JPH04208272A - Epoxidized tetrahydrobenzyl alcohol composition - Google Patents

Abstract

PURPOSE:To provide the subject composition mainly composed of an epoxidized tetrahydrobenzyl alcohol, containing a bicyclocompound, another epoxy compound formed by intramolecular transfer of the epoxy group, etc., as other components and useful as a raw material of polymers or a diluent. CONSTITUTION:With 93-97wt.% compound of formula I, 1.0-2.5wt.% compound of formula II, 0.1-2.0wt.% compound of formula III and 0.5-4.0wt.% compound of formula IV are blended to obtain the objective epoxidized tetrahydrobenzyl alcohol composition. The compound of formula I as the main component is obtained by epoxidizing tetrahydrobenzyl alcohol in the presence of an oxidizing agent (e.g. peracetic acid). The compounds of formula II and III are bicyclocompounds formed by intramolecular attack of the methylol (CH2OH) oxygen on an epoxy carbon and the compound of formula IV is a compound formed by intramolecular transfer of the epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel composition based on epoxidized tetrahydrobenzyl alcohol.

More specifically, it relates to a novel composition consisting primarily of a mixture of four types of compounds.

(Prior Art) In recent years, epoxy compounds have become increasingly useful in a wide variety of fields, and compounds obtained by epoxidizing ethylenically unsaturated compounds such as tetrahydrobenzyl alcohol have become particularly important.

Epoxidized tetrahydrohensyl alcohol, which is a specific example thereof, can provide a polyether compound having a hydroxyl group by polymerizing the epoxy group.

Furthermore, it is a useful substance used as a diluent for epoxy resins.

(Problems to be Solved by the Invention) However, epoxidized tetrahydrohensyl alcohol consisting of a mixture of mainly four types of compounds as in the present invention has not been disclosed.

As a result of intensive studies, the present inventor discovered that the composition of epoxidized tetrahydrohensyl alcohol, which is mainly a mixture of four types of compounds, is an important composition that can be used as a polymer raw material or a diluent. , completed the present invention.

(Structure of the Invention) That is, the present invention provides an epochinated tetrahydropencyl alcohol composition comprising a compound represented by the following formula (+-1) as a main component and containing the following three types of compounds. It is.

The epoxidized tetrahydrobenzyl alcohol composition of the present invention, which mainly consists of a mixture of four types of compounds, will be described in detail below.

First, the manufacturing process of the epoxidized tetrahydropencyl alcohol (hereinafter abbreviated as ETHB) composition of the present invention will be explained.

Tetrahydrobenzyl alcohol represented by the following general formula (11), which is a starting material for the reaction, is a colorless and transparent liquid, and is used as an intermediate material for epoxy resins, inks, paints, and adhesives.

Industrially, tetrahydrobenzyl alcohol is produced by hydrogenating tetrahydrobenzaldehyde in the presence of a catalyst.

Epoxidized tetrahydrobenzyl alcohol of the present invention (
ETHB, which is the main component in the composition (hereinafter abbreviated as ETHB)
can be produced by epoxidizing the tetrahydrobenzyl alcohol in the presence of an oxidizing agent.

Any oxidizing agent that can be used can epoxidize unsaturated bonds, such as performic acid, peracetic acid, perpropionic acid, m
- Organic peracids such as chloroperbenzoic acid, hydroperokinds such as tert-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, diisopropylbenzene hydroperoxide,
Examples include hydrogen peroxide.

Among these, organic peracids, especially peracetic acid, are most preferred for industrial processes.

The oxidizing agent may be used in combination with a catalyst; for example, in the case of an organic peracid,
Alkali such as soda carbonate and acids such as sulfuric acid can be used as catalysts.

Similarly, in the case of hydroburoquinde, a compound having a known catalytic ability such as molybdenum hexacarbonyl can be used in combination, and in the case of hydrogen peroxide, a compound having a known catalytic ability such as a mixture of tungstic acid and caustic soda can be used in combination.

The reaction may be carried out continuously or batchwise, but in the case of continuous reaction, a piston flow type reaction is preferred.

In the case of a batch method, a semi-batch method in which the organic peracid is sequentially charged is preferable.

When carrying out the reaction in batches, first, a predetermined amount of tetrahydrobenzyl alcohol is charged into a reaction vessel, a catalyst and a stabilizer are dissolved therein as required, and an oxidizing agent is dropped into the reaction vessel.

The molar ratio of oxidizing agent to tetrahydrobenzyl alcohol is theoretically 1, but in practice it is in the range of 0.1 to 10, preferably 0.5 for producing compositions such as the present invention.
-2, more preferably 0.8-1.5.

When the molar ratio of the oxidizing agent and tetrahydrobenzyl alcohol is greater than 10, it is preferable in terms of the conversion rate of the tetrahydrobenzyl alcohol, shortening the reaction time, and reducing losses due to polymerization, but side reactions due to excess oxidizing agent and selectivity of the oxidizing agent may be reduced. It is not preferable to recover the degraded and unreacted oxidizing agent because it requires a great deal of cost.

On the other hand, when the molar ratio of the oxidizing agent and tetrahydrobenzyl alcohol is 0.1 or less, the conversion rate and selectivity of the oxidizing agent are high, which is preferable in terms of preventing side reactions of the products caused by the oxidizing agent, but unreacted Tetrahydrobenzyl alcohol has drawbacks such as the high expense required to recover it.

The reaction temperature is below the upper limit where the epoxidation reaction takes precedence over the decomposition reaction of the oxidizing agent, for example, 70°C for peracetic acid.
The following is 15 for tert-butyl hydroperoxide.
The temperature is preferably 0°C or lower.

If the reaction temperature is low, it will take a long time to complete the reaction, so it is preferable to carry out the reaction at 0° C. for peracetic acid and 20° C. for tajaribucal hydroperoxide.

Also, during epoxidation, a side reaction occurs in which the epoxy group is crushed by organic acids, alcohols, and water due to by-products from the oxidizing agent, so select a temperature from the temperature range mentioned above that will reduce the amount of side reaction. Implement.

The reaction pressure is generally operated at normal pressure, but it can also be carried out under elevated or low pressure.

Although the reaction can be carried out in the absence of a solvent, it is preferable to carry out the reaction in the presence of a solvent since this is effective in lowering the viscosity of the reaction crude liquid and stabilizing it by diluting the oxidizing agent.

Solvents used include aromatic compounds such as benzene, toluene and xylene, halides such as chloroform, dimethyl chloride, carbon tetrachloride and chlorobenzene, ester compounds such as ethyl acetate and butyl acetate, acetone,
Ketone compounds such as methyl isobutyl ketone, ether compounds such as 1,2-dimethoxyethane, etc. can be used.

It is desirable to use the solvent in an amount of 0.5 to 6 times the amount of tetrahydrobenzyl alcohol.

When the amount is less than 0.5 times, the stabilizing effect due to dilution of the oxidizing agent is small, resulting in a decrease in yield.

Even if the amount is increased by more than 6 times, the effect remains the same and recovery of the solvent requires a large amount of money, so it is wasteful.

Furthermore, in order to avoid the formation of an explosive mixture within the system, nitrogen gas is usually blown into the system.

The blowing position may be either directly into the liquid or into the gas phase.

The amount of blowing can be selected arbitrarily, but too much will result in solvent loss.

The end point of the reaction can be confirmed by the concentration of the remaining oxidizing agent or by gas chromatography.

The epoxidation product reaction crude liquid obtained in the reaction can be purified by distillation of low-boiling components such as solvents, low-boiling substances, unreacted raw materials, and catalysts, neutralization, and treatment with adsorbents and ion exchange resins. .

If a final product of usable quality can be obtained without purification, it can be omitted.

In particular, when using an organic peracid as an oxidizing agent, if low boiling point components are removed without neutralizing the reaction crude liquid, ET due to the organic acid
Since loss increases due to ring opening of the epoxy group of HB or cyclization with the methylol group, it is preferable to neutralize before removing low boiling point components.

Examples of alkaline aqueous solutions used for neutralization include Na
OHSK OH-, K2CO3, Na2CO
3. Solutions such as N a HCO3, K HCO3, N H3, etc. can be used, the concentrations thereof being freely selectable within wide limits.

From the viewpoint of liquid separation or loss, NaOH aqueous solution, Na2c
o. It is desirable to use an aqueous solution.

In the neutralization water washing step, it is important to neutralize and remove the organic acid as well as remove the remaining organic peracid in order to stably operate the next low boiling point removal step.

Therefore, the amount of alkali used is 0.5 to 3 times, preferably 0.8 to 3 times the equivalent amount of organic acid in the reaction crude liquid.
It is best to use 1.5 times the amount, and it is not economical to increase the amount more than necessary.

Further, if the equivalence ratio is lowered more than necessary, it is not a good idea because a large amount of water is required to remove the organic acid, and the loss of solvents and the like to the lower water layer also increases.

If the bottoms are made into a product by removing low-boiling components without washing with water after neutralization, neutralized salts will remain in the product, so it is desirable to wash with water after neutralization.

Neutralization and water washing are carried out at 10-90°C, preferably at 10-5°C.
It is best to carry out the process in a temperature range of 0°C.

It is also desirable to blow nitrogen gas during neutralization washing to avoid the formation of an explosive mixture.

A thin film evaporator or the like may be used to remove low-boiling components from the reaction crude liquid that has been neutralized or washed with water.

The heating temperature in the low-boiling removal step may be 50 to 180°C, preferably 80 to 100°C.

Although the pressure can be arbitrarily selected depending on the physical properties of the low-boiling components, it is common to operate under reduced pressure depending on the heating temperature.

In addition, nitrogen is usually blown into the system in order to avoid the formation of an explosive mixture within the system or to facilitate the distillation of low-boiling components.

The blowing position can be selected arbitrarily, but the blowing is usually carried out from the line where the bottom liquid is distilled off.

The amount of blowing can be selected arbitrarily, but the upper limit depends on the capacity of the vacuum system,
Alternatively, -12= is naturally limited from the viewpoint of whether the bottom liquid flows down stably or the recovery loss when collecting the distilled low-boiling components with a condenser.

The bottom liquid obtained in this way has a purity of 95 to 96% of the four types of composition, which is the same level as the product, or is slightly cloudy, and high-boiling components are removed to obtain a product of higher purity. .

The high-boiling removal step is carried out in the same manner as the low-boiling removal step, but the degree of reduced pressure or heating temperature is generally increased to obtain a product as a distillate.

Next, the commercialized ETHB composition will be described. The main component, ETHB, has the following general formula (1-1)% Formula% As a result of research, ETHB composition contains methylol (CH
20H) Bicyclo compounds in which oxygen attacks the epoxy carbon in the molecule and cyclizes [represented by the following general formulas (1-2) and (1-3)] and compounds in which the epoxy group moves within the molecule [represented by the following general formulas] (1-4)] etc. were found to be included.

- of the bicyclo compound (1-2) is ETHB
It was found that it is easily formed by applying heat to (+-1).

Another bicyclo compound (1-3) is (I-
Compared to 2), the strain energy is large and the ring structure is unstable, so it is thought that it is difficult to form.

Furthermore, in the epoxidation reaction, when the dilution ratio with ethyl acetate or the like is reduced, the proportion of compounds (+-2) and (1-4>) in the ETHB composition increases.

These compounds (1-2), (1-3) and (1-4
), (1-2) and (1-4) are likely to be produced.

In addition, when an organic peracid is used as an oxidizing agent, if the neutralization step is omitted and the low-boiling removal step is directly performed, the ETHB composition will contain a large amount of bicyclo compounds (+-2>).

The content of (+-1), (1-2), (1-3) and (1-4) can be confirmed using gas chromatography, 1H-NMR and 13C-NMR. can.

(1-1) is 1H-
3,3 corresponding to NMR methylol hydrogen and hydroxyl groups
and 4.2 ppm peak, furthermore, from the 3.2 ppm peak indicating hydrogenation of epoxide, the 67.0 ppm peak indicating methylol carbon in "'C-NMR," and the 51.0 ppm peak indicating epoxy carbon. peak, 23.8 indicating cyclohexyl cyclic carbon other than epoxy carbon
．． It can be confirmed by the peak at 24.0.28.8.36.0 ppm.

(+-2) is from the peak at retention time 8.5 in gas chromatography, 'H-NMR peak at 3.80 ppm indicating ether methylene protons and other peaks at 2.33, 3.57 ppm,'' C
This can be confirmed by the -NMR peak at 71.3 ppm indicating ether methylene and the peak at 68.2 ppm indicating methine alcohol.

(+-3) is from the peak at retention time 6.5 in gas chromatography, and from the peak around 3.80 ppm which indicates protons of ether methylene in H-NMR, 71.0 indicates ether methylene in 13C-NMR.
ppm peak, 68.9p indicating alcohol methine
This can be confirmed by the pm peak.

(1-4) is 3.3 ppm, which indicates methylol hydrogen and hydroxyl group in 'H-NMR, from the peak at retention time 8.9 in gas chromatography.

From the two peaks at 4.2 ppm, the peak at 67.2 ppm indicates methylol carbon in 13C-NMR, and the peak at 21.0.2 indicates cyclohexyl cyclic carbon other than epoxy carbon.
5,0.28.0.32. This can be confirmed by the Qppm peak.

The production ratio of each component in the epoxidized tetrahydrobenzyl alcohol composition of the present invention can be roughly controlled within the numerical ranges below.

(1-1): 93-97% by weight (1-2): 1. 0-2.5% by weight (1-3)
: 0. 1-2.0% by weight (1-4) 20.
5 to 4.0% by weight [Example 1] 770 g of tetrahydrobenzyl alcohol and 320 g of ethyl acetate were placed in a reactor with a capacity of 8 g and equipped with a jacket for water cooling.
After adding 0 g, 30% peracetic acid solution in ethyl acetate 196
5 g was added dropwise over 4 hours. During the dropwise addition, the reaction temperature was 30°C.
The temperature of the hot water flowing into the jacket was adjusted to maintain the temperature at ℃.

Even after the dropwise addition was completed, the temperature of the reaction solution was maintained at 30° C. for 4 hours to complete the reaction.

Conversion rate based on tetrahydrobenzyl alcohol is 98%,
Epoxycyclohexene alcohol standard selection rate is 98%
The yield was 96%.

After cooling 5935 g of the reaction crude liquid to room temperature, 20% NaOH
Add 2057 g of the aqueous solution and stir for 1 hour, then leave to stand for 30 minutes to separate the liquids.

After separation, low-boiling components of the upper layer liquid were removed.

A glass Smith-type thin film evaporator is used to remove low-boiling components.
At a pressure of 150 Torr and a heating temperature of 90 to 95° C., nitrogen gas was supplied from the bottom liquid distillation line at 5 ON ρ/Hr.

High-boiling components were also removed using a glass Smith type thin film evaporator under conditions of a pressure of 2 Torr and a heating temperature of 150°C.

As a result of gas chromatography analysis, the purity of the product is 97.
%Met.

The production ratio of each component in the epoxidized tetrahydrobenzyl alcohol composition was as follows.

(1-1,): 96. 5% by weight (1-2)
+2. 5% by weight (1-3): 0. 1% by weight (1-4): 0.9% by weight [Example 2] The same operation as in Example 2 was performed except that the reaction temperature was 25°C.

The yield was 89%.

The production ratio of each component in the epoxidized tetrahydrobenzyl alcohol composition was as follows.

(1-1): 93. 5% by weight (+-2) ・2.0% by weight (1-3) ・2.0% by weight (+-4): 2. 5% by weight [Example 3] The same operation as in Example 2 was performed except for using 871 g of a 30% aqueous solution of peracetic acid in ethyl acetate.

Epoxycyclohexene alcohol standard selectivity is 95
%Met.

The production ratio of each component in the epoxidized tetrahydrohensyl alcohol product was as follows.

(I-1): 95. 0% by weight (1-2): 1. 2% by weight (1-3): 1. 0% by weight (1-4): 2. 8% by weight [Example 4] The same operation as in Example 2 was performed except for using 349 g of a 30% aqueous solution of peracetic acid in ethyl acetate.

Epoxycyclohexene alcohol standard selectivity is 10
It was 0%.

The production ratio of each component in the epoxidized tetrahydrohensyl alcohol composition was as follows.

(1-1,): 94.0% by weight (1-2) + 1.5% by weight (1-3)’: 0. 5% by weight (1-4):, 4. 0% by weight

[Brief explanation of the drawing]

FIG. 1 is Char 1 showing the results of gas chromatograph analysis of the composition in [Example 1]. FIG. 2 is a chart showing the results of 1H-NMR analysis of the same composition. FIG. 3 is a chart showing the results of C-NMR analysis of the same composition.

Claims (1)

[Claims] The following general formula ( I -1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... ( I -1
) The main component is the compound represented by the following three types of compounds ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... ( I -2
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・( I -3
) An epoxidized tetrahydrobenzyl alcohol composition comprising: