JPH05156209A - Production of rosin alcohol - Google Patents

Abstract

PURPOSE:To directly produce a rosin alcohol useful as a rubber additive, a plasticizer for synthetic resin, etc., in high yield without passing through a rosin ester as an intermediate by hydrogenating a rosin in the presence of a specific catalyst. CONSTITUTION:A rosin alcohol is produced in high yield by hydrogenating a rosin at 150-400 deg.C under a pressure of 10-300kg/cm<2> in the presence of 1-50 pts.wt. (based on 1 pt.wt. of the rosin) of a catalyst produced by supporting 0.01-20wt.% (in terms of metal) of ruthenium and 0.1-20mol (based on 1mol of ruthenium) of tin on a carrier (preferably alumina), preferably a catalyst containing ruthenium and tin dispersed in a gel derived from a hydrolyzed product of a metal alkoxide and obtained by dissolving a carrier metal alkoxide, a ruthenium compound and a tin compound in an organic solvent, adding water to the solution, heating the mixture under stirring at 60-100 deg.C under normal pressure or reduced pressure and drying by heating under reduced pressure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to additives such as rubber additives, plasticizers for synthetic resins, fiber aids, chewing gum bases, etc., and a process for producing rosin alcohol used as a synthetic raw material.

[0002]

2. Description of the Related Art Generally, as a method for producing an alcohol from a carboxylic acid, the carboxylic acid is first converted into an ester, and then a copper-chromium oxide catalyst is present, at 250 to 350 ° C.
Hydrogenation method under high temperature and high pressure of 200-300 kg / cm ² (H. Adkins, Journal of American Chemical Society (J. Am. Chem.
Soc.), 53, 1095 (1931)) and the like are known. In addition, as a method for producing rosin alcohol, a reagent reduction method is known in which the methyl ester of abietic acid, which is one of the main components of rosin, is dissolved in an organic solvent and reduced using sodium alcoholate to obtain abietinol. ..

However, in these methods, the carboxylic acid as a raw material cannot be reduced to an alcohol unless it is once esterified, and a multi-step and complicated reaction operation is inevitable, the yield cannot be said to be high, and it cannot be reused. It has the disadvantage that different reagents must be used.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing rosin alcohol by a simple operation and in high yield.

[0005]

Means for Solving the Problems To solve the above problems, the present inventors have conducted extensive studies focusing on hydrogenation catalysts, and as a result, have used a catalyst having ruthenium and tin supported on a carrier. As a result, they have found that rosin alcohol can be obtained directly from rosin with a high yield, and have completed the present invention.

That is, the present invention relates to a method for producing rosin alcohol, which comprises hydrogenating rosin in the presence of a catalyst in which ruthenium and tin are supported on a carrier.

[0007]

EXAMPLES Examples of rosin which is a raw material in the production method of the present invention include natural rosins such as gum rosin, wood rosin and tall oil rosin, which can be used as they are.
In addition, natural rosin contains various resin acids such as abietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, parastophosphoric acid, neoabietic acid, levopimaric acid. May be used alone.

The present invention makes it essential to use, as a catalyst, a catalyst in which ruthenium and tin are supported on a carrier.

The amount of ruthenium supported on the catalyst is usually about 0.01 to 20% (weight%, the same applies hereinafter), and more preferably 0.1 to 10% in terms of metal. The ratio of ruthenium to tin is 1: 0.1 to 1:20 in terms of molar ratio of metal,
Further, it is preferably 1: 1 to 1:10.

The catalyst carrier is not particularly limited, and various known carriers can be used, such as alumina, silica,
Examples include zirconia and titania. Of these, alumina is particularly preferable.

The method for supporting ruthenium and tin on the carrier is not particularly limited, and various known methods such as impregnation method, coprecipitation method and sol-gel method may be used, but the catalyst used in the production method of the present invention is not limited thereto. However, it is preferably prepared by the sol-gel method.

The preparation method by the sol-gel method is a method for preparing a catalyst by utilizing the gelation action of the hydrolysis product of a metal alkoxide. The details will be described below.

First, the carrier metal alkoxide, the ruthenium compound and the tin compound are dissolved in an organic solvent, water is added, and the mixture is heated and stirred at about 60 to 100 ° C. under normal pressure or reduced pressure to give the carrier metal alkoxide and ruthenium. The organic solvent solution of the compound and the tin compound is hydrolyzed to form a gel-like substance. By heating and drying this gel-like substance under reduced pressure, a carrier gel in which a ruthenium compound and a tin compound are uniformly dispersed can be obtained.

Examples of the alkoxide of the carrier metal include methoxides, ethoxides, iso-propoxides, n-propoxides, n-butoxides, sec-butoxides of metals such as aluminum, silicon, zirconium and titanium.
Examples include tert-butoxide.

Examples of the ruthenium compounds include ruthenium salts such as ruthenium chloride and ruthenium bromide,
Examples thereof include acetylacetone ruthenium and the like, ruthenium chelate complexes bonded with chelating agents such as ethylenediamine, phenanthroline, and bipyridyl, carbonyl ruthenium complexes, organic ruthenium complexes such as n-thenocene, and ruthenium alkoxides.

Examples of the tin compound include tin salts such as tin chloride and tin alkoxide.

As the organic solvent, for example, a monohydric alcohol such as methanol or ethanol, a polar organic solvent such as ethylene glycol, propylene glycol, hexylene glycol or glycerin can be used.

The catalyst is used after being subjected to a reduction treatment by a usual hydrogen gas flow reduction method. In this case, the treatment temperature is usually about 50 to 900 ° C, preferably 300 to 800 ° C.
The treatment time is usually 1 to 10 hours, preferably 3 to 5 hours. After the reduction treatment, the catalyst is filled in the reactor and used.

The amount of the catalyst used is usually about 0.1 to 50 parts, preferably 1 to 20 parts with respect to 1 part of rosin (parts by weight, the same applies hereinafter) in the case of a batch system.

The hydrogenation reaction in the present invention is usually carried out at 150-
It is carried out at a temperature of about 400 ° C., preferably in the range of 200 to 300 ° C., usually at a pressure of 10 to 300 kg / cm ² , preferably 30 to 150 kg / cm ² .

Further, a solvent is not particularly required in the hydrogenation reaction, but a solvent such as toluene, decalin, dioxane or methyldiglyme may be used. Further, the reaction system may be either a flow system or a batch system.

The reaction time of the hydrogenation reaction depends on the kind of raw material rosin, the supported amounts of ruthenium and tin, the preparation conditions of the catalyst,
It depends on the amount of the catalyst used, the type of solvent, the reaction temperature, and the hydrogen pressure, but it is usually about 1 to 100 hours, preferably 1 to 50 hours.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of catalyst (sol-gel method) 2.0 g of ruthenium-trisacetylacetonate and 20 ml of concentrated nitric acid were added to a 100 ml eggplant-shaped flask and stirred at 80 ° C. for 16 hours. Then, excess concentrated nitric acid was distilled off with an evaporator, and the obtained ruthenium compound was dissolved in 10 ml of ethanol. In a 100 ml Erlenmeyer flask, 3.0 g of tin-tetraethoxide was dissolved in 10 ml of ethanol.

Separately, 95.8 g of aluminum-trisisoproxide and 200 g of hexylene glycol were added to a 1 liter eggplant-shaped flask and stirred at 130 ° C. to prepare a solution. After allowing to cool to 80 ° C, add the above ruthenium-ethanol solution and tin-ethanol solution to 100 mmHg.
The mixture was stirred under reduced pressure at 80 ° C for 4 hours. Then, 50 g of water was added and the mixture was stirred for 3 hours under the same conditions to obtain a gel-like substance. This gel-like substance was heated and dried under reduced pressure with an evaporator in an oil solution at 170 ° C, and 32.6 g of alumina gel (ruthenium content 2.0%, tin content 4.7%) in which ruthenium compound and tin compound were uniformly dispersed was obtained. I got it. further,
The obtained alumina gel was calcined in air at 400 ° C. for 2 hours and then reduced in a hydrogen stream at 600 ° C. for 4 hours to prepare a catalyst.

(2) Hydrogenation reaction 20.0 g of dehydroabietic acid (having a purity of 93% by gas chromatographic analysis) and 180 g of decalin were charged in an electromagnetic stirring autoclave having an internal volume of 500 ml, and the method of the above (1) was used. 2.0 g of the catalyst prepared according to 1. was added, and the reaction was carried out under the reaction conditions of a hydrogen pressure of 100 kg / cm ² and a temperature of 280 ° C. The reaction solution was appropriately extracted and analyzed. After reacting for 12 hours, 89% pure dehydroabiethyl alcohol 1
I got 7.9g.

The analysis of the product is carried out by gas chromatography after removing the catalyst from the reaction solution by filtration and distilling off the solvent with an evaporator. The retention time of the product and the retention time of commercially available dehydroabietyl alcohol are shown. The agreement confirmed the production of dehydroabietyl alcohol. In addition, as a result of measuring the IR spectrum of the product, 1700 derived from the carbonyl group found in the raw material rosin was obtained.
absorption of cm ^-1 is significantly reduced, absorption near 3400 cm ^-1 derived from the hydroxyl group of the corresponding products dehydroabietyl ethyl alcohol was observed.

Example 2 Chinese gum rosin (acid value 170) 5 in an autoclave
(1) of Example 1 was charged with 0.0 g and decalin 150 g.
Add 5.0 g of the catalyst prepared by the above method, and add hydrogen pressure 100 kg.
The reaction was performed under the reaction conditions of / cm ² and a temperature of 80 ° C. After reacting for 16 hours, the reaction product was taken out, the catalyst was filtered off, and the solvent was distilled off with an evaporator to obtain 43.0 g of a product.

The acid value of the product was 1 or less, and the IR spectrum was measured. As a result, the absorption of 1700 cm ^-1 derived from the carbonyl group found in the raw material rosin was reduced and the product derived from the hydroxyl group of 3400 cm ^-1. Absorption around ^-1 was observed.

Example 3 (1) Preparation of catalyst (impregnation method) Alumina (Catalyst Chemical Co., Ltd., trade name ACP) 26.6 g
To the solution, a solution prepared by dissolving 1.5 g of ruthenium trichloride hydrate and 2.6 g of tin dichloride hydrate in 20 ml of ethanol was added, and after stirring for 30 minutes, the solvent was distilled off with an evaporator. Further, it was calcined in air at 400 ° C. for 2 hours, and then reduced in a hydrogen stream at 600 ° C. for 4 hours to prepare a catalyst.

(2) Hydrogenation reaction The catalyst used in (2) of Example 1 was the same as that of Example 3.
The hydrogenation reaction was performed in the same manner as in (2) of Example 1 except that the catalyst prepared in (1) was replaced. The reaction solution was appropriately extracted and analyzed. After 16 hours of reaction, 16.0 g of 75% pure dehydroabietyl alcohol was obtained.

The product was analyzed in the same manner as in Example 1 to confirm the production of dehydroabiethyl alcohol. Further, as a result of measuring the IR spectrum of the product, the absorption at 1700 cm ^-1 derived from the carbonyl group found in the raw material rosin was significantly reduced, and the absorption of hydroxyl group of the corresponding dehydroabietyl alcohol at 3400 cm ^-1 near Absorption was observed.

Example 4 (1) Preparation of catalyst (coprecipitation method) A solution of 106.5 g of aluminum-trisisoproxide in 200 g of dioxane was added to a solution of ruthenium trichloride hydrate 1.
A solution prepared by dissolving 5 g of tin dichloride hydrate and 2.6 g of tin dichloride hydrate in 50 ml of 2-propanol was added and stirred sufficiently. Further, 28% aqueous ammonia solution was added to precipitate a precipitate, which was filtered, washed with ethanol, and dried under reduced pressure. Further, the obtained catalyst was calcined in air at 400 ° C. for 2 hours and then reduced in a hydrogen stream at 600 ° C. for 4 hours.

(2) Hydrogenation reaction The catalyst used in (2) of Example 1 was the same as that of Example 4.
The hydrogenation reaction was performed in the same manner as in (2) of Example 1 except that the catalyst prepared in (1) was replaced. The reaction solution was appropriately extracted and analyzed. After reacting for 12 hours, 16.0 g of 72% pure dehydroabiethyl alcohol was obtained.

The product was analyzed in the same manner as in Example 1 to confirm the production of dehydroabiethyl alcohol. Further, as a result of measuring the IR spectrum of the product, the absorption at 1700 cm ^-1 derived from the carbonyl group found in the raw material rosin was significantly reduced, and the absorption of hydroxyl group of the corresponding dehydroabietyl alcohol at 3400 cm ^-1 near Absorption was observed.

Example 5 (1) Preparation of catalyst (sol-gel method) 92.2 g of tetraethoxysilane was added to ethylene glycol 200
A solution of ruthenium trichloride hydrate (1.5 g) and tin dichloride hydrate (2.6 g) dissolved in 50 ml of 2-propanol was added to the solution dissolved in g, and the mixture was stirred under reduced pressure at 60 to 70 ° C for 3 hours. Then, 33 g of water was added to this solution and stirred to obtain a gelatinous gel. The gel was crushed to an appropriate size and dried under reduced pressure at 110 ° C. using an evaporator.
After firing in air at 400 ° C for 2 hours, in a hydrogen stream
A reduction treatment was carried out at 600 ° C. for 4 hours to prepare a catalyst.

(2) Hydrogenation reaction A hydrogenation reaction was carried out in the same manner as in (2) of Example 1 except that the catalyst prepared in (1) of Example 5 was used as the catalyst in (2) of Example 1. I did. The reaction solution was appropriately extracted and analyzed. 20
After reacting for a period of time, 16.5 g of 71% pure dehydroabietyl alcohol was obtained.

The product was analyzed in the same manner as in Example 1 to confirm the production of dehydroabietyl alcohol. Further, as a result of measuring the IR spectrum of the product, the absorption at 1700 cm ^-1 derived from the carbonyl group found in the raw material rosin was significantly reduced, and the absorption of hydroxyl group of the corresponding dehydroabietyl alcohol at 3400 cm ^-1 near Absorption was observed.

[0039]

According to the present invention, rosin alcohol can be produced directly from rosin without passing through the rosin ester and in high yield.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuichi Niwa, 1st east of Tsukuba City, Ibaraki Prefectural Institute of Chemical Technology (72) Inventor Fujio Mizuo 1st east of Tsukuba City, Ibaraki Pref. In-house

Claims (3)

[Claims] 1. A process for producing rosin alcohol, which comprises hydrogenating rosin in the presence of a catalyst comprising ruthenium and tin supported on a carrier. 2. The method according to claim 1, wherein the carrier is alumina. 3. The method according to claim 1, wherein the catalyst is a catalyst in which ruthenium and tin are dispersed in a gel derived from a hydrolysis product of a metal alkoxide.