JPH029496A - Water treating agent - Google Patents

Abstract

PURPOSE:To obtain a water treating agent which is excellent in scale preventive effect and to perpetuates this effect by incorporating sulfonated substance of conjugated diene shown in the specified general formula and/or a polymer and/or a copolymer of this sulfonated substance. CONSTITUTION:Sulfonated substance is produced by allowing sulfur trioxide as a sulfonating agent to react with conjugated diene shown in a formula I (R<1>-R<6> shows hydrogen atom, 1-8C alkyl group, 6-20C aryl group or -SO3X. Wherein X shows hydrogen atom, metallic atom, ammonium group or amino group. At least one of R<1>-R<6> shows -SO3X). A water treating agent is obtained by incorporating the sulfonated substance and/or a polymer and/or a copolymer of this sulfonated substance. This water treating agent does not incorporate phosphorus and does not form insoluble salt for metallic ions and is excellent in scale preventive effect and perpetuates said effect.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel water treatment agent, and more specifically, in water systems such as boilers, heat exchangers, condensers, piping, etc.
This invention relates to a water treatment agent used to prevent scale formation.

[Conventional technology]

Traditionally, polymerized phosphates and carboxylic acid polymer compound salts have been used as water treatment agents to prevent corrosion and scale formation on metal surfaces that come into contact with water in boilers, heat exchangers, condensers, piping, etc. It is used.

However, although polymerized phosphoric acid is effective, it is considered problematic that it causes various secondary problems.1 For example, it is easily hydrolyzed to orthophosphoric acid, so its scale suppression ability is not permanent; In addition, wastewater containing phosphorus causes the problem of eutrophication of lakes and marshes, so the amount used must be restricted.

On the other hand, carboxylic acid-based polymer compound salts form insoluble salts when the metal ion concentration increases and become ineffective. For example, high concentrations of calcium ions can cause water to become cloudy due to the formation of insoluble salts, which can also lead to precipitation, promoting the formation of scale deposits.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art, and provides a water treatment agent that does not contain phosphorus, does not generate insoluble salts with metal ions, has an excellent scale prevention effect, and has a permanent effect. The purpose is to

Means for Solving Problem C] The present invention provides a sulfonated product of a conjugated diene represented by formula (1) (hereinafter referred to as "sulfonated product") and/or a polymer and/or copolymer of the sulfonated product. The present invention provides a water treatment agent containing a polymer (hereinafter referred to as a "sulfonated polymer").

[In the formula, Rl and R6 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or -SO,
X, where X is a hydrogen atom, a metal atom (preferably an alkali metal atom and/or an alkaline earth metal atom), an ammonium group or an amino group, and R'-
At least one of R- is -5O3X. ] The sulfonated product 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.

In the present invention, examples of the conjugated diene used in the sulfonated product include 1,3-butadiene, 1,2-butadiene, 2-pentadiene, 1,3-pentadiene,
2.3-pentadiene, isoprene, 1.2-hexadiene, 1,3-hexadiene, 1,4-hexadiene,
1.5-^.

Xadiene, 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-
In addition to heptadiene, 1,6-hebutadiene, 2,3-hebutadiene, 2.5-hebutadiene, 3.4-hebutadiene, 3,5-hebutadiene, 2-phenylbutadiene, etc., various branched Examples include dienes.

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

N-dimethylformamide and dioxane are preferred.

The amount of the sulfonating agent is usually 0.1 to 10 mol in terms of sulfur dioxide, preferably 0.
．． If the amount is less than 0.1 mol, the reaction yield will be low, while if it exceeds 10 mol, unreacted sulfur dioxide will increase, and after neutralization with alkali, a large amount of sodium sulfate will be produced, resulting in poor purity. This is not preferable because it lowers the temperature.

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 is slow (and uneconomical);
If the temperature exceeds 00°C, side reactions may occur and the product may turn black, which is not preferable.

Thus, a cyclic intermediate in which sulfur trioxide is cyclically bonded to a conjugated diene (a cyclic sulfonic acid ester of a conjugated diene, -F
C name sultone (hereinafter referred to as "cyclic intermediate") is produced.

The sulfonated compound represented by the general formula (1) 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").

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 t-butoxide, potassium t-butoxide, etc. alkali metal alkoxide;
Organic metals such as methyllithium, ethyllithium, n-butyllithium, 36C butyllithium, amyllithium, propyl sodium, methylmagnesium chloride, ethylmagnesium bromide, propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum, etc. Compounds; aqueous ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine,
Examples include amines such as pyridine and piperazine; metal compounds such as sodium, 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 0.1 to 3 mol, preferably 0.1 to 3 mol. If the amount is less than 0.1 mol, the conversion of cyclic bonds into double bonds may not be promoted, and the cyclic compound may remain as a cyclic compound, or a hydroxyolefin represented by the general formula may be produced, and the polymerization performance may be impaired. Compounds with almost no amount are 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 θ
It is carried out at ~+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 (r) 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.

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 sulfonated product polymer is obtained by (co)polymerizing the sulfonated product represented by the above general formula (1), but during this polymerization, in addition to the sulfonated product, it is also copolymerized with It is also possible to copolymerize other possible monomers (hereinafter referred to as "other monomers") at 99% by weight or less, preferably from 1 to 98% by weight, and more preferably from 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; mono- or dicarboxylic acids or anhydrides of dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; butadiene, isoprene, 2
-Chloro-1,3-butadiene, ■-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, methalylacetate, acrylamide, methacrylamide, N - methylol acrylamide, glycidyl acrylate, glycidyl methacrylate,
Acrolein, allyl alcohol, etc. are used.

In order to obtain this sulfonated polymer, for example, the sulfonated compound represented by the general formula (1) and, if necessary, other monomers that can be copolymerized with the sulfonated compound are mixed in water or an organic solvent such as water or an organic solvent. Radical polymerization is carried out using a radical polymerization initiator, a chain transfer agent, etc. in the presence of a polymerization solvent.

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 511 parts.

As a 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 radical initiator, chain transfer agent, etc., various electrolytes and pH1i
Using a conditioning agent, etc., 50 to 1.000 parts by weight of water or 50 parts by weight of an organic solvent per 100 parts by weight of the total monomer.
~1,000 parts by weight, and the radical initiator, chain transfer agent, etc. are used in the amounts within the above range, and the polymerization temperature is -50~1,000 parts by weight.
Radical polymerization is carried out under polymerization conditions of +200°C, preferably 0 to +150°C, particularly preferably +5 to +80°C, and a polymerization time of 0.1 to 40 hours.

The method of adding the monomer containing the sulfonated compound as a main component is not particularly limited, and any method such as a bulk addition method, a continuous addition method, or a divided addition method may be used. The polymerization conversion rate is 10% or more,
In particular, it is preferably 30% or more.

Further, the above polymerization method 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-R"R'-C-R' [In general formulas (n) to (IV), R1-Rh is the same as in the above general formula (1)] The weight average molecular weight of the combined sodium polystyrene sulfonate cannot be determined uniquely depending on the intended use, but
Usually 500 to 5,000°, preferably 1,000 to 5
00,000.

The sulfonated polymer thus obtained can be produced in the acid form, alkali metal, alkaline earth metal, or
Can be interchanged with salts such as ammonium and amines.

The structure of the sulfonated product used in the present invention or the sulfonated polymer obtained therefrom can be recognized from the absorption of 000° of the sulfone group by infrared absorption spectrum, and the composition ratio of these can be determined by the acid and It can be determined by alkaline titration.

Furthermore, the structure can be confirmed by the presence of alkyl groups, olefinic hydrogen, etc. by nuclear magnetic resonance spectroscopy.

The water treatment agent of the present invention contains the above-mentioned sulfonated product and/or sulfonated polymer as an active ingredient, and can be injected into the target water system all at once or intermittently or continuously in the same manner as conventional methods.

The amount added varies depending on the water system, but is usually 0.1 to 110
At 0 ppm, preferably from 1 to 50 ppm, a sufficient scale prevention effect is exhibited.

The scale preventing effect of the water treatment agent of the present invention is effective against calcium phosphate scale, calcium carbonate scale, zinc phosphate scale, zinc phosphonate scale, silica scale, and the like.

In addition to the scale prevention effect, the present invention is also effective as a cleaning agent for pipes, an agent for preventing slime deposition, a polymer flocculant, and as a treatment agent for domestic wastewater, industrial wastewater from the pulp industry, the steel industry, and the like.

In addition, upon use, a known water treatment agent (scaling inhibitor), metal corrosion inhibitor, alkali agent, slime inhibitor, bactericide, etc. can be further added as necessary.

Known water treatment agents include polyacrylates, partial hydrolysates of polyacrylamide, maleic acid polymers, itaconic acid polymers, acrylic acid copolymers containing hydroxyethyl methacrylate, etc. as metal corrosion inhibitors. Examples of these include oxycarboxylic acids, thiazoles, triazoles, amines, and hydroxamic acids.

In addition, slime inhibitors include chlorine agents such as chlorine gas, calcium hypochlorite, sodium hypochlorite, and sodium chloride isocyanurate, quaternary ammonium salts,
Examples include bromine-based drugs and organic nitrogen-sulfur-based drugs.

Furthermore, one of the characteristics of the water treatment agent of the present invention is that it does not contain phosphorus compounds, but if necessary, it may be combined with a phosphoric acid water treatment agent such as a phosphate or a phosphonate, or a corrosion inhibitor. You may.

〔Example〕

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 1 Methylene chloride 400 which had been subjected to dehydration and deoxidation treatment in advance after replacing with nitrogen in a four-hole flask with an internal volume of 11
mj! Next, 31 ml of dehydrated and deoxidized dioxane was added, and the mixture was cooled to 5 to 10° C. with stirring.

Next, 15 mf 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 addition was complete, stirring was continued for an additional 30 minutes. .

Next, 100 mj of an aqueous solution in which 14.4 g of sodium hydroxide was dissolved! The product (crude 2
50.2 g of sodium methyl-1,3-butadiene-1-sulfonate was obtained.

After dissolving this solution in 300 cc of water, 200 cc of toluene was added and vigorously shaken to extract the toluene soluble content, 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
J) 2g, 30mj! After putting it in a pressure bottle and replacing it with chlorine, add 0.06g of sodium persulfate.
Polymerization was carried out for 2 hours in a rotating polymerization tank at 70°C.

The polymerization conversion rate of the polymer was 65%, and as a result of gel perminisilane chromatography (GPC) analysis, the weight average molecular weight in terms of sodium polystyrene sulfonate (hereinafter referred to as "weight average molecular weight") was 20,000, and the sulfonate The amount of acid groups was determined by titration to be 5.5 milliequivalents/g.

Nuclear magnetic resonance spectrum ('H-NMR) of the obtained polymer
) and an infrared absorption spectrum, it was found that this polymer had the following repeating structural units as its main components.

H-C-3O,Na (wherein, m and n represent the number of repeating structural units corresponding to the weight average molecular weight, [by gas resonance spectrum, m:
The ratio of n was found to be approximately 54:46. ) Reference Example 2 MBSN synthesized in Reference Example 1 and methacrylic acid were copolymerized.

That is, 13 g (0,076 mol) of MBSN and 6.5 g (0,076 mol) of methacrylic acid were
The mixture was placed in a ml pressure-resistant bottle, 58.5 g of water and 0.20 g of potassium persulfate were added, the mixture was capped, and polymerization was carried out at 70° C. for 5 hours.

The polymerization conversion rate of the copolymer was 74%, and the weight average molecular weight was 28,500.

The obtained copolymer was dialyzed using a cellulose tube to remove low molecular weight components, and then a nuclear magnetic resonance spectrum and an infrared absorption spectrum were measured.

When the copolymerization composition of both was determined from nuclear magnetic resonance spectroscopy, it was found that MBSN/methacrylic acid (molar ratio) -29/7
It was 1.

Examples 1 to 5, Comparative Examples 1 to 2 (calcium phosphate scale prevention evaluation) In an Erlenmeyer flask with an internal volume of 300 ml, 5 ppm of scale inhibitor, 10 ppm of phosphate ion (PO,'-),
Calcium ion (Ca 2 *) is 1100pp,
So that the carbonate ion (Go, ”) becomes xooppm,
Distilled water, scale inhibitor (water treatment agent) aqueous solution, sodium orthophosphate/decahydrate aqueous solution, calcium chloride/2
An aqueous salt solution and an aqueous sodium bicarbonate solution were added to adjust the total amount to 200 g. Thereafter, it was placed in a constant temperature bath at 60° C. and heated for 15 hours to promote scale generation.

After cooling at room temperature, it was filtered with a 0.45 μm membrane filter, and phosphorus ions were quantified according to the molybdenum blue method of JIS KOIOI. The results are shown in Table 1.

Comparative Examples 1 and 2 also show cases in which no scale inhibitor was added and cases in which polyacrylic acid was used.

In addition, MBS used in the synthesis of copolymers (water treatment agents)
N is the same as that obtained in Reference Example 1, and each copolymer was produced according to Reference Example 2. The same applies to the following examples.

Table 1 Examples 6-7, Comparative Examples 3-4 (zinc phosphate scale prevention evaluation) Internal volume 300 mj! In an Erlenmeyer flask, 5 ppm of scale inhibitor, 6 ppm of phosphate ion (Po, 3-),
Calcium ion (Ca'') is 1100pp, carbonate ion (CCh''-) is looppm.

Distilled water, a scale inhibitor aqueous solution, sodium orthophosphate/decahydrate aqueous solution, calcium chloride/dihydrate aqueous solution, sodium bicarbonate aqueous solution and zinc chloride were added so that the zinc ion (Zn'') was 3.5 ppm. Total 2
The weight was adjusted to 00g. Thereafter, it was placed in a constant temperature bath at 60° C. and heated for 15 hours to promote scale formation.

After cooling at room temperature, it was filtered with a 0.45 μm membrane filter, and phosphorus ions were quantified according to the molybdenum blue method of JIS KOIOI. The results are shown in Table 2.

Comparative Examples 3 and 4 also show cases in which no scale inhibitor was added and cases in which sodium polyacrylate was used.

(Leaving space below) Table 2 Examples 8 to 11 Comparative Examples 5 to 6 (Zinc phosphonate scale and zinc carbonate scale prevention evaluation) In an Erlenmeyer flask with an internal volume of 300 mJ, 10 ppm of a scale inhibitor and phosphonic acid (1-hydroxyethylidene) were placed. -1,1-diphosphonic acid,
Made by Mitsubishi Monsanto Chemical ■, Dequest 2010) 3p
p.m.

Calcium ion (Ca'') is 300ppm, magnesium ion (Mg'') is 150ppm, carbonate ion7
(Cow ”-) is 200 ppm, zinc ion (Z
Distillation Table 3 [Effects of the Invention] According to the present invention, scale prevention water that does not contain phosphorus compounds that can prevent precipitation even in systems with high metal ion concentrations is produced. A processing agent is obtained.

Patent Applicant Japan Synthetic Rubber Co., Ltd. Representative Patent Attorney Shirai Shige Precipitation, scale inhibitor aqueous solution, sodium orthophosphate
Add 12-hydrate aqueous solution, calcium chloride/dihydrate aqueous solution, magnesium chloride aqueous solution, sodium bicarbonate aqueous solution, phosphonic acid and zinc phosphite aqueous solution, and make a total of 200
It was adjusted so that it became g. Thereafter, it was placed in a constant temperature bath at 60° C. and heated for 15 hours to promote scale formation.

After cooling at room temperature, it was filtered with a 0.45 μm membrane filter, and phosphorus ions were quantified according to the molybdenum blue method of JIS KOIOI. The results are shown in Table 3.

Comparative Examples 5 and 6 also show cases in which no scale inhibitor was added and cases in which sodium polyacrylate was used.

(Margin below)

Claims (1)

[Claims] (1) A water treatment agent containing a sulfonated product of a conjugated diene represented by the general formula (I) and/or a polymer and/or copolymer of the sulfonated product. ▲There are 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. )