JPH0662597B2 - Novel epoxy compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel epoxy compound and a method for producing the same.

It is well known that monoethers of (poly) ethylene glycol and (poly) propylene glycol exhibit hydrophilicity, and they are used in many fields. A well-known example is a nonionic surfactant obtained by ring-opening addition of ethylene oxide and propylene oxide to a hydrophobic compound. In addition, the polymerized product of hydroxyethyl methacrylate is well compatible with water due to the action of ethylene glycol ether, and has excellent physical properties as a contact lens material and the like.

[Conventional technology and problems]

All of the above-mentioned utilization examples are produced by adding ethylene oxide or propylene oxide to an active hydrogen compound such as a phenol compound or a carboxylic acid. However, in the production, since alkylene oxide has a low boiling point, a pressure resistant reactor or There is a limitation that a recovery device or the like is required, and it cannot always be manufactured by an ordinary reactor.

Furthermore, for example, when bisphenol A or a polyhydric acid is converted into a glycol ether by this method, it is known that in the presence of a commonly used alkaline catalyst, the active hydrogen having strong acidity tends to be etherified. It is difficult to partially leave free hydroxyl groups because the hydroxyl groups of the raw material are etherified first rather than extended.

[Means for solving problems]

DISCLOSURE OF THE INVENTION The inventors of the present invention found a novel epoxy compound that can replace ethylene oxide and propylene oxide, as a result of diligent research on means for eliminating these restrictions, and introducing a glycol ether chain more easily and with a high degree of freedom. Reached

That is, the present invention provides a novel epoxy compound represented by the general formula (I), allyl alcohol, methacrylic alcohol, 3-buten-1-ol, 3-methyl-3-buten-1ol (isoprenol), 3- One or more unsaturated alcohols selected from cyclohexenyl carbinol and one of epoxides selected from ethylene oxide, propylene oxide or butylene oxide.
The present invention provides a method for producing an epoxy compound represented by the general formula (I), which comprises reacting two or more species, and then epoxidizing with an oxidizing agent.

Next, the present invention will be described in detail.

The compound represented by the general formula (I) of the present invention is particularly useful for the purpose of imparting hydrophilicity to a lipophilic substance by adding it to a lipophilic substance, and the epoxide used as a raw material is ethylene oxide or propylene oxide. Is a preferable raw material for the purpose of imparting hydrophilicity.

In the present invention, the number of moles of epoxide added is 1 mole or more and less than 100 moles per 1 mole of unsaturated alcohol.
Addition of unsaturated alcohol and epoxide is carried out by adding sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, trimethylamine to alcohol. , Triethylamine, tributylamine, pyridine, picoline,
Alkaline compounds such as 2-methylimidazoline and 2-ethylimidazoline, or hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid,
This can be carried out by a known method in which an epoxide is added and reacted under normal pressure or pressure in the presence of an acidic compound such as formic acid, propionic acid, citric acid, and boron trifluoride.

Further, the catalyst is not limited to the above, sodium iodide, potassium iodide, sodium bromide, potassium bromide, sodium chloride, potassium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, tetra-n-butyl titanate. It is possible to use a known substance having a catalytic activity, such as dibutyltin dilaurate or the like, or to carry out the reaction only by heat.

The catalyst concentration is selected from the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the reaction mixture.

It is advantageous to select the temperature of the addition reaction from the range of 10 to 150 ° C., which is industrially easy to carry out, depending on the type and amount of the catalyst.

The addition reaction is carried out in a solvent inert to the reaction, such as 1,2-
It may be carried out in the presence of dimethoxyethane, anisole, chloroform, etc., but since the purification process is simplified,
It is preferable to carry out without solvent.

The reaction product addition reaction crude liquid obtained by the reaction can be purified by distilling off, neutralizing, treating with an adsorbent or an ion exchange resin, such as a solvent, a low boiling substance, an unreacted raw material and a catalyst. When the boiling point of the addition product is low, it may be purified by flash distillation or precision distillation.

The purification treatment can be selected according to the physical properties such as the boiling point, melting point and viscosity of the addition product, the yield of the next step and the quality requirements of the final product. It can be omitted if a final product of usable quality is obtained without purification treatment.

The compound of the present invention can be obtained by epoxidizing the unsaturated group thus obtained with an addition product of an unsaturated alcohol and an epoxide with an oxidizing agent.

Any oxidizing agent can be used as long as it can epoxidize an unsaturated bond, and organic peracids such as performic acid, peracetic acid, m-chloroperbenzoic acid, trifluoroperacetic acid and perbenzoic acid, tertiary butyl hydroperoxide. Examples thereof include hydroperoxides such as cumyl hydroperoxide, tetralyl hydroperoxide and diisopropylbenzene hydroperoxide, hydrogen peroxide and the like.

The oxidizing agent may be used in combination with a catalyst, for example, in the case of organic peracid,
An alkali such as sodium carbonate or an acid such as sulfuric acid may be used as a catalyst. Similarly, in the case of hydroperoxide, a compound having known catalytic ability such as molybdenum hexacarbonyl,
In the case of hydrogen peroxide, a known compound having a catalytic ability such as a mixture of tungstic acid and caustic soda can be used in combination.

The number of moles of the oxidizing agent per unsaturated bond is preferably 1 or more in order to shorten the reaction time. A suitable molar ratio varies depending on the addition product to be epoxidized, but is usually selected from a value of 1 to 50.

The reaction temperature is lower than the upper limit value such that the epoxidation reaction has priority over the decomposition reaction of the oxidant. For example, peracetic acid is 70 ° C or lower, and tertiary butyl hydroperoxide is 150 ° C.
The following are preferred.

When the reaction temperature is low, it takes a long time to complete the reaction. Therefore, it is preferable to carry out the reaction at a lower limit of 0 ° C. for peracetic acid and 20 ° C. for tertiary butyl hydroperoxide.

In addition, during epoxidation, a side reaction occurs in which the epoxy group is destroyed by organic acids, alcohols, and water due to by-products from the oxidizing agent.Therefore, select a temperature that reduces the amount of side reaction from the temperature range described above. Carry out.

The solvent has the effect of reducing the viscosity of the crude reaction liquid and stabilizing it by diluting the oxidizer.It is aromatic compounds such as benzene, toluene, xylene, chloroform, dimethyl chloride, carbon tetrachloride, halides such as chlorobenzene, and acetic acid. Ester compounds such as ethyl and butyl acetate, ketone compounds such as acetone and methyl isobutyl ketone, ether compounds such as 1,2-dimethoxyethane and the like can be used.

The crude liquid for the epoxidation reaction can be purified by distilling off the solvent and low boiling substances. If the boiling point of the reaction product is low, it can be purified by flash distillation or precision distillation.

〔The invention's effect〕

The novel epoxy compound obtained by the present invention has an alkylene glycol chain and one epoxy group at the end.

Such a compound of the present invention can be modified with an alkylene glycol chain by subjecting the substance to an addition reaction with a substance having a functional group that causes an addition reaction with an epoxy group such as a hydroxyl group, a carboxyl group and an amino group, resulting in alkylene. It is possible to give the substance properties such as affinity of the glycol chain for water and other hydroxyl groups and ions. or,
By using the epoxy compound of the present invention in the above addition reaction, a pressure-resistant reactor and a recovery device are unnecessary as compared with the case of using ethylene oxide, propylene oxide, and butylene oxide, and by using an epoxy compound whose chain length is adjusted in advance, Can introduce the correct chain length,
In addition, it has become possible to leave unreacted functional groups in the raw material by adjusting the charged molar ratio.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples and application examples.

Reference Example 1 A 2-autoclave charged with 200 g of benzene, 43 g of isoprenol, and 18 g of triethylamine was charged with 660 g of ethylene oxide over 8 hours with stirring. During this time, heating was controlled so that the internal temperature was 150 ° C. After the completion of charging, the reaction was completed by keeping the internal pressure at 150 ° C until the internal pressure became constant, and then the reaction crude liquid was taken out from the autoclave.

The reaction crude liquid was heated to 100 ° C. under reduced pressure of 10 Torr to remove low boiling point to obtain 701 g of a product. Gas chromatographic consumption of trace amount of raw isoprenol, and infrared absorption spectrum at 1650 cm ^-1 shows that C =
It was confirmed that a C double bond was observed, that an OH group was absorbed at 3450 cm ^-1, and that this product was an isoprenol ethylene oxide 30 mol adduct from the mass balance.

Example-1 200 g of a compound obtained by adding 30 mol of ethylene oxide to isoprenol was dissolved in 100 g of ethyl acetate, and peracetic acid was added thereto.
g was added dropwise over 1 hour. During this time, the reaction temperature is 40 ° C
Kept at. After the peracetic acid was charged, the mixture was aged at 40 ° C. for 5 hours.

After the reaction was completed, the crude liquid was concentrated to obtain 202 g of a transparent liquid. This compound is the compound from the absorption of the OH groups in the 3450 cm ^-1 to the special absorption seen by epoxy groups 1260 cm ^-1 in the infrared absorption spectrum at 0.89% oxirane oxygen content is seen the general formula (I) It was confirmed that the structure was

Example-2 200 g of a compound obtained by adding 10 mol of ethylene oxide to isoprenol was dissolved in 100 g of ethyl acetate, and 96 g of peracetic acid was added thereto.
g was added dropwise over 1 hour. During this time, the reaction temperature is 40 ° C
Kept at. After the peracetic acid was charged, the mixture was aged at 40 ° C. for 5 hours.

After the reaction was completed, the crude liquid was concentrated to obtain 207 g of a transparent liquid. This compound has a oxirane oxygen content of 2.3% and a special absorption due to an epoxy group is observed at 1260 cm ^-1 in an infrared absorption spectrum, and an OH group absorption is observed at 3450 cm ^-1. It was confirmed that the structure was

Example-3 51 g of a compound obtained by adding 20 mol of ethylene oxide to isoprenol was dissolved in 26 g of ethyl acetate, and 29 g of peracetic acid was added thereto.
Was added dropwise over 1 hour. During this time, the reaction temperature was kept at 40 ° C. After the peracetic acid was charged, the mixture was aged at 40 ° C. for 5 hours.

After the reaction was completed, the crude liquid was concentrated to obtain 52 g of a transparent liquid. This compound is the compound from the absorption of the OH groups in the 3450 cm ^-1 to the special absorption seen by epoxy groups 1260 cm ^-1 in the infrared absorption spectrum 1.27 percent oxirane oxygen content is seen the general formula (I) It was confirmed that the structure was

Example 4 68 g of a compound obtained by adding 20 mol of ethylene oxide to allyl alcohol was dissolved in 35 g of ethyl acetate, and 33 g of peracetic acid was added thereto.
g was added dropwise over 1 hour. During this time, the reaction temperature is 60 ° C
Kept at. After the peracetic acid was charged, the mixture was aged at 60 ° C. for 5 hours.

After completion of the reaction, the crude liquid was concentrated to obtain 69 g of a transparent liquid. This compound has an oxygen content of oxirane of 0.91% and has a special absorption due to an epoxy group at 1260 cm ^-1 in the infrared absorption spectrum, and an absorption of an OH group at 3450 cm ^-1. ) Structure was confirmed.

Application Example 1 114 g of bisphenol A and the compound 131.5 obtained in Example-2
g was reacted in the presence of 1.3 g of 2-methylimidazole at 150 ° C. until no oxirane oxygen was detected, and a brownish viscous liquid was obtained. When this liquid was analyzed by gel permeation chromatography, one of the hydroxyl groups of bisphenol A was polyethylene glycol etherified, unreacted bisphenol A, and two hydroxyl groups of a small amount of bisphenol A were polyethylene glycol etherified. The presence of these compounds was recognized, and the weight ratio of monoetherified bisphenol A to unreacted bisphenol A was about 7: 3.

It was found that bisphenol A having a polyethylene glycol chain and leaving a free phenolic hydroxyl group capable of being resinified with formalin was synthesized.

Comparative Application Example 1 If, instead of the compound of the present invention used in Application Example 1 above, a corresponding molar number of ethylene oxide was charged and reacted, ethylene oxide was present in a molar ratio of 2 or more with respect to the hydroxyl group of bisphenol A. In addition, bisphenol A
Since the hydroxyl groups of are more reactive than the alcoholic hydroxyl groups, it is clear that almost all of the phenolic hydroxyl groups are converted into glycol ethers having a shorter chain length than in Application Example 1, and such substances include formalin and resin. I can't make it happen.

That is, the present invention allows for selective glycol etherification that could not be achieved by known methods, for example:
A wide range of applications can be expected as a modified phenolic resin raw material.

Claims (2)

[Claims] 1. A novel epoxy compound represented by the general formula (I). 2. Allyl alcohol, methallyl alcohol,
3-buten-1-ol, 3-methyl-3-butene-1
-All (isoprenol), one or two or more kinds of unsaturated alcohols selected from 3-cyclohexenylcarbinol are reacted with one or more kinds of epoxides selected from ethylene oxide, propylene oxide or butylene oxide. Then, a method for producing an epoxy compound represented by the general formula (I), which comprises epoxidizing with an oxidizing agent.