CN1297551C - New process for producing liquid methyl tetrahydro phthalic anhydride - Google Patents
New process for producing liquid methyl tetrahydro phthalic anhydride Download PDFInfo
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- CN1297551C CN1297551C CNB2005100174112A CN200510017411A CN1297551C CN 1297551 C CN1297551 C CN 1297551C CN B2005100174112 A CNB2005100174112 A CN B2005100174112A CN 200510017411 A CN200510017411 A CN 200510017411A CN 1297551 C CN1297551 C CN 1297551C
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- Prior art keywords
- phthalic anhydride
- acid
- methyl tetrahydro
- tetrahydro phthalic
- tetrahydrophthalic anhydride
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Abstract
The present invention discloses a novel method for producing liquid methyl tetrahydrophthalic anhydride, which comprises the following steps: rough methyl tetrahydrophthalic anhydride which is produced by the reaction of solid methyl tetrahydrophthalic anhydride or mixed pentose with cis-butenedioic anhydride is used as raw material, and isomerization reaction is carried out for 1 to 5 hours at the temperature of 130 DEG C to 160 DEG C in the presence of acid isomerization catalysts; alkalescent compounds which have same quantity with the acid catalysts are subsequently added, and the reaction continues for 15 to 30 minutes; then, decompression distillation is carried out to obtain liquid methyl tetrahydrophthalic anhydride. The solidifying point, the stability, the viscosity, the chroma and other indexes of the liquid methyl tetrahydrophthalic anhydride which is produced by the method meet the levels of the products of the same class abroad.
Description
Technical field
The present invention relates to a kind of novel method of producing methyl tetrahydro phthalic anhydride, relate in particular to a kind of novel method of producing liquid methyl tetrahydro phthalic anhydride.
Background technology
Liquid methyl tetrahydro phthalic anhydride is the good solidifying agent of Resins, epoxy, it has characteristics such as low melting point, low toxicity, low volatility, and is easy to use, with the reactive behavior height of Resins, epoxy, compatibility is good, uses the electrical insulation properties and the mechanical property of epoxy resin cured product of this solidifying agent good.In recent years, along with motor, electronics, electrical apparatus industry improve constantly the insulating property reliability requirement, the application development of such solidifying agent is rapid, has market outlook preferably.But the home-made liquid methyl tetrahydro phthalic anhydride is compared with the like product of import, is still existing bigger gap qualitatively, is presented as that mainly color is dark, viscosity big, poor stability.
At present, relevant bibliographical information the production method of liquid methyl tetrahydro phthalic anhydride, be raw material with the solid methyl tetrahydro phthalic anhydride usually, in the presence of certain temperature and catalyzer, carry out isomerization reaction, form the eutectic system of several isomer,, obtain liquid methyl tetrahydro phthalic anhydride through underpressure distillation.The isomerization catalyst that is adopted is generally acidic cpd.Owing to need to distill after the isomerization reaction, and still-process still need keep comparatively high temps and long period, therefore isomerization reaction and side reaction are still among proceeding, and along with the product that steams is many more, catalyst concn in the remaining part is increasing, cause decomposition, polymerization and the carbonization of product more remarkable, have a strong impact on the stability and the yield of product, color also can be deepened.
Summary of the invention
The object of the invention is to provide a kind of novel method of producing liquid methyl tetrahydro phthalic anhydride, and the yield increase of product, stable raising, viscosity and colourity are reduced.
In order to realize the object of the invention, technical solution of the present invention is as follows:
The present invention is raw material with solid methyl tetrahydro phthalic anhydride or mixing carbon five with the thick methyl tetrahydro phthalic anhydride that the cis-butenedioic anhydride reaction generates, in the presence of the heterogeneous acidic catalyzer, carried out isomerization reaction 1～5 hour in 130～160 ℃, add alkaline compound again with an acidic catalyst equivalent, continue reaction 15～30 minutes, underpressure distillation then obtains liquid methyl tetrahydro phthalic anhydride.Key problem in technology is after isomerization reaction, before the underpressure distillation, in system, add an amount of alkaline compound, make it to generate inert substance, thereby stop proceeding of isomerization reaction and side reaction, quality raising, the yield of product are increased with catalyst reaction.
The isomerization catalyst that adopts in this reaction is that following compounds is wherein a kind of: phosphoric acid, sulfuric acid, Phenylsulfonic acid, alkyl benzene sulphonate (ABS), a benzene trisulfonic acid, naphthene sulfonic acid, Vanadium Pentoxide in FLAKES, aluminum chloride, zinc chloride etc.
The alkaline compound that adopts in this reaction is that following compounds is wherein a kind of: sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Sodium Benzoate, carbonatoms are 2～20 the straight chain and sodium salt, sylvite and the calcium salt etc. of branched chain type lipid acid.
Beneficial effect of the present invention is: the liquid methyl tetrahydro phthalic anhydride zero pour that makes with this method is below-15 ℃, and can keep stable for a long time, viscosity is lower than 50mPas (25 ℃), colourity is lower than 160 (platinum-cobalt look number), reach external like product level, improved the liquid methyl tetrahydro phthalic anhydride product yield simultaneously.The present invention helps to promote the competitive power of homemade liquid methyl tetrahydro phthalic anhydride in the world market.
The tool present embodiment
For the present invention is described in detail better, it is as follows to give an actual example:
Embodiment 1
In the 250ml there-necked flask, add solid methyl tetrahydro phthalic anhydride 100g, after the heat fused, add vitriol oil 2.0g, be warming up to 130 ℃, stirring reaction 5 hours adds Calcium hydrogen carbonate 4.1g again, continued stirring reaction 15 minutes, and carried out underpressure distillation then, the stable cut of boiling point in the middle of collecting.Product yield 90.4%, colourity 140 (platinum-cobalt look number), viscosity 41mPas (25 ℃) ,-15 ℃ place 15 days after no crystallization or curing phenomenon.
Embodiment 2
In the 250ml there-necked flask, add solid methyl tetrahydro phthalic anhydride 100g, after the heat fused, add phosphoric acid 0.5g, be warming up to 160 ℃, stirring reaction 3 hours adds sodium stearate 3.1g again, continued stirring reaction 15 minutes, and carried out underpressure distillation then, the stable cut of boiling point in the middle of collecting.Product yield 91.8%, colourity 120 (platinum-cobalt look number), viscosity 37mPas (25 ℃) ,-15 ℃ place 15 days after no crystallization or curing phenomenon.
Embodiment 3
In the 250ml there-necked flask, add cis-butenedioic anhydride 59g, after the heat fused, mix carbon five to wherein adding, react and heat release, keeping temperature of reaction is 80～90 ℃, and low boilers was removed in decompression after reaction finished, and added tosic acid 1.5g, be warming up to 150 ℃, stirring reaction 1 hour adds Sodium Benzoate 1.1g again, continues stirring reaction 30 minutes, carry out underpressure distillation then, the stable cut of boiling point in the middle of collecting.Product yield 88.5%, colourity 140 (platinum-cobalt look number), viscosity 43mPas (25 ℃) ,-15 ℃ place 15 days after no crystallization or curing phenomenon.
Claims (3)
1, a kind of method of producing the liquid tetrahydrophthalic anhydride, it is characterized in that, is raw material with solid methyl tetrahydro phthalic anhydride or mixing carbon five with the thick methyl tetrahydro phthalic anhydride that the cis-butenedioic anhydride reaction generates, in the presence of the heterogeneous acidic catalyzer, carry out isomerization reaction in 130～160 ℃, react after 1～5 hour, add alkaline compound with an acidic catalyst equivalent, continue reaction 15～30 minutes, underpressure distillation then obtains the liquid methyl tetrahydro phthalic anhydride product.
2, the method for production liquid tetrahydrophthalic anhydride as claimed in claim 1, it is characterized in that the heterogeneous acidic catalyzer that is adopted is that following compounds is wherein a kind of: phosphoric acid, sulfuric acid, Phenylsulfonic acid, alkyl benzene sulphonate (ABS), a benzene trisulfonic acid, naphthene sulfonic acid, Vanadium Pentoxide in FLAKES, aluminum chloride, zinc chloride.
3, the method for production liquid tetrahydrophthalic anhydride as claimed in claim 1, it is characterized in that, the alkaline compound that is added before the distillation is that following compounds is wherein a kind of: sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Sodium Benzoate, carbonatoms are 2～20 the straight chain and sodium salt, sylvite and the calcium salt of branched chain type lipid acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100174112A CN1297551C (en) | 2005-03-11 | 2005-03-11 | New process for producing liquid methyl tetrahydro phthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100174112A CN1297551C (en) | 2005-03-11 | 2005-03-11 | New process for producing liquid methyl tetrahydro phthalic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1683353A CN1683353A (en) | 2005-10-19 |
| CN1297551C true CN1297551C (en) | 2007-01-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100174112A Expired - Fee Related CN1297551C (en) | 2005-03-11 | 2005-03-11 | New process for producing liquid methyl tetrahydro phthalic anhydride |
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| CN (1) | CN1297551C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284825B (en) * | 2008-06-03 | 2010-08-04 | 河南省科学院化学研究所有限公司 | Synthetic method of tetramethylene maleic anhydride |
| KR101301885B1 (en) * | 2009-07-27 | 2013-08-29 | 후지쯔 가부시끼가이샤 | Node device, storage medium, and method for transmitting frame |
| 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 |
| CN109824639B (en) * | 2019-03-04 | 2022-12-02 | 嘉兴南洋万事兴化工有限公司 | Methyl tetrahydrophthalic anhydride and preparation method thereof |
| CN110256387B (en) * | 2019-06-28 | 2020-06-30 | 南京欣久医药科技有限公司 | Preparation method of medical intermediate |
| CN112661735B (en) * | 2021-01-15 | 2023-12-22 | 浙江正大新材料科技股份有限公司 | Continuous production system and method for methyltetrahydrophthalic anhydride |
| CN115043805B (en) * | 2022-06-07 | 2023-07-28 | 嘉兴学院 | Method for preparing liquid methyl tetrahydrophthalic anhydride by isomerization catalysis |
| CN115385881B (en) * | 2022-10-27 | 2023-01-31 | 淄博鲁华泓锦新材料集团股份有限公司 | Continuous production method suitable for isomerization of methyl tetrahydrophthalic anhydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0272A (en) * | 1987-10-27 | 1990-01-05 | Agfa Gevaert Nv | Pre-sensitized image forming material ideal for use as lithographic plate |
| JPH02292275A (en) * | 1989-05-08 | 1990-12-03 | Hitachi Chem Co Ltd | Production of acid anhydride mixture and epoxy resin hardener |
| JPH02292274A (en) * | 1989-05-08 | 1990-12-03 | Hitachi Chem Co Ltd | Production of acid anhydride mixture and epoxy resin hardener |
-
2005
- 2005-03-11 CN CNB2005100174112A patent/CN1297551C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0272A (en) * | 1987-10-27 | 1990-01-05 | Agfa Gevaert Nv | Pre-sensitized image forming material ideal for use as lithographic plate |
| JPH02292275A (en) * | 1989-05-08 | 1990-12-03 | Hitachi Chem Co Ltd | Production of acid anhydride mixture and epoxy resin hardener |
| JPH02292274A (en) * | 1989-05-08 | 1990-12-03 | Hitachi Chem Co Ltd | Production of acid anhydride mixture and epoxy resin hardener |
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| CN1683353A (en) | 2005-10-19 |
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