH was adjusted to 9, and a copolymer aqueous solution having a solid content concentration of 30% by weight was obtained. Examples 1 to 5 In a beaker having a capacity of 200 ml, 120 parts by weight of aluminum hydroxide (average particle size: 0.5 μm) was placed, and Production Example 1 was added thereto.
2.4 parts by weight of the aqueous dispersant solution obtained in (1) to (5% by weight of the solid content of the dispersant relative to aluminum hydroxide) and water (78.3 parts by weight). Next, a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used for 10 rpm at 3000 rpm.
The mixture was stirred for minutes to prepare an aqueous slurry of aluminum hydroxide having a solid content of 60% by weight. The viscosity of this slurry is 2
It measured at 60 rpm (Rotor No. 4) at 5 ° C. using a B-type viscometer (DLV-B type, manufactured by Tokyo Keiki Co., Ltd.). Table 1 shows the obtained results. Comparative Examples 1 to 3 Comparative Example 1 is a water-soluble salt of the copolymer obtained in Production Example 6, Comparative Example 2 is a water-soluble salt of the copolymer obtained in Production Example 7, and Comparative Example 3 is a commercially available polyacrylate. Were used as dispersants, and aqueous slurries of aluminum hydroxide were prepared in the same manner as in Examples 1 to 5, and their viscosities were measured. Table 1 shows the obtained results.

[0037]

[Table 1]

[0038]

By using the dispersant of the present invention, it is possible to obtain a high-concentration aqueous slurry of a high-concentration aluminum compound which has a smaller amount of addition to the aluminum compound than the conventional one and has excellent dispersibility. The obtained aqueous slurry of the aluminum compound has a low viscosity and a high fluidity, and further, has excellent aging stability. Further, by using the dispersant of the present invention, it is possible to provide a slurry having a higher concentration than before. The aqueous slurry of the aluminum compound containing the dispersant of the present invention can be effectively used for various fields such as papermaking, coatings, and fine ceramics.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-99334 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/12 B01F 17/52

Claims (1)

(57) [Claims] 1. A Ri Do a water-soluble salt of a copolymer of a hydrolyzate of maleic anhydride and an aliphatic conjugated diene, and male anhydrous
The content of the acid unit is 54 to 90 mol%.
Characterized as a dispersant for aluminum compounds.