JPH03265690A - Dispersant and solid fuel slurry composition - Google Patents

Abstract

PURPOSE:To obtain a solid fuel slurry composition having high concentration and improved in vibration stability and shelf stability by using a dispersant comprising a specified copolymer. CONSTITUTION:40-95wt.% sulfonated conjugated diene of formula I (wherein R<1> to R<6> are each H, 1-8C alkyl, 6-20C aryl, or -SO3X (wherein X is H, a metal atom, ammonium or amino), provided that at least one of them is -SO3X], 3-50wt.% compound of formula II (wherein R7 is H or methyl; Y is X), and 2-30wt.% compound of formula III (wherein R8 is R7; Z is a divalent 2-4C alkylene oxide residue subjected to ring-opening addition; R9 is H or 1-30C alkyl) are subjected to radical polymerization in water in an amount of 50-1,000 pts.wt. based on 100 pts.wt. total monomers in the presence of a radical polymerization initiator and a chain transfer agent at -50 to 200 deg.C for 0.1 to 40hr to give a dispersant comprising a copolymer having a weight-average molecular weight of 1,000 to 1,500,000. 0.01-10wt.% of this dispersant is incorporated into a slurry containing 50-80wt.% solid fuel having such a particle diameter distribution that the percentage of particles passing through a 200-mesh sieve is 70wt.% or higher, thus giving an objective slurry composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a dispersant effective for dispersing and stabilizing the dispersion of solid fuels, cement, dyes, pigments, metal oxides, scales, etc. .

[Prior Art] In recent years, various dispersant compositions have been proposed in which a dispersant is blended into a dispersion of solid fuel, cement, dye, pigment, carbon black, metal oxide, or the like. For example, in the past, an energy structure based on petroleum has been adopted, but in recent years, due to the depletion of petroleum resources, solid fuels such as coal, petroleum coke, and pitch have been rediscovered, and various ways of using them are being considered. There is.

However, since these solid fuels are solid unlike limb fuels such as petroleum, it is difficult to transport them by ordinary pipelines, tank trucks, etc. For this reason, various techniques have been proposed in which solid fuel such as coal is pulverized, dispersed in water, and treated as a slurry in the same way as a liquid.

In this case, it is possible to create a slurry with a low viscosity by using a slurry with a low concentration of solid fuel and a large amount of water, but this is not a good idea in terms of fuel efficiency. In addition, the slurry thus obtained has the disadvantage that the solid fuel settles when left standing.

As a method of increasing the solid fuel concentration, a method has been proposed in which various dispersants are added to the slurry to improve the dispersibility of the solid fuel in water. It has been reported that the fluidity of solid fuel slurries to which various dispersants are added is significantly improved compared to when no dispersants are added, and that it is possible to produce highly concentrated solid fuel slurries by using dispersants. There is. Since the solid fuel slurry produced in this manner is generally transported, stored, and used as a fuel, the slurry is required to have good vibration stability and long-term static stability. However, the current situation is that vibration stability and long-term stability have not yet reached a fully satisfactory level.

In the case of a cement composition, the strength of concrete or mortar produced from it increases as the water/cement ratio decreases, but on the other hand, when it is hard mixed, fluidity decreases and workability deteriorates. There are also well-known methods of adding dispersants to cement compositions in order to improve this decrease in fluidity, or to lower the water/cement ratio and increase strength while maintaining a certain fluidity. ing.

In the case of paints and/or pigments, for example, in the case of basic paints, by adding an anionic surfactant to the basic paint, a paint composition with excellent dispersibility, leveling properties, prevention of equipment contamination, etc. can be created. has also been proposed.

Furthermore, in the case of metal oxides (ceramics) such as ferrite, this forming method involves, for example, mixing the raw material of the metal oxide with water to form a slurry composition, and then pulverizing it with a pulverizer such as a ball mill or sand mill. grinding process),
This is then spray-dried (spray-drying process), then press-formed and calcined (calcination process), then water is added to form a slurry composition, pulverized in a pulverizer, a binder is added (pulverization process), and spray-dried. This is then formed into granules (spray drying process), and finally press-molded and sintered (sintering process). In the grinding step, various dispersants are used in combination in the metal oxide water slurry composition. The main purpose of this dispersant is to reduce the viscosity of the slurry composition. In other words, when the concentration of the slurry composition is increased to reduce energy consumption in the next step, the spray drying process, the viscosity increases. In addition, it has compatibility with the binder, improves filling properties during press molding, and does not remain in the final molded product after sintering and does not deteriorate the properties of the molded product, such as In the case of ferrite, it is necessary that it does not deteriorate the magnetic properties.

Furthermore, natural rubber, synthetic rubber, etc. have their tensile strength,
Carbon black is added to provide mechanical strength such as wear resistance. At this time, in order to impart mechanical strength, carbon black must be sufficiently dispersed, and a dispersant for this purpose is required.

Furthermore, attempts have been made to develop various scale inhibitors for the purpose of preventing corrosion and scale formation on metal surfaces that come into contact with water in boilers, heat exchangers, condensers, piping, and the like.

However, with conventional dispersion compositions of this kind, it has not yet been possible to obtain a dispersant that fully satisfies the requirements such as reducing the viscosity of the composition, compatibility, filling properties, and preventing deterioration of the properties of the final molded product. is the current situation.

[Problem to be solved by the invention] The present invention has been made against the background of conventional technical problems, and
The present invention provides a specific dispersant that imparts excellent dispersibility and dispersion stability to dispersions of solid fuels, cement, etc. Particularly when applied to solid fuel, it is an object of the present invention to provide a solid fuel slurry composition that is excellent in high concentration, vibration stability, and long-term storage stability.

[Means for Solving the Problems] The present invention provides (a) a sulfonated product of a conjugated diene represented by the general formula (I), and RI 8 alkyl group, aryl group having 6 to 20 carbon atoms is 15o3 x
Here, X is a hydrogen atom, a metal atom, an ammonium group, or an amino group, and at least one of R1 to R6 is -8O3X. ) (b) A compound represented by the general formula (II), and 7 CH2=C... (II) ooy (wherein R7 is hydrogen or a methyl group, Y is a hydrogen atom, a metal atom, an ammonium group Or it is an amino group.

) (C) Compound 8 represented by (I[[) in the general formula CH2=C... (m) COO-Z-R9 (wherein, R8 is hydrogen or a methyl group, and Z is a ring-opening addition A dispersant consisting of a copolymer having as a constituent unit a divalent alkylene oxide residue having 2 to 4 carbon atoms, and R9 is hydrogen or an alkyl group having 1 to 30 carbon atoms, and a dispersant using the same. The present invention provides a solid fuel slurry composition.

It is one of the constituent components of the copolymer used in the present invention (
Component a) can be obtained by the method described in JP-A-1-263103.

The conjugated diene used in component (a) is, for example, 1
, 3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4- xadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2
．． 3-dimethyl-1,3-butadiene, 2-ethyl-1
゜3-butadiene, 1,2-hebutadiene, 1,3-hebutadiene, 1,4-hebutadiene, 1,5 heptadiene, 1,6-hebutadiene, 2,3-hebutadiene, 2
．． 5-hebutadiene, 3.4-hebutadiene, 3,5-
Examples include hebutadiene, 2-phenylbutadiene, and various branched dienes.

These conjugated dienes can be used alone or in combination of two or more.

To sulfonate this conjugated diene, usually sulfur dioxide alone or a complex of sulfur trioxide and an electron-donating compound are used.

Here, the electron-donating compounds include ethers such as N,N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, and diethyl ether; amines such as pyridine, piperazine, trimethylamine, triethylamine, and tributylamine; dimethyl sulfide, diethyl Examples include sulfides such as sulfide; nitrile compounds such as acetonitrile, ethylnitrile, and propylnitrile; among these, N.

N-dimethylformamide and dioxane are preferred.

The amount of the sulfonating agent is usually 0.1 to 10 mol, preferably 0.1 to 10 mol in terms of sulfur trioxide, per 1 mol of conjugated diene.
．． If the amount is less than 0.1 mol, the reaction yield will be low; on the other hand, if it exceeds 10 mol, unreacted sulfur trioxide will increase, and after neutralization with alkali, a large amount of sodium sulfate will be produced, reducing the purity. This is not preferable because it reduces the

During this sulfonation, it is also possible to use a solvent that is inert to the sulfonating agent, sulfur trioxide, such as halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, and dichloromethane. ; nitro compounds such as nitromethane and nitrobenzene; liquid sulfur dioxide, and aliphatic hydrocarbons such as propane, butane, pentane, hexane, and cyclohexane.

These solvents can be used in combination of two or more kinds as appropriate.

The reaction temperature for this sulfonation is usually -70 to +200
°C, preferably -30 to +50 °C; below -70 °C, the sulfonation reaction slows down and is not economical;
If the temperature exceeds 200°C, side reactions may occur and the product may turn black, which is not preferable.

In this way, a cyclic intermediate (cyclic sulfonic acid ester of a conjugated diene, general name: sultone, hereinafter referred to as "cyclic intermediate") in which sulfur trioxide is cyclically bonded to a conjugated diene is produced.

The sulfonated compound represented by the general formula (I) used in the present invention can be obtained by treating this cyclic intermediate with a basic compound to change the cyclic bond into a double bond to which a sulfone group is bonded. (hereinafter referred to as "double bonding").

Examples of this basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium-1-butoxide, potassium-t-butoxide, etc. alkali metal alkoxide;
Organic materials such as methyllithium, ethyllithium, n-butyllithium, 5ec-butyllithium, amyllithium, propyl sodium, methylmagnesium chloride, ethylmagnesium bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum, etc. Metal compounds; Amines such as aqueous ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, piperazine; sodium,
Mention may be made of metal compounds such as lithium, potassium, calcium and zinc.

These basic compounds can be used alone or
Moreover, two or more types can also be used together.

Among these basic compounds, alkali metal hydroxides are preferred, and sodium hydroxide is particularly preferred.

The amount of the basic compound used is, per mole of conjugated diene,
Usually, the amount is 0.1 to 3 mol, preferably 0.5 to 3 mol, and if it is less than 0.1 mol, the formation of a cyclic bond into a double bond will not be promoted, and the cyclic compound may remain as it is, or the general formula % A hydroxyolefin represented by the formula % is produced, and a compound having almost no polymerization performance is produced.

On the other hand, if it exceeds 10 moles, a large amount of unreacted alkali remains and the purity of the product decreases, which is not preferable.

When forming this cyclic intermediate into a double bond, the basic compound can be used in the form of an aqueous solution, or dissolved in an organic solvent inert to the basic compound.

Examples of the organic solvent include, in addition to the above-mentioned various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, propatool, isopropanol, and ethylene glycol.

These solvents can be used in combination of two or more kinds as appropriate.

When the basic compound is used as an aqueous solution or an organic solvent solution, the concentration of the basic compound is usually about 1 to 70% by weight, preferably about 10 to 50% by weight.

In addition, the reaction temperature for forming a double bond is usually -30 to +15
0°C, preferably -10 to +70°C, more preferably O
It is carried out at a temperature of ~+50°C, and can be carried out under normal pressure, reduced pressure or increased pressure.

Furthermore, the reaction time for forming a double bond is usually 0.1 to 24
time, preferably 0.5 to 5 hours.

Further, in forming this double bond, the desired sulfonated product represented by the general formula (I) can also be obtained by adding water or alcohol to the cyclic intermediate and then performing a dehydration reaction or a dealcoholization reaction.

The cation type of the sulfonated product thus obtained is not particularly limited, but in order to make it water-soluble, hydrogen, alkali metals, alkaline earth metals, ammonium, amines, etc. are preferable.

Examples of the alkali metal include sodium and potassium, and examples of the amine include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Examples of alkaline earth metals include polyamines, morpholine, piperidine, etc., and calcium, magnesium, etc. as alkaline earth metals.

Additionally, these cationic species can be interchanged with other cationic species by various ion exchange techniques.

Next, as an example of component (b) of the copolymer used in the present invention, acrylic acid (salt) or methacrylic acid (salt)
can be mentioned.

Examples of component (C) of the copolymer used in the present invention include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene Polyalkylene glycol mono(meth)acrylates such as glycol mono(meth)acrylate; methoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol-polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate Acrylate, ethoxypolyethylene glycol
Alkoxypolyalkylene glycol (meth)acrylate alkoxylated with an alkyl group having 1 to 3 carbon atoms, such as polypropylene glycol (meth)acrylate;
Alkenoxypolyalkylene glycol (meth) alkenoxylated with an alkenyl group having 2 to 3 carbon atoms such as allyloxypolyethylene glycol (meth)acrylate
Acrylate, Butoxypolyethylene glycol (meth)acrylate, Butoxypolypropylene glycol (
meth)acrylate, octyloxypolyethylene glycol (meth)acrylate, octyloxypolyethylene glycol-polypropylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, naphthoxypolyethylene glycol (meth)acrylate , phenoxypolypropylene glycol (meth)acrylate, naphthoxypolyethylene glycol-polypropylene glycol (meth)acrylate, p-methylphenoxypolyethylene glycol (meth)acrylate, benzyloxypolyethylene glycol (meth)acrylate, cyclohexoxypolyethylene glycol (meth)acrylate, In addition to cyclopentenoxypolyethylene glycol (meth)acrylate, pyrisiloxypolyethylene glycol (meth)acrylate, chenyloxypolyethylene glycol (meth)acrylate, etc., as the terminal group of polyalkylene glycols, alkyl groups with 4 to 30 carbon atoms, alkenyl Examples include terminal ether type polyalkylene glycol mono(meth)acrylates having a monovalent organic group derived from an alkyl group, a cyclic alkyl group, a cyclic alkenyl group, and a heterocyclic compound having an aryl group as a substituent.

Components (a), (b) and (c) can be copolymerized using a known radical polymerization initiator.

Examples of radical polymerization initiators include persulfate initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate; inorganic initiators such as hydrogen peroxide; cumene hydroperoxide, isopropylbenzene hydroperoxide, and paramenthane hydroperoxide. Examples include organic peroxides such as peroxide and benzoyl peroxide; and organic initiators typified by azo initiators such as azobisisobutyronitrile.

Solvents used in radical polymerization include, for example, water or alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as xylene, toluene, and benzene; and butane, pentane, hexane, cyclohexane, and heptane. Mention may be made of aliphatic hydrocarbons.

Among these polymerization solvents, water or methanol is preferred.

During radical polymerization, in addition to the radical initiator, various electrolytes, pH adjusters, chain transfer agents, etc. are used in combination as necessary, and the total amount of water is 50 to 1.0 parts per 100 parts by weight of monomers. 000 parts by weight, or 50 to 1.00 parts by weight of organic solvent.
000 parts by weight, and the radical initiator, chain transfer agent, etc. are used in amounts within the above range, and the polymerization temperature is -50 to +20.
0°C, preferably 0 to +150°C, particularly preferably +
Radical polymerization is carried out under polymerization conditions of 5 to +80°C and a polymerization time of 0.1 to 40 hours.

The method of adding the monomer containing the sulfonated product as a main component is not particularly limited, and any method such as a batch addition method, a continuous addition method, or a divided addition method may be employed.

The dispersant of the present invention is useful as a dispersant for solid fuels (powder), cement, pigments, and the like.

When the dispersant of the present invention is used as a dispersant for solid fuel slurry, the proportion of component (a) in the copolymer used is usually 40 to 95% by weight, preferably 70 to 90% by weight. If the content is less than 40%, the vibration stability of the slurry will be poor, and if it exceeds 95%, the long-term storage stability will be insufficient.

In addition, the proportion of component (b) is usually 3 to 50% by weight, preferably 10 to 30% by weight; if it is less than 3%, long-term storage stability is insufficient, and if it exceeds 50%, vibration stability becomes worse.

On the other hand, the proportion of component (c) is usually 2 to 30% by weight, preferably 5 to 20% by weight; if it is less than 2%, long-term storage stability is insufficient, and if it exceeds 30%, good dispersion is not achieved. A large amount of copolymer is required to create this condition, which is not economical.

The weight average molecular weight of the copolymer used in the present invention is usually 1.000 to 1,500,000, preferably 3.0.
00 to 1,000,000.

Solid fuels that can be used with the copolymers of the present invention include coal, petroleum coke, pitch, and charcoal. Among these, the coal may be lignite, sub-bituminous coal, bituminous coal, anthracite coal, etc., or may be coal obtained by cleaning these coals, and is not particularly limited.

Petroleum coke is residual coke that is obtained by thermally decomposing asphalt, pitch, etc., which are obtained as heavy residues from distillation during petroleum refining, at higher temperatures to distill cracked oil, and is generally used for coal containing minerals. In comparison, it is extremely difficult to get wet with water.

Pitch is a heavy residue obtained by distilling petroleum distillation and tar obtained by coal carbonization, leaving an oil content, and its softening point is preferably 50 to 180°C, and lower than 50°C. If it is low, it is difficult to grind. Pitch contains almost no ash and moisture compared to coal, and can be made into a high calorific value slurry fuel.

The particle size of these solid fuels may be any particle size as long as it is powder, but since the pulverized coal currently burned in thermal power plants is 70% by weight or more of 200 mesh pass, this The particle size is a rough guideline. However, the copolymer used in the present invention is not affected by particle size or type of solid fuel, and exhibits excellent effects on any solid fuel powder.

The above-mentioned copolymer can be used in combination with surfactants, additives, etc. described later, if necessary, to form a solid fuel composition having a solid fuel concentration of 50 to 80% by weight, preferably 60 to 75% by weight, although not particularly limited. added.

The viscosity of the solid fuel composition decreases as the amount of copolymer added increases, so the amount added can be selected depending on the desired viscosity, and is usually 0.01 to 10% of the total amount of the composition.
It may be 0.0% by weight, but from the viewpoint of workability and economy.
5 to 1% by weight is preferred.

In addition, a nonionic or anionic dispersant is used in combination with this solid fuel composition as required.

Nonionic dispersants include, for example, alkyl polyether alcohols, alkylaryl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyalkylene oxide block copolymers, and ethylene oxide-based dispersants containing these. , jetanolamine type, anhydrosorbitol type, glycoside type, gluconamide type,
Commercially available products such as glycerin-based and glycidol-based products can be used as dispersants or particle wetting agents. Among these, polyether compounds obtained by adding alkylene oxides such as ethylene oxide and/or propylene oxide to alkylphenols and formalin condensates of alkylphenols are preferred. Among these, those in which the number of moles of alkylene oxide added is preferably 4 to 800 moles, more preferably 20 to 600 moles, and 50 to 300 moles.
Particularly preferred are moles.

Examples of anionic dispersants include dodecylbenzenesulfonate, oleate, alkylbenzenesulfonate, dialkylsulfosuccinate, ligninsulfonate, alcohol ethoxysulfate, secondary alkanesulfonate, α-olefinsulfonic acid, Commercially available products such as carboxylic acid type, sulfuric acid ester type, sulfonic acid type, phosphoric acid ester type, and alkylaryl sulfonate type containing these can be used as dispersants or wetting agents.

Among these, examples of anionic dispersants include alkylbenzenesulfonates, ligninsulfonates, alkylnaphthalenesulfonates and their formalin condensates, styrenesulfonates and their polymers, α-olefinsulfonates and their polymers. Coalescence, aliphatic diene (
Sulfonated products of co)polymers, (meth)acrylic acid (salts)
and polyalkylene oxide mono(meth)acrylate copolymers, oleate, dialkyl sulfosuccinate, tripolyphosphate, hexametaphosphoric acid, pyrophosphoric acid, phosphonic acid, etc.

The solid fuel composition also contains natural polymers such as xanthan gum and guar gum, modified cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, and clay minerals such as montmorillonite, attapulgite, sepiolite, hectorite, kaolin, and bentonite. By using them together, even better stability may be obtained.

Examples of additives include chelating agents for trapping polyvalent metals contained in ash in solid fuel, potassium tetrapolyphosphate, sodium citrate, sodium gluconate, sodium polyacrylate, and polycarboxylic acids. Moreover, an antifoaming agent can also be added to suppress foaming. As the antifoaming agent, for example, silicone emulsion is used.

Freezing point depressants can also be added to prevent freezing in winter. As the freezing point depressant, for example, a lower alcohol such as ethylene glycol or a polyhydric alcohol is used.

Note that the method for producing the solid fuel composition is not particularly limited, and consists of mixing the copolymer, solid fuel, and water in a desired manner. For example, solid fuel is dry-pulverized in advance and then mixed into an aqueous solution containing a copolymer, a slurry is made and then the copolymer is added, and solid fuel, water, and copolymer are mixed in a mill. Any method can be carried out, such as a method in which the fuel is added and mixed while being pulverized.

The copolymer in this composition has excellent dispersibility not only for solid fuels but also for cement, dyes, pigments, metal oxides, and the like.

When the copolymer of the present invention is used as a dispersant for cement, examples of the cement include ordinary Portland cement, early strength Portland cement, ultra early strength Portland cement,
Various types of Portland cement such as moderate heat Portland cement, sulfate-resistant Portland cement, white iron Portland cement; blast furnace cement, silica cement, fly ash cement, alumina cement, solidite,
Known cements such as calcium silicate; or mixed cements made by combining two or more of these; and cements made by mixing these cements with inorganic substances such as gypsum.

The dispersant used in the present invention disperses these cements in water, and can also be used in mortar or concrete containing sand or gravel. Furthermore, cement admixtures used depending on the purpose of use, such as air entraining agents, AE water reducing agents, rapid setting agents, waterproofing agents, rust preventives, emulsions for cement, etc., may be optionally added.

Furthermore, this cement composition can also be used in combination with conventionally known high-performance water reducing agents and fluidizing agents, such as naphthalene sulfonic acid condensates, melamine sulfonic acid condensates, lignin sulfonic acids, and the like.

The amount of the dispersant of the present invention used in the cement composition can be varied depending on the purpose of use, the type of cement, the amount mixed, etc., so it cannot be determined with certainty.
Generally, when it is used in an amount of 0.002 to 5% by weight, preferably 0.05 to 2% by weight based on cement, a cement composition with less aggregate separation and less breathing can be obtained.

The amount of water added to cement is determined based on the physical properties of the composition after hardening, and is not particularly limited, but is usually 20 to 80 parts by weight, preferably 25 to 80 parts by weight, based on 100 parts by weight of cement. Regardless of the amount of water added, the dispersant of the present invention can highly disperse cement in water and has a small slump loss.

In addition, when a cement composition is used as mortar or concrete, the aggregate/cement ratio, in which sand or gravel is added to cement, cannot be unambiguously determined because it varies depending on the purpose of use, but it is usually , more than 150 inches of cement is used per 1 d.

To prepare a cement composition, after kneading cement, water, or sand or gravel added as necessary, the above-mentioned dispersant is added before hardening, and the mixture is further stirred (
It can be produced by a method in which a dispersant is added and kneaded at the same time as cement, water, and sand or gravel added as needed (simultaneous addition method). At this time, a known cement admixture may be added as necessary. The cement composition thus obtained can be cured by conventional curing.

In addition, high-strength secondary cement products can be manufactured by steam curing and centrifugal molding.

This cement composition is characterized by the addition of the dispersant used in the present invention, and when the dispersant of the present invention is added in the same formulation, extremely high fluidity can be obtained, making it easier to work. On the other hand, when the fluidity is kept the same, those with the addition of the dispersant of the present invention can lower the water/cement ratio, thus producing cement compositions with high strength and less cracking. I can do it.

Therefore, this cement composition can be used in many applications that require high workability and high quality, including artificial lightweight concrete, expanded concrete, honeycomb concrete, shielding concrete, hot summer concrete,
Cold concrete, presto concrete, precast concrete, paving concrete, dam concrete, concrete subjected to the action of seawater, concrete using sea sand, concrete using the sliding form method, concrete with an exposed finish, concrete with a tiled finish, fluidization Applied to concrete, etc.

Next, the dyes and/or pigments used in the dispersion of the present invention include di- and triallylmethane dyes, vinylon dyes, rhodamine dyes, acridine dyes, safranin dyes, oxazine dyes, quinoline dyes, thiazole dyes, basic azo dyes, azomethine dyes and polymethine or azopolymethine dyes, basic dyes such as basic anthraquinone dyes, quinophthalone dyes, phthalocyanine dyes, acid dyes, chromium-containing dyes, chromium dyes, disperse dyes; ultramarine blue, cadmium yellow red red Inorganic pigments such as , chrome yellow, lead white, titanium white, and carbon black; and organic pigments such as azo, triphinylmethane, quinoline, anthraquinone, and phthalocyanate pigments.

In the case of dye and/or pigment compositions, the dispersant is
If necessary, it may be used in combination with additives such as the surfactant, etc., but is not particularly limited, but dye and/or pigment concentration 0
．． 01-59% by weight, preferably 0.1-40% by weight of the composition.

The amount of dispersant added is usually 0.0 based on the total amount of the composition.
The content may be 1 to 50% by weight, but from the viewpoint of workability and economy, 0.1 to 30% by weight is preferable.

The method for producing this dye and/or pigment composition is not particularly limited, and consists of mixing a dispersant, a dye and/or pigment, and water in a desired manner. For example, the pigment is dry ground in advance and then mixed into an aqueous solution containing a dispersant; the dispersant is added after making a slurry; the pigment, water, and dispersant are added to a mill and the pigment is mixed. Any method can be used, such as a method of mixing while pulverizing.

This dye and/or pigment composition has excellent dispersibility and, for example, in the case of a basic dye composition, the cation of the water-soluble basic dye and the anion of the anionic dispersant are relatively strong. It has binding strength and forms a poorly soluble complex salt, and does not undergo ionic dissociation like conventional basic dyes at normal temperatures.

Therefore, there is no contamination or adhesion to the human body or various objects that occurs with basic dye powders and liquid products, and due to the formation of a relatively stable strategy, so-called changes over time are extremely small. In addition, as mentioned above, this basic dye composition forms a poorly soluble complex salt, which is finely dispersed by the power of an excessive anionic dispersant, but in the dye bath, it gradually increases as the temperature rises. This complex salt is decomposed and only the base dye is adsorbed onto the fibers, resulting in extremely good level dyeing properties, so that a commonly used level dyeing agent is not necessarily required. In addition, this basic dye composition can also be used for complex dyeing with dyes that cannot generally be used together with basic dyes, such as acidic, dispersed or direct dyes, since basic dyes tend to form complexes. It has the great feature of being stable and capable of neutral staining.

Furthermore, the dye or pigment containing the dispersant of the present invention has bright colors and good level dyeing properties.

Next, the metal oxides used as the dispersion of the present invention include Groups 1 to 2 of the periodic table, preferably group 1 of the periodic table,
(2) and (2) groups of water (these are insoluble or poorly soluble metal oxides; preferred specific examples include Fed5Fe2
03, MnO, ZnO.

CooSNipSA1203.5i02, MgO.

It is a single substance or a mixture such as CaO, especially M'0
-Fe2O3 (where M' is a divalent metal, e.g. Mn
, Fe5Co, N15CuSZn, etc.) are preferred. In addition to this metal oxide, it is also preferable to disperse silicon compounds such as silicon nitride and monovalent silicon.

There is no particular restriction on the particle size of the metal oxide, but it is preferably 0.01 to 500 μm, and more preferably 0.01 to 500 μm.
30 μm, particularly preferably 0. It is 1 to 10 μm.

The temperature of the metal oxide can be increased by adding a dispersant, but it is usually in the range of 50 to 90% by weight, preferably 60 to 85% by weight, based on the total metal oxide composition.

The amount of the dispersant added depends on the type and particle size of the metal oxide, but is 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on the metal oxide. If it is less than 0.01% by weight, the viscosity reduction of the composition will not be sufficient, while if it exceeds 10% by weight, the viscosity reduction effect will not increase proportionally, and the resulting molding There is also a risk that the characteristics of the product may deteriorate.

The metal oxide composition contains the above-mentioned dispersant, metal oxide and water as essential components, and optionally the above-mentioned surfactant,
It contains additives and a third component such as a binder, and can be prepared by adding metal oxide powder to an aqueous dispersant solution and stirring, or by adding a small amount of water to metal oxide powder. Examples include a method of forming a cake into a cake, adding an aqueous solution of a dispersant to the cake, and stirring the mixture.

This metal oxide composition can reduce the viscosity so that a highly concentrated slurry composition is obtained without deteriorating the properties of the final molded article, such as the magnetic properties in the case of ferrite. In addition, this metal oxide composition has effects such as being compatible with additives such as a binder and having good filling properties during press molding. Therefore, in the case of a powder slurry of a ceramic material such as alumina, this metal oxide composition can be used as it is or after being processed and then molded and sintered to form magnetic cores or manufacture magnetic tapes. It can be suitably used.

In addition, as the dispersion of the present invention, boiler heat exchangers,
Examples include scale that forms in condensers, piping, etc. The sulfonates (salts) of the present invention, like conventional scale dispersants, can be injected into the target aqueous system all at once or intermittently. The amount added varies depending on the water system, but usually
0. About 1 to 1 ooppm is used.

In addition, in use, known scale inhibitors, metal corrosion inhibitors, alkaline agents, bactericidal agents, etc. can be further added as necessary.

Known scale inhibitors include polyacrylates, partial hydrolysates of polyacrylamide, maleic acid polymers, itaconic acid polymers, acrylic acid copolymers containing hydroxyethyl methacrylate, and metal corrosion inhibitors. Examples of the agents include oxycarboxylic acids, thiazoles, triazoles, amines, and hydroxams.

Moreover, carbon black can be mentioned as the dispersion of the present invention. Examples of the carbon black used include carbon black such as )iAF%l5AFSSAF, and preferably has an iodine adsorption amount (IA) of 60.
/g or more, and oil absorption (DBP) is 80m1/100g
The above carbon blacks are used. The amount of the dispersant used in the present invention varies depending on the type of carbon black.
Although it cannot be determined unambiguously, it is usually 0.01 to 10 g per 100 g of carbon black.

[Implementation example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples, % is based on weight.

Further, in the Examples, various measurements were performed in accordance with the following.

Dispersibility was evaluated by measuring the initial viscosity of the slurry at 25°C.

The standing stability was evaluated by the change in the initial slurry viscosity and the slurry viscosity after standing, and the difference in coal concentration between the upper and lower parts of the slurry after standing.

That is, the viscosity change was evaluated by leaving the coal slurry for 30 days, measuring the viscosity after the standing, and comparing it with the initial viscosity. In addition, viscosity after 30 days/initial viscosity = P, and when P was 1 or less, it was evaluated as ○, and when P exceeded 1, it was evaluated as ×.

Moreover, the coal concentration difference was evaluated by putting the coal slurry into a cylinder that can be separated into an upper layer, a middle layer, and a lower layer, and leaving it for 30 days, and then evaluating the coal concentration difference between the upper layer and the lower layer.

Coal concentration in the lower layer (%) - Difference in coal concentration in the upper layer (%) =
Q, if Q is 2 or less, ○, if Q is more than 2, ×
It was evaluated as follows.

Low additive properties are achieved by reducing the amount of dispersant or copolymer to 0.0% relative to coal.
Evaluation was made by comparing the viscosity of a 3% coal slurry and the viscosity of a 0.5% coal slurry. In addition, 0. The viscosity of the coal slurry at 3% The viscosity of the coal slurry at 10.5% = S, and when S was 1.3 or less, it was evaluated as ○, and when S exceeded 1.3, it was evaluated as ×.

Vibration stability is 200 cpm for slurry, amplitude 20 m1
vibration was applied for 10 hours, and evaluation was made based on the presence or absence of hard pack formation. It should be noted that a case where no hard pack was generated was evaluated as ○, and a case where even a small amount of hard pack was generated was evaluated as ×.

Reference Example 1 After replacing the fourth flask with internal volume 12 with nitrogen, 400 m of methylene chloride was previously subjected to dehydration and deoxidation treatment.
j! Next, dioxane 31- which had been subjected to dehydration and deoxygenation treatment was added, and the mixture was cooled to 5 to 10°C while stirring.

Next, sulfur trioxide 15d (28.8 g = 0.36 mol) was added dropwise to form a complex of sulfur trioxide and dioxane. Further, the reaction was continued for 15 minutes.

To this solution, 150 d of a methylene chloride solution containing 24.5 g (0.36 mol) of isoprene (2-methyl-1,3-butadiene) was added dropwise over 1 hour, and after the addition was complete, stirring was continued for an additional 30 minutes. Ta.

Next, 100 - of an aqueous solution in which 14.4 g of sodium hydroxide was dissolved was added, the internal pressure of the flask was reduced, and the flask was gradually heated in a water bath to distill and remove the solvent and dioxane, and then dry. 50.2 g of product (crude sodium 2-methyl-1,3-butadiene-1-sulfonate) was obtained. This product is called monomer (a) [component (a)].

Reference Examples 2-3.6-8 At the preparation ratio shown in Table 1, component (a), component (b), (
C) Place the ingredients, water and potassium persulfate in a pressure bottle;
Polymerization was carried out at a temperature of 90° C. for 10 hours. After polymerization, the product was neutralized using sodium hydroxide and water was removed to obtain a product as a yellow powder.

Reference Examples 4 to 5 Component (a), water, and potassium persulfate were charged into a 300-mm round bottom flask that had been completely substituted with nitrogen in the proportions shown in Table 1. After maintaining the internal temperature at 70°C, a mixture of components (b) and (c) was added dropwise over 6 hours. After dropping, stirring was continued for 4 hours to carry out polymerization. After polymerization, water was removed after neutralization using ammonia to obtain a product as a yellow powder.

Examples 1 to 7, Comparative Examples 1 to 5 Coal was produced in Australia and 8
0%, ash content of 6.5%, and sulfur content of 1.6%.

The copolymers, inorganic stabilizers, or dispersants listed in Table 2 are added to water in advance, and a predetermined amount of coal particles are gradually added to the water, and the mixture is heated to 3.00 rpm using a homomixer.
The mixture was stirred for 15 minutes to prepare a coal slurry with a concentration of 70%.

The coal slurry thus obtained was also evaluated. The results are shown in Table-2.

As is clear from Table 2, the slurry composition obtained by the present invention has a low viscosity and is excellent in static stability, vibration stability, and low additive property.

In addition, by using it together with a known dispersant for coal slurry,
Slurries and lees with excellent properties can be obtained (Example 5, Comparative Example 4).

Furthermore, there is no problem when used in combination with an inorganic stabilizer (Example 6.7).

Examples 8 to 10, Comparative Examples 6 to 7 In a forced mixing mixer with an internal volume of 251, 7.91 kg of fine aggregate (inner river river sand in Mie Prefecture) of 0 to 5 Ill and coarse aggregate (inner river sand in Mie Prefecture) 9. 74kg (5-10mm, 1
Weight mixing ratio of 0 to 15 mm and 15 to 20 mm = 3:
4:3), 3.20 kg of ordinary Portland cement (manufactured by Asano Cement ■: Mitsubishi Cement ■: Onoda Cement ■ (weight ratio) = 1:1:1), and 1.2 kg of water. 75kg
, and 0.48 kg of air entrainment agent (pinsol),
The mixture was mixed for 3.5 minutes to obtain fresh concrete. When I measured the slump and entrained air amount of this thing, it was 8.0 cm.
and 4.3%.

After 15 minutes, a 40% aqueous solution of the sulfonated product (group) obtained in Reference Examples 2 to 4 was added to this, and after stirring for 30 seconds, the amount added and the amount of air entrained when the slump was 18 cm ± 1 cm. , and also table the slump value for 30 minutes after stirring.
Shown in 3.

For comparison, Table 3 shows the results obtained when a commercially available condensate of sodium naphthalene sulfonate and a condensate of sodium melamine sulfonate were similarly added. These results show that, compared to commercially available fluidizers, the dispersant made of a sulfonated compound (salt) of the present invention provides high fluidity and low slump loss to concrete with a small amount added.

Furthermore, the ready-mixed concrete and fluidized concrete obtained as described above were subjected to standard curing, and JIS A11
Table 3 shows the results of measuring the compressive strength after 28 days of age according to 08. The compressive strength of fresh concrete (slump 18 cm) is 375 to 385 kg/cm, and the concrete to which the dispersant made of the sulfonate (salt) of the present invention has been added has a slump of 18 cm ± 1 cm, although it is fluidized. First, it can be seen that compressive strength almost equal to that of fresh concrete can be obtained.

The following margins are Example 11, Comparative Example 8 To 100 parts of α-hemihydrate gypsum (including a setting retarder), 30 parts of water
The dispersants shown in Table 4 were added in the amounts shown in Table 4, and after stirring for 30 seconds, the dispersion was immediately measured (
Flow value measurement, viscosity measurement) and breathing water amount measurement were performed, and the results shown in Table 4 were obtained.

Here, the flow value measurement is carried out using a diameter 4
A gypsum slurry was injected into a cylindrical tube with a diameter of 0 cm and an internal volume of 90 m1, the tube was pulled up, and the spread of the gypsum slurry on a glass plate was measured.

In addition, the viscosity was measured using a BL type viscometer with rotor No.
, measured at 3.60 rpm.

Furthermore, the amount of breathing water is 200 m1 with a diameter of 25 mm.
100 ml of gypsum slurry was put into a graduated cylinder, and after being allowed to stand for 1 hour, the amount of water bled onto the surface of the slurry was measured.

Table 4 Example 12 Basic yellow staining C01, Basic Yellow 11 (
C, 1,48055) was added to 400 parts of water and stirred well.

To this, the sulfonated salt 6 obtained in Reference Example 2 was added as a dispersant.
When 0 part was gradually added, a poorly soluble dye complex salt was formed and gradually finely dispersed, which could be made into a commercially available liquid product.

Further, by drying this fine dispersion using a known conventional technique, for example, a spray drying method, 100 parts of a dispersion of the yellow dye was obtained regardless of which dispersant was used.

The dispersion in this example was more easily dispersed by conventional techniques, such as by subjecting the dye complex salt to a mixing action, such as using a colloid mill or stirring the dye complex salt mixture in the presence of sand. .

Example 13 Basic orange dye C, I, Basic Orange 21 (C
, 1,48035) was added to 350 parts of water, stirred well, and the pH was made neutral by adding 2 parts of anhydrous sodium carbonate. When 70 parts of the sulfonated salt obtained in Reference Example 3 was added as a dispersant to this, a sparingly soluble dye salt precipitated.

Further, the above-mentioned orange dye dispersion 100 is obtained by finely dispersing it by applying the known dispersion technique as described above and drying it.
I got g.

Examples 14-15, Comparative Example 9 The scale inhibiting effect of the scale inhibiting agent comprising the dispersant of the present invention was investigated according to the following procedure.

In other words, 170 m of water is placed in an Erlenmeyer flask with an internal volume of 250 m1.
g and 1.56% aqueous solution of calcium chloride trihydrate 1
0g1 and each of the sulfonated products (salts) obtained in Reference Examples 1 and 2. 10g of 04% aqueous solution (20ppm based on the obtained supersaturated calcium carbonate aqueous solution)
After mixing and addition of 10 g of a 3% aqueous solution of sodium bicarbonate, the total amount was made up to 200 g with water. The resulting supersaturated solution of 530 ppm calcium carbonate was sealed and heated to 70°C.
The mixture was heat-treated for 3 hours. Next, after cooling, the precipitate was separated by P using a 0.45 μm membrane filter, and the P solution was filtered through J
Analyzed according to IS KOIOI.

The results are shown in Table 4. From the above results, it can be seen that the sulfonated product (salt) of the present invention is excellent in suppressing scale precipitation of calcium carbonate.

Table-5 This inhibition rate = [(Calcium concentration in P solution after test) - (
Calcium concentration in P solution after dispersant-free test'))/
[530-(Calcium concentration in P liquid after dispersant-free test)] [Effects of the invention] The dispersant of the present invention has a higher concentration of solid fuel, cement, pigments, dyes, and metal oxides than conventional dispersants. Excellent dispersion and stabilization effects for , scale, carbon black, etc.

In particular, the solid fuel slurry using the dispersant of the present invention is Compared to the slurry obtained by conventional techniques, Excellent initial dispersibility, static stability, and vibration stability.

Claims (2)

[Claims] (1) (a) There are sulfonated products of conjugated dienes represented by the general formula (I), and ▲mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, R^1 to R^6 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or -SO_
3X, where X is a hydrogen atom, a metal atom, an ammonium group, or an amino group, and at least one of R^1 to R^6 is -SO_3X. ) (b) Compounds represented by general formula (II), and ▲mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R_7 is hydrogen or a methyl group, and Y is a hydrogen atom or A metal atom, an ammonium group, or an amino group.) (c) Compound represented by the general formula (III) ▲ Numerical formula, chemical formula, table, etc. are available ▼ ... (III) (In the formula, R_8 is hydrogen or is a methyl group, Z is a ring-opening addition of a divalent alkylene oxide residue having 2 to 4 carbon atoms, and R_9 is hydrogen or an alkyl group having 1 to 30 carbon atoms.) A dispersant consisting of a combination. (2) A solid fuel slurry composition using the dispersant according to claim (1).