JPH08299777A - Dispersant - Google Patents

Abstract

PURPOSE: To obtain a dispersant having extremely superior surface activating ability and dispersing ability by incorporating repeating units each having a sulfo group bonded to the o-position of a benzene ring and repeating units each having a sulfo group bonded to the m- or p-position of a benzene ring in a specified ratio into a polymer. CONSTITUTION: This dispersant is a sulfo group-contg. arom. polymer having repeating units (1) and repeating units (2) represented by the formulae as essential constituent units in a molar ratio of 98:2 to 80:20 and having a wt. average mol.wt. of 1,000-1,000,000. In the formulae, X is H or methyl and M is H, an alkali metal, an alkaline earth metal or an org. amine. In each of the repeating units 1, -SO3 M is at the 3-, 4- or 5-position of the benzene ring. In each of the repeating units 2, (n) is 0 or 1. This dispersant has extremely superior characteristics as a coal-aq. slurry dispersant, etc., and can also be used as a fiber treating agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sulfonic acid group-containing aromatic polymer dispersant capable of favorably dispersing pulverized coal, carbon black, cement, dyes, pigments, agricultural chemicals, fertilizers and the like.

Conventionally, a dispersant for dispersing inorganic pigments such as calcium carbonate, clay, titanium oxide and alumina, hydraulic inorganic materials such as cement and gypsum, fuels such as coal, coke and pitch, and dyes in water. In general, an aqueous dispersant is widely used as a scale inhibitor for water treatment. Examples of these aqueous dispersants include polyacrylic acid and its copolymers, polycarboxylic acid-based dispersants such as copolymers of α-olefin and maleic anhydride, salts of formalin condensates of naphthalene sulfonic acid, and lignin sulfone. Sulfonic acid dispersants such as acid salts, salts of melamine sulfonic acid formalin condensates, polystyrene sulfonates, and salts of sulfonates of copolymers of styrene and maleic anhydride are known. These water-soluble dispersants are important as dispersants for organic materials or inorganic materials, but the surface activity and dispersibility of conventional water-soluble dispersants for organic materials or inorganic materials are not yet sufficient. The current situation.

[0002]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dispersant having extremely excellent surface activity and dispersibility.

The present invention relates to a sulfonic acid group-containing aromatic polymer, wherein a repeating unit having a sulfonic acid group bonded to the ortho position of the benzene ring and a sulfone group at the meta or para position of the benzene ring. It was made based on the finding that a polymer having a repeating unit to which an acid group is bonded at a specific ratio has an extremely excellent dispersion effect and surface activity. That is, the present invention provides a repeating unit 1
And 2 are essential constitutional units, and the molar ratio of repeating unit 1 / repeating unit 2 is 98/2 to 80/20, and the weight average molecular weight thereof is 1,000 to 1,000,000.
And a dispersant comprising the sulfonic acid group-containing aromatic polymer.

[0003]

Embedded image

(In repeating units 1 and 2, X is hydrogen or hydrogen.
Is a chill group, M is hydrogen, alkali metal, alkaline earth
Metals, NH_Four, Organic amines. Repeating unit 1
Medium, SO ₃The M group is at any of the 3 to 5 positions of the benzene ring.
And in repeating unit 2, n is 0 or 1. ) Here, as the repeating unit 2, when n is 0, SO₃
The M group is at either the 2 or 6 position of the benzene ring,
When n is 1, one SO₃M group is the 2nd position of the benzene ring
And another SO₃When the M group is in the 6-position,
1 SO₃M group is either 2-position or 6-position of the benzene ring
Crab and another SO₃M group has 3 to 5 benzene rings
It may be in one of the ranks.

The essential monomer units constituting the sulfonic acid group-containing aromatic polymer of the present invention include, for example, styrene sulfonic acid or a salt thereof, α-methylstyrene sulfonic acid or a salt thereof, and these may be used alone or in combination. can do. Of these, 2 to 20 mol%, preferably 2 to 10 mol% is the repeating unit 2 having a sulfonic acid group at the ortho position, and the rest is the repeating unit 1. When the amount of the repeating unit 2 is less than 2 mol%, the dispersibility is insufficient, while when it exceeds 20 mol%, the performance may not be satisfied similarly. Examples of the basic substance forming the salt include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal waters such as calcium hydroxide, magnesium hydroxide and barium hydroxide. Oxides, ammonia or aqueous ammonia, or organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, or the like. Polyethylene oxide adducts can be used.

The polymers of the present invention contain repeat units 1 and 2
Although it can be composed of only one, other repeating units can be copolymerized if desired. Examples of such other repeating units include the following monomers. For example, styrene, α-methylstyrene, vinyltoluene,
Aromatic hydrocarbon monomers such as vinylnaphthalene, vinyltoluenesulfonic acid or salts thereof, aromatic sulfonic acid monomers such as vinylnaphthalenesulfonic acid or salts thereof,
Conjugated dienes such as butadiene, isoprene, pentadiene and cyclopentadiene, sulfonates of conjugated dienes such as butadiene, isoprene, pentadiene and cyclopentadiene or salts thereof, olefins such as ethylene, propylene, butene and isobutylene, acrylic acid, methacrylic acid , Maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid or monovalent metal salts of these acids,
Examples thereof include divalent metal salts, ammonium salts, organic amine salts, and esters of these acids with hydroxyl group-containing compounds such as alcohol, polyethylene glycol and isethionic acid. These other monomers may be used alone or in combination of two or more.

When the other monomer is used in combination, the content of the repeating units 1 and 2 is 50% by weight or more, preferably 70 to 98% by weight. If it is less than 50% by weight, the water-soluble polymer obtained may not have sufficient surface activity or dispersibility. The polymer of the present invention is obtained by polymerizing a monomer capable of deriving the above repeating unit by a known method (radical polymerization, anionic polymerization, cationic polymerization, etc.), and the weight average molecular weight thereof is 1,000 to 1,000,000.
00, preferably 2,500 to 50,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 1,000, the resulting water-soluble polymer has insufficient surface activity and dispersibility. On the other hand, if it exceeds 1,000,000, these properties may not be satisfied. . As a method for producing such a polymer, generally, a method of polymerizing a monomer corresponding to the repeating unit 1 having no sulfonic acid group and then sulfonation, and a monomer corresponding to the repeating unit 1 having no sulfonic acid group And sulfonation after the copolymerization with other monomers, a method of copolymerizing a sulfonic acid group-containing monomer of repeating units 11 and 2, a sulfonic acid group-containing monomer of repeating units 1 and 2 and others There is a method of copolymerizing with the above monomer, and any method may be used. Among these, industrially, it is economical to carry out by the method.

In the present invention, the amount of repeating units 1 and 2 in the obtained polymer can be controlled within a specific range by, for example, sodium p-styrenesulfonate and / or m.
It is preferable to employ a method such as a method of copolymerizing sodium styrenesulfonate and o-styrenesulfonic acid or a method of sulfonating polystyrene with sulfuric anhydride. The content of repeating units 1 and 2 in the polymer used in the present invention can be determined, for example, as follows.
First, the total sulfonic acid group content in the polymer was calculated from the ratio of carbon atoms and sulfur atoms measured by elemental analyzer, and the amount of sulfonic acid groups bonded to the para position was determined by the NMR spectrum measurement of the aromatic ring. The repeating unit 2 is calculated as the amount of sulfonic acid groups bonded to the ortho position by calculating from the proton ratio and subtracting the amount of sulfonic acid groups bonded to the para position from the total sulfonic acid group content. The dispersant comprising the aromatic polymer of the present invention can be used for dispersing various dispersoids such as carbonaceous fine powder, cement, dye and / or pigment, and metal oxide.

Here, as the carbonaceous fine powder, anthracite,
Coal such as bituminous coal, sub-bituminous coal and lignite; petroleum coke, pitch; carbon black by-produced from a chemical plant, carbon black obtained by carbonizing an organic matter; charcoal and other energy sources used. These carbonaceous materials are pulverized so that they do not substantially contain particles of 1 mm or more.
The content of μm or less is preferably 50% by weight or more, more preferably 60 to 100% by weight. For coal containing a large amount of ash, a flotation method, an underwater granulation method (Oil Agglomeration method) or the like can be applied to perform deashing treatment for cleaning. The fuel composition of carbonaceous fine powder can be obtained by pulverizing the carbonaceous material by a dry pulverizing method or a wet pulverizing method to form an aqueous slurry, and the dispersant is subjected to an appropriate step so as to be contained in the final aqueous slurry. It can be added. For example, when a carbonaceous fine powder is obtained by a dry pulverization method, a dispersant is dissolved or dispersed in water, and the fine powder is added to this to prepare a high-concentration water slurry by an appropriate mixing device. When the wet pulverization method is adopted, the additive may be added to the water used in advance, or may be added during or after the wet pulverization.

In the case of carbonaceous fine powder-water slurry, it is preferable that the fine carbonaceous powder is composed of 50 to 80% by weight, preferably 60 to 75% by weight, a dispersant and water. The dispersant is
The carbonaceous fine powder is suitably added so as to be contained in the fuel composition in an amount of 0.05 to 5% by weight, preferably 0.1 to 2% by weight. In addition, if necessary, one or more kinds of other dispersants, nonionic or anionic surfactants, water-soluble polymers and the like can be used in combination with the fuel composition of carbonaceous fine powder. . When used in combination, the dispersant of the present invention may be added in an amount of 1 to 30% by weight. Other dispersants include, for example, lignin sulfonates, alkylnaphthalene sulfonates and their formalin condensates, sulfonates of aliphatic diene (co) polymers such as isoprene and butadiene, and salts thereof,
Examples thereof include (meth) acrylic acid-based (co) polymers and salts thereof.

Examples of the nonionic surfactant include, for example,
Alkyl polyether alcohol, alkylallyl polyether alcohol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyalkylene oxide block copolymer, obtained by adding alkylene oxide such as ethylene oxide and / or propylene oxide to alkylphenol Examples of the polyether compound include those having an average alkylene oxide addition mole number of 1 to 100 moles, and more preferably 2 to 50 moles. Examples of the anionic surfactant include alkylbenzene sulfonate, tripolyphosphate, hexametaphosphoric acid, pyrophosphoric acid, phosphonic acid and the like. Further, natural polymers such as xanthan gum and guar gum, modified cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, and thickeners such as clay minerals such as montmorillonite, kaolin and bentonite can be added.

Next, in the present invention, as the cement used as the dispersoid, ordinary Portland cement,
Various types of Portland cement such as early strength Portland cement, super early strength Portland cement, moderate heat Portland cement, sulfate resistant Portland cement, white iron Portland cement; blast furnace cement, silica cement,
Known cements such as fly ash cement, alumina cement, solidit, and calcium silicate; or mixed cement obtained by combining two or more kinds of these; and cements obtained by mixing these cements with an inorganic substance such as gypsum . The polymer dispersant of the present invention disperses these cements in water, and can also be used for mortar or concrete containing sand or gravel. In addition, a cement admixture used depending on the purpose of use, such as an air entraining agent, an AE water reducing agent, a quick-setting agent, a waterproofing agent, a rust preventive, and a cement emulsion, can be optionally added. In addition, the cement composition may be used in combination with a conventionally known high-performance water reducing agent, a fluidizing agent, such as a formalin condensate of naphthalene sulfonic acid, a formalin condensate of melamine sulfonic acid, or lignin sulfonic acid. You can also

The amount of the dispersant of the present invention used in the cement composition is usually 0.002 to 5% by weight, preferably 0.05 to 2% by weight based on the cement. To prepare a cement composition, cement, water or sand added as necessary, after kneading, gravel, before adding the dispersant before hardening, a method of further stirring (post-addition method), cement, Water and sand added as needed,
It can be manufactured by a method of adding a dispersant at the same time as gravel and kneading (simultaneous addition method). At this time, a known cement admixture material may be added if necessary. The cement composition thus obtained can be hardened by ordinary curing. The cement composition to which the dispersant of the present invention is added has an extremely high fluidity at the same blending amount, whereby workability is remarkably improved. On the other hand, when the fluidity is the same, the dispersant of the present invention was added. Since the water / cement ratio can be lowered, a cement composition having high strength and less cracks can be produced.

The dyes and / or pigments which can be dispersed by the dispersant of the present invention include di- and triallylmethane dyes, pyronin dyes, rhodamine dyes, acridine dyes, safranine dyes, oxazine dyes, quinoline dyes, thiazole dyes, Azo dyes, azomethine dyes, polymethine or azopolymethine dyes, anthraquinone dyes, quinophthalone dyes, basic dyes such as phthalocyanine dyes, acid dyes, chromium-containing dyes, chromium dyes, disperse dyes, etc .; ultramarine blue, cadmium yellow, red iron oxide,
Inorganic pigments such as chrome yellow, lead white, calcium carbonate, kaolin, clay, titanium oxide, and satin white; one or more of organic pigments such as azo, triphenylmethane, quinoline, anthraquinone, and phthalocyanine A mixture of In the case of a dye and / or pigment composition, the dispersant of the present invention is optionally used in combination with an additive such as the above-mentioned surfactant, but is not particularly limited, and the dye and / or pigment concentration is 0.01 to 50. %, Preferably 0.1-40% by weight of the composition. The amount of the dispersant added is usually 0.
The amount may be from 01 to 50% by weight, but from the viewpoint of workability and economy, 0.1 to 30% by weight is preferable.

The method for producing the dye and / or pigment composition is not particularly limited, and the dispersant, dye and / or pigment and water can be mixed by a desired method. For example, a method in which a pigment is previously pulverized by a dry method and then mixed in an aqueous solution in which a dispersant is dissolved; a method in which a dispersant is added after making a slurry; a pigment, water and a dispersant are added to a mill,
It can be carried out by any method such as a method of pulverizing and mixing the pigments. The dye and / or pigment composition is not only excellent in dispersibility, but also stains various kinds of articles,
There is no adhesion, the color is vivid, and the level dyeability is good.
Next, the metal oxide that can be dispersed with the polymer dispersant of the present invention is a metal oxide that is insoluble or sparingly soluble in water, such as FeO, Fe ₂ O ₃ , MnO, ZnO and Co.
_{O, NiO, Al 2 0 3} , Si0 2, MgO, include separately or mixtures of such CaO, in particular, MO · Fe ₂
O ₃ (where M is a divalent metal such as Mn, Fe or C
O, Ni, Cu, Zn, etc.) are preferable. In addition to this metal oxide, silicon compounds such as silicon nitride and silicon carbide are also preferable. The particle size of the metal oxide is not particularly limited, but is 0.01 to 500 μm, preferably 0.1 to 30 μm. The concentration of this metal oxide can be increased by adding a dispersant, but it is usually 50 to 90% by weight, preferably 60 to 85% by weight. The addition amount of the dispersant depends on the kind and particle diameter of the metal oxide, but is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the metal oxide.

The metal oxide composition contains a dispersant, a metal oxide, and water as essential components, and if necessary, a third component such as the above-mentioned surfactant, additive, and binder may be added. it can. The preparation method is a method in which a metal oxide powder is added to an aqueous dispersant solution and mixed, or a small amount of water is added to the metal oxide powder to form a cake, and an aqueous solution of a dispersant is added to and mixed with the cake. And so on. The polymer dispersant of the present invention can also disperse scale produced in a boiler, a heat exchanger, a condenser, a pipe or the like. The dispersant of the present invention can be injected into the target water system at once or intermittently, like the conventional scale dispersants. The addition amount varies depending on the target water system, but is usually about 0.1 to 100 ppm. Upon use, known scale inhibitors, metal corrosion inhibitors, alkaline agents, bactericides, etc. can be added, if necessary. Further, the polymer dispersant of the present invention is a dispersant for carbon black and carbon fiber, in addition to the above-described applications; a surfactant for agricultural chemicals, fertilizers, feeds, etc .;
It can be used as a synthetic rubber, a synthetic resin, an emulsifier for emulsions, an antistatic agent for paper, a fiber treating agent and the like.

[0017]

Since the dispersant of the present invention has extremely excellent properties as a coal-water slurry dispersant, a cement dispersant, a dye dispersant and a scale dispersant, it can also be used as a fiber treatment agent or a scale inhibitor. can do. Next, the present invention will be described in more detail with reference to examples.

【Example】

Reference Example 1 (Production of Polymer Dispersant) 100 parts by weight of polystyrene having a weight average molecular weight of 7,000 was added.
It was dissolved in 400 parts by weight of 1,2-dichloroethane, and 1.0 part by weight of acetophenone was further added to prepare a raw material solution.
This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with SO ₃ , which is a sulfonating agent, to carry out a sulfonation reaction at 45 ° C. In this case, feed rate, feed solution 24 g / min, SO ₃ 4.25 g / min, molar ratio of SO ₃ to styrene units in the polystyrene
1.15, the reactor has a jacket and a capacity of 400 m
1 was used. The obtained sulfonated product was neutralized with a 10% sodium hydroxide aqueous solution, then separated and concentrated to obtain a sodium polystyrene sulfonate aqueous solution. The weight average molecular weight of the obtained sodium polystyrene sulfonate (Polymer A) was 14,000, the total sulfonic acid group introduction ratio to the styrene unit was 102%, the sulfonic acid group introduction ratio to the para position was 90%, and the ortho position to the ortho position. Sulfonic acid group introduction rate is 12
%Met. Polymers C, D, H, I and J were obtained in the same manner as in Reference Example 1 except that the raw material polymers were different from each other to obtain their sulfonated products.

Reference Example 2 (Production of Polymer Dispersant) 10 parts by weight of styrene, 80 parts by weight of sodium p-styrenesulfonate, 10 parts of sodium o-styrenesulfonate.
Parts by weight were suspended in 400 parts by weight of purified water. This was replaced with nitrogen, 0.8 parts by weight of potassium persulfate and 1.5 parts by weight of ammonium persulfate were added, and polymerization was carried out at 50 ° C. for 6 hours. The weight average molecular weight of the obtained sodium polystyrene sulfonate was 100,000. Polymers E, F, G, A, C and D were obtained by polymerizing corresponding monomers in the same manner as in Reference Example 2. Comparative Reference Example 1 (Production of Polymer Dispersant for Comparison) After dissolving 100 parts by weight of polystyrene having a weight average molecular weight of 20,000 in 400 parts by weight of 1,2-dichloroethane, 1,000 parts by weight of concentrated sulfuric acid was added, and the temperature was adjusted to 80 ° C. And stirred for 3 hours. The reaction mixture was diluted with 1,000 parts by weight of water and then neutralized with an aqueous sodium hydroxide solution. After concentration, sodium sulfate was removed by a recrystallization method to obtain a sodium polystyrenesulfonate aqueous solution. The weight average molecular weight of the obtained sodium polystyrene sulfonate was 40,000, the total sulfonic acid group introduction ratio to the styrene unit was 100%, the sulfonic acid group introduction ratio to the para position was 60%, and the sulfonic acid group introduction to the ortho position. The rate was 40%.

The weight average molecular weight of the obtained polymer and the ratio of repeating units 1 and 2 were measured as follows. (1) Molecular weight of polymer Standard polystyrene sodium sulfonate was used as a standard substance, and TSK-G3 manufactured by Tosoh Corporation as a separation column.
000SW and G4000SW (7.5mm ID x 30c
m) was used and the ultraviolet ray detector (measuring wavelength 238 nm) was used to determine by the GPC method. (2) Measurement of ratio of repeating units 1 and 2 in polymer When the polymer is a sulfonated product of a homopolymer of an aromatic hydrocarbon monomer, an elemental analyzer (E manufactured by Carlo Erba Co., Ltd.
A-1108 type) was calculated from the ratio of carbon atoms and sulfur atoms measured by a sulfonic acid group per unit of aromatic ring (when the water-soluble polymer contains a sulfate,
The amount was determined by ion chromatography, and the sulfur atom amount was subtracted from the sulfur atom amount obtained by the elemental analyzer. ). The rate of sulfonic acid group introduction at the para position of the aromatic ring is ¹ H
-NMR spectrum (JNM-EX2 manufactured by JEOL Ltd.)
70 type) and the peak intensity (a) near 7.6 ppm
And the peak intensity (b) around 8.1 ppm (b / 2) /
It was determined as (a / 3 + b / 2) × 100. Regarding the introduction rate of the sulfonic acid group at the ortho position of the aromatic ring, the value obtained by subtracting the introduction rate at the para position from the introduction rate of the sulfonic acid group determined by an elemental analyzer was taken as the introduction rate.

When the polymer is a sulfonated product of a copolymer of an aromatic hydrocarbon monomer and a conjugated diene, the sulfonic acid group introduction rate of the conjugated diene monomer unit is set to 100%, and the sulfonic acid group of the aromatic hydrocarbon monomer unit is set. The introduction rate was calculated from the ratio of carbon atoms and sulfur atoms measured by an elemental analyzer (when the water-soluble polymer contains a sulfate, its amount is quantified by ion chromatography, and the amount of the sulfur atom is measured by an elemental analyzer. Subtracted from the amount of sulfur atom obtained in.). The rate of sulfonic acid group introduction at the para position of the aromatic ring is ¹
The H-NMR spectrum was measured and determined from the peak intensity (a) near 7.6 ppm and the peak intensity (b) near 8.1 ppm as (b / 2) / (a / 3 + b / 2) × 100. The introduction rate of the sulfonic acid group at the ortho position of the aromatic ring was defined as the value obtained by subtracting the introduction rate at the para position from the introduction rate of the sulfonic acid group determined by an elemental analyzer. Next, the dispersant of the present invention and the comparative dispersant are summarized in Table 1.

[0021]

[Table 1] Table-1 Dispersants used ───────────────────────────────────── Co-polymer Polymonomer composition (mol%) Mw X10³ Mw / Mn Mar A Styrene (100) 7 2.5 B Styrene P-Styrenes O-Styrenes 100 3.5 (10) Sulfonic acid Na (80) Sulfonic acid Na (10) C Styrene (70) Isoprene (30) 20 2.1 D α-Methylmethacrylic acid 15 2.0 Styrene (90) PEG200 Ester (10) E P-Styrene O-Styrene Sul Isoprene Sul 35 3.0 Rufonic Acid Na (75) Phonic Acid Na (5) Honide Na Salt (20) F P-Styrene O-Styrene S Acrylic Acid Na 80 3.5 Rufonic acid Na (92) Ruponic acid Na (3) (5) GP-Styrene Lu O-Styrene sul 200 3.0 Rhuphonic acid NH_Four(97) Phonic acid NH_Four(3) H α-methyl isoprene 30 2.5 styrene of methacrylic acid (50) (40) PEG400 ester (10) I styrene (60) butadiene (20) methacrylic acid (20) 50 2.8 J styrene (90) maleic anhydride ( 10) 40 2.2 K Styrene (100) 10 2.7L Styrene (100) 20 3.0 B Styrene P-Styrenes 14 3.0 (10) Rhphonic acid Na (90) Rhostyrene (100) 20 1.9 C P-Styrenes Isoprene Sulfur 35 3.0 Rhphonic acid Na (80) Rufonide Na salt (20) D P-Styrenes O -Styrene acrylate Na 80 3.5Rufonic Acid Na (67) Rufonic Acid Na (28) (5)
 

[0022]

[Table 2] Table-1 (continued) ─────────────────────────────────── Sulfonates (salts) Sulfonic acid group introduction rate to poly aromatic ring Unit 1 / Mw X10 ³ Mw / Mn mer (mol%) Unit 2 Total introduction rate Unit 1 Unit 2 (molar ratio) A 102 90 10 88/12 14 4.5 B − − 89 / 11 − − C 86 78 8 91/9 40 2.5 D 90 75 15 83/17 32 2.4 E 94/6 − − F 97/3 − − G 97/3 − − H 80 76 4 95/5 50 3.5 I 88 74 14 84/16 85 4.0 J 90 72 18 80/20 80 3.5 K 100 98 2 98/2 20 4.8 L 100 80 20 80/20 40 5.0 b 100/0 − − b 100 60 40 60/40 40 2.7 C 100 / 0-D 71/29 --- In the table, unit 1 represents repeating unit 1 and unit 2 represents repeating unit 2. Example 1 (Coal-water slurry dispersant) As the coal, Workworth coal having the properties shown in Table 2 was used.

[0023]

[Table 3] Table-2 Coal properties In a 6 liter (inner diameter 19 cm) stainless steel ball mill that contains stainless steel balls at a filling rate of 50%,
Dispersant shown in Table 1 at a content of 0.6% by weight with respect to coal, water 46
Workworth charcoal 1 crushed to 5g and particle size 3mm or less
After charging 000g, rotate at 65rpm, measure the particle size of the coal with a laser diffraction type particle size distribution meter, particle size 74
It was pulverized so that the number of particles having a size of μm or less was 80%. After crushing, the coal-water slurry was taken out from the ball mill and stirred with a homomixer at 4000 rpm for 10 minutes, and then the viscosity and stability of the coal-water slurry were determined.
The results are shown in Table-3.

[0024]

[Table 4] Table-3 ─────────────────────────────────── Dispersant Coal-water slurry Dispersant Name Addition amount Coal concentration Viscosity stability (% to coal) (%) (mPa · s) Sieving amount (%) Feeling No. 1 polymer (A) 0.6 70.5 700 4.5 ○ No .2 Polymer (B) 0.6 70.6 770 4 ○ No. 3 Polymer (C) 0.6 70.5 820 7 ○ No. 4 Polymer (D) 0.6 70.4 880 5 ○ No. 5 Polymer (E) 0.5 69.0 800 8 ○ No. 6 Polymer (F) 0.5 69.0 810 9 ○ No. 7 Polymer (G) 0.5 69.2 750 7 ○ No. 8 Polymer ( H) 0.5 69.1 850 6 ○ No. 9 polymer (I) 0.5 69.0 870 8 ○ No. 10 polymer (G) 0.6 70.4 760 8 ○ No. 11 polymer (K) 0.6 7 0.5 700 4 ○ No.12 Polymer (L) 0.6 7 0.5 710 4 ○ Comparative example No. 1 polymer (a) 0.6 68.3 700 12 ○ No. 2 polymer (b) 0.6 68.3 750 12 ○ No. 3 polymer (c) 0.6 68.3 850 15 △ No. 4 Polymer (D) 0.6 68.3 880 16 △

Each characteristic was obtained as follows. (A) Viscosity The viscosity at 100 sec ^-1 down was measured with a Haake viscometer. (B) Stability Put the coal-water slurry in a 250 ml wide-mouthed plastic bottle, and
After standing at 5 ° C for 10 days, determine the amount on the sieve (% by weight relative to the total amount of slurry) when opened on a 16 # sieve, and stir the hardness of the slurry remaining in the plastic bottle with a spatula. Evaluate the feel of the following criteria,
Seeking stability. ○: Slurry is soft △: Slurry is hard ×: Slurry is extremely hard Example 2 (cement dispersant) In accordance with JASS 5T-402 (fluidizing agent quality standard for concrete) of the Japan Building Society, concrete fluidity and The air volume was evaluated. The materials used and the formulation are shown below.

Materials used Cement: Ordinary Portland cement (specific gravity 3.15) Fine aggregate: Kashima land sand (specific gravity 2.62) Coarse aggregate: Tsukui Lake crushed stone (specific gravity 2.66) Blend composition Cement: 320 parts by weight Water: 179 parts by weight Fine aggregate: 794 parts by weight Coarse aggregate: 991 parts by weight Air entraining agent: 0.028% added so that the amount of air in the base concrete is 4.5% Eirich type mixer (100 liters) 50 liters of concrete according to the above formulation were mixed for 90 seconds. The slump value of the green concrete was 8.0 cm. Table 4 shows the results of measuring the slump and the air amount after standing for 15 minutes and adding the dispersant of the present invention of 0.1% by weight to cement and kneading for 30 seconds. From these results, it can be seen that the dispersant of the present invention imparts high fluidity to concrete with a small addition amount as compared with the commercially available fluidizing agents. Furthermore, the green concrete and the fluidized concrete obtained as described above were subjected to standard curing to obtain JIS A
The results of measuring the compressive strength after 28 days of age according to 1108 are shown in Table 4. The compressive strength of green concrete (slump 8 cm) is 375 to 385 kg / cm ² , and the concrete to which the dispersant of the present invention is added has a compressive strength almost equal to that of green concrete despite being fluidized. I understand.

[0027]

[Table 5] Table-4 ─────────────────────────────────── Dispersant Amount of dispersant added Slump Air Quantity Compressive strength (% to cement) (cm) (%) (kg / cm ² ) Invention No. 11 Polymer (A) 0.20 18.2 4.5 385 No. 12 Polymer (C) 0.20 18 1 4.3 380 No. 13 Polymer (F) 0.25 18.0 4.3 375 Comparative Example No. 5 Naphthalene Sul 0.55 15.2 4.7 355 Fluorinate condensate of Na fonate No. 6 Polymer (a) 0.35 18.1 4.5 380 No. 7 Polymer (c) 0.35 18.0 4.3 375

Example 3 (Dye Dispersant) Basic Yellow Dye C. I. Basic Yellow 11
40 parts of (C.I. 48055) was added to 400 parts of water and well stirred. When 60 parts of the dispersant of the present invention was gradually added to this, a sparingly soluble dye complex salt was formed and finely dispersed in order, and a liquid product could be obtained. Alternatively, by mixing using a known dispersion technique, such as a sand mill,
Further, the dye complex salt could be easily dispersed.
The results are shown in Table-5.

[Table 6] Table-5 ─────────────────────────────────── The present invention Dispersant Dye Dispersant Addition amount (double dye) No.14 Polymer (B) CI Basic Yellow 11 1.5 No.15 Polymer (D) CI Basic Orange 21 2.0

Example 4 (Fiber treatment agent) 17 g of triphenylmethane dye C.I. Basic Blue 5, 17 g of the dispersant of the present invention, 46 g of water and 10 g of ethylene glycol were mixed in a sand mill to obtain a uniform base. A liquid composition of a reactive dye was prepared. The above basic dye liquid composition 1.8 parts, acetic acid 0.1 part, sodium acetate 0.1 part.
To 1,000 parts of a dyeing bath containing 05 parts, 20 parts of acrylic fiber cloth (made by Mitsubishi Rayon, Bonnell 10) was added at 30 ° C. Next, it heated up to 80 degreeC and hold | maintained for 10 minutes. The temperature was further raised to 100 ° C. over 20 minutes, and then dyeing was performed for 60 minutes. Dyeing cloth is washed with water, soaping,
Dried. By this dyeing, a blue dyed cloth having excellent levelness and dyeing property (dying rate 93%) was obtained. The results are shown in Table-6.

[Table 7] Table-6 ──────────────────────────────────── The present invention Dispersant Dye Dispersion Amount of agent added Dyeing rate (Double dye) (%) No.16 Polymer (E) C.I.Basic Blue 5 1.0 93 No.17 Polymer (G) C.I.Basic Yellow 11 1.0 85No.18 Polymer (H) CI Basic Red 18 0.75 90

Example 5 (Scale Preventing Agent) The scale preventing effect of the dispersant of the present invention was investigated by the following procedure. 170 g water in an Erlenmeyer flask with an internal volume of 250 ml
Add 10g of 1.56% calcium chloride dihydrate in water
Then, 10 g of a 0.04% aqueous solution of the dispersant of the present invention (20 ppm based on the resulting supersaturated calcium carbonate aqueous solution) was mixed, and 10 g of a 3% aqueous solution of sodium bicarbonate was further added, and the total amount was made 200 g with water. . The resulting supersaturated solution of calcium carbonate (530 ppm) was sealed and heat-treated at 70 ° C. for 3 hours. Then after cooling, the precipitate is reduced to 0.4
The filtrate is separated by a 5 μm membrane filter and the filtrate is JIS
It was analyzed according to K0101. The results are shown in Table-7. However, the inhibition rate was calculated by the following formula. Inhibition rate (%) = 100 × [(Ca concentration in filtrate)-(Ca concentration in filtrate without dispersant)] / [530- (Ca concentration in filtrate without dispersant)]

[Table 8] Table-7 ──────────────────────────────── Dispersant Scale inhibition rate (%) Invention No. .19 Polymer (A) 99.0 Invention No. 20 Polymer (I) 98.5 Invention No. 21 Polymer (J) 99.0 Comparative Example No. 8 Sodium polyacrylate 75.0

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[Procedure amendment]

[Submission date] June 8, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

When the other monomer is used in combination, the content of the repeating units 1 and 2 is 50% by weight or more, preferably 70 to 98% by weight. If it is less than 50% by weight, the water-soluble polymer obtained may not have sufficient surface activity or dispersibility. The polymer of the present invention is obtained by polymerizing a monomer capable of deriving the repeating unit by a known method (radical polymerization, anionic polymerization, cationic polymerization, etc.), and the weight average molecular weight thereof is 1,000 to 1,000.
50,000, preferably 2,500 to 500,000,
More preferably, it is 5,000 to 100,000.
If the weight average molecular weight is less than 1,000, the resulting water-soluble polymer has insufficient surface activity and dispersibility. On the other hand, if it exceeds 1,000,000, these properties may not be satisfied. . As a method for producing such a polymer, generally, a method of polymerizing a monomer corresponding to the repeating unit 1 having no sulfonic acid group and then sulfonation, and a monomer corresponding to the repeating unit 1 having no sulfonic acid group And sulfonation after the copolymerization with another monomer, a method of copolymerizing a monomer containing a sulfonic acid group of repeating units 1 and 2, a monomer containing a sulfonic acid group of repeating units 1 and 2 and others There is a method of copolymerizing with the above monomer, and any method may be used. Among these, industrially, it is economical to carry out by the method.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

In the present invention, the amount of repeating units 1 and 2 in the obtained polymer can be controlled within a specific range by, for example, sodium p-styrenesulfonate and / or m.
It is preferable to employ a method such as a method of copolymerizing sodium styrenesulfonate and sodium o-styrenesulfonate or a method of sulfonating polystyrene with sulfuric anhydride. The content of repeating units 1 and 2 in the polymer used in the present invention can be determined, for example, as follows. First, the total sulfonic acid group content in the polymer was calculated from the ratio of carbon atoms and sulfur atoms measured by an elemental analyzer, and the amount of sulfonic acid groups bonded to the para position was N.
Calculated from the proton ratio of the aromatic ring by MR spectrum measurement, subtracting the amount of the sulfonic acid group bonded to the para position from the total sulfonic acid group content, the repeating unit 2 was calculated as the amount of the sulfonic acid group bonded to the ortho position. Ask for. The dispersant comprising the aromatic polymer of the present invention can be used for dispersing various dispersoids such as carbonaceous fine powder, cement, dye and / or pigment, and metal oxide.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Table 2]

Claims (1)

[Claims] 1. Repeating units 1 and 2 are essential constituent units.
The molar ratio of repeating unit 1 / repeating unit 2 is 98/2 to
80/20 polymer, the weight average molecule of which is
Sulfonic acid group content of 1,000-1,000,000
A dispersant composed of an aromatic polymer. [Chemical 1](In repeating units 1 and 2, X is hydrogen or a methyl group.
, M is hydrogen, alkali metal, alkaline earth metal, N
H_Four, Organic amines. SO in repeat unit 1 ₃M
The group is located at any of positions 3 to 5 of the benzene ring, and
In the unit 2, n is 0 or 1. )