JPH0466883B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a polymer of a sulfonated norbornene derivative. [Prior Art] 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. The present inventors have already invented a sulfonated product of dicyclopentadiene and a polymer thereof (Japanese Patent Application No. 58-160417, etc.). The compound is a sulfonated organic substance, and the acid is useful as a catalyst, cation exchange agent, etc. as a common sulfonic acid. This compound also has
It is extremely useful as an emulsifier and dispersant,
A dispersant for inorganic fine particles such as cement, gypsum, and CaCO ₃ It has extremely excellent performance as a dispersant for organic fine particles such as coal, petroleum coke, and dyes, but on the other hand, this compound has a deep black color. Therefore, in its manufacturing and usage processes,
This method had the disadvantage of coloring wastewater and products using it. [Object of the Invention] In view of the current situation, the present inventors conducted extensive studies to find a compound that maintains high dispersibility, and found that a compound containing 9 carbon atoms and two double bonds in the molecule.
The present invention was achieved by discovering that a polymer of sulfonated products of ~12 specific norbornene derivatives has extremely excellent dispersibility and that the color tone of the polymer is greatly improved. [Structure of the Invention] That is, the present invention provides a process in which a norbornene derivative having 9 to 12 carbon atoms and represented by the following general formula (A) or (B) is prepared by removing the double bond of the norbornene ring of the norbornene derivative in the presence of a sulfonating agent. This is a method for producing a polymer of a sulfonated norbornene derivative, which is characterized by sulfonating and polymerizing the obtained sulfonated product in the presence of an acidic compound catalyst. In the formula, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ is an alkylene group having 1 to 3 carbon atoms. , R ₆ and R ₇ represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, R ₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and θ represents 0 or 1. Note that the group at the 6-position may also be at the 5-position. Next, the present invention will be explained in detail. In the present invention, the norbornene derivatives represented by the above general formulas (A) and (B) are subjected to a Diels-Alder reaction with dienes excluding cyclopentadiene as the diene component and cyclodienes having 4 to 7 carbon atoms as the dienophile component. Obtained by thermal decomposition of naphtha. Examples of dienes having 4 to 7 carbon atoms used as the dienophile component include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, and 2,3-pentadiene. , isoprene, 1,2
-hexadiene, 1,3-hexadiene, 1,4
-hexadiene, 1,5-hexadiene, 2,3
-hexadiene, 2,4-hexadiene, 2,3
-dimethyl-1,3-butadiene, 2-ethyl-
1,3-butadiene, 1,2-heptadiene,
1,3-heptadiene, 1,4-heptadiene,
1,5-heptadiene, 1,6-heptadiene,
2,3-heptadiene, 2,4-heptadiene,
2,5-heptadiene, 3,4-heptadiene,
These include 3,5-heptadiene and various branched dienes having 7 carbon atoms. When cyclopentadiene and the dienophile are subjected to the Diels-Alder reaction, a norbornene derivative is produced in which double bonds other than the double bond of the norbornene ring having 9 to 12 carbon atoms and the double bond that acted as the dienophile remain. This representative
For example, 5-vinyl-norbornene-2,5-
ethylidene-norbornene-2,5-methylene-
6-methylnorbornene-2,5-propenyl-
norbornene-2,5-vinyl-6-methylnorbornene-2,5-isopropenyl-norbornene-2,5-methyl-5-vinyl-norbornene-2,5-allyl-norbornene-2,5-vinyl-6- Examples include ethylnorbornene-2 and 5-butenyl-norbornene-2. In order to produce a sulfonated product of a norbornene derivative, various production methods can be considered. For example, it can be produced by sulfonating the double bond of the above-mentioned norbornene derivative by the method shown below. The sulfonation reaction applied to unsaturated compounds, especially unsaturated aliphatic or unsaturated alicyclic compounds, is
EEGilbert's book “Sulfonation and Related Reactions”
Reaction”), Interscience Publishers Inc. (1965
(2010), and also by Charles
Chalrs J. Norton et al.
The Journal of Organic Chemistry
Sulfonation can also be achieved by the addition reaction of sulfites to unsaturated bonds, as shown in the study on page 4158 (1968). However, there has been no example of preferential sulfonation of one of two types of double bonds in a molecule, but as a result of intensive studies by the present inventors, sulfite is preferentially sulfonated on the double bond of the norbornene ring. By adding salts, a sulfonated norbornene compound containing one double bond in the molecule was obtained. As the sulfonating agent in this case, acidic sulfites, metasulfites, or sulfites of alkali metals are usually used alone or as a mixture. The amount of the sulfonating agent is usually 0.1 to 2.0 molar ratio, preferably 0.5 to 2.0 molar ratio per mole of norbornene derivative.
The molar ratio is 1.5, more preferably 1 to 1.5 molar. If the molar ratio is less than 0.1, the reaction yield will be low, and 20
The amount of disulfonated products exceeding the molar ratio increases. When the amount of the sulfonating agent is less than 1 mole per mole of the norbornene derivative, a mixture of the sulfonated norbornene derivative and the non-sulfonated norbornene derivative is formed;
Only the sulfonated norbornene derivative may be extracted from the mixture by extraction (using n-hexane, etc. as the solvent) or distillation, or a mixture of the sulfonated norbornene derivative and the non-sulfonated norbornene derivative may be extracted. It may be directly polymerized by the method described later. In that case as well, the sulfonated polymer can be separated from the non-sulfonated polymer by extraction (for example, n-hexane is used as the solvent) or distillation. In the sulfonation reaction, the use of a catalyst is not necessarily required, but 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 the inorganic oxidizing agent include nitrates, sulfites, chlorates, etc., and nitrates are particularly effective. Although the amount of the inorganic oxidizing agent is not particularly limited, an effective molar ratio of 0.02 to 0.15, preferably 0.05 to 0.1 molar, per mole of norbornene derivative. Furthermore, it is desirable to use an appropriate solvent to allow the reaction to proceed uniformly and smoothly. Examples of solvents that can be advantageously used include 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, a mixed solvent of lower alcohol and water, especially a mixed solvent of methyl alcohol and water, is recommended as an excellent solvent. The reaction temperature is usually 50-200℃, preferably 70-150℃
C., more preferably 90 to 130.degree. 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 formation of inorganic salts, the pH of the reaction system is usually 2 to 9, preferably 5.
Keep it at ~7. For example, when a compound of formula () is reacted with sodium bisulfite in an appropriate solvent, the compound of formula () is preferentially obtained. Such sulfonated norbornene derivatives are new substances. The sulfonated norbornene derivatives are usually represented by the following general formulas (C) and (D). (In the formula, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms, R ₃ and R ₄ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ₅ is alkylene having 1 to 3 carbon atoms. group, R ₆ and R ₇ are alkyl groups having 1 to 3 carbon atoms or hydrogen atoms, R ₈ and R ₉ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, M is a hydrogen atom, an alkali metal atom, an alkaline earth atom represents a metal atom, ammonium group or amine; when M is an alkaline earth metal atom, α represents 2; when M is other than an alkaline earth metal atom, α represents 1; θ represents 0 or 1; ) In this sulfonated product, the cationic species (M in general formulas (C) and (D)) is not particularly limited, but in order to make it water-soluble, hydrogen, alkali metals, alkaline earth Preferred are similar metals, ammonium, amines, and the like. Examples of the alkali metals include sodium and potassium, and examples of amines include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, and triethylene. Polyamines such as tetramine, alkaline earth metals such as morpholine and piperidine include calcium,
Examples include magnesium. These cationic species can also be interchanged with other cationic species by various ion exchange techniques. In the manner described above, the sulfonated product of the norbornene derivative represented by the general formula (C) or (D) is obtained. In the present invention, the polymer of sulfonated norbornene derivatives refers to a polymer obtained by polymerizing the same sulfonated norbornene derivatives mentioned above, or a monomer that can be polymerized with the sulfonated norbornene derivatives mentioned above. (hereinafter referred to as copolymerized monomer). The method for producing this polymer is as follows. For example, a sulfonated norbornene derivative represented by the above general formula (C) or (D), or a comonomer thereof and a comonomer, in the presence of an acidic compound catalyst,
Reaction temperature usually -20~300℃, preferably 80~180℃
A polymer is produced by carrying out a polymerization reaction over a period of several hours to several tens of hours. In the above polymerization reaction, in order to carry out the reaction smoothly, a polymerization reaction solvent can be used.As such a polymerization reaction solvent, polar solvents such as water, hydrocarbons, Any one can be used, such as halogenated hydrocarbons. The acidic compound catalyst includes sulfuric acid, phosphoric acid,
Hydrogen fluoride, boron trifluoride and its chains, aluminum chloride, aluminum bromide, tin tetrachloride,
Examples include Lewis acids such as zinc chloride and titanium trichloride, and organic protonic acids. Among them, sulfuric acid can be cited as a typical example. 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. esters, unsaturated sulfonic acids and esters thereof, aliphatic, alicyclic, aromatic alcohols or phenols, or alcohols or diols having amino groups, ester groups, nitrile groups, carboxylic acid groups, sulfonic acid groups, etc. One or more types can be used in any proportion. By varying the type of copolymer monomer used, the surfactant properties of the polymer can be varied. When a polymer is produced from the above-mentioned sulfonated norbornene derivative and a comonomer and used as a dispersant for cement, the sulfonated norbornene derivative/polymer is used to maintain low air entrainment. The coalescence (% by weight) is at least 50%, preferably at least 70%. The general structure of the polymer obtained by the method of the present invention is shown below. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ ,
R ₉ , M, α and θ are the same as in general formulas (C) and (D), and n represents the degree of polymerization. ) The molecular weight of the polymer of the sulfonated norbornene derivative obtained by the 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. You can force it. When the polymer of the sulfonated norbornene derivative obtained by the method of the present invention is used as a cement dispersant, the weight average molecular weight is preferably 500 or more, more preferably 1000 or more, and 2000 to 100,000. is most preferred. Furthermore, the polymer of sulfonated norbornene derivatives obtained by the method of the present invention can be mutually converted into acid form or salts of alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange method or neutralization reaction. Can be exchanged. [Effects of the Invention] As will be understood from the Examples described below, the polymer of the sulfonated norbornene derivative obtained by the method of the present invention has an excellent surfactant effect, so it is suitable for use with organic materials or inorganic materials. It is extremely useful as a surfactant for materials (e.g., cement, gypsum, dyes, coal, petroleum coke, petroleum pitch, etc.) and can be widely used, for example, as an emulsifier, dispersant, wetting agent, detergent, and smoothing agent. Furthermore, the polymer of sulfonated norbornene derivatives obtained by the method of the present invention is particularly useful as a dispersant for cement; in this case,
As will be understood from the description of the examples below, the dispersibility of cement in water can be significantly improved, and therefore a water reduction effect can be obtained in the cement construction method. Further, since the polymer of the sulfonated norbornene derivative obtained by the method of the present invention hardly entrains air, it is possible to produce high-strength concrete, and furthermore, this concrete has very little discoloration. [Examples] Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples. The weight average molecular weight described in the present invention is calculated by converting the results measured by GPC (gel permeation chromatography) based on a calibration curve created using several types of polystyrene sulfonic acids with different molecular weights as standard substances. It is. Examples 1 to 7 2 mol of the norbornene derivative shown in Table 1, 2 mol (208 g) of sodium hydrogen sulfite,
0.4 mol (20 g) of potassium nitrate, 750 ml of isopropyl alcohol, and 250 g of distilled water were charged, and the mixture was sealed and reacted at a temperature of 110° C. for 5 hours while mixing under strong stirring. Thereafter, after cooling to room temperature, the reaction mixture was taken out, 100 ml of distilled water and 300 ml of n-hexane were added, mixed thoroughly, the separated n-hexane layer and the precipitate were removed, and the remainder was concentrated and evaporated to dryness to form a pale yellow solid. was gotten. This solid was extracted with n-hexane for 1 hour using a Soxhlet extractor to remove unreacted substances, and the remaining liquid was dried and dissolved in 500 ml of glacial acetic acid, and acetic acid insoluble components such as inorganic salts were filtered off. The obtained acetic acid soluble portion was concentrated to dryness to obtain a white-yellow solid. This solid was washed with ethanol and further dried to obtain the sodium salt Bg of the sulfonated norbornene derivative shown in Table 1. The results are shown in Table 1. Next, the following polymerization reaction was carried out using the sulfonated product. 135 g of the above sulfonated product and 58 g of distilled water are placed in a three-necked flask equipped with a stirrer and a thermometer.
After preparing and dissolving, add 98% sulfuric acid 135 while cooling the whole.
g was added dropwise over about 30 minutes with stirring, then heated in an oil bath, and polymerized over a period of 35 hours at a temperature of 110 to 125° C., taking samples along the way and checking the degree of polymerization by GPC. After polymerization, add 300ml of distilled water to the reactor and dissolve.
After neutralizing with calcium carbonate and removing the precipitate, the solution was sodated with sodium carbonate to obtain a sodium salt, and the solution was dried to obtain a brown solid in the amount shown in Table 2.

[Table] The infrared absorption spectrum of the sulfonated product of Example 1 is shown in FIG. The absorption of the double bond based on the norbornene ring disappears around 1560 cm ^-1 and remains in the vinyl group, and the strong absorption based on the sulfone group appears around 1050 and 1180 cm ^-1 . It can be seen that this is a compound added to the double bond of the norbornene ring. The sulfonated products obtained in Examples 2 to 7 were also 1560 cm
Near ^-1 , the double bond based on the norbornene ring is absorbed and disappeared, and the remaining double bonds remain.
In addition, strong absorption based on the sulfone group appears near 1050 and 1180 cm ^-1 , which indicates that the compound has a sulfone group added to the double bond of the norbornene ring, based on the infrared absorption spectrum, as in Example 1. It was confirmed.

【table】

[Table] The infrared absorption spectrum of the polymer obtained in Example 1 is shown in FIG. 2, and the GPC chart is shown in FIG. 3. Compared to Figure 1, the vinyl group has largely disappeared,
From Figure 3, it is proven that it is a polymer. Also, the sulfone group remains. From these facts, it can be seen that this is a polymer in which polymerization has proceeded due to vinyl groups. Similar to Example 1, it was confirmed from the infrared absorption spectra and GPC charts that the polymers obtained in Examples 2 to 7 were polymerized due to residual double bonds. Examples 8 to 11 150 g of the sulfonated norbornene derivative obtained in Example 1 and the compounds shown in Table 3 were each charged with Cg and polymerized using the same recipe as in Example 1. The results are shown in Table 3.

[Table] Reference Example 1 4% aqueous solutions of the polymers obtained in each of Examples 1 to 11 above were prepared and their surface tensions were measured at a temperature of 20°C. The results are shown in Table 4. As can be seen from these results, the polymer obtained by the method of the present invention exhibits less foaming and has excellent surfactant action. In addition, 2 g of the polymers obtained in Examples 1 to 11 and 50 g of distilled water were added to 200 g of commercially available cement "Boltland Cement" (manufactured by Onoda Cement Co., Ltd.) and mixed by hand for 3 minutes. Using a 98.9 cc flow cone, the flow values shown in Table 4 were obtained. On the other hand, when the material obtained by the method of the present invention without the addition of the polymer was kneaded by hand in the same manner and the flow value was measured, a flow value of only 86 mm was obtained. Further, the coloring property of the cement paste to which the polymer obtained by the method of the present invention was added was very small. The results show that the polymer obtained by the method of the present invention has extremely excellent dispersibility of cement in water and has very low coloring property.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 shows a sulfonated norbornene derivative obtained by the method of the present invention in Example 1, and FIG. 2 shows a polymer of sulfonated norbornene derivative obtained by the method of the present invention in Example 1. FIG. 3 is a GPC diagram of a sulfonated norbornene derivative () and a polymer () of a sulfonated norbornene derivative obtained by the method of the present invention in Example 1. be.

Claims (1)

[Claims] 1. 9 carbon atoms represented by the following general formula (A) or (B)
-12 norbornene derivatives, characterized in that the double bond of the norbornene ring of the norbornene derivative is sulfonated in the presence of a sulfonating agent, and the obtained sulfonated product is polymerized in the presence of an acidic compound catalyst. Method for producing sulfonated polymers. In the formula, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ is an alkylene group having 1 to 3 carbon atoms. , R ₆ and R ₇ represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, R ₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and θ represents 0 or 1. Note that the group at the 6-position may also be at the 5-position.