CN109384757A - A kind of high-purity 3- methyl tetrahydro phthalic anhydride and preparation method thereof - Google Patents
A kind of high-purity 3- methyl tetrahydro phthalic anhydride and preparation method thereof Download PDFInfo
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- CN109384757A CN109384757A CN201811613472.9A CN201811613472A CN109384757A CN 109384757 A CN109384757 A CN 109384757A CN 201811613472 A CN201811613472 A CN 201811613472A CN 109384757 A CN109384757 A CN 109384757A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The present invention provides a kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: (1) C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride, is dripped off latter insulation reaction 50-90 minutes；The C5 hydrocarbon reaction liquid includes the trans-m-pentadiene for including 40-50 parts, 25-35 parts of cis-form m-pentadiene, 20-30 parts of cyclopentene, 5-15 parts of pentamethylene according to mass parts according to mass percent C5 hydrocarbon reaction liquid；(2) crystallisation by cooling filters, and drying obtains high-purity 3- methyl tetrahydro phthalic anhydride.C5 hydrocarbon reaction liquid can also include the hydro carbons of other C5.The present invention uses crystallization and purification 3- methyl tetrahydro phthalic anhydride, and unconventional distillation, the 3- methyl tetrahydro phthalic anhydride isomers for having the advantages that (1) obtains are few, and purity is high, content is up to 99% (mass fraction).(2) it does not need to distill product, low energy consumption for production process, and generates without residue, pollutes small.
Description
Technical field
The present invention relates to a kind of preparation methods and preparation method thereof of high-purity 3- methyl tetrahydro phthalic anhydride, belong to methyl tetrahydro
Phthalic anhydride technical field.
Background technique
Methyl tetrahydro phthalic anhydride is a kind of novel organic acid anhydride based epoxy resin curing agent of function admirable, is electronic information material
Important intermediate in terms of material, medicine, pesticide, resin, national defense industry, while can also be used in the row of coating, plasticizer, pesticide
Industry.Since acid anhydride type curing agent has better heat-resisting, chemical-resistant stability compared with amine curing agent, and remain at relatively high temperatures
Keep excellent physically and electrically performance.In recent years, as motor, electronics, electrical apparatus industry are to insulation performance and reliability requirement
Continuous improvement, the application development of such curing agent is rapid, have preferable market prospects.
Methyl tetrahydro phthalic anhydride has two kinds of structures of 3- methyl tetrahydro phthalic anhydride and 4- methyl tetrahydro phthalic anhydride, usually in use, to make
With conveniently, will use the two and the mixture of their isomers, to be maintained under room temperature even low temperature still for liquid.But at certain
In a little special applications, especially using methyl tetrahydro phthalic anhydride as when synthesis material, very high purity is needed.Wherein 3- methyl
The synthetic method of tetrahydrophthalic anhydride routine is that pentadiene is reacted with cis-butenedioic anhydride, then obtains methyl tetrahydro phthalic anhydride by distilation,
The purity of the 3- methyl tetrahydro phthalic anhydride obtained in this way is lower, generally in the 4- methyl tetrahydro phthalic anhydride of 90% or so and 1-2%,
Remaining is essentially a variety of isomers of 3- methyl tetrahydro phthalic anhydride.
Summary of the invention
The present invention in view of the deficienciess of the prior art, provide a kind of high-purity 3- methyl tetrahydro phthalic anhydride preparation method and
Preparation method is low with the 3- methyl tetrahydro phthalic anhydride purity for solving the problems, such as that existing preparation method of purification obtains.
The technical scheme to solve the above technical problems is that a kind of preparation side of high-purity 3- methyl tetrahydro phthalic anhydride
Method, comprising the following steps: (1) C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride, is dripped off latter insulation reaction 50-90 minutes；It is described
C5 hydrocarbon reaction liquid includes 40-50 parts of trans-m-pentadiene, 25-35 parts of cis-form m-pentadiene, 20- according to mass percent
30 parts of cyclopentene, 5-15 parts of pentamethylene, trans-m-pentadiene therein participate in reaction, are left cis-form m-pentadiene, ring penta
Alkene and pentamethylene are not involved in reaction；(2) crystallisation by cooling filters, and drying obtains high-purity 3- methyl tetrahydro phthalic anhydride.C5 hydro carbons is anti-
Answering liquid can also include the hydro carbons of other C5 of 1-5 mass parts.
The present invention is further arranged to, and the cis-butenedioic anhydride is molten condition or is dissolved in solvent A.
Preferably, the melting temperature is 60 DEG C or so, because 62 DEG C of four fusing point of 3- first, can melt when greater than fusing point.
The present invention is further arranged to, and the cooling velocity of crystallization process is 1-50 DEG C/h.
The present invention is further arranged to, and crystallisation by cooling is to 0-30 DEG C.
The present invention is further arranged to, the solvent A be one of hydro carbons, aromatic hydrocarbons, halogenated hydrocarbons, ketone or ether substance or
The mixture of many kinds of substance.
Preferably, it is most economical that the solvent, which is the component do not reacted with cis-butenedioic anhydride such as cis-form m-pentadiene as recrystallisation solvent,
's.
The present invention is further arranged to, and mixture made from step (1) is evaporated solvent therein, and solvent A is added, then
Carry out the operation of step (2).
Preferably, the condition of evaporation is 60-90 DEG C of temperature, pressure -0.05Mpa-0Mpa.
The present invention is further arranged to, and the drying is to dry in room temperature into 60 DEG C of clean vacuum environments.
The present invention is further arranged to, and the temperature of the insulation reaction is 0-100 DEG C, and the pressure of insulation reaction is 0-
1MPa, lower reaction temperature is advantageously.
It is a further object to provide utilize high-purity 3- methyl tetrahydro phthalic anhydride made from the above method.
In the preparation process in accordance with the present invention, to solvent for the use of it should pay attention to two, first is that can be used in reaction process
Solvent does not use solvent, and difference is in reaction temperature, and when not using solvent, reaction temperature need to be greater than the fusing point of cis-butenedioic anhydride；Using molten
The temperature range of agent is bigger.Second is that must have solvent in crystallization process, it can be again using not anti-with cis-butenedioic anhydride in C5 hydrocarbon reaction liquid
The component answered such as cis-form m-pentadiene, cyclopentene, pentamethylene and other hydro carbons, can also rejoin solvent A, use solvent A
Before can choose and boil off the component that do not react with cis-butenedioic anhydride in C5 hydrocarbon reaction liquid or do not boil off.
In conclusion the present invention uses crystallization and purification 3- methyl tetrahydro phthalic anhydride, and unconventional distillation has beneficial below
Effect:
(1) obtained 3- methyl tetrahydro phthalic anhydride isomers produced by the present invention is few, purity is high, the 3- first of obtained non-isomery
The content of base tetrahydrophthalic anhydride up to 99% (mass fraction) more than.
(2) preparation method of the invention does not need to distill product, and low energy consumption for production process, and generates without residue, dirty
It contaminates small.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: cis-butenedioic anhydride is melted, C5 hydro carbons is anti-
Liquid is answered to be slowly dropped into cis-butenedioic anhydride melt, at 100 DEG C after dripping off, 0.7MPa is carried out insulation reaction 50 minutes, with cooling velocity for 2
DEG C/h carry out crystallisation by cooling, until 30 DEG C, filtering, dried in 50 DEG C of clean environments.C5 hydrocarbon reaction liquid is according to mass parts
Including the trans-m-pentadiene including 40-50 parts, 28 parts of cis-form m-pentadiene, 25 parts of cyclopentene, 14 parts of pentamethylene.?
To high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.4%.
Embodiment 2
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: slowly drip C5 hydrocarbon reaction liquid
Enter in the cis-butenedioic anhydride of molten condition, at 50 DEG C after dripping off, 0.1MPa is carried out insulation reaction 60 minutes, with cooling velocity be 25 DEG C/
Hour carries out crystallisation by cooling, and until 25 DEG C, filtering is dried in 40 DEG C of clean environments.C5 hydrocarbon reaction liquid is according to mass parts packet
Include the trans-m-pentadiene including 50 parts, 30 parts of cis-form m-pentadiene, 20 parts of cyclopentene, 6 parts of pentamethylene.It obtains high-purity
Spend 3- methyl tetrahydro phthalic anhydride, purity 99.5%.
Embodiment 3
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: cis-butenedioic anhydride is added in toluene solution, is added
C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution by hot mixing solution, and at 0 DEG C after dripping off, insulation reaction 90 is carried out under normal pressure
Minute, at 80 DEG C, solvent is boiled off under the conditions of -0.02Mpa, adds toluene solvant crystallisation by cooling, is dried in 60 DEG C of clean environments
It is dry.C5 hydrocarbon reaction liquid includes the trans-m-pentadiene for including 40 parts according to mass parts, 35 parts of cis-form m-pentadiene, 30 parts
Cyclopentene, 15 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.6%.
Embodiment 4
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: cis-butenedioic anhydride will be added in chloroformic solution,
Mixed solution is heated, C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution, at 70 DEG C after dripping off, 0.1MPa carries out insulation reaction
70 minutes, at 6 DEG C, solvent is boiled off under the conditions of -0.05Mpa, adds chloroform solvent crystallisation by cooling, is dried in 35 DEG C of clean environments
It is dry.C5 hydrocarbon reaction liquid includes the trans-m-pentadiene for including 43 parts according to mass parts, 25 parts of cis-form m-pentadiene, 22 parts
Cyclopentene, 11 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.4%.
Embodiment 5
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: cis-butenedioic anhydride is added in acetone soln, is added
C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution by hot mixing solution, and at 80 DEG C after dripping off, 0.4MPa carries out insulation reaction 80
Minute, at 90 DEG C, solvent is boiled off under the conditions of 0Mpa, adds acetone solvent crystallisation by cooling, is dried in 40 DEG C of clean environments.C5
Hydrocarbon reaction liquid includes the trans-m-pentadiene for including 46 parts, 30 parts of cis-form m-pentadiene, 28 parts of ring penta according to mass parts
Alkene, 5 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.5%.
Embodiment 6
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: cis-butenedioic anhydride is added in diethyl ether solution, is added
C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution by hot mixing solution, and at 40 DEG C after dripping off, 0.6MPa carries out insulation reaction 60
Minute, with cooling velocity for 20 DEG C/h of progress crystallisation by cooling, until 10 DEG C, filtering is dried in 60 DEG C of clean environments.C5
Hydrocarbon reaction liquid includes the trans-m-pentadiene for including 42 parts, 35 parts of cis-form m-pentadiene, 27 parts of ring penta according to mass parts
Alkene, 15 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.8%.
Embodiment 7
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: by the mixed of pentane and 2- N-Propyl Bromide
It closes solution to be added in cis-butenedioic anhydride, heats mixed solution, C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution, at 30 DEG C after dripping off,
0.8MPa is carried out insulation reaction 55 minutes, with cooling velocity for 10 DEG C/h of progress crystallisation by cooling, until 25 DEG C, and filtering, 55
It is dried in DEG C clean environment.C5 hydrocarbon reaction liquid includes the trans-m-pentadiene for including 40 parts according to mass parts, 26 parts cis-
Pentadiene, 30 parts of cyclopentene, 7 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.5%.
Embodiment 8
A kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, comprising the following steps: by methyl ethyl ketone and tert-butyl
Cis-butenedioic anhydride is added in the mixed solution of methyl ether, heats mixed solution, C5 hydrocarbon reaction liquid is slowly dropped into cis-butenedioic anhydride solution, after dripping off
At 20 DEG C, 1MPa is carried out insulation reaction 65 minutes, with cooling velocity for 1 DEG C/h of progress crystallisation by cooling, until 30 DEG C, and filtering,
It is dried in 58 DEG C of clean environments.C5 hydrocarbon reaction liquid includes the trans-m-pentadiene for including 50 parts according to mass parts, 25 parts
Cis-form m-pentadiene, 21 parts of cyclopentene, 10 parts of pentamethylene.Obtain high-purity 3- methyl tetrahydro phthalic anhydride, purity 99.2%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high-purity 3- methyl tetrahydro phthalic anhydride, which comprises the following steps: (1) by C5 hydro carbons
Reaction solution is slowly dropped into cis-butenedioic anhydride, is dripped off latter insulation reaction 50-90 minutes；The C5 hydrocarbon reaction liquid includes according to mass parts
40-50 parts of trans-m-pentadiene, 25-35 parts of cis-form m-pentadiene, 20-30 parts of cyclopentene, 5-15 parts of pentamethylene；
(2) crystallisation by cooling filters, and drying obtains high-purity 3- methyl tetrahydro phthalic anhydride.
2. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 1, which is characterized in that the cis-butenedioic anhydride is
Molten condition is dissolved in solvent A.
3. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 1, which is characterized in that crystallization process
Cooling velocity be 1-50 DEG C/h.
4. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 1, which is characterized in that crystallisation by cooling is extremely
0-30℃。
5. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 2, which is characterized in that the solvent A
For one of hydro carbons, aromatic hydrocarbons, halogenated hydrocarbons, ketone or ether substance or the mixture of many kinds of substance.
6. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 2, which is characterized in that by step (1)
Mixture obtained evaporates solvent therein, solvent A is added, then carry out the operation of step (2).
7. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 6, which is characterized in that the condition of evaporation
It is 60-90 DEG C of temperature, pressure -0.05Mpa-0Mpa.
8. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 1, which is characterized in that the drying is
It is dried in room temperature into 60 DEG C of clean vacuum environments.
9. the preparation method of high-purity 3- methyl tetrahydro phthalic anhydride according to claim 1, which is characterized in that the heat preservation is anti-
The temperature answered is 0-100 DEG C, and the pressure of insulation reaction is 0-1MPa.
10. high-purity 3- methyl tetrahydro phthalic anhydride made from a kind of any one of -9 the methods according to claim 1.
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| CN201811613472.9A CN109384757A (en) | 2018-12-27 | 2018-12-27 | A kind of high-purity 3- methyl tetrahydro phthalic anhydride and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574149A (en) * | 2021-01-11 | 2021-03-30 | 浙江阿尔法化工科技有限公司 | Method for polymerizing methyl tetrahydrophthalic anhydride or tetrahydrophthalic anhydride and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977060A (en) * | 2012-12-11 | 2013-03-20 | 南通市福来特化工有限公司 | Method for producing liquid methyl tetrahydrophthalic anhydride |
| CN112574149A (en) * | 2021-01-11 | 2021-03-30 | 浙江阿尔法化工科技有限公司 | Method for polymerizing methyl tetrahydrophthalic anhydride or tetrahydrophthalic anhydride and application |
-
2018
- 2018-12-27 CN CN201811613472.9A patent/CN109384757A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977060A (en) * | 2012-12-11 | 2013-03-20 | 南通市福来特化工有限公司 | Method for producing liquid methyl tetrahydrophthalic anhydride |
| CN112574149A (en) * | 2021-01-11 | 2021-03-30 | 浙江阿尔法化工科技有限公司 | Method for polymerizing methyl tetrahydrophthalic anhydride or tetrahydrophthalic anhydride and application |
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| AUTHOR ZHONG, HUA M.; RAWAL, VIRESH H.: "1,3-Pentadiene", 《E-EROS ENCYCLOPEDIA OF REAGENTS FOR ORGANIC SYNTHESIS》 * |
| 张举明等: "甲基四氢苯酐合成工艺的研究", 《化工时刊》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112574149A (en) * | 2021-01-11 | 2021-03-30 | 浙江阿尔法化工科技有限公司 | Method for polymerizing methyl tetrahydrophthalic anhydride or tetrahydrophthalic anhydride and application |
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