JPH02113084A - Drilling muddy water adjuster - Google Patents

Abstract

PURPOSE:To obtain the title novel adjuster providing muddy water having extremely excellent heat resistance and salt resistance, containing a sulfone group-containing conjugated diene compound [(co)polymer thereof], etc. CONSTITUTION:The aimed adjuster containing one or more selected from (A) a sulfone group-containing conjugated diene compound (especially preferably isoprene), (B) a (co)polymer of the component A and (C) a sulfonated conjugated diene (co)polymer. Sulfur trioxide alone and a complex of sulfur trioxide and an electron donative compound such as N-dimethylformamide or dioxane are used as a sulfonating agent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a muddy water conditioner for a stabilizing liquid used in civil engineering work, development of various mining industries, exploration, geothermal utilization, etc. when excavating deeply into the ground. .

[Background Art] In civil engineering work, oil poling, and exploration drilling in various mining industries, the muddy water method is used for noise prevention, ease of construction, safety, and economy.

In this muddy water construction method, the functions of the stabilizing liquid include preventing ground collapse, preventing groundwater, oil and gas from blowing out, supporting earth pressure, maintaining the excavated surface, transporting earth and sand, and acting as a lubricant. .

As this stabilizer, a bentonite slurry based on bentonite and water is generally used, but in order to maintain the above-mentioned functions well, various slurry conditioners are usually added.

Typical examples of muddy water conditioners include sodium lignin sulfonate, sodium polyphosphate, sodium polyacrylate, sodium humate, and carboxymethyl cellulose.

[Problems to be Solved by the Invention] However, all of these regulators have the disadvantage of poor heat resistance and salt resistance.

On the other hand, in recent years, there has been an increase in the use of seawater mud in applications such as deep-drilled oil wells and geothermal development defenses under high temperature and high pressure conditions, as well as seawater mud. Furthermore, even in the general muddy water construction method, mixing of cement components during concrete pouring after excavation is unavoidable. Therefore, bentonite slurry using conventional sewage conditioners tends to gel or become highly viscous due to heat, inorganic salts, cement, etc., and its performance is not fully satisfactory.

An object of the present invention is to provide a muddy water conditioner that has excellent cement resistance (no gelation due to cement, etc.), heat resistance, and salt resistance.

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned conventional technical problems, the present inventors found that when using a specific new muddy water conditioner,
The present invention was achieved by discovering that muddy water with extremely excellent heat resistance and salt resistance can be obtained.

That is, the present invention provides (a) a sulfone group-containing conjugated diene compound, and (b) a (co) sulfone group-containing conjugated diene compound.
The present invention provides a drilling mud conditioner having excellent heat resistance and salt resistance and containing as an active ingredient at least one selected from sulfonated products of polymers and conjugated diene (co)polymers.

The present invention will be described below.

(a) The sulfone group-containing conjugated diene compound and (b) its (co)polymer used here include -Tsuriyo (
I) Sulfonated compound R+ R6 C= C-C= C(I) R2R3R4R5 (wherein, R1-R6 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms) , or -303
X, where X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an amino group, and at least one of R1-R6 is -so3x. ) and a (co)polymer of the sulfonated product.

The sulfonated conjugated diene polymer (c) is a sulfonated conjugated diene (co)polymer.

Here, the sulfonated compound (I) used in the present invention is a compound in which a sulfone group is introduced into a conjugated diene while leaving two double bonds of the diene.

Examples of the conjugated diene used in the sulfonated product, component (a) of the present invention, include 1,3-butadiene, 1,2
-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-
Hexadiene, 1,3-hexadiene, 1,4-hexadiene, 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-hebutadiene, 1゜6-hebutadiene, 2,3-hebutadiene, 2゜5-hebutadiene, 3
, 4-hebutadiene, 3°5-hebutadiene, 2-phenylbutadiene, and various branched dienes.

Among these, 1,3-butadiene and isoprene are preferred, and isoprene is particularly preferred.

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

The sulfonated product of the conjugated diene can be produced by, for example, sulfonating the double bond of the conjugated diene by the method shown below.

That is, a conjugated diene can be sulfonated using sulfonation agent as a sulfonating agent under known conditions as described in Experimental Chemistry Course edited by the Chemical Society of Japan.

As the sulfonating agent in this case, in addition to sulfur dioxide alone, a complex of sulfur trioxide and an electron-donating compound is usually 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 in terms of sulfur trioxide per 1 mol of conjugated diene, preferably 0.
．． 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, a solvent inert to sulfur trioxide, which is a sulfonation agent, can be used, such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, dichloromethane, etc. Hydrocarbons; nitro compounds such as nitromethane and nitrobenzene; aliphatic hydrocarbons such as liquid sulfur dioxide, 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.
The temperature is preferably -30 to 50 DEG C. If the temperature is less than 70 DEG C., the sulfonation reaction slows down and is not economical, while if it exceeds 200 DEG C., side reactions may occur and the product may turn black, which is not preferred.

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

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

These basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; carbonate compounds such as sodium carbonate and potassium carbonate; sodium methoxide, sodium ethoxide, and potassium methoxide. alkali metal alkoxides such as hydrogen, sodium t-butoxide, potassium t-butoxide; methyllithium, ethyllithium, n-butyllithium, 5ee-butyllithium, amyllithium,
propyl sodium, methylmagnesium chloride,
Ethylmagnesium bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc,
Organic metal compounds such as triethylaluminum and triisobutylaluminum; aminos such as aqueous ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, and piperazine; metal compounds such as sodium, lithium, potassium, calcium, zinc, and aluminum. can be mentioned.

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

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

The amount of the basic compound used is, per mole of conjugated diene,
Usually, it is 0.1 to 3 mol, preferably 0.5 to 3 mol. 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 alk remains,
The purity of the product decreases, which is undesirable.

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 various organic solvents described above, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, propatool, isopropyl alcohol, and ethylene gelcol.

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 150
°C, preferably -10 to 70 °C, more preferably 0 to 5 °C
It is carried out at 0°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°C.
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 interexchanged with a wide variety of cationic species by various ion exchange techniques.

The polymer (b) of the present invention is one obtained by (co)polymerizing the sulfonated product represented by the above general formula (I), but in this polymerization, in addition to the sulfonated product, it is also possible to copolymerize with this. It is also possible to copolymerize other monomers (hereinafter referred to as "other monomers") in an amount of 99% by weight or less, preferably 1 to 98% by weight, and more preferably 10 to 90% by weight.

Other copolymerizable monomers include styrene, α-
Aromatic compounds such as methylstyrene, vinyltoluene, p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc. Alkyl esters of acrylic acid or methacrylic acid; anhydrides of mono- or dicarboxylic acids or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, sodium p-styrenesulfonate, methallylsulfone Sulfonic acids and their salts such as sodium acid, sodium allylsulfonate, sodium 2-acrylamidopropanesulfonate, sodium vinylsulfonate; butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3- Aliphatic conjugated dienes such as butadiene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate-1, methalyl acetate, acrylamide,
methacrylamide, N-methylolacrylamide,
Glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol, etc. are used.

The polymer (b) is prepared by adding the sulfonated compound represented by the above-mentioned binding margin (I) and, if necessary, other monomers copolymerizable therewith with a polymerization solvent such as water or an organic solvent. Radical polymerization is carried out in the presence of a radical polymerization initiator, a chain transfer agent, etc.

Here, the organic solvent for polymerization used in radical polymerization includes, for example, alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as xylene, toluene, and benzene; butane, pentane, hexane,
Aliphatic hydrocarbons such as cyclohexane and heptane can be mentioned.

Among these polymerization solvents, water or methanol is preferred.

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.

The amount of this radical polymerization initiator used is the total amount of monomers 1
00 parts by weight, preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight.

As the chain transfer agent, t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, octylmercaptan, t-hexylmercaptan, n-
Mercaptans such as hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used in an amount of about 0.001 to 10 parts by weight per 100 parts by weight of the total monomers.

In addition, in order to promote radical polymerization, for example, reduction of sodium pyrobisulfite, sodium sulfite, sodium bisulfite, ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-ascorbic acid and its salts, sodium hydrogen sulfite, etc. Chelating agents; chelating agents such as glycine, alanine, and sodium ethylenediaminetetraacetate can also be used in combination.

During radical polymerization, in addition to the above-mentioned radical initiators, chain transfer agents, etc., various electrolytes, pH adjusters, etc. are used in combination as necessary, and 50 to 1 part of water is added to 100 parts by weight of the total monomers. ,000 parts, or organic solvent 50~
1.000 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 2.
00°C, preferably 0 to 150°C, particularly preferably 5 to 150°C
Radical polymerization is carried out under polymerization conditions of 80° C. and 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 finger heating method, a continuous addition method, or a divided addition method may be employed.

The final polymerization conversion rate of the obtained sulfonated polymer is preferably 10% or more, particularly 30% or more.

Furthermore, the polymerization method of the present invention is not limited to the above-mentioned radical polymerization, and the desired sulfonated polymer can also be obtained by conventionally known anionic polymerization.

The sulfonated polymer thus obtained has the following general formula (■), general formula (III) and/or general formula (
It has a repeating structural unit represented by IV).

R' -C-R2 R5-C-R6 (In general formulas (II) to (IV), R1-R6 is
Same as general formula (I) above. ) The weight average molecular weight in terms of sodium polystyrene sulfonate of the sulfonated polymer thus obtained cannot be determined uniquely depending on the intended use, but
Usually 500-5,000°000, preferably 1.0
00 to 500,000.

The sulfonated polymer obtained by the present invention can be mutually exchanged into an acid form or a salt of an alkali metal, alkaline earth metal, ammonium, amine, etc. by an ion exchange method or a neutralization reaction.

In addition, the sulfonated polymer thus obtained can have the following properties if no salt is formed on the sulfonated product prior to polymerization
It is then neutralized in an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. to obtain a water-soluble or hydrophilic polymer salt in which at least some of the sulfonic groups form a salt. . Here, the cation species for forming a salt in the sulfone groups of the sulfonated polymer, that is, the cation species of the sulfonated product, are not particularly limited, but in order to make the sulfonated polymer water-soluble, the above-mentioned hydrogen atoms, alkali Metals, alkaline earth metals, ammonium, amines, etc. are preferred.

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

In this way, an aqueous solution of the water-soluble (co)polymer salt is prepared, but in the present invention, if necessary, these salts are separated from the aqueous solution and dried to obtain a solid water-soluble (co)polymer salt. Can be done.

The degree of neutralization of the sulfonic groups may be appropriately selected within a range that makes the (co)polymer salt water-soluble or water-dispersible, and the sulfonic groups may form different salts. .

The sulfonated conjugated diene polymer (c) can be produced by sulfonating a (co)polymerized conjugated diene compound.

Examples of such conjugated diene compounds include 1°3-butadiene, 1,2-butadiene, 1,2-pentadiene,
1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene,
2,3-hexadiene, 2,4-hexadiene, 2,3
-dimethyl=1,3-butadiene, 2-ethyl-1,3
-Butadiene, 1,2-heptadiene, 1,3-hebutadiene, 2,3-hebutadiene, 2,4-hebutadiene, 3,4-hebutadiene, 3,5-hebutadiene, etc., as well as branched carbon Various dienes of numbers 4 to 7 can be mentioned.

These conjugated diene compounds are polymerized using the above-mentioned radical polymerization initiator, anionic polymerization initiator or cationic polymerization initiator, and then sulfonated using the above-mentioned sulfonating agent, and then neutralized with the above-mentioned alkali amine. can get.

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

Further, in the present invention, other copolymerizable monomers (hereinafter referred to as "other monomers") can also be used in combination with the conjugated diene compound.

Other monomers include aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. , 2-hydroxyethyl acrylate, 2
- Alkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate, niacrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid,
Mono- or dicarboxylic acids or dicarboxylic acid anhydrides such as itaconic acid; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate, meta-allyl acetate. 1. Unsaturated group-containing compounds such as acrylamide, methacrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol, and the like.

These other monomers can be used alone or in combination of two or more.

When these other monomers are used together, the amount of these monomers used is 70% or less of the total monomers, preferably 1 to 5%.
It is about 0% by weight, more preferably about 2 to 30% by weight.

The molecular weight of the sulfonated conjugated diene polymer cannot be determined unambiguously because its properties vary depending on the salt concentration in the muddy water, the composition and particle size of inorganic substances in the muddy water components, etc.
Usually, the number average molecular weight is 300 to 5,000,000. Preferably it is 1,000 to 1,000,000.

The above (a) to (c) can be used as a solution as a drilling mud conditioner, or after drying, they may be appropriately ground into powder or granules. Such powder or granular products are easily dissolved in water upon use.

The amount of the drilling mud conditioner of the present invention to be used is preferably 0.01 to 10% by weight, more preferably 0.1 to 10% by weight based on the mud.
It is 5% by weight.

In addition, when using the drilling mud conditioner of the present invention, conventionally known dispersants such as various polyphosphoric acids, ligninsulfonic acids, nitrofumic acids, phosphonic acids, polycarboxylic acids, etc. may be used to the extent that their excellent effects are not diminished. , carboxymethyl cellulose, a water-soluble polymer compound such as a starch derivative, a surfactant, a pH 2 moderating agent such as soda ash, and an anti-sludge agent such as cottonseed residue.

The drilling mud conditioning agent of the present invention is applied to mud mainly consisting of a bentonite suspension or a suspension containing attapulgite, asbestos, or sepiolite. Furthermore, as a base for muddy water, it can be applied not only to fresh water but also to muddy water based on seawater or muddy water to which a large amount of salts such as chloride are added.

[Effects of the Invention] The drilling mud conditioner of the present invention exhibits excellent heat resistance and salt resistance. It is particularly effective in sewage containing a large amount of various ions, such as seawater mud, and muddy water that cannot avoid being contaminated with cement components.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Further, in the examples, % and parts are based on weight unless otherwise specified.

Reference Example A After replacing nitrogen in a four-loaf flask with an internal volume of 12, 400 m of methylene chloride was subjected to dehydration and deoxidation treatment in advance.
1 and then dehydrated and deoxidized dioxane 3
1 ml was added and cooled to 5-10° C. with stirring.

Next, 15 ml of sulfur trioxide (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 ml 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 dropwise addition was completed, stirring was continued for an additional 30 minutes. .

Next, 30 ml 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 to dryness. 53.1 g of crude sodium 2-methyl-1,3-butadiene-1-sulfonate was obtained.

After dissolving this product in 300 cc of water, 200 cc of toluene was added and vigorously shaken to extract toluene-soluble components, and the aqueous solution was dried.

Next, the sodium 2-methyl-1゜3-butadiene-1-sulfonate (hereinafter referred to as rMBSN) obtained in this way was
Add 2g of acrylic acid and 40ml of water containing 4g of acrylic acid and 1.9g of sodium hydroxide, place in a 100ml pressure bottle, replace with nitrogen, and add 0.2g of ammonium sulfate.
Polymerization was carried out at 70°C for 2 hours using 1gtJ [I engineering].

The polymerization conversion rate of the polymer was 82%, and as a result of gel permeation chromatography (GPC) analysis, the weight average molecular weight in terms of sodium polystyrene sulfonate was 45.
000, and the acid equivalent was 9°6 mEquivalent/g.

Reference Example B MBSN was homopolymerized in the same manner as Reference Example A, and the polymerization conversion rate was 65%, the weight average molecular weight was 130,000°, and the acid equivalent was
A polymer solution of 15.7 m equivalent/g was obtained.

Reference Example C An MBSN-acrylamide copolymer was obtained by using acrylamide instead of acrylic acid in Reference Example A. The results are shown in Table-1.

Reference Example D A copolymer of MBSN and sodium styrene sulfonate was polymerized in the same manner as in Reference Example A. The results are shown in Table-1.

Reference Example E Acrylic acid and sodium methallylsulfonate were used as MBSN, and dotesyl mercaptan was used as a molecular weight regulator. The results are shown in Table-1.

Reference Example F ■ 35% of isoprene was placed in a pressure-resistant reaction vessel. After charging 0.44 g of Or, n-butyllithium and 200 g of cyclohexane and polymerizing at 60° C. for 2 hours, 1 g of isopropyl alcohol (IPA) was added to stop the polymerization.

Next, after distilling off the solvent and unreacted monomers under reduced pressure, 1
, diluted with 50 g of 2-dichloroethane.

■ Next, add 3 sulfuric anhydride to 100 g of dioxane in a separate container.
2.9 g was added while keeping the internal temperature at 25° C., and stirred for 2 hours to obtain a sulfuric anhydride-diogysan complex.

(2) The complex obtained in (2) above was added to the polymer solution obtained in (2) above over a period of 2 hours while maintaining the internal temperature at 20°C. After the addition, stirring was continued for 2 hours, and then 18% of sodium hydroxide was added. After adding Og and 150 g of water, the mixture was stirred at 80° C. for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a yellow powder sulfonate salt product.

Reference Example G During the polymerization of isoprene in Reference Example F, 3.0 g of styrene was added and polymerization was carried out in the same manner. The results are shown in Table-1.

Reference Example H Isoprene and butadiene were used in place of isoprene in Reference Example F, and polymerization was carried out in the same manner, followed by sulfonation. Display the results -
Shown in 1.

Reference Example ■ Isoprene and methyl methacrylate were used instead of isoprene in Reference Example F, and the polymerization was carried out in the same manner as before, followed by sulfonation. The results are shown in Table-1.

Examples 1 to 9 and Comparative Examples 1 to 4 Reference Examples 1 to 2 in 100 parts by weight of water and 8 parts by weight of bentonite
Drilling mud conditioner A-J obtained in
0.03 parts of each were added to prepare muddy water.

Next, 2 parts by weight of Portland cement was added, stirred with a turbine blade at 5.00 rpm for 5 minutes, and then allowed to stand still. The funnel viscosity of the bentonite mud was measured after 5 minutes and 30 minutes. The results are shown in Table-1.

Examples 10 to 18 and Comparative Examples 5 to 8 Mud water was prepared in the same manner as in Example 1. 5. Add 7 quantitative amounts of the following mixture of salt composition in seawater (synthetic seawater salt) to this. O
After stirring at OOrpm for 5 minutes, the mixture was allowed to stand still. After 5 minutes, the viscosity was measured at 60 rpm and 60 rpm using a B-type viscometer. The results are shown in Table-2.

As the above mixture, a mixture containing the following synthetic seawater salt components was used.

CaSO44gS MgSO46g.

MgCl2 10g, KCI 2g
.

NaC 178g From the above results, it can be seen that the muddy water using the muddy water conditioner of the present invention has good cement resistance and seawater resistance.

Claims (1)

[Claims] (1) (a) Sulfone group-containing conjugated diene compound, (b)
A drilling mud conditioner comprising at least one selected from (co)polymers of sulfonic group-containing conjugated diene compounds and (c) sulfonated products of conjugated diene (co)polymers.