KR100614077B1 - The method of separation and purification of Hwang Chil paint and flavours from resin of Dendropanax morbifera Lev - Google Patents

Abstract

According to the present invention, a) using the ethanol to extract the hwangchil paint component and clove component mixture fractions from the Hwangchil wood resin solution to separate from the solid fraction; b) extracting the clove component from the hwangchil paint component and clove component mixture fraction using a pentane or hexane solvent to separate the hwangchil paint component fraction and clove component fraction; And c) evaporating the yellow lacquer paint component fraction separated in the above step under reduced pressure to remove water and a solvent, and a clove component fraction separated in the step b) under c) reduced pressure. Provided is a method for separating and purifying cloves contained in a yellow lacquer resin liquid, the method comprising distilling to remove a solvent.

The method of separating, purifying, and refining the yellow lacquer paint of the present invention and the refining component of the clove component has a high recovery rate of the clove component and the solvent, and has the effect of obtaining a safe clove component and the yellow lacquer paint without harm to the human body.

Hwangchil, paint, cloves, purification method, extraction, ethanol, hexane, pentane, evaporation

Description

The method of separation and purification of Hwang Chil paint and flavors from resin of Dendropanax morbifera Lev}

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of an apparatus used to separate and purify a yellow lacquer paint and a clove component from a yellow lacquer resin.

The present invention relates to a method for separating and purifying the hwangchi paint and clove components from the Hwangchil wood resin solution.

When hwangchil cuts the bark of the hwangchil tree, the tree secretes milky white liquid to heal the wound, which is oxidized in the air and gradually turns yellow. It has been harvested and used as a natural golden paint. Hwangchil is a resin liquid that can only be collected from the wild wood that grows in our country all over the world. It is also a golden transparent paint that has undergone many cracking processes due to its dignity.

Hwangchil-tree (Dendropanax morbifera Lev.) Is an evergreen broad-leaved arborescent of the genus Elm and Ogalpi, and is native to Korea. The leaves are shifted, and their shape is not uniform in five shapes depending on the amount of sunlight. The young branches are green and glossy, the flowers bloom in June, and the fruits 7-19mm long ripen black. The plant is a subtropical plant that grows in an area where the minimum temperature is below 2 ℃ and the average annual temperature is 12 ~ 15 ℃. Hwangchil-tree, which secretes yellow lacquer from around the world, is a rare species that grows only in the southwestern part of the Korean peninsula, the coast, islands, and Jeju Island, and its quantity is extremely limited. Currently, island areas include Sinan, Jindo, Wando, and Jeju Island, and coastal areas include Haenam, Jangheung, Gangjin, Goheung, Seungju, Gwangyang, and Yeosu.

Hwangchil is called golden color because it is golden. The golden color of Hwangchil is more brilliant when exposed to the sun. Unlike black lacquer, the pattern and color of the product is preserved and golden color is applied to it. In addition, it boasts excellent coating ability on any material such as wood, metal, leather, and paper. Applying yellow lacquer on furniture, upholstery, and soothers can have a surprising effect on your hair and your mind and body. It also has a fascinating and fascinating fragrance, and if used as a perfume, it will be greatly loved by women around the world. Hwangchil has been excellent in treating inflammation as long as it has been given to the public.

Hwangchil tree was considered more precious because of its limited yield, and overfishing was so poor that it was not preserved properly. The best natural paints, which were decorated with gold from the Three Kingdoms period, have disappeared into the back of history because of human greed and ignorance.

The brilliant golden paint lacquer symbolized the Chinese imperial authority. Among the special products we tribute, they had no choice but to cherish the yellow lacquer. Hence, Hwang-chil was a valuable treasure for Jang Bogo, who had monopolized East Asian maritime trade. These are the contents of a Chinese librarian who records Hwangchil as a record.

Tang Tai sent a reaper to Baekje chairman, got the specialty gold lacquer and painted it on the armor. When the sun shined, the gold shone brilliantly.-Bookbuwon-gu

Hwangchil comes from three islands in the Southwest Sea of Baekje, and in June when the sap is collected and painted on the water, it looks like gold and attracts attention. -Energization

Hwangchil was also treated as a gold lacquer during the Goryeo, and was treated with gold. Moreover, Chinggis Khan, who built the Mongolian Empire, used a golden and bright yellow lacquered tent (Gel, Ordo) on each road.

In 1217 (1217), he was asked to produce timber in Mongolia. He also requested special products such as lacquer, non-tree, Roh Tae-mok, and ume as instructions of the Midwest. May the king announce to Midwest

 "As we gathered together, we lost all the lacquer when it came out of the land, and the mountains are the islands of the South Sea. But now the places of Josai's history are coming and going. The craftsman who makes the juice will be sent out from the province where the lacquer is produced. " -Korea Temple

Hwangchil wood is called 千 金 木 and the gin is written as benzo. -Officer's sixteen

Hwangchil is the main producer of Jeolla-do. -Haedong History

Wando Chil Hwangchil is brilliant like glass / rare wood, rumored in the world / Last year, after the king releases Hwangchil's detention / Sprouts and branches grow out of the cut-outs.

Jeong Yak-yong recorded the public deceit in the vicinity of Gangjin where Dasan was once decimated in Mokmin's letter. "The tyranny of the local officials around the Hwangchil public was so severe that the unbearable people made holes in the Hwangchil and citron and put a reef to dry it, or sneaked it with an ax at night." It is called.

Although the Hwangchil tree suffered from the angry people as the tree of the dead, it is believed that the temple protected forests and the trees in the deep mountains left seeds and continued the vegetation.

There is a fertility poem that shows the whole picture of Hwangchil. He praised the excellence of the world's famous Hwangchil, and said that the Hwangchil tree before the extinction has been revived after being exempted from public deeds.

"You haven't seen it, the incense / gold sap filled with 弓 福山 is clear and shines brightly. It peels and peels off the juice. It's like a lacquer. / The ripe gardenia paint, how can you compare it? / The calligrapher's 硬 黃紙 is better here. / 蠟 紙 Both embossed and colorless retreat. / Because the tree's fame is known in the world. / Year after year, I transfer it to Kobe by work./ There is no way to stop the frosts./ The locals regarded this tree as 惡 木 / Nightly sneaked up with an ax. Like a mysterious rebirth, the wind blows and the rain gives rise to dead stumps,

The above records confirm that Hwangchil has gained a reputation as a golden glitter paint from the Three Kingdoms period to the end of Joseon Dynasty. But for some reason, the tradition of pickling, refining, painting, etc., has been lost for more than 200 years. Today, research has been conducted by some scholars.

Separation and purification method of paint lacquer is known in Korean Patent No. 0186682, but it cannot be used for food because acetone is used for purification, and the boiling point of acetone is low (56 ℃) and it is lost in vacuum filtration or solvent recovery process. Since the amount of solvent is large, it causes pollution of water and air, and it is used as a paint with the clove component intact, so that the clove component is evaporated and used in the air during the application process (coating process) or after coating. There is a problem that can not be.

Generally, steam distillation method is used to extract clove components such as natural fragrances. However, in the case of Hwangchil, the paint component has the property of being easily cured by light or heat. It is not suitable because it results in lowering the quality of the paint. (Special 2000-0050522)

The clove component of Hwangchil sap contains a small amount of Terpene and Sesquiterpene, which are different depending on the time and place of collection, but germacrene-d, β-selinene, α-amorphene , α-selinene, δ-cadinene, γ-cadinene, T-muurolol, β-elemene, bicyclo [4,4,0] dec-1-en-2-isopropyl-5-methyl-9-methylene, β-cadinene , germacrene-B, α-copaene, α-humulene, α-cadinene and small amounts of linalool L, α-terpinene, α-cubebene, α-ylangene, (+)-calarene, 3,7-guaiadine, (-)- Contains isoledene, β-cubebene, limonene, aromadendrene, cadina-1,4-diene.

The cloves contained in Hwangchil not only have a value as a benzoic odor that makes the mind and body clear and comfortable, but also have various pharmacological effects, so they are more valuable as perfumes, functional foods, beverages or medicines than as paints.

The pharmacological effect of clove contained in Hwangchil is α-Cubebene, an essential oil component of Melisa officinalis , which is effective in epilepsy, neuropathy, insomnia, fainting, hysteria, migraine, depression, dizziness, and intestine such as stomach pain or flatulence. Along with the disease, it also works on the digestive system and is used for hyperthermia and blood circulation. β-Elemene regulates diuretics, tonics, aphrodisiacs and headaches, bed-wetting (sleeping urine), affects the central nervous system and hormone system, has a tonic effect, stimulates nerves, and is good for male hormone system as well as treating depression Also used for. β-Selinene has been identified in Atractylodes macrodephala , an oxidizing plant used for appetite stimulants, vomiting and diarrhea, and vomiting during pregnancy. chamomilla It is an ingredient found in. Germacrene D comprises 19% of the essential oil of Platostoma africanum , a West African spice, and is used as a treatment for neuralgia, menstrual irregularities, headache, hematuria and hemostatics. Β-sitosterol found in Hwangchil trees is used to treat prostatic hypertrophy ("cytonyl") used as a treatment for bladder dysfunction (urinary disorders, nocturnal enuresis, urinary incontinence, anemia, etc.) before and after prostate hyperplasia, prostatitis, neurostatic prostate disease (Hyundai Pharm.) (Monthly Forestry Information No. 109, Kim Se-hyun)

It is known that the hexane fraction of Hwangchil has strong anticancer activity, and the ethyl acetate fraction has antioxidant activity (see Korean Patent Publication No. 2000-0004499).

The present invention has a high recovery rate of the clove component and the solvent, and is safe and harmless to the human body. It is to provide a method for separating and purifying the clove components.

In order to achieve the object of the present invention,
a) extracting the yellow lacquer paint component and the clove component mixture fraction from the hwangchil wood resin solution using ethanol to separate the solid fraction from the solid content fraction;
b) extracting the clove component from the hwangchil paint component and clove component mixture fraction using a pentane or hexane solvent to separate the hwangchil paint component fraction and clove component fraction; And
c) there is provided a method of separating and purifying the yellow lacquer paint, comprising the step of removing the water and the solvent by evaporating the fraction of the yellow lacquer paint component separated in the above step under reduced pressure.
In order to achieve another object of the present invention,
a) extracting the yellow lacquer paint component and the clove component mixture fraction from the hwangchil wood resin solution using ethanol to separate the solid fraction from the solid content fraction;
b) extracting the clove component from the hwangchil paint component and clove component mixture fraction using a pentane or hexane solvent to separate the hwangchil paint component fraction and clove component fraction; And
c) there is provided a method for separating and purifying the clove components contained in the yellow lacquer resin liquid, which comprises distilling the clove component fraction separated in the above step under a reduced pressure to remove the solvent.
Separation and purification method of the yellow lacquer paint according to the present invention can be carried out in the apparatus as illustrated in FIG. However, the device is intended for laboratory use and scale-up on a commercial scale can alter the configuration or arrangement of the device.
In the separation and refining method of the yellow lacquer paint according to the present invention, step a) is carried out by adding the yellow lacquer resin liquid to the extraction tank 4 in which the filter cloth is installed and extracting solvent, preferably ethanol, about the weight of the yellow lacquer resin liquid. Slowly add to the extraction tank (4) at 1: 1.25 w / v ratio and stir to dissolve the Hwangchil wood resin solution in the solvent, and then send some of the solvent passed through the filter cloth to the flask (2) of the rotary evaporator (1) , According to a conventional vacuum extraction method. In other words, the refrigerant is circulated in the condenser and the collector, and the evaporated solvent is condensed in the condenser and returned to the extraction tank by evaporating the solvent in the flask while rotating the rotary evaporator while depressurizing the inside of the system by operating a vacuum pump or the like. The solvent from which the paint and the clove components are extracted from the resin liquid is refluxed back into the flask. This extraction process continues during step a). In this step a), the fraction of the yellow lacquer paint component and the clove component mixture is collected into a flask of a rotary evaporator, and the solid fraction remains in the filter cloth of the extraction tank 4. Extraction conditions that are not presented above can be applied to those skilled in the art that are commonly used in the art.
In the method of separating and purifying the yellow lacquer paint according to the present invention, step b) is a C5-C7 aliphatic hydrocarbon solvent, for example, a pentane or hexane solvent, in the mixture of the yellow lacquer paint component and the clove component separated in step a). This is carried out by adding a ratio of about 1: 0.28 w / v relative to the weight of the fraction of the yellow lacquer paint component and the clove component, stirring to dissolve the clove component and separating the solvent layer to separate the clove component fraction dissolved in the solvent. The conditions of the operations involved in this step, such as addition of solvent and separation of solvent layer, are conventional.
In the method for separating and purifying the yellow lacquer paint according to the present invention, step c) is a step of removing water and solvent from the yellow lacquer paint component from which the clove component has been removed in the step b). About 50 ° C. under reduced pressure of 20 to 50 mmHg in the evaporator to reduce atmospheric pressure or reduced pressure conditions, preferably the yellowing paint May be carried out at a temperature of degree. It is carried out until the color of the paint is clear and there is no more condensation of water and solvent.
In the separation and purification method of the clove component contained in the Hwangchil wood resin solution according to another object of the present invention, step a) and step b) are the same as the step a) and step b) of the separation and purification method of the hwangchil paint Is performed.
In the separation and purification method of the clove component contained in the Hwangchil wood resin liquid according to another object of the present invention, step c) is carried out under a reduced pressure of 100-200 mmHg in a conventional evaporator, for example, a rotary evaporator. It is carried out by evaporation of water and solvent from the clove component fraction separated at.
Hwangchil paint separated and purified according to the present invention should block the contact of oxygen because it is polymerized by heating and light irradiation in an oxygen atmosphere, and the hwangchil paint for paints or spray paint as it is high viscosity Suitable diluents are required because they are not suitable for use. As a solvent, it is soluble in acetone, ethyl acetate, and alcohols, but insoluble in aliphatic hydrocarbons such as pentane, hexane, and heptane. Therefore, in order to use the yellow lacquer paint for brushing or spraying, it is appropriate to dilute it with a solvent such as acetone, ethyl acetate, C1C4 alcohols or cellosolve, and keep it away from temperature, light and oxygen. Preferably, the mixture of acetone: butanol (weight ratio 1: 9 to 9: 1) is mixed with 120% by weight of the yellow lacquer and transferred to a brown bottle that can block light to inject dried nitrogen to completely remove oxygen and seal it. And frozen.
<Example>
Removal of Solids from Hwangchil Resin Liquid

Solid components were separated from the Hwangchil wood resin liquid in the following order using a 2L scale purification device shown in FIG.

2kg of Hwangchil wood resin solution collected from July-August 2000 in Haenam, Jeollanam-do, was placed in the filter cloth inside the extraction tank (4) of the Hwangchil tableting apparatus shown in FIG. 1, and 2.5L of alcohol ethanol (hereinafter solvent) was poured slowly. Stir well to mix with. At this time, a part of the solvent dissolved in the yellow lacquer by opening the three-pronged valve was allowed to flow out of the filter cloth and flow down to the flask 2. Cover the lid of the extraction tank, close the three-hole valve at the bottom of the extraction tank, and operate the reflux freezer to circulate the refrigerant cooled to -10 ℃ ~ -20 ℃ to the reflux cooler and freeze collector and operate the water pump to reach 30 ~ 100mmHg. Decompression was maintained. The rotary evaporator was operated to heat the flask while rotating to maintain the water bath pot temperature at 40 ° C. The solvent is evaporated and liquefied in the reflux condenser, and the liquefied solvent is collected in the extraction apparatus, and the yellow lacquer is dissolved. When the solvent is filled in the extraction tank, the solvent dissolved in the yellow lacquer is slowly passed through the filter cloth and collected in the flask 2 of the rotary evaporator. At this time, it is also possible to flow down to the flask 2 through the three-hole valve (5) below the extraction tank.

When the solvent flowing through the filter cloth becomes almost colorless, only solids remain in the filter cloth of the extraction tank, and all of the yellow lacquer used for cloves and paints is collected in the flask (2). After the yellow lacquer was completely extracted, the solvent filled in the extraction tank opened the three-prong valve 5 toward the solvent recovery tank 9 to recover the solvent. Purification was completed when the solvent was not refluxed in the reflux condenser. Solid content was taken out and dried in 105 degreeC oven, and 178g (9%) was obtained.

Analysis of Clove Ingredients in Recovered Solvent

Analysis of the clove components contained in the solvent was separated and analyzed using HP-5973N MSD and HP-1 capillary column connected to HP-6890 GC, and the component identification and accuracy by Willy275 libray were investigated. 1].

TABLE 1

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order ingredient content(%) accuracy(%) One α-pinene 37.0 99 2 β-selinene 11.0 99 3 α-selinene 10.0 99 4 germacrene-d 9.9 99 5 α-armophene 8.7 99 6 δ-cadinene 7.4 99 7 α-copaene 4.0 99 8 β-elemene 3.2 99 9 α-ylangene 3.2 99 10 γ-cadinene 3.1 99 11 α-cubebene 2.5 99 12 α-humulene trace 99 13 β-pinene trace 97 14 (+)-calarene trace 93

Separation of Clove Ingredients and Paints and Analysis of Clove Ingredients

500 ml of hexane was added to the clove and paint mixture from which the solids were removed, and the mixture was attached to a rotary evaporator under reduced pressure, and the flask was rotated at 40 ° C. for 5 minutes to dissolve the clove contained in the yellow lacquer in the solvent. It was left in the freezer for a while. The next day, when the yellow lacquer component and the solvent layer were separated, the solvent was removed and the solvent was evaporated under reduced pressure evaporator under conditions of 40 ° C. and 100 to 200 mm Hg. At this time, the reflux condenser was kept at -10 ° C or less to prevent loss of the solvent. The solvent was evaporated and the remaining clove component was 622 g (31%).

Clove components were separated and analyzed using HP-5973N MSD and HP-1 capillary column connected to HP-6890 GC, and the component identification and accuracy by Willy275 libray were investigated. Indicated.

TABLE 2

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order ingredient content(%) accuracy(%) One germacrene-d 17.2 99 2 β-selinene 16.1 99 3 α-amorphene 13.7 99 4 α-selinene 11.8 99 5 δ-cadinene 11.7 99 6 γ-cadinene 7.5 98 7 T-muurolol 5.5 98 8 β-elemene 3.9 99 9 bicyclo [4,4,0] dec-1-en-2-isopropyl-5-methyl-9-methylene 3.0 99 10 β-cadinene 2.2 98 11 germacrene-B 2.1 99 12 α-copaene 1.8 99 13 α-humulene 1.8 96 14 α-cadinene 1.7 98 15 linalool L trace 97 16 α-terpinene trace 97 17 α-cubebene trace 99 18 α-ylangene trace 98 19 (+)-calarene trace 93 20 3,7-guaiadine trace 94 21 (-)-isoledene trace 94 22 β-cubebene trace 94 23 limonene trace 98 24 aromadendrene trace 95 23 cadina-1,4-diene trace 96

Purification of Yellow Paint

After the clove component was separated, a small amount of hexane and moisture remained in the remaining paint component, which was removed by evaporating hexane and moisture until the color of the paint was clear under conditions of 50 ° C. and 20-50 mm Hg in a vacuum rotary evaporator. The evaporated water and hexane are collected in a solvent recovery flask, and when evaporation is completed, no more hexane and water are collected. Obtained 863 g (43%) of a paint coating for paint.

Treatment for long term storage of refined yellow lacquer paint

10% by weight of acetone: butanol mixed solvent in a 5: 5 weight ratio was mixed with yellow lacquer, and transferred to a brown bottle for 10 minutes to inject dried nitrogen to completely remove oxygen, and then stored in a freezer at -10 ℃ It was.

The method of refining the yellow lacquer from Hwangchil-tree is not clear in literature or in the way of oral tradition. The reason for this was that Hwangchil's veins were cut off for over 200 years, and that all of its production was sent to China and Mongolia, rather than domestically, and most of the domestic feed was lost or removed.

The present invention is a new method for purifying the yellow lacquer, and the solid content is separated using ethanol in the newly designed yellow lacquer tablet device, and the recovered ethanol has the characteristics that it can be used as a raw material of liquor or food beverage. The refining method using the yellow lacquer refining apparatus designed for this purpose is simple and fast, and maintains a low temperature in the refining process and avoids contact with air. Particularly, clove components of terpenes or sesquiterpenes included in yellow lacquer are volatilized into the air easily when the yellow lacquer is used for paint as it is. Hwangchil of the paint component remaining after the separation of the clove component has the characteristics that can be painted after evaporating the water as it is.

Another feature of the present invention is that the solvent used for purification is alcohol ethanol, pentane, or hexane to reduce human or environmental pollution, minimize the amount of use, as well as long-term storage of the refined yellow lacquer coating by polymerization In order to prevent the curing of the low temperature, kept in a nitrogen atmosphere to be stored.

Claims (6)

delete a) extracting the yellow lacquer paint component and the clove component mixture fraction from the hwangchil wood resin solution using ethanol to separate the solid fraction from the solid content fraction; b) extracting the clove component from the hwangchil paint component and clove component mixture fraction using a pentane or hexane solvent to separate the hwangchil paint component fraction and clove component fraction; And c) a method of separating and purifying the hwangchi paint from the hwangchil wood resin solution comprising the step of evaporating the hwangchi paint component fractions separated in the step under reduced pressure to remove water and solvent. a) extracting the yellow lacquer paint component and the clove component mixture fraction from the hwangchil wood resin solution using ethanol to separate the solid fraction from the solid content fraction; b) extracting the clove component from the hwangchil paint component and clove component mixture fraction using a pentane or hexane solvent to separate the hwangchil paint component fraction and clove component fraction; And c) distilling the clove component fraction separated in the step under reduced pressure to remove the solvent, the method for separating and purifying the clove component from the hwangchil wood resin solution. delete delete delete

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