JP2001335525A - Hydroxyalkyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hydroxyalkyl ether having a merit capable of shortening a duration for polycondensation without any addition of trimethylol propane which is a polymerization regulator, and useful as a secondary component of the gas barrier polyester resin with a 1,3-bis(2-hydroxyalkoxy)benzene which is obtained by reacting resorcinol with an alkylene oxide in high yield at low cost. SOLUTION: This hydroxyalkyl ether comprises a 1,3-bis(2-hydroxyalkoxy) benzene expressed by general formula (1) (wherein n expresses 2-5 integer) as a main ingredient and contains 1-10 wt.% o a compound expressed by general formula (5) (wherein n expresses 2-5 integer) based on the main ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hydroxyalkyl ether useful as a gas barrier polyester resin. More specifically, 1,3-bis (2-hydroxyalkoxy) benzene obtained by reacting resorcinol with an alkylene oxide is a main component,
In the reaction between resorcinol and alkylene oxide, 1,3-bis (2-hydroxyalkoxy)
The present invention relates to a hydroxyalkyl ether composition for a gas barrier polyester resin, which contains a compound produced as a homologous compound corresponding to benzene.

[0002]

2. Description of the Related Art 1,3-bis (2-hydroxyalkoxy) benzene is a useful material as a raw material or a crosslinking agent for polyesters, polyurethanes, polycarbonates and the like. In particular, it is used as a raw material for a gas barrier polyester resin. For example, Japanese Patent Publication No. 51-4997 describes an improved method for producing a target compound from a reaction to a production. Conventionally, this compound has been studied as a reaction material and a purification method for obtaining a higher purity and a higher yield as the various raw materials or the cross-linking agent,
Methods have been proposed to achieve these goals. However, according to these conventional production methods, in order to obtain the target compound with high purity, a method of using a large excess of water as a reaction condition and a method of performing crystallization purification as a purification means have been adopted. However, such a method has problems of high productivity and high cost, such as a low volumetric efficiency of the reaction, a low purification yield, a problem of wastewater treatment in crystallization purification and an increase in equipment. On the other hand, when this compound is used as a raw material,
Depending on the target product obtained, its effects on product quality and production efficiency are not sufficiently known.

[0003]

An object of the present invention is to produce 1,3-bis (2-hydroxyalkoxy) benzene obtained by reacting resorcinol with an alkylene oxide by using the compound as a main component and by-producing it. An object of the present invention is to find out the properties of a product containing a corresponding compound and the usefulness of using the same as a resin material.

[0004]

Means for Solving the Problems The present inventors have intensively studied the above-mentioned problems, and have found that the resorcinol and the alkylene oxide can be reacted in the presence of a basic catalyst to obtain 1,3-butane.
General formula (5) in which bis (2-hydroxyalkoxy) benzene is simultaneously formed

Embedded image (In the formula, n is an integer of 2 to 5) When it contains 1 to 10% by weight of the compound represented by the formula (1), it has been found that it is useful as a raw material for a gas-barrier polyester resin, and has reached the present invention.

That is, the present invention relates to a hydroxyalkyl ether containing 1,3-bis (2-hydroxyalkoxy) benzene as a main component obtained by reacting resorcinol with an alkylene oxide, represented by the general formula (5):

Embedded image (Wherein n is an integer of 2 to 5) a hydroxyalkyl ether containing 1 to 10% by weight of a compound represented by the formula: It is an ether composition. Preferably, the content of 1,3-bis (2-hydroxyalkoxy) benzene as the main component is 85.
~ 95% by weight of a hydroxyalkyl ether composition. When the composition of the present invention is used as a second resin raw material of a gas barrier polyester resin, processability and gas barrier performance are improved.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In producing 1,3-bis (2-hydroxyalkoxy) benzene by reacting resorcinol and alkylene oxide in the presence of a basic catalyst, the target compound is represented by the general formula (1). With the 1,3-bis (2-hydroxyalkoxy) benzene, the compounds represented by the general formulas (2), (3), (4) and (5) are by-produced. These by-product compounds are those in which the reaction between the resorcinol hydroxy group and ethylene oxide is insufficient, or that the reaction between resorcinol and ethylene oxide is irregular. And a compound in which a hydroxylalkyl group is substituted by a benzene nucleus in addition to a reaction of a hydroxy group. In the present invention, these compounds are referred to as 1,3-
It was generically called a homologous compound of bis (2-hydroxyalkoxy) benzene. Conventionally, the production of 1,3-bis (2-hydroxyalkoxy) benzene has been carried out while minimizing the content of these by-product compounds. However, in the present invention, when these compounds, particularly the compound represented by the general formula (5) is contained in 1,3-bis (2-hydroxyalkoxy) benzene in an amount of 1 to 10% by weight, 1,3
It has been found that -bis (2-hydroxyalkoxy) benzene promotes the above effects.

[0007]

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Embedded image In the above general formula, n is an integer of 2 to 5.

The hydroxyalkyl ethers and compositions of the present invention comprise 1,3-bis (2-hydroxyalkoxy) represented by the general formula (1) obtained by reacting resorcinol and alkylene oxide in the presence of a basic catalyst.
1 to 10% by weight of a compound represented by the general formula (5), which is a by-product corresponding to benzene, is contained;
The composition may contain a small amount of the compound represented by the formula (4). In addition, 1,3-
The content of bis (2-hydroxyalkoxy) benzene is preferably 80 to 95% by weight. In the composition of the present invention, particularly preferably, 80 to 95% by weight of the compound represented by the formula (1-1), which is obtained by reacting resorcinol and ethylene oxide, and 1 to 5% by weight of the compound 1 represented by the formula (5-1) 10% by weight as an essential compound, and a small amount of other compounds of the formulas (2-1), (3-1) and / or
Alternatively, the composition may contain one or more compounds represented by the formulas (4-1).

[0009]

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That is, the composition of the present invention comprises the compounds represented by the general formulas (1) and (5) as essential compounds, and comprises the general formulas (2), (3) and (4). Or preferably contains one or more compounds represented by the formulas (1-1) and (5-
The compound represented by the formula (1) is defined as an essential compound,
1) A composition which may contain one or more compounds represented by formulas (3-1) and (4-1).

The hydroxyalkyl ether or composition of the present invention containing 1,3-bis (2-hydroxyalkoxy) benzene as a main component and a by-product compound corresponding to the component is produced by the following production method. Can be.
That is, to produce 1,3-bis (2-hydroxyalkoxy) benzene according to the present invention, resorcinol is used as one raw material. The resorcinol is not particularly limited as long as it is a compound available as a raw material, and may be used after purification if necessary. The alkylene oxide as another raw material is ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, or the like, and is preferably ethylene oxide. The amount of these raw materials used is 2 to 2.5 mole ratio of alkylene oxide to resorcinol. The reaction is
The reaction is performed in a solvent, and water is used as the solvent. The amount of water used is in the range of 1 to 20 molar ratio with respect to resorcinol. Examples of the basic catalyst include inorganic basic compounds such as oxides, hydroxides, carbonates and bicarbonates of alkali metals or alkaline earth metals, and organic bases such as amines, quaternary ammonium hydroxide compounds and phosphines. Compounds. The amount of these basic catalysts used is in the range of 0.01 to 1 molar ratio with respect to resorcinol. Reaction temperatures range from 50 to 150 ° C.

The reaction can be carried out within the range of each of the above reaction conditions. Preferably, each reaction condition is selected from the above range, for example, 1 to 20 mol of solvent water to resorcinol, 0.01 to 1.0 mol of caustic soda to resorcinol, and alkylene oxide to resorcinol. 2.0-2.5 mol, reaction temperature 5
By reacting at 0 to 100 ° C, a composition comprising the composition of the present invention is produced. After completion of the reaction, an acid is added to the reaction mixture to neutralize the basic catalyst. As the acid for neutralizing the basic catalyst, an inorganic acid such as phosphoric acid, sulfuric acid and hydrochloric acid, or an organic acid such as acetic acid and p-toluenesulfonic acid can be used. The pH of the reaction solution is in the range of 5-7. The reaction mixture after neutralization and the generated neutralized salt are subjected to a dehydration operation under normal pressure or reduced pressure to remove water added to the reaction system and neutralized water, and to precipitate a neutralized salt, which is usually used. The neutralized salt is separated by the filtration device.

The composition of the present invention can be produced by the above method. A hydroxyalkyl ether containing the compound represented by the general formula (5), which is mainly composed of 1,3-bis (2-hydroxyalkoxy) benzene of the present invention, preferably 1,3-bis (2-hydroxyethoxy) benzene is used. A hydroxyalkyl ether containing a compound represented by the formula (5-1) as a main component is
By using as the second component polyester resin raw material of the polyester resin, it is possible to produce a polyester resin having improved gas barrier properties in an improved step. That is, when the hydroxyalkyl ether composition having the composition defined in the present invention is used as a raw material of the second component polyester resin of the gas barrier polyester resin, the polymerization rate can be appropriately improved, and the gas barrier property is improved. It was not known at all. Conventionally, as a raw material for producing gas barrier polyester resin, the production of high-purity hydroxyalkyl ether
Among the techniques that have been oriented in this technical field, the composition of the present invention does not require the addition of trimethylolpropane, a polymerization regulator indispensable in the prior art, and shortens the polymerization time. It is industrially and technically valuable that the obtained polyester resin has improved gas barrier properties. Thus, the hydroxyalkyl ether composition of the present invention useful for a gas barrier polyester resin could be provided.

[0014]

The present invention will be further described below with reference to Synthesis Examples and Examples. Synthesis Example 1 SUS with a content of 1 liter equipped with a thermometer and a stirrer
After replacing the reactor made of -316 with nitrogen, 110
g (1.0 mol) of resorcinol and 90 g of water (5.0 mol) in an aqueous solution prepared by dissolving 2.2 g (0.055 mol) of caustic soda were replaced with nitrogen again.
The pressure in the reaction vessel was set to 0.1 MPa under a nitrogen pressure, and the temperature was raised to 75 ° C. while stirring and dissolving. Next, liquid ethylene oxide was supplied at a rate of about 1 g per minute, and the supply was stopped at a total weight of ethylene oxide of 92 g (2.09 mol).
The supply of ethylene oxide was stopped. The reaction temperature during the supply of ethylene oxide is controlled at 90 ± 2 ° C., and the temperature after the supply of ethylene oxide is similarly controlled at 80 ± 2 ° C.
Aged for hours. A part of the reaction solution was taken out, neutralized with an equivalent amount of phosphoric acid, and then subjected to composition analysis by gas chromatography. The results are shown in Table 1.

Synthesis Example 2 An experiment was conducted under the same conditions as in Synthesis Example 1 except that the amount of water added was 36 g (2.0 mol), and the composition of the reaction solution was analyzed in the same manner. Carried out.

Synthesis Example 3 Under the conditions of Synthesis Example 1, the amount of water added was 414 g (23.
An experiment was performed under the same other conditions except that the amount was 0 mol), and the composition of the reaction solution was analyzed in the same manner.

[0017]

[Table 1]

Synthesis Example 4 Of the conditions of Synthesis Example 1, the amount of ethylene oxide supplied was 1
An experiment was performed under the same conditions except that the amount was set to 01 g (2.30 mol), and the composition of the reaction solution was similarly analyzed. Table 2 shows the results.

SYNTHESIS EXAMPLE 5 Under the conditions of Synthesis Example 1, the supply amount of ethylene oxide was 8
An experiment was performed under the same other conditions except that the amount was 6 g (2.00 mol), and the composition of the reaction solution was similarly analyzed. Table 2 shows the results.

[0020]

[Table 2]

SYNTHESIS EXAMPLE 6 The amount of sodium hydroxide added was 2.8 out of the conditions of Synthesis Example 1.
An experiment was performed under the same other conditions except that the amount was changed to g (0.07 mol), and the composition of the reaction solution was similarly analyzed. The results are shown in Table-3.

Synthesis Example 7 Of the conditions in Synthesis Example 1, the amount of caustic soda was changed to 1.2.
An experiment was performed under the same other conditions except that the amount was changed to g (0.03 mol), and the composition of the reaction solution was similarly analyzed. The results are shown in Table-3.

[0023]

[Table 3]

Synthesis Example 8 Of the conditions in Synthesis Example 1, the reaction temperature and the aging temperature were set to 100 ° C.
An experiment was conducted under the same conditions except for
Similarly, the composition of the reaction solution was analyzed. The results are shown in Table-4.

Synthesis Example 9 An experiment was performed under the same conditions as in Synthesis Example 1 except that the reaction temperature and the aging temperature were set to 60 ° C., and the composition of the reaction solution was similarly analyzed. The results are shown in Table-4.

Synthesis Example 10 Of the conditions of Synthesis Example 1, the reaction temperature and the aging temperature were set to 130 ° C.
An experiment was conducted under the same conditions except for
Similarly, the composition of the reaction solution was analyzed. The results are shown in Table-4.

[0027]

[Table 4]

Example 1 An experiment was conducted in which the reaction conditions were optimized based on the results of Synthesis Examples 1 to 10. The reaction conditions were as follows: water = 5.0, caustic soda = 0.07, ethylene oxide = 2.10 in molar ratio to resorcinol, and the reaction temperature was 60 ° C. The results are shown in Table-5.

[0029]

[Table 5]

A comparison was made between the time required for the polycondensation of the second component of the gas-barrier polyester resin obtained from Example 1 and a conventional product (all conditions were the same except for the raw material). Example 1: 2 hours and 30 minutes Conventional product: 3 hours and 00 minutes Gas barrier property improvement rate of gas-barrier polyester resin molded article (molded article to which 10% by weight of second component resin was added) Example 1: 25% improvement rate Conventional product: Improvement rate 20% Measurement method: Measurement of CO ₂ gas barrier properties according to JIS-K7126

Example 2 After the temperature of the reaction solution of Synthesis Example 1 was lowered to 60 ° C., 9.8 g of a 50% aqueous phosphoric acid solution was added at room temperature while controlling the temperature.
(0.05 mol phosphoric acid equivalent) was added. The solution was collected 30 minutes after stirring and the vinegar pH was measured.
Met. Next, attach a cooler and trap to the reactor,
Dehydration under reduced pressure was started from 60 ° C., and reached 120 ° C. in 3 hours. The ultimate pressure is 10 mmHg-Abs, and 120
As a result of performing a dehydration operation at 1 ° C. for 1 hour, the water concentration of the composition after dehydration was 0.11%. Next, a pressure filter was attached to the reactor, and the neutralized salt was filtered while the liquid temperature was controlled at 120 ° C. The obtained composition was 199 g and the yield was 9
8.5%. Further analysis of the obtained composition revealed that sodium ion was 17 ppm and phosphate ion was 98 ppm.

[0032]

According to the present invention, it is possible to produce a hydroxyalkyl ether composition containing 1,3-bis (2-hydroxyalkoxy) benzene as a main component at low cost and high yield. In addition, in this reaction, when the composition in which ethylene oxide was used as the alkylene oxide was used as the raw material of the second component polyester resin of the gas-barrier polyester resin, the addition of trimethylolpropane, which is a polymerization regulator, compared to the conventional product. Is unnecessary and the polycondensation time can be shortened. Further, by molding the second component polyester resin into a gas barrier polyester resin, the gas barrier property is improved as compared with the conventional second component polyester. Therefore, the composition of the present invention is extremely useful industrially as a raw material for polyurethane or polycarbonate or a crosslinking agent.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kyokichi Watanabe 1-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AA03 AB48 AC43 GN06 GP03 GP10 4J029 AA03 AB04 AB07 AC02 BF20 FC32 HA01

Claims (6)

[Claims] 1. A compound of the general formula (1) obtained by reacting resorcinol with an alkylene oxide. (Where n is an integer of 2 to 5)
3-bis (2-hydroxyalkoxy) benzene as a main component, and 1 to 10% by weight of the general formula (5) based on the main component (In the formula, n is an integer of 2 to 5.) A hydroxyalkyl ether containing a compound represented by the formula: 2. The method according to claim 1, wherein the 1,3-bis (2-hydroxyalkoxy) benzene is 1,3-bis (2-hydroxyethoxy) benzene, and the compound represented by the general formula (5) is represented by the formula (5-1). ) 2. The hydroxyalkyl ether according to claim 1, which is a compound represented by the formula: 3. The content of 1,3-bis (2-hydroxyalkoxy) benzene as a main component is 85 to 95% by weight.
The hydroxyalkyl ether according to claim 1 or 2, wherein 4. A compound of the general formula (1) (Where n is an integer of 2 to 5)
3-bis (2-hydroxyalkoxy) benzene as a main component, and 1 to 10% by weight of the general formula (5) based on the main component (Wherein, n is an integer of 2 to 5.) A hydroxyalkyl ether composition for a gas-barrier polyester resin, comprising a compound represented by the formula: 5. The method according to claim 1, wherein the 1,3-bis (2-hydroxyalkoxy) benzene is 1,3-bis (2-hydroxyethoxy) benzene, and the compound represented by the general formula (5) is represented by the formula (5): Formula 6 The hydroxyalkyl ether composition for a gas-barrier polyester resin according to claim 4, which is a compound represented by the following formula: 6. The content of 1,3-bis (2-hydroxyalkoxy) benzene as a main component is 85 to 95% by weight.
The hydroxyalkyl ether composition for a gas-barrier polyester resin according to claim 4 or 5, wherein