JPH02131442A - Production of trans-1,4-cyclohexanedimethanol and powder thereof - Google Patents

Abstract

PURPOSE:To obtain trans-1, 4-cyclohexanedimethanol in high yield by distilling a mixture of cis form and trans form of 1,4-cyclohexanedimethanol in the presence of an alkali or heating in the presence of an alkali and distilling and to obtain readily handleable trans form by powdering the trans form. CONSTITUTION:A mixture of cis form and trans form of 1,4- cyclohexanedimethanol(CHDM) is distilled in the presence of an alkali or heated in the presence of an alkali (preferably at 160-200 deg.C) to prepare a substance having a high content of trans-1, 4-cyclohexanedimethanol, which is distilled to give trans-1, 4-cyclohexanedimethanol. Dried granular trans-1,4- cyclohexanedimethanol powder is readily obtained by kneading 1, 4-CHDM having a high content of trans form while cooling and molding or by cooling, solidifying and opening.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing trans-14-cyclohexaline methanol and its powder, which is useful as a raw material or chemical intermediate for polyester paints, fibers, resins, etc. [Prior art] 1,4-cyclohexalinemethanol (hereinafter referred to as 1.4-
The industrial production of CHDM (sometimes abbreviated as CHDM) is carried out by a conventional distillation method, for example, by hydrogenating cf, 1,4-cyclohexane dicanoleboic acid dimethyl ester in the presence of a copper chromium catalyst and then distilling it. There is a way to get it.

The 1,4-CHDM thus obtained usually consists of about 70% trans isomer and about 30% cis isomer, and is a waxy or maskite-like substance at room temperature. Comparing the properties of the cis-isomer and trans-isomer, the melting point of the high-purity cis-isomer is below room temperature and usually exists as a liquid, whereas the melting point of the high-purity trans-isomer is 60 to 60%.
4°C, and exists as a solid at room temperature. Regarding its derivatives, it has been found that polyester resins produced from trans-isomers have higher glass points and softening points, and have superior properties. Therefore, trans-1,4-CHDM is desired as a raw material, and demand for it is expected to increase. Such trans-1.4-C
Examples of conventional HDM manufacturing methods include the following. ■ Acta Pharmaceuty Power/Sweat Power (Ac
ta Pharmaceutica SuetLca)
5 (5), 4 pp. 49-456 (1968
) of l,4-CHDM, as introduced in
A method for trimethylsilylation of a trans mixture and chromatographic separation on a diglycerol column, ■ Journal of Liquid Chromatography
(Journal of Liquid Chrom
IO (6) 1077-10
1.4-C as introduced on page 84 (1987)
Chromatographic separation of cis-trans mixtures of HDM using a cyclodextrin-bonded silica gel column, ■ Journal of the Chemical Society
(Journal of Chemical S
14-C, as introduced on page 404-407 (1953)
A method of converting a cis-trans mixture of HDM into a dibenzoate, reductively crystallizing it using the difference in crystallinity, and then hydrolyzing it again to obtain trans-1.4-CHDM. [Problems to be Solved by the Invention] However, in the case of products obtained through industrial production through ordinary distillation, the amount of trans isomer distilled out with high purity is extremely small, and the majority is about 30% of cis isomer. The result is a mixture containing a certain amount of Thus, a mixture containing about 30% cis isomer has a melting point of about 40°C,
Therefore, there were many problems in handling.

For example, when distributed commercially, it requires an expensive drum container because it is moth-shaped or muskit-shaped, and it must be heated to 50 to 60°C before use.
It takes time and effort to heat and melt at a temperature of There were issues such as the high cost of the products manufactured as raw materials.

In addition, the conventional transformer 1.4-C shown in ■~■ above
HDM manufacturing methods are analytical or laboratory methods, which have problems such as low yield, high cost, and complicated manufacturing operations, and are not suitable for commercial production. This was not a satisfactory method for producing 1.4-CHDM or its powder.

Against this background, the commercially advantageous transformer 1.4-
There has been a strong desire to develop a method for producing CHDM and its powder.

[Means for Solving the Problems] As a result of extensive research in order to solve the above problems, the present inventors have distilled a mixture of cis and trans forms of 1,4-cyclohexaline methanol in the presence of an alkali. We succeeded in obtaining highly pure trans-1,4-CHDM in a high yield by heating it in the presence of an alkali or distilling it, and furthermore, by pulverizing it, it is extremely easy to handle. We succeeded in obtaining trans-1.4-CHDM powder and completed the present invention. The content of the present invention will be explained in detail below. The 1,4-CHDM used in the present invention may be a mixture of cis and trans forms, and the manufacturing method is not critical. A solvent may be used, for example, water, methanol, ethanol, etc., and the concentration of 1.4-CHDM is 50 to 1
00% by weight is preferable, but reaction without a solvent is preferable since no extra operations are required afterwards. The alkali that can be used in the present invention includes, for example, sodium,
These include hydroxides of alkali metals or alkaline earth metals such as potassium and lithium, various alcoholates such as sodium methoxide and sodium ethoxide, and amines such as ethanolamine. The amount of alkali used is 0.4-CHDM.
1 to 5% by weight is preferred. This is because if the amount of alkali used is less than 0.1% by weight, the amount of trans isomer produced is small, and if it is used in excess of 5% by weight, problems such as the formation of a polymer with ether bonds occur, so it is preferable. That's because there isn't.

The alkali can be added in the form of powder, but since the solubility of alkali in 1,4-CHDM is generally low, it is added after being dissolved in a small amount of water or an organic solvent, or the alkali is added in the form of an alcoholate. It is preferable to add it in liquid form. The alkali can be added in advance before distillation, after heating, or during distillation. When adding an alkali during distillation, it is also possible to add the alkali after a fraction with a high proportion of trans isomers has been distilled out and distill while producing more trans isomers. On the other hand, if alkali is added and heated before distillation, set conditions are as follows. The heating temperature is 150 to 250°C, more preferably 160 to 200°C. When the temperature is 150℃, it is not preferable because the reaction time until the formation of trans isomer reaches the maximum is unfavorable.
It is not preferable to carry out the test at temperatures exceeding ℃ because there are disadvantages such as an increase in the amount of by-products of ether bonds. Time varies depending on the temperature and the amount and type of alkali added, but for example, if the amount of alkali added is 2% by weight at 160"C, it will take about 1 hour, and if the amount of alkali added is 0.5% at 200"C, it will take about 30 minutes. By doing this, the amount of trans isomer produced reaches its peak. Also, as the distillation conditions, it is preferable to have a temperature of 150°C to 200°C and a degree of vacuum of 1 to 50 mm Hg. However, if the degree of pressure reduction is less than 1 mmHg, it is disadvantageous because it requires high costs for industrial equipment and power;
This is because if the distillation temperature is exceeded, the distillation temperature will become too high, and although isomerization will proceed, decomposition reactions and etherification reactions will occur, which is undesirable.

For example, after reducing 1,4-cyclohexanedicarboxylic acid dimethyl ester in the presence of a copper chromium catalyst, 1.4
- When a reaction product containing CHDM as a main component is obtained, it usually contains about 70% trans isomer, but it is mixed with 180% by weight of sodium hydroxide in the presence of 0.5% by weight (based on the weight of the above reactant)
By heating to ℃ and holding for about 60 minutes, the content of trans isomer is reduced to 8 by isomerizing the cis isomer to trans isomer.
It can be increased to about 5%. However, with this isomerization alone, the content of trans isomer is 8
In some cases, the proportion remains as low as around 0%, so a distillation operation is then performed, which reduces the trans isomer content to 8%.
5% or more, it is possible to obtain a content of at least about 90%. On the other hand, when an alkali is added during distillation, a trans isomer with a purity of 95% or more is obtained from a reactant containing 1.4-CHDM at a yield of 9.
It can be obtained at about 5% by weight. Note that the distillation method can be either batchwise or continuous, but in order to differentiate the subtle differences between trans and cis isomers and obtain a fraction containing a large amount of trans isomers, it is preferable to have a large number of theoretical plates. Distillation conditions with at least 10 to 20 theoretical plates are preferred. The melting point of 1.4-CHDM with a high trans isomer content of about 85% or more obtained in this way is:
Although it varies depending on the content of trans isomer, it is generally around 60°C. Therefore, since 1.4-CHDM with a high trans isomer content forms a relatively hard solid by cooling, it can be easily processed by using methods such as kneading while cooling and then molding, or cutting after cooling and solidifying. , it is possible to obtain smooth granular trans=1.4-CHDM powder. By using this trans-1.4-CHDM or trans-1,4-CHDM powder, it is possible to produce derivatives such as polyester resins with high glass points and excellent properties, and even 1.4- CHDM
This will expand the range of applications for this material and the derivatives produced using it. For example, 1.4-CH with a trans isomer content of 80% or more
DM, more preferably 1.4-CHDM with a trans isomer content of 90% or more, containing 50 to 97 mol% as a glycol component, and 3 to 50 mol% of ethylene glycol as another glycol component, and terephthal. The polyester copolymer obtained by reacting with a dicarboxylic acid component such as an acid is a conventional product, that is, the trans isomer content is 80%.
Compared to products produced in the same manner using less than 1.4-CHDM, the heat resistance is significantly improved. Furthermore, when producing the above polyester copolymer, various properties can be further improved by adding various improving agents such as fibrous reinforcing agents, flame retardants, anti-coloring agents, antistatic agents, heat resistant agents, and weathering agents, if desired. It is also possible to strengthen it. Therefore, trans-1.4 obtained by the method of the present invention
- Polyester resin with excellent heat resistance, fire resistance, weather resistance, deformation resistance, anti-static properties, etc. by using CHDM or trans-1.4-CHDM powder or by adding various types of improved cutting to it. It is also possible to produce derivatives such as Examples] Examples of the present invention will be described in detail below. 1 4-CH
250 kg of DM's 1,4-cyclohexanedicarboxylic acid dimethyl ester and copper chromium catalyst [manufactured by C-5.1 Chemical Company] 2
Put 5 kg into a 550 liter autoclave,
The mixture was stirred at 0°C, and after hydrogen absorption was completed, it was filtered to remove the catalyst, and the resulting filtrate was distilled to obtain raw materials (1) and (2). As a result of analyzing raw material (■) and raw material (2) by gas chromatography, it was found that raw material (■) contained 45% cis form and 55% trans form, and raw material (2) contained 26% cis form and 74% trans form. Ta. In addition, raw material (2) was chewy and could not be crushed, and contained 1% raw material and 96.9% trans form. The softening point of material ■ is approximately 40℃.
It was a sticky solid (waxy) and could not be crushed. Mix 50g of raw material ■ with 2g of 50% sodium hydroxide aqueous solution and put it in a 100ml eggplant-shaped flask.
The mixture was heated in an oil bath at 180° C. for 30 minutes with stirring, and then cooled to room temperature to obtain Substance A containing a high content of trans-1,4-cyclohexalinemethanol. As a result of analyzing the substance A by gas chromatography,
The composition was 15.4% cis isomer and 84.6% trans isomer. Next, substance A was prepared using 20 theoretical plates and a reduced pressure of 10 mmHg.
, 30 g of fraction Aa was obtained by distilling at a distillation temperature of 152 to 163°C. As a result of analyzing the fraction Aa, the composition was found to be cis isomer 3. Mix 50g of raw material ■ and 0.2g of 50% sodium hydroxide aqueous solution, put into a 100ml eggplant-shaped flask, heat in an oil bath at 200℃ for 3 hours with stirring, and then cool to room temperature. The mixture was cooled to a temperature of 100.degree. C. to obtain Substance B containing a high content of trans-1,4-cyclohexalinemethanol. As a result of analyzing the substance B, the composition was found to be 17.7% cis-isomer;
The trans isomer content was 82.3%. Next, substance B was distilled under the same conditions as those shown in Example 1, except that the degree of vacuum was changed to 40 mmHg and the distillation temperature was changed to 185 to 188°C, to obtain 30 g of fraction Ba. ．． As a result of analyzing the fraction Ba, the composition was found to be 3.9% of the cis isomer.
It was 96.1% trans isomer.

Mix 50g of raw material ■ and 1.0g of a 20% sodium hydroxide aqueous solution, put into a 100ml eggplant-shaped flask, heat in an oil bath at 160°C for 2 hours with stirring, and then cool to room temperature. The substance C was cooled to a high content of trans-1,4-cyclohexalinemethanol.As a result of analyzing the substance C, the composition was 16.3% of the cis isomer,
The trans isomer content was 83.7%. Next, Substance C was distilled under the same conditions as in Example 1, except that the number of theoretical plates was changed to 10, to obtain 30 g of fraction Ca. As a result of analyzing the Ca fraction, the composition was 90% cis isomer and 91.0% trans isomer.夾m2A 50g of raw materials ■ and 100% concentration sodium methyler}
0.5 g of trans-1,4-cyclohexaline was mixed, placed in a 100 ml eggplant-shaped flask, heated in an oil bath for 1 hour at 180°C while stirring, and then cooled to room temperature. Substance D was obtained. As a result of analyzing the substance D, the composition was 14.8% cis-isomer;
The trans isomer content was 85.2%. Next, Substance D was distilled under the same conditions as in Example 2, except that the number of theoretical plates was changed to 10, to obtain 30 g of fraction Da. As a result of analyzing the fraction Da, the composition was 8.6% cis isomer,
It was 91.4% trans isomer. ILL 25 3 kg of raw material ■ was put into a 5 liter flask, and a rectification column with 20 theoretical plates (30 mm in diameter, 1 m in length, with a Raschig ring) was used to reduce the pressure to 10 mmHg and distill the temperature to 152 to 1.
Distilled at 63°C, 0.72 kg of fraction Ea and 2. OOk
It was divided into a fraction Eb and a fraction Eb. The composition of fraction Ea is 3.4% cis isomer and 9% trans isomer.
It was 6.6%. On the other hand, the composition of fraction Eb was 33.2% cis-isomer and 66.8% trans-isomer. Next, 2 kg of fraction Eb and 80 g of 50% sodium hydroxide aqueous solution were placed in a 3 liter flask equipped with a stirrer.
The temperature was gradually raised to 180°C for 30 minutes, then cooled to room temperature and neutralized with hydrochloric acid in the same amount as the alkali to obtain Substance F. Thereafter, substance F was analyzed and found to have a composition of 15.8% cis isomer and 84.2% trans isomer. Further, this substance F was put into a 5 liter flask and distilled in the same manner as above to obtain 0.64 kg of fraction Ga and 1.10 kg of fraction Gb. The composition of the fraction Ga was 2.2% cis isomer and 97.8% trans isomer. On the other hand, the composition of fraction Gb was 22.2% cis isomer and 77.8% trans isomer.
Put 0g into a 5 liter flask and add a distillation column with 20 theoretical plates (30 mm in diameter, 1 m in length, with a rasp ring)
Distillation was carried out at a reduced pressure of 10 mmHg and a distillation temperature of 153 to 162°C, and 0.6 kg of fraction Ha. 0.8 kg of distillate Hb,
1.2 kg of fraction Hc was obtained. The composition of the fraction Ha is 3.6% cis isomer and 96% trans isomer.
4%, the composition of the fraction Hb is 24% cis isomer. The composition of the fraction Hc was 2.2% cis-isomer and 97.8% trans-isomer. Add 16 g of sodium methylate to 800 g of Inu JLL Nie raw material ■, and prepare a theoretical plate number of 20 Pi (diameter 30 mm, length 1 m, with Raschig ring), degree of vacuum 40 mm Hg, distillation temperature 185-1
Distilled at 88°C. 500 g of fraction J was obtained.

As a result of analyzing this fraction J by gas chromatography, the composition was 96.4% trans isomer and 3.6% cis isomer.
%Met. Furthermore, distillate J was poured into a stainless steel vat at 70°C, left overnight, and then cut with a frozen cutter [Model FZ, manufactured by Shonan Sangyo ■] to obtain a white trans-1 4-CHDM material that is easy to handle. I got the end.

The melting point of this product was 62°C.

Put 800g of raw material ■ and 8g of sodium hydroxide into a 1 liter stainless steel autoclave and heat at 180℃ for 2 hours.
Heated for an hour. After cooling, distillation was carried out in the same manner as in Example 7 to obtain fraction K. The fraction K was poured into a mold, solidified by cooling, and pulverized. Analysis of this product revealed that it was a white powder that contained 968% trans isomer and 3.2% cis isomer, with a melting point of 62°C and was easy to handle. Inu 1'' 800 g of raw material ■ and 6 g of sodium alcoholate were placed in a distillation column with 10 theoretical plates (30 mm in diameter, 0.5 m in length, with a Raschig ring), and the pressure was reduced to 40 mmHg and the distillation temperature was 185 to 188°C. Distillation was performed to obtain 500 g of fraction L. The fraction L is transferred to a jacketed 21-goo [desktop type 2-dah, PN
V-1 model, manufactured by Irie Shokai 4] for 10 minutes, left overnight and pulverized with a frozen cutter to obtain white easily handled trans-14-CHDM powder. Analysis of this product revealed that it had a composition of 90.3% trans isomer and 9.7% cis isomer, and had a melting point of 58°C.

800 g of raw material (1) and 5 g of sodium alcoholate were placed in a distillation column with 10 theoretical plates (30 mm in diameter, 0.5 m in length, with a Raschig ring), the degree of vacuum was 40 mmHg, and the distillation temperature was 185 ~ Distilled at 188°C to obtain 500g of fraction M. The fraction M was kneaded for 10 minutes in a jacketed 21-glue, left for 1 hour, and then molded using a Beretter [Model EXD-100, manufactured by Fuji Paudal Co., Ltd.] to a diameter of 3 mm and a length of 10 to 50 mm. Trans-1.4-CHDM pellets were obtained. Analysis of this product revealed that it had a composition of 968% trans isomer and 3.2% cis isomer, and had a melting point of 62°C. [Effect of the invention] As described above, according to the present invention, trans-14-CH
It becomes possible to manufacture DM efficiently and economically. In addition, the present invention provides a commercially advantageous powder form of trans-1.4-CHDM that is solid at room temperature, easy to handle, does not require a special storage container, and can be stored in an inexpensive container. It can be manufactured to Furthermore, by using the trans-1.4-C HDM obtained by the present invention or its powder, and by adding various improving agents thereto, it is possible to improve heat resistance, fire resistance, weather resistance, deformation resistance, and training. It becomes possible to produce derivatives such as polyester resins that have excellent effects such as electrical properties, and in turn, it is possible to expand the uses of 1,4-CHDM. Patent applicant: Towa Kasei Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] 1. A method for producing trans-1,4-cyclohexaline methanol, which comprises distilling a mixture of cis and trans forms of 1,4-cyclohexaline methanol in the presence of an alkali. 2 A mixture of the cis and trans forms of 1,4-cyclohexaline methanol is heated in the presence of an alkali to prepare a product with a high content of trans-1,4-cyclohexaline methanol, and then distilled. transformer-1
, 4-cyclohexalinemethanol manufacturing method. 3 A mixture of cis and trans 1,4-cyclohexaline methanol is distilled in the presence of an alkali to prepare a product with a high content of trans-1,4-cyclohexaline methanol, and then powdered. , trans-
A method for producing 1,4-cyclohexaline methanol powder. 4. Heating a mixture of cis and trans 1,4-cyclohexaline methanol in the presence of an alkali to prepare a product with a high content of trans-1,4-cyclohexaline methanol, followed by distillation and further pulverization. A method for producing trans-1,4-cyclohexaline methanol powder, characterized by: