JPS6248705A - Water-soluble polymer salt and water-soluble copolymer salt - Google Patents

Abstract

PURPOSE:To obtain the titled salt suitable as a dispersing agent for inorganic pigment and organic fine powder and giving a slurry having excellent stability to aging, by (co)polymerizing sulfonated aliphatic diene or said sulfonated compound and other sulfonated compound. CONSTITUTION:The objective water-soluble (co)polymer salt can be produced by (1) polymerizing the sulfonated product of a 4-7C aliphatic diene (e.g. 1,3- pentadiene) or copolymerizing said sulfonated compound with the sulfonated product of a compound having tricyclodecane skeleton and/or tricyclodecene skeleton in the molecule (e.g. dicyclopentadiene) and (2) converting a part of the resultant (co)polymer to a salt.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to water-soluble salts of novel (co)polymers.

[Conventional technology]

Conventionally, it has been used as 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, dyes, etc., or water treatment. Aqueous dispersants are generally widely used as scale inhibitors.

Examples of these aqueous dispersants include polyacrylic acid and copolymers thereof, olefins such as ethylene, isobutylene, amidino, hexene, and diisobutylene, and α typified by maleic anhydride.

In addition to polycarboxylic acid dispersants such as copolymers with β-unsaturated dicarboxylic anhydrides and polycarboxylate salt polymers such as polymaleic acid, salts of condensates of napucrenesulfonic acid, and ligninsulfonic acid sorter. , sodium polystyrene sulfonate, salts of copolymers of styrene sulfonic acid and maleic anhydride, and the like are known.

[Problem that the invention seeks to solve]

In general, organic compounds such as sulfonic acid and its derivatives are strong acids comparable to sulfuric acid, and are widely used industrially due to their properties.

Moreover, since the salt is water-soluble, it is important as a surfactant for organic or inorganic materials.

However, most of the sulfonated products conventionally synthesized are aromatic sulfonated products, and few examples of aliphatic sulfonated products are known.

Furthermore, as will be described later, the polymer or copolymer of the present invention having a sulfone group in its aliphatic skeleton is completely unknown.

The present inventors have conducted intensive studies to obtain a polymer or copolymer of a sulfonated product having an aliphatic skeleton. As a result, the sulfonated product of an aliphatic diene can be polymerized because it has a double bond. It was discovered that this sulfonated polymer has extremely excellent surface activity, and is particularly excellent in coal and cement dispersion properties, leading to the present invention.

Means for Solving Problem C] That is, the first invention of the present invention is a method of polymerizing a sulfonated product of an aliphatic diene having 4 to 7 carbon atoms, and in which the sulfone group present in the polymer is The second invention provides a water-soluble polymer salt characterized in that at least a portion thereof forms a salt; It is made of a copolymer with a sulfonated compound having a tricyclodecane skeleton and/or a tricyclodecene skeleton, and that at least a part of the sulfone groups present in the copolymer forms a salt. The present invention provides water-soluble polymer salts having the following characteristics.

In the present invention, the aliphatic dienes having 4 to 7 carbon atoms containing two double bonds in the molecule (hereinafter sometimes referred to as "aliphatic dienes") used in the first invention include: For example, l,3-butadiene, l,2-butadiene, l,2-penkdiene, 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-heptadiene,
1.5-hebutadiene, 1.6-hebutadiene, 2.3
Examples include -hebutadiene, 2.5-hebutadiene, 3,4-hebutadiene, 3.5-heptadiene, and various branched dienes having 4 to 7 carbon atoms.

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

Further, in the present invention, dicyclopentadiene can be mentioned as a typical example of the compound having a tricyclodecane skeleton or tricyclodecene skeleton used in the second invention (hereinafter, these compounds will be referred to as " (sometimes referred to as "dicyclopentadines"), these skeletons are shown below.

(That is, tricyclo(5,2,1,02°6]decane or decene) Specific examples of such dicyclopentadiene include dicyclopentadiene, dimethyldicyclopentadiene, and the like.

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

Various methods can be used to produce sulfonated products of aliphatic dienes or dicyclopentadines. For example, the double bond of these aliphatic dienes or dicyclopentadines can be sulfonated by the method shown below. It can be manufactured using

That is, sulfonation reactions applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, are described in Gilbert's book "Sulfonation and Related Reactions J.
e1atedReaction”), Interscience Bubble Social Sciences, Inc. (I
tersciencePublishers Inc.
) (1965), and Charles J.
Orton et al., The Journal of Organic Chemistry
anic chemistry) 4158 pages (19
Sulfonation can also be achieved by the addition reaction of sulfites to unsaturated bonds, as shown in the study of 1968).

As the sulfonating agent in this case, acidic sulfites, medic sulfites, or sulfites of alkali metals are usually used alone or as a mixture.

The amount of the sulfonating agent is usually 0, 1 to 4 mol, preferably 0.5 to 2 mol, more preferably 1 to 1 mol, per mol of aliphatic diene or dicyclopentadiene.
．． It is 5 moles. If it is less than 0.1 mol, the reaction yield will be low, while if it exceeds 4 mol, a large amount of disulfonated product will be produced.

If the amount of sulfonating agent is less than 1 mole per mole of aliphatic diene or dicyclopentadiene, a mixture of sulfonated and non-sulfonated derivatives will be formed; For example, n
The sulfonated product alone may be removed from the mixture by distillation (using -hexane, etc.), or the mixture of the sulfonated product and the non-sulfonated product may be directly (co)polymerized by the method described below.

In that case as well, the sulfonated (co)polymer is extracted (
The non-sulfonated (co)polymer can be separated from the non-sulfonated (co)polymer using, for example, n-hexane as a solvent) or by distillation.

Although the use of a catalyst is not necessarily required in the sulfonation reaction, the use of a catalyst such as an inorganic oxidizing agent is usually effective in improving the yield and shortening the reaction time. Examples of the inorganic oxidizing agent include nitrates, nitrites, chlorates, etc., and nitrates are particularly effective.

The amount of the inorganic oxidizing agent is not particularly limited, but is 0.02 to 0.15 mol, preferably 0.05 to 0.
．． 1 mole is effective.

Furthermore, it is preferable to use an appropriate solvent in order to allow the reaction to proceed uniformly and smoothly.

Examples of solvents that can be advantageously used include water, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, and tertiary butyl alcohol, lower glycols, ketones, ethers, and esters. can be mentioned.

Two or more of these solvents can be used in combination as appropriate. Among these, a mixed solvent of lower alcohol and water, especially a mixed solvent of methyl alcohol and water, is recommended as an excellent solvent.

The reaction temperature is usually 50 to 200°C, preferably 70 to 200°C.
It is carried out at 150°C, more preferably from 90 to 130°C, and can be carried out either at normal pressure or under increased pressure.

In order to suppress the progress of side reactions and reduce the production of inorganic salts, the pH of the reaction system is usually maintained at 2 to 9, preferably 5 to 7.

The content of sulfone groups in the sulfonated product varies depending on the conditions of the sulfonation reaction, but usually at least two of the aliphatic dienes or dicyclopentadiene
It is preferred that 0 mol% or more, preferably 40 mol% or more, be sulfonated from the viewpoint of dispersibility of the resulting composition.

In addition, the obtained sulfonated product can be formed into a salt prior to (co)polymerization, and the cationic species of the sulfonated product in this case is not particularly limited, but in order to make it water-soluble, hydrogen, alkali metals, alkaline earth metals,
Ammonium, amines, etc. are preferred.

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

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

Next, the (co)polymer of the sulfonated aliphatic dienes (and the sulfonated dicyclopentadines) used in the present invention refers to at least one of the sulfonated aliphatic dienes. A polymer obtained by polymerizing seeds (first invention), or a random copolymer obtained by copolymerizing the above-mentioned sulfonated aliphatic diene and sulfonated dicyclopentadiene. (Second
invention).

The method for producing such a (co)polymer is as follows.

For example, the sulfonated products of aliphatic dienes (and the sulfonated products of dicyclopentadiene) are reacted in the presence of an acidic compound catalyst at a reaction temperature of usually -20 to 300°C, preferably 80 to 180°C for several hours to several hours. A (co)polymer can be produced by carrying out a polymerization reaction for 10 hours.

In the above (co)polymerization reaction, a polymerization reaction solvent can be used to smoothly carry out the reaction, and such a polymerization reaction solvent may include a polar solvent such as water, or carbonization as long as it does not interfere with the (co)polymerization reaction. Any hydrogens, halogenated hydrocarbons, etc. can be used.

Examples of the acidic compound catalyst include Lewis acids such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, titanium trichloride, and organic protonic acids. be able to. Among them, sulfuric acid can be cited as a typical example.

In addition, in the present invention, when a copolymer is obtained by copolymerizing a sulfonated product of aliphatic dienes and a sulfonated product of dicyclopentadiene (second invention), the copolymerization ratio of both is Sulfonated product of aliphatic dienes/sulfonated product of dicyclopentadiene (molar ratio) -10 to 1
00/90 to 0, preferably 15 to 100/85 to 0, and it is preferable that the aliphatic diene content is 10 mol % or more from the viewpoint of dispersibility.

Further, when (co)polymerizing these sulfonated aliphatic dienes (and sulfonated dicyclopentadines), it is also possible to copolymerize other comonomers.

Such comonomers include aliphatic, alicyclic, and aromatic hydrocarbons having olefinic double bonds, unsaturated amides, unsaturated alcohols, unsaturated esters, unsaturated nitriles, unsaturated carboxylic acids, and their like. esters, unsaturated sulfonic acids and their esters, etc., or aliphatic, ring group,
One or more kinds of aromatic alcohols or phenols, or alcohols or diols having an amino group, an ester group, a nitrile group, a carboxylic acid group, or a sulfonic acid group can be used in any proportion. In particular, from the standpoint of dispersibility, those copolymerized with unsaturated carboxylic acids such as acrylic acid and methacrylic acid are preferred.

By varying the type of comonomer used, the surfactant properties of the polymer can be varied.

In this case, when a copolymer is produced from the sulfonated product of the present invention and the B-mer and used as a dispersant for solid fuel, in order to suppress foaming, 50% by weight is required. The content is preferably 70% by weight or more, more preferably 90% by weight or more.

The molecular weight of the (co)polymer obtained by the present invention can be changed as appropriate by the reaction conditions, particularly the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature and reaction time.

The weight average molecular weight of the thus obtained (co)polymer of the present invention before forming a salt depends on the reaction conditions, especially the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature. , can be changed as appropriate depending on the reaction time.

For example, when a (co)polymer is used as a dispersant for solid fuel, the properties cannot be unambiguously determined because they vary depending on the type of solid fuel, particle size, etc., but usually the weight average molecular weight is 500 or more. It is preferably 1,000 or more, more preferably 2,000 to 100,0
00 is particularly preferred.

Further, when the sulfonated (co)polymer of the present invention is used as a cement dispersant, the weight average molecular weight is 500.
It is preferably at least 2:000, more preferably at least 2:000, and particularly preferably from 3,500 to 50,000.

The (co)polymer of 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 (co)polymer obtained in this way can be obtained by:
The water-soluble ((
A salt of the co)polymer is obtained.

The cationic species for forming a salt on the sulfonic groups of the (co)polymer used in the present invention, that is, the cationic species of the sulfonated product, are not particularly limited. , alkali metals, alkaline earth metals,
Ammonium, amines, etc. are preferred.

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,
Examples of the alkaline earth metal include polyamines such as diethylenetriamine and triethylenetetramine, morpholine, and piperidine, and calcium and magnesium.

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. I can do it.

Note that the water-soluble (co)polymer salts of the present invention (first invention and second invention) can be mutually exchanged into an acid form or a salt such as an amine by an ion exchange method or a neutralization reaction. be able to.

Further, the degree of the sulfonic group in the middle phase 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 (co)polymer of the present invention can be obtained by (co)polymerizing a sulfonated aliphatic diene (and a sulfonated dicyclopentadiene), but is not limited thereto. , the aliphatic dienes (and dicyclopentadiene) may be (co)polymerized first, the resulting (co)polymer may then be sulfonated by the method described above, and finally the salt may be formed.

The structure of the water-soluble (co)polymer salt of the present invention can be confirmed from the absorption of sulfonic groups by infrared absorption spectrum, and the composition ratio can be determined by acid/alkali titration of potential difference, conductivity, etc. .

Furthermore, the structure can be confirmed by the presence of dicyclopentane rings and the like by nuclear magnetic resonance spectroscopy.

The water-soluble (co)polymer salt of the present invention contains one or more types of dispersants, optionally nonionic or anionic surfactants, chelating agents, antifoaming agents, freezing point depressants, wetting agents, and others. Although not particularly limited, it is added to a fine powder slurry of solid fuel or the like at a concentration of 40 to 80% by weight in combination with additives such as dispersants.

The amount of water-soluble (co)polymer salt added at this time can be selected depending on the desired viscosity, since the viscosity of the slurry decreases as the amount increases. .01-10% by weight, preferably 0.05-10% by weight
It may be 5% by weight, but from the viewpoint of workability and economy, it may be 0.0% by weight.
05 to 1% by weight is preferred.

As described above, the (co)polymer used in the present invention easily becomes water-soluble when it is formed into a salt, and when dicyclopentadiene is copolymerized, the cyclic structure of the component Perhaps because it has a harder structure and imparts lipophilicity to the molecule, it has the ability to strongly adsorb to various lipophilic pigments, greatly improving its dispersibility in various powders. , and the stability over time of the resulting slurry is also improved.

The water-soluble (co)polymer salt of the present invention can be used with various inorganic pigments such as calcium carbonate, clay, titanium oxide, gypsum, alumina, silica, magnesia, cement, etc., as well as coal, petroleum coke, pinch, charcoal, etc. It is suitably used as a dispersant for fine powder of organic substances.

〔Example〕

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

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

In addition, the weight average molecular weights described in the Examples were calculated by converting the results determined by Gesile Vermeation Chromatography (GPC) using a calibration curve prepared using several types of polystyrene sulfonic acids with different molecular weights as standard substances. It is something.

That is, the eluate was prepared by dissolving acetonitrile and a 0.5N aqueous sodium sulfate solution at a weight ratio of 3N, and the column was a TSK-GEL manufactured by Toyo Soda.
G300. OSW and TSK-GEL G200
0SW in series, and was measured using a UV detection group.

From the obtained GPC chart total area was calculated to determine the weight average molecular weight.

Example 1 1,000 g of 1,3-pentadiene was placed in a stainless steel autoclave with a capacity of 30 ρ and equipped with a stirring device and a thermometer.
0 g, sodium bisulfite 1.530 g, potassium nitrate 62.5 g, methyl alcohol 3β, and distilled water 1
, 500g, and the internal pressure in the autoclave was 1 at room temperature.
．． After nitrogen was supplied until the concentration reached 0 kg/cnl·G, the valve was sealed and the mixture was allowed to react at 110° C. for 5 hours while being mixed under strong stirring.

After that, let it cool to room temperature, remove most of the methyl alcohol by distillation, add distilled water and petroleum ether, mix thoroughly, remove the separated petroleum ether layer and precipitate, and concentrate the resulting aqueous layer. and distilled to dryness. This was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated using a centrifuge.

By concentrating the obtained acetic acid soluble portion, 1,200 g of a white solid was obtained. This is referred to as sulfonated compound A.

Next, 1.0 k of the sulfonated product A was placed in a No. 5,01 glass-lined autoclave equipped with a stirring device.
g, 1.0 kg of sulfuric acid, and 0.45 kg of water, 120
The polymerization reaction was carried out at ℃ for 12 hours.

After the reaction was completed, liming was performed with calcium carbonate to remove sulfuric acid, and the solid content obtained was 0.9 kg.

The molecular weight distribution of this product is shown in FIG. 3 as a GPC chart. The weight average molecular weight calculated from this is 9.80
It was 0.

Also, a chart of the infrared absorption spectrum of this product (I
R chart) is shown in Figure 1, and it is recognized that it has a sulfone group, and the surface tension of a 4% aqueous solution of this substance is 63
．． It was high at 8 dyn/CII+.

24 g of the obtained polymer was dissolved in 1.000 g of water,
Strongly acidic cation exchange resin 1,0 which has been converted into acid form
After standing for day and night, the filtrate from which the resin was removed by filtration was dried.

The solid content obtained was 18 g.

When we conducted an elemental analysis of this material, we found that it contained 39.0% carbon.
, hydrogen 6.6%, sulfur 22.1%, oxygen 32.3%, and the theoretical values of the polymer of the present invention, carbon 40.0%, hydrogen 6%.
, 7%, sulfur 21.3%, and oxygen 32.0%.

Next, when this product was subjected to neutralization titration with sodium hydroxide, it was neutralized with an equivalent amount of sodium hydroxide. These results indicate that in the polymer after the cation exchange treatment, the sulfone groups were converted into sodium salts after being neutralized.

The surface tension of a 4% aqueous solution of this polymer salt is 64.2dy
It was marked n/.

Example 2 When the acid type polymer of Example 1 was neutralized with potassium hydroxide, calcium hydroxide, aqueous ammonia, and monoethanolamine, the neutralization was completed in equivalent amounts. Water was removed from these under reduced pressure to separate the polymer. These are polymers of sodium, calcium, ammonium or monoethanolamine salts.

The GPC chart and IR chart of these polymers were almost the same as those of Example 1.

In addition, as a result of elemental analysis of these polymers, potassium salt,
It was confirmed that (calcium) 1/2 salt, ammonium salt, monoethanolamine salt, etc. were contained in an equivalent amount to the sulfone group.

Example 3 In Example 1, a polymer was obtained by changing the polymerization temperature to 130°C.

The weight average molecular weight of this product was 14.300, and the same spectra as the IR chart and GPC chart shown in Figs. 1 and 2 were obtained.

The surface tension of a 4% aqueous solution of this substance is 64.6.
It was dyn/cn.

Example 4 In Example 1, a polymer was obtained by changing the polymerization temperature to 100°C.

The weight average molecular weight of this product was 5,200, and the
Spectra similar to the IR chart and GPC chart shown in FIG. 3 and FIG. 3 were obtained.

The surface tension of a 4% aqueous solution of this substance is 60.3d.
It was yn/country.

Example 5 In a stainless steel autoclave with a capacity of 30β equipped with a stirring device and a thermometer, 3,000 g of dicyclopentadiene was added.
0g, sodium bisulfite 1.888g, potassium nitrate 91.7g, methyl alcohol 12j! After adding 3,000 g of distilled water and supplying nitrogen at room temperature until the internal pressure in the autoclave reached 1.0 kg/crA-G,
Close the valve and heat at 130℃ for 5 minutes while mixing under strong stirring.
The reaction was allowed to take place over a period of time.

After that, it was left to cool to room temperature, most of the methyl alcohol was removed by distillation, distilled water and n-hexane were added and mixed thoroughly, and the separated n-hexane layer and precipitate were removed to obtain an aqueous layer. was concentrated and distilled to dryness.

After drying, it was dissolved in glacial acetic acid, and acetic acid-insoluble components such as inorganic salts were filtered off.

The obtained acetic acid soluble portion was solidified to dryness to obtain a white-yellow solid. This solid was washed with ethanol and further dried to obtain a sulfonated product of dicyclopentadiene 2,40.
Obtained 0 kg. This is referred to as sulfonated compound B.

Next, 0.7 kg of the sulfonated product A obtained in Example 1, 0.3 kg of the sulfonated product B,
1.0 kg of sulfuric acid and 0.45 kg of water were charged, and a polymerization reaction was carried out at 120° C. for 12 hours.

After the reaction was completed, liming was performed with calcium carbonate to remove sulfuric acid, and the solid content obtained was 0.9 kg.

The molecular weight distribution of the obtained copolymer is shown in FIG. 4 (GPC chart). The weight average molecular weight calculated from this is
There were 13,200.

Also, a chart of the infrared absorption spectrum of this product (I
R chart) is as shown in FIG. 2, and it was recognized that it had a sulfone group, and the surface tension of a 4% aqueous solution of this product was as high as 70.3 dyn/■.

24 g of the obtained copolymer was dissolved in 1,000 g of water, and a strongly acidic ion exchange resin 1, which had been converted into an acid form, was dissolved in 1,000 g of water.
After standing for day and night, the filtrate from which the resin was removed by filtration was dried.

The solid content obtained was 17 g.

When we conducted an elemental analysis of this material, we found that it contained 52.5% carbon.
, hydrogen 5.8%, sulfur 16.8%, oxygen 24.9%, and the theoretical values of the polymer of the present invention, carbon 52.8%, hydrogen 5
．． 7%, sulfur 16.6%, and oxygen 24.9%.

Next, when this product was subjected to neutralization titration with sodium hydroxide, it was neutralized with an equivalent amount of sodium hydroxide. These results indicate that in the polymer after the cation exchange treatment, the sulfone groups were converted into sodium salts after being neutralized.

Usage example 1 (Testing the dispersibility of coal) The coal is from Australia, and 200 mesh passes are used for 7
6%, 6.5% ash, and 1.6% sulfur were used.

Dispersant described in Example 1.3.4.5 (coal 0.5
%) and gradually put a predetermined amount of coal particles into it,
A coal slurry having a concentration of 70% was prepared by stirring for 15 minutes at 3.00 rpm using a homomixer. Further, the viscosity of the coal slurry thus obtained was measured at 25°C.

The evaluation results are shown in Table 1.

Table 1: The viscosity of the slurry was measured in the same manner as above except that no dispersant was added.
It was 0.0OOcps or more.

Use example 2 5 g of each of the dispersants described in Example 1.3.4.5
A total of three types of aqueous solutions were prepared by adding and dissolving the mixture in 6 g of distilled water.

After adding 200 g of commercially available Portland cement (manufactured by Chichibu Cement ■) to each of these aqueous solutions and kneading by hand for 3 minutes, using a flow cone with an internal volume of 98.9 cc,
The results of measuring the flow value according to R5201 are
Shown in the table.

Table 2: When the flow value was measured in the same manner as above except that no dispersant was added, the flow value was only 1.
It was 101-.

〔Effect of the invention〕

The water-soluble (co)polymer salt of the present invention has excellent dispersibility in both inorganic substances such as inorganic pigments and hydraulic inorganic materials, and organic substances such as coal, pitch, and coke, and has excellent dispersibility in the resulting slurry. It is possible to provide a novel dispersant that provides stability over time and shows almost no coloration.

[Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum of the polymer salt shown in Example 1, Figure 2 is an infrared absorption spectrum of the copolymer salt shown in Example 5, and Figure 3 is a GPC chart of the polymer salt shown in Example 1. , FIG. 4 is a GPC chart of the copolymer salt shown in Example 5. Patent Applicant Japan Synthetic Rubber Co., Ltd. Agent Patent Attorney Shige Takashi Shirai Figure 3 GPC Count Figure 4 GPC Count

Claims (4)

[Claims] (1) A water-soluble polymer obtained by polymerizing a sulfonated aliphatic diene having 4 to 7 carbon atoms, and at least a part of the sulfone groups present in the polymer form a salt. salt. (2) The water-soluble polymer salt according to claim 1, wherein the aliphatic diene is 1,3-pentadiene. (3) a sulfonated product of an aliphatic diene having 4 to 7 carbon atoms;
Consisting of a copolymer with a sulfonated compound having a tricyclodecane skeleton and/or tricyclodecene skeleton in the molecule, and at least a part of the sulfone groups present in the copolymer form a salt. A water-soluble copolymer salt characterized by: (4) The water-soluble copolymer salt according to claim 3, wherein the aliphatic diene is 1,3-pentadiene.