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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- CN
- China
- Prior art keywords
- reaction
- anhydride
- acid
- producing liquid
- tetrahydrophthalic anhydride
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- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000007514 bases Chemical class 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- IZPNTDOWOBGHEG-UHFFFAOYSA-M sodium benzene formate Chemical compound [Na+].[O-]C=O.C1=CC=CC=C1 IZPNTDOWOBGHEG-UHFFFAOYSA-M 0.000 claims 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 6
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MHWVMMHIJHHXQP-UHFFFAOYSA-N benzene-1,2,3-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1S(O)(=O)=O MHWVMMHIJHHXQP-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Furan Compounds (AREA)
Abstract
本发明公开了一种生产液体甲基四氢苯酐的新方法，通过如下方法实现：以固体甲基四氢苯酐或混合碳五与顺酐反应生成的粗甲基四氢苯酐为原料，在酸性异构化催化剂的存在下，于130～160℃进行异构化反应1～5小时，再加入与酸性催化剂等当量的弱碱性化合物，继续反应15～30分钟，然后减压蒸馏，得到液体甲基四氢苯酐。用该方法生产的液体甲基四氢苯酐凝固点、稳定性、粘度、色度等指标达到国外同类产品水平。The invention discloses a new method for producing liquid methyltetrahydrophthalic anhydride, which is realized by the following method: using solid methyltetrahydrophthalic anhydride or crude methyltetrahydrophthalic anhydride produced by the reaction of mixed carbon five and maleic anhydride as raw material, In the presence of an isomerization catalyst, carry out isomerization reaction at 130-160°C for 1-5 hours, then add a weakly basic compound equivalent to the acidic catalyst, continue the reaction for 15-30 minutes, and then distill under reduced pressure to obtain a liquid Methyltetrahydrophthalic anhydride. The freezing point, stability, viscosity, chromaticity and other indicators of liquid methyl tetrahydrophthalic anhydride produced by this method have reached the level of similar foreign products.
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)
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 |
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| 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 |
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| Publication Number | Publication Date |
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| 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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Families Citing this family (9)
| 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 | The 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 | A kind of method for preparing liquid methyltetrahydrophthalic 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 |
| CN117865915A (en) * | 2023-12-19 | 2024-04-12 | 浙江皇马科技股份有限公司 | A kind of synthetic method of liquid methyltetrahydrophthalic anhydride |
Citations (4)
| 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 |
| JPH0232072A (en) * | 1988-07-22 | 1990-02-01 | Tonen Corp | Steric isomerization of methyl-delta-4-tetrahydrophthalic anhydride |
| 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 (4)
| 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 |
| JPH0232072A (en) * | 1988-07-22 | 1990-02-01 | Tonen Corp | Steric isomerization of methyl-delta-4-tetrahydrophthalic anhydride |
| 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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| Publication number | Publication date |
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| CN1683353A (en) | 2005-10-19 |
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