CN1736996A - A kind of novel method of producing methyl hexahydrophthalic anhydride - Google Patents
A kind of novel method of producing methyl hexahydrophthalic anhydride Download PDFInfo
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- CN1736996A CN1736996A CN 200510017718 CN200510017718A CN1736996A CN 1736996 A CN1736996 A CN 1736996A CN 200510017718 CN200510017718 CN 200510017718 CN 200510017718 A CN200510017718 A CN 200510017718A CN 1736996 A CN1736996 A CN 1736996A
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- hexahydrophthalic anhydride
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Abstract
The invention discloses a kind of novel method of producing methyl hexahydrophthalic anhydride, this method is that the decylization carbon five of isoprene, m-pentadiene is raw material with cis-butenedioic anhydride and main component, in the presence of catalyzer, directly absorb isoprene, m-pentadiene generation methyl tetrahydro phthalic anhydride with cis-butenedioic anhydride, methyl tetrahydro phthalic anhydride generates methyl hexahydrophthalic anhydride through catalytic hydrogenation reaction in the presence of composite catalyst; Composite catalyst is selected high reactivity, the high-selectivity catalyst of development voluntarily for use, the reaction conditions gentleness, overcome the defective in the present methyl hexahydrophthalic anhydride production process, the selectivity of reaction is significantly improved, product yield is brought up to 90-95% from 65-75%, and temperature of reaction is reduced to 120 ℃ by 170 ℃, has reduced production cost, has reduced environmental pollution.
Description
Technical field
The present invention relates to a kind of new process for producing of Chemicals, relate in particular to a kind of new process for producing of methyl hexahydrophthalic anhydride.
Background technology
Methylhexahydrophthalic anhydride is called for short methyl hexahydrophthalic anhydride (MHHPA), is colourless transparent liquid, molecular formula C
9H
120
3, molecular weight 168.19, proportion 1.162g/cm
3, relative density d
4 251.168, flash-point 〉=160 ℃, vapour pressure 0.7kPa/127 ℃, be dissolved in benzene, toluene, acetone, tetracol phenixin, chloroform, glycol, ethyl acetate, be slightly soluble in sherwood oil.Methyl hexahydrophthalic anhydride has saturated stable six-membered ring structure, exists with liquid state again, is the important intermediate of electronic information material, medicine, agricultural chemicals, resin, national defense industry aspect.Be widely used in recent years, be mainly used in epoxy curing agent, coating, softening agent, tackiness agent, sterilant, rust-preventive agent etc.
When methyl hexahydrophthalic anhydride is used as the Resins, epoxy acid anhydride type curing agent, except that the general property with methyl tetrahydro phthalic anhydride (but purity height, lighter color, viscosity is low, volatility is little, loss on heating is little, stable performance, working life long, zero pour is low and room temperature under long-term storage etc.), also have the performance more superior: colourless transparent liquid than methyl tetrahydro phthalic anhydride, add after people's promotor except the color and luster of promotor own, basic nondiscoloration, curable epoxide thing lighter color; Excellent heat resistance, particularly under 150 ℃, the curable epoxide thing has good machinery and electrical property; Weathering resistance is outstanding, not influenced by photo-thermal, and moisture resistance is good; The reactive behavior height, gel time is short.Be used for electric and electronic applications, have that fusing point mixture viscosity low, that form with cycloaliphatic epoxy resin is low, working life characteristics such as length, cured article thermotolerance height, electrical properties in high temperatures excellence.It is specially adapted to outdoor cured article and requires anti-outdoor UV-light, product that moisture resistance is good as casting outdoor insulator, electrical condenser, photodiode and movement entertainment equipment etc. except that being applicable to methyl tetrahydro phthalic anhydride use field.
Methyl hexahydrophthalic anhydride is normally made by shortening by methyl tetrahydro phthalic anhydride, will be in the process of hydrogenation through two these links of bond activation of methyl tetrahydro phthalic anhydride, this a pair of key is easy to again shift, cause hydrogenation not thorough, generate byproduct transposition methyl tetrahydro phthalic anhydride, simultaneously under the effect of hydrogen atom, condensation also very easily takes place in acid anhydrides, hydrogenolysis, side reaction such as crosslinked grade, generation is difficult to isolating high boiling point and lower-boiling impurity, not only influence reaction conversion ratio, selectivity and yield, and high boiling point by-products produced easily coking under temperature of reaction, be adsorbed on catalyst surface, cause poisoning of catalyst.Methyl tetrahydro phthalic anhydride and isomer thereof and methyl hexahydrophthalic anhydride boiling point are approaching, and boiling point is high again, and reaction finishes the back and is difficult to effectively separate by traditional separation methods such as rectifying, has a strong impact on quality product.Therefore, the selection of reinforcement highly selective and high activated catalyst is the key of producing methyl hexahydrophthalic anhydride.
Summary of the invention
The object of the invention is to provide a kind of novel method of producing methyl hexahydrophthalic anhydride, makes reaction conversion ratio, yield and the selectivity of methyl hexahydrophthalic anhydride improve, and reduces production of by-products in the reaction process.
For realizing purpose of the present invention, technical solution of the present invention is as follows:
With cis-butenedioic anhydride and main component is that the decylization carbon five of isoprene, m-pentadiene is raw material, in the presence of catalyzer, directly absorb isoprene, m-pentadiene generation methyl tetrahydro phthalic anhydride with cis-butenedioic anhydride, methyl tetrahydro phthalic anhydride generates methyl hexahydrophthalic anhydride through catalytic hydrogenation reaction in the presence of composite catalyst.
Isoprene cis-butenedioic anhydride 4-methyl tetrahydro phthalic anhydride 4-methyl hexahydrophthalic anhydride
M-pentadiene cis-butenedioic anhydride 3-methyl tetrahydro phthalic anhydride 3-methyl hexahydrophthalic anhydride
The reaction synoptic diagram
Concrete reactions steps is as follows:
In the presence of temperature 50-120 ℃ and 0.5-3 gram catalyzer (as aluminum chloride, zinc chloride etc.), in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, generate methyl tetrahydro phthalic anhydride through Diels-Alder reaction.In the methyl tetrahydro phthalic anhydride that is generated, add skeleton nickel 1-5 gram and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymer 0.1-0.5 gram then, in temperature 100-140 ℃, the autoclave of hydrogen pressure 1-4MPa, carried out catalytic hydrogenation reaction 2-6 hour, the cooled and filtered catalyzer, underpressure distillation promptly gets methyl hexahydrophthalic anhydride, yield 90-95%.Under the similarity condition, if only nickel catalyzator is arranged, do not add two (two diphenylphosphine oxidative ethane) tetrabormated two copper polymers, reaction needs 4-5 hour, and yield is 65-75% only.
The core technology of methyl hexahydrophthalic anhydride production is a selection of catalysts, existing commercial catalyzer is all undesirable to the hydrogenation of methyl tetrahydro phthalic anhydride, through concentrating on studies for many years, we develop efficient composite catalyst, have very high activity and selectivity for hydrogenation reaction, can significantly reduce temperature of reaction, improve product yield and reduce environmental pollution.Composite hydrogenation catalyst used in the present invention is made up of skeleton nickel and two (two diphenylphosphine oxidative ethane) tetrabormated two copper polymers, oneself has applied for national inventing patent and has obtained mandate: ZL991024222, " a kind of synthetic method of copper bromide polymer and application thereof ".
The synthetic method of two (two diphenylphosphine oxidative ethane) tetrabormated two copper polymers is as follows:
Cupric bromide 2.2-6.6 gram is dissolved in the 50-80 milliliter chloroparaffin kind solvent (as methylene dichloride, trichloromethane), adds two diphenyl phosphine oxide cupric nitrate 9.8-18.9 grams, stirred 24-72 hour under the room temperature, have red powder shape material to generate.
Beneficial effect of the present invention is: decylization carbon five is ethylene by-product things of a kind of cheapness, is the feedstock production methyl hexahydrophthalic anhydride with decylization carbon five, has strengthened the deep processing and utilization to carbon five, has realistic meaning; High reactivity, the highly selective composite catalyst of development voluntarily selected in this reaction for use, the reaction conditions gentleness, environmentally friendly, overcome the defective in the present methyl hexahydrophthalic anhydride production process, the selectivity of reaction is significantly improved, and product yield is brought up to 90-95% from 65-75%, and temperature of reaction is reduced to 120 ℃ by 170 ℃, reduce production cost, reduced environmental pollution.
Description of drawings
Figure is this method process flow sheet.
Embodiment
For the present invention is described in detail better, as follows for embodiment:
Embodiment 1
In the presence of 50 ℃ of temperature and 3 gram aluminum chloride, in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, generate methyl tetrahydro phthalic anhydride through Diels-Alder reaction.In the methyl tetrahydro phthalic anhydride that is generated, add skeleton nickel 1 gram and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymers, 0.1 gram then, in the autoclave of 140 ℃ of temperature, hydrogen pressure 4MPa, carried out catalytic hydrogenation reaction 4 hours, the cooled and filtered catalyzer, underpressure distillation gets colourless liquid methyl hexahydrophthalic anhydride 152 grams, yield 90.3%.
Embodiment 2
In the presence of 80 ℃ of temperature and 1.5 gram aluminum chloride, in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, reaction generates methyl tetrahydro phthalic anhydride.In the methyl tetrahydro phthalic anhydride that is generated, add skeleton nickel 2.5 grams and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymers, 0.3 gram then, in the autoclave of 120 ℃ of temperature, hydrogen pressure 2MPa, carried out catalytic hydrogenation reaction 5 hours, the cooled and filtered catalyzer, underpressure distillation gets colourless liquid methyl hexahydrophthalic anhydride 157 grams, yield 93.3%.
Embodiment 3
In the presence of 120 ℃ of temperature and 0.5 gram zinc chloride, in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, reaction generates methyl tetrahydro phthalic anhydride.In the methyl tetrahydro phthalic anhydride that is generated, add skeleton nickel 5 grams and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymers, 0.5 gram then, in the autoclave of 100 ℃ of temperature, hydrogen pressure 1MPa, carried out catalytic hydrogenation reaction 6 hours, the cooled and filtered catalyzer, underpressure distillation gets colourless liquid methyl hexahydrophthalic anhydride 155 grams, yield 92.2%.
Embodiment 4
In the presence of 100 ℃ of temperature and 1.5 gram zinc chloride, in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, reaction generates methyl tetrahydro phthalic anhydride.In the methyl tetrahydro phthalic anhydride that is generated, add skeleton nickel 3 grams and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymers, 0.4 gram then, in the autoclave of 120 ℃ of temperature, hydrogen pressure 3MPa, carried out catalytic hydrogenation reaction 4 hours, the cooled and filtered catalyzer, underpressure distillation gets colourless liquid methyl hexahydrophthalic anhydride 159 grams, yield 94.6%.Comparative examples
In the presence of 100 ℃ of temperature and 1.5 gram zinc chloride, in 98 gram cis-butenedioic anhydrides, add decylization carbon five (its main component is isoprene and m-pentadiene) gradually, generate methyl tetrahydro phthalic anhydride through Diels-Alder reaction.In the methyl tetrahydro phthalic anhydride that is generated, only add skeleton nickel 3 grams then, in the autoclave of 120 ℃ of temperature, hydrogen pressure 3MPa, carried out catalytic hydrogenation reaction 4 hours, cooled and filtered catalyzer, underpressure distillation get little yellow liquid methyl hexahydrophthalic anhydride 118 grams, yield 70.3%.
Claims (2)
1, a kind of novel method of producing methyl hexahydrophthalic anhydride, it is characterized in that, with cis-butenedioic anhydride and main component is that the decylization carbon five of isoprene, m-pentadiene is raw material, in the presence of catalyzer such as aluminum chloride or zinc chloride, under 50-120 ℃ of temperature, directly absorb isoprene, m-pentadiene with cis-butenedioic anhydride, reaction generates methyl tetrahydro phthalic anhydride, add composite hydrogenation catalyst then, under temperature 100-140 ℃, hydrogen pressure 1-4Mpa, carried out catalytic hydrogenation reaction 2-6 hour, after filtration, underpressure distillation obtains methyl hexahydrophthalic anhydride.
2, the novel method of production methyl hexahydrophthalic anhydride as claimed in claim 1, it is characterized in that, when carrying out catalytic hydrogenation reaction by cis-butenedioic anhydride and the resulting methyl tetrahydro phthalic anhydride of decylization carbon five reactions, the composition of the composite hydrogenation catalyst that is added and consumption are: with respect to per 98 gram raw material cis-butenedioic anhydrides, need to add skeleton nickel 1～5 gram and two (two diphenylphosphine oxidative ethane) tetrabormated, two copper polymers, 0.1～0.5 gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100177182A CN1313456C (en) | 2005-06-22 | 2005-06-22 | Novel method for producing methyl hexahydrobenzene anhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100177182A CN1313456C (en) | 2005-06-22 | 2005-06-22 | Novel method for producing methyl hexahydrobenzene anhydride |
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|---|---|
| CN1736996A true CN1736996A (en) | 2006-02-22 |
| CN1313456C CN1313456C (en) | 2007-05-02 |
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|---|---|---|---|
| CNB2005100177182A Expired - Fee Related CN1313456C (en) | 2005-06-22 | 2005-06-22 | Novel method for producing methyl hexahydrobenzene anhydride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977061A (en) * | 2012-12-11 | 2013-03-20 | 南通市福来特化工有限公司 | Method for producing liquid methylhexahydrophthalic anhydride |
| CN104650019A (en) * | 2013-11-15 | 2015-05-27 | 嘉兴市南洋塑料化工有限公司 | New preparation process of raw materials for producing methyl tetrahydrophthalic anhydride |
| CN109225227A (en) * | 2018-09-12 | 2019-01-18 | 濮阳市盛源能源科技股份有限公司 | A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW475926B (en) * | 1996-06-06 | 2002-02-11 | Sumitomo Chemical Co | Novel ester compound and thermosetting resin composition using the same |
| JPH10212285A (en) * | 1997-01-30 | 1998-08-11 | Yuka Shell Epoxy Kk | Production of carboxylic anhydride |
| CN1117115C (en) * | 1999-02-10 | 2003-08-06 | 河南省科学院化学研究所 | Copper bromide polymer, its synthesis method and its application |
-
2005
- 2005-06-22 CN CNB2005100177182A patent/CN1313456C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977061A (en) * | 2012-12-11 | 2013-03-20 | 南通市福来特化工有限公司 | Method for producing liquid methylhexahydrophthalic anhydride |
| CN104650019A (en) * | 2013-11-15 | 2015-05-27 | 嘉兴市南洋塑料化工有限公司 | New preparation process of raw materials for producing methyl tetrahydrophthalic anhydride |
| CN109225227A (en) * | 2018-09-12 | 2019-01-18 | 濮阳市盛源能源科技股份有限公司 | A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride |
| CN109225227B (en) * | 2018-09-12 | 2021-08-31 | 濮阳市盛源能源科技股份有限公司 | Ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and preparation method thereof |
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| CN1313456C (en) | 2007-05-02 |
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