JPS5962562A - Sulfonated dicyclopentadiene - Google Patents

Abstract

NEW MATERIAL:The sulfonated dicyclopentadiene of formula I (M is H, alkali metal, alkaline earth metal, ammonium or amine; n is 1 or 2). USE:Synthetic intermediate of dyes, cement additives, etc., a surface active agent, etc. PROCESS:The compound of formula I can be prepared by sulfonating dicyclopentadiene of formula II, and if necessary, converting to sulfonic acid salt. The sulfonating agent used in the sulfonation reaction is usually an alkali metal bisulfite, metasulfite or sulfite, or their mixture. There is no particular restriction in the amount of the agent; however, the molar ratio of the agent to the compound of formula II is 0.1-2.0, preferably 0.5-1.2, especially 0.5-1.0.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel sulfonated dicyclopentadiene containing a cyclopentadiene skeleton and a sulfonic acid group in the molecule.

In general, sulfonic acids and many of their derivatives are strong acids comparable to mineral acids, and their salts are water bathable and can impart unique properties to organic and inorganic materials, and are also useful as synthetic intermediates for organic compounds. This is very important. However, conventionally,
Most of the synthesized sulfonated compounds are aromatic and aliphatic sulfonated compounds, and there are almost no examples of sulfonated compounds of alicyclic compounds.

The present inventors have conducted extensive research into the synthesis and properties of sulfonated products using alicyclic compounds as starting materials, and have discovered that a compound represented by the following general formula (1) can be synthesized. The present invention was achieved based on the recognition that C is an extremely useful substance as a surfactant or its intermediate.

That is, the present invention is based on the general formula (1) (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 dicyclopentadiene represented by σ is provided.

In the compound of general formula (1) above, M is usually hydrogen, alkali metal, ammonium or amine.
-1, and when M is an alkaline earth metal, it is 11-2.

) - The alkali metals include sodium, potassium, etc., and the amine includes methylamine.

Alkylamines such as triethylamine, ethylamine, globylamine, dimethylamine, diethylamine, trimedelamine, triethylamine, butylamine, dibutylamine, tributylamine, polyamines such as ethylenediamine, diethylenetriamine, morpholine, piperidine, etc., and alkaline earth metals such as calcium , Magnenoum, etc. can be exemplified. Moreover, these M can be mutually exchanged with other types of M by various ion exchange techniques.

When M is an alkali metal and Nη is used as M, the above general formula (1) fd, is obtained. In addition, when M is an alkaline earth metal, M is C
When a is used, the above general formula becomes.

Various manufacturing methods can be considered to produce a rod from the compound of general formula (I) of the present invention, but for example, the following general formula (II)
) by the method of sulfonating dicyclopentadiene and then converting it into a sulfonate as necessary to produce the general formula (
The compound of 1) can be produced.

Sulfonation reactions applicable to vesicular J11 compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, are described in the book by A. Gilbcrt [Sulfonation and Related Reactions J. (”5ulfnation
and Re1atedI also c;Iction”
), Intersciencecc l'ubl
ishers Inc.

(A detailed summary was given in 19 (i5), and also by Charles J.
Norton et al., The Jou
RNA of Organic Chemises
Sulfonation can also be carried out by the addition reaction of sulfites to unsaturated bonds, as shown in the study of Try )ll 1.58 (1968). However, one of them is preferential sulfonation of one of the two types of double bonds such as dicyc[J pentadiene].
"Does not show any signs.

The present inventors have conducted intensive research to obtain a sulfonated compound having a reactive double bond, and as a result, we have obtained a sulfonated compound with a double bond remaining in the synclopentadiene/clopentene ring.
By preferentially adding sulfites to the current double bond of norbornene, IJV succeeded in obtaining the compound of general formula (1).

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

4-'' of the sulfonating agent is not particularly limited, but is 0.1 to 2.0 per mole of cyfclopentadiene.
The molar ratio is preferably 0.5 to 1.2 molar ratio, more preferably 0.5 to 1.0 molar ratio.

If the molar ratio is less than 0.1, the reaction yield will be low, and if the molar ratio exceeds 20, compounds that also sulfonate the cyclopentene ring double bond will be produced in large quantities.

Although it is not always necessary to use a catalyst 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 inorganic oxidizing agents include nitrates, + nitrates, chlorates, etc., but nitrates are particularly effective; 0.02 to 0.1 per mole of
5 molar ratio, preferably 0.05 to 0.01 molar ratio is effective.

In order for the reaction to proceed uniformly and smoothly, it is desirable to use an appropriate solvent. Examples of solvents that can be used for the treatment include water, lower alcohols such as methyl alcohol, ethyl alcohol, flobyl alcohol, inopropyl alcohol, phthyl alcohol, and tertiary butyl alcohol, lower glycols, ketones,
Examples include ethers and esters.

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

The reaction temperature is usually 50-200°C, preferably 70-15°C.
0°C, more preferable 11. The process is carried out at 9°C 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, pi-1 of the reaction system is usually maintained at 2 to 9, b:f, -4 and 5 to 7.

The compound of general formula (1) is generally a white to slightly yellow solid, and depending on the use, the types of M can be exchanged with each other by ion exchange techniques such as fili.

The sulfonated dicyclopentadiene of the present invention is useful as a synthetic intermediate for dyes, admixtures for cement, etc., and can be obtained by combining the sulfonated 7-cyclopentadiene of the present invention with a strong acid such as sulfuric acid. The compound can be used as a cement mixer with a water-reducing effect. - The sulfonated dicyclopentadiene salts of the present invention can also be used as surfactants, such as emulsifiers, dispersants, wetting agents, and detergents.

It can be used as a smoothing agent.

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

[Example 1] A 30β stainless steel autoclave equipped with a sealed electromagnetic induction stirring device was used as a reaction vessel. This has a purity of 95
Dicyclopentadiene 20009, sodium bisulfite 1200f, potassium nitrate 122F, inopropyl alcohol 8000 ml, and distilled water 2000 ml were added.

Next, the entire system was purged with nitrogen, sealed, and reacted at 110° C. for 5 hours while mixing under strong stirring. After cooling to room temperature, inorganic salts precipitated from the reaction mixture were removed by suction and concentrated under reduced pressure to a concentration of about 4B. Add distilled water 2. Add 1.58 OC and petroleum ether;
After thorough mixing and separation, unreacted di/clopentadiene from the petroleum ether layer was extracted and removed.

The remaining aqueous layer was concentrated to dryness under reduced pressure, and the white-yellow insoluble matter was separated and removed using a centrifuge.

The acetic acid soluble portion was concentrated to dryness under reduced pressure [7 to obtain a pale yellow solid of 1480 f. The remaining acetic acid was removed from this pale yellow 1-year-old body using a Soxhlet extractor with 995% pure ethanol for 1 hour, and then it was dried. Elemental analysis of this shows that C = 50.4 coefficient, 14 = 5.3 coefficient, 5
= 14.0 coefficient (calculated value C: 508 2, H: 5.5 coefficient,
S: Section 13.6). Further, when this solid was dissolved in distilled water and cation exchanged (Na ions were removed using 91 fat) and the sulfonic acid meter was measured, it showed a value of 102% of the calculated value.

Well, when I measured the infrared absorption spectrum of this thing using the KBr tablet method, it was 750ff-1 and 1390cm.
There is an absorption based on the cyclopentene ring double bond in dicyclopentadiene, and the absorption of Absorption based on the sulfone group was observed, and it was confirmed that the norbornene 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 (5).

The surface tension of a 4% by weight aqueous solution of this product at a temperature of 5° C. was measured to be 40 dyn/c+n, indicating that it has high surface activity.

Compound (5) was dissolved in distilled water, Na ions were removed using a cation exchange resin, and the solution was concentrated to dryness to obtain a solid sulfonate compound (5). Next, 157% of the sulfoheptidic acid of the above compound (5) was added to a 300 d capacity three I" flask equipped with a rapid flow condenser and a stirring device. Charge 6.9 f of 97-purity sulfuric acid and raise the reaction temperature to 120 ml while stirring.
The polymerization reaction was carried out at ℃ for 5 hours.

After the reaction is completed, sulfuric acid is removed by liming and sodium chloride operations, and the Na salt of the polymer is 15. ! I got M'.

When the Na salt of this polymer was analyzed by gel Vermine Soyo 7 chromatography, the number average molecular weight was 10'0.
Obtain a graph with the main peak at the 00 position.

The Na salt of this polymer was dissolved in distilled water, and the Na ion was removed using a cation exchange resin.
The amount of acid was determined by titration and found that it had 96% sulfonate groups based on 71 moles of zinclopenotage.

The surface tension of a 4% by weight aqueous solution of the Na salt of this polymer at 5°C was measured to be 63 dyn/? ? It was m.

Next, 22 liters of Na salt of this polymer was dissolved in 50 liters of distilled water, and Portland cement/'l-20 manufactured by Chichibu Cement ■ was dissolved.
After adding 0f and kneading for 3 minutes, the inner diameter was 60 mm φ + iv
A flow test was conducted in accordance with JISR5201 physical test method for cement using a flow cone with a JFt of 98.8 cm, and the flow value was measured to be 190 mm. The raw specific gravity of the cement paste at this time was 2.23F/7. On the other hand, after kneading 50 tons of distilled water without adding Na salt and 20'Of this polymer for 3 minutes, the flow value was 87 balls, and the raw specific gravity of the cement paste was 2.24y/7.
Met.

From this, it can be seen that when the polymer of the sulfonated Di7 Clope/Taje/ 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]

The figure shows an infrared absorption spectrum of the zincclopenxyenosulfo/compound obtained in Example IK.

Claims (1)

[Claims] General formula (1) (In the formula, M is hydrogen, an alkali metal, or an alkaline earth metal. Amonium or amine, n is ■ or an integer of 2. ) A sulfonated product of dicyclopencdiene represented by