JPS59137455A - Sulfonated hydroxydicyclopentadiene - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (M is H, alkali metal, alkaline earth metal, ammonium or amine; n is 1 or 2). USE:Useful as a surfactant, e.g. an emulsifying agent, dispersing agent, wetting agent, detergent or smoothing agent and a synthetic intermediate therefor and further a synthetic intermediate for dyes, cement admixtures. PROCESS:A hydroxydicyclopentadiene of formula II is sulfonated with a sulfonating agent, e.g. an acid sulfite, metasulfite or sulfite of an alkali metal, and if necessary converted into a sulfonate to give the aimed compound of formula I . The reaction carried out in the presence of an inorganic oxidizing agent, e.g. a nitrate, is effective for improving the yield and reducing the reaction time. The amount of the sulfonating agent to be used is 0.5mol or more based on one mol compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has a cyclopentadiene skeleton and a hydroxyl group in the molecule.
This invention relates to a novel sulfonated product of hydroxydicyclopentadiene containing a sulfonic acid group.

In general, 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. It is very important as such. However, most of the conventionally synthesized sulfonated compounds are aromatic, aliphatic, etc. sulfonated compounds, and there are almost no examples of sulfonated alicyclic compounds.

As a result of extensive research into the synthesis and properties of sulfonated products using alicyclic compounds as starting materials, the present inventors discovered that a compound represented by the following general formula (I) could be synthesized, and this compound The present invention was achieved based on the recognition that this substance is extremely useful as an activator or an intermediate thereof.

That is, 5 the present invention is based on the general formula (I) (wherein M is hydrogen, an alkali metal, an alkaline earth metal,
ammonium or amine, n is an integer of 1 or 2; ) A novel sulfonated product of hydroxydicyclopentadiene is provided.

In the compound of general formula (1) above, when M is usually hydrogen, alkali metal, ammonium or amine, n =
1, and when M is an alkaline earth metal ('1bn=2
It is.

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

Note that these M's can be interchanged with M's of other species by various ion exchange techniques.

When M is an alkali metal and Na is used as M, the above h[i general formula (I) is as follows. When the dimension M is an alkaline earth metal, C as M
When a is used, the above general formula becomes.

In order to produce the compound of the general formula (I) of the present invention, various production methods can be considered. For example, sulfonation of hydroxydicyclopentadiene shown in the following general formula (■),
Thereafter, it can be produced by a method of converting it into a sulfonate, if necessary.

The sulfonation reaction applied to unsaturated compounds, unsaturated aliphatic or unsaturated alicyclic compounds is
-E-Gilbert) (D Book "Sulfonation and Related Reactions J")
Related Reaction”),■nte
rscience public-shers Inc.
(1965), and Charles J. Twoton ((:balrs・J-No.
rton) et al., The Journal of Organic
Chemistry (The Journal of Or-
ganic chemistry) 4158 pages (1
Sulfonation can also be achieved by the addition reaction of sulfites to unsaturated bonds, as shown in the work of 1996).

However, no example of sulfonation of a monocyclopentene moiety such as hydroxydicyclopentadiene has been shown.

As a result of extensive research in order to obtain a sulfonated compound having a hydroxyl group, the present inventors have discovered that the compound of general formula (I) can be obtained by adding a sulfite to the cyclopentene double bond of hydroxydicyclopentadiene. succeeded in obtaining it.

As the sulfonating agent in this case, acidic sulfites, metasulfites or sulfites of alkali metals are usually used alone or in mixtures.

The type of sulfonating agent is not particularly limited, but
-C is used in a molar ratio of, for example, 2.0 per mole of hydroxydicyclopentadiene. If the molar ratio is less than 0.1, the reaction yield will be low, so it is usually preferable to use a molar ratio of 0.05 or more.

The sulfonation reaction does not necessarily require the use of a catalyst, but it is usually possible to use a catalyst such as an inorganic oxidizing agent.
It has effects such as improving yield and shortening reaction time.

Examples of inorganic oxidizing agents 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 per mole of hydroxydicyclopentadiene.
．． A molar ratio of 15, preferably 0.05 to 0.1 is effective.

Furthermore, it is desirable to use an appropriate solvent in order to allow the reaction to proceed uniformly and smoothly. Solvents which can be advantageously used are, for example, water or methyl alcohol, ethyl alcohol, flovir alcohol, inflovir alcohol, butyl alcohol. 39th butyl alcohol, lower alcohols, lower glycols, ketones, ethers, esters, etc.

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

The reaction temperature is usually 50 to 200 tll', preferably 70
It is carried out at ~150C, more preferably at 90-12OC, and can be carried out either at normal pressure or under elevated pressure.

In order to suppress the progress of side reactions and to reduce the formation of inorganic salts, it is desirable to maintain the pH of the reaction system generally between 2 and 9, preferably between 5 and 7.

The compound of general formula (I) is generally a white to slightly yellow solid, and depending on the application, the types of M can be exchanged with each other by various ion exchange techniques.

The sulfonated product of hydroxydicyclopentadiene of the present invention is useful as a synthetic intermediate for dyes, admixtures for cement, etc., and the sulfonated product of hydroxydicyclopentadiene of the present invention can be polymerized with a strong acid such as sulfuric acid. The compound obtained can be used as a cement admixture with a water-reducing effect.

Moreover, the hydroxydicyclopentadiene sulfonate salt of the present invention can be used as a surfactant, such as an emulsifier, a dispersant, a wetting agent, a detergent, a leveling agent, etc. in its t-t.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 A 3.0 mm stainless steel autoclave equipped with a sealed electromagnetic induction stirring device was used as a reaction vessel. To this were added 2,000 g of hydroxydicyclopentadiene, 2,000 g of sodium bisulfite, 2,009 g of potassium nitrate, 8,000 g of isopropyl alcohol, and 2,000 rnl of distilled water.

Next, the entire system was purged with nitrogen, sealed, and reacted at 110C for 6 hours while mixing with strong stirring. After cooling to room temperature, the inorganic salts precipitated from the reaction mixture were removed by suction filtration, and the filtrate was concentrated under reduced pressure to a volume of about 4 mm.

Add 20 g of distilled water and 5 g of petroleum ether to this,
After thorough mixing and separation, unreacted hydroxydicyclopentadiene was extracted into the petroleum ether layer and removed.

The remaining aqueous layer was concentrated to dryness under reduced pressure to give a white yellow solid 260
I got 09. This solid was mixed with 4 glacial acetic acid and OJl, and N
Acetic acid-insoluble components consisting of inorganic salts such as aH803 and Na2SO3 were separated and removed using a centrifuge.

The acetic acid soluble portion was concentrated to dryness under reduced pressure to obtain 23009 as a pale yellow solid. This pale yellow solid was extracted with 99.5% pure ethanol for 1 hour to remove residual acetic acid using a Soxhlet extractor, and then dried. Elemental analysis of this shows that C = 47.9%, H = 6.2chi, 5 = 12.9chi (calculated value from the molecular formula C: 47.2%%H: 51chi, S
:12.6%). Further, this solid was acidified in distilled water, Na ions were removed using a cation exchange resin, and the amount of the added sulfonic acid was determined in a koji room, and the value was 93% of the calculated value.

In addition, when the infrared absorption spectrum of this product was measured using the KBr tablet method, there was an absorption based on a hydroxyl group at b 3440r:m-'', and an absorption at <750cm'' and The absorption at 1390 cm decreased, and in its place strong absorption based on sulfone groups was observed and measured at 1190 cm and 1, Q50 cm, confirming that the cyclopentene ring double bond was sulfonated. (See drawing).

As a result of the above analysis, it was confirmed that the product was a compound having the following structural formula (A).

When the surface tension of a 4% by weight aqueous solution of this product was measured at a temperature of 25°C, it was found to be 4 odynes/cm, indicating that it has high surface activity.

The above compound (A) was dissolved in distilled water, Na ions were removed using a cation exchange resin, and then concentrated to dryness to obtain the solid sulfonic acid of the above compound (A).

The i30 vessel was then equipped with a reflux condenser and a stirring device.
In a 0ml Mitsuroh flask, add 309% of the above compound (A) sodium sulfonate. Panic acid 579 with a purity of 97% was charged, and a polymerization reaction was carried out at a reaction temperature of 130 C for 20 hours under stirring.

After the reaction was completed, sulfuric acid was removed by liming and sorption to obtain Na salt 319 of the polymer.

When the Na salt of the conopolymer was analyzed by gel permeation chromatography, a chromatograph with a main peak at a molecular weight of 4000 was obtained. Dissolve the Na salt of this polymer in distilled water and use a cation exchange resin to
When the amount of sulfonic acid in the product from which the a ions were removed was determined by titration, it was found that it had 88% sulfonic acid groups per mole of hydroxydicyclopentadiene.

The surface tension of a 4% by weight aqueous solution of the Na salt of this polymer at 25r was measured to be 68 dyn/cm.

Next, 200 μl of Portland cement manufactured by Chichibu Cement Co., Ltd. was added to a solution of 29% Na salt of this polymer dissolved in 509 μm of distilled water and kneaded for 3 minutes.
A flow cone with a height of 35 cm and an internal volume of 98.8 cm3 was prepared, and a flow test was conducted according to the physical test method for cement of JIS R5201, and the flow value was measured to be 160 cm.

Also, the raw specific gravity of the cement paste at this time was 2,1797.
It was cm3.

On the other hand, when no Na salt is added to this polymer, the no flow value is 1.
d, 87 mm and the raw specific gravity of the cement paste is 2.
It was 2497 cm3.

From this, it can be seen that when the polymerized product of sulfonated hydroxydicyclopentadiene of the present invention is used as a dispersant for cement, the dispersion effect of cement in water is extremely excellent.

[Brief explanation of the drawing]

1 is a diagram showing an infrared absorption spectrum of the hydroxydicyclopentadiene sulfonate obtained in Example 1. FIG. (Cm-1)

Claims (1)

[Claims] General formula (I) (in the formula, 1M is hydrogen, an alkali metal, an alkaline earth metal,
ammonium or amine, n is an integer of 1 or 2; ) A sulfonated product of hydroxydicyclopentadiene.