JPH0240091B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polymer or copolymer (hereinafter referred to as a (co)polymer) of a sulfonated dicyclopentadiene containing 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 products conventionally synthesized are aromatic, aliphatic, etc.
Few examples of sulfonated alicyclic compounds are known. Furthermore, no (co)polymer having a sulfonic acid group in the cyclopentadiene skeleton is known. The present inventors conducted intensive studies to obtain a polymer or copolymer of a sulfonated product having a cyclopentadiene skeleton, and found that the sulfonated product of cyclopentadiene can be polymerized because it has a double bond. For example, the inventors have discovered that it is possible to form a (co)polymer by heating in the presence of an acidic compound catalyst, leading to the present invention.
This sulfonated (co)polymer has extremely excellent surface activity, and is particularly excellent in cement dispersion. That is, the present invention provides a method for producing a polymer or copolymer of an acid or salt of a sulfonated dicyclopentadiene represented by the following general formula. general formula (In the formula, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium, or an amine, and n is an integer of 1 or 2.) The present invention will be specifically explained below. Examples of the alkali metal in the above general formula include sodium and potassium, and examples of the amine include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, and tributylamine; Examples include polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; morpholine, piperidine, etc., and alkaline earth metals include calcium,
Examples include magnesium and zinc.
Moreover, these M can be mutually exchanged with other types of M by various ion exchange techniques or neutralization reactions. The dicyclopentadiene used in the present invention may contain impurities such as other hydrocarbons and water as long as the reaction is not adversely affected. Further, there is no particular problem even if alkyl-substituted dicyclopentadiene such as methyl-based dicyclopentadiene is mixed. In the sulfonated dicyclopentadiene used in the present invention, Gilbert (EE
Gilbert's book "Sulfonation and Related Reactions"
(“Sulfonation and Related Reaction”)
Described in detail in Interscience Publishers Inc. (1965). Also, Charles J. Norton and others
Of Organic Chemistry
Journal of Organic Chemistry) 4158 pages (1968
Sulfonated compounds can also be obtained by the addition reaction of sulfites to unsaturated bonds, as shown in the study of 2010). As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually 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 used at a ratio of 0.1 to 10 molecules per molecule of dicyclopentadiene. 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, an appropriate solvent may be used to allow the reaction to proceed uniformly and smoothly. Solvents that can be advantageously used include, for example, water, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, tertiary alcohol,
Examples include lower alcohols such as butyl alcohol, lower gelicols, ketones, ethers, and esters. 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 in the sulfonation reaction is usually 50~
200℃, preferably 70-150℃, more preferably 90
~120°C, and can be carried out either at normal pressure or under increased pressure. Further, in order to suppress the progress of side reactions and reduce the production of unnecessary inorganic salts, it is desirable to maintain the pH of the reaction system generally at 2 to 9, preferably 5 to 7. The sulfonated product thus obtained can be separated from unreacted organic compounds by extraction with water, for example. By this operation, unreacted inorganic salts present in the aqueous phase can be separated by a method such as crystallization. This sulfonated product is a mixture of those with one sulfonic acid group and those with two sulfonic acid groups per molecule, and the ratio of these depends on the type and amount of the sulfonating agent and the amount of the sulfonating agent and dicyclopentadiene. The ratio can be changed as appropriate depending on the type and amount of the inorganic oxidizing agent or solvent, the reaction temperature, etc. The sulfonated product may be any of the two types of sulfonated products mentioned above, but it is preferable that the sulfonated product has a double bond remaining in order to facilitate the progress of polymerization when polymerizing to obtain a polymer. preferably contains 20% or more of those having one sulfonic acid group per molecule, more preferably 50% or more, and 80%
The above is even more preferred. Further, the number of sulfonic acid groups in the sulfonated product can be determined by a conventional method such as titration with an alkali. The base of sulfonic acid is sodium,
There are alkali metal salts such as potassium, alkyl amines such as methylamine and ethylamine, alkaline earth metal salts such as calcium and magnesium, and ammonium salts. The method for producing the (co)polymer of the present invention includes dicyclopentadiene having a sulfonic acid group represented by the above general formula, or the dicyclopentadiene and a monomer copolymerizable therewith, for example, in the presence of an acidic compound catalyst. This method involves polymerization below. Acidic compound catalysts used as polymerization catalysts include Lewis acids such as sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, and titanium trichloride. Alternatively, organic protonic acids can be mentioned. In the presence of such a catalyst, a sulfonated dicyclopentadiene or a monomer copolymerizable with it is heated at a reaction temperature of -20 to 300°C, preferably 80 to 180°C, for several hours to several tens of hours. A polymer is obtained by carrying out a polymerization reaction. In this polymerization reaction, a polymerization reaction solvent can be used to smoothly conduct the reaction, and as long as it does not hinder the polymerization reaction, polar solvents such as water, hydrocarbons, halogenated solvents, etc. Any material such as hydrocarbons can be used. In addition, in order to adjust the surface activity of the polymer, HLB (interfacial activity properties) can also be changed. Comonomers include aliphatic, alicyclic, and aromatic hydrocarbons having olefinic double bonds, unsaturated amides, unsaturated alcohols, unsaturated esters, unsaturated nitriles, unsaturated carboxylic acids, and their like. One or more types of esters, unsaturated sulfonic acids, and their esters can be used in any proportion. However, when the copolymer obtained by the production method of the present invention is used as a cement dispersant, the content of sulfonated substances in the copolymer is preferably 50% or more, in order to keep air entrainment low. It is 70% or more, more preferably 90% or more. The molecular weight of the (co)polymer obtained by the production method of the present invention can be changed as appropriate depending on the reaction conditions, especially the type and amount of the acidic compound catalyst, the type and amount of the solvent, or the reaction temperature and reaction time. Can be done. When the (co)polymer obtained by the production method of the present invention is used as a dispersant for cement, the number average amount is preferably 500 or more, more preferably 2000 or more, and 3500 to 50,000. is most preferred. Furthermore, the (co)polymer obtained by the production method of the present invention can be mutually exchanged into acid form or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange method or neutralization reaction. can. Since the (co)polymer obtained by the production method of the present invention is as described above, it has an excellent surfactant effect, as will be understood from the examples described below, and is therefore suitable for use with organic materials or It is extremely useful as a surfactant for inorganic materials, and can be widely used, for example, as an emulsifier, dispersant, wetting agent, detergent, and smoothing agent. Furthermore, (co) obtained by the production method of the present invention
Polymers are particularly useful as dispersants for cement, and in this case, as will be understood from the description of the examples below, they can significantly improve the dispersibility of cement in water, and therefore You can obtain the water reduction effect of cement construction method, and
Since there is little foaming, air entrainment is extremely low, and therefore high strength concrete can be obtained. Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples. In addition, the number average molecular weight described in the present invention is
The results measured by GPC (gel permeation chromatography) were converted using a calibration curve created using several types of polystyrene sulfonic acids with different molecular weights as standard substances. Example 1 3000 g of dicyclopentadiene, 1888 g of sodium bisulfite, 91.7 g of potassium nitrate, 12 g of isopropyl alcohol, and 3000 g of distilled water were placed in a stainless steel autoclave with a capacity of 30 and equipped with a stirrer and a thermometer, and the mixture was heated in the autoclave at room temperature. After nitrogen was supplied until the internal pressure reached 1.0 Kg/cm ² (gauge pressure), the valve was sealed and the reaction was carried out at 110° C. for 5 hours while mixing under strong stirring. After that, it was allowed to cool to room temperature, and after removing most of the isopropyl alcohol by distillation, distilled water and petroleum ether were added and thoroughly mixed, the separated petroleum ether layer and precipitate were removed, and the resulting aqueous layer was concentrated. , distilled to dryness. This was dissolved in glacial acetic acid, and the acetic acid insoluble portion consisting of inorganic salts was separated using a centrifuge.
By concentrating the obtained acetic acid soluble portion, 2800 g of a white solid was obtained. (This is sulfonated compound A

Let it be [formula]. ) This aqueous solution of sulfonated compound A was converted into an acid form using an ion exchange resin, and then the water was concentrated to dryness to obtain an acid form of the sulfonated compound. (This is sulfonated compound B

Let it be [formula]. ) Next, 15 g of the above sulfonated compound B and 6.88 g of sulfuric acid were placed in a 300 ml three-necked flask equipped with a reflux condenser and a stirring device, and the mixture was heated at 120°C for 26 hours.
The polymerization reaction was carried out over a period of time. After completion of the reaction, liming and sodation were performed, and the solid content obtained was 15.5 g, and the number average molecular weight of this polymer was 10,000. This will be referred to as "Sample 1". When the polymer of Sample 1 was converted into an acid form using an ion exchange resin and titrated with potassium hydroxide, it was found to be a polymer having 0.96 sulfonic acid groups per 1 dicyclopentadiene. In addition, water was added to sample 1 to make a 4% aqueous solution, and the surface tension was measured at a temperature of 25°C.
It was 63 dyn/cm. The IR chart of this product is shown in Figure 1, and it shows that it has a sulfonic acid group (1190 cm ^-1 and 1050 cm
^-1 ), it can also be seen that the absorption of double bonds is becoming weaker. Example 2 The same treatment as in Example 1 was carried out except that sulfonated compound A was used, and the number average molecular weight of the polymer was 1600.
I got something. This will be referred to as "Sample 2." When this aqueous solution of Sample 2 was converted into an acid form using an ion exchange resin and titrated with potassium hydroxide, it was found to be a polymer having 0.79 sulfonic acid groups per 1 dicyclopentadiene. The surface tension of the 4% aqueous solution of sample 2 is
It was 69.2 dyn/cm. Example 3 In Example 1, the polymerization reaction was carried out using a sulfonated product.
Using 30g of A, add 125g of sulfuric acid and 11.4g of water, and
The reaction was carried out at 170°C for 28 hours. Otherwise, the same treatment was performed to obtain a polymer having a number average molecular weight of 8000, which was designated as "Sample 3". When the sulfonation rate was measured in the same manner, it was found to have 0.59 sulfonic acid groups per 1 dicyclopentadiene. The surface tension of the 4% by weight aqueous solution was 65 dyn/cm. Example 4 2 g each of Samples 1 to 3 obtained in Examples 1 to 3 were added to 50 g of distilled water and dissolved to prepare a total of four types of aqueous solutions. Commercially available Portland cement (manufactured by Chichibu Cement Co., Ltd.) 200 g was added to each of these aqueous solutions.
After adding g and kneading by hand for 3 minutes, the flow value was measured according to JISR5201 using a flow cone with an internal volume of 98.9 cc.The results are shown in the following table.

[Table] On the other hand, in Example 4, the flow value was measured in the same manner as in Example 4 except that none of Samples 1 to 3 were added, and the flow value was only 87 mm. As understood from Examples 1 to 3 above, the polymer obtained by the production method of the present invention has an excellent surface-active effect, and as understood from Example 4, the polymer obtained by the production method of the present invention When the polymer obtained by the production method is used as a dispersant for cement, the dispersion effect of cement in water is extremely large and excellent. Example 5 Capacity 300 equipped with reflux condenser and stirring device
Put 13g of sulfonated compound A, 2g of dicyclopentadiene, and 6.88g of sulfuric acid into a ml three-neck flask,
A copolymerization reaction was carried out at a temperature of 120°C for 20 hours.
After the reaction, liming and sodation were performed, and the solid content obtained was 15.0 g, and the surface tension of the 4% by weight aqueous solution of the obtained copolymer was 40 dyn/
cm, and showed excellent surfactant action.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the infrared absorption spectrum of the dicyclopentadiene sulfonated polymer obtained in Example 1.

Claims (1)

[Scope of Claims] 1. A sulfonated dicyclopentadiene compound A represented by the following general formula, or a polymer of a sulfonated dicyclopentadiene characterized by polymerizing A and a monomer copolymerizable therewith. or a method for producing a copolymer. general formula (In the formula, M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, ammonium or an amine, and n is an integer of 1 or 2.)