CN104327015A - Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst - Google Patents
Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst Download PDFInfo
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- CN104327015A CN104327015A CN201410475057.7A CN201410475057A CN104327015A CN 104327015 A CN104327015 A CN 104327015A CN 201410475057 A CN201410475057 A CN 201410475057A CN 104327015 A CN104327015 A CN 104327015A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- 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
- 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
- B01J31/0281—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- 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
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Abstract
The invention discloses a green synthetic method of epoxy unsaturated fatty acid methyl ester. the method comprises the following steps: under the action of a catalyst and an oxidizing agent, unsaturated fatty acid methyl ester is subjected to an epoxidation reaction at the temperature of 50-70 DEG C; and after the reaction, post-treatment is carried out to obtain epoxy unsaturated fatty acid methyl ester, wherein the catalyst is a hydrophobic rhenium ionic liquid and the oxidizing agent is hydrogen peroxide. The invention also discloses a hydrophobic rhenium ionic liquid catalyst. In comparison with a traditional formic acid epoxidation method, the preparation method provided by the invention has advantages as follows: a corrosive liquid will not be generated during the whole process, and equipment will not be corroded; and meanwhile, generation of a lot of wastewater and exhaust gas is avoided after the reaction, environmental pollution is reduced, and green catalysis is realized.
Description
Technical field
The invention belongs to technical field of fine, specifically relate to a kind of green synthesis method and catalyzer of epoxy unsaturated fatty acid methyl ester.
Background technology
Epoxy aliphatic acid methyl ester is a kind of novel environment-friendly polyvinyl chloride elasticizer, plasticizing efficiency is high, consistency good, Heat stability is good, goods low-temperature performance is excellent, completely or partially can substitute o-benzene plasticiser DOP, be widely used in PVC product as food packaging film, medical article material, toy etc.Also can be used as celluosic resin and elastomeric non-toxic plasticizer and tenderizer simultaneously.
The production of current epoxy aliphatic acid methyl ester adopts solventless method, and with formic acid or acetic acid under the effect of the vitriol oil, hydrogen peroxide is that oxygenant and unsaturated fatty acid methyl ester initial ring method for oxidation generate epoxy aliphatic acid methyl ester.Although this method is than solvent method progress, there is the vitriol oil serious to equipment corrosion, constitute a threat to safety in production, formic acid volatility is large, forms waste gas, and wastewater flow rate is large simultaneously, is unfavorable for the shortcomings such as energy-saving and emission-reduction.
Ionic liquid is tasteless, do not fire, its vapour pressure is extremely low, and excellent solvability, has good solubility energy to organism and inorganics, and reaction can be made to carry out under homogeneous phase condition.Due to the premium properties that ionic liquid is many, ionic liquid is developed rapidly.
Ionic liquid is of a great variety, and therefore the positively charged ion of ionic liquid and the selection of negatively charged ion are arranged in pairs or groups very important to dissimilar reaction.
Publication number be CN200810195076A patent document discloses adopt 1-methyl-3-butylimidazolium tetrafluoroborate ion liquid to make reaction medium, [Bmim] W
10o
23make catalyzer, use Witconol 2301 at ambient pressure, the hydrogen peroxide dripping 30% carries out epoxidation reaction, and generate epoxyoleic acid methyl esters, the method two kinds of ionic liquids complete epoxy reaction, add cost.
Publication number is the reaction that patent document discloses a kind of hydrophobic rhenium ion liquid as catalyst epoxidation of cyclohexene of CN200910220634A, preparation epoxidized cyclohexene, and the oxygenant of employing is urea peroxide, and rhenium ionic liquid structure is:
But relative to tetrahydrobenzene, ester group is contained on the one hand in long-chain mixing unsaturated fatty acid methyl ester, it is water-soluble larger with tetrahydrobenzene difference, in long-chain unsaturated fatty acid methyl esters, double bond structure is comparatively complicated on the other hand, when adopting above-mentioned ionic liquid and oxygenant to carry out epoxidation reaction, catalytic effect is not very desirable, and speed of response is comparatively slow, and the oxirane value of the product obtained is lower.And directly adopt long-chain unsaturated fatty acid methyl esters epoxidation conventional oxidants hydrogen peroxide time, because hydrogen peroxide generally exists in form of an aqueous solutions, the rhenium ionic liquid hydrophobicity in above-mentioned document and water tolerance undesirable, cause reaction result poor.
Summary of the invention
The invention provides a kind of green synthesis method of epoxy unsaturated fatty acid methyl ester, it is serious to equipment corrosion that solution exists in producing at present, has the problems such as a large amount of waste water and gas, reduce the pollution to environment, realize green catalysis, catalyzer recoverable, realizes cleaner production simultaneously.
The present invention also provides a kind of hydrophobic rhenium ion liquid as catalyst agent, and excellent catalytic effect, preparation method is simple.
A green synthesis method for epoxy unsaturated fatty acid methyl ester, comprising:
Under catalyzer and oxygenant effect, unsaturated fatty acid methyl ester carries out epoxidation reaction under 50 ~ 70 DEG C of conditions, and reaction terminates, and aftertreatment obtains epoxy unsaturated fatty acid methyl ester;
Described catalyzer is hydrophobicity rhenium ionic liquid, and its structure is as follows:
Described oxygenant is hydrogen peroxide.
As preferably, the process of feeding intake is: first unsaturated fatty acid methyl ester is heated to 40 ~ 50 DEG C, adds catalyzer, add oxygenant, be then warming up to temperature of reaction.When adopting this technical scheme, before being warming up to temperature of reaction, being conducive to ensureing that reaction system mixes, avoiding side reaction to occur.
As preferably, the epoxidation reaction time is 2 ~ 4h, and the concrete time can be determined according to real reaction situation.
As preferably, described last handling process is: after reaction terminates, stratification, upper strata is oil reservoir, lower floor is water layer and ionic liquid, separatory, obtains target product epoxy unsaturated fatty acid methyl ester after the moisture that upper strata oil reservoir vacuum removal is remaining on a small quantity, and lower floor's vacuum removing moisture reclaims ionic liquid and oxygenant or do not process the oxygenant directly adding high density treats next utilization.Adopt this technical scheme, the cleaner production without discharging of waste liquid can be realized.
Described unsaturated fatty acid methyl ester can select sterling or the mixture of multiple unsaturated fatty acid methyl ester.Such as, the unsaturated fatty acid methyl ester between C12 ~ C22 can be selected, mainly the unsaturated fatty acid methyl ester of C12 ~ C18, can side chain be had, carbochain also can have other groups such as hydroxyl.Fatty acid methyl ester is the product of grease methyl alcohol transesterify, also can be the esterification products of the lipid acid methyl alcohol from grease.Described grease can be animal raw fat, such as lard, butter, also can be vegetative grease, such as soybean oil, plam oil, Oleum Cocois, castor-oil plant wet goods.
As preferably, the iodine number of described unsaturated fatty acid methyl ester is 50% ~ 115%;
Described hydrogen peroxide generally adopts the form of the aqueous solution to add, the mass percent concentration of solution is 10 ~ 80%, commercially available hydrogen peroxide can be adopted, mass percent concentration is 27.5%, 30%, 35%, 50%, as preferably, hydrogen peroxide concentration is 50%, the addition of hydrogen peroxide is relevant with the iodine number of unsaturated fatty acid methyl ester, concentration be 50% hydrogen peroxide addition be: 0.00267 × iodine number × grease (unsaturated fatty acid methyl ester) quality ~ 0.00428 × iodine number × oil quality, described hydrophobic rhenium ion liquid as catalyst agent addition is 0.1% ~ 3% of unsaturated fatty acid methyl ester quality, more preferably 0.2% ~ 0.5%.
Described hydrophobicity rhenium ionic liquid preparation method is as follows:
(1) 1-dodecyl-3-Methylimidazole bromine salt preparation: 1-dodecyl-3-Methylimidazole bromine salt can adopt commercially available prod, also can be prepared by following method: N-Methylimidazole and bromo-dodecane are reacted 4 ~ 5 hours in 125 ~ 135 DEG C, obtain light yellow viscous liquid, spend the night with under washed with diethylether 40 ~ 50 DEG C/100 ~ 133Pa condition, obtain light brown wax solid, i.e. 1-dodecyl-3-Methylimidazole bromine salt; 1-dodecyl-3-Methylimidazole bromine salt also adopts commercial products;
(2) hydrophobicity rhenium ionic liquid preparation: get 1-dodecyl-3-Methylimidazole bromine salt and be dissolved in the distilled water of heat, rapid stirring, the slow dropping ammonium perrhenate aqueous solution, 80 ~ 90 DEG C of violent stirring 4 ~ 7 hours, leave standstill, topple over and fall upper strata aqueous phase, wash lower floor's ionic liquid with water to neutral, vacuum removing moisture, 60 ~ 70 DEG C/100 ~ 133Pa dried in vacuo overnight, obtain yellow viscous liquid, i.e. alkyl imidazole rhenium ionic liquid;
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) compared with traditional formic acid method epoxidizing method, the whole process of preparation method of the present invention can not produce corrosive liquid, can not produce etching problem to equipment, avoids producing the problems such as a large amount of waste water and gas after the reaction of the present invention simultaneously, reduce the pollution to environment, realize green catalysis.
(2) oxygenant of the present invention and the equal recoverable of catalyzer, realizes clean words and produces, reduce preparation cost simultaneously.
(3) with publication number be CN200810195076A existing document compared with, hydrophobicity rhenium ionic liquid of the present invention is double does solvent and catalyzer, does not need extra solvent, reduces post-processing difficulty, reduce further preparation cost simultaneously.
(4) long alkyl chains of hydrophobicity rhenium ionic liquid of the present invention, be greater than publication number for the long alkyl chains in hydrophobicity rhenium ionic liquid disclosed in the patent documentation of CN200910220634A, hydrophobicity is stronger, water tolerance is better, coordinate with moisture more hydrogen peroxide oxidant, also can reach good catalytic oxidation effect; And catalyzer in CN200910220634A due to hydrophobicity poor, so anhydrous oxygenant urea peroxide can only be selected.
Embodiment
Introduce enforcement of the present invention in more detail by the following examples, but the present invention is not limited only to these embodiments, the scope that these embodiments do not limit the present invention in any way.
The unsaturated fatty acid methyl ester that embodiment part adopts is purchased from the remarkable new forms of energy Development Co., Ltd of Fujian Longyan, Tangshan Jin Lihai Oil Co., Ltd, Ningbo Jie Sen green energy resource Technology Co., Ltd. respectively.
The hydrophobic rhenium ion liquid as catalyst agent structure that embodiment part adopts is shown below:
The preparation method of above-mentioned hydrophobic rhenium ion liquid as catalyst agent is:
Get N-Methylimidazole (1mmol) and bromo-dodecane (1.5mmol) adds in the round-bottomed flask with reflux condensing tube respectively, 125 ~ 135 DEG C are stirred 5 hours, obtain light yellow viscous liquid, with washed with diethylether 3 times, spend the night under 40 ~ 50 DEG C/100 ~ 133Pa condition, obtain light brown wax solid, i.e. 1-dodecyl-3-Methylimidazole bromine salt; Getting 1-dodecyl-3-Methylimidazole bromine salt is dissolved in the distilled water of heat, rapid stirring, slowly drips the ammonium perrhenate aqueous solution (20ml, 0.1mol/L), 80 ~ 90 DEG C of violent stirring 6 hours, leave standstill, topple over and fall upper strata aqueous phase, wash lower floor's ionic liquid with water to neutral, vacuum removing moisture, 60-70 DEG C/100 ~ 133Pa dried in vacuo overnight, obtains yellow viscous liquid, i.e. alkyl imidazole rhenium ionic liquid.
Embodiment 1
By iodine number be 55% unsaturated fatty acid methyl ester 500g be placed in there-necked flask, be heated to 60 DEG C, add the agent of 1g hydrophobic rhenium ion liquid as catalyst, drip the hydrogen peroxide 88.35g that concentration is 50%, 60 DEG C are reacted 3 hours, stratification, the moisture that upper strata oil reservoir vacuum removal is remaining on a small quantity, obtain target product epoxy aliphatic acid methyl ester, oxirane value is 2.65%, and iodine number is 5.6%.The epoxy aliphatic acid methyl ester oxirane value that the unsaturated fatty acid methyl ester of the same iodine number of formic acid method epoxy obtains is 2.62%, and iodine number is 5.1%.Lower floor is ionic liquid and hydrogen peroxide mixture, and the concentration of hydrogen peroxide is about 12%, makes hydrogen peroxide concentration bring up to about 30%, be directly used in lower secondary response under low temperature after the remove portion that reduces pressure moisture.
Embodiment 2
By iodine number be 90% unsaturated fatty acid methyl ester 500g be placed in there-necked flask, be heated to 50 DEG C, add the agent of 2.5g hydrophobic rhenium ion liquid as catalyst, drip the hydrogen peroxide 132.52g that concentration is 50%, 62 DEG C are reacted 2 hours, stratification, the moisture that upper strata oil reservoir vacuum removal is remaining on a small quantity, obtain target product epoxy aliphatic acid methyl ester, oxirane value is 3.49%, and iodine number is 6.0%.The epoxy aliphatic acid methyl ester oxirane value that the unsaturated fatty acid methyl ester of the same iodine number of formic acid method epoxy obtains is 3.37%, and iodine number is 5.7%.Lower floor is ionic liquid and hydrogen peroxide mixture, and the concentration of hydrogen peroxide is about 14%, makes hydrogen peroxide concentration bring up to about 30%, be directly used in lower secondary response under low temperature after the remove portion that reduces pressure moisture.
Embodiment 3
By iodine number be 115% unsaturated fatty acid methyl ester 500g be placed in there-necked flask, be heated to 40 DEG C, add the agent of 2.5g hydrophobic rhenium ion liquid as catalyst, drip the hydrogen peroxide 199.58g that concentration is 50%, 60 DEG C are reacted 4 hours, stratification, the moisture that upper strata oil reservoir vacuum removal is remaining on a small quantity, obtain target product epoxy aliphatic acid methyl ester, oxirane value is 4.57%, and iodine number is 5.0%.The epoxy aliphatic acid methyl ester oxirane value that the unsaturated fatty acid methyl ester of the same iodine number of formic acid method epoxy obtains is 4.16%, and iodine number is 4.3%.Lower floor is ionic liquid and hydrogen peroxide mixture, and the concentration of hydrogen peroxide is about 10%, makes hydrogen peroxide concentration bring up to about 30%, be directly used in lower secondary response under low temperature after the remove portion that reduces pressure moisture.
Comparative example 1
The structure of the catalyzer adopted is:
Its preparation method is with the method in the patent documentation of publication number CN101735175A.
Oxygenant adopts urea peroxide, and mole number is identical with the mole number of hydrogen peroxide in embodiment 3.
Other conditions adopt the reaction conditions in embodiment 3, after reaction terminates, utilize extraction into ethyl acetate product epoxy aliphatic acid methyl ester wherein.Prove through detecting, the oxirane value of the epoxy aliphatic acid methyl ester prepared by the method is 3.57%, and iodine number is 3.70%, the performance index of product in embodiment 3.Possible cause is because double bond structure in raw fatty acid methyl esters is complicated, selects oxidation urea lower as oxidant reaction activity.
Comparative example 2
The structure of the catalyzer adopted is:
Oxygenant adopts concentration to be the hydrogen peroxide of 50%, and add-on is with embodiment 3.Other conditions adopt the reaction conditions in embodiment 3, after reaction terminates, adopt the treatment process of embodiment 3 to obtain product epoxy aliphatic acid methyl ester.Prove through detecting, the oxirane value of the epoxy aliphatic acid methyl ester prepared by the method is 3.67%, and iodine number is 3.75%, is also starkly lower than the performance index of product in embodiment 3.Reason may be because, above-mentioned catalyzer hydrophobicity and water tolerance poor, in this reaction system, catalytic performance is not good.
From above-described embodiment, compared with carrying out epoxidation with traditional formic acid method, oxirane value and the iodine number of the epoxy aliphatic acid methyl ester adopting method of the present invention to prepare are high, and can continuous prodution be realized, hydrogen peroxide and ionic liquid etc. be recoverable all, avoid producing a large amount of waste water simultaneously, be suitable for industrialized production.
Claims (10)
1. a green synthesis method for epoxy unsaturated fatty acid methyl ester, comprising:
Under catalyzer and oxygenant effect, unsaturated fatty acid methyl ester carries out epoxidation reaction under 50 ~ 70 DEG C of conditions, and reaction terminates, and aftertreatment obtains epoxy unsaturated fatty acid methyl ester;
Described catalyzer is hydrophobicity rhenium ionic liquid, and its structure is as follows:
Described oxygenant is hydrogen peroxide.
2. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 1, is characterized in that, the process of feeding intake is: first unsaturated fatty acid methyl ester is heated to 40 ~ 50 DEG C, adds catalyzer, add oxygenant, be then warming up to temperature of reaction.
3. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 1, is characterized in that, described last handling process is: reaction terminates stratification, and upper strata oil reservoir obtains target product epoxy unsaturated fatty acid methyl ester after removing moisture; Lower floor's removing moisture reclaim catalyzer and oxygenant or directly with the oxygenant mixing reuse newly added.
4. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 1, is characterized in that, the iodine number of described unsaturated fatty acid methyl ester is 50% ~ 115%.
5. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 4, is characterized in that, described hydrogen peroxide adopts the form of the aqueous solution to add, and its mass percent concentration is 10 ~ 80%.
6. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 5, it is characterized in that, the mass percent concentration of aqueous hydrogen peroxide solution is 50%, and the addition of aqueous hydrogen peroxide solution is: 0.00267 × iodine number × unsaturated fatty acid methyl ester quality ~ 0.00428 × iodine number × unsaturated fatty acid methyl ester quality; Described iodine number is the iodine number of unsaturated fatty acid methyl ester.
7. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 1, is characterized in that, the addition of described hydrophobicity rhenium ionic liquid is 0.1% ~ 3% of unsaturated fatty acid methyl ester quality.
8. the green synthesis method of epoxy unsaturated fatty acid methyl ester according to claim 1, it is characterized in that, described hydrophobicity rhenium ionic liquid preparation method is as follows: get 1-dodecyl-3-Methylimidazole bromine salt and be dissolved in distilled water, add the ammonium perrhenate aqueous solution, and 80 ~ 90 DEG C are reacted 4 ~ 7 hours, leave standstill, remove upper strata aqueous phase, wash lower floor's ionic liquid with water to neutral, dewater, 60 ~ 70 DEG C, 100 ~ 133Pa dried in vacuo overnight, obtain hydrophobicity rhenium ionic liquid.
9. a hydrophobic rhenium ion liquid as catalyst agent, is characterized in that, its structure is shown below:
10. hydrophobic rhenium ion liquid as catalyst agent according to claim 9, is characterized in that, described hydrophobic rhenium ion liquid as catalyst agent is prepared by 1-dodecyl-3-Methylimidazole bromine salt and ammonium perrhenate.
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| CN201410475057.7A CN104327015A (en) | 2014-09-17 | 2014-09-17 | Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst |
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| CN201410475057.7A CN104327015A (en) | 2014-09-17 | 2014-09-17 | Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141271A (en) * | 2017-06-23 | 2017-09-08 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate |
| CN107325890A (en) * | 2017-06-23 | 2017-11-07 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method based on perrhenate ions liquid |
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
| CN109438393A (en) * | 2018-10-29 | 2019-03-08 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
-
2014
- 2014-09-17 CN CN201410475057.7A patent/CN104327015A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| IULIUS I. E. MARKOVITS ET.AL: "《Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins》", 《CHEM. EUR. J.》 * |
| IULIUS I. E. MARKOVITS ET.AL: "《Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins》", 《CHEM. EUR. J.》, vol. 19, 31 December 2013 (2013-12-31), pages 5972 - 5979 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
| CN107141271A (en) * | 2017-06-23 | 2017-09-08 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method based on molybdenum multi-metal oxygen hydrochlorate |
| CN107325890A (en) * | 2017-06-23 | 2017-11-07 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method based on perrhenate ions liquid |
| CN107325890B (en) * | 2017-06-23 | 2021-03-16 | 辽宁石油化工大学 | Method for synthesizing epoxy plasticizer based on perrhenate ionic liquid |
| CN109438393A (en) * | 2018-10-29 | 2019-03-08 | 辽宁石油化工大学 | A kind of epoxy plasticizer synthetic method |
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