CN105712954A - Method of preparing 1, 2-epoxyoctane through epoxidation of 1-octene - Google Patents
Method of preparing 1, 2-epoxyoctane through epoxidation of 1-octene Download PDFInfo
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- CN105712954A CN105712954A CN201410740440.0A CN201410740440A CN105712954A CN 105712954 A CN105712954 A CN 105712954A CN 201410740440 A CN201410740440 A CN 201410740440A CN 105712954 A CN105712954 A CN 105712954A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method of preparing 1, 2-epoxyoctane through epoxidation of 1-octene. The method is characterized by including: mixing catalyst, oxidizer, 1-octene and solvent; reacting for 1-8 h at 10-100 DEG C and 0.01-1.00 Mpa to obtain 1, 2-epoxyoctane. The method is mild in reaction condition, sufficient in reaction and high in product selectivity and has good application prospect, the catalyst is recyclable, and the solvent and the oxidizer are wide in application range.
Description
Technical field
The present invention relates to a kind of method that 1-octene epoxidation prepares 1,2-octylene oxide, a kind of method being specifically related to quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst 1-octene synthesis 1,2-octylene oxide.
Background technology
1,2-octylene oxide is a kind of critically important industrial chemicals, is widely used in workers and peasants' production industries such as plasticizer, additive, stabilizer.Olefin epoxidation process traditional at present is mainly chlorohydrination, conjugated oxidation and crosses acid system etc., all have that environmental pollution is serious, production cost is high, complex process, side-product are many and the shortcoming such as post processing is difficult, and traditional handicraft set is used in 1-octene epoxidation and prepares 1,2-octylene oxide has a lot of weak point and technological deficiency, so the epoxidation reaction that the main source of 1,2-octylene oxide is 1-octene obtains.
CN1029932129A (application number) reports one and prepares 1, the method of 2-octylene oxide, is with 1-octene for raw material, passes through epoxidation reaction, it is characterized in that being in that epoxidation reaction adopts hydrogen peroxide to be oxidant, reaction medium is polar solvent, and catalyst is phosphotungstic acid quaternary, is obtained by reacting 1,2-octylene oxide content >=95%, yield >=75%, catalyst and recycling 3 times, evaluate yield >=75%.But there is hydrogen peroxide use cause greatly having in production process bigger potential safety hazard although the method yield is higher, catalyst reclaims difficult and cycle-index is low, the shortcoming such as oxidant and solvent narrow application range.
Yan Fang etc. (<<chemistry and biological engineering>>, 2013,30 (3): 46-49.) with dehydroabietylamine phosphotungstate for catalyst, hydrogen peroxide is oxidant, investigate solvent-free respectively, non-polar solven and the reaction result in polar solvent, but to there is selectivity low for its reaction result, the problems such as by-product is many, low conversion rate.
Therefore, it is possible to make 1-octene highly selective be converted into 1,2-octylene oxide and to have high product yield be theoretical or actual production all has very important significance.
Summary of the invention
The present invention be directed to a kind of 1-octene epoxidation of the deficiencies in the prior art proposition and prepare 1,2-octylene oxide method, the method synthetic route reaction equation is:
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows:
After the mixing of catalyst, oxidant, 1-octene, solvent, react 1～8 hour when 10～100 DEG C and 0.01～1.00Mpa, prepare 1,2-octylene oxide.
Catalyst is quaternary ammonium salt phosphor-tungstic heteropoly acid, and chemical formula is QmPWpO4+3p, wherein, Q is cationic moiety, uses R1R2R3N or with [R1R2R3R4N+] represent, R1R2R3N or [R1R2R3R4N+] in R1、R2、R3、R4It is C respectively5～C20The alkyl of straight or branched, C4～C18Cycloalkyl, one in benzyl, R1、R2、R3、R4Can be identical or differ；2≤m≤7, p=2,3 or 4.
One or two or more kinds in alcohols solvent, aromatic solvent, ether solvent, esters solvent, nitrile solvents or halogenated hydrocarbon solvent of the solvent that reaction uses.
The alcohols solvent that uses of reaction is methanol or ethanol is a kind of or two kinds；
Described aromatic solvent is one or two or more kinds in toluene, ethylo benzene, dimethylbenzene, trimethylbenzene, monosubstituted C6～C9 virtue halogenated aryl hydrocarbon or polysubstituted C6～C9 virtue halogenated aryl hydrocarbon；
The ether solvent that uses of reaction be glycol dimethyl ether, diethylene glycol dimethyl ether or methyl tertiary butyl ether(MTBE) one or two or more kinds；
The esters solvent that uses of reaction be ethyl acetate, trioctyl phosphate or tributyl phosphate one or two or more kinds；
The nitrile solvents that uses of reaction is acetonitrile or benzonitrile is a kind of or two kinds；
The halogenated hydrocarbon solvent that reaction uses is one or two or more kinds in C1～C4 halogenated alkane.
One or more in the aqueous hydrogen peroxide solution that oxidant is 10～70% that reaction uses, peracetic acid, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide.
The molar ratio of 1-octene and oxidant is 0.1～25:1,1-octene and molecular proportion of catalyst is 100～2000:1, and the mass ratio of solvent and 1-octene is 1～100:1.
Reaction temperature is preferably 40～65 DEG C, and reaction pressure is 0.5～1.0MPa preferably, preferably 2～6 hours response time.
Beneficial effects of the present invention
The present invention prepares that 1,2-octylene oxide method reaction condition is gentle, reaction fully, selectivity of product is high, catalyst can be recycled, solvent and oxidant applied widely.
Detailed description of the invention
Embodiment 1
1-octene is 0.5mol, and oxidant is 50% aqueous hydrogen peroxide solution 0.5mol, and catalyst is [π-C5H5NC16H33]3(PO4)(W03)4] for 1mmol, solvent is ethyl acetate and volume of toluene ratio is 1:1 mixed solvent 150ml, with 40 DEG C after reaction mass mixing, reacts 2.5 hours when 0.5MPa, and reaction result is shown in table 1.Product draws through H nuclear-magnetism analysis of spectrum:1HNMR (parameterneat) δ 2.91 (s, 1H), δ 2.74 (s, 2H), δ 2.47 (s, 3H), δ 1.53 (s, 4H) * 1, δ 1.46 (s, 5H) * 1, δ 1.31 (s, 6H), δ 0.91 (s, 7H), it is determined that be 1,2-octylene oxide.
Table 11-octene epoxidation reaction result
Embodiment 2
1-octene is 0.7mol, oxidant tert-butyl hydroperoxide 0.8mol, and catalyst is [(CH)3C16H33N](PO4)(W03)4] for 5mmol, solvent dichloroethane solvent 200ml, with 45 DEG C after reaction mass mixing, react 2 hours when 0.5MPa, reaction result is shown in table 2.Product draws through H nuclear-magnetism analysis of spectrum:1HNMR (parameterneat) δ 2.91 (s, 1H), δ 2.74 (s, 2H), δ 2.47 (s, 3H), δ 1.53 (s, 4H) * 1, δ 1.46 (s, 5H) * 1, δ 1.31 (s, 6H), δ 0.91 (s, 7H), it is determined that be 1,2-octylene oxide.
Table 21-octene epoxidation reaction result
Embodiment 3
1-octene is 0.1mol, oxidant peracetic acid 0.1mol, and catalyst is [(CH)3C18H37N](PO4)(W03)4] for 1mmol, solvent is glycol dimethyl ether and acetonitrile volume ratio is 1:1 mixed solvent 100ml, with 60 DEG C after reaction mass mixing, reacts 4 hours when 0.8MPa, and reaction result is shown in table 3.Product draws through H nuclear-magnetism analysis of spectrum:1HNMR (parameterneat) δ 2.91 (s, 1H), δ 2.74 (s, 2H), δ 2.47 (s, 3H), δ 1.53 (s, 4H) * 1, δ 1.46 (s, 5H) * 1, δ 1.31 (s, 6H), δ 0.91 (s, 7H), it is determined that be 1,2-octylene oxide.
Table 31-octene epoxidation reaction result
Embodiment 4
1-octene is 0.5mol, and oxidant is 30% aqueous hydrogen peroxide solution 0.75mol, and catalyst is [π-C5H5NC12H25]3(PO4)(W03)4] for 3mmol, solvent is ethanol 50ml, with 50 DEG C after reaction mass mixing, reacts 5 hours when 0.75MPa, reaction result is shown in table 4.Product draws through H nuclear-magnetism analysis of spectrum:1HNMR (parameterneat) δ 2.91 (s, 1H), δ 2.74 (s, 2H), δ 2.47 (s, 3H), δ 1.53 (s, 4H) * 1, δ 1.46 (s, 5H) * 1, δ 1.31 (s, 6H), δ 0.91 (s, 7H), it is determined that be 1,2-octylene oxide.
Table 41-octene epoxidation reaction result
Claims (6)
1. the method that a 1-octene epoxidation prepares 1,2-octylene oxide, it is characterised in that: after the mixing of catalyst, oxidant, 1-octene, solvent, react 1～8 hour when 10～100 DEG C and 0.01～1.00Mpa, prepare 1,2-octylene oxide.
2. in accordance with the method for claim 1, it is characterised in that: catalyst is quaternary ammonium salt phosphor-tungstic heteropoly acid, and chemical formula is QmPWpO4+3p, wherein, Q is cationic moiety, uses R1R2R3N or with [R1R2R3R4N+] represent, R1R2R3N or [R1R2R3R4N+] in R1、R2、R3、R4It is C respectively5～C20The alkyl of straight or branched, C4～C18Cycloalkyl, one in benzyl, R1、R2、R3、R4Identical or differ；2≤m≤7, p=2,3 or 4.
3. in accordance with the method for claim 1, it is characterised in that: one or two or more kinds in alcohols solvent, aromatic solvent, ether solvent, esters solvent, nitrile solvents or halogenated hydrocarbon solvent of described solvent；
Described alcohols solvent is the one in methanol or ethanol or two kinds；
Described aromatic solvent is one or two or more kinds in toluene, ethylo benzene, dimethylbenzene, trimethylbenzene, monosubstituted C6～C9 virtue halogenated aryl hydrocarbon or polysubstituted C6～C9 virtue halogenated aryl hydrocarbon；
Described ether solvent is one or two or more kinds in glycol dimethyl ether, diethylene glycol dimethyl ether or methyl tertiary butyl ether(MTBE)；
Described esters solvent is one or two or more kinds in ethyl acetate, trioctyl phosphate or tributyl phosphate；
Described nitrile solvents is the one in acetonitrile or benzonitrile or two kinds；
Described halogenated hydrocarbon solvent is one or two or more kinds in C1～C4 halogenated alkane.
4. in accordance with the method for claim 1, it is characterised in that: described oxidant be 10～70% aqueous hydrogen peroxide solution, peracetic acid, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, one in isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide.
5. method according to claim 1, it is characterised in that: the molar ratio of 1-octene and oxidant is 0.1～25:1,1-octene and molecular proportion of catalyst is 100～2000:1, and the mass ratio of solvent and 1-octene is 1～100:1.
6. method according to claim 1, it is characterised in that: reaction temperature is preferably 40～65 DEG C, and reaction pressure is 0.5～1.0MPa preferably, preferably 2～6 hours response time.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19628296A1 (en) * | 1996-07-12 | 1998-01-15 | Nitrochemie Gmbh | 1,2-Epoxy-octane preparation in good yield at reduced cost |
| CN1278808A (en) * | 1997-11-14 | 2001-01-03 | 杜邦药品公司 | Process for the selective oxidation of organic compounds |
| DE10164467A1 (en) * | 2001-12-20 | 2003-07-10 | Inst Angewandte Chemie Berlin | Catalyst for epoxidation of olefinic compounds comprises tungsten, molybdenum, vanadium or titanium bound to a polyaniline support |
| WO2003101976A1 (en) * | 2002-06-03 | 2003-12-11 | Sumitomo Chemical Company, Limited | Process for producing epoxide |
| CN102993129A (en) * | 2012-11-23 | 2013-03-27 | 南昌大学 | Method for preparing 1,2-epoxyoctane |
-
2014
- 2014-12-05 CN CN201410740440.0A patent/CN105712954A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19628296A1 (en) * | 1996-07-12 | 1998-01-15 | Nitrochemie Gmbh | 1,2-Epoxy-octane preparation in good yield at reduced cost |
| CN1278808A (en) * | 1997-11-14 | 2001-01-03 | 杜邦药品公司 | Process for the selective oxidation of organic compounds |
| DE10164467A1 (en) * | 2001-12-20 | 2003-07-10 | Inst Angewandte Chemie Berlin | Catalyst for epoxidation of olefinic compounds comprises tungsten, molybdenum, vanadium or titanium bound to a polyaniline support |
| WO2003101976A1 (en) * | 2002-06-03 | 2003-12-11 | Sumitomo Chemical Company, Limited | Process for producing epoxide |
| CN102993129A (en) * | 2012-11-23 | 2013-03-27 | 南昌大学 | Method for preparing 1,2-epoxyoctane |
Non-Patent Citations (2)
| Title |
|---|
| 颜芳，等: "脱氢枞胺磷钨酸盐催化1-辛烯的氧化反应研究", 《化学与生物工程》 * |
| 黎林清，等: "金属四羧酸酞菁对烯烃的催化环氧化", 《应用化学》 * |
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