JPH029582B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a condensate of a sulfonated cyclopentadiene derivative containing a cyclopentadiene skeleton, a benzene ring, and a sulfonic acid group. In general, organic compounds such as sulfonic acid and its derivatives are strong acids comparable to sulfuric acid, and are widely used industrially due to their properties. Moreover, since the salt is water-soluble, it is extremely important as a surfactant for organic or inorganic materials. However, most of the sulfonated compounds conventionally synthesized are aromatic or aliphatic sulfonated compounds, and few examples of sulfonated alicyclic compounds are known. As a result of intensive studies on sulfonated products using alicyclic compounds and derivatives thereof as starting materials, the present inventors have found that cyclopentadiene derivative sulfonated products having a specific structure can be condensed with aldehydes. The inventors have discovered that the resulting condensate has an extremely excellent surfactant effect on organic or inorganic materials, and have completed the present invention. That is, an object of the present invention is to provide a method for producing a condensate by condensing a sulfonated cyclopentadiene derivative represented by the following general formula. general formula (In the formula, R ₁ , R ₂ and R ₃ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₄ and R ₅ are the same or different groups, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. represents an atom or an alkyl group having 1 to 3 carbon atoms, n represents 1 or 2, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium or an amine. Explain. In the present invention, a sulfonated cyclopentadiene derivative represented by the above general formula is condensed to produce a condensate. In the present invention, the condensate refers to condensates obtained by condensing the same sulfonated cyclopentadiene derivatives represented by the general formula above, as well as different sulfonated cyclopentadiene derivatives represented by the general formula above. or a mixture of a sulfonated cyclopentadiene derivative represented by the above general formula and a condensation monomer other than the sulfonated cyclopentadiene derivative represented by the above general formula that can be condensed with the sulfonated cyclopentadiene derivative represented by the above general formula. It also represents the condensate obtained. In the general formula, n=1 when M is hydrogen, alkali metal, ammonium or amine, and n=2 when M is an alkaline earth metal. Examples of the alkali metals mentioned above include sodium and potassium; examples of amines include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, and tributylamine; ethylenediamine, diethylenetriamine; ,
Examples include polyamines such as triethylenetetramine; morpholine, piperidine, etc.; examples of alkaline earth metals include calcium, magnesium, zinc, etc. Further, these M can be mutually exchanged with other types of M by various ion exchange techniques or neutralization reactions. In the sulfonated cyclopentadiene derivative represented by the above general formula, preferred R ₁ , R ₂ and R ₃ are hydrogen, methyl group, propyl group and butyl group, and preferred R ₄ and R ₅ are hydrogen. be. Various manufacturing methods can be considered to produce the sulfonated cyclopentadiene derivative represented by the general formula, but for example, the compound of the following structural formula () is sulfonated, and then, if necessary, the compound is converted into a sulfonate. A sulfonated cyclopentadiene derivative represented by the general formula can be produced. Structural formula() (R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same as in the above general formula) Here, the sulfonation method includes the book "Sulfonation and Related Reaction" by EEGilbert. ”),
It is described in detail in Interscience Publishers Inc. (1965), and the sulfonation method applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, is selected appropriately depending on the state of the reaction system. be able to. Also Charles G. Norton.
J. Norton et al., The Journal of Organic Chemistry
The sulfonated cyclopentadiene derivative represented by the above general formula can also be obtained by the addition reaction of sulfites to an unsaturated bond, as shown in the study in J. Organic Chemistry, p. 4158 (1968). As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually used alone or in mixtures. In this sulfonation reaction, the use of a catalyst is not necessarily required, but the reaction time can usually be shortened by using a catalyst such as an inorganic oxidizing agent. Examples of inorganic oxidizing agents include nitrates, nitrites,
Examples include chlorates, but nitrates are particularly preferred. Furthermore, it is desirable to use an appropriate solvent to allow the reaction to proceed uniformly and smoothly. Solvents that can be advantageously used include, for example, water, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, and tertiary butyl alcohol, lower glycols, ketones, ethers, and esters. Examples include. Two or more of these solvents can be used in combination as appropriate.
Among these, mixed solvents of lower alcohols and water, especially mixed solvents of propyl alcohol and water, are recommended as excellent solvents. The reaction temperature is usually 50-200℃, preferably 70-150℃
C, more preferably 90 to 120 C, and can be carried out either at normal pressure or under increased pressure. In order to suppress the progress of side reactions and reduce the production of unnecessary inorganic salts, the pH of the reaction system is usually maintained at 2 to 9, preferably 5 to 7. The compound represented by the above structural formula () can be obtained, for example, by a Friedel-Crafts reaction between a compound represented by the following structural formula () and a compound represented by the following structural formula (). Structural formula() (R ₁ , R ₂ , and R ₃ are the same as in the general formula above) Structural formula () (R ₄ and R ₅ are the same as in the above general formula) Examples of the compound represented by the above structural formula ( ), ethylbenzene,
n-propylbenzene, iso-propylbenzene,
Methyl ethylbenzene (o-, m-, p-), 1,
2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, iso-propyltoluene (o-, m-, p
-), amylbenzene, hexylbenzene, amyltoluene (o-, m-, p-) and other mono-, di- or trialkyl-substituted benzenes. In this case, the alkyl group has 1 to 1 carbon atoms.
6, and tetralin, which is a compound in which two alkyl groups mutually form a ring, can also be used. Particularly preferred compounds represented by the structural formula () are those in which R ₃ is hydrogen, such as benzene, toluene, xylene, propylbenzene,
Butylbenzene is mentioned. Further, the compound represented by the above structural formula () is a dimer consisting of one or two types of cyclopentadiene, and examples of the cyclopentadiene include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, etc. Examples include alkylcyclopentadiene. Among these, dicyclopentadiene is preferred from the standpoint of availability and economy. Catalysts for synthesizing the compound represented by the structural formula () by Friedel-Crafts reaction between the compound represented by the structural formula () and the compound represented by the structural formula () include acidic compounds;
Examples include Lewis acids or organic protonates such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and complexes thereof, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, and titanium trichloride. The reaction can be carried out using known methods, such as JP-A-52-
133968, for example, in the presence of the above-mentioned catalyst, the compound represented by the structural formula () and the compound represented by the structural formula () are heated preferably at 0 to 100°C, particularly preferably at 20 to 70°C. It can be obtained by reacting for about 1 to 5 hours. Further, the compound represented by the above structural formula () can also be synthesized by a Friedel-Crafts reaction between a compound represented by the structural formula () and a compound represented by the following structural formula (). Structural formula() (R ₄ and R ₅ are X as in the general formula above
is a hydroxyl group or a halogen. ) Examples of the compound represented by the above structural formula () include hydroxy-dihydro-dicyclopentadiene, chloro-dihydro-dicyclopentadiene, and bromo-dihydro-dicyclopentadiene. The Friedel-Crafts reaction between the compound represented by the structural formula () and the compound represented by the structural formula () is similar to the Friedel-Crafts reaction between the compound represented by the structural formula () and the compound represented by the structural formula (). It can be carried out using a catalyst, a similar reaction temperature, and a similar reaction time. Since the compound represented by the above structural formula () has a halogen atom that is active in Friedel-Crafts reaction,
By performing a Friedel-Crafts reaction using this, a compound represented by the structural formula () can be obtained with high selectivity. The cyclopentadiene derivative sulfonated product represented by the above general formula is generally a white to slightly yellow solid, but the starting material structural formula ()
It can vary depending on the type of the compound represented by the formula (), the compound represented by the structural formula (), and the compound represented by the structural formula (), as well as the combination thereof. A sulfonated cyclopentadiene derivative represented by the above general formula obtained by the method described above, or a cyclopentadiene derivative represented by the above general formula that can be condensed with the sulfonated cyclopentadiene derivative represented by the above general formula. Mixtures with condensation monomers other than sulfonated products (hereinafter referred to as "condensation compositions")
The invention is carried out by condensing, for example with an aldehyde, in the presence of an acid catalyst. The sulfonated cyclopentadiene derivatives represented by the above general formula may be the same, or several different sulfonated products may be used in combination as long as they fall within the range represented by the above general formula. 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, but in order to achieve a high degree of condensation and avoid unnecessary side reactions,
The number of moles is preferably 0.5 to 2 times the total number of moles of the condensation composition, and more preferably 0.8
~1.5 times the number of moles. 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 to 3 times the number of moles. This is 0.0001
If it is less than twice the number of moles, the reaction rate will be low and the degree of condensation will be low, while if it exceeds ten times the number of moles, carbonization reaction will easily occur. In addition, when the condensation composition contains a sulfonated cyclopentadiene derivative in which M is a hydrogen atom in the general formula, the sulfonated cyclopentadiene derivative itself becomes an acid, which also acts as an acid catalyst. Therefore, 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, when carrying out the present invention using a condensation composition consisting only of the sulfonated cyclopentadiene derivative represented by the above general formula, and when water is used as the solvent, the amount used is The number of moles is 2 to 100 times the total number of moles,
Preferably it is 5 to 20 times the molar number. Further, the condensation reaction temperature is 30 to 150°C, preferably 70 to 120°C. Condensation monomers other than the sulfonated cyclopentadiene derivative represented by the above general formula include:
Examples include benzene derivatives such as benzene, toluene, xylene, and phenol; sulfonic acids or salts thereof of benzene derivatives; naphthalene derivatives; sulfonic acids or salts thereof of naphthalene derivatives such as sodium β-naphthalenesulfonate; It is not limited to these. 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 resulting condensate. 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 sulfonated cyclopentadiene derivative represented by the above general formula in the condensation composition. The content ratio is preferably 20 mol% or more, more preferably 50 mol%
This is within the above range. 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 application. For example, when used as a dispersant for cement, a condensate in which 2 to 100 units of a sulfonated cyclopentadiene derivative represented by the above general formula is condensed is used. is preferred. The condensate obtained by the method of the present invention 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. It is useful and can be widely used, for example, as an emulsifier, a dispersant, a wetting agent, a cleaning agent, and a leveling agent. In particular, when used as a dispersant for 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 Capacity 3 comprising reflux condenser and stirring device
Put 1270 g of toluene and 12 g of boron trifluoride/phenol complex into a three-necked flask, raise the temperature to 50°C, and add dicyclopentadiene while stirring.
A mixed solution of 417 g and 320 g of toluene was added dropwise over about 1 hour, and the reaction was further continued at this temperature for 2 hours. After the reaction is complete, the catalyst is decomposed with an aqueous sodium carbonate solution and washed with water, and the oil layer is distilled under reduced pressure to obtain the toluene adduct of dicyclopentadiene.
Obtained 423g. Next, capacity 3 is equipped with a stirring device and a thermometer.
200 g of the toluene adduct of dicyclopentadiene mentioned above, 97.8 g of sodium bisulfite, 8.0 g of potassium nitrate, 1360 ml of isopropyl alcohol, and 200 ml of distilled water were placed in a stainless steel autoclave, and the internal pressure in the autoclave was adjusted to 1.0 kg/kg at room temperature.
After supplying air until the pressure reaches cm ² (gauge pressure), close the valve and adjust the temperature while mixing under vigorous stirring.
The reaction was carried out at 110°C for 5 hours. Then, 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 mixed thoroughly. After removing the separated petroleum ether layer and precipitate, the remainder was concentrated and evaporated to dryness to give 139 g of pale yellow powder. was gotten.
This powder was extracted with petroleum ether for 1 hour using a Soxhlet extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 300 ml of glacial acetic acid to separate the acetic acid-insoluble components consisting of inorganic salts. By concentrating the obtained acetic acid soluble portion, 129 g of a white-yellow solid was obtained. This solid was purified by ethanol extraction to obtain the sodium salt of the sulfonated toluene adduct of dicyclopentadiene. Capacity 0.2, then equipped with a stirring device and a thermometer
30 mmol of the above sodium salt, 30 mmol of formaldehyde, 30 mmol of sulfuric acid, and 270 mmol of distilled water were placed in a three-necked flask, and the temperature was 80°C.
The condensation reaction was carried out for 24 hours. After adding 100 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 a liquid. Sodium carbonate was added to this solution with stirring until the pH reached 9, and then filtered to obtain a solution. Dry this liquid
11.2 g of brown powder was obtained. The infrared absorption spectrum of this brown powder is shown in FIG. This shows that the scissor vibration absorption (1450 cm ^-1 ) of the condensed methylene group is extremely strong. Further, when the molecular weight was measured by aqueous GPC (gel permeation chromatography), the number average molecular weight was 4,900. 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. Furthermore, quantitative analysis of the elements was conducted to examine its composition, and the composition was found to be 61.5% carbon atoms, 6.8% hydrogen atoms, and 10.1% sulfur atoms. From these results, it was confirmed that the brown powder described above was a condensate represented by the following structural formula. (In the formula, m represents an integer of 1 or more.) The composition of this structural formula is, when m = 14, carbon atoms account for 61.0%, hydrogen atoms account for 7.1%, and sulfur atoms account for 9.9%.
%, which agrees extremely well with the above-mentioned measured value. Example 2 In Example 1, xylene was used instead of toluene.
Using 1060g, this and 350g of dicyclopentadiene
g was reacted in the same manner as in Example 1 to obtain 340 g of a xylene adduct of dicyclopentadiene. 124 g of the sodium salt of the sulfonated xylene adduct of dicyclopentadiene was obtained in the same manner as in Example 1, except that 200 g of this xylene adduct was used. Next, using this sodium salt, a condensation reaction was carried out in the same manner as in Example 1 to obtain 10.3 g of brown powder.
In addition, when the molecular weight was measured by aqueous GPC,
The number average molecular weight was 5,400. Further quantitative analysis of the elements revealed that 63.0% were carbon atoms, 7.5% hydrogen atoms, and 9.4% sulfur atoms.
It was hot. From these results, it was confirmed that the above-mentioned brown powder was a condensate having a structure in which xylene was substituted for toluene in the structural formula shown in Example 1. The composition of this structural formula is, when m = 15, carbon atoms account for 62.1%, hydrogen atoms account for 7.4%, and sulfur atoms account for 9.5%.
%, which agrees extremely well with the above-mentioned measured value. Example 3 Benzene instead of toluene in Example 1
Using 1950g, this and dicyclopentadiene 630
g was reacted in the same manner as in Example 1 to obtain 203 g of a benzene adduct of dicyclopentadiene. 122 g of the sodium salt of the sulfonated benzene adduct of dicyclopentadiene was obtained in the same manner as in Example 1, except that 200 g of this benzene adduct was used. Next, using this sodium salt, a condensation reaction was carried out in the same manner as in Example 1 to obtain 10.1 g of brown powder.
In addition, when the molecular weight was measured by aqueous GPC,
The number average molecular weight was 3100. Furthermore, quantitative analysis of the elements was conducted to find out its composition, and it was found that 59.8% of carbon atoms, 6.8% of hydrogen atoms, and 10.6% of sulfur atoms.
It was hot. From these results, it was confirmed that the above-mentioned brown powder was a condensate having a structure in which benzene was substituted for toluene in the structural formula shown in Example 1. The composition of this structural formula is, when m = 9, carbon atoms account for 59.9%, hydrogen atoms account for 6.7%, and sulfur atoms account for 10.4%.
%, which agrees extremely well with the above-mentioned measured value. Example 4 A condensate according to the present invention was obtained in the same manner as in Example 1, except that 60 mmol of sulfuric acid was used. When the molecular weight of this condensate was measured by aqueous GPC,
The number average molecular weight is 18600, and its distribution is from 650 to
It ranged from 100,000. Example 5 1 g of the condensate obtained in Example 1 was added to distilled water.
The solution was dissolved in 30 g and brought into contact with 30 g of a strong acid type cationic ion exchange resin to obtain an acid type condensate in which 98% of the calculated amount was replaced with hydrogen atoms instead of sodium atoms. Example 6 An aqueous calcium hydroxide solution was added to the acid-type condensate obtained in Example 5 with stirring until the pH reached 7 to obtain a calcium salt-type condensate in which calcium atoms were substituted for hydrogen atoms. Obtained. Example 7 28.5 mmol of the sodium salt of the sulfonated toluene adduct of dicyclopentadiene obtained in Example 1, 1.5 mmol of phenol, 30 mmol of formaldehyde, 30 mmol of sulfuric acid, and 270 mmol of distilled water were prepared in the same manner as in Example 1. A condensation reaction was carried out to obtain 9.6 g of brown powder. Also water system
When the molecular weight was measured by GPC, the number average molecular weight was 5,800. Furthermore, quantitative analysis of the elements was conducted to examine the composition, and the results matched the calculated values within a 2% error range. Example 8 7.5 mmol of the sodium salt of the sulfonated toluene adduct of dicyclopentadiene obtained in Example 1, 22.5 mmol of toluene, 30 mmol of formaldehyde, 30 mmol of sulfuric acid, and 270 mmol of distilled water were prepared in the same manner as in Example 1. A condensation reaction was carried out to obtain 4.5 g of yellowish white powder. Also water-based GPC
When the molecular weight was measured, the number average molecular weight was
It was 4200. Furthermore, quantitative analysis of the elements was conducted to examine the composition, and the results matched the calculated values within a 4% error range. Example 9 20 mmol of sodium salt of the sulfonated toluene adduct of dicyclopentadiene obtained in Example 1, 10 mmol of sodium β-naphthalene sulfonate, 30 mmol of formaldehyde,
30 mmol of sulfuric acid and 270 mmol of distilled water were subjected to a condensation reaction in the same manner as in Example 1 to obtain 12.8 g of brown powder. Further, when the molecular weight was measured by aqueous GPC, the number average molecular weight was 4,300. Furthermore, quantitative analysis of the elements was conducted to examine the composition, and the results matched the calculated values within a 4% error range. Example 10 4% aqueous solutions of the condensates obtained in each of Examples 1 to 9 above were prepared and their surface tensions were measured at a temperature of 25°C. The results are shown in Table 1.

[Table] As can be seen from the results, the condensate obtained according to the present invention foamed well and had excellent surfactant action. In addition, 2 g of the condensate obtained in Example 1 and 50 g of distilled water were added to 200 g of the commercially available cement "Portland Cement" (manufactured by Chichibu Cement Co., Ltd.), mixed by hand for 3 minutes, and the flow value (inner volume: 98.9 cc) was mixed by hand for 3 minutes. A flow of 150 mm was obtained when the flow cone was measured 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 was not added, a flow of only 87 mm was obtained. This result shows that the condensate has a very large and excellent dispersion effect of cement in water.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of the condensate obtained in Example 1.

Claims (1)

[Scope of Claims] 1. A method for producing a condensate, which comprises condensing a sulfonated cyclopentadiene derivative represented by the following general formula. general formula (In the formula, R ₁ , R ₂ and R ₃ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₄ and R ₅ are the same or different groups and represent a hydrogen atom. or represents an alkyl group having 1 to 3 carbon atoms, n represents 1 or 2, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium or an amine.)