JPS6152829B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel compound, isocyanuric acid (3-mercaptopropyl) ester, a method for producing the same, and a polymerization regulator. In addition to being used as polymerization regulators, the compounds obtained by the present invention can be used as synthetic resin raw materials, crosslinking agents, vulcanizing agents, epoxy resin curing agents, metal complex forming reagents, antioxidants, biochemical drugs, It has a wide range of uses as a lubricating oil additive, etc., and is a compound that has never been obtained as a single product until now. Further, by utilizing the present invention, tris(3-mercaptopropyl) isocyanurate can be economically obtained from, for example, triallyl isocyanurate. Mercaptans are usually used in reactions between organic halogen compounds and sodium bisulfide, reactions between alcohols and hydrogen sulfide using thoria at high temperatures, hydrolysis of S-alkylisothiuronium salts, and reactions between alcohols and phosphorous pentasulfide. It is well known that it can be synthesized by However, no matter which method is applied, the isocyanuric acid (3-
It was not possible to obtain mercaptopropyl ester. The present inventors have conducted research on the synthesis of isocyanuric acid esters for many years, and have now succeeded in obtaining isocyanuric acid (3-mercaptopropyl) ester as a new sulfur-containing isocyanurate by an industrially advantageous method. It is. That is, isocyanuric acid (3-mercaptopropyl) ester, which is a new compound according to the present invention, has the general formula (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a γ-mercaptopropyl group, or an allyl group.) The present inventors prepared an allyl isocyanuric acid ester and a thiol acid represented by the general formula R ³ COSH (in the formula, R ³ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms) in a polar solvent. It was revealed that isocyanuric acid (3-mercaptopropyl) ester can be industrially advantageously produced by recovering the solvent from the reaction mixture, hydrolyzing the resulting reaction product, and then purifying it. Further, as the polar solvent, a solvent selected from the group consisting of formic acid, formate ester, acetic acid, acetate ester, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetic anhydride, butyrolactone, and acetophenone is used. It was also revealed that it is desirable to use one carbonyl compound solvent for both. Furthermore, the present inventors have found that the isocyanuric acid (3
- In the method for producing (mercaptopropyl) ester, the reaction can be made smoother by carrying out the reaction in a polar solvent in the presence of a radical catalyst, by carrying out the reaction with ultraviolet irradiation, or by using these in combination. I found out. Furthermore, the present inventors have found that when obtaining the isocyanuric acid (3-mercaptopropyl) ester, the yield and purity of the target product can be further improved by performing hydrolysis and then purification in a non-oxidizing atmosphere. It has been clarified. The isocyanuric acid allyl ester used in the present invention is shown in the following figure. Among these, triallyl isocyanurate is an important raw material because it is a compound that is supplied industrially in large quantities. Next, the general formula R ³ COSH (in the formula, R ³ represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms).
The thiol acids represented by are thiol formic acid (HCOSH), thiol acetic acid (CH ₃ COSH), thiol propionic acid (CH ₃ CH ₂ COSH), and thiol butyric acid (CH ₃ CH ₂ CH ₂ COSH) alone or in combination.
It is a mixture of more than one species or a mixture of these with a corresponding carboxylic acid containing 30% by weight or more. The above triallyl isocyanurate and general formula
The way in which it is combined with the thiol acid represented by R ³ COSH influences the reaction mode, and when the above limited triallyl isocyanurate is combined with the above limited thiol acid, the reaction proceeds smoothly. However, when the above-mentioned limiting conditions are removed, for example, increasing the number of carbon atoms in the alkyl group in R ³ inhibits the steric hindrance of the atomic group and the permeability constant. The desired reaction cannot occur smoothly. Therefore, since the present inventors have confirmed that isocyanuric acid (3-mercaptopropyl) ester cannot be successfully obtained under conditions other than those of the present invention,
Care must be taken in selecting raw material compounds. Polar solvents as used in the present invention are non-oxidizing, non-basic, non-strongly acidic (including non-Lewis acidic) and non-polymerizable liquids that have a conductivity constant (also referred to as a medium constant) of 6 or more. It points. Typical examples include water, hydrogen sulfide, formic acid, nitromethane, methanol, acetonitrile, thiol acetic acid, methyl formate, ethanol, ethylene glycol, acetone, methyl acetate, nitroethane, nitropropane, propanol, isopropanol, propylene glycol, and methoxy. ethanol, acetic anhydride,
Methyl ethyl ketone, ethyl formate, ethyl acetate,
Propyl formate, glycol monoacetate, various butanols, dimethylmalonate, cyclopentanol, 2-pentanone, 3-pentanone, amyl alcohol, isoamyl alcohol, O-dichlorobenzene, nitrobenzene, cyclopentanone, cyclohexanone, dimethyl oxalate ,
diethyl oxalate, cyclohexanol, 2
-hexanone, methyl isobutyl ketone, diisobutyl ketone, butyrolactone, diacetone alcohol, mesityl oxide, acetylacetone,
Acetonylacetone, alkoxyethyl, acetate, benzonitrile, various nitrotoluenes, various methylcyclohexanones, various methylcyclohexanols, various heptanones, acetophenones,
Methyl benzoate, 2-octanone, glycerin triacetate, a terpene compound having a carbonyl group, etc. may be used alone or as a mixture of two or more thereof, or a mixture with an inert solvent containing 50% by weight or more of these. When triallyl isocyanurate is used as the allyl isocyanurate ester, particularly useful ones are formic acid, formate, acetic acid, acetate, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetic anhydride, It is butyrolactone and acetophenone alone or a mixture of two or more thereof, or a mixture with an inert solvent containing 50% by weight or more of these. The inert solvents referred to here are hydrocarbons, halogenated hydrocarbons, ethers,
This refers to carbon disulfide, etc. Next, a general explanation will be given of the reaction of isocyanuric acid allyl ester and thiol acid represented by the general formula R ³ COSH in a polar solvent. Now, isocyanuric acid allyl ester is abbreviated as (=N) _-CH2CH = _CH2 . (=N)−CH ₂ CH=CH ₂ +R ³ COSH →(=N)−CH ₂ CH ₂ CH ₂ SCOR ³ …(1) (=N)−CH ₂ CH ₂ CH ₂ SCOR ³ +H ₂ O → (=N)-CH ₂ CH ₂ CH ₂ SH + R ³ COOH ...(2) According to Markownikov's law, the product of formula (1) is a radical addition reaction, and even after the hydrolysis of (2), the product of formula (1) is a radical addition reaction. Since this history remains unchanged, if a radical catalyst or the like is used, it should proceed regardless of the reaction solvent or the like. However, according to many experiments conducted by the present inventors, this reaction proceeds only in inorganic and organic solvents having an appropriate conductivity constant as described above.
It was discovered that the selection of solvent is important, as is the case with onium production reactions such as the Menshyutkin reaction and the Michael-Arbuzov reaction, and in the presence of an appropriate solvent, the reaction proceeds smoothly without producing side reactions, just like ionic reactions. It was discovered that However, in the subsequent selection of reaction conditions, we found that a more effective effect of the solvent was achieved through the combination of a radical catalyst and ultraviolet rays following the setting of the solvent, but we did not find a reaction product corresponding to the allylic rearrangement reactant. be interested. This reaction is carried out at 0-150°C, particularly preferably at 20-110°C.
The reaction takes place and proceeds at ℃, and the reaction time is approximately 10 to 1000 minutes, depending on the amount of reaction. In most cases, the reaction is carried out under normal pressure, but in cases where hydrogen sulfide pressure is required or in particular when a low boiling point solvent is used, it is carried out under increased pressure. Separation of the reactant from the reaction mixture is called solvent recovery in the present invention, and this recovery is carried out by distillation or evaporation of the solvent under normal pressure or reduced pressure, and when water is used as the solvent, cooling is performed. Recrystallization separation can be performed. However, it goes without saying that this solvent separation should be carried out in consideration of economic issues, and whether or not solvent recovery is sufficient should be reflected in the operation including this point. Furthermore, when carrying out the method of the present invention, care should be taken to select raw materials, solvents, and conditions while considering the yield of the target product. The combination must be considered to avoid secondary decomposition of reactants as much as possible. Examples thereof will be shown in Examples below. The process of hydrolyzing and then purifying the reaction product thus obtained consists of the following steps and operations. The reaction (2) can be achieved by any one of (a) acidic hydrolysis, (b) neutral hydrolysis, and (c) alkaline hydrolysis. A non-oxidizing mineral acid such as hydrochloric acid, sulfuric acid, or phosphoric acid is used as a catalyst for acidic hydrolysis, and the reaction is carried out at a reaction temperature of 20 to 110°C and an acid concentration of about 0.2 to 15.0%. Neutral hydrolysis is carried out in hot water at 100°C or higher under pressure, but the liquid becomes more acidic as acetic acid is liberated. Alkaline hydrolysis is carried out at 40-120°C in the presence of aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, calcium carbonate, calcium hydroxide, calcium carbonate. In the presence of a calculated amount of alkali, alkali acetate is produced, but in the presence of an excess of alkali, a mercaptide is produced, so in this case the reaction must be acidified to liberate the mercaptan. Although either reaction is relatively easy, a small amount of surfactant may be used in combination to further promote hydrolysis and aid dispersion in water. The reaction mixture is subjected to a solvent extraction method, a steam distillation method, an oil layer separation method, a salting-out method, a centrifugation method, etc. to separate isocyanuric acid (3-mercapetopropyl) ester, which is then washed with water, dried, decolorized, distilled or Purified through any method such as recrystallization. What should be noted here is that it is preferable to perform these steps, from hydrolysis to the end of purification, in a non-oxidizing atmosphere as much as possible to avoid a decrease in purity due to the contamination of disulfides caused by the presence of an oxidizing agent. should be operated to prevent this. The non-oxidizing organic radical catalyst used in the present invention refers to a catalyst that acts as an oxidizing agent among radical catalysts, such as oxygen, ozone, persulfate, percarbonate, perchlorate, perborate, perborate, etc. manganate,
Excluding perorganic acids, hydrogen peroxide and ozonide,
It is a radical reaction initiator that is used in ordinary addition polymerization reactions but is not often used in oxidation reactions. Specific examples include benzoyl peroxide, para (or ortho or meta) chlorobenzoyl peroxide, para (or ortho or meta) methylbenzoyl, paramethoxybenzoyl peroxide, paranitrobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, ditertiary butyl peroxide, caproyl peroxide, isooctanoyl peroxide, Lauroyl oxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetyl peroxide, propionyl peroxide, 2,4-dichlorobenzoyl peroxide, tertiary-butylcumyl peroxide, dicumyl peroxide, tertiary-butyl peracetate, diisopropyl peroxydicarbonate , di-secondary butyl peroxydicarbonate, azobis-2,4-dimethylvaleronitrile, azobis-2-methylbutyronitrile, azobisisobutyronitrile, 2,2'-azobis-(2-amidinopropane) dihydrochloric acid It refers to salts, azobis-2-cycloalkylidene cyanide, and compounds in which the nitrile group is changed to a carbomethoxy group or a carboethoxy group, either singly or in a mixture of two or more. When using such radical catalysts, the decomposition temperature of the radical catalyst in the reaction mixture (30 to 150
It is desirable to carry out the reaction at a temperature (especially preferably 40 to 120°C), and light may or may not be present. The amount of radical catalyst added to the reaction mixture should be set within the range of 0.05 to 5.0%; if it is unnecessarily large or the reaction temperature is too high, the isocyanuric acid allyl ester itself may Polymerization and resin formation occur, resulting in a significant decrease in the yield of the target product of the present invention. The ultraviolet light referred to in the present invention refers to light that is absorbed by isocyanuric acid allyl ester or thiol acid,
From the ground state to the photoexcited state (there are singlet states and triplet states, which have different energy states and lifetimes, but this state crosses between systems and still activates the molecule) It is a type of electron beam that is necessary to impart energy to create active chemical species with different electron configurations.
Generally, the wave number (λ-1) is around 10 ⁴ to 10 ⁵ cm ^-1 , but the method of the present invention has a wavelength (λ) of 200 to 500 nm.
Particularly preferably, a wavelength of 250 to 400 nm (generally, shorter wavelengths are more preferable) is conveniently used, as reaction time can be shortened and side reactions can be reduced. Ultraviolet light can be obtained by using ordinary ultraviolet lamps, mercury lamps, fluorescent lamps, xenon lamps, tungsten lamps, sunlight, or arc lamps.
By using a mercury lamp for chemical reactions, it is possible to easily obtain and use light of the required wavelength without having to select the light beams. The non-oxidizing atmosphere as used in the present invention refers to an atmosphere that oxidizes mercaptans when hydrolyzing or purifying the mixture obtained by the reaction of isocyanuric acid allyl ester and thiol acid represented by the general formula R ³ COSH. Excluding oxidizing agents such as organic active halogen compounds, hydrogen peroxide, permanganates, chromic acid, nitric acid, halogens, organic peracids, persulfuric acid, selenium dioxide, iron chloride, potassium ferricyanide, oxygen (air) and ozone Refers to the reaction atmosphere. Isocyanuric acid (3-mercaptopropyl) obtained from the raw materials (), (), () of the present invention
The general term ester includes compounds shown by the following structures and properties (the structural formulas are based on elemental analysis values, IR (infrared absorption spectra) and
confirmed by nmr (nuclear magnetic resonance spectrum)). Products when the above () is used as raw material The product shown in parentheses is mono(3-mercaptopropyl) isocyanurate, which is a viscous liquid with almost no odor and becomes a white solid when cooled. Further, this compound is insoluble in hydrocarbons, soluble in alcohols, ketones, and aqueous alkaline solutions, easily soluble in dimethyl formaldehyde, and slightly soluble in water. Products when the above () is used as raw material The product shown in parentheses is bis(3-mercaptopropyl) isocyanurate, which is a viscous liquid with a slight odor that solidifies on cooling. Moreover, this material is soluble in polar organic solvents and alkaline aqueous solutions. The product shown in parentheses is allyl isocyanurate (3-mercaptopropyl), which is a viscous liquid with a slight odor that solidifies on cooling. Moreover, this material is soluble in polar organic solvents and alkaline aqueous solutions. In addition, bromine can be added to the product and quantitative determination can be made thereby. Products when the above () is used as raw material The product shown in parentheses is tris(3-mercaptopropyl) isocyanurate, which is a viscous heavy liquid with a slight odor.
When cooled, it becomes a glassy substance. In addition, this substance is soluble in organic solvents and alkaline aqueous solutions,
Reaction with 2,4-dinitrofluorinated benzene gives the corresponding trithioether (mp 104°C). The product denoted by () is allyl-bis(3-mercaptopropyl) isocyanurate, which is a viscous heavy liquid with a slight odor that becomes glassy on cooling. This product is also soluble in organic solvents and adds one molecule of bromine. It may turn yellow during storage, so it is best to store it protected from light. The product indicated by () is diallyl-(3-mercaptopropyl) isocyanurate,
This is a colorless to pale yellow liquid with a slight odor, becomes grease-like when cooled, and may be solidified by radical-generating reagents. Moreover, this material is quite soluble in organic solvents. In principle, which of the above () to () to be produced can be arbitrarily determined depending on the type of raw material, the amount of the general formula R ³ COSH used, or the reaction conditions. Regarding the relationship between () and (), when either one is the main product, the other becomes a by-product, and the relationship between () () and () is different when either one is the main product. These have the relationship of becoming by-products. Furthermore, the present inventors have repeatedly considered various uses of isocyanuric acid (3-mercaptopropyl) ester, which is the target product of the present invention, and have found that in the polymerization or copolymerization reaction of organic compounds having unsaturated hydrocarbon acids, In particular, when 0.01 to 10 parts by weight of isocyanuric acid (3-mercaptopropyl) ester is mixed with 100 parts by weight of the organic compound, the step of polymerizing or copolymerizing the organic compound can be significantly controlled; They discovered that it is possible to adjust the degree of polymerization to any desired degree. Organic compounds having unsaturated hydrocarbon residues include ethylene, propylene, butylene, pentene, styrene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinyl ether, vinyl ketone, divinylbenzene, butadiene. , cyclopentadiene, acrylonitrile, acrylic acid alkyl ester, methacrylic acid alkyl ester, allyl ether, diallyl phthalate, triallyl trimellistate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, dialkyl maleate, Indicates one or a mixture of two or more selected from maleic acid diallyl ester, maleimide, itaconic acid dialkyl ester, fumaric acid dialkyl ester, oleic acid, oleic acid ester, etc., and in some cases, two or more organic compounds are reacted sequentially. In some cases. Isocyanuric acid (3-mercaptopropyl) ester as a polymerization regulator according to the present invention can be used in the same manner as conventionally known mercaptans, and compared to mercaptans, it can be used in a small amount and has very little odor. Since it is weak and has a low vapor pressure, it has the advantage that there is no environmental pollution due to odor during the manufacturing process, and that no odor remains in the obtained polymer. As described above, isocyanuric acid (3-mercaptopropyl) ester is very effective as a polymerization regulator, but it must be used in all cases of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Applicable and requires no special precautions. still,
Polymerization reactions in which isocyanuric acid (3-mercaptopropyl) ester is effective as a polymerization regulator are limited to radical polymerization reactions. That is, it is applied to non-catalytic thermal polymerization reactions and catalytic radical polymerization reactions using organic or inorganic peroxide catalysts, azo compound catalysts, redox catalysts, etc. The present inventors have clarified through numerous experiments that isocyanuric acid (3-mercaptopropyl) ester can be obtained in good yield by the above-described method using isocyanuric acid allyl ester and thiol acetic acid as raw materials. Several representative examples will be extracted from the experimental examples and shown as the following examples. Example 1 124 g of triallyl isocyanurate and 126 g of thiol acetic acid were placed in a flask that could be irradiated with ultraviolet rays.
g, 1000 g of acetone, and 500 g of acetic acid were reacted at 30°C for 100 minutes while irradiating with ultraviolet light, and the reaction mixture was distilled under reduced pressure to yield 950 g of acetone and 470 g of acetic acid.
The residue was dissolved in about 10 times the amount of methanol, 50 g of concentrated hydrochloric acid was added, and the mixture was boiled and refluxed for 6 hours.
Next, after neutralizing by adding anhydrous sodium carbonate, methanol was distilled off in a nitrogen stream from the methanol solution obtained by passing it through a column packed with neutral activated alumina, and further drying under reduced pressure yielded tris isocyanurate (3 -mercaptopropyl)
mp. -27 to -26°C, ^n29D _1.5561 was obtained in about 98% yield. The elemental analysis value as C ₁₂ H ₂₁ N ₃ O ₃ S ₃ is C=
41.28%, H=6.08%, N=11.63%, S=27.10
%, (calculated values are C=41.03%, H=5.98%, N=
11.97%, S=27.35%). This compound is 2,4-dinitrochlorobenzene or 2,4
- By reacting with dinitrofluorobenzene, it was confirmed as tris(2,4-dinitrophenyl)thioether (mp. 104°C). The nmr and ir spectra of tris(3-mercaptopropyl) isocyanurate were as follows. nmr (CDCl ₃ ); τ 6.0 (triplet, 2H), 7.0~7.6 (multiplet, 2H),
7.8-8.3 (quintuple line, 2H), 8.4-8.7 (triple line,
1H) ir；νcm ^-1 2980, 2560, 1680, 1440, 760 Example 2 12.4 g of triallyl isocyanurate and 120 g of thiol acetic acid were placed in a flask that could be irradiated with ultraviolet rays.
("Organic Synthesis", 4 volumes, 928 pages, 1967 edition, John Wiley & Sons, Inc.,
Hydrogen sulfide dissolved in acetic anhydride) and 200 g of methyl ethyl ketone were reacted for 2.8 hours at 25 to 35°C while irradiated with ultraviolet light, and most of the acetic acid and methyl ethyl ketone were recovered by distillation under reduced pressure. 5% sodium hydroxide aqueous solution
400ml was added and boiled for 1 hour. After cooling, the reaction mixture is acidified with concentrated hydrochloric acid and extracted with benzene. The extract is dried over anhydrous magnesium sulfate and distilled in an argon stream to obtain tris(3-) isocyanurate.
Mercaptopropyl) is obtained as a viscous distillation residue, which is decolorized and purified using activated carbon and activated clay to obtain an oily product with a temperature of -27 to -26°C and ^n29D _of 1.5559. The yield was about 92% and it was confirmed as 2,4-dinitrophenyl ether. Example 3 Triallyl isocyanurate in a photochemical flask
15.0g, thiol acetic acid 5.0g and acetone 130ml
and irradiated with ultraviolet rays in a nitrogen stream at 20℃.
After the reaction was carried out for 30 minutes and acetone was recovered from the reaction mixture, the residue was separated using a column chromatography device. The column was packed with activated alumina and operated at room temperature using benzene as a developing solution to separate the products. Each separated product was then hydrolyzed with a 5% aqueous sodium hydroxide solution according to the method of Example 2. When the reaction product is extracted and purified, tris isocyanurate (3-
mercaptopropyl), allyl isocyanurate,
Bis(3-mercaptopropyl) and diallyl mono(3-mercaptopropyl) isocyanurate were obtained in a weight ratio of 3:1:3 (total yield: about 90%). All operations in this experiment were performed in a nitrogen atmosphere.
The elemental analysis values of allyl bis(3-mercaptopropyl) isocyanurate as C ₁₂ H ₁₉ N ₃ O ₃ S ₂ are C = 45.38%, H = 6.10%, N = 13.18%, S =
20.34% (calculated values are C=45.43%, H=5.99%, N
= 13.25%, S = 20.19%). Furthermore, since the bromine number of this product was 48.6 (calculated value was 50.5), it was determined that it contained one allyl group.
The nmr and ir spectra were as follows. nmr (CDCl ₃ ); τ 3.9-4.4 (multiplet, 1H), 4.5-4.9 (multiplet,
2H), 5.5 (double line, 2H), 6.0 (triple line, 4H),
7.1~7.5 (multiplet, 4H), 7.8~8.2 (quintet,
4H), 8.4-8.6 (triple line, 2H) ir; νcm ^-1 3100, 2550, 1680, 1450, 755 On the other hand, the element of diallyl mono(3-mercaptopropyl) isocyanurate as C ₁₂ H ₁₇ N ₃ O ₃ S The analysis values are C=49.90%, H=6.13%, N=14.63%,
S = 10.85% (calculated values are C = 50.88%, H = 6.01
%, N=14.84%, S=11.31%). Furthermore, since the bromine number of this product was 57.8 (calculated value was 56.5), it was determined that it contained two allyl groups. The nmr and ir spectra were as follows. nmr (CDCl ₃ ); τ 3.8-4.4 (multiplet, 2H), 4.5-4.9 (multiplet,
4H), 5.5 (double line, 4H), 6.0 (triple line, 2H),
6.9-7.4 (multiplet, 2H), 7.8-8.2 (quintet,
2H), 8.3 to 8.6 (multiplet, 1H) ir; νcm ^-1 3100, 2980, 2540, 1670, 1455, 760, Example 4 12.6 g of thiol acetic acid used in Example 1
When the same operation as in Example 1 was carried out using 1.7 mol of thiol acid shown in the following table instead of 1.7 mol of thiol acid, tris(3-mercaptopropyl isocyanurate) was obtained with the yield shown in Table 1. )was gotten.

[Table] In the above table, the UV and yield values are those of Example 1.
These are the results of the reaction carried out while irradiating ultraviolet rays, and the results shown as LPO and yield are those obtained in Example 1 when 5 g of lauroyl peroxide was dissolved in acetic acid, a solvent, without irradiating ultraviolet rays. This is the result of an experiment. This experimental operation was performed in a nitrogen stream. Example 5 Diallyl isocyanurate 5.0g, thiol acetic acid
4.0g, 40ml of ethanol saturated with hydrogen sulfide,
40 ml of ethyl acetate, 80 ml of methyl isobutyl ketone,
After reacting at 40°C for 2 hours while irradiating with ultraviolet rays, the solvent was recovered by distillation, and the residue was poured into 100 ml of 5% potassium hydroxide aqueous solution.
After boiling for an hour, it was cooled and extracted with benzene, and the extract was concentrated in a nitrogen stream. The resulting residue was decolorized and purified using activated carbon and silica gel, resulting in approximately 80% bis(3-mercaptopropyl) isocyanurate. It was obtained in a yield of . Elemental analysis values as C ₉ H ₁₅ N ₃ O ₃ S ₂ are C = 39.15%, H = 5.20%, N = 15.45
%, S = 22.65% (calculated values are C = 38.99%, H =
5.42%, N=15.16%, S=23.10%). nmr (CDCl ₃ ); τ 2.1 (broad singlet, 1H), 5.9–6.2 (triplet,
4H), 7.0 to 7.3 (multiplet, 4H), 7.8 to 8.3 (quintet, 4H), 8.3 to 8.4 (triplet, 2H) ir; νcm ^-1 3250, 2950, 2540, 1680, 1470, 760, Example 6 The raw material isocyanurate acid, thiol acid, and solvent shown in Table 2 were placed in a flask, stirred in the presence of a catalyst or ultraviolet light, and reacted under the conditions shown in Table 2. After that, the mixture was cooled and the solvent was removed at a low temperature. It was distilled off and collected under reduced pressure. The hydrolyzate shown in Table 2 with a 1 molar concentration of the residue
After boiling in a nitrogen stream for 2 hours and cooling the reaction mixture, the reaction mixture was neutralized with 10% hydrochloric acid.
Extracted with benzene. After benzene was distilled off and recovered from the benzene extract under reduced pressure, the products shown in Table 2 were obtained.

【table】

[Table] Example 7 Monoallyl isocyanurate in a photochemical flask
15.0g, thiol acetic acid 7.4g and acetone 150ml
was added, and the reaction was carried out at 25°C for 1 hour while irradiating with ultraviolet rays. After recovering acetone from the reaction mixture, the residue was mixed with 50 ml of methanol, 50 ml of 10% aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 1 hour. Dilute hydrochloric acid was added to the reaction mixture to make it slightly alkaline, and the mixture was extracted with benzene. After drying the benzene layer with anhydrous sodium sulfate, it was passed through a column packed with neutral activated alumina, then the benzene was distilled off in a nitrogen stream, and further dried under reduced pressure, resulting in approximately 65% of mono(3-mercaptopropyl) isocyanurate. It was obtained in a yield of . The elemental analysis value as C ₆ H ₉ N ₃ O ₃ S is C = 35.62
%, H = 4.63%, N = 21.3%, S = 14.98% (calculated values are C = 35.47%, H = 4.43%, N = 20.69%, S
= 15.76%). Isocyanuric acid mono(3
The nmr and ir spectra of -mercaptopropyl) were as follows. nmr (CDCl ₃ ); τ 1.9-2.1 (broad singlet, 2H), 6.0-6.3 (triplet, 2H), 7.0-7.2 (multiplet, 2H), 7.7-8.2
(quintet, 2H), 8.2-8.6 (triplet, 1H) ir: νcm ^-1 3260, 2980, 2540, 1675, 1470, 755, Example 8 20.0 g of diallyl isocyanurate and thiol acetic acid
Dissolve 7.3 g in 180 ml of acetone and react at 25°C for 2 hours while irradiating with ultraviolet rays. Acetone was recovered, and the residue was mixed with 50 ml of methanol to give a 10%
50 ml of sodium hydroxide was added and the mixture was heated under reflux for 1 hour. The reaction mixture was made slightly alkaline by adding dilute hydrochloric acid, and then extracted with benzene. After drying the benzene layer with anhydrous sodium sulfate, it was determined by thin layer chromatography that it contained three types of reaction products.
Two of the components were found to be diallyl isocyanurate and bis(3-mercaptopropyl) isocyanurate. The remaining component was separated by column chromatography (35 g of silica gel was packed into a column with a length of 25 cm), and
After distilling off benzene and drying under reduced pressure, isocyanuric acid monoallyl mono(3-mercaptopropyl)
was obtained in a yield of 35%. Elemental analysis values as C ₉ H ₁₃ N ₃ O ₃ S are C = 43.50%, H = 5.40%, N = 17.33%,
S = 12.94% (calculated values are C = 44.44%, H = 5.35
%, N=17.28%, S=13.17%). Furthermore, since the bromine number of this product was 64.3 (calculated value was 65.8), it was determined that it contained one allyl group. The nmr and ir spectra were as follows. nmr (CDCl ₃ ); τ 2.0-2.2 (broad singlet, 1H), 3.9-4.4 (multiplet, 1H), 4.5-4.9 (multiplet, 2H), 5.5 (doublet, 2H), 5.9-6.2 (Mie line, 2H), 6.9-7.2
(multiplet, 2H), 7.7~8.2 (quintet, 2H), 8.1~
8.4 (triple line, 1H) ir; νcm ^-1 3240, 2980, 2550, 1685, 1475, 755 Example 9 In a 200 ml glass ampoule, 27 g of styrene, 105 g of benzene, 0.12 g of AIBN, and tris isocyanurate (3- 0.9 g of mercaptopropyl) was charged, and after sufficiently purging with nitrogen gas, polymerization was carried out at 60°C for 3 hours. After the reaction, the reaction solution was poured into methanol to precipitate a polymer, which was separated and dried. Measurement of reduced viscosity with 2g/-benzene
It was 0.022/g. For comparison, polymerization was carried out in the same manner as above except that tris(3-mercaptopropyl) isocyanurate was not used, and the reduced viscosity was 0.067/
It was hot at g. Example 10 Instead of 27g of styrene in Example 9
Polymerization was carried out in the same manner as in Example 9 except that 28 g of MMA was used. The reduced viscosity was measured at 2 g/-benzene and found to be 0.014/g. For comparison, polymerization was carried out in the same manner as above except that tris(3-mercaptopropyl) isocyanurate was not used, and the reduced viscosity was 0.059/
It was hot at g. Example 11 Acrylonitrile in a 200ml glass ampoule
18g, methyl acrylate 6g, DMF112g,
After 0.12 g of AIBN and 0.6 g of bis(3-mercaptopropyl) isocyanurate were charged and the mixture was sufficiently purged with nitrogen gas, polymerization was carried out at 60° C. for 3 hours. Reduced viscosity to 4g/-
When measured with DMF, it was 0.027/g. For comparison, polymerization was carried out in the same manner as above except that bis(3-mercaptopropyl) isocyanurate was not used, and the reduced viscosity was 0.090/g. Example 12 In a 700 ml glass-lined autoclave equipped with a stirrer, 180 g of ion-exchanged water, saponification degree
79.8% partially saponified polyvinyl alcohol 0.18
g, 0.18 g of lauroyl peroxide, 120 g of vinyl chloride monomer and 0.12 g of allyl bis(3-mercaptopropyl) isocyanurate,
Polymerization was carried out at 64°C for 12 hours. The produced polymer was separated, washed with water, and then dried. The degree of polymerization of this product was 650. For comparison, polymerization was carried out in the same manner as above except that allyl bis(3-mercaptopropyl) isocyanurate was not used, and a polymer with a degree of polymerization of 810 was obtained.

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom, a γ-methylpropyl group, or an allyl group.) Isocyanuric acid (3-mercaptopropyl) ester. 2. Isocyanuric acid (3-mercaptopropyl) ester according to claim 1, wherein R ¹ and R ² represent a γ-mercaptopropyl group. 3 R ¹ represents a γ-mercaptopropyl group,
The isocyanuric acid (3-mercaptopropyl) ester according to claim 1, wherein R ² represents an allyl group. 4. Isocyanuric acid (3-mercaptopropyl) ester according to claim 1, wherein R ¹ and R ² represent an allyl group. 5 R ¹ represents a γ-mercaptopropyl group,
Isocyanuric acid (3-mercaptopropyl) ester according to claim 1, wherein R ² represents a hydrogen atom. 6. The isocyanuric acid (3-mercaptopropyl) ester according to claim ¹ , wherein R 1 represents an allyl group and R ² represents a hydrogen atom. 7. Isocyanuric acid (3-mercaptopropyl) ester according to claim 1, wherein R ¹ and R ² represent hydrogen atoms. 8 Isocyanuric acid allyl ester and general formula
R ³ COSH (in the formula, R ³ is a hydrogen atom or 1 carbon atom
~3 lower alkyl group. ) is reacted with thiol acid in a polar solvent, the solvent is recovered from the mixture, the resulting reaction product is hydrolyzed, and then purified. A method for producing isocyanuric acid (3-mercaptopropyl) ester represented by the formula (wherein R ¹ and R ² are the same or different and represent a hydrogen atom, a γ-methylpropyl group, or an allyl group). 9 The polar solvent is at least one selected from the group consisting of formic acid, formate ester, acetic acid, acetate ester, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetic anhydride, butyrolactone, and acetophenone. The isocyanuric acid (3-
Method for producing mercaptopropyl) ester. 10 Isocyanuric acid (3-
Method for producing mercaptopropyl) ester. 11. The method for producing isocyanuric acid (3-mercaptopropyl) ester according to claim 8, wherein the reaction is carried out in a polar solvent while being irradiated with ultraviolet rays. 12. The method for producing isocyanuric acid (3-mercaptopropyl) ester according to claim 8, wherein the reaction is carried out in a polar solvent in the presence of a radical catalyst and while being irradiated with ultraviolet rays. 13. The isocyanuric acid according to any one of claims 8, 10, 11, or 12, characterized in that the purification after hydrolysis of the reactant is carried out in a non-oxidizing atmosphere. Acid (3-
Method for producing mercaptopropyl) ester. 14 General formula used for polymerization or copolymerization reaction of organic compounds having unsaturated hydrocarbon residues A polymerization regulator comprising an isocyanuric acid (3-mercaptopropyl) ester represented by the formula (wherein R ¹ and R ² are the same or different and represent a hydrogen atom, a γ-methylpropyl group, or an allyl group). 15 Organic compounds with unsaturated hydrocarbon residues
Claim 14, characterized in that the amount of isocyanuric acid (3-mercaptopropyl) ester used is 0.01 to 10 parts by weight per 100 parts by weight.
Polymerization regulator as described in section.