CN107325890B - Method for synthesizing epoxy plasticizer based on perrhenate ionic liquid - Google Patents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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Abstract
The invention relates to a method for synthesizing an epoxy plasticizer based on perrhenate ionic liquid. The technical scheme is as follows: with the anion being ReO4 ‑The perrhenate ionic liquid is used as a catalyst, and H is directly used2O2As an oxidant, adopting a solvent-free method to catalyze soybean oil or fatty acid methyl ester to carry out epoxidation reaction so as to synthesize the epoxy plasticizer. The reaction temperature is 30-60 ℃, and the reaction time is 2-6 h. And after the reaction is finished, centrifugally separating out the catalyst, washing the oil phase to be neutral by using deionized water, and distilling to obtain the epoxy product. The catalyst used in the invention is insoluble in raw oil, is easy to recycle and does not pollute the environment, and the obtained epoxy plasticizer has higher quality.
Description
Technical Field
The invention belongs to the field of chemical synthesis methods, and particularly relates to a synthesis method of an epoxy plasticizer based on perrhenate ionic liquid.
Background
The epoxy plasticizer is a compound with epoxy groups in the molecular structure, is an excellent plasticizing and stabilizing agent, and has the outstanding advantages of no toxicity, good heat resistance and good light resistance compared with phthalate esters on the market. In the industrial polyvinyl chloride resin processing industry, the polyvinyl chloride resin plasticizer not only has a plasticizing effect on PVC, but also can stabilize active chlorine atoms on a polyvinyl chloride chain, and epoxy groups in the structure can absorb hydrogen chloride generated by light and heat degradation, so that the continuous decomposition effect of PVC is prevented, the stabilizer function is realized, and the service life of PVC products can be prolonged. The epoxy plasticizer has excellent water resistance and oil resistance, and is also a good auxiliary stabilizer, so the epoxy plasticizer is widely applied in the modern plastic industry. The epoxy plasticizer comprises epoxy fatty glyceride and epoxy fatty methyl ester, the epoxy fatty glyceride is developed and applied earlier at home and abroad, and natural oil esters such as soybean oil, linseed oil, cottonseed oil, corn oil, rapeseed oil, palm oil, peanut oil and the like are used for epoxidation, wherein the yield of the epoxy soybean oil is the largest, and is up to 200000t in 1999. In recent years, as biodiesel has become a research hotspot, epoxidized fatty acid esters have also attracted more and more attention as downstream products of biodiesel.
The research on the synthesis of epoxidized soybean oil by a chemical method is early at home and abroad, and more research results are reported, wherein the optimization of process conditions and the selection of a catalyst are the key points of the research. The method for synthesizing epoxidized soybean oil by chemical catalysis is divided into a traditional inorganic acid catalysis method, an ion exchange resin catalysis method, a metal catalysis method and the like according to different types of catalysts. The traditional inorganic acid and strong acid cation exchange resin is a catalyst commonly used for the oil epoxidation of fatty acid ester and soybean oil, and a large amount of acid waste water is generated in the using process of the catalyst, so that the environmental pollution is serious.
Disclosure of Invention
The invention aims to provide a method for synthesizing an epoxy plasticizer based on perrhenate ionic liquid, which is simple, has less catalyst dosage, is green and environment-friendly, and has a high plasticizer epoxy value.
The technical scheme adopted by the invention is as follows: a method for synthesizing an epoxy plasticizer based on perrhenate ionic liquid comprises the following steps: and mixing a proper amount of perrhenate ionic liquid catalyst with the raw material oil, dropwise adding an oxidant into a mixed system of the perrhenate ionic liquid and the raw material oil, and reacting for 2-6 hours at 30-60 ℃.
The method for synthesizing the epoxy plasticizer based on the perrhenate ionic liquid comprises the following steps: tetraalkylammonium perrhenate ionic liquids having the structure shown as (I):
wherein R is1、R2、R3And R4Is methyl, ethyl, n-butyl or n-hexadecyl.
The method for synthesizing the epoxy plasticizer based on the perrhenate ionic liquid comprises the following steps: imidazole perrhenate ionic liquid with the structure shown as (II):
wherein n is 1 to 8.
In the method for synthesizing the epoxy plasticizer based on the perrhenate ionic liquid, the oxidant is H2O2。
According to the method for synthesizing the epoxy plasticizer based on the perrhenate ionic liquid, the dosage of the perrhenate ionic liquid catalyst is 1-20% of the mass of the raw material oil, and the dosage of the oxidant is 10-100% of the mass of the raw material oil.
According to the synthesis method of the perrhenate ionic liquid-based epoxy plasticizer, the raw material oil is unsaturated vegetable oil or fatty acid methyl ester. Preferably, the unsaturated vegetable oil is soybean oil.
The invention has the beneficial effects that:
1. the invention will be based on ReO4 -The anionic perrhenate ionic liquid is firstly used for synthesizing the epoxy plasticizer, and the catalyst has high activity and small using amount.
2. According to the invention, the perrhenate ionic liquid is used as a catalyst to carry out grease epoxidation reaction containing unsaturated double bonds, the catalyst is insoluble in the reaction raw oil, the catalyst can be separated out by centrifugation after the reaction is finished, and the separation method is simple.
3. The invention adopts a solvent-free method to directly use H2O2The epoxy resin is an epoxy agent, avoids the use of organic solvents and organic carboxylic acids, is green and environment-friendly, and has low reaction cost.
4. According to the invention, after the reaction is finished, the catalyst is centrifugally separated, the oil phase is washed to be neutral by deionized water, and the epoxy product can be obtained by reduced pressure distillation, so that the post-treatment process is simple.
5. The epoxide obtained by the method of the invention has good quality, the epoxide number is more than 5.5 percent, and the acid value is less than 1mg KOH/g. The invention not only has good epoxidation catalysis effect, but also has easy recycling of the catalyst and no environmental pollution.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not intended to limit the scope of the present invention.
Example 11-butyl-3-methylimidazole perrhenate Ionic liquid ([ Bmim)]ReO4) Plasticizer for catalytically synthesizing epoxidized soybean oil
[Bmim]ReO4The structural formula is shown as the following formula:
0.5g of [ Bmim ] is weighed]ReO4The catalyst and 20g of refined soybean oil were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid with water to be neutral, and drying to obtain a yellow oily product which is the epoxy soybean oil plasticizer.
The epoxy value of the epoxidized soybean oil plasticizer is determined to be 6.35 percent according to GB/T1677-.
The separated catalyst is washed by ether and can be reused after being dried. The epoxy values of the epoxidized soybean oil plasticizer used five times were 6.29%, 6.22%, 6.18%, 6.12% and 6.08%, respectively.
Example 21-butyl-3-methylimidazole perrhenate Ionic liquid ([ Bmim)]ReO4) Plasticizer for catalytic synthesis of epoxy fatty acid methyl ester
[Bmim]ReO4The structural formula is shown as the following formula:
0.5g of [ Bmim ] is weighed]ReO4Catalyst and 20g of fatty acid methyl esterIn a 50mL three-necked flask equipped with a reflux condenser and a thermometer, 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid to be neutral by using water, and drying to obtain a yellow oily product which is the epoxy fatty acid methyl ester plasticizer.
The epoxy value of the epoxy fatty acid methyl ester plasticizer is 6.46 percent according to GB/T1677-2008, and the acid value of the epoxy fatty acid methyl ester plasticizer is 0.41mg KOH/g according to GB/T1668-2008.
The separated catalyst is washed by ether and can be reused after being dried. Epoxy values of the epoxidized fatty acid methyl ester plasticizer used five times were 6.37%, 6.29%, 6.20%, 6.17% and 6.10%, respectively.
Example 31-hexyl-3-methylimidazole perrhenate Ionic liquid ([ Hmim)]ReO4) Plasticizer for catalytically synthesizing epoxidized soybean oil
[Hmim]ReO4The structural formula is shown as the following formula:
0.5g of [ Hmim ] was weighed]ReO4The catalyst and 20g of refined soybean oil were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid with water to be neutral, and drying to obtain a yellow oily product which is the epoxy soybean oil plasticizer.
The epoxy value of the epoxidized soybean oil plasticizer is determined to be 6.25 percent according to GB/T1677-.
The separated catalyst is washed by ether and can be reused after being dried. The epoxy values of the epoxidized soybean oil plasticizer used five times were 6.21%, 6.15%, 6.09%, 6.01% and 5.94%, respectively.
Example 41-hexyl-3-methylimidazole perrhenate Ionic liquid ([ Hmim)]ReO4) Plasticizer for catalytic synthesis of epoxy fatty acid methyl ester
[Hmim]ReO4The structural formula is shown as the following formula:
0.5g of [ Hmim ] was weighed]ReO4The catalyst and 20g of fatty acid methyl ester were slowly added dropwise to a 50mL three-necked flask equipped with a reflux condenser and a thermometer while stirring 5g H2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid to be neutral by using water, and drying to obtain a yellow oily product which is the epoxy fatty acid methyl ester plasticizer.
The epoxy value of the epoxy fatty acid methyl ester plasticizer is 6.34 percent according to GB/T1677-2008, and the acid value of the epoxy fatty acid methyl ester plasticizer is 0.40mg KOH/g according to GB/T1668-2008.
The separated catalyst is washed by ether and can be reused after being dried. Epoxy values of the epoxidized fatty acid methyl ester plasticizer used five times were 6.30%, 6.22%, 6.16%, 6.07% and 6.00%, respectively.
Example 5 ammonium tetramethylperrhenate Ionic liquid ([ N (CH)3)4]ReO4) Plasticizer for catalytically synthesizing epoxidized soybean oil
[N(CH3)4]ReO4The structural formula is shown as the following formula:
0.5g of [ N (CH) is weighed3)4]ReO4The catalyst and 20g of refined soybean oil were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly raising the temperature to 60 ℃, and stirring at the constant temperature of 60 DEG CStirring for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid with water to be neutral, and drying to obtain a yellow oily product which is the epoxy soybean oil plasticizer.
The epoxy value of the epoxidized soybean oil plasticizer is determined to be 6.30 percent according to GB/T1677-.
The separated catalyst is washed by ether and can be reused after being dried. The epoxy values of the epoxidized soybean oil plasticizer used five times were 6.28%, 6.20%, 6.14%, 6.08% and 6.01%, respectively.
Example 6 ammonium tetramethylperrhenate Ionic liquid ([ N (CH) ]3)4]ReO4) Catalytic synthesis of epoxy fatty acid methyl ester plasticizer [ N (CH)3)4]ReO4The structural formula is shown as the following formula:
0.5g of [ N (CH) is weighed3)4]ReO4The catalyst and 20g of fatty acid methyl ester were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid to be neutral by using water, and drying to obtain a yellow oily product which is the epoxy fatty acid methyl ester plasticizer.
The epoxy value of the epoxy fatty acid methyl ester plasticizer is 6.36 percent according to GB/T1677-2008, and the acid value of the epoxy fatty acid methyl ester plasticizer is 0.37mg KOH/g according to GB/T1668-2008.
The separated catalyst is washed by ether and can be reused after being dried. Epoxy values of the epoxidized fatty acid methyl ester plasticizer used five times were 6.31%, 6.24%, 6.14%, 6.09% and 6.03%, respectively.
Example 7 ammonium tetrabutylperrhenate Ionic liquid ([ N (C)4H9)4]ReO4) Catalytic synthesisEpoxidized soybean oil plasticizer
[N(C4H9)4]ReO4The structural formula is shown as the following formula:
0.5g of [ N (C) is weighed4H9)4]ReO4The catalyst and 20g of refined soybean oil were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, washing the reaction liquid with water to be neutral, and drying to obtain a yellow oily product which is the epoxy soybean oil plasticizer.
The epoxy value of the epoxidized soybean oil plasticizer is determined to be 6.10 percent according to GB/T1677-.
The separated catalyst is washed by ether and can be reused after being dried. The epoxy values of the epoxidized soybean oil plasticizer used five times were 6.07%, 6.01%, 5.93%, 5.88% and 5.81%, respectively.
Example 8 ammonium tetrabutylperrhenate Ionic liquid ([ N (C)4H9)4]ReO4) Catalytic synthesis of epoxy fatty acid methyl ester plasticizer [ N (CH)3)4]ReO4The structural formula is shown as the following formula:
0.5g of [ N (C) is weighed4H9)4]ReO4The catalyst and 20g of fatty acid methyl ester were put in a 50mL three-necked flask equipped with a reflux condenser and a thermometer, and 5g H was slowly added dropwise with stirring2O2(30%) and slowly heated to 60 ℃ and stirred at the constant temperature of 60 ℃ for 6 h. After the reaction is finished, after the reaction liquid is cooled to room temperature, centrifugally separating out the catalyst, and reactingWashing the solution with water to neutrality, and drying to obtain yellow oily product as epoxy fatty acid methyl ester plasticizer.
The epoxy value of the epoxy fatty acid methyl ester plasticizer is 6.16 percent according to GB/T1677-2008, and the acid value of the epoxy fatty acid methyl ester plasticizer is 0.44mg KOH/g according to GB/T1668-2008.
The separated catalyst is washed by ether and can be reused after being dried. Epoxy values of the epoxidized fatty acid methyl ester plasticizer used five times were 6.16%, 6.11%, 6.04%, 6.00% and 5.93%, respectively.
The above examples show that unsaturated vegetable oils such as soybean oil and methyl esters of fatty acids can be synthesized in H by using the method for synthesizing epoxy plasticizer based on perrhenate ionic liquid2O2The epoxidation reaction is carried out under oxidation to obtain an epoxy plasticizer product with a higher epoxy value and a lower acid value. The catalyst of the perrhenate ionic liquid is insoluble in raw oil in the reaction process, and the catalyst is easy to recover and reuse after the reaction is finished. The catalytic process avoids the use of the traditional strong acid catalyst, the reaction process is simple and easy to operate, and a new process route is provided for the synthesis of the epoxy plasticizer.
Claims (1)
1. A method for synthesizing an epoxy plasticizer based on perrhenate ionic liquid is characterized by comprising the following steps: mixing 0.5g of perrhenate ionic liquid catalyst with 20g of soybean oil or fatty acid methyl ester, and adding 5g of 30% H2O2Dropwise adding the perrhenate ionic liquid and a soybean oil or fatty acid methyl ester mixed system, and reacting for 6h at 60 ℃;
the perrhenate ionic liquid is as follows: 1-butyl-3-methylimidazole perrhenate ionic liquid, 1-hexyl-3-methylimidazole perrhenate ionic liquid, tetramethyl ammonium perrhenate ionic liquid or tetrabutyl ammonium perrhenate ionic liquid.
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|---|---|---|---|---|
| US5118822A (en) * | 1991-09-30 | 1992-06-02 | Arco Chemical Technology, L.P. | Olefin epoxidation using a perrhenate catalyst and an organic hydroperoxide |
| CN101591588A (en) * | 2009-06-24 | 2009-12-02 | 江南大学 | The method of organic rhenium oxide-urea peroxide catalytic preparation epoxy soybean oil or epoxyfatty acid first (second) ester |
| CN104327015A (en) * | 2014-09-17 | 2015-02-04 | 浙江嘉澳环保科技股份有限公司 | Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst |
| CN104387343A (en) * | 2014-11-21 | 2015-03-04 | 辽宁大学 | Method for epoxidizing olefin |
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Patent Citations (4)
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|---|---|---|---|---|
| US5118822A (en) * | 1991-09-30 | 1992-06-02 | Arco Chemical Technology, L.P. | Olefin epoxidation using a perrhenate catalyst and an organic hydroperoxide |
| CN101591588A (en) * | 2009-06-24 | 2009-12-02 | 江南大学 | The method of organic rhenium oxide-urea peroxide catalytic preparation epoxy soybean oil or epoxyfatty acid first (second) ester |
| CN104327015A (en) * | 2014-09-17 | 2015-02-04 | 浙江嘉澳环保科技股份有限公司 | Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst |
| CN104387343A (en) * | 2014-11-21 | 2015-03-04 | 辽宁大学 | Method for epoxidizing olefin |
Non-Patent Citations (1)
| Title |
|---|
| Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins;Iulius I. E. Markovits et.al;《Chem. Eur. J》;20130305;第19卷(第19期);第5973页左栏的结果和讨论部分，以及右栏表1 * |
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