JPH0482880A - Production of glycidyl compound - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the subject compound by cyclizing a halohydrin derivative prepared from alcohols, etc., and epihalohydrins, etc., in the presence of a dehydrohalogenating agent, introducing CO2 thereinto, neutralizing a basic compound and removing the residual basic compound using silica and alumina. CONSTITUTION:A halohydrin derivative obtained by addition reaction of a compound selected from alcohols, phenols, carboxylic acids and amines with epihalohydrins and/or halohydrins is cyclized in the presence of a dehydrohalogenating agent [e.g. a basic compound such as an alkali (earth) metal hydroxide]. After completing the cyclizing reaction, carbon dioxide is then introduced into the aforementioned reaction system to neutralize the basic compound. The basic compound remaining in the above-mentioned neutralized substance is subsequently removed with a solid acid consisting essentially of silica and alumina to afford the objective compound.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing a glycidyl compound, more specifically, a method for producing a highly purified glycidyl compound by applying an industrially advantageous method. Regarding.

[Prior Art] Conventionally, glycidyl compounds have been produced by the following method.

That is, alcohols, phenols, carboxylic acids, amines, etc. and epihalohydrins and/or halohydrins are heated in the presence of a solvent or in the absence of a solvent, optionally in the presence of a catalyst, to cause an addition reaction, thereby producing a halohydrin. Gain,
Next, dehydrohalogenation is performed using a basic compound such as sodium hydroxide to close the ring. Thereafter, the salts produced as by-products during the ring closure and the remaining basic compounds were washed with water or filtered, and volatile substances were distilled off under heating and reduced pressure to obtain the desired product.

3. Detailed Description of the Invention [Problems to be Solved by the Invention] However, when producing a glycidyl compound that has relatively strong hydrophilic properties, dissolves in water, and easily emulsifies with water, Since the produced glycidyl compound is dissolved or emulsified in an aqueous system, the conventional water washing operation is difficult, and furthermore, the produced glycidyl compound is eluted into the washing water, resulting in a decrease in the yield of the target product. In addition, after the ring-closing reaction, if dehydration and solvent removal is performed only by filtration, or if dehydration and solvent removal is performed under heating conditions without the remaining basic compound being completely removed by water washing, the epoxy group of the glycidyl compound may be removed. By reacting with the remaining basic compound to form a polymer or cleavage of the epoxy group,
The epoxy equivalent and viscosity of the final product increased, leading to a decrease in product quality.

On the other hand, the method of neutralizing the remaining basic compound after the ring-closing reaction using a mineral acid such as phosphoric acid or hydrochloric acid has the risk of complicating the manufacturing process and reducing product quality.

In other words, if the amount of mineral acid added is too large, this excessive amount of mineral acid will cleave the epoxy group of the glycidyl compound and cause a decrease in product quality. In order to add basic compounds, it was necessary to measure the remaining amount of basic compounds in advance.

Therefore, with the aim of obtaining high-quality glycidyl compounds in good yields, it has been desired to develop a method for efficiently removing the remaining basic compounds as a post-treatment technique following the ring-closing reaction.

The inventors of the present invention have conducted extensive research to solve these problems, and have discovered the following facts. (1) After the completion of the ring-closing reaction, the by-produced salt is dissolved and removed with the minimum amount of water necessary to saturately dissolve it, or the by-produced salt is removed by filtration or centrifugation, and then the system A method of neutralizing basic compounds remaining in the system by introducing carbon dioxide into the system (this method prevents an increase in epoxy equivalent and viscosity during the subsequent dehydration and solvent removal steps).

(2) When neutralizing using carbon dioxide, even if excess carbon dioxide is introduced into the system, it will vaporize and be discharged outside the system, so product quality will not deteriorate. This hardly occurs, and it is sufficient to continue introducing carbon dioxide until neutralization is confirmed by color reaction of phenolphthalein, etc.

Therefore, the manufacturing process becomes simple.

(3) By using adsorption treatment using solid acids mainly composed of silica and alumina, dehydration and
It is possible to reduce the basic compound of about 101) m, which cannot be completely removed only by desolvation and filtration, to 1 pDm or less.

The present invention was completed based on this knowledge, and provides a novel method for producing glycidyl compounds with high quality and high yield under relatively simple and industrially advantageous conditions. The purpose is to provide.

[Means for Solving the Problems] The method for producing a glycidyl compound according to the present invention includes a compound selected from alcohols, phenols, carboxylic acids, and amines (hereinafter collectively referred to as "raw materials ■"), epihalohydrins, and / or addition reaction with halohydrins (in the method of producing a glycidyl compound by ring-closing the resulting halohydrin in the presence of a basic compound, after the ring-closing reaction is completed, (1) carbon dioxide is introduced into the reaction system) and (2) a step of removing the basic compound remaining in the neutralized product using a solid acid mainly composed of silica and alumina. Features.

Alcohols that are raw materials for glycidyl compounds include:
Aliphatic monoalcohols such as butanol, pentanol, hexanol, octatool, allyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, propylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,5
- Aliphatic polyhydric alcohols such as bentanediol, 3-methyl-1,5-bentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, cyclohexanol, cyclohexanediol, 1,4-cyclohexanetriol -le, 2,2
-Alicyclic alcohols such as bis(4-hydroxycyclohexyl)propane [hydrogenated hisphenol△], bis(4-hydroxycyclohexyl)methane, and cyclohexanetriol, and their alkylene oxide adducts such as ethylene oxide and propylene oxide, and phenol and alkylene oxide adducts such as carboxylic acids and isocyanuric acid.

Examples of phenols include phenol, alkylphenol, resorcinol, bisphenol A, and the like.

Examples of carboxylic acids include aliphatic monocarboxylic acids having 1 to 22 carbon atoms such as acetic acid, propionic acid, acrylic acid, methacrylic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, and oleic acid; oxalic acid, malonic acid, Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sepatic acid, maleic acid, fumaric acid and their anhydrides; phthalic acid, isophthalic acid, prephthalic acid, trimerisolic acid, benzoic acid, tert-butylbenzoic acid Aromatic carboxylic acids such as acids and their anhydrides; Alicyclic carboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, methylna-1-rabidolphthalic acid and their anhydrides; Isocyanuric acid, Examples include heterocyclic carboxylic acids such as J tylene urinary chord and hydantoin.

Examples of the amines -C include aniline, aminephenol, alkyl-substituted aminophenol, 4,4-diaminodiphenylmethane, benzylamine, xylylene diamine, and triaminobenzene.

Further, as epihalohydrins and halohydrins, epichlorohydrin, epibromhydrin, β-methylepichlorohydrin, β-methylepibromhydrin, glycerol-1,3-dichlorohydrin, etc. are representative examples, and these may be used alone or Two or more types are used in combination.

In the addition reaction, a catalyst can be used if desired. Such catalysts include stannic chloride and its hydrates, boron trifluoride, boron trichloride and complex salts thereof, Lewis acids such as Friedel-Crafts catalysts, mono-lithium hydroxides,
Basic compounds such as alkali metal or alkaline earth metal hydroxides and carbonates such as barium hydroxide and potassium carbonate;
Various compounds such as quaternary ammonium salts such as tetramethylammonium chloride and benzyltrimedelammonium chloride are exemplified, and these catalysts are appropriately selected and used depending on the type of raw material (2) to which the method of the present invention is applied. . For example, Lewis acids are used for alcohols. In this case, it is preferable that moisture in the raw materials be removed as much as possible. Furthermore, basic compounds are used for phenols, and quaternary ammonium salts are used for carboxylic acids.

Examples of the basic compound (dehydrohalogenating agent) used in the present invention include hydroxides, carbonates, oxides, and alcolades of alkali metals and alkaline earth metals such as sodium, potassium, magnesium, and calcium. It is used in solid or solution form.

The carbon dioxide applied in the present invention refers to carbon dioxide alone or a gas mainly composed of carbon dioxide, and more specifically, carbon dioxide gas or dry ice, or carbon dioxide gas with air, nitrogen, argon, etc. The form and concentration of carbon dioxide are not particularly limited as long as the desired effects of the present invention are not impaired.

The carbon dioxide should be continuously introduced into the system until it is confirmed that the neutralization is completed by the color reaction of phenolphthalein, etc.; There is no need to manage it.

The solid acid mainly composed of silica and alumina used in the present invention may be one that can adsorb and remove basic compounds remaining in the glycidyl compound, and specifically, bentonite 1~, perlite, Natural minerals such as kaolin, zeolite, and live bamboo shoots, or other solid silicic acid minerals derived from them that have similar properties, and artificially synthesized solid silicic acids that have similar properties to the above-mentioned natural minerals. For example, compounds with high acidity such as synthetic aluminum silicate are recommended.

The preferred amount of the solid acid added is about 0.05 to 3% by weight based on the target glycidyl compound.

The glycidyl compound according to the present invention is usually produced as follows. That is, the raw material T, epihalohydrin, addition reaction catalyst, and optionally a solvent are suitably charged into a predetermined reactor;
The addition reaction is carried out under heating and stirring at a temperature of about 100%. At this time, the equivalent ratio of epihalo didolino to active hydrogen in raw material (1) is usually about 0.8 to 2. Alternatively, epihalohydrin can be used in large excess and itself used as a reaction solvent. This reaction is usually carried out at normal pressure, with a pressure of 0.5 to 6
The process can be completed in about an hour, and a halohydrin compound compatible with raw material processing can be obtained.

Next, a basic compound is usually added in an amount of about 1.0 to 2.0 times equivalent to the hydrolyzable chlorine of the halohydrin. At this time, a phase transfer catalyst may be added in an amount of about 0.05 to 0.5% by weight based on the halohydrin body in order to promote the ring-closing reaction. Such phase transfer catalysts include quaternary ammonium salts such as benzyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and their bromides, 12-crown-4-ether, 15-crown -5] Crown ethers such as Nythyl are exemplified.

Next, dehydrogenation is carried out under reduced pressure (usually up to about 20 mml-tg) to normal pressure at about 30 to 100° C. for 0.5 to 6 hours to carry out a ring-closing reaction. At this time, water may be distilled off to maintain a high alkali concentration.

For the glycidyl compound composition thus obtained, if necessary, a solvent inert to the reactants (for example, benzene, toluene, xylene, hexadi, heptane, octane, medyl) is added for the purpose of reducing the viscosity of the system. ”-tyl ketone, methyl in-butyl ketone, etc.), and then, if necessary, basic compounds and by-product salts are removed by washing with water and/or
Or filter it.

After that, carbon dioxide is introduced into the system to neutralize the remaining basic compound.

After neutralization is completed, volatile substances, specifically water or the volatile solvent applied in the above treatment, are distilled off under heating and reduced pressure. By carrying out this operation, it is possible to avoid deactivation of the subsequently applied solid acid.

Next, a predetermined amount of a silica-alumina solid acid is added to the above system, and the mixture is stirred for about 30 minutes, usually at a temperature of 50 to 100'C, preferably under reduced pressure of about 3 to 20 mml-1g. In this process, a trace amount of the basic compound that remains after being neutralized in the above step is adsorbed by the solid acid. Thereafter, the system is filtered or centrifuged to recover and remove solids, yielding a highly purified glycidyl compound in high yield.

After the ring-closing reaction, without introducing carbon dioxide for neutralization,
If the solvent is removed with weak water under heating or reduced pressure, polymerization or cleavage of epoxy groups will occur, increasing the epoxy equivalent and viscosity of the final product. On the other hand, when the adsorption treatment with the solid acid according to the present invention is not used together, or when the solid acid is charged before weak water and desolvation, about 10 ppm of the basic compound remains and the desired effect of the present invention is not achieved. It is difficult to obtain.

[Example] The present invention will be described in detail below with reference to Examples.

The evaluation method for each item is as follows.

Epoxy equivalent: Based on perchloric acid method.

Organic chlorine content: Based on Volhard method.

Viscosity (25°C): Based on a B-type rotational viscometer.

Sodium content: Based on tip analysis method.

Example 1 Into a reactor equipped with a rotary stirrer, a decanter, a thermometer and a gas inlet tube, 134 g of methylolpropane (1.
0 mol), xylene 4. 1 Prepare 9, 100'C
, dehydrated under reduced pressure for 1 hour, then 100°Cl2Om
Dexylene was removed at mHg for 20 minutes (raw material pretreatment step). After cooling to 60°C, 4.3 J of boron trifluoride ether complex salt was added, and epichlorohydrin 27i (3
, 0 mol) was added dropwise at 60°C over 1 hour, and then
Stirring was continued for 0 minutes to complete the addition reaction (addition reaction step).

Then, after cooling to 40°C, 120 g of solid sodium hydroxide was added at 40°C for 130 minutes, and the temperature was increased to 11°C at 40°C.
The ring-closing reaction was completed by continuing stirring for a certain period of time (ring-closing reaction step).
. After filtering out by-produced sodium chloride and unreacted solid sodium hydroxide, carbon dioxide gas was bubbled into the filtrate at 40°C until the filtrate stopped turning red due to phenoltutalein (about 10 minutes). The remaining sodium hydroxide in the form of an aqueous solution was neutralized (neutralization step). Furthermore, 8
Dehydration and solvent removal were performed for 2 hours with 0'Cl 3 mmHg. After that, 3 parts of Kyoward 7003N (Fg, synthetic aluminum silicate manufactured by Wa Kagaku Kogyo ■) was added and heated at 80°C13+n.
After stirring for 30 minutes at m1-10, the solid matter was filtered out (
purification process). As a result, the epoxy weight was 122, the organic chlorine content was 7.0%, and the viscosity at 25°C was 11.
301 g (yield 99.7%) of the target trimethylolpropane polyglycidyl ether having 0 cp was obtained. In addition, the sodium content in the glycidyl compound is
It was below the detection limit (0.1 ppm, the same applies hereinafter).

Example 2 A 6-mol adduct of bisphenol A ethylene oxide 4929 (''1.0 mol) and xylene 769 were charged into the same reactor as in Example 1, and dehydrated at 100'C for 1 hour under reduced pressure.80°C. After cooling to, stannic chloride pentahydrate 3,
29 and epichlorohydrin '194y (2,
1 mol) was added dropwise over 80'(,,30 minutes, and then 1 mol)
Stirring was continued for 30 minutes at 00°C to complete the addition reaction.

Then, after cooling to 80°C, 0.79% of benzyl 1-limethylammonium chloride was added, and 1779% of a 50% aqueous solution of 1-lium hydroxide was added at 80°C for 30 minutes.
0°(.

Stirring was continued for 2 hours to complete the ct'C ring closure reaction. Add distilled water 2507 and stir for 130 minutes at 60'C to dissolve the by-produced sodium chloride. Leave to stand to remove the brine layer, and stir until the oil layer stops turning red due to phenolphthalein (about 10 minutes). ) The remaining sodium hydroxide was neutralized by blowing in carbon dioxide gas. Furthermore, 120'C, 3
After 2 hours of dehydration and solvation in mlll-ill, 39 g of Kyoward 7003N was added, and the mixture was stirred at 80'C13 Hg for 30 minutes. After that, it is filtered and the epoxy equivalent is 36.
5. Glycidyl ether 6019 (yield 98.6%), which is a 6 mole adduct of bisphenol Δ/ethylene oxide, having an organic chlorine content of 1.7% and a viscosity of 11000P was obtained. Note that the sodium content in the glycidyl compound was below the detection limit.

Example 3 In a reactor similar to Example 1, 161 (1 mol) of 4-methylhexahydrophthalic anhydride and 250 mol of epichlorohydrin were added.
s (2,7 mol), tetramethylammonium chloride 3
．． 3g of distilled water and 30SJ of distilled water were charged, and after stirring at 80'C for 5 hours to complete the addition reaction, 1 to 149q of toluene were added. Next, azeotropic dehydration was performed while dropping 213 J of a 45% sodium hydroxide aqueous solution over 12 hours at 80° C. to complete the ring-closing reaction. Thereafter, the remaining sodium hydroxide was neutralized by stirring at 40° C. while adding dry ice until the ring-closing reaction product stopped turning red quickly due to phenolphthalein. Furthermore, 120'CC13m
After dehydration and solvent removal for 2 hours at 1llH, Kyoward 7
Add 33 ml of 00SN and heat to 80'C.

Stirred with 3ml HO for 30 minutes. After that, it is filtered and has an epoxy equivalent of 171 and contains organic chlorine! 0.6%, viscosity 52
4-Methylhexahydrophthalic anhydride diglycidyl ester 2989 (yield 93.3%) having 0CP was obtained. In addition, the sodium content in the glycidyl compound is
It was below the detection limit.

Comparative Example 1 The same procedure as in Example 1 was carried out except that carbon dioxide gas was not blown in, and 291 g (yield: 96.4%) of the desired 1-limethylolpropane polyglycidyl ether was obtained. Incidentally, the epoxy equivalent of this product was 190, the organic chlorine content was 6.9%, and the viscosity was 2200 P.

Comparative Example 2 The reaction was carried out in the same manner as in Example 2, except that carbon dioxide gas was not blown in. After the ring-closing reaction, water washing was repeated until the red color was no longer caused by phenolphthalein, and the remaining hydroxide 1
Although the lithium was removed, the oil layer was significantly emulsified in the second and subsequent water washing operations, and it took a long time to separate the water layer.

Further, 120'C13m+u days (1 to 2 hours of dehydration and desolvation, then filtration revealed that the target diglycidyl ether of bisphenol△・ethylene oxide 6 moles adduct was 56b'j (yield 92.7%) Incidentally, this product had an epoxy equivalent of 364, an organic chlorine content of 1.8%, and a viscosity of 1080CP.

Comparative Example 3 The reaction was carried out in the same manner as in Example 3, except that carbon dioxide gas was not blown in. After the ring-closing reaction, the remaining sodium hydroxide was removed by repeatedly washing with water until the red color was no longer affected by phenolphthalein. Furthermore, 120'C, 3mm1-1 (
After removing the solvent with fB2 water for 2 hours and filtering, 254 g (yield 79.4%) of the desired diglycidyl methylhexahydrophthalic anhydride was obtained.

Incidentally, this product had a nipoxy equivalent of 164, an organic brine content of 0.6%, and a viscosity of 510 cP.

Comparative Example 4 After dehydration and solvent removal, filtering was carried out as it was without adding Kyoward 700SN, but the method was shielded according to Example 2, and the desired diglycidyl ether of bisphenol Δ and 6 moles of ethylene oxide adduct was obtained. 6039 (yield 99.0%) was obtained. By the way, the epoxy equivalent of this product is 364, the chlorine content is 7%, and the viscosity is 110.
I got it with 0CP. Note that the sodium content in the glycidyl compound was 4.3DprT1.

[Effects of the Invention] The method for producing a glycidyl compound according to the present invention easily and reliably inactivates the basic compound remaining after the ring-closing reaction, thereby reducing the polypolymer equivalent and viscosity of the final product, and the remaining base. The quality, such as the content of sexual compounds, can be significantly improved.
Moreover, it becomes possible to improve the yield.

Patent applicant: Shin Nihon Rika Co., Ltd.

Claims (1)

[Claims] 1. A halohydrin compound obtained by an addition reaction between a compound selected from alcohols, phenols, carboxylic acids, and amines and epihalohydrins and/or halohydrins is ring-closed in the presence of a basic compound. In the method for producing a glycidyl compound, after the completion of the ring-closing reaction, (1) introducing carbon dioxide into the reaction system to neutralize the basic compound, and (2) containing silica and alumina as the main components. A method for producing a glycidyl compound, comprising the step of removing basic compounds remaining in the neutralized product using a solid acid.