JPH029583B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a sulfonated product of a cyclopentadiene derivative. 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 discovered that specific cyclopentadienes and/or
Or, when dicyclopentadiene is reacted with a specific benzene derivative, a compound with a benzene derivative added to the skeleton of cyclopentadiene and/or dicyclopentadiene, a compound having a skeleton of cyclopentadiene and/or dicyclopentadiene, etc. A mixture of several types of reaction products such as coalescence is obtained, and since the sulfonated product or its salt of this mixture is water-soluble, it has an excellent surfactant effect on organic or inorganic substances, and is particularly effective in dispersing cement. They also found that the condensate obtained by condensing the sulfonated product of the above mixture or its salt with an aldehyde has an even better surfactant effect, particularly an excellent cement dispersion effect.The present invention has been achieved. It was completed. An object of the present invention is to react a specific cyclopentadiene and/or a specific dicyclopentadiene with a compound represented by the following general formula () and sulfonate the reaction product mixture obtained. An object of the present invention is to provide a method for producing a sulfonated product. General formula () (In the formula, R ₁ and R ₂ are the same or different groups,
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) The present invention will be specifically explained below. In the present invention, a cyclopentadiene represented by the following general formula () and/or a dicyclopentadiene represented by the following general formula () and a compound represented by the above general formula () are combined in the presence of a catalyst such as an acidic compound. The reaction product mixture obtained by the reaction described below is sulfonated, thereby producing a sulfonated product. General formula () (In the formula, R ₃ is a hydrogen atom or has 1 to 3 carbon atoms.
represents an alkyl group. ) General formula () (In the formula, R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Specific compounds that can be represented by these general formulas () or () include, for example, cyclopentadiene. , methylcyclopentadiene,
Examples include alkylcyclopentadiene such as ethylcyclopentadiene and propylcyclopentadiene, and dimers formed by arbitrary combinations of these alkylcyclopentadienes, such as dicyclopentadiene. Further, the cyclopentadienes or dicyclopentadienes used in the present invention may contain impurities as long as they do not interfere with the reaction. Examples of the compound represented by the general formula () used in the present invention include benzene, toluene, xylene (o-, m-, p-), ethylbenzene, n-propylbenzene, iso-propylbenzene, methylethylbenzene (o- ,m-,p
-), n-butylbenzene, sec-butylbenzene, tert-butylbenzene, iso-propyltoluene (o-, m-, p-), amylbenzene, hexylbenzene, amyltoluene (o-, m-,
Examples include benzene derivatives such as mono- or dialkyl-substituted benzenes such as p-). The alkyl group in this case has 1 to 6 carbon atoms, and tetralin, which is a compound in which two alkyl groups mutually form a ring, can also be used. Among these, R ₁ and R ₂ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferred are benzene, toluene, xylene,
Examples include propylbenzene and butylbenzene. In the present invention, these compounds may be used alone, or two or more different compounds may be used in combination. In the present invention, when the specific cyclopentadiene and/or dicyclopentadiene is reacted with the compound represented by the general formula (), an acidic compound is usually used as a catalyst. sulfuric acid, phosphoric acid,
Examples include Lewis acids or organic protonic acids such as hydrogen fluoride, boron trifluoride and complexes thereof, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, and titanium trichloride. In the presence of such an acidic compound, cyclopentadiene and/or dicyclopentadiene and the compound represented by the above general formula () are mixed in a molar ratio of usually 100:1 to 1:100, and a solvent is added to this as appropriate. is added, and the reaction temperature is usually -20~
The reaction is carried out at 150 DEG C., preferably from 0 DEG to 120 DEG C., for several hours to obtain a reaction product mixture. The reaction product mixture thus obtained is a reaction product obtained by adding one molecule of the compound represented by the general formula () to one molecule of dicyclopentadiene, and a reaction product obtained by adding one molecule of the compound represented by the general formula () to two molecules of dicyclopentadiene. In addition to several types of adducts such as reaction products to which one molecule of the compound represented by is added, polymers of cyclopentadienes and/or dicyclopentadienes, and compounds represented by the general formula () to the polymers are also used. It is a mixture of various compounds including added reaction products. The ratio of various reaction products in this reaction product mixture can be changed as appropriate depending on the type of catalyst, reaction temperature, charging ratio of reaction raw materials, etc. The lower limit of the molecular weight of this reaction product mixture is the reaction product obtained by adding one molecule of the compound represented by the general formula () to one molecule of cyclopentadiene, and the upper limit varies depending on the reaction conditions and is not particularly limited. The number average molecular weight is preferably 10,000 or less from the viewpoint of ease of proceeding with the sulfonation reaction described below. This number average molecular weight is
The results of permeation chromatography (permeation chromatography) were converted from a calibration curve created using several types of polystyrene with different molecular weights as standard materials. Furthermore, the surface active properties of the sulfonated product, which will be described later, can be controlled by adding other dienes or olefins to the reaction raw materials in advance and co-reacting these as well. Methods for sulfonating such reaction product mixtures are described in EEGilbert's book “Sulfonation and Related Reactions”.
and Related Reaction”), Interscience
Publishers Inc. (1965), and 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. Can be done. Also Charles G. Norton.
J. Norton et al., The Journal of Organic Chemistry
Sulfonated products can also be obtained by the addition reaction of sulfites to unsaturated bonds, as shown in the study in J. Organic Chemistry, p. 4158 (1968). In this case, the sulfonating agent is usually an alkali metal acid sulfite, metasulfite,
Alternatively, sulfites are used alone or in mixtures. The amount of these sulfonating agents varies depending on the degree of sulfonation required and cannot be determined unconditionally, but is usually at a ratio of 0.1 to 10 molecules per remaining double bond in the reaction product mixture. used. The number of moles of double bonds remaining in the reaction product mixture can be determined by iodometric titration, and is usually determined per molecule of cyclopentadiene and/or dicyclopentadiene as the reaction raw material.
Double bonds remain at a ratio of 0.3 to 1. 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 the inorganic oxidizing agent include nitrates, nitrites, chlorates, etc., with nitrates being 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. In addition, in order to more uniformly dissolve the polymer having a cyclopentadiene and/or dicyclopentadiene skeleton in the reaction product mixture,
Solvents that are inert in the sulfonation reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, aliphatic hydrocarbons such as pentane, heptane, and decane, and cyclic ethers such as tetrahydrofuran, can also be used in combination. The reaction temperature in the sulfonation reaction is usually 50~
200℃, preferably 70-150℃, more preferably 90
It is carried out at ~120°C, and can be carried out either at normal pressure or under pressure. In addition, 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 2 to 9.
Preferably it is kept at 5-7. The sulfonated products thus obtained are typically 20 to 20% of the remaining double bonds in the reaction product mixture.
It is 100% sulfonated. The degree of sulfonation can be determined by converting the obtained sulfonated product into an acid form by an ion exchange method and subjecting it to alkaline titration. Since the sulfonated product obtained by the method of the present invention is as described above, it has an excellent surfactant action as will be understood from the examples described later, and therefore it can be used as an organic material or an inorganic material. It is extremely useful as a surfactant, such as an emulsifier,
It can be widely used as a dispersant, wetting agent, cleaning agent, and smoothing agent. The sulfonated product obtained by the method of the present invention is a sulfonated product of a reaction product mixture in which several types of reaction products are mixed,
This sulfonated product has a sufficient effect as a whole, and therefore there is no need to carry out separation and purification, which is normally difficult to carry out.As a result, the manufacturing process can be significantly omitted, and the reaction Compared to the case where the various reaction products in the product mixture are isolated and sulfonated, the sulfonation of the reaction product mixture proceeds more easily and can be applied over a wide range from low molecular weight to high molecular weight. Since the sulfonation is achieved at a high reaction rate over a period of time, sulfonated products can be advantageously obtained. In addition, the sulfonated product obtained by the method of the present invention can be processed by ion exchange method or neutralization reaction, etc.
They can be interchanged into acid forms or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. The sulfonated product obtained as described above can be condensed with, for example, an aldehyde in the presence of an acid catalyst using this as a condensation monomer to form a condensate. Examples of the aldehyde include formaldehyde, acetaldehyde, and propionaldehyde, among which formaldehyde is preferred from the viewpoint 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,
In the sulfonated product, the number of moles is preferably 0.5 to 2 times the number of moles of the compound represented by the general formula () added to the skeleton of the cyclopentadiene and/or dicyclopentadiene, more preferably The number of moles is 0.8 to 1.5 times higher. In the condensation of the sulfonated product, other condensation monomers such as benzene, toluene, xylene,
Benzene derivatives such as phenol; sulfonic acids or salts thereof of benzene derivatives; naphthalene derivatives; sulfonic acids or salts thereof of naphthalene derivatives such as sodium β-naphthalene sulfonate, etc. may be condensed together singly or in an appropriate combination of two or more. good. By appropriately selecting these, it is possible to freely control the surface active properties of the resulting condensate. Further, during the condensation, the low boiling point compound or high boiling point compound in the sulfonated product may be appropriately removed before condensation. As the acid catalyst in the condensation reaction, sulfuric acid can be cited as a typical example. The amount used is not particularly limited, but it is usually 0.0001 to 10 times the number of moles, preferably 0.01 to 5 times the number of moles, and more preferably 0.05 times the number of moles of the condensation monomer.
~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. Furthermore, when the sulfonated product is in the acid form, it 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 to be used may be selected appropriately taking into account the reaction rate, solubility, etc., but is usually based on 1 part by weight of the condensation reaction raw material mixture.
0.01 to 10 parts by weight, and the condensation reaction temperature is usually
The temperature is 30 to 150°C, preferably 70 to 120°C. 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 desirable to select the degree of condensation depending on the application. For example, when used as a dispersant for cement as described later, the number average molecular weight of the condensate is 500.
~30000 is preferable, more preferably
It is 800-10000. Note that this number average molecular weight is for water-based
Can be measured by GPC (gel permeation chromatography), and is converted from a calibration curve created using several types of sodium polystyrene sulfonate, sodium anthracene sulfonate, and sodium benzene sulfonate as standard substances with different molecular weights. This is what I did. As mentioned above, the condensate obtained by condensing the sulfonated product obtained by the method of the present invention also has an excellent surface-active effect, so it is extremely useful as a surfactant for organic or inorganic materials. can be,
For example, it can be widely used as an emulsifier, a dispersant, a wetting agent, a cleaning agent, and a smoothing agent. The condensate is a condensate obtained by condensing the sulfonated product obtained as described above, and the condensate has a sufficient effect as a whole, and therefore is difficult to carry out normally. It is not necessary to carry out a certain separation and purification, and as a result, a large number of manufacturing steps can be omitted. Furthermore, when the sulfonated product or its condensate obtained by the method of the present invention is used as a dispersant for cement, the dispersibility of cement in water is significantly improved, as will be understood from the examples described below. Therefore, an excellent water reduction effect can be obtained 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 was completed, the catalyst was decomposed with a sodium carbonate solution and washed with water, and then the oil layer was distilled under reduced pressure to remove 1360 g of unreacted toluene and 35 g of dicyclopentadiene, yielding 601 g of a residue. When the remaining double bonds in this residue were examined by iodometric titration, it was found that 0.96 equivalents of double bonds remained per mole of reacted dicyclopentadiene. In addition, when the molecular weight distribution of the residue was investigated by GPC (gel permeation chromatography), it was found that the molecular weight of a compound (approximately 63% by weight) in which 1 mol of toluene was added to 1 mol of dicyclopentadiene.
Compounds with various molecular weights existed, with a lower limit of 224 and a polystyrene equivalent molecular weight of 8,000. Next, capacity 3 is equipped with a stirring device and a thermometer.
The above residue in the stainless steel autoclave
20g, sodium bisulfite 20g, potassium nitrate 2g, isopropyl alcohol 300ml and distilled water
50g was added, and the internal pressure in the autoclave at room temperature
After supplying air until the pressure reached 1.0 Kg/cm ² (gauge pressure), the valve was sealed, and the mixture was reacted at a temperature of 110° C. for 3 hours with vigorous stirring. After that, it was left to cool to room temperature, and after removing most of the isopropyl alcohol by distillation, 1 part of distilled water and 1.5 parts of petroleum ether were added and thoroughly mixed, and the separated petroleum ether layer and precipitate were removed to obtain the aqueous layer. Concentrate and evaporate to dryness. This was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated. By concentrating the obtained acetic acid soluble content, 25.8 g of yellow solid was obtained.
I got it. This will be referred to as "Sample 1". When this sample 1 was dissolved in distilled water, converted into an acid form using an ion exchange resin, and titrated with sodium hydroxide, approximately 96% of the remaining double bonds were found to be sulfonated. The solubility of this sample 1 in water is 40
When water was added to Sample 1 to make a 4% by weight aqueous solution and the surface tension was measured, it was found to be 48.9 dyn/cm. Example 2 In Example 1, toluene initially charged
The reaction was carried out in the same manner as in Example 1, except that 1510 g of ethylbenzene was used instead of 1270 g, and 320 g of ethylbenzene was used instead of 320 g of dropped toluene, and 1590 g of unreacted ethylbenzene and 52 g of dicyclopentadiene were distilled off to obtain 588 g of a residue. When the residual double bonds in this residue were investigated by iodometric titration, it was found that
0.95 per mole of reacted dicyclopentadiene
An equivalent amount of double bonds remained. In addition, when the molecular weight distribution of the residue was investigated in the same manner as in Example 1,
1 mol of dicyclopentadiene to 1 mol of ethylbenzene
Molecular weight of the compound (approximately 58% by weight) with moles added
Compounds with various molecular weights existed, with a lower limit of 238 and a compound with a polystyrene equivalent molecular weight of 11,000. Next, sulfonation treatment was carried out in the same manner as in Example 1 to obtain 23.8 g of a yellow solid. This will be referred to as "Sample 2." When this sample 2 was dissolved in distilled water, converted into an acid form using an ion exchange resin, and titrated with sodium hydroxide, approximately 92% of the remaining double bonds were found to be sulfonated. The solubility of this sample 2 in water is
30% by weight or more, and by adding water to this sample 2,
A wt% aqueous solution was prepared and its surface tension was measured and found to be 47.3 dyn/cm. Example 3 In Example 1, toluene initially charged
Use 1510 g of xylene instead of 1270 g, and add 300 g of dicyclopentadiene and 320 g of xylene as the dropping solution.
The reaction was carried out in the same manner as in Example 1 except that a mixed solution of 100 g of piperylene with a purity of 70% was used, and 1560 g of unreacted xylene, 33 g of dicyclopentadiene and 48 g of piperylene were distilled off to obtain 563 g of a residue. When the remaining double bonds in this residue were examined by iodometric titration, it was found that 0.92 mol of double bonds remained per 1 mol of reacted dicyclopentadiene. In addition, when the molecular weight distribution of the residue was investigated in the same manner as in Example 1, the lower limit was the molecular weight of 238 for a compound in which 1 mole of xylene was added to 1 mole of dicyclopentadiene (approximately 61% by weight), and a compound with a polystyrene equivalent molecular weight of 10,500 It was widely distributed. Next, sulfonation treatment was carried out in the same manner as in Example 1 to obtain 22.9 g of a yellow solid. This will be referred to as "Sample 3." When this sample 3 was dissolved in distilled water, converted into an acid form using an ion exchange resin, and titrated with sodium hydroxide, approximately 94% of the remaining double bonds were found to be sulfonated. The solubility of this sample 3 in water is 30
When water was added to this sample 3 to make a 4% by weight aqueous solution and the surface tension was measured, it was found to be 43.8 dyn/cm. Reference Example 1 Sample 1 obtained in Example 1 was placed in a three-neck flask with a capacity of 0.2 and equipped with a stirrer and a thermometer.
mmol, formaldehyde 30 mmol, sulfuric acid 30
Prepare 270 mmol of distilled water and the temperature
A condensation reaction was carried out at 80°C 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. Further, soda carbonate was added to this liquid while stirring until the pH reached 9, and then filtered to obtain a liquid. This liquid was dried to obtain 11.6 g of brown powder. This will be referred to as "Sample 4." When the molecular weight distribution of sample 4 was measured by aqueous GPC (gel permeation chromatography), it was found that 5 of the total compounds with a molecular weight of 500 or less
% by weight or less, and a large peak appeared at a molecular weight of 4,300. Note that this molecular weight was 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. Also, the solubility of sample 4 in water is 30% by weight.
The above is the result of adding water to this sample 4 to make a 4% by weight aqueous solution and measuring its surface tension.
It was 51.3 dyn/cm. Reference Example 2 A condensation reaction was carried out in the same manner as in Reference Example 1, except that Sample 2 obtained in Example 2 was used, and 10.1 g of brown powder was also obtained. This will be referred to as "Sample 5." When the molecular weight distribution of this sample 5 was measured in the same manner as in Reference Example 1, compounds with a molecular weight of 500 or less accounted for 3% by weight or less of the total, and a large peak appeared at a molecular weight of 4,800. The solubility of Sample 5 in water was 25% by weight or more, and when water was added to Sample 5 to prepare a 4% by weight aqueous solution, the surface tension was measured to be 50.8 dyn/cm. Reference Example 3 2 g each of Samples 1 to 5 obtained in Examples 1 to 3 and Reference Examples 1 and 2 were added to 50 g of distilled water and dissolved to prepare a total of 5 types of aqueous solutions. After adding 200 g of commercially available Portland cement (manufactured by Chichibu Cement Co., Ltd.) to each of these aqueous solutions and kneading by hand for 3 minutes, using a flow cone with an internal volume of 98.9 cc,
Flow values were measured according to JIS R5201. The results are shown in the table below.

[Table] On the other hand, when the flow value was measured in the same manner except that none of Samples 1 to 5 was added, it was only 87 mm. As understood from the above Examples 1 to 3 and Reference Examples 1 and 2, the sulfonated products and condensates thereof obtained by the method of the present invention foam well and have excellent surfactant action. Moreover, as understood from Reference Example 3, when the sulfonated product or its condensate obtained by the method of the present invention is used as a dispersant for cement, the dispersion effect of cement in water is extremely large. It turns out that it is excellent.

Claims (1)

[Scope of Claims] 1 Cyclopentadiene represented by the following general formula () and/or dicyclopentadiene represented by the following general formula () and the following general formula ()
1. A method for producing a sulfonated product, which comprises sulfonating a reaction product mixture obtained by reacting a compound represented by: General formula () (In the formula, R ₁ and R ₂ are the same or different groups,
Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) General formula () (In the formula, R ₃ is a hydrogen atom or has 1 to 3 carbon atoms.
represents an alkyl group. ) General formula () (In the formula, R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)