CN110698436A - Synthetic method of aliphatic epoxy compound - Google Patents
Synthetic method of aliphatic epoxy compound Download PDFInfo
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- CN110698436A CN110698436A CN201911072337.2A CN201911072337A CN110698436A CN 110698436 A CN110698436 A CN 110698436A CN 201911072337 A CN201911072337 A CN 201911072337A CN 110698436 A CN110698436 A CN 110698436A
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- aliphatic
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- oxidizing agent
- epoxy compound
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 37
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- -1 aliphatic olefin Chemical class 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 28
- 239000006227 byproduct Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000002432 hydroperoxides Chemical group 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 49
- 238000001914 filtration Methods 0.000 claims description 13
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- VUSWCWPCANWBFG-UHFFFAOYSA-N cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1 VUSWCWPCANWBFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 abstract description 6
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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
- C07D303/44—Esterified with oxirane-containing hydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention provides a synthetic method of an aliphatic epoxy compound, which comprises the following steps: mixing aliphatic olefin, a molybdenum-containing solid epoxidation catalyst and an oxidant, and reacting to prepare the aliphatic epoxy compound; wherein by-products are continuously removed during the reaction, said by-products comprising at least by-products from the oxidizing agent; the oxidant is selected from organic hydroperoxides, and the aliphatic olefin has a boiling point higher than the boiling point of the by-product from the oxidant. The method has the characteristics of easily obtained raw materials, simple and flexible operation, simple equipment, low cost, no need of adding additional solvent, high reaction rate, high product quality, high conversion rate and the like, the prepared product can meet the requirements of high-end epoxy resin, and the problems of large consumption of reaction solvent, high price of catalyst, easiness in ring opening of epoxy bonds, poor product quality, low conversion rate and the like in the prior art can be solved.
Description
Technical Field
The invention belongs to the technical field of aliphatic epoxy compounds, and particularly relates to a synthetic method of an aliphatic epoxy compound.
Background
Compared with the traditional bisphenol A epoxy resin, the epoxy resin prepared from the aliphatic epoxy compound has the characteristics of good thermal stability, high weather resistance, excellent electrical insulation performance and the like because the aliphatic epoxy compound does not contain residual chlorine and aromatic groups, so that the epoxy resin prepared from the aliphatic epoxy compound is widely applied to the fields of coatings, packaging, electronics, automobiles and the like.
Aliphatic diepoxides which are commercially produced at present are mainly 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the two aliphatic diepoxides are synthesized industrially by a peracid method of United states carbon chemical company (see U.S. Pat. No. 4,2716123), but the method needs to use high-concentration peroxyacetic acid, is easy to explode and has great safety hazard.
Chinese patent document CN101250169A discloses a method for preparing an aliphatic epoxy compound, which uses an oxidation system using hydrogen peroxide as an oxygen source and heteropoly acid as a catalyst to catalyze and epoxidize aliphatic olefin to prepare the aliphatic epoxy compound. However, since the aliphatic epoxy compound is sensitive to both acid and water, the above method has problems of easy hydrolysis and ring opening of the product, and the catalyst used in the method is expensive and difficult to separate from the product having a high boiling point, which is not suitable for industrial production.
Chinese patent document CN102596924A discloses a method for preparing corresponding epoxy compounds by respectively oxidizing cyclohexene and limonene with tert-butyl hydroperoxide, which adopts a reaction rectification tower filled with a resin-supported molybdenum catalyst for reaction, and can improve the selectivity of the reaction. However, this reaction apparatus is only suitable for the epoxidation of olefins containing not more than 14 carbon atoms, and the conversion rate for the epoxidation of olefins with high boiling points is significantly reduced, and the operation of the apparatus is unstable; and the molar ratio of the olefin to the peroxide is too high, so that the subsequent products are difficult to separate, the epoxy value of the products is reduced, and the like.
Further, the aliphatic epoxy compound is required to have a specific epoxy equivalent and viscosity as a precursor of the epoxy resin. Thus, high conversions are to be ensured during the preparation, high epoxide equivalents are to be maintained (i.e.further hydrolysis and polymerization of the product is to be prevented), and high selectivities are also required for the aliphatic diepoxides. Because aliphatic epoxies and their precursor aliphatic olefins are generally high boiling compounds, large excesses of aliphatic olefins cannot be used to control the hydrolysis reaction, and hydrolysis can generally only be inhibited by diluting the system to reduce the chance of water contact with the epoxy product. This leads to problems such as large system size, low efficiency, and difficulty in product separation (especially a diepoxy product having a high boiling point), and there is a need for an efficient and safe process for the epoxidation of high boiling olefins.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing an aliphatic epoxy compound, which has the characteristics of easily available raw materials, simple and flexible operation, simple equipment, low cost, no need of adding an additional solvent, high reaction rate, high product quality, high conversion rate and the like, the prepared product can meet the requirements of high-end epoxy resin, and the problems of high reaction solvent consumption, high catalyst price, difficult control of the reaction process, easy ring opening of an epoxy bond, poor product quality, low conversion rate and the like in the prior art can be solved.
The purpose of the invention is realized by the following technical scheme:
a method of synthesizing an aliphatic epoxy compound, the method comprising the steps of:
mixing aliphatic olefin, a molybdenum-containing solid epoxidation catalyst and an oxidant, and reacting to prepare the aliphatic epoxy compound;
wherein by-products are continuously removed during the reaction, said by-products comprising at least by-products from the oxidizing agent; the oxidant is selected from organic hydroperoxides; the aliphatic olefin has a boiling point higher than that of a by-product from the oxidant.
According to the invention, the organic hydroperoxide is selected from tert-butyl peroxides, for example from tert-butyl hydroperoxide.
According to the invention, the oxidizing agent is introduced in the form of a solution. For example, the oxidizing agent is introduced in the form of a tert-butanol solution of the oxidizing agent; the tert-butyl alcohol solution of the oxidant is specifically tert-butyl alcohol solution of tert-butyl hydroperoxide. The concentration of the oxidizing agent in the solution is 30 to 65 wt%, preferably 45 to 55 wt%.
According to the invention, when the oxidizing agent is selected from tert-butyl peroxide, the by-product from the oxidizing agent is tert-butanol.
According to a preferred embodiment of the invention, the method comprises the steps of:
an aliphatic olefin having a boiling point higher than that of t-butyl alcohol, a molybdenum-containing solid epoxidation catalyst and t-butyl peroxide are mixed and reacted, and a by-product including t-butyl alcohol is continuously removed during the reaction to prepare the aliphatic epoxy compound.
According to the present invention, the reaction takes place without additional solvent addition at atmospheric pressure, i.e. the aliphatic olefin is directly converted to an aliphatic epoxy compound without additional solvent addition at atmospheric pressure.
According to the invention, the aliphatic olefin is selected from aliphatic olefins of linear or cyclic structure with more than 8 carbon atoms containing at least one carbon-carbon double bond; for example, aliphatic olefins having a linear or cyclic structure of 8 or more carbon atoms containing at least two carbon-carbon double bonds; and further for example, from aliphatic olefins of linear or cyclic structure of 8 to 24 carbon atoms (e.g., 8, 10, 12, 14, 16, 20, 22, 24 carbon atoms) containing at least two carbon-carbon double bonds; wherein the double bond may be in a linear or cyclic structure, preferably the double bond is in a cyclic structure, preferably the cyclic structure contains 4 to 7 carbon atoms (e.g. 4, 5, 6 or 7 carbon atoms). The synthesis method is particularly suitable for synthesizing high-carbon aliphatic olefins.
Illustratively, the olefin is selected from 3, 4-cyclohexene-1-carboxylic acid 3, 4-cyclohexen-1-ylmethyl ester or bis ((3, 4-cyclohexenyl) methyl) adipate.
According to the present invention, the reaction temperature is 70-120 deg.C, preferably 80-110 deg.C, and by-products (such as t-butanol, etc.) are continuously distilled at the corresponding temperature, and the reaction time is 1-2 hr.
According to the invention, after the reaction is finished, a refined product can be obtained through filtration and distillation.
According to the invention, the filtration mode is suction filtration and centrifugal filtration, and the filtration temperature is 60-100 ℃, preferably 70-80 ℃. Wherein the solid catalyst is removed by filtration.
According to the invention, the distillation is reduced pressure distillation, the distillation temperature is 100-130 ℃, preferably 110-125 ℃, the vacuum degree is 0.09-0.095MPa, and the distillation time is 0.5-3hr, preferably 1-1.5 hr. Wherein the aliphatic epoxy compound is obtained by distillation.
According to the invention, the molar ratio of double bonds in the aliphatic olefin to oxidizing agent is from 1:1 to 4, preferably from 1:1.5 to 2.5.
According to the present invention, the solid epoxidation catalyst is, for example, a solid molybdenum oxide compound or a supported molybdenum oxide compound, wherein the valence of molybdenum is + 6. For example, the catalyst is molybdenum trioxide (MoO)3) Silica supported Mo (VI) or molecular sieve supported Mo (VI).
According to the invention, the catalyst is in the form of particles having a particle size of 80-800 mesh, preferably 200-400 mesh.
According to the invention, the amount of catalyst used is 1 to 5%, preferably 2 to 3.5%, of the total mass of the reaction system.
According to the invention, the epoxy equivalent of the aliphatic epoxy compound is 100-200 Gm/Eq.
According to the present invention, the apparatus for carrying out the synthesis method is not particularly limited, and the synthesis method does not require rectification treatment and therefore does not need to be carried out in process equipment such as a rectification column which is complicated in operation; meanwhile, the synthesis method of the present application can be carried out in, for example, a tank reactor or a flask-type reaction apparatus, and is simple and easy to implement because it does not require a reflux ratio, a reboiler at the bottom of the reaction apparatus, or parameters such as the number of effective plates, and is suitable for industrial and large-scale production.
The invention has the beneficial effects that:
the invention provides a synthetic method of an aliphatic epoxy compound, which has the characteristics of readily available raw materials, simple and flexible operation, simple equipment, low cost, no need of adding an additional solvent, high reaction rate, high product quality, low epoxy equivalent, high conversion rate and the like.
Drawings
Fig. 1 is a schematic view of the structure of a reaction apparatus for carrying out the method for synthesizing an aliphatic diepoxide.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The reaction apparatus used in the following examples is shown in FIG. 1, which is not intended to limit the scope of the present invention, and all apparatus of reaction flask and reaction vessel type having the same flow path function and simultaneously performing reaction and distillation are considered as the scope of the present invention.
As shown in FIG. 1, wherein 1 is a reaction part, a mixed system of olefin, oxidant and solid catalyst is filled in, the reaction materials are uniformly mixed by magnetic or mechanical stirring, and a heat source is provided by external oil bath or electric heating. And 2, a reaction monitoring thermometer is used for monitoring the temperature in the reaction process in real time to ensure that the by-product is continuously distilled out of the system along with the reaction. 3 is a condensation recovery unit for distilling the by-product. And 4 is a byproduct receiving unit.
Example 1:
a500 ml three-necked flask was charged with 25.37g of 3, 4-cyclohexene-1-carboxylic acid-3, 4-cyclohexen-1-ylmethyl ester and 100.63g of TBHP-TBA solution (TBHP 46.05 wt%). Adding 3.20g of catalyst molybdenum trioxide (400 meshes), heating to 90-100 ℃, starting to extract fractions such as byproduct tert-butyl alcohol, reacting for 15min, continuously heating to 100-110 ℃ for about 70min, continuously extracting fractions such as byproduct tert-butyl alcohol, and sampling to monitor the reaction process. After the reaction, 67g of by-product tert-butyl alcohol and the like are co-extracted, the temperature is reduced to 80 ℃, and crude reaction liquid 42.11g is obtained by filtration.
And (3) distilling the filtered reaction solution at 120 ℃ under the vacuum degree of-0.095 MPa for 1.5 hours under reduced pressure to obtain 28.87g of a colorless transparent product, and detecting the obtained product, wherein the epoxy equivalent is 130Gm/Eq, and the viscosity is 250mPa.s (25 ℃).
Example 2:
a500 ml three-necked flask was charged with 42.00 g of bis ((3, 4-cyclohexenyl) methyl) adipate and 100.63g of TBHP-TBA solution (TBHP 46.05 wt%). Adding 3.50g of catalyst molybdenum trioxide (400 meshes), heating to 90-100 ℃, starting to extract fractions such as byproduct tert-butyl alcohol, reacting for 15min, continuously heating to 100-110 ℃ for about 70min, continuously extracting fractions such as byproduct tert-butyl alcohol, and sampling to monitor the reaction process. After the reaction is finished, 64.30g of by-product tert-butyl alcohol and the like are co-extracted, the temperature is reduced to 80 ℃, and crude reaction liquid 70.11g is obtained by filtration.
The reaction solution after filtration is distilled under vacuum degree of-0.095 MPa and under reduced pressure at 125 ℃ for 1.5 hours to obtain 46.07g of light yellow product, and the obtained product is detected to have epoxy equivalent of 194Gm/Eq and viscosity of 540mPa.s (25 ℃).
Comparative example 1:
a500 ml three-necked flask was charged with 25.07g of 3, 4-cyclohexene-1-carboxylic acid-3, 4-cyclohexen-1-ylmethyl ester and 100.00g of TBHP-TBA solution (TBHP 46.05 wt%). Adding 3.20g of catalyst molybdenum trioxide (400 meshes), heating to 95 ℃, carrying out reflux reaction for 3 hours, and sampling to monitor the reaction process. Then, the temperature was reduced to 50 ℃ and the reaction mixture was filtered to obtain 122.70g of a crude reaction mixture.
And (3) distilling the filtered reaction solution at 50 ℃ for 0.5 hour under the vacuum degree of-0.095 MPa, heating to 120 ℃, continuing to rectify the reaction solution under reduced pressure for 2.0 hours to obtain 26.74g of a colorless transparent product, and detecting the obtained product, wherein the epoxy equivalent is 960Gm/Eq, and the viscosity is 210mPa.s (25 ℃).
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of synthesizing an aliphatic epoxy compound, the method comprising the steps of:
mixing aliphatic olefin, a molybdenum-containing solid epoxidation catalyst and an oxidant, and reacting to prepare the aliphatic epoxy compound;
wherein by-products are continuously removed during the reaction, said by-products comprising at least by-products from the oxidizing agent; the oxidant is selected from organic hydroperoxides, and the aliphatic olefin has a boiling point higher than the boiling point of the by-product from the oxidant.
2. The process according to claim 1, wherein the organic hydroperoxide is selected from tert-butyl peroxides, such as tert-butyl hydroperoxide.
3. The method of claim 1 or 2, wherein the oxidizing agent is introduced in the form of a solution. For example, the oxidizing agent is introduced in the form of a tert-butanol solution of the oxidizing agent, in particular a tert-butanol solution of tert-butyl hydroperoxide. The concentration of the oxidizing agent in the solution is 30 to 65 wt%, preferably 45 to 55 wt%.
4. The process of any of claims 1-3, wherein when the oxidizing agent is selected from t-butyl peroxide, the byproduct from the oxidizing agent is t-butanol.
5. The method according to any one of claims 1-4, wherein the method comprises the steps of:
an aliphatic olefin having a boiling point higher than that of t-butyl alcohol, a molybdenum-containing solid epoxidation catalyst and t-butyl peroxide are mixed and reacted, and a by-product including t-butyl alcohol is continuously removed during the reaction to prepare the aliphatic epoxy compound.
6. The process of any of claims 1-5, wherein the reaction occurs without additional solvent at atmospheric pressure, i.e., the aliphatic olefin is directly converted to an aliphatic epoxy compound without additional solvent at atmospheric pressure.
7. The process according to any one of claims 1 to 6, wherein the aliphatic olefin is selected from aliphatic olefins of linear or cyclic structure of 8 or more carbon atoms containing at least one carbon-carbon double bond; for example, aliphatic olefins having a linear or cyclic structure of 8 or more carbon atoms containing at least two carbon-carbon double bonds; and further for example from aliphatic olefins of linear or cyclic structure of 8 to 24 carbon atoms containing at least two carbon-carbon double bonds; wherein the double bond may be in a linear or cyclic structure, preferably the double bond is in a cyclic structure, preferably the cyclic structure contains 4 to 7 carbon atoms (e.g. 4, 5, 6 or 7 carbon atoms).
Preferably, the olefin is selected from 3, 4-cyclohexene-1-carboxylic acid 3, 4-cyclohexen-1-ylmethyl ester or bis ((3, 4-cyclohexenyl) methyl) adipate.
8. The process according to any one of claims 1 to 7, wherein the reaction temperature is 70 to 120 ℃, preferably 80 to 110 ℃, and the by-product (e.g. t-butanol, etc.) is continuously distilled off at the corresponding temperature, and the reaction time is 1 to 2 hr.
Preferably, after the reaction is finished, a refined product can be obtained by filtration and distillation.
Preferably, the filtration mode is suction filtration and centrifugal filtration, and the filtration temperature is 60-100 ℃, preferably 70-80 ℃. Wherein the solid catalyst is removed by filtration.
Preferably, the distillation is vacuum distillation, the distillation temperature is 100-.
9. The process according to any one of claims 1 to 8, wherein the molar ratio of double bonds in the aliphatic olefin to oxidant is from 1:1 to 4, preferably from 1:1.5 to 2.5.
10. The process as claimed in any of claims 1 to 9, wherein the solid epoxidation catalyst is, for example, a solid molybdenum oxide compound or a supported molybdenum oxide compound, wherein the molybdenum has a valence of + 6. For example, the catalyst is molybdenum trioxide (MoO)3) Silica supported Mo (VI) or molecular sieve supported Mo (VI).
Preferably, the catalyst is in the form of particles having a particle size of 80-800 mesh, preferably 200-400 mesh.
Preferably, the catalyst is used in an amount of 1 to 5%, preferably 2 to 3.5%, of the total mass of the reaction system.
Preferably, the synthesis is carried out in a tank reactor or flask-type reaction apparatus.
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