JP2003002880A - Method for producing polyvalent alcohol polyglycidyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for highly selectively producing a polyvalent alcohol polyglycidyl ether having low viscosity. SOLUTION: The method for producing the polyvalent alcohol polyglycidyl ether is characterized by reacting a polyvalent alcohol with an epihahohydrin in the presence of an acidic catalyst to prepare a halohydrin ether, reacting the halohydrin ether with a dehydrohalogen-ating agent, and by using a mixture of a boron trifluoride-complex with tin tetrachloride as the above acidic catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyhydric alcohol polyglycidyl ether, and more specifically, to produce a halohydrin ether by reacting a polyhydric alcohol with epihalohydrin. The present invention relates to a method for producing a polyhydric alcohol polyglycidyl ether having a high selectivity and a low viscosity, which uses an acidic catalyst mixture.

[0002]

2. Description of the Related Art Polyhydric alcohol polyglycidyl ether is used as a reactive diluent, a raw material, a modifier for synthetic resins, a modifier, an adhesive for paper, fibers, and polymeric materials. Conventionally, as a method for producing the same, 1) alcohol and epihalohydrin are mixed with sulfuric acid, boron trifluoride / ethyl ether,
The reaction is carried out in the presence of an acidic catalyst such as tin tetrachloride to produce a halohydrin ether, and this halohydrin ether is then reacted with a dehydrohalogenating agent to effect ring closure. 2
A stepwise method and 2) a method of producing an alcohol glycidyl ether of an alcohol and an epihalohydrin all at once using an alkaline aqueous solution by a one-step method are known.

According to the method 1), it is difficult to selectively obtain a polyhydric alcohol polyglycidyl ether, and a higher polymer is produced. That is, in the case of producing a polyhydric alcohol polyglycidyl ether from a polyhydric alcohol and epihalohydrin, if the equivalent ratio of the two is close to 1, a higher-grade polymer-forming reaction becomes dominant and the polyhydric alcohol polyglycidyl ether yield Is quite low.

In the method 2), the reaction is generally carried out in a two-phase system of an alkaline aqueous solution and an organic phase. Therefore, side reactions such as cleavage of the oxirane ring and addition of epihalohydrin to the glycidyl ether are likely to occur, and as a result, the yield of the desired glycidyl ether is reduced by by-products of oligomers and polymers.

The present invention relates to the improvement of the two-step method of the above 1), but various proposals have been made so far to improve this method. For example, JP-A-61-1
In 178974, it has been proposed to carry out a reaction between a polyhydric alcohol and epihalohydrin at a low temperature of -20 to + 5 ° C in the presence of a boron trifluoride ethyl ether catalyst in order to suppress a side reaction. In this method, not only is it difficult to control the reaction, but it is inevitable to add equipment such as a refrigerating device, which requires a large capital investment.

British Patent No. 2166738 describes
It has been proposed to use metal perchlorates as catalysts for the production of adducts of epoxy compounds with alcohols. This method shows good reactivity when the epoxy compound is ethylene oxide and the alcohol is monovalent, but the reactivity is not sufficient when the epoxy compound is epihalohydrin and the alcohol is divalent or higher.

JP-A-5-271211 discloses an ether bond-containing secondary polyhydric alcohol produced by adding a polyhydric alcohol and a monoepoxy compound in the presence of a Lewis acid catalyst, and epichlorohydrin. There has been proposed a method of ring-closing with an alkali in the presence of a phase transfer catalyst. This method has the advantage that an aliphatic polyglycidyl ether having a relatively low epoxy equivalent can be obtained, but it is not a practical method because the yield is extremely low.

Japanese Unexamined Patent Publication (Kokai) No. 5-271138 proposes a method in which a primary monohydric or dihydric alcohol and epichlorohydrin are cyclized with an alkali in the presence of a specific metal complex catalyst. According to this method, the yield was relatively good, but the epoxy equivalent of the obtained aliphatic polyglycidyl ether was large and was not practically satisfactory.

[0009]

DISCLOSURE OF THE INVENTION In view of the state of the art as described above, the present inventors have earnestly studied to provide a method for producing a polyhydric alcohol glycidyl ether compound having high selectivity and low viscosity. As a result, they have found that the above object can be achieved by using a mixture of two specific Lewis acids as an acidic catalyst, and have reached the present invention.

[0010]

[Means for Solving the Problems] That is, the present invention comprises reacting a polyhydric alcohol with epihalohydrin in the presence of an acidic catalyst to produce a halohydrin ether, and then reacting with a dehydrohalogenating agent. In the method for producing polyhydric alcohol polyglycidyl ether, a mixture of boron trifluoride complex and tin tetrachloride is used as the acidic catalyst, which is a method for producing polyhydric alcohol polyglycidyl ether.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Polyhydric alcohol and epihalohydrin
The reaction of the polyhydric alcohol with epihalohydrin in the present invention is carried out using a mixture of two specific types of acidic catalysts, boron trifluoride complex and tin tetrachloride, as a catalyst. These two types of catalysts are preferably used as a mixture from the beginning of the reaction in terms of reaction rate and selectivity,
It is also possible to use only tin tetrachloride at the beginning of the reaction, and add boron trifluoride complex after the start of the reaction to use it as a mixture of two kinds. By this reaction, the desired halohydrin ether is produced, and it becomes possible to obtain the polyhydric alcohol polyglycidyl ether having a low viscosity with a high selectivity.

The boron trifluoride complex is an ether complex such as a methyl ether complex, an ethyl ether complex, a propyl ether complex or an n-butyl ether complex, an organic acid complex such as an acetic acid complex or a phenol complex, a piperidine complex or a monoethylamine complex. It is selected from amine complex, water complex salt and the like. Easy availability, easy handling (melting point,
From the viewpoint of (boiling point), catalytic activity, easiness of removal, etc., ether complex is preferable, and ethyl ether complex is most preferable.

The tin tetrachloride is selected from hydrates such as anhydrides, trihydrates, pentahydrates and octahydrates, but the anhydrides are preferred because of their availability, stability and catalytic activity. preferable.

In order to make this reaction proceed smoothly, the polyhydric alcohol and the catalyst are mixed at a temperature of 25 to 100 ° C., preferably 60.
After heating to ˜85 ° C., epihalohydrin is preferably added dropwise and reacted. When the heating temperature is lower than 25 ° C, the initial reaction is very slow and the temperature rise is small. Therefore, if you accidentally add too much epihalohydrin, once the temperature begins to rise, it will not be possible to suppress the temperature rise,
In the worst case, there is a risk of causing a runaway reaction. vice versa,
If it is higher than 100 ° C, it will adversely affect the material and
Coarse liquid coloring is likely to occur.

The mixing molar ratio of boron trifluoride complex: tin tetrachloride in the catalyst mixture is 2: 1 to 1: 4, preferably 1: 1. If the mixing molar ratio is higher than 2: 1,
The reaction is fast, but the selectivity is low. On the contrary, when it is lower than 1: 4, the selectivity is high, but the reaction is slow. It is considered that this is because tin tetrachloride has a low catalytic activity, so that the reaction is slow and the epihalohydrin is selectively added to the primary alcohol. Since the boron trifluoride complex has a high catalytic activity, the reaction is fast and it is considered that epihalohydrin can be added without distinction between primary and secondary alcohols. Therefore, boron trifluoride ethyl ether assists the reaction of tin tetrachloride. It is thought to be because it is doing.

The amount of the catalyst mixture used is 0.1 to 6 mol%, preferably 0.2 to 0.4, in terms of the total amount of boron trifluoride complex and tin tetrachloride, based on the polyhydric alcohol.
Mol% is good. If the amount of the catalyst mixture used is more than 6 mol%, the final product may be colored. On the other hand, if the amount is less than 0.1 mol%, the reaction becomes slow, and in an extreme case, the reaction may stop halfway and a product of desired quality may not be obtained.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-
Dimethyl alcohols such as 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethylpropanediol, etc., alkylene oxide adducts thereof, polytetramethylene ether glycol, bisphenol A ethylene oxide adducts, etc .; trimethylol propane,
1,2,6-hexanetriol, pentaerythritol, sorbitol, dipentaerythritol, glycerin, diglycerin, etc., selected from trivalent or higher alcohols such as alkylene oxide adducts thereof, alkylene oxide adducts of phenol novolac, etc. . Dihydric alcohols are preferable, those having 5 or more carbon atoms are more preferable, and 1,6-hexanediol and bisphenol A ethylene oxide adduct are particularly preferable. The epihalohydrin is selected from, for example, epibromohydrin, epichlorohydrin, epiiodohydrin, β-methylepibromohydrin, β-methylepichlorohydrin and the like. From the viewpoint of easy availability, epichlorohydrin is preferable.

The amount of epihalohydrin used is 0.9 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, per one hydroxyl group of the polyhydric alcohol. When the amount of epihalohydrin used is less than 0.9 equivalents, hydroxyl groups that are not glycidyl etherified remain and the purity decreases, and WPE and viscosity increase. On the other hand, if the amount exceeds 1.5 equivalents, the reaction rate decreases, a large amount of epihalohydrin high molar adduct is formed, and WPE, viscosity, and chlorine content increase, which is not preferable.

Reaction with dehydrohalogenating agent The reaction product of the above polyhydric alcohol and epihalohydrin is usually aged after the completion of the reaction and, if necessary, without isolation and purification of the resulting halohydrin ether. , And then react with a dehydrohalogenating agent. As the dehydrohalogenating agent, a strong alkali such as lithium hydroxide,
Sodium hydroxide, potassium hydroxide and the like are preferable,
Other weak alkalis such as magnesium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and the like can also be used. Particularly, sodium hydroxide is preferable. These dehydrohalogenating agents are
Although it is preferably used as an aqueous solution, in some cases a powder or solid dehydrohalogenating agent can be added simultaneously with or separately from water. Preferably 10
~ 50% aqueous solution is preferably added, more preferably 2
It is 0 to 50%.

When a monovalent alkali such as sodium hydroxide is used as the dehydrohalogenating agent, the amount used is 1 to 2 equivalents, preferably 1.
2-1.5 equivalents are good. When a divalent alkali such as barium hydroxide is used, the amount thereof is 0.5 to 1.5 equivalents, preferably 0.5 to 1.5, relative to the polyhydric alcohol.
1.0 equivalent is good. Further, when alkali carbonate is used, it is preferable to use 1.2 to 1.5 times the amount of alkali hydroxide with respect to the polyhydric alcohol.
When the amount of the alkali used is less than the lower limit with respect to the polyhydric alcohol, the halohydrin ether group that is not glycidyl etherified remains to lower the purity, and when the amount exceeds the upper limit, it is wasteful. Not only is water added to the produced glycidyl ether, but the side product such as glyceryl etherification reduces the purity of the product, which is not preferable.

The reaction temperature with the dehydrohalogenating agent is 20
To 100 ° C., more preferably 30 to 80 ° C.
Is the range. The reaction time with the dehydrohalogenating agent varies depending on the amount of the dehydrohalogenating agent used and the use of a solvent, but is usually 0.1 to 10 hours.

Isolation of the polyhydric alcohol polyglycidyl ether after completion of the dehydrohalogenation reaction can be carried out by a conventional method. For example, if necessary, a water-insoluble solvent such as hydrocarbon is added and washed with water. After removing the produced salt, the target polyhydric alcohol polyglycidyl ether can be obtained by performing solvent removal, dehydration, and filtration.

Since the polyhydric alcohol polyglycidyl ether of the present invention is excellent in dilutability, reactivity and compatibility with other epoxy resins and curing agents, it is preferably used as a reactive diluent for epoxy resin. it can. Further, the physical properties of the cured product are equal to or higher than those of the polyhydric alcohol polyglycidyl ether produced by the conventional production method, and are very excellent. The polyhydric alcohol polyglycidyl ether of the present invention is generally used for bisphenol A type epoxy resin, but in addition to this, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin. It is also possible to combine with various epoxy resins or reactive diluents other than the present invention. In addition, as the curing agent, all commonly used curing agents such as polyamine-based, polyamide-based, acid anhydride-based, phenol novolac-based, and imidazole-based can be used. Moreover, additives such as a solvent, a filler, a flame retardant, a release agent, and a coloring agent can be used if necessary. The polyhydric alcohol polyglycidyl ether of the present invention is used in addition to reactive diluents for epoxy resins, reactive diluents / raw materials / modifiers for various synthetic resins, modifiers / adhesives for paper / fiber / polymer materials. It can also be used as an agent.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% are based on weight.

Of polyhydric alcohol polyglycidyl ether
Manufacturing

Example 1 1 equipped with a stirrer, a dropping funnel and a thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
Hexanediol 141.8 parts, boron trifluoride ethyl ether 0.26 parts and tin tetrachloride 0.47 parts were charged,
Heated to 80 ° C. 222.1 parts of epichlorohydrin (1 equivalent per one hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 85 ° C. After aging for 1 hour while maintaining the temperature at 80 to 85 ° C, it was cooled to 45 ° C. 528.0 parts of 22% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for 4 hours. After cooling to room temperature and separating and removing the aqueous phase, the remaining oil phase was washed several times with water, and then heated under reduced pressure to remove unreacted epichlorohydrin and water to obtain the desired 1,6- 283.3 parts of hexanediol diglycidyl ether were obtained (yield 95%, selectivity 62%). The WPE of the obtained product was 143. The general analysis results are shown in Table-1.

[0026]

Example 2 1 equipped with a stirrer, dropping funnel and thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
-Prepare 141.8 parts of hexanediol, 0.13 part of boron trifluoride ethyl ether and 0.70 part of tin tetrachloride,
Heated to 80 ° C. 244.3 parts of epichlorohydrin (1.1 equivalent per hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 85 ° C. 80-85
After aging for 1 hour while maintaining the temperature at ℃, it was cooled to 45 ℃. 528.0 parts of 22% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for 4 hours. After cooling to room temperature, the aqueous phase was separated and removed, and the remaining oil phase was washed several times with water, and then heated under reduced pressure to remove unreacted epichlorohydrin and water to obtain the desired 1,6- 280.6 parts of hexanediol diglycidyl ether were obtained (94% yield,
Selectivity 63%). The WPE of the obtained product was 144. The general analysis results are shown in Table-1.

[0027]

Example 3 1 equipped with a stirrer, a dropping funnel and a thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
Hexanediol 141.8 parts and tin tetrachloride 0.70
Parts were charged and heated to 80 ° C. 122.2 parts of epichlorohydrin (0.55 equivalents per hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 85 ° C. At this point, there was almost no fever, so 80
After aging for 1 hour while maintaining at -85 ° C, GC analysis revealed that unreacted epichlorohydrin remained. Therefore, boron trifluoride ethyl ether 0.13
When additional parts were added, heat was generated, so the remaining 122.1 parts of epichlorohydrin (0.55 equivalents per one hydroxyl group of diol) was added dropwise, and while maintaining the temperature at 80 to 85 ° C, 1
After aging for time, it was cooled to 45 ° C. 528.0 parts of 22% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for 4 hours. After cooling to room temperature, the aqueous phase was separated and removed, and the remaining oil phase was washed several times with water, and then heated under reduced pressure to remove unreacted epichlorohydrin and water to obtain the desired 1,6- Hexanediol diglycidyl ether 2
80.6 parts were obtained (94% yield, 63% selectivity).
The WPE of the obtained product was 144. The general analysis results are shown in Table-1.

[0028]

Example 4 2 equipped with stirrer, dropping funnel and thermometer
300 parts of bisphenol A ethylene oxide 4 mol adduct preheated to 45 ° C. in an L volume glass flask,
1.4 parts of boron trifluoride ethyl ether and tin tetrachloride 2.
6 parts were charged and heated to 65 ° C. 153 parts of epichlorohydrin (1.1 equivalent per hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 70 ° C. After aging for 0.5 hour while maintaining the temperature at 65 to 70 ° C, it was cooled to 45 ° C. Isobutanol (454 g) was added as a separating solvent, and the mixture was stirred and mixed, then 235 parts of a 25% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for 1 hour. Cool to room temperature to separate and remove the aqueous phase,
The remaining oil phase was washed with water several times, and then heated under reduced pressure to remove unreacted epichlorohydrin, water, and isobutanol as a solvent, and to obtain the desired bisphenol A ethylene oxide 4 mol adduct diglycidyl ether. 369.8 parts were obtained (94% yield, 86.1% selectivity). The WPE of the obtained product was 307. The general analysis results are shown in Table-1.

[0029]

[Comparative Example 1] 1 equipped with a stirrer, a dropping funnel and a thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
-Hexanediol 141.8 parts and tin tetrachloride 0.94
Parts were charged and heated to 80 ° C. 244.3 parts of epichlorohydrin (1.1 equivalent per hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 85 ° C. After aging for 3 hours while maintaining at 80 to 85 ° C,
Cooled to 45 ° C. The reaction rate of epichlorohydrin is 8
The reaction was interrupted at this stage because the reaction was insufficient with 5%. 528.0 parts of 22% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for 4 hours. After cooling to room temperature to separate and remove the aqueous phase, the remaining oil phase was washed with water several times, and then heated under reduced pressure to react unreacted epichlorohydrin,
Water was removed to obtain 268.6 parts of the target 1,6-hexanediol diglycidyl ether (yield 90
%, Selectivity 50%). The WPE of the obtained product was 160. The general analysis results are shown in Table-1.

[0030]

Comparative Example 2 1 equipped with a stirrer, a dropping funnel and a thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
-Hexanediol 141.8 parts and boron trifluoride ethyl ether 0.51 parts were charged and heated to 80 ° C.
244.3 parts of epichlorohydrin (one per hydroxyl group of diol: 1.
1 equivalent) was added dropwise. After aging for 1 hour while maintaining the temperature at 80 to 85 ° C, it was cooled to 45 ° C. 528.0 parts of 22% aqueous sodium hydroxide solution was added, and the mixture was heated to 45 ° C. and vigorously stirred for an hour. After cooling to room temperature, the aqueous phase was separated and removed, and the remaining oil phase was washed several times with water, and then heated under reduced pressure to remove unreacted epichlorohydrin and water to obtain the desired 1,6- Hexanediol diglycidyl ether 28
3.6 parts were obtained (yield 95%, selectivity 55%). The WPE of the obtained product was 156. The general analysis results are shown in Table-1.

[0031]

Comparative Example 3 1 equipped with a stirrer, a dropping funnel and a thermometer
In a L-volume glass flask, 1,6 preheated to 45 ° C
Hexanediol 141.8 parts and tin tetrachloride 0.70
Parts were charged and heated to 80 ° C. 122.2 parts of epichlorohydrin (0.55 equivalents per hydroxyl group of diol) was added dropwise over a period of time so that the temperature did not exceed 85 ° C. At this point, there was almost no fever, so 80
After aging for 1 hour while maintaining at -85 ° C, GC analysis revealed that unreacted epichlorohydrin remained. Therefore, when 0.70 part of tin tetrachloride was added, abnormal heat was generated, so it was determined that the polymerization reaction had proceeded, and quench water was added to stop the polymerization reaction.
Cooled to room temperature. When the composition was analyzed by GPC, a large amount of high molecular weight substances (polymers) were formed.

[0032]

Comparative Example 4 2 equipped with stirrer, dropping funnel and thermometer
300 parts of bisphenol A ethylene oxide 4 mol adduct preheated to 45 ° C. in an L volume glass flask,
2.6 parts of tin tetrachloride were charged and heated to 65 ° C. The addition of epichlorohydrin was started but no exotherm occurred. 2.6 parts of tin tetrachloride was added and the reaction temperature was adjusted to 90.
The temperature was raised to 0 ° C, but no exotherm occurred, so it was judged that the reaction had not progressed, and the experiment was stopped.

[0033]

Comparative Example 5 2 equipped with a stirrer, dropping funnel and thermometer
300 parts of bisphenol A ethylene oxide 4 mol adduct preheated to 45 ° C. in an L volume glass flask,
Charged with 1.41 parts of boron trifluoride ethyl ether, 65
Heated to ° C. 153 parts of epichlorohydrin (hydroxyl group of diol 1
1.1 equivalent per piece) was added dropwise. After aging for 0.5 hour while maintaining the temperature at 65 to 70 ° C, it was cooled to 45 ° C. 454 g of isobutanol was added as a separation solvent,
After stirring and mixing, a 25% aqueous sodium hydroxide solution 235
A portion was added and the mixture was heated to 45 ° C. and vigorously stirred for 1 hour. After cooling to room temperature and separating and removing the aqueous phase, the remaining oil phase was washed with water several times, and then heated under reduced pressure to remove unreacted epichlorohydrin, water, and isobutanol as a solvent. As a result, 367.7 parts of diglycidyl ether of 4 mol of bisphenol A ethylene oxide was obtained (yield 94%,
Selectivity 81.4%). The WPE of the obtained product was 326. The general analysis results are shown in Table-1.

[0034]

[Table 1]

The following can be seen from Table-1. From Comparative Example 1, Comparative Example 3 and Comparative Example 4 in which the acid catalyst was a tin tetrachloride catalyst alone, the reaction rate was low, so the reaction was stopped late or did not proceed at all. Further, in Comparative Example 2 and Comparative Example 5 in which the boron trifluoride / ethyl ether catalyst alone was used, since the reaction rate of epichlorohydrin was high,
The reaction is fast, but the selectivity is low. Example 1 and Example 2 in which boron trifluoride / ethyl ether and tin tetrachloride were used in combination.
In Examples 3 and 4, the reaction rate is high because the epichlorohydrin reaction rate is high, and the selectivity is also high. From Example 1 and Example 2, it can be seen that increasing the molar ratio ([epichlorohydrin] / [1,6-hexanediol]) increases the viscosity, but Comparative Example 2 and Example 2 are compared. As a result, it was found that the viscosity was lower in Example 2 even with the same molar ratio. Furthermore, from Example 3 and Comparative Example 3, when the addition reaction of epichlorohydrin was stopped by the tin tetrachloride catalyst alone, if boron trifluoride / ethyl ether was added, the reaction of ordinary epichlorohydrin It can be seen that, when the addition reaction proceeds and tin tetrachloride is added, an undesired side reaction (polymerization reaction) proceeds.

Performance evaluation as a diluent

Example 5 1,6-Hexanediol diglycidyl ether obtained in Example 1 (hereinafter referred to as “diluent”), epoxy resin (manufactured by JER, trade name: E-82)
8) and curing agent (manufactured by JER, trade name: B-002W)
Was mixed in a predetermined amount, and the performance evaluation as a diluent was performed according to the procedure described below. Table 2
Table 3 shows the evaluation results.

[0037]

[Example 6] The performance evaluation was performed in the same manner as in Example 5 except that the diluent obtained in Example 2 was used. Table of compounding amount
2 and Table 3 show the evaluation results.

[0038]

Example 7 Performance evaluation was performed in the same manner as in Example 5 except that the diluent obtained in Example 3 was used. Table of compounding amount
2 and Table 3 show the evaluation results.

[0039]

Comparative Example 6 Performance evaluation was performed in the same manner as in Example 5 except that the diluent obtained in Comparative Example 2 was used. Table of compounding amount
2 and Table 3 show the evaluation results.

[0040]

Comparative Example 7 Performance evaluation was performed in the same manner as in Example 5 except that the diluent was not used as a blank. Table of compounding amount
2 and Table 3 show the evaluation results.

[0041]

[Table 2]

Performance Evaluation Procedure 1000 mPa · s Dilution rate Epoxy resin (manufactured by JER, trade name: E-828) is mixed with a predetermined amount of diluent, and two or three kinds of dilution resins (epoxy resin and epoxy resin) having different dilution ratios are mixed. (Mixture with diluent). The viscosity of the prepared diluted resin is measured, and a viscosity-dilution ratio graph is prepared. From the graph prepared, the viscosity is 1
The dilution rate (ratio of the amount of the diluent to the amount of the diluted resin: unit%) when 000 mPa · s is obtained. In the performance evaluation of the following items, based on the value of this dilution rate,
A diluted resin having a viscosity of 1000 mPa · s was mixed and prepared, and each item was measured and compared.

Curing characteristics (pot life) A diluting resin (resin adjusted to 1000 mPa · s) and a curing agent (manufactured by JER, trade name: B-002W) are left in a constant temperature bath at 23 ° C. for 1 day. In the disposable cup,
A predetermined amount of each of the diluted resin and the curing agent is weighed, vigorously stirred with a glass rod for about 1 minute, and a thermocouple is set in the central portion of the resin. The temperature change of the cured resin is measured with the start of stirring as 0 hour. The temperature at the time of the highest temperature is displayed as the maximum heat generation temperature, and the time at that time is displayed as the maximum heat generation time.

Bending Strength / Flexural Modulus [Preparation of Specimen] Specimen was prepared according to JIS K6911. [Measurement of Bending Strength and Bending Elastic Modulus] The width and thickness of the test piece were measured with a micrometer at 4 to 5 points up to a unit of 0.01 mm, and the average value was measured as the width W of the test piece.
Record as thickness h. On the other hand, tensile compression tester SV-2
01 (made by Imada Seisakusho), test speed 2mm /
It is measured at min, the change of the load at this time is recorded, the maximum load P and the change (slope) F of the initial load are read, and the bending strength and the bending elastic modulus are calculated from the following formulas.・ Bending strength σ = (3PL) / (2Wh ² ) ・ Bending elastic modulus E = (L ³ × F) / (4Wh ³ ) where, σ = bending strength (MPa) ・ E = bending elastic modulus ( MPa) -P = maximum load (N) -F = inclination (N / mm) -L = distance between fulcrums (64 mm) -W = width of test piece (mm) -h = thickness of test piece (mm) To do.

Glass transition temperature (Tg) A predetermined amount of diluted resin (resin adjusted to 1000 mPa · s) and a curing agent are mixed and stirred for about 1 minute. About 1 mg of this stirred mixture is weighed, put in an aluminum pan for DSC measurement, covered with an aluminum cover for DSC measurement, and sealed with a sample sealer. Each of the sealed sample pans is cured in a constant temperature bath adjusted to 23 ° C. for 24 hours, and then in a constant temperature bath adjusted to 80 ° C. for another 3 hours. For cured products, differential scanning calorimeter D
The glass transition temperature is measured using SC20 (manufactured by Seiko Denshi Kogyo). The measurement conditions were −40 to 160 ° C. (heating rate: 20 ° C./min).

Tensile strength [Preparation of test piece] A test piece was prepared in accordance with JIS K6911. [Measurement of Tensile Strength] The width and thickness of the test piece are measured with a micrometer to a unit of 0.01 mm at 4 to 5 points, and the minimum values are recorded as the width W and the thickness t of the test piece. On the other hand, the tensile / compression tester SV-201 (made by Imada Seisakusho) is used to measure at a test speed of 2 mm / min. The change in load at this time is recorded, the maximum load P (load when the test piece breaks) is read, and the tensile strength is calculated from the following formula.・ Tensile strength σ _P = P / A = P / (t × W) where: σ _P = tensile strength (MPa) ・ P = maximum load (N) ・ A = minimum cross-sectional area of test piece (mm ² ) ・ t = thickness of test piece (mm) ・ W = width of test piece (mm)

[0047]

[Table 3]

The following can be seen from Table-3. Comparing Example 5 and Example 6 with Comparative Example 6, the polyhydric alcohol polyglycidyl ether obtained in the present invention was 1000
It can be seen that the dilution rate is low and the dilution effect is high. It can be seen that the other performances, pot life and cured product properties are not deteriorated. Further, from Examples 6 and 7, the addition reaction of epichlorohydrin was started with the tin tetrachloride catalyst alone, and when the reaction was stopped, boron trifluoride / ethyl ether was added, and epichlorohydride was added. It can be seen that the product obtained by proceeding the phosphorus addition reaction also exhibits the same performance as the product obtained with the mixed catalyst.

[0049]

According to the present invention, a polyhydric alcohol polyglycidyl ether having a high selectivity and a low viscosity can be obtained. Further, the polyhydric alcohol polyglycidyl ether obtained in the present invention has a low dilution rate of 1000 mPa · s, not only has a high dilution effect, but also does not deteriorate the pot life and the cured product properties, and therefore, is used as a diluent. High utility value.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Yoshimura             710 Rokuromi, Yokkaichi-shi, Mie Yokkaichi-go             Within Cheng Co., Ltd. (72) Inventor Koji Ishikawa             710 Rokuromi, Yokkaichi-shi, Mie Yokkaichi-go             Within Cheng Co., Ltd. F term (reference) 4C048 AA01 BB09 CC02 JJ05 UU05                       XX02

Claims (10)

[Claims] 1. A polyhydric alcohol and epihalohydrin,
A method for producing a halohydrin ether by reacting in the presence of an acidic catalyst, and then reacting with a dehydrohalogenating agent to produce a polyhydric alcohol polyglycidyl ether, wherein boron trifluoride complex is used as the acidic catalyst. A method for producing a polyhydric alcohol polyglycidyl ether, which comprises using a mixture of bismuth and tin tetrachloride. 2. The method for producing a polyhydric alcohol polyglycidyl ether according to claim 1, wherein the boron trifluoride complex is a boron trifluoride ethyl ether complex. 3. A polyhydric alcohol polyglycidyl ether according to claim 1, wherein the mixing molar ratio of boron trifluoride complex: tin tetrachloride is 2: 1 to 1: 4. Method. 4. The polyhydric alcohol according to claim 1, wherein the amount of the acidic catalyst mixture used is 0.1 to 6 mol% based on the polyhydric alcohol. Method for producing alcohol polyglycidyl ether. 5. A hydroxyl group of polyhydric alcohol of 0.
The method for producing a polyhydric alcohol polyglycidyl ether according to any one of claims 1 to 4, wherein 9 to 1.5 equivalents of epihalohydrin are used. 6. The method for producing polyhydric alcohol polyglycidyl ether according to claim 1, wherein the polyhydric alcohol is a dihydric alcohol. 7. The method for producing a polyhydric alcohol polyglycidyl ether according to claim 6, wherein the polyhydric alcohol has 5 or more carbon atoms. 8. The method for producing a polyhydric alcohol polyglycidyl ether according to claim 7, wherein the polyhydric alcohol is 1,6-hexanediol. 9. The method for producing a polyhydric alcohol polyglycidyl ether according to claim 7, wherein the polyhydric alcohol is a bisphenol A ethylene oxide adduct. 10. A method for using the polyhydric alcohol polyglycidyl ether obtained by the production method according to claim 1, which is used as a reactive diluent for an epoxy resin.