CN101284825B - Synthetic method of tetramethylene maleic anhydride - Google Patents
Synthetic method of tetramethylene maleic anhydride Download PDFInfo
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- CN101284825B CN101284825B CN2008100499527A CN200810049952A CN101284825B CN 101284825 B CN101284825 B CN 101284825B CN 2008100499527 A CN2008100499527 A CN 2008100499527A CN 200810049952 A CN200810049952 A CN 200810049952A CN 101284825 B CN101284825 B CN 101284825B
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Abstract
The invention belongs to the organic chemistry synthetic field, and in particular discloses a novel method for producing tetramethyle maleic anhydride which is realized through the following steps: butadiene and maleic anhydride are taken as raw materials; a diene addition reaction and an isomerization reaction are synchronously performed, under the existence of composite polymerization retarder consisting of p-hydroxyanisole, tetrachlorobenzoquinone, triphenyl phosphate and 4-tert-butyl catechol as well as composite isomerization catalyst consisting of phosphorus pentoxide, phosphoric acid, concentrated sulfuric acid and polyphosphate, to directly produce the tetramethyle maleic anhydride. Compared with the prior art, the tetramethyle maleic anhydride produced by the method has excellent performance indexes and single composition, improves the yield of the tetramethyle maleic anhydride product at the same time, decreases the production cost, and has popularization and application value.
Description
Technical field
The invention belongs to the synthetic field of organic chemistry, be specifically related to a kind of new synthetic method of tetramethylene maleic anhydride.
Background technology
Tetramethylene maleic anhydride, promptly 3,4,5, the 6-tetrahydronaphthalic anhydride is a kind of important chemical product, has been widely used, can be used as epoxy curing agent, also can be used for softening agent, Synolac, unsaturated polyester resin and tensio-active agent, wetting agent, emulsifying agent, weedicide, plant growth inhibitor, sterilant, sterilant, insect-proof agent, fibre finish, lubricating oil additive etc.
Tetrahydrophthalic anhydride is owing to the difference of position of double bond has four kinds of isomer, and tetramethylene maleic anhydride is meant Δ 1-tetrahydrophthalic anhydride, and is as shown below:
Δ 1-tetrahydrophthalic anhydride Δ 2-tetrahydrophthalic anhydride Δ 3-tetrahydrophthalic anhydride Δ 4-tetrahydrophthalic anhydride
104 ℃ of 59 ℃ of fusing points of 79 ℃ of fusing points of 74 ℃ of fusing points of fusing point
At present, tetramethylene maleic anhydride synthetic is that the diene addition reaction by 1,3-butadiene and cis-butenedioic anhydride obtains Δ 4-tetrahydrophthalic anhydride, obtains through catalytic isomerization again, and be as shown below:
This is reflected under 50 ℃-100 ℃ and the normal pressure and carries out, but very easily follows side reaction such as olefinic polymerization, and this yield for product, purity and exterior quality etc. all cause very adverse influence.Reduce temperature of reaction and can reduce the generation of side reaction, but the organic solvent that at this moment needs to add capacity goes out difficulty to prevent product crystallization on reactor wall otherwise reaction generates hot type, and raw material wrapped up by product, reaction is carried out not exclusively.The use of organic solvent can reduce yield undoubtedly, increase and pollute, and used organic solvent is generally benzene, dimethylbenzene is noxious solvent.Nonetheless, product still needs to be further purified the requirement that just can reach quality standards.Most importantly the product of producing at present all is its mixtures, it is applied be subjected to a certain degree limiting.Tetramethylene maleic anhydride is used as raw materials such as agricultural chemicals, require it to have characteristics such as purity height, composition are single, stable and just can reach result of use preferably, tetramethylene maleic anhydride is particularly important to synthesizing of novel agrochemical.We have invented the novel method of the synthetic tetramethylene maleic anhydride of a kind of orientation for this reason, synthesize the tetramethylene maleic anhydride of single component.
Summary of the invention
The object of the invention is to provide the novel method of the synthetic single tetramethylene maleic anhydride of composition of a kind of orientation.
In order to realize the object of the invention, technical solution of the present invention is as follows:
This method is that the starting raw material reaction makes the solid tetrahydrophthalic anhydride with divinyl and cis-butenedioic anhydride, utilizes tetrahydrophthalic anhydride can be isomerizated into this character of tetramethylene maleic anhydride under certain condition again, explores the novel method that two steps, one still is produced tetramethylene maleic anhydride.
Concrete reactions steps is as follows: (1) is heated to fusing with cis-butenedioic anhydride, opens and stirs, and adds stopper and isomerization catalyst, and divinyl is fed the cis-butenedioic anhydride liquation from the bottom; Keeping temperature of reaction is 50-100 ℃, and nonreactive divinyl is from another outlet recovery that is cooled; (2) composition with gas-chromatography trace analysis reaction mixture changes, and when cis-butenedioic anhydride content reduces to zero, stops to feed divinyl, improves temperature of reaction to 120-180 ℃, continues reaction 3-8 hour, and underpressure distillation gets the faint yellow solid tetramethylene maleic anhydride.
The two or more at least compound heterogeneous catalyst that catalyzer adopts cheap Vanadium Pentoxide in FLAKES, phosphoric acid, the vitriol oil, polyphosphoric acid or polyphosphoric acid salt to form, its consumption is the 1%-3% of cis-butenedioic anhydride weight; The two or more at least composite polymerization inhibitor that stopper adopts MEHQ, tetrachlorobenzoquinone, triphenyl phosphite or 4-tert-butyl catechol to form, its consumption is the 0.5%-0.8% of cis-butenedioic anhydride weight.
Beneficial effect of the present invention is: (1) adopts compound isomerization catalyst, raw material direct reaction under the effect of compound isomerization catalyst, isomerization reaction and diene addition reaction are almost carried out simultaneously, and isomerisation degree is good, obtain the tetramethylene maleic anhydride of one-component; (2) temperature of reaction is low, and aftertreatment is simple, and product gets final product purifying through simple distillation, and yield is up to 85-90%, and purity reaches more than 98%, and form and aspect are good, and cost is low, helps applying of tetramethylene maleic anhydride.
Specific implementation method
For the present invention is illustrated better, as follows for embodiment:
Embodiment 1:
The 100g cis-butenedioic anhydride is heated to fusing, adds the 0.1g tetrachlorobenzoquinone, 0.3g MEHQ and 1.0g polyphosphoric acid and 1.0g phosphoric acid feed divinyl in the cis-butenedioic anhydride liquation, keep 80-85 ℃ of temperature of reaction; Change with the composition of gas-chromatography trace analysis reaction mixture, after cis-butenedioic anhydride content reduces to zero, improve temperature of reaction to 150 ℃, continue reaction 3 hours; Underpressure distillation gets faint yellow solid tetramethylene maleic anhydride 139g, purity 98.2%, yield 89%.
Embodiment 2:
The 100g cis-butenedioic anhydride is heated to fusing, adds 0.3g 4-tert-butyl catechol, 0.3g MEHQ and the 1.0g vitriol oil and 1.0g sodium polyphosphate, divinyl is fed in the cis-butenedioic anhydride liquation, keep 70-75 ℃ of temperature of reaction; Change with the composition of gas-chromatography trace analysis reaction mixture, after cis-butenedioic anhydride content reduces to zero, improve temperature of reaction to 160 ℃, continue reaction 6 hours; Underpressure distillation gets faint yellow solid 148g, purity 98.6%, yield 95%.
Embodiment 3:
The 100g cis-butenedioic anhydride is heated to fusing, adds 0.2g triphenyl phosphite, 0.4g tetrachlorobenzoquinone and 1.0g phosphoric acid, the 2.0g sodium polyphosphate feeds divinyl in the cis-butenedioic anhydride liquation, keeps 75-80 ℃ of temperature of reaction; Change with the composition of gas-chromatography trace analysis reaction mixture, after cis-butenedioic anhydride content reduces to zero, improve temperature of reaction to 180 ℃, continue reaction 2 hours; Underpressure distillation gets faint yellow solid 146g, purity 98.5%, yield 92%.
Embodiment 4:
The 100g cis-butenedioic anhydride is heated to fusing, adds 0.2g triphenyl phosphite, 0.3g 4-tert-butyl catechol and the 0.5g Vanadium Pentoxide in FLAKES and the 1.5g vitriol oil, divinyl is fed in the cis-butenedioic anhydride liquation, keep 85-90 ℃ of temperature of reaction; Change with the composition of gas-chromatography trace analysis reaction mixture, after cis-butenedioic anhydride content reduces to zero, improve temperature of reaction to 170 ℃, continue reaction 5 hours; Underpressure distillation gets faint yellow solid tetramethylene maleic anhydride 140g, purity 98.8%, yield 90%.
Claims (2)
1. the synthetic method of tetramethylene maleic anhydride, it is characterized in that, with the divinyl is raw material direct production tetramethylene maleic anhydride, this method realizes as follows: (1) is heated to fusing with cis-butenedioic anhydride, open and stir, add composite polymerzation inhibitor and compound isomerization catalyst, divinyl is fed the cis-butenedioic anhydride liquation from the bottom; Keeping temperature of reaction is 50-100 ℃, and nonreactive divinyl is from another outlet recovery that is cooled; (2) composition with gas-chromatography trace analysis reaction mixture changes, and when cis-butenedioic anhydride content reduces to zero, stops to feed divinyl, improves temperature of reaction to 120-180 ℃, continues reaction 3-8 hour; Underpressure distillation gets the faint yellow solid tetramethylene maleic anhydride; Compound heterogeneous catalyst adopts phosphoric acid or the vitriol oil and Vanadium Pentoxide in FLAKES, polyphosphoric acid, polyphosphoric acid salt, and one of them is mixed; Composite polymerization inhibitor adopts MEHQ, tetrachlorobenzoquinone, triphenyl phosphite or the two or more compositions of 4-tert-butyl catechol.
2. the synthetic method of tetramethylene maleic anhydride as claimed in claim 1 is characterized in that, the composite polymerzation inhibitor consumption is the 0.5%-0.8% of cis-butenedioic anhydride weight; Compound isomerization catalyst consumption is the 1%-3% of cis-butenedioic anhydride weight.
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| CN2008100499527A CN101284825B (en) | 2008-06-03 | 2008-06-03 | Synthetic method of tetramethylene maleic anhydride |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004405A2 (en) * | 1978-03-20 | 1979-10-03 | Chemische Werke Hüls Ag | Process for the formation of high-purity tetrahydrophthalic acid anhydride |
| CN1660831A (en) * | 2004-02-24 | 2005-08-31 | 河南省科学院化学研究所 | New method for producing liquid tetrahydrophthalic anhydride |
| CN1683353A (en) * | 2005-03-11 | 2005-10-19 | 河南省科学院化学研究所 | New process for producing liquid methyl tetrahydro phthalic anhydride |
| CN1865256A (en) * | 2006-06-15 | 2006-11-22 | 兰州大学 | 6,7-dihydroligustilide and alkylidene phthalide synthesis method |
-
2008
- 2008-06-03 CN CN2008100499527A patent/CN101284825B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004405A2 (en) * | 1978-03-20 | 1979-10-03 | Chemische Werke Hüls Ag | Process for the formation of high-purity tetrahydrophthalic acid anhydride |
| CN1660831A (en) * | 2004-02-24 | 2005-08-31 | 河南省科学院化学研究所 | New method for producing liquid tetrahydrophthalic anhydride |
| CN1683353A (en) * | 2005-03-11 | 2005-10-19 | 河南省科学院化学研究所 | New process for producing liquid methyl tetrahydro phthalic anhydride |
| CN1865256A (en) * | 2006-06-15 | 2006-11-22 | 兰州大学 | 6,7-dihydroligustilide and alkylidene phthalide synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| JP平3-215480A 1991.09.20 |
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Address after: 450002 Henan Province, Zhengzhou City Red Road No. 56 Co-patentee after: Puyang Huicheng Electronic Material Co., Ltd. Patentee after: Henan Academy of SciencesChemistry Institute Co., Ltd. Address before: 450002 Henan Province, Zhengzhou City Red Road No. 56 Co-patentee before: Puyang Huicheng Chemical Co., Ltd. Patentee before: Henan Academy of SciencesChemistry Institute Co., Ltd. |