CN106905853B - Preparation method of rosin glycol ester - Google Patents
Preparation method of rosin glycol ester Download PDFInfo
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- CN106905853B CN106905853B CN201710103336.4A CN201710103336A CN106905853B CN 106905853 B CN106905853 B CN 106905853B CN 201710103336 A CN201710103336 A CN 201710103336A CN 106905853 B CN106905853 B CN 106905853B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Abstract
A preparation method of rosin glycol ester is characterized in that carboxylate is used as a catalyst, and the rosin glycol ester is prepared by reacting rosin and the catalyst at a mass ratio of 100: 1-1000: 1, a mass ratio of rosin to glycol of 4: 1-9: 1, an absolute pressure of a reaction system of 50-90 kPa and a reaction temperature of 100-180 ℃ for 1-10 hours. Compared with the prior art: 1. the catalyst has high catalytic activity; 2. the reaction requires low temperature and short reaction time; 3. no other auxiliary agent is needed in the reaction process.
Description
Technical Field
The invention relates to a preparation method of rosin glycol ester, in particular to a novel method for preparing rosin glycol ester by catalyzing esterification reaction of rosin and glycol with carboxylate.
Background
Rosin glycol ester is a semi-plastic resin, can be used as a binder and a plasticizer, and has wide application in the aspects of enzyme immobilization, paper neutral sizing and the like. The prior method for producing the rosin glycol ester is mainly formed by catalyzing esterification reaction of rosin and glycol at 250-260 ℃ by using zinc powder or boric acid as a catalyst, and has the problems of high reaction temperature, long reaction time, dark product color and the like. Aiming at the problems, the carboxylate is adopted as the catalyst to catalyze the esterification reaction of rosin and glycol to prepare the rosin glycol ester, and the method has the advantages of low reaction temperature, short reaction time, light product color, no need of adding other additives in the reaction process and the like.
Disclosure of Invention
The invention aims to replace the traditional production method for preparing rosin glycol ester by catalyzing rosin and glycol with a catalyst, and develop a novel method for preparing rosin glycol ester by catalyzing rosin and glycol with a carboxylic acid catalyst under the conditions of low temperature and short time reaction.
Based on the above, the invention relates to a preparation method of rosin glycol ester, which is characterized in that carboxylate is used as a catalyst, and the rosin glycol ester is prepared by reacting for 1-10 hours at a mass ratio of rosin to catalyst of 100: 1-1000: 1, a mass ratio of rosin to glycol of 4: 1-9: 1, an absolute pressure of a reaction system of 50-90 kPa and a reaction temperature of 100-180 ℃; the carboxylate catalyst is one of zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc citrate, zinc naphthenate, zinc oxalate, zinc lactate, zinc gluconate, iron acetate, iron stearate, iron citrate, iron naphthenate, iron oxalate, iron lactate or iron gluconate.
The method is characterized in that the reaction conditions are that the mass ratio of rosin to carboxylate catalyst is 120: 1-500: 1, the mass ratio of rosin to glycol is 5: 1-8: 1, the reaction temperature is 120-170 ℃, the absolute pressure of the reaction system is 60-80 kPa, and the reaction time is 4-8 h.
The invention solves the technical problem by the following technical scheme:
the specific technical scheme is illustrated by taking an iron oxalate catalyst as an example.
Putting 100.0g of rosin, 0.5g of catalyst iron acetate and 20.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in a reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 50kPa, heating to 160 ℃, and stirring for reaction for 6 hours to obtain a product, namely rosin glycol ester, wherein the yield is 95.4%, the acid value is 8.3mgKOH/g, and the color is light yellow, and the yield of the rosin glycol ester is equal to the ratio of the mass of the obtained product to the total mass of the rosin and the glycol.
Compared with the traditional reaction, the invention is characterized in that:
1. the catalyst has high catalytic activity.
2. The reaction requires low temperature and short reaction time.
3. No other auxiliary agent is needed in the reaction process.
Detailed description of the invention
The process of the present invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1: 100.0g of rosin, 0.5g of catalyst iron acetate and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 160 ℃, and the reaction is stirred for 6 hours, so that the product rosin glycol ester is obtained, the yield is 95.4%, the acid value is 8.3mgKOH/g, and the color and luster are light yellow.
Comparative example 1: 100.0g of rosin, 0.5g of catalyst zinc powder and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 160 ℃, and the product, namely rosin glycol ester, is obtained after stirring reaction for 6 hours, wherein the yield is 96.6%, the acid value is 28.3mgKOH/g, and the color and luster are yellow.
Comparative example 2: 100.0g of rosin, 0.5g of boric acid serving as a catalyst and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 160 ℃, and the reaction is stirred for 6 hours to obtain a product, namely rosin glycol ester, wherein the yield is 96.9%, the acid value is 19.8mgKOH/g, and the color is yellow.
Comparative example 3: 100.0g of rosin and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 160 ℃, and after stirring reaction is carried out for 6 hours, the product rosin glycol ester is obtained, the yield is 98.8%, the acid value is 56.5mgKOH/g, and the color is reddish yellow.
Comparative example 4: 100.0g of rosin, 0.25g of catalyst zinc powder and boric acid respectively and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 160 ℃, and after stirring reaction is carried out for 6 hours, the product rosin glycol ester is obtained, the yield is 96.4%, the acid value is 15.3mgKOH/g, and the color is yellow.
Comparative example 5: putting 100.0g of rosin, 2.0g of catalyst zinc powder and 20.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 50kPa, heating to 260 ℃, and stirring for reaction for 10 hours to obtain a product, namely rosin glycol ester, wherein the yield is 95.8%, the acid value is 9.7mgKOH/g, and the color is yellowish brown.
Comparative example 6: 100.0g of rosin, 2.0g of boric acid serving as a catalyst and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 260 ℃, and the reaction system is stirred for 10 hours to obtain a product, namely rosin glycol ester, wherein the yield is 94.8%, the acid value is 11.6mgKOH/g, and the color is yellowish red.
Example 2: 100.0g of rosin, 1.0g of catalyst zinc acetate and 25.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 180 ℃, and the product, namely rosin glycol ester, is obtained after stirring reaction for 1h, wherein the yield is 96.6%, the acid value is 16.6mgKOH/g, and the color and luster are light yellow.
Example 3: 100.0g of rosin, 0.1g of zinc propionate catalyst and 11.1g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 90kPa, the reaction system is heated to 100 ℃, and the reaction system is stirred for 10 hours to obtain the product, namely rosin glycol ester, wherein the yield is 96.0%, the acid value is 12.4mgKOH/g, and the color and luster are light yellow.
Example 4: 100.0g of rosin, 0.8g of catalyst zinc butyrate and 18.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 60kPa, the reaction system is heated to 180 ℃, and after stirring reaction is carried out for 6 hours, the product rosin glycol ester is obtained, wherein the yield is 95.4%, the acid value is 8.3mgKOH/g, and the color and luster are light yellow.
Example 5: putting 100.0g of rosin, 0.4g of catalyst zinc stearate and 15.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in a reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 80kPa, heating to 150 ℃, and stirring for reaction for 6 hours to obtain a product, namely rosin glycol ester, wherein the yield is 93.1%, the acid value is 9.1mgKOH/g, and the color is light yellow.
Example 6: putting 100.0g of rosin, 0.9g of catalyst zinc citrate and 18.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in a reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 60kPa, heating to 170 ℃, and stirring for reaction for 5 hours to obtain a product, namely rosin glycol ester, wherein the yield is 92.8%, the acid value is 8.6mgKOH/g, and the color is light yellow.
Example 7: 100.0g of rosin, 0.4g of catalyst zinc naphthenate and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 180 ℃, and after stirring reaction is carried out for 4 hours, the product rosin glycol ester is obtained, the yield is 93.2%, the acid value is 8.8mgKOH/g, and the color and luster are light yellow.
Example 8: 100.0g of rosin, 0.5g of catalyst zinc oxalate and 15.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 80kPa, the reaction system is heated to 140 ℃, and the reaction is stirred for 9 hours, so that the product rosin glycol ester is obtained, the yield is 93.9%, the acid value is 9.8mgKOH/g, and the color and luster are light yellow.
Example 9: 100.0g of rosin, 0.9g of catalyst zinc lactate and 22.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 60kPa, the reaction system is heated to 165 ℃, and the product, namely rosin glycol ester, is obtained after stirring reaction for 5 hours, wherein the yield is 95.4%, the acid value is 9.3mgKOH/g, and the color and luster are light yellow.
Example 10: 100.0g of rosin, 0.5g of zinc gluconate serving as a catalyst and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, the air in the reaction system is replaced by nitrogen with 200kPa for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 70kPa, the reaction system is heated to 150 ℃, and the reaction is stirred for 6 hours to obtain a product, namely rosin glycol ester, wherein the yield is 93.7%, the acid value is 9.8mgKOH/g, and the color and luster are light yellow.
Example 11: 100.0g of rosin, 1.0g of catalyst ferric stearate and 25.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 60kPa, the reaction system is heated to 120 ℃, and the reaction is stirred for 4 hours, so that the product rosin glycol ester is obtained, the yield is 92.6%, the acid value is 10.3mgKOH/g, and the color and luster are light yellow.
Example 12: 100.0g of rosin, 0.8g of ferric citrate as a catalyst and 20.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by nitrogen with 200kPa for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 60kPa, the reaction system is heated to 170 ℃, and the reaction is stirred for 8 hours to obtain the product, namely rosin glycol ester, wherein the yield is 92.8%, the acid value is 8.9mgKOH/g, and the color is light yellow.
Example 13: 100.0g of rosin, 0.5g of catalyst iron naphthenate and 15.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 50kPa, the reaction system is heated to 140 ℃, and the reaction is stirred for 7 hours, so that the product rosin glycol ester is obtained, the yield is 93.7%, the acid value is 10.3mgKOH/g, and the color and luster are light yellow.
Example 14: 100.0g of rosin, 0.5g of catalyst iron oxalate and 15.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 90kPa, the reaction system is heated to 120 ℃, and the reaction is stirred for 9 hours to obtain the product rosin glycol ester, wherein the yield is 93.2%, the acid value is 9.3mgKOH/g, and the color and luster are light yellow.
Example 15: 100.0g of rosin, 1.0g of catalyst iron lactate and 14.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, air in the reaction system is replaced by 200kPa nitrogen for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 80kPa, the reaction system is heated to 175 ℃, and after stirring reaction is carried out for 4 hours, the product rosin glycol ester is obtained, wherein the yield is 93.1%, the acid value is 8.9mgKOH/g, and the color and luster are light yellow.
Example 16: putting 100.0g of rosin, 0.65g of catalyst ferric gluconate and 24.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 80kPa, heating to 160 ℃, and stirring for reaction for 7 hours to obtain a product, namely rosin glycol ester, wherein the yield is 93.9%, the acid value is 8.6mgKOH/g, and the color is light yellow.
Claims (1)
1. A preparation method of rosin glycol ester is characterized in that 100.0g of rosin, 0.4g of catalyst zinc stearate and 15.0g of glycol are put into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, after air in the reaction system is replaced by nitrogen with 200kPa for 5 times, the vacuum system is started, the absolute pressure of the reaction system is controlled to be 80kPa, the reaction system is heated to 150 ℃, and after stirring reaction is carried out for 6 hours, the product rosin glycol ester is obtained;
or putting 100.0g of rosin, 0.5g of zinc oxalate as a catalyst and 15.0g of glycol into a reaction kettle with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 80kPa, heating to 140 ℃, and stirring for reaction for 9 hours to obtain a product, namely rosin glycol ester;
or putting 100.0g of rosin, 0.5g of zinc gluconate serving as a catalyst and 20.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 70kPa, heating to 150 ℃, and stirring for reaction for 6 hours to obtain a product, namely rosin glycol ester;
or putting 100.0g of rosin, 1.0g of catalyst ferric stearate and 25.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 60kPa, heating to 120 ℃, and stirring for reaction for 4 hours to obtain a product, namely rosin glycol ester;
or putting 100.0g of rosin, 0.5g of catalyst iron naphthenate and 15.0g of glycol into a reaction kettle provided with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 50kPa, heating to 140 ℃, and stirring for reaction for 7 hours to obtain a product, namely rosin glycol ester;
or putting 100.0g of rosin, 0.5g of catalyst iron oxalate and 15.0g of glycol into a reaction kettle with a stirrer, a thermometer, an oil-water separator and a vacuum system, replacing air in the reaction system with 200kPa nitrogen for 5 times, starting the vacuum system, controlling the absolute pressure of the reaction system to be 90kPa, heating to 120 ℃, and stirring for reaction for 9 hours to obtain the product, namely rosin glycol ester.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013344A (en) * | 2012-12-18 | 2013-04-03 | 富川瑶族自治县威龙林化有限公司 | Preparation method for rosin pentaerythritol ester |
| CN104017496A (en) * | 2013-02-28 | 2014-09-03 | 湖州益邦化学制品有限公司 | Ultraviolet light polymerized low polymer synthesized by utilizing rosin derivatives and preparation method of polymer |
| CN104399533A (en) * | 2014-11-10 | 2015-03-11 | 广西民族大学 | Homogeneous composite catalyst and application thereof in preparation of rosin ester |
| CN105916950A (en) * | 2013-09-27 | 2016-08-31 | 阿利桑那化学公司 | Rosin esters and compositions thereof |
| CN106349941A (en) * | 2016-08-29 | 2017-01-25 | 广西梧州通轩林产化学有限公司 | Method for preparing ester gum |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4650607A (en) * | 1985-05-09 | 1987-03-17 | Westvaco Corporation | Method for rosin esterification |
| JP2539811B2 (en) * | 1987-01-29 | 1996-10-02 | 荒川化学工業株式会社 | Method for producing rosin ester |
-
2017
- 2017-02-24 CN CN201710103336.4A patent/CN106905853B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013344A (en) * | 2012-12-18 | 2013-04-03 | 富川瑶族自治县威龙林化有限公司 | Preparation method for rosin pentaerythritol ester |
| CN104017496A (en) * | 2013-02-28 | 2014-09-03 | 湖州益邦化学制品有限公司 | Ultraviolet light polymerized low polymer synthesized by utilizing rosin derivatives and preparation method of polymer |
| CN105916950A (en) * | 2013-09-27 | 2016-08-31 | 阿利桑那化学公司 | Rosin esters and compositions thereof |
| CN104399533A (en) * | 2014-11-10 | 2015-03-11 | 广西民族大学 | Homogeneous composite catalyst and application thereof in preparation of rosin ester |
| CN106349941A (en) * | 2016-08-29 | 2017-01-25 | 广西梧州通轩林产化学有限公司 | Method for preparing ester gum |
Non-Patent Citations (1)
| Title |
|---|
| Zn2+类催化剂催化松香酯化反应;曾广建等;《广州化工》;19901231;第18卷(第4期);第1-5页 * |
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