JPS59184152A - Production of sulfonated substance - Google Patents

Abstract

NEW MATERIAL:A sulfonated substance containing a norbornene ring or cyclohexene ring and benzene nucleus and sulfonic acid group in the molecule thereof. EXAMPLE:Sodium salt of sulfonated toluene adduct of 5-vinylnorbornene-1. USE:A synthetic intermediate for surfactants. A condensate obtained by condensing the sulfonated or disulfonated substance with an aldehyde exhibits improved surface activity. The condensate obtained from the disulfonated substance is particularly useful for a dispersing agent for cement. PREPARATION:A reaction product obtained by adding a compound of formula I (R1 and R2 are h or 1-2C alkyl) to a 9-12C norbornene compound containing two double bonds in the molecule or 8-12C cyclohexene compound containing two double bonds in the molecule is further sulfonated to afford the aimed sulfonated substance, which is if necessary sulfonated to give a disulfonated substance. The sulfonated substance which is an exemplified compound can be subjected to a condensing reaction to afford the condensate expressed by formula II(m>=1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing novel sulfonated products, disulfonated products, and condensates thereof, which contain a norbornene ring or cyclohexene ring, a benzene nucleus, and a sulfonic acid group in the molecule.

Sulfonic acids and many of their derivatives are strong acids comparable to mineral acids, and their salts are water-soluble and can impart unique properties to organic and inorganic materials, and can also be used as synthetic intermediates for organic compounds. Very important.

However, most of the sulfonated products synthesized conventionally are aromatic, aliphatic, etc. sulfonated products, and there are almost no examples of sulfonated products and disulfonated products of norbornene compounds and cyclohexene compounds.

As a result of extensive research into the synthesis and properties of sulfonated compounds and disulfonated compounds using norbornene compounds or compounds having a cyclohexene ring as starting materials, the present inventors found that the number of carbon atoms containing two double bonds in the molecule 9
~120 Norbornene compound or 2 double bonds in the molecule
A cyclohexene compound having 8 to 12 carbon atoms is reacted with a compound represented by the general formula The present inventors have discovered that the condensate obtained by condensing this sulfonated product or the resulfonated product (disulfonated product) of the sulfonated product with an aldehyde has extremely excellent surfactant action, and has arrived at the present invention. .

That is, the present invention provides a norbornene compound having 9 to 12 carbon atoms containing 2 double bonds in the molecule or a cyclohexene compound having 8 to 12 carbon atoms containing 2 double bonds in the molecule with the general formula (I). A method for producing a sulfonated product of a norbornene derivative or a cyclohexene derivative, which comprises sulfonating a reaction product obtained by adding the compound represented by the formula, wherein the molecule contains two double bonds and has 9 carbon atoms.
~12 norbornene compounds or 2 double bonds in the molecule
A norbornene derivative or a cyclohexene derivative, which is obtained by sulfonating a reaction product obtained by adding a compound represented by the general formula α) to a cyclohexene compound having 8 to 12 carbon atoms, and resulfonating the sulfonated product. A method for producing a disulfonated product and a norbornene compound having 9 to 12 carbon atoms containing two double bonds in the molecule, or a norbornene compound having 8 to 12 carbon atoms containing two double bonds in the molecule
The present invention provides a method for producing a condensate of 12 cyclohexene compounds represented by the general formula α).

R1 Next, the present invention will be explained in detail.

The norbornene compound used as a starting material in the present invention has 9 to 9 carbon atoms and contains 2 double bonds in the molecule.
For example, it is a norbornene compound obtained by a Diels-Alder reaction of cyclopentadiene and a diene having 4 to 7 carbon atoms. For example, it is expressed as the general formula 〇.

Specifically representative examples include 5-vinyl-norbornene-11,5-vinyritinnorbornene-1,4
-,7'tyrene-5-methyl-norbornene-1,5-
7'lovenylnorbornene-1,4-viny/l/-5-
Methyl-norbornene-1,5-infurobenylnorbornene-1,4-1f-5-vinylnorbornene-1
, 5-allylnorbornene-1,4-ethyl-5-vinylnorbornene-1,5-butenylnorbornene-1, and the like.

In the present invention, the cyclohexene compound which is the starting material is selected from cyclohexene compounds having 8 to 12 carbon atoms and containing two double bonds in the molecule. It is something that can be done. This cyclohexe/compound contains a conjugated diene having 4 to 6 carbon atoms such as 1,3-butadiene, 1,3-pentadiene, isoprene, and 1,3-hexadiene as the A component, and a conjugated diene of the human component as the B component. In addition, 1,2-butadiene, 1,4-pentadiene, and cyclopentagenato, which are dienes having 4 to 6 carbon atoms, are used in a Diels-Alder reaction with diene as component A and genophile as component B. It is a product that is

For example, the general formula of a cyclohexene compound obtained when 1,3-butadiene is used as the diene component is represented by formula (m).

Specific examples of these include 4-vinyl-cyclohexene, 4-vinylidene-cyclohexene, 4-methylene-5
-Methyl-cyclohexene, 4-isof4henyl-cyclohexene, 4-propenyl-cyclohexene, 4-vinyl-5-methyl-cyclohexene, 3-methyl-4-
Vinyl-Schifftetrahexene, 4-methyl-4-vinyl-cyclohexene, 4-butenyl-cyclohexene, tetrahydroindene, etc. When using other conjugated dienes as the diene component, further substituents are added to the cyclohexene ring of the above compound. It becomes a cyclohexe/compound with .

The compound of general formula α) used in the present invention is one selected from benzene, toluene, xylene, methylethylbenzene, diethylbenzene, and ethylbenzene.

Addition of the compound of general formula (0) to the norbornene compound or cyclohexene compound described above can be carried out by a 7-Liedl-Crafts reaction. As a catalyst for this,
Acidic compounds such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide,
Examples include Lewis acids such as tin tetrachloride, zinc chloride, and titanium trichloride, and organic protonic acids. The above norbornene compound or cyclohexe/compound and the compound of general formula q) are heated preferably at 0 to 100°C, particularly preferably at 20 to 7°C.
It can be obtained by reacting at 0°C for about 1 to 5 hours.

For example, when a Friedel-Crafts reaction is carried out in the presence of BP using 5-vinylnorbornene-1 as a norbornene compound and toene as a compound of general formula 〇),
A derivative represented by the following formula (IV) is mainly produced.

After the compound of general formula (I) is added to the norbornene compound or cyclohexene compound in this manner, the remaining double bond can be sulfonated. - The above-mentioned sulfonation method includes Gilbert (E, E,
G11bert) [Sulfonation and Related Reactions]
(”5ulfonation and Re1ate
d Reaction, Interscience
Publishers Inc. (1965), the sulfonation method applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, should be selected appropriately depending on the state of the reaction system. I can do it.

Matatayars 9 Jay Twoton (Charls J
, Norton et al., The Journal of Organic e-Chemistry
Organic Chemistry) 4158 pages (1
A sulfonated product of norbornene derivatives or cyclohexene derivatives represented by the above general formula can also be obtained by the addition reaction of sulfites to unsaturated bonds, as shown in the research of 1996). As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually used alone or in combination. 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 usually has the effect of shortening the reaction time. Examples of the inorganic oxidizing agent include nitrates, nitrites, chlorates, etc., and nitrates are particularly effective.

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

Solvents that can be used advantageously include, for example, water, or methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol,
Examples include lower alcohols such as tertiary butyl alcohol, lower glycols, ketones, ethers, and esters.

Two or more of these solvents can be used in combination as appropriate. Among them, lower alcohols and water are recommended as excellent solvents.

The reaction temperature is usually 50-200°C, preferably 70-15°C.
It is carried out at 0°C, more preferably at 90 to 120°C, and can be carried out either at normal pressure or under elevated 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.

For example, by using a derivative of formula (IV) and reacting it with sodium bisulfite in a suitable solvent, a compound of formula (V) below is obtained.

Such sulfonated compounds are new substances.

In addition, this sulfonated product [cationic species ((V
In ), Na) 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 metals include sodium, potassium, rum, etc.; examples of amines include methylamine, triethylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine,
Examples of alkaline earth metals include alkylamines such as butylamine, digtylamine, and trimethylamine, polyamines such as ethylenediamine and diethylenetriamine, morpholine, and piperidine, and calcium and magnesium as alkaline earth metals. Further, these cationic species can be mutually exchanged with other cationic species by various ion exchange methods.

Sulfonated products of norbornene derivatives or cyclohexene derivatives obtained by the above methods, or sulfonated products of norbornene derivatives or cyclohexene derivatives, and condensation monomers other than sulfonated products of norbornene derivatives or cyclohexene derivatives that can be condensed therewith. (hereinafter referred to as "condensation composition")
A condensate can be obtained by condensing an aldehyde with the following in the presence of an acid catalyst.

The above condensates include condensates obtained by condensing the same sulfonates used in the present invention, as well as condensates obtained by condensing different sulfonates used in the present invention, Alternatively, it also represents a condensate obtained by condensing a mixture of the sulfonated product used in the present invention and a condensation monomer other than the sulfonated product used in the present invention that can be condensed with the sulfonated product.

The sulfonated norbornene derivatives or cyclohexene derivatives used in the condensation may be the same, or several different sulfonated products may be used in combination as long as they fall within the scope of the present invention.

Examples of the aldehyde include formaldehyde, acetaldehyde, propionaldehyde, and the like, and among these, formaldehyde is preferred in terms of reactivity. The amount used can be selected within a fairly wide range, or in order to increase the degree of condensation and avoid unnecessary side reactions, it is necessary to select from 0.5 to
It is preferably twice the number of moles, more preferably 0
．． The number of moles is 8 to 1.5 times higher.

A typical example of the acid catalyst is sulfuric acid. The amount used is 0.0001 to 10 times the total number of moles of the condensation composition, preferably 0.01 to 5 times the number of moles, and more preferably 0.05 times the number of moles.
~3 times the number of moles. If this is less than 0.0001 times the number of moles, the reaction rate will be low and the degree of condensation will be low, while if it exceeds 10 times the number of moles, carbonization reaction will likely occur. In addition, when the condensation composition contains a sulfonic acid of a norbornene derivative or a cyclohexene derivative, the sulfonated product itself becomes an acid, which also acts as an acid catalyst. It can be calculated as the number of moles of

In order to carry out a uniform condensation reaction, it is preferable to use water, lower alcohol, formic acid, acetic acid, etc. as a solvent for the condensation reaction. The amount used may be appropriately selected in consideration of reaction rate, solubility, etc.

For example, when a condensation product is produced using a condensation composition consisting only of a sulfonated product of a norbornene derivative or a cyclohexene derivative, when water is used as the solvent, the amount used is The number of moles is 2 to 100 times, preferably 5 to 20 times, the total number of moles of the compound.

Moreover, the condensation reaction temperature is 30 to 150°C, preferably 70 to 120°C.

Condensation monomers other than sulfonated products used in the present invention include, for example, benzene, toluene, xylene, benzene derivatives such as phenol; sulfonic acids or salts thereof of benzene derivatives; 7-talene derivatives; β-naphthalene sulfonic acid Examples include, but are not limited to, sulfonic acids of naphthalene derivatives such as sodium or salts thereof. Moreover, you may use these in combination of 2 or more types. By appropriately selecting these, it is possible to freely control the HLB (surfactant properties) of the condensate obtained in the present invention.

The amount of these used is preferably within a range that does not impair the properties of the condensate, and taking into consideration the solubility in water, for example, the content of the sulfonated compound used in the present invention in the condensation composition is as follows: The amount is preferably 20 molti or more, more preferably 50 molti or more.

Further, the degree of condensation of the resulting condensate can be appropriately selected by changing reaction conditions such as the amount of acid catalyst, the condensation reaction temperature, and the condensation reaction time. Further, it is necessary to select the degree of condensation depending on the use. For example, when used as a dispersant for cement, a condensate in which 2 to 100 units of the sulfonated product used in the present invention are condensed is preferable.

In addition, the cationic species of the condensate can be extracted using normal ion exchange techniques.
Various exchanges are possible.

As will be understood from the description of the examples below, the above-mentioned condensates have excellent surfactant properties and are therefore extremely useful as surfactants for organic or inorganic materials, such as emulsifiers, It can be widely used as a dispersant, wetting agent, cleaning agent, and smoothing agent, and especially when used as a dispersant for cement, it can significantly improve the dispersibility of cement in water, thus improving the water reduction effect in cement construction methods. Obtainable.

The above condensate has excellent dispersibility of cement, but
Since this condensate has a relatively low surface tension, it foams a lot and is difficult to use when used as a concrete mixture, especially when high strength of concrete is required. The present inventors have found that this drawback can be improved by re-sulfonating the sulfonated product (ie, creating a disulfonated product).

As a method for resulfonation, it can be carried out by the above-mentioned crucible. During the reaction, the molar ratio (crystalline) of sulfuric acid and sulfonated product is not particularly limited, but is preferably 0.1 to 5. If it is less than 0.1, the yield will decrease, and if it exceeds 5, side reactions such as carbonization reactions may occur. The reaction temperature is not particularly limited, but from the viewpoint of reaction rate, side reactions, etc., it is preferably 50 to 150°C, and 80°C to 150°C.
-130 degreeC is more preferable. Furthermore, water, organic acids, organic solvents, alcohols, etc. can also be used as solvents to facilitate the reaction. On the other hand, if water is used as a solvent, the viscosity during the reaction can be kept low, but the reaction progresses slowly. Therefore, the reaction rate can be increased by simultaneously adding a solvent that is azeotropic with water, such as heptane, and carrying out the reaction while removing water. This method is also applied when the reaction is performed while removing water from sulfuric acid.

In this way, a sulfone group can be introduced into the compound represented by the general formula (I) added to the norbornene compound or cyclohexene compound. Compound i can be obtained by condensing the disulfonated product thus obtained with an aldehyde in the presence of a catalyst. The condensates include condensates obtained by condensing the same disulfonated norbornene derivatives or cyclohexene derivatives, as well as condensates obtained by condensing different disulfonated norbornene derivatives or cyclohexene derivatives. or a mixture of the disulfonated product used in the present invention and a condensation monomer other than the disulfonated product used in the present invention that can be condensed with the disulfonated product used in the present invention.

Examples of the aldehyde include formaldehyde, acetaldehyde, and tetrapionaldehyde, and among these, formaldehyde is preferred in terms of reactivity. The amount used can be selected within a fairly wide range, but in order to increase the degree of condensation and avoid unnecessary side reactions, it is recommended to
It is preferably twice the number of moles, more preferably 0
．． The number of moles is 8 to 1.5 times higher.

A typical example of the acid catalyst is sulfuric acid. The amount used is 0.0001 to 10 times the total number of moles of the condensation composition, preferably 0.01 to 5 times the number of moles, and more preferably 0.05 times the number of moles.
~3 times the number of moles. If this is less than 0.0001 times the number of moles, the reaction rate will be low and the degree of condensation will be low, while if it exceeds 10 times the number of moles, carbonization reaction will likely occur. Further, when the condensation composition is a sulfonic acid, the sulfonated product itself becomes an acid, and this also acts as an acid catalyst, so this number of moles can be calculated as the number of moles of the acid catalyst.

In order to carry out a uniform condensation reaction, it is preferable to use water, lower alcohol, formic acid, acetic acid, etc. as a solvent for the condensation reaction. The amount used may be appropriately selected in consideration of reaction rate, solubility, etc.

For example, in the case of producing the condensate of the present invention using a condensation composition consisting only of the disulfonated compound used in the present invention, when water is used as the solvent, the amount used is based on the total number of moles of the disulfonated compound. The number of moles is 2 to 100 times, preferably 5 to 20 times.

Moreover, the condensation reaction temperature is 30 to 150°C, preferably 70 to 120°C.

Condensation monomers other than disulfonated compounds used in the present invention include, for example, benzene derivatives such as benzene, toluene, xylene, and phenol; sulfonic acids of benzene derivatives or salts thereof; naphthalene derivatives; sodium β-naphthalene sulfonate, etc. Examples include naphthalene derivatives of sulfonic acid or salts thereof, but are not particularly limited thereto. Moreover, you may use these in combination of 2 or more types. By appropriately selecting these, it is possible to freely control the HLB (surfactant properties) of the condensate obtained in the present invention. The amount of these used is preferably within a range that does not impair the properties of the condensate, and taking into consideration the solubility in water, for example, the content of the disulfonated compound used in the present invention in the condensation composition is is preferably 20 moy% or more, more preferably 50 moy% or more.

Further, the degree of condensation of the resulting condensate can be appropriately selected by changing reaction conditions such as the amount of acid catalyst, the condensation reaction temperature, and the condensation reaction time. It is also necessary to select the degree of condensation depending on the use; for example, when used as a dispersant for cement, a condensate in which 2 to 100 units of the disulfonated product used in the present invention are condensed is preferred.

The cation species of the disulfonated product and its condensate in the present invention are not particularly limited, but in order to maintain water solubility, hydrogen, alkali metals, alkaline earth metals, ammonium, and amines are preferred.

Examples of the alkali metals include sodium and potassium, and examples of amines include alkylamides such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, digtylamine, and trimethylamine; ethylenediamine, diethylenetriamine, and trimethylamine; Examples include polyamines such as ethylenetetramine; morpholine, piperidine, etc.; examples of alkaline earth metals include calcium, magnesium, zinc, etc. These cationic species can also be exchanged with other cationic species by various ion exchange techniques or neutralization reactions.

The condensate based on the above-mentioned disulfonated compound has an excellent surfactant effect, as will be understood from the explanation of the examples below, and is therefore extremely useful as a surfactant for organic or inorganic materials. For example, it can be widely used as an emulsifier, dispersant, wetting agent, detergent, and leveling agent. In particular, when used as a dispersant for seven-piece cement, it can significantly improve the dispersibility of cement in water. Therefore, it is possible to obtain the water reduction effect in the cement construction method.

Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples.

Example 1 Toluene 1270f9 and boron trisulfide.
After adding 20g of phenol complex and raising the temperature to 50℃,
5-vinylnorbornene-14001 without stirring! A mixed solution of 320 g of toluene and 320 g of toluene was added dropwise over about 1 hour, and the mixture was further reacted at this temperature for 2 hours. After the reaction was completed, the catalyst was decomposed with an aqueous sodium carbonate solution and washed with water, and then the oil layer was distilled under reduced pressure to obtain 279 g of a toluene adduct of 5-vinylnorbornene-1 (addition product).

Next, 100 g of the above-mentioned additive was added to a stainless steel autocraze with a capacity of 31, equipped with a stirring device and a temperature needle.
Sodium bisulfite so, oy, potassium nitrate 4.0
Ii, 700 ml of methyl alcohol and 20 ml of distilled water
1, add N, and mix under atmospheric stirring at a temperature of 1.
The reaction was carried out at 15°C for 5 hours. Thereafter, after cooling to room temperature, the reaction mixture was taken out, 50 mJ of distilled water and 1500 rrll of petroleum ether were added and thoroughly mixed, and the residue after removing the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to extract and remove the light yellow color. After drying the remaining liquid, add 300 nl of glacial acetic acid.
The acetic acid insoluble portion consisting of inorganic salts was separated. By concentrating the obtained acetic acid soluble content, the sodium salt of the sulfonate of the white-yellow toluene adduct (sulfonate A
) was obtained.

Example 2 Diethyltoluene 140 (Nil) and 23 g of boron trifluoride/phenol complex were placed in a three-necked flask with a capacity of 3 and equipped with a reflux condenser and a stirring device, and the temperature was raised to 55°C, followed by stirring. A mixed solution of 400y of 5-ethylidenenorbornene and 3209% of diethyltoluene was added dropwise over about 1 hour, and the reaction was further continued at this temperature for 2 hours.

After the reaction is complete, decompose the catalyst with an aqueous sodium carbonate solution.
61! Obtained.

Next, equipped with a stirring device and a thermometer, the capacity of 31 sodium hydrogen oxide 50 g, potassium nitrate s, og, isopropyl alcohol 700 mA! and 200ml of distilled water,
N, 5 at a temperature of 120°C while mixing under strong stirring in an atmosphere.
The reaction was allowed to take place over a period of time. Then, after cooling to room temperature, the reaction mixture was taken out and distilled water (50ml) was added! and petroleum ether 150
0 mIJ was added and thoroughly mixed, and the residue except for the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to obtain pale yellow powder 1011. This powder was extracted with petroleum ether for 1 hour using a Soxt extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 300 m/ml of glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated by P. By concentrating the obtained acetic acid soluble content, 87 g of a white-yellow solid sodium salt of the sulfonate (sulfonate B) was obtained.

Example 3 100 OF benzene and 8 g of boron trifluoride/phenol complex were placed in a three-bottle flask with a capacity of 3 and equipped with a reflux condenser and a stirring device, and the temperature was raised to 48°C. A mixed solution of 400 g of propenylnorbornene and 320 g of benzene was added dropwise over about 1 hour, and the mixture was further reacted at this temperature for 2 hours. After the reaction was completed, the catalyst was decomposed with an aqueous sodium carbonate solution and washed with water, and the outside of the oil layer was distilled under reduced pressure to obtain 3361 benzene adducts of 5-isopropenylnorbornene (adduct C).

Next, 100 g of the above-mentioned benzene adduct of 5-isopropenylnorbornene and 70.0 I! of sodium bisulfite were placed in a stainless steel autoclave with a capacity of 31, equipped with a stirring device and a thermometer. , potassium nitrate, 800 mJ of isopropyl alcohol, and 300 mAt of distilled water were added, and the mixture was heated to a temperature of 10°C while stirring under strong stirring in a cold atmosphere.
The reaction was carried out at 5°C for 5 hours. Thereafter, after cooling to room temperature, the reaction mixture was taken out, 50 ml of distilled water and 1,500 ml of petroleum ether were added and thoroughly mixed, and the residue after removing the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to give a pale yellow powder. 78g was obtained. Socks this powder.
Unreacted substances were removed by extraction with petroleum ether using an extractor for 1 hour, and the residual liquid was dried and dissolved in 300 ml of glacial acetic acid to remove acetic acid-insoluble components consisting of inorganic salts. A white-yellow solid 69II was obtained by concentrating the obtained acetic acid soluble portion. This solid was purified by ethanol extraction to obtain the sodium salt of the sulfonated benzene adduct of 5-isopropenylnorbornene (sulfonated product C).

Example 4 1270 g of xylene and boron trisulfide/phenol complex 2011 were placed in a three-necked flask with a capacity of 31 and equipped with a reflux condenser and a stirring device, and the temperature was raised to 57°C.
While stirring, 4-ethyl-5-vinylnorbornene 46
A mixed solution of 0 g and 320 g of xylene was added dropwise over about 1 hour, and the reaction was further continued at this temperature for 2 hours.

After the reaction, the catalyst was decomposed with an aqueous sodium carbonate solution and washed with water, and the oil layer was distilled under reduced pressure to obtain 4-ethyl-5-
xylene adduct of vinylnorbornene (adduct D)
43g was obtained.

Next, 100 g of the above adduct was placed in a stainless steel autoclave with a capacity of 31, equipped with a stirrer and a thermometer.
Sodium bisulfite 60.0g, potassium nitrate s, o
I! , ethanol so Oml and distilled water 200ml
Enter, N! Temperature 11 while mixing under strong stirring under atmosphere.
The reaction was carried out at 0°C for 5 hours. After cooling to room temperature, the reaction mixture was taken out and distilled water was added at 50 mA. and 150 Oml of petroleum ether were added and thoroughly mixed, and the residue except for the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to obtain 76 g of pale yellow powder. This powder was extracted with petroleum ether for 1 hour using a Soxtet extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 300 m/ml of glacial acetic acid to remove acetic acid-insoluble components consisting of inorganic salts. By concentrating the obtained acetic acid soluble portion, 711 g of a white-yellow solid was obtained.

This solid was then purified by ethanol extraction to obtain the sodium salt of the sulfonate adduct (sulfonate D).
I got it.

Examples 5-8 30 mmol of the sulfonated products of Examples 1-4 in a 0.21-capacity three-necked flask equipped with a stirrer and a thermometer,
30 mmol of formaldehyde, 30 mmol of sulfuric acid, and 270 mmol of distilled water were charged, and a condensation reaction was carried out at a temperature of 80° C. for 24 hours. Distilled water 100% to the obtained reaction product
After adding g, calcium carbonate was added with stirring until the pH reached 7, and then the resulting mixture was filtered to obtain an r solution. Sodium carbonate was added to this P solution with stirring until the pH reached 9, and then filtered to obtain a F solution. This R liquid was dried to obtain a brown powder in the amount shown in Table 1.

The molecular weights of these condensates were measured by aqueous GPC (gel permeation chromatography) and the results are shown in Table 1. In addition, the number average molecular weight in this specification is
It is calculated from a calibration curve created using several types of sodium polystyrene sulfonate, sodium anthracene sulfonate, and sodium benzene sulfonate with different molecular weights as standard substances.

In addition, as a result of infrared analysis, the above-mentioned sulfonated compound A (in the formula m
represents an integer greater than or equal to 1. ) Table-1 Examples 9 to 12 Sulfonated compound A and the compound shown in Table-2 were each added to 15 mm
Condensation was carried out in the same manner as in Example 5. The results are shown in Table-2.

Table 2 Example 13 Four aqueous solutions of the condensates according to the present invention obtained in each of Examples 5 to 12 above were prepared, and their surface tensions at a temperature of 25°C were measured. The results are shown in Table 3.

As understood from this result, the condensate according to the present invention is
It foamed well and had an excellent surfactant effect.

In addition, 2 g of the condensate according to the present invention obtained in Examples 5 to 12 and 50 g of distilled water were added to commercially available cement "Portland Cement" (manufactured by Chichibu Cement ■) 20019, and after hand kneading for 3 minutes, the flow value (content 70- with a product of 98.9cc
Table 3 shows the results of the measurements (measured using a cone according to JIS R5201). On the other hand, when the flow value was measured after kneading by hand in the same manner except that the condensate according to the present invention was not added, a flow of only 87 m111 was obtained. This result shows that the condensate according to the present invention has a very large and excellent dispersion effect of cement in water.

Table 3 Examples 14 to 18 Component A in Table 4 and 12 g of boron trifluoride/phenol complex were placed in a three-bottle flask with a capacity of 3 and equipped with a reflux condenser and a stirring device, and the temperature was raised to 50°C. Thereafter, component B shown in Table 4 was added dropwise to the mixture over about 1 hour while stirring, and the reaction was further continued at this temperature for 2 hours. After the reaction was completed, the catalyst was decomposed with an aqueous sodium carbonate solution and washed with water, and then the oil layer valve was distilled under reduced pressure to obtain a component A adduct (C) of component B.

Next, the above adduct (c) soll was placed in a stainless steel autoclave with a capacity of 11 equipped with a stirring device and a thermometer.
, Sodium Bisulfite 3011 Potassium Nitrate 3.0#
, 200ml of isopropyl alcohol and 70ml of distilled water
j, and the internal pressure in the autoclave at room temperature is 1. (1/
After supplying air to cII (gauge pressure), the pulp was sealed and reacted at a temperature of 120° C. for 5 hours while mixing under strong stirring. Then, after cooling to room temperature, the reaction mixture was taken out and distilled water was added at 20 mA! and petroleum ether 5
After removing the separated petroleum ether layer and precipitate, the residue was concentrated and evaporated to dryness to obtain a pale yellow powder. This powder was extracted with petroleum ether for 1 hour using a Sox L-extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 300 mj of glacial acetic acid, and the acetic acid-insoluble components consisting of inorganic salts were separated. A white-yellow solid (D) was obtained by concentrating the obtained acetic acid soluble portion. This solid was purified by ethanol extraction to obtain the sodium salt of the sulfonated adduct of component A to component B.

The results are shown in Table 4.

Table 4 Examples 19 to 23 Using the sulfonated products obtained in Examples 1◆ to 18, the following condensation reactions were carried out.

In a three-neck flask with a capacity of 0.21 and equipped with a stirrer and a thermometer, 30 mmol of the above sodium salt, 30 mmol of formaldehyde, 30 mmol of sulfuric acid and 2 ml of distilled water were added.
70 mmol was charged and a condensation reaction was carried out at a temperature of 80° C. for 24 hours. After adding 100.9 g of distilled water to the obtained reaction product, calcium carbonate was added with stirring until the pH reached 7, and then the obtained mixture was filtered to obtain liquid f. Sodium carbonate was added to this r-liquid while stirring until the pH reached 9, and then filtered to obtain an r-liquid. This r liquid was dried to obtain a brown powder in the amount shown in Table 5.

Table 5 shows the results of measuring the molecular weight by aqueous GPC (Gel Permeation System). Note that the number average molecular weight in this specification refers to several types of sodium polystyrene sulfonate and Ant 2 with different molecular weights.
It is calculated from a calibration curve created using sodium sensulfonate and sodium benzenesulfonate as standard substances.

Table 5 Examples 24 to 27 15 mmol of each of the sulfonated product obtained in Example 14 and the compounds shown in Table 6 were charged and condensed using the same recipe as in Example 19. The results are shown in Table 6.

Table 6 Example 28 Four aqueous solutions of the condensates according to the present invention obtained in each of Examples 19 to 27 above were prepared and heated at a temperature of 25°C.
The surface tension was measured. The results are shown in Table 7. As understood from the results, the condensate according to the present invention is
It foamed well and had an excellent surfactant effect.

In addition, 2I of the condensate according to the present invention obtained in Examples 19 to 27 and 50I of distilled water were added to commercially available cement "Portland Cement" (manufactured by Chichibu Cement ■) 201', and after hand kneading for 3 minutes, the value of 7o-value was (values measured according to JI8 IL5201 using a tube-cone with an internal volume of 98.9 cc), the flows shown in Table 7 were obtained. - When the flow value was measured after kneading by hand in the same manner except that the condensate invented by Rikiki was not added, the flow value was only 8711.
I only got 1+ and 70-. This result shows that the condensate according to the present invention has a very large and excellent dispersion effect of cement in water.

Table 7 Examples 29 to 32 Component A shown in Table 7 and 12 g of boron trifluoride/phenol complex were placed in a three-necked flask with a capacity of 31 mm and equipped with a reflux condenser and a stirring device, and the temperature was raised to 50°C. After heating, component B shown in Table 8 was added dropwise over about 1 hour while stirring, and the mixture was further reacted at this temperature for 2 hours. After the reaction is completed, the catalyst is separated with an aqueous IJ solution and washed with water, and the oil layer is distilled under reduced pressure to obtain an adduct Cg (shown in Table 8) in which component A is added to component B. Ta.

Next, in a stainless steel autoclave with a capacity of 11 and equipped with a stirring device and a thermometer, the above-mentioned adduct 5011, 309 sodium bisulfite, 3 g of potassium nitrate, 200 ml of isopropyl alcohol, and 70 mA of distilled water were added. Put it in,
The internal pressure in the autoclave at room temperature is 2. OKp/cffl
After air was supplied until the temperature reached 200° C., the valve was sealed and the reaction was carried out at a temperature of 120° C. for 5 hours while mixing under strong stirring.

After that, after cooling to room temperature, the reaction mixture was taken out and distilled water
0mA! and 500 mJ of petroleum ether were added and thoroughly mixed, and the residue except for the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to obtain a powder. This powder was extracted with petroleum ether for 1 hour using a Sox L-extractor to remove unreacted substances, and the remaining liquid was dried and then dissolved in 100 ml of glacial acetic acid to separate acetic acid-insoluble components consisting of inorganic salts. By concentrating the obtained soluble matter, a white-yellow solid Dg (shown in Table 8) was obtained. The solid was purified by ethanol extraction to obtain the sodium salt of a sulfonated adduct in which component A was added to component B.

Next, 60 mmol of the above sodium salt and g of sulfuric acid were placed in a 0.21-capacity three-necked flask equipped with a stirrer and a thermometer.
Q mmol was charged and reacted at 100°C for 3 hours. After that, 10 cc of n-hebutane was added, and 11
After reacting at 0°C for 2 hours, n-hebutane and water were azeotropically removed at 80°C under reduced pressure. Thereafter, the mixture was cooled to room temperature, 300 cc of water was added, and sulfuric acid was removed by precipitation with CaCO. The water-soluble content was dried to obtain a disulfonated compound Eg (shown in Table 8). The sulfonation rate of the thus obtained disulfonated product per mole of the skeleton in which component A was added to component B was measured by a conventional method. These results are summarized in Table 8.

Table 8 Examples 33-36 30 mmol of the disulfonated products of Examples 29-32, 30 mmol of formaldehyde, 30 mmol of sulfuric acid and 270 mmol of distilled water in a three-necked flask with a capacity of 0.27 and equipped with a stirrer and a thermometer. 2 at a temperature of 80℃.
The condensation reaction was carried out for 4 hours. After adding 100.9 g of distilled water to the obtained reaction product, calcium carbonate was added with stirring until the pH reached 7, and then the obtained mixture was filtered to obtain an R liquid. Sodium carbonate was added to this r-liquid with stirring until the pH reached 9, and the mixture was filtered to obtain an r-liquid.

This R liquid was dried to obtain a brown powder in the amount shown in Table 9.

The molecular weights of these condensates were measured by aqueous GPC (gel permeation chromatography) and the results are shown in Table 9. Note that the number average molecular weight in this specification refers to several types of polystyrene sulfonate soda with different molecular weights,
It is calculated from a calibration curve created using sodium ant-2sene sulfonate and sodium benzenesulfonate as standard substances.

Table 9 Examples 37 to 40 15 mmol each of the disulfonated product obtained in Example 29 and the compounds shown in Table 10 were charged and condensed using the same recipe as in Example 32. The results are shown in Table 10.

Table 1 10 Example 41 Four aqueous solutions of the condensates according to the present invention obtained in each of Examples 33 to 40 above were prepared and heated at a temperature of 25°C.
The surface tension was measured. The results are shown in Table 11.

As understood from this result, the condensate according to the present invention is
It foamed well and had an excellent surfactant effect.

In addition, 2 g of the condensate according to the present invention obtained in Examples 33-4° and 50 g of distilled water were added to 200 g of a commercially available cement "Portland Cement" (manufactured by Chichibu Cement ■), mixed by hand for 3 minutes, and the flow value ( 70- with an internal volume of 98.9cc
When the values measured according to JIS R5201 using a cone were determined, the flows shown in Table 11 were obtained.

- When the flow value was measured after kneading by hand in the same manner except that the condensate invented by Riki was not added, it was only 87111.
I could only get a flow of . This result shows that the condensate according to the present invention has a very large and excellent dispersion effect of cement in water.

Table 11 Examples 42 to 45 Component A shown in Table 12 and boron trifluoride/phenol complex 12F were placed in a three-bottle flask with a capacity of 3 and equipped with a reflux condenser and a stirring device, and the temperature was raised to 50°C. After warming, component B shown in Table 12 was added dropwise over about 1 hour while stirring, and the mixture was further reacted at this temperature for 2 hours. After the reaction is completed, the catalyst is decomposed with an aqueous sodium carbonate solution.
After washing with water, the oil layer was distilled under reduced pressure to obtain an adduct Cg (shown in Table 12) in which component A was added to component B.

Next, the above-mentioned adduct 5011, 30 g of hydrogen sulfite, 30 g of hydrogen sulfite, 3 g of potassium nitrate, 200 ml of isopropyl alcohol, and 70 ml of distilled water were placed in a stainless steel autoclave with a capacity of 11 and equipped with a stirring device and a thermometer, and the internal pressure in the autoclave was adjusted at room temperature. 2. OKt/
After supplying air until cd, the valve was sealed and the mixture was reacted at a temperature of 120° C. for 5 hours while mixing under strong stirring.

After that, after cooling to room temperature, the reaction mixture was taken out and distilled water
0 mJ and 500 ml of petroleum ether were added and thoroughly mixed, and the residue except for the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to obtain a powder. This powder was extracted with petroleum ether for 1 hour using a Sox L-extractor to remove unreacted substances, and the remaining liquid was dried, then dissolved in 100 mA' of glacial acetic acid, and the acetic acid-insoluble components consisting of inorganic salts were separated by P. By concentrating the obtained soluble matter, a white-yellow solid Dg (shown in Table 12) was obtained. The solid was purified by ethanol extraction to obtain the sodium salt of a sulfonated adduct in which component A was added to component B.

Next, a three-roar glass with a capacity of 0.21, equipped with a stirrer and a thermometer: rK 60 mmol of the above-mentioned sodium salt.

G Q mmol of sulfuric acid was charged and reacted at 100°C for 3 hours. After that, 10 cc of n-heptane was added and the reaction was carried out at 110°C for 2 hours, and then heated to 80°C under reduced pressure.
In , n-hebutane and water were azeotropically removed. Thereafter, the mixture was cooled to room temperature, 300 cc of water was added, and sulfuric acid was removed by precipitation with CaCO. The water-soluble content was dried to obtain a disulfonated compound Eg (shown in Table 12). The disulfonated product thus obtained was converted into component B by a conventional method.
The sulfonation rate per mole of the skeleton to which the component was added was measured.

These results are summarized in Table 12.

Table 12 Examples 46 to 49 Using the disulfonated products obtained in Examples 42 to 45, the following condensation reaction was carried out.

30 mmol of the above sodium salt, 30 mmol of formaldehyde, 30 mmol of sulfuric acid and 2 ml of distilled water were placed in a 0.2 mm three-necked flask equipped with a stirrer and a thermometer.
A condensation reaction was carried out at a temperature of 80° C. for 24 hours. After adding 100.9 g of distilled water to the obtained reaction product, calcium carbonate was added with stirring until the pH reached 7, and then the obtained mixture was filtered to obtain liquid f. Sodium carbonate was added to this r liquid with stirring until the pH reached 9, and then filtered to obtain f liquid. This R liquid was dried to obtain a brown powder in the amount (D) shown in Table 13.

In addition, the molecular weight was measured by aqueous GPC (gel permeation chromatography). Note that the number average molecular weight in this specification is calculated from a calibration curve prepared using several types of sodium polystyrene sulfonate, sodium anthracene sulfonate, and sodium benzene sulfonate having different molecular weights as standard substances.

Table 13 Examples 50 to 53 15 mmol each of the disulfonated product obtained in Example 42 and the compounds shown in Table 14 were charged and condensed in the same manner as in Example 46. The results are shown in Table 14.

Table 14 Example 54 Four aqueous solutions of the condensates according to the present invention obtained in each of Examples 46 to 53 above were prepared, and the temperature was 25°C.
The surface tension was measured. The results are shown in Table 15.

As understood from this result, the condensate according to the present invention is
It foamed well and had an excellent surfactant effect.

In addition, 2.9 g of the condensate according to the present invention obtained in Examples 46 to 53 and 50 g of distilled water were added to commercially available cement "Portland Cement" (manufactured by Chichibu Cement ■) 2001I.
After kneading by hand for a minute, the flow value (value measured according to JIS R5201 using a flow cone with an internal volume of 98.9 cc) was determined, and the flows shown in Table 15 were obtained. - When the flow value was measured after kneading by hand in the same manner except that the condensate invented by Shiki was not added, it was only 87.
Only a flow of 11 m+ was obtained. This result shows that the condensate according to the present invention has a very large and excellent dispersion effect of cement in water.

Table 15

Claims (1)

[Claims] 1) 9 to 120 carbon atoms containing two double bonds in the molecule
The general formula (I
) A method for producing a sulfonated product of a norbornene derivative or a cyclohexene derivative, which comprises sulfonating a reaction product obtained by adding a compound represented by the following formula. R1 2) Norbornene compounds with 9 to 12 carbon atoms containing two double bonds in the molecule or cyclohexene compounds with 8 to 12 carbon atoms containing two double bonds in the molecule (general 2〇)
1. A method for producing a disulfonated product of a norbornene derivative or a cyclohexene derivative, which comprises resulfonating a sulfonated product obtained by sulfonating a reaction product obtained by adding a compound represented by the formula. R3 3) 9 to 120 carbon atoms containing two double bonds in the molecule
General formula G) for norbornene compounds or cyclohexene compounds having 8 to 12 carbon atoms and containing two double bonds in the molecule.
A sulfonated product of a norbornene derivative and a low chlorohexene derivative obtained by sulfonating the reaction product obtained by adding a compound represented by the following. R1