CN100391931C - Direct synthesis process of propyl gallate with Tala powder - Google Patents
Direct synthesis process of propyl gallate with Tala powder Download PDFInfo
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- CN100391931C CN100391931C CNB2006100860709A CN200610086070A CN100391931C CN 100391931 C CN100391931 C CN 100391931C CN B2006100860709 A CNB2006100860709 A CN B2006100860709A CN 200610086070 A CN200610086070 A CN 200610086070A CN 100391931 C CN100391931 C CN 100391931C
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Abstract
The present invention relates to direct synthesis process of propyl gallate with Tala powder. The direct synthesis process includes soaking Tala powder in n-propanol, filtering to depurate, decolorizing with active carbon and diatomite, filtering, adding acidic catalyst, ester interchange reaction at 80-110 deg.c for 5-12 hr, filtering at room temperature to eliminate impurity, concentrating the liquid phase, dissolving the concentrate in 5-10 times of water, and re-crystallization to obtain the product. The process is superior to traditional technological process, simple and environment friendly.
Description
Technical field
The present invention relates to a kind of method for preparing Tenox PG, particularly draw the method for the directly synthetic system Tenox PG of powder by tower.
Background technology
Tenox PG is a kind of derivative of gallic acid, mainly as food antioxidant.It has safe, good in oxidation resistance, being widely used in food oils, feed, fried food product, dried fish product, biscuit, can and cured meat product, is one of good oil antioxidant of United Nations's grain tissue (FAO) and the World Health Organization (WTO) approval use.In addition, it can also promote vasodilation, has thrombus dissolving and anticoagulant effect, can be used as the medicine for the treatment of cardiovascular and cerebrovascular.
At present, industrial preparation Tenox PG is many to be raw material with gallic acid and n-propyl alcohol, adopts in the presence of an acidic catalyst, and the esterification of dewatering is synthesized into.The price of the raw materials used gallic acid of this method is high, and in the preparation of gallic acid, produces a large amount of colorful wastewaters, and environmental pollution is serious, and purification of waste water processing cost height.
Summary of the invention
The purpose that the present invention relates to provides a kind of method of drawing the direct synthesizing gallic acid propyl ester of powder by tower, and operational path is simple, environmental friendliness.
Tower draws beanpod through dry, pulverize after the gained of powder by trees Caesalpinia spinosaKuntze (Caesalpinia aspinosa kuntze).Caesalpinia spinosaKuntze country of origin South America is now at ground establishing in large scale such as Yunnan Province of China, Sichuan.Tower draws that tannin content is 55%-61% in the powder, and its tannin structure is the gallic acid ester of quinic acid.
The present invention with tower draw the method for the direct synthesizing gallic acid propyl ester of powder be tower to draw powder and n-propyl alcohol be raw material, under acid catalysis, realize by following chemical reaction:
The inventive method the following step:
Draw powder under the temperature of 100 ℃ of room temperature～∠, to soak extraction 0.5-4 hour in tower with the n-propyl alcohol of 1～8 times of weight; Filter, filtrate adds tower and draws the gac of grain weight amount 1-5% and the diatomite of 5-10%, 60-70 ℃ of following adsorption bleaching, remove by filter sorbent material, add an acidic catalyst that the raw material tower draws grain weight amount 1-10% in the filtrate, 80-110 ℃ was reacted 5-12 hour down, cools to room temperature, filtering and impurity removing matter, 100 ℃ of following reduction vaporizations of filtrate ∠ are concentrated into dried; Add 5-10 times of water in the enriched material, heating cools to 5-20 ℃ after making its dissolving, crystallization filter the Tenox PG crude product.
More than said acid catalyst can be: organic acid, mineral acid or salt wherein are preferably methylsulfonic acid, sulfuric acid, hydrochloric acid or anhydrous hydrogen chloride.
Refining: crude product is with 5-10 times of water, and 60-90 ℃ of dissolving adds gac in the solution, decolouring, filters, and gets filtrate, is cooled to 5-20 ℃, separates out crystallization;
Dry: crystallization adopts vacuum-drying to get anhydrous Tenox PG product.
The present invention draws the direct and n-propyl alcohol prepared in reaction Tenox PG of powder extracting solution with tower, having got rid of tower draws powder to change into the processing step of gallic acid, thereby greatly reduce production cost, having removed the sewage discharge that causes in the preparation gallic acid process from, is low, the eco-friendly operational path again of a kind of cost.
The present invention also has following advantage:
(1) adopt the n-propyl alcohol extraction column to draw powder, the yield height, impurity is few, filtration is easy.
(2) adopt acid catalyzed reaction, consumption is few, and product color is shallow.
(3) production technique is simple, helps suitability for industrialized production.
Embodiment
Describe in detail bright below in conjunction with embodiment furtherly to the present invention.
Embodiment 1:
The raw material tower draws 800 milliliters of powder 100g, n-propyl alcohols, stirs down in 60 ℃, soaks and extracts 3 hours, becomes slurries; Add 5g gac, 6g diatomite in slurries, 80 ℃ decoloured 15 minutes down, propose filter with final vacuum.Filtrate adds 5 milliliters of catalyzer methylsulphonic acids, and back flow reaction was cooled to 20 ℃ after 10 hours, filters, and filtrate evaporated under reduced pressure desolventizes to doing, and collects the n-propyl alcohol that steams, for using next time; Solid-phase material is poured in 150 milliliters of cold water with 60 ℃ of dissolvings of 50mL hot water, stirs, be cooled to 5-20 ℃, crystallization filter gallic acid propyl alcohol crude product, crude product 150 ml waters, heat 90 ℃ of dissolvings, use the 3g gac, decoloured 15 minutes, vacuum filtration, filtrate are cooled to 5-20 ℃, and crystallization is separated out, filter, get filter cake, vacuum-drying (80 ℃), get Tenox PG 19g, content 99%.
Embodiment 2:
The raw material tower draws 800 milliliters of powder 100g, n-propyl alcohols, stirs down in 60 ℃, soaks and extracts 3 hours.To add 5g gac, 8g diatomite in the above-mentioned slurries, 80 ℃ decoloured 15 minutes, and vacuum is proposed filter.Filtrate adds 5 milliliters of catalyst sulfuric acids, and back flow reaction was cooled to 20 ℃ after 10 hours, filters, and filtrate decompression is concentrated into dried.Reclaim n-propyl alcohol, for using next time; Solid is poured in 150 milliliters of cold water with 60 ℃ of dissolvings of 50mL hot water, stirs, be cooled to 10 ℃, crystallization is separated out, filter crude product, use the 3g gac, 150 ml waters heat 90 ℃ of dissolvings, decoloured 15 minutes, vacuum filtration, filtrate is cooled to 5 ℃ of crystallizations, filter, take out filter cake with vacuum-drying (80 ℃), get Tenox PG 20g, content 98.5%.
Example 3:
Tower draws powder 100g, and 800 milliliters of n-propyl alcohols under 60 ℃, stir, and extract 3 hours.In above-mentioned slurries, add the 5g gac, 5g diatomite, 80 ℃ decoloured vacuum filtration 15 minutes.Contain the n-propyl alcohol solution 20mL of 10% hydrogenchloride filtrate adding, and back flow reaction was cooled to 20 ℃ after 10 hours, filters, and filtrate decompression is concentrated into dried.Reclaim n-propyl alcohol, for using next time.Residual solid is poured in 150 milliliters of cold water with 60 ℃ of dissolvings of 50mL hot water, stirs, be cooled to 10 ℃, separate out crystallization, filter crude product, use 150mL water, heat 90 ℃ of dissolvings, add the 3g gac, decoloured 15 minutes, vacuum filtration, filtrate is cooled to 10 ℃, crystallization is filtered, and takes out filter cake, vacuum-drying (80 ℃) gets Tenox PG 22g, content 99.2%.
Claims (6)
1. tower draws the method for the direct synthesizing gallic acid propyl ester of powder, it is characterized in that tower draws powder to soak with n-propyl alcohol and extracted 0.5～4 hour, filter, get filtrate, add tower and draw the gac of grain weight amount 1-5% and the diatomite of 5-10%, adsorption bleaching, filter, get filtrate, draw the 1-10% of grain weight amount to add an acidic catalyst by tower in the filtrate, be warming up to 80-110 ℃, reacted 5-12 hour; Cool to room temperature, filtering and impurity removing matter, filtrate＜100 a ℃ reduction vaporization is concentrated into dried; Enriched material adds 5-10 times of water, and heating cools to 5-20 ℃ after making its dissolving, separates out crystallization, filter dewater the Tenox PG crude product.
2. tower according to claim 1 draws the method for the direct synthesizing gallic acid propyl ester of powder, it is characterized in that adding in the said crude product gac of 3-10% weight, with 5-10 times of water, 60-90 ℃ makes dissolving crude product, decolouring, filter, get filtrate, be cooled to 5-20 ℃, crystallization is separated out, and crystallization gets anhydrous Tenox PG through vacuum-drying.
3. tower according to claim 1 draws the method for the direct synthesizing gallic acid propyl ester of powder, and the immersion amount that it is characterized in that n-propyl alcohol is 1～8 times that tower draws the grain weight amount, and soaking temperature is room temperature～＜100 ℃.
4. tower according to claim 1 draws the method for the direct synthesizing gallic acid propyl ester of powder, it is characterized in that said gac and diatomite are at 60-70 ℃ of following adsorption bleaching.
5. the method for drawing the direct synthesizing gallic acid propyl ester of powder according to claim 1 or 2 or 3 or 4 described towers is characterized in that said an acidic catalyst is organic acid or mineral acid.
6. tower according to claim 5 draws the method for the direct synthesizing gallic acid propyl ester of powder, it is characterized in that said an acidic catalyst is methylsulfonic acid, sulfuric acid, hydrochloric acid or anhydrous hydrogen chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100860709A CN100391931C (en) | 2006-07-24 | 2006-07-24 | Direct synthesis process of propyl gallate with Tala powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100860709A CN100391931C (en) | 2006-07-24 | 2006-07-24 | Direct synthesis process of propyl gallate with Tala powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1887850A CN1887850A (en) | 2007-01-03 |
| CN100391931C true CN100391931C (en) | 2008-06-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100860709A Expired - Fee Related CN100391931C (en) | 2006-07-24 | 2006-07-24 | Direct synthesis process of propyl gallate with Tala powder |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781216B (en) * | 2009-12-10 | 2013-07-17 | 张家界奥威科技有限公司 | Novel process for preparing propylgallate directly from gallnuts |
| CN102351705B (en) * | 2011-08-25 | 2012-07-04 | 江西新先锋医药有限公司 | Propylgallate compound and pharmaceutical composition thereof |
| CN103709039B (en) * | 2013-12-25 | 2015-04-22 | 南京龙源天然多酚合成厂 | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4613683A (en) * | 1984-02-02 | 1986-09-23 | Basf Aktiengesellschaft | Preparation of alkyl gallates |
| CN1057255A (en) * | 1991-04-10 | 1991-12-25 | 湖北省竹山县林产化工厂 | Utilize tower to draw powder to produce gallic acid |
-
2006
- 2006-07-24 CN CNB2006100860709A patent/CN100391931C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4613683A (en) * | 1984-02-02 | 1986-09-23 | Basf Aktiengesellschaft | Preparation of alkyl gallates |
| CN1057255A (en) * | 1991-04-10 | 1991-12-25 | 湖北省竹山县林产化工厂 | Utilize tower to draw powder to produce gallic acid |
Non-Patent Citations (4)
| Title |
|---|
| 塔拉粉直接碱水解制备没食子酸的工艺研究及应用. 张笳鸿等.林产化学与工业，第15卷第1期. 1995 |
| 塔拉粉直接碱水解制备没食子酸的工艺研究及应用. 张笳鸿等.林产化学与工业，第15卷第1期. 1995 * |
| 没食子酸丙酯及其衍生物的合成研究进展. 张霞等.河北化工，第5期. 2004 |
| 没食子酸丙酯及其衍生物的合成研究进展. 张霞等.河北化工，第5期. 2004 * |
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| CN1887850A (en) | 2007-01-03 |
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Effective date of registration: 20100709 Address after: 614000 Linjiang Road, hi tech Zone, Sichuan, Leshan Co-patentee after: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry Patentee after: Leshan Sanjian Biochemical Sci-Tech Co., Ltd. Co-patentee after: Nanjing Longyuan Natural Polyphenols Synthesis Factory Address before: 614000 Linjiang Road, hi tech Zone, Sichuan, Leshan Patentee before: Leshan Sanjian Biochemical Sci-Tech Co., Ltd. |
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