CN105017179A - Catalytic synthesis method for limonene-1,2-epoxide - Google Patents
Catalytic synthesis method for limonene-1,2-epoxide Download PDFInfo
- Publication number
- CN105017179A CN105017179A CN201510310114.0A CN201510310114A CN105017179A CN 105017179 A CN105017179 A CN 105017179A CN 201510310114 A CN201510310114 A CN 201510310114A CN 105017179 A CN105017179 A CN 105017179A
- Authority
- CN
- China
- Prior art keywords
- limonene
- epoxide
- boron
- solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a catalytic synthesis method for limonene-1,2-epoxide. The catalytic synthesis method takes boron tungsten heteropoly acid salt as a catalyst, and takes inorganic salt as an additive. With no solvent being present, the limonene reacts with aqueous hydrogen peroxide with the mass concentration of 30% at 40 DEG C for 6-30 h, then the organic layer is centrifugal separated, and separation and purification are performed by using high speed countercurrent chromatography, so as to generate limonene-1,2-epoxide. According to the catalytic synthesis method for limonene-1,2-epoxide, the preparation process of catalyst-boron tungsten heteropoly acid salt and the catalytic process of limonene are optimized, so that the problems such as poor selectivity of limonene catalytic reaction and great difficulty in reaction are overcome, and the yield and purity of synthesis of limonene-1,2-epoxide are effectively improved. The yield can reach greater than 7%, and the purity can reach greater than 91%.
Description
Technical field
The invention belongs to the field of catalyzing and synthesizing, be specifically related to the method that one catalyzes and synthesizes limonene-1,2-epoxide.
Background technology
Limonene claims again limonene, limonene, and chemistry 1-methyl-4-(1-methyl ethylene) tetrahydrobenzene by name, limonene is the monocyclic terpene class be extensively present in natural plant essential oils, and in lemon, sweet orange, shaddock, content is up to 80% ~ 95%.Limonene can synthesize many organic compound through deep processing, particularly can synthesize limonene-1,2-epoxide by selective epoxidation under the effect of catalyzer and oxygenant.
Limonene-1; 2-epoxide is very useful intermediate in organic synthesis; there is very active response characteristic and excellent physical property; because there is very active epoxide group in its molecular structure, can by obtaining a series of important organic compound with the ring-opening reaction of multiple nucleophilic reagent.These compounds are widely used in medicine, essence and flavoring agent.For improving the yield of limonene-1,2-epoxide, Chinese scholars has carried out large quantifier elimination to synthetic method.
CN 103272649 A discloses a kind of two-phase catalyst containing tungsten boron and preparation method thereof and the application in epoxidation, prepares epoxy cyclohexane system for hydrogen peroxide oxidation tetrahydrobenzene.This catalyzer is in water oil phase middle layer, itself be insoluble to tetrahydrobenzene reaction medium, under hydrogen peroxide effect, with hydrogen peroxide formed a kind of easily and the active specy of alkene generation electrophilic addition, this active specy has certain solvability at oil phase, bring active oxygen atom into oil phase, make its highly selective synthesis epoxy cyclohexane, product is single; Environmentally friendly, production cost is low, is easy to large-scale industrial application.
But, a limonene double bond more than tetrahydrobenzene, the oxygen in epoxidation reagent is under parent's electricity attack of double bond, and the alkene on 8,9 also can be oxidized by initial ring, causes the epoxidised selectivity of limonene to be difficult to control; Secondly, due to limonene two para-orienting groups more than tetrahydrobenzene, under solid space steric effect, the epoxidation difficulty of limonene 1,2 alkene is larger; In addition, in the catalytic oxidation process of limonene, have the competition process of enol oxidation and epoxidation two different mechanism, make limonene epoxidation more difficult, above factor causes the synthesis yield of limonene-1,2-epoxide low, and the cycle is long.
Summary of the invention
A kind of catalyzed oxidation limonene is the object of the present invention is to provide to synthesize the method for limonene-1,2-epoxide.
Above-mentioned purpose is achieved through the following technical solutions:
One catalyzes and synthesizes limonene-1, the method of 2-epoxide, it is characterized in that: it is using boron heteropoly tungstate as catalyzer, inorganic salt as auxiliary agent, under the condition of organic solvent-free, by limonene and mass concentration be 30% aqueous hydrogen peroxide solution under the temperature condition of 40 DEG C, react 6 ~ 30h, then centrifugation goes out organic layer, adopts high speed adverse current chromatogram to carry out separation and purification, obtains limonene-1,2-epoxide
The mol ratio of described hydrogen peroxide and limonene is 1 ~ 4: 1;
The mass ratio of described boron heteropoly tungstate and aqueous hydrogen peroxide solution is 0.04 ~ 0.06: 1;
The mass ratio of described inorganic salt and aqueous hydrogen peroxide solution is 0.01 ~ 0.03: 1.
Preferably, the mol ratio of described hydrogen peroxide and limonene is 2: 1.
Preferably, the mass ratio of described boron heteropoly tungstate and aqueous hydrogen peroxide solution is 0.05: 1.
Preferably, the time of described reaction is 24h.
Preferably, described inorganic salt are Repone K.
Preferably, the two-phase solvent system of described high speed adverse current chromatogram is normal hexane: methyl alcohol: the volume ratio of water is the mixed solvent of 2: 1: 1.
Preferably, described boron heteropoly tungstate is prepared by the following method: in the sodium tungstate solution of 0.5mol/L, add dilute sulphuric acid, the mol ratio of sulfuric acid and sodium wolframate is made to be 1.5: 1, generate flaxen wolframic acid turbid solution after reaction, continuing slowly to drip mass concentration in flaxen turbid solution is the H of 30%
2o
2solution, clarifies just to turbid solution, obtains peroxide tungstic acid; In peroxide tungstic acid, add the boric acid that molar weight is 1/3 of sodium wolframate, in 60 DEG C of reaction 0.5h, obtain boron heteropoly tungstic acid solution; The palmityl trimethyl ammonium chloride that molar weight is 1/3 of sodium wolframate is added again in boron heteropoly tungstic acid solution, in 80 DEG C of reaction 1h, generate quaternised boron heteropoly tungstic acid precipitation, after reaction terminates, be cooled to room temperature, suction filtration also by deionized water wash precipitation, obtains faint yellow solid and at 40 DEG C of oven drying 24h, obtains boron heteropoly tungstate.
The invention has the beneficial effects as follows:
1) the present invention is by being optimized the preparation technology of boron heteropoly tungstic acid salt catalyst and the Catalytic processes of limonene, overcome limonene catalyzed reaction poor selectivity, the difficult problems such as reaction difficulty is large, improve yield and the purity of the synthesis of limonene-1,2-epoxide effectively.Yield can reach more than 7%, and purity reaches more than 91%.
2) catalytic is fast, and efficiency is high, non-toxic solvent, decreases environmental pollution.
Embodiment
Embodiment 1
1) preparation of boron heteropoly tungstic acid catalyzer
Take 16.491g tungstate dihydrate acid sodium, be dissolved in 100ml distilled water, stir and form the sodium tungstate solution of 0.5mol/L.In sodium tungstate solution, add dilute sulphuric acid, the mol ratio making sulfuric acid and sodium wolframate is 1.5: 1, obtains flaxen wolframic acid precipitation after reaction.In faint yellow turbid solution, slowly drip mass concentration is the H of 30%
2o
2solution, just disappears to precipitation, obtains the flaxen peroxide tungstic acid of clear.Take appropriate boric acid solid (molar weight of boric acid is 1/3 of sodium wolframate), proceed in there-necked flask by itself and peroxide tungstic acid, 60 DEG C of reaction 0.5h, obtain boron heteropoly tungstic acid solution.Add palmityl trimethyl ammonium chloride (molar weight is 1/3 of sodium wolframate) again, in 80 DEG C of reaction 1h, obtain quaternised boron heteropoly tungstic acid precipitation.After reaction terminates, be cooled to room temperature, use a large amount of deionized water wash with Büchner funnel suction filtration, obtain faint yellow solid particle, at 40 DEG C of oven drying 24h, obtain boron heteropoly tungstic acid catalyzer.
2) limonene-1,2-epoxide is catalyzed and synthesized
Get limonene (95%) 7.16g (0.05mol), hydrogen peroxide (30%) 11.33g (0.1mol), prepared catalyzer 0.5665g, Repone K 0.15g, add in there-necked flask, with violent mechanical stirring, at 40 DEG C, react 24h.After reaction solution cooling, obtain organic phase by the centrifugation of 4000r/min, 10min.
3) purifying
By normal hexane: methyl alcohol: the volume ratio preparation two-phase solvent system of water=2:1:1, organic phase centrifugation obtained is dissolved in 10ml two-phase solvent (under the upper phase of 10mL+10mL phase), adopt the high speed adverse current chromatogram system of head-tail elution mode, the upper phase that fixes mutually, after filling spiral tube with the flow velocity of 30mL/min, open HSCCC, adjustment engine speed is 850rpm, moving phase is entered with the flow pump of 2.0mL/min, separation temperature is 25 DEG C, in time having continuous print moving phase to flow out, illustrative system balances, now inject sample solution, effluent liquid adopts UV-detector to detect, wavelength is 254nm.The purity of limonene-1,2-epoxide is analyzed again by GC-MS.The purity of limonene-1,2-epoxide is 91.7%.
Test example 1: the synthesising process research of catalyzer
1) determination of sulfuric acid and sodium wolframate ratio
Change the add-on of dilute sulphuric acid, make the mol ratio of sulfuric acid and sodium wolframate be respectively 0.5:1,1:1,1.5:1,2:1,2.5:1, the step 1 of other processing parameter and embodiment 1) identical.
With obtained catalyst synthesis limonene-1,2-epoxide, the step 2 of method and embodiment 1) identical, catalyzed reaction terminates the content of limonene-1, the 2-epoxide in rear detection organic phase and calculated yield, the results are shown in Table 1.
Table 1 dilute sulphuric acid consumption is on the impact of catalytic effect
| H 2SO 4With Na 2WO 4Mol ratio | The yield (%) of limonene-1,2-epoxide |
| 0.5:1 | 3.2165±0.1289 |
| 1:1 | 2.9893±0.1684 |
| 1.5:1 | 3.5389±0.0787 |
| 2:1 | 1.4162±0.1297 |
| 2.5:1 | 0.9345±0.0230 |
When the molar weight of sulfuric acid is 1.5 times of sodium wolframate, obtained catalyst best results.
2) determination of boric acid and sodium wolframate ratio
Change the add-on of boric acid, make the mol ratio of sodium wolframate and boric acid be respectively 1:9,1:3,1:1,3:1,9:1, other technique, parameter and test method are all identical with embodiment 1.
Table 2 boric acid consumption is on the impact of catalytic effect
| The mol ratio of sodium wolframate and boric acid | Yield (%) |
| 1:9 | 2.2443±0.1808 |
| 1:3 | 2.4685±0.0541 |
| 1:1 | 2.1480±0.0308 |
| 3:1 | 2.8473±0.0255 |
| 9:1 | 2.3416±0.0755 |
When the ratio of sodium wolframate and boric acid is 3:1, the catalytic activity of catalyzer is best.
3) determination of palmityl trimethyl ammonium chloride and sodium wolframate ratio
Change the add-on of palmityl trimethyl ammonium chloride, make the mol ratio of palmityl trimethyl ammonium chloride and sodium wolframate be respectively 1:9,1:3,1:1, other technique, parameter and test method are all identical with embodiment 1.
Table 3 palmityl trimethyl ammonium chloride consumption is on the impact of catalytic effect
When the consumption of palmityl trimethyl ammonium chloride is Na
2wO
41/3 time, catalytic effect is best.
4) determination of boron heteropoly tungstic acid and palmityl trimethyl ammonium chloride temperature of reaction, the results are shown in Table 4.
Table 4 synthesis temperature is on the impact of catalytic effect
| Synthesis temperature | Yield (%) |
| 60℃ | 2.4852±0.1118 |
| 70℃ | 1.9825±0.1314 |
| 80℃ | 2.8587±0.0471 |
| 90℃ | 2.7125±0.2236 |
When the temperature of reaction of boron heteropoly tungstic acid and palmityl trimethyl ammonium chloride is 80 DEG C, the yield of limonene-1,2-epoxide is the highest.
5) determination in boron heteropoly tungstic acid and palmityl trimethyl ammonium chloride reaction times, the results are shown in Table 5.
Table 5 synthesis temperature is on the impact of catalytic effect
| Generated time | Yield (%) |
| 1h | 2.4806±0.1487 |
| 1.5h | 2.4527±0.2650 |
| 2h | 2.3543±0.0803 |
| 2.5h | 2.2883±0.0862 |
The reaction times of boron heteropoly tungstic acid and palmityl trimethyl ammonium chloride is 1 hour, and the yield of limonene-1,2-epoxide is the highest.
Test example 2: the synthesising process research of limonene-1,2-epoxide
1) different catalysts is on the impact of reaction
Adopt different catalyzer synthesis limonene-1,2-epoxide, other technique, parameter all with the step 2 of embodiment 1) identical, catalyzed reaction terminates the content of limonene-1, the 2-epoxide in rear detection organic phase and calculated yield, the results are shown in following table.
Table 6 different catalysts is to the impact of limonene-1,2-epoxide yield
| Catalyzer title | Yield (%) |
| Boron heteropoly tungstate | 3.5438±0.0787 |
| PW/SiO 2 | 2.9825±0.1314 |
| PW quaternary ammonium salt | 3.2587±0.0471 |
As can be seen from Table 1, comparatively conventional catalyzer, the catalytic activity of boron heteropoly tungstic acid salt catalyst is stronger.
2) determination of hydrogen peroxide and limonene ratio
React with the hydrogen peroxide of different mol ratio and limonene, other technique, parameter all with the step 2 of embodiment 1) identical.
Table 7 hydrogen peroxide add-on is to the impact of limonene-1,2-epoxide yield
| The mol ratio of hydrogen peroxide and limonene | Yield (%) |
| 1:2 | 2.8165±0.0235 |
| 1:1 | 2.9673±0.1684 |
| 2:1 | 3.5438±0.0787 |
| 4:1 | 2.4162±0.1297 |
| 8:1 | 2.3345±0.0545 |
When the ratio of hydrogen peroxide and limonene is 2:1, the yield of limonene-1,2-epoxide is the highest.
3) determination of catalyzer and hydrogen peroxide ratio
Add the catalyzer of different ratios, other technique, parameter all with the step 2 of embodiment 1) identical.
Table 8 catalyzer usage quantity is to the impact of limonene-1,2-epoxide yield
| The mass ratio of catalyzer and aqueous hydrogen peroxide solution | Yield (%) |
| 0.0125:1 | 2.5735±0.1808 |
| 0.025:1 | 2.8685±0.0541 |
| 0.05:1 | 3.2480±0.3077 |
| 0.1:1 | 2.6473±0.0255 |
| 0.2:1 | 2.2561±0.0755 |
When the mass ratio of catalyzer and aqueous hydrogen peroxide solution is 0.05:1, limonene-1,2-epoxide yield is the highest.
4) different inorganic salt are on the impact of reaction
Adopt different inorganic salt to be auxiliary agent, other technique, parameter all with the step 2 of embodiment 1) identical.
The different inorganic salt of table 9 are to the impact of limonene-1,2-epoxide yield
| Inorganic Salts | Yield (%) |
| KCl | 3.6015±0.2015 |
| NaCl | 3.4335±0.0376 |
| Na 2CO 3 | 3.3967±0.0546 |
| K 2CO 3 | 3.5621±0.1372 |
| none | 3.2480±0.3077 |
KCl best results.
5) determination in reaction times
Adopt the different reaction times, other technique, parameter all with the step 2 of embodiment 1) identical.
Table 10 reaction times is to the impact of limonene-1,2-epoxide yield
| Reaction times | Yield (%) |
| 6h | 3.5438±0.0787 |
| 12h | 4.5335±0.1138 |
| 18h | 6.3154±0.0255 |
| 24h | 7.0621±0.1372 |
| 30h | 7.0744±0.3077 |
24h and 30h otherness is also little, is Reaction time shorten, selects 24h more suitable.
Claims (7)
1. one kind catalyzes and synthesizes limonene-1, the method of 2-epoxide, it is characterized in that: it is using boron heteropoly tungstate as catalyzer, inorganic salt as auxiliary agent, under the condition of organic solvent-free, by limonene and mass concentration be 30% aqueous hydrogen peroxide solution under the temperature condition of 40 DEG C, react 6 ~ 30h, then centrifugation goes out organic layer, adopts high speed adverse current chromatogram to carry out separation and purification, obtains limonene-1,2-epoxide
The mol ratio of described hydrogen peroxide and limonene is 1 ~ 4: 1;
The mass ratio of described boron heteropoly tungstate and aqueous hydrogen peroxide solution is 0.04 ~ 0.06: 1;
The mass ratio of described inorganic salt and aqueous hydrogen peroxide solution is 0.01 ~ 0.03: 1.
2. catalyze and synthesize the method for limonene-1,2-epoxide as claimed in claim 1, it is characterized in that: the mol ratio of described hydrogen peroxide and limonene is 2: 1.
3. catalyze and synthesize the method for limonene-1,2-epoxide as claimed in claim 1, it is characterized in that: the mass ratio of described boron heteropoly tungstate and aqueous hydrogen peroxide solution is 0.05: 1.
4. catalyze and synthesize the method for limonene-1,2-epoxide as claimed in claim 1, it is characterized in that: the time of described reaction is 24h.
5. catalyze and synthesize the method for limonene-1,2-epoxide as claimed in claim 1, it is characterized in that: described inorganic salt are Repone K.
6. catalyze and synthesize the method for limonene-1,2-epoxide as claimed in claim 1, it is characterized in that: the two-phase solvent system of described high speed adverse current chromatogram is normal hexane: methyl alcohol: the volume ratio of water is the mixed solvent of 2: 1: 1.
7. catalyze and synthesize limonene-1 as claimed in claim 1, the method of 2-epoxide, it is characterized in that: described boron heteropoly tungstate is prepared by the following method: in the sodium tungstate solution of 0.5mol/L, add dilute sulphuric acid, the mol ratio of sulfuric acid and sodium wolframate is made to be 1.5: 1, generate flaxen wolframic acid turbid solution after reaction, continuing slowly to drip mass concentration in turbid solution is the H of 30%
2o
2solution, clarifies just to turbid solution, obtains peroxide tungstic acid; In peroxide tungstic acid, add the boric acid that molar weight is 1/3 of sodium wolframate, in 60 DEG C of reaction 0.5h, obtain boron heteropoly tungstic acid solution; The palmityl trimethyl ammonium chloride that molar weight is 1/3 of sodium wolframate is added again in boron heteropoly tungstic acid solution, in 80 DEG C of reaction 1h, generate quaternised boron heteropoly tungstic acid precipitation, after reaction terminates, be cooled to room temperature, suction filtration also by deionized water wash precipitation, obtains faint yellow solid and at 40 DEG C of oven drying 24h, obtains boron heteropoly tungstate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510310114.0A CN105017179A (en) | 2015-06-08 | 2015-06-08 | Catalytic synthesis method for limonene-1,2-epoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510310114.0A CN105017179A (en) | 2015-06-08 | 2015-06-08 | Catalytic synthesis method for limonene-1,2-epoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105017179A true CN105017179A (en) | 2015-11-04 |
Family
ID=54407530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510310114.0A Pending CN105017179A (en) | 2015-06-08 | 2015-06-08 | Catalytic synthesis method for limonene-1,2-epoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105017179A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008499A (en) * | 2017-04-13 | 2017-08-04 | 上海科技大学 | Terpenoid can be converted into the combination catalyst and method of aromatic hydrocarbon |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN113045514A (en) * | 2021-03-31 | 2021-06-29 | 福州大学 | Method for preparing limonene epoxidation product |
| US11053264B2 (en) * | 2017-12-04 | 2021-07-06 | International Business Machines Corporation | Limonene-based, non-halogenated flame retardants for polymeric applications |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110146997A1 (en) * | 2009-12-17 | 2011-06-23 | Nguyen Philip D | Formation Conditioning Fluids Comprising Peroxides and Methods Relating Thereto |
| CN103272649A (en) * | 2013-06-04 | 2013-09-04 | 浙江大学 | Tungsten and boron-containing two-phase catalyst, and preparation method and application thereof in epoxidation |
-
2015
- 2015-06-08 CN CN201510310114.0A patent/CN105017179A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110146997A1 (en) * | 2009-12-17 | 2011-06-23 | Nguyen Philip D | Formation Conditioning Fluids Comprising Peroxides and Methods Relating Thereto |
| CN103272649A (en) * | 2013-06-04 | 2013-09-04 | 浙江大学 | Tungsten and boron-containing two-phase catalyst, and preparation method and application thereof in epoxidation |
Non-Patent Citations (5)
| Title |
|---|
| ADRIEN MOURET，等: "Eco-friendly solvents and amphiphilic catalytic polyoxometalate nanoparticles: a winning combination for olefin epoxidation", 《GREEN CHEM》 * |
| CASUSCELLI,S.G.，等: "Effect of reaction conditions on limonene epoxidation with H2O2 catalyzed by supported Keggin heteropolycompounds", 《APPLIED CATALYSIS A: GENERAL》 * |
| MARADUR, SANJEEV P.等: "Mesoporous Polymeric Support Retaining High Catalytic Activity of Polyoxotungstate for Liquid-Phase Olefin Epoxidation using H2O2", 《CHEMCATCHEM》 * |
| N.K. KALA RAJ，等: "Selective oxidation of limonene over sodium salt of cobalt containing sandwich-type polyoxotungstate [WCo3(H2O)2{W9CoO34}2]10−", 《APPLIED CATALYSIS A: GENERAL》 * |
| YONG DING，等: "Synthesis of Epoxides Catalyzed by a Halide-Free Reaction-Controlled Phase-Transfer Catalytic System: [(CH3(CH2)17)2N(CH3)2]3[PW4O32]/H2O2/Dioxan/Olefin", 《AUST.J.CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008499A (en) * | 2017-04-13 | 2017-08-04 | 上海科技大学 | Terpenoid can be converted into the combination catalyst and method of aromatic hydrocarbon |
| CN107008499B (en) * | 2017-04-13 | 2019-12-31 | 上海科技大学 | Combined catalyst and method capable of converting terpenoids into aromatic hydrocarbons |
| US11053264B2 (en) * | 2017-12-04 | 2021-07-06 | International Business Machines Corporation | Limonene-based, non-halogenated flame retardants for polymeric applications |
| CN108358872A (en) * | 2018-03-21 | 2018-08-03 | 天津市职业大学 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
| CN113045514A (en) * | 2021-03-31 | 2021-06-29 | 福州大学 | Method for preparing limonene epoxidation product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105017179A (en) | Catalytic synthesis method for limonene-1,2-epoxide | |
| CN103172516B (en) | Method for producing methyl methoxyacetate by methylal vapor-phase carbonylation by using supported heteropoly acid catalyst | |
| CN108484545A (en) | A kind of method and system of continuous synthesis furandicarboxylic acid | |
| CN103012334A (en) | Method for preparing gamma-valerolactone with high selectivity under mild condition | |
| CN108440463B (en) | Method for preparing 5-hydroxymethylfurfural by catalysis of supported metal molecular sieve catalyst | |
| CN105642353A (en) | Cobalt, chromium or zinc complex conjugated micropore polymer catalyst as well as preparation method and application thereof | |
| CN107159217A (en) | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use | |
| CN105622400A (en) | Acrylate synthesis method | |
| CN105441521A (en) | Synthetic method of vitamin A palmitate | |
| CN102267882A (en) | Method for preparing acrolein by catalyzing dehydration of glycerol with immobilized acidic ionic liquid | |
| CN107537576B (en) | Immobilized catalyst of silane coupling molecular sieve and double-salt ionic liquid | |
| CN103204840B (en) | Method for preparing cyclic carbonate by using functional guanidinium ionic liquid | |
| CN103724172B (en) | The synthesis technique of diacetone alcohol | |
| CN103242269B (en) | A kind of preparation method of furfural | |
| CN108031488A (en) | A kind of production method of graphene-based composite catalyst of carried heteropoly acid ionic liquid and the application in limonene derivatives | |
| CN104926782A (en) | Method for preparing cyclic carbonate using isothiourea salt ionic liquid | |
| CN103977839B (en) | A kind of ionic organic metal tungstates epoxidation catalyst and preparation method thereof | |
| CN102942548B (en) | Delta-dodecalactone synthesis method | |
| CN102093184B (en) | Method for preparing benzaldehyde by performing catalytic oxidation on cinnamyl aldehyde or cinnamon oil and special catalyst thereof | |
| CN112898245B (en) | Method for synthesizing 5-hydroxymethyl furfural | |
| CN102746146B (en) | Preparation method of ethyl acetate | |
| CN102002033B (en) | Protection method for astaxanthin intermediate | |
| CN111346668A (en) | Preparation and application of modified beta molecular sieve catalyst | |
| CN106831655B (en) | A method of epoxidized soybean oil is catalyzed and synthesized under the conditions of no carboxylic acid | |
| CN101497592B (en) | Preparation of 3,4-di-O-acetyl-L-rhamnal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Pan Sidie Inventor after: Xie Lin Inventor after: Li Shengrui Inventor after: Xu Xiaoyun Inventor after: Wang Kexing Inventor before: Pan Sidie Inventor before: Li Shengrui Inventor before: Xu Xiaoyun Inventor before: Wang Kexing |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151104 |