CN105017186B - A kind of new synthetic method of 2 methyl maleic anhydride - Google Patents
A kind of new synthetic method of 2 methyl maleic anhydride Download PDFInfo
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- CN105017186B CN105017186B CN201510457895.6A CN201510457895A CN105017186B CN 105017186 B CN105017186 B CN 105017186B CN 201510457895 A CN201510457895 A CN 201510457895A CN 105017186 B CN105017186 B CN 105017186B
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- methyl maleic
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- synthetic method
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- itaconic acid
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- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 24
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- KOQFJKQRPZRORH-UHFFFAOYSA-N 1-benzyl-3-methylpyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1CC1=CC=CC=C1 KOQFJKQRPZRORH-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JENCQZUEOOGQSJ-UHFFFAOYSA-N 2-ethynoxyethyl(trimethyl)silane Chemical group C[Si](C)(C)CCOC#C JENCQZUEOOGQSJ-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003897 citraconoyl group Chemical group C(\C(\C)=C/C(=O)*)(=O)* 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 229960003019 loprazolam Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of new synthetic method of 2 methyl maleic anhydride, its method are as follows：Catalyst is added into itaconic acid, after mixing, is warming up to 160 ~ 200 DEG C, then 3 ~ 5h of insulation reaction, the water of reaction generation is constantly steamed in course of reaction, it is 2 methyl maleic anhydrides to be evaporated under reduced pressure after water all steams and obtain pale yellowish oil liquid.The present invention is by using above-mentioned technology, and its is simple to operate, and process conditions are low, low for equipment requirements, and reaction yield is high, and the yield of the obtained methyl maleic anhydride of target product 2 is more than 85%, and purity can reach 98%, suitable industrialized production.
Description
Technical field
The invention belongs to technical field of chemical synthesis of refining, and in particular to a kind of anti-recovery agent 1, the double (citraconoyls of 3-
Formimino group) benzene intermediate 2- methyl maleic anhydrides new synthetic method.
Background technology
Anti-recovery agent is a kind of rubber chemicals newest both at home and abroad, and it can make vulcanized network keep stable, vulcanization
Glue rubber performance under heated or dynamic condition will not decline.Double (citraconimidomethyl) benzene of 1,3- are a kind of comparatively ideal anti-
Recovery agent, it can produce heat stable carbon carbon cross-bond, with the polysulfide bond of compensation fracture, so that the friendship of vulcanizate
Join density and physical property keeps constant.The sulfur resistive that sizing material can not only be improved is reverted performance, and can also improve sizing material after over cure
Elasticity, reduce heat, improve tearing strength and anti-wear performance, this has for the fatigue performance and renovation number of tire
Important meaning.And 2- methyl maleic anhydrides are the key intermediates of double (citraconimidomethyl) benzene of 1,3-.
The method for producing 2- methyl maleic anhydrides in the prior art, such as EP0495544, Y.Kita et al.,
J.Org.Chem.,51,1986,pp.4150-4158、M.C.Galanti et al.,J.Org.Chem.,47, 1982,
pp.1572-1574、A.V.Galanti et al.,J.Pol.Sci: Pol.Chem.Ed.,Vol.19, 1981,pp.451-
475 document reports itaconic acid and dehydrating agent chloroacetic chloride, acetic anhydride or trimethylsilyl ethoxy acetylene etc. are reacted, then are added
Enter caused water in high boiling solvent elimination reaction, obtain clothing health acid anhydride, then carry out high temperature rearrangement reaction and obtain 2- methyl Malaysia
Acid anhydrides, such method easily produce accessory substance so that the separation of 2- methyl maleic anhydrides becomes extremely difficult, so as to obtain
The 2- methyl maleic anhydrides of high-purity.WO9506026, EP0317394 and R.W.McCabe et al., J. Chem.
Research (s), 1985, pp.356-357, in CN103739539 documents, it was recently reported that itaconic acid in a solvent, with to toluene sulphur
Acid or the method that Loprazolam or disodium hydrogen phosphate are catalyst preparation 2- methyl maleic anhydrides；EP3321703 、CN1077563
With CN104387347 document reports itaconic acid in a solvent, side using tertiary amine as catalyst preparation 2- methyl maleic anhydrides
Method；Such method during 2- methyl maleic anhydrides are prepared due to use a large amount of high boiling solvents, with 2- citraconic acids
The boiling point of acid anhydride relatively, causes separation difficult, also cannot get the 2- methyl maleic anhydrides of high-purity.GB827638 and
US2966498 document reports or are carried out dehydration under the catalysis of alkali metal salt and obtain 2- first using the itaconic acid of melting
Base maleic anhydride, but reaction yield is low, and process conditions are harsher, are not suitable for industrialized production.
The content of the invention
The purpose of the present invention is to overcome the contamination of raw material for producing the use of 2- citraconic acids anhydride process in the prior art big, molten
Agent recovery is difficult, not environmentally the defects of, there is provided a kind of environmental pollution is small, and high income, production cost is low, and to equipment corrosion
The new synthetic method of small 2- methyl maleic anhydrides.
The new synthetic method of described a kind of 2- methyl maleic anhydrides, it is characterised in that this method is as follows：Into itaconic acid
Catalyst is added, after mixing, is warming up to 160 ~ 200 DEG C, then 3 ~ 5h of insulation reaction, reaction generation is constantly steamed in course of reaction
Water, it is 2- methyl maleic anhydrides to be evaporated under reduced pressure after water all steams and obtain pale yellowish oil liquid, and water is all steamed to not having
Untill having water outlet.
The new synthetic method of described a kind of 2- methyl maleic anhydrides, it is characterised in that the catalyst is organic base.
The new synthetic method of described a kind of 2- methyl maleic anhydrides, it is characterised in that the catalyst is triethylamine, second
Diamines, pyridine or tetramethylethylenediamine.
The new synthetic method of described a kind of 2- methyl maleic anhydrides, it is characterised in that the dosage of the catalyst is clothing health
The 1 ~ 5% of sour quality.
The new synthetic method of described a kind of 2- methyl maleic anhydrides, it is characterised in that the dosage of the catalyst is clothing health
The 1.5-2.5% of sour quality.
A kind of a kind of new synthetic method of described 2- methyl maleic anhydrides, it is characterised in that 2- methyl maleic anhydrides
New synthetic method, it is characterised in that soaking time be 170 ~ 180 DEG C.
For the present invention by using above-mentioned technology, its is simple to operate, and process conditions are low, low for equipment requirements, and reaction yield is high,
The yield of obtained target product 2- methyl maleic anhydrides is more than 85%, and purity can reach 98%, suitable industrialized production.
Embodiment
The present invention is further illustrated with reference to specific embodiment, but protection scope of the present invention is not limited to this.
Example 1：Itaconic acid 260g (2mol) is sequentially added into 250ml three-necked flasks, pyridine 5.2g (2%wt), oil bath adds
Heat is to 170 DEG C, and as itaconic acid progressively melts, air-distillation removes the water of dereaction generation, continues reaction to steam to there is no water,
Stop reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtaining lurid oily liquids is
2- methyl maleic anhydride 192.6g, yield is up to 86%, through vapor detection purity up to 99%.
In the embodiment, catalyst replaces pyridine with triethylamine, ethylenediamine or tetramethylethylenediamine, can obtain equally
Technique effect.Dosage is 1 ~ 5%, 1.5-2.5% of itaconic acid quality.
Example 2：Itaconic acid 260g (2mol), tetramethylethylenediamine 6.5g (2.5% are sequentially added into 250ml three-necked flasks
Wt), oil bath heating is to 175 DEG C, and as itaconic acid progressively melts, air-distillation removes the water of dereaction generation, continues reaction to not
There is water to steam again, stop reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oil
Shape liquid is 2- methyl maleic anhydride 197.1g, and yield is up to 88%, through vapor detection purity up to 99.5%.
Example 3 sequentially adds itaconic acid 260g (2mol), pyridine 6.5g (2.5%wt), oil bath into 250ml three-necked flasks
180 DEG C are heated to, as itaconic acid progressively melts, air-distillation removes the water of dereaction generation, continues reaction to there is no water steaming
Go out, stop reaction, reduce reaction temperature to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oily liquids i.e.
For 2- methyl maleic anhydride 194.2g, yield is up to 86.7%, through vapor detection purity up to 99.5%.
Example 4：Itaconic acid 260g (2mol), triethylamine 2.6g (1.0%wt) are sequentially added into 250ml three-necked flasks,
Oil bath heating is to 200 DEG C, as itaconic acid progressively melts, air-distillation remove dereaction generation water, continue reaction to there is no
Water steams, and stops reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oily liquid
Body is 2- methyl maleic anhydride 190.7g, and yield is up to 85.1%, through vapor detection purity up to 98%.
Example 5：Itaconic acid 260g (2mol), triethylamine 13g (5.0%wt) are sequentially added into 250ml three-necked flasks, oil
Bath is heated to 160 DEG C, and as itaconic acid progressively melts, air-distillation removes the water of dereaction generation, continues reaction to there is no water
Steam, stop reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oily liquids
As 2- methyl maleic anhydrides 190.7g, yield is up to 85.1%, through vapor detection purity up to 98.5%.
Example 6：Itaconic acid 260g (2mol), ethylenediamine 3.9g (1.5%wt) are sequentially added into 250ml three-necked flasks,
Oil bath heating is to 185 DEG C, as itaconic acid progressively melts, air-distillation remove dereaction generation water, continue reaction to there is no
Water steams, and stops reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oily liquid
Body is 2- methyl maleic anhydride 193.2g, and yield is up to 86.2%, through vapor detection purity up to 99.2%.
Example 7：Itaconic acid 260g (2mol), ethylenediamine 7.8g (3%wt) are sequentially added into 250ml three-necked flasks, oil
Bath is heated to 190 DEG C, and as itaconic acid progressively melts, air-distillation removes the water of dereaction generation, continues reaction to there is no water
Steam, stop reaction.Reaction temperature is reduced to 130 DEG C or so, device is changed to be evaporated under reduced pressure, obtains lurid oily liquids
As 2- methyl maleic anhydrides 195.0g, yield is up to 87.0%, through vapor detection purity up to 99.2%.
Claims (3)
1. a kind of new synthetic method of 2- methyl maleic anhydrides, it is characterised in that this method is as follows：Catalysis is added into itaconic acid
Agent, after mixing, 160 ~ 200 DEG C, then 3 ~ 5h of insulation reaction are warming up to, the water of reaction generation is constantly steamed in course of reaction, treats water
It is 2- methyl maleic anhydrides to be evaporated under reduced pressure after all steaming and obtain pale yellowish oil liquid, and the catalyst is triethylamine, second
Diamines or tetramethylethylenediamine, the dosage of the catalyst are the 1 ~ 5% of itaconic acid quality.
A kind of 2. new synthetic method of 2- methyl maleic anhydrides according to claim 1, it is characterised in that the catalyst
Dosage be itaconic acid quality 1.5-2.5%.
A kind of a kind of 3. new synthetic method of 2- methyl maleic anhydrides according to claim 1, it is characterised in that 2-
The new synthetic method of methyl maleic anhydride, it is characterised in that soaking time is 170 ~ 180 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB827638A (en) * | 1957-07-29 | 1960-02-10 | Pfizer & Co C | Preparation of citraconic anhydride |
| US2966498A (en) * | 1958-04-23 | 1960-12-27 | Pfizer & Co C | Preparation of citraconic anhydride |
| CN1077563C (en) * | 1995-06-21 | 2002-01-09 | 罗纳·布朗克化学公司 | Process for preparation of citraconic anhydride |
| CN103739539A (en) * | 2013-12-24 | 2014-04-23 | 武汉径河化工有限公司 | Method for preparing anti-vulcanization reversion agent 1,3-bis(citraconimidomethyl)benzene |
| CN104387347A (en) * | 2014-11-19 | 2015-03-04 | 山东阳谷华泰化工股份有限公司 | Preparation method of 2-methyl maleic anhydride and 1,3-bis(citraconoyl formimino)-benzene |
-
2015
- 2015-07-30 CN CN201510457895.6A patent/CN105017186B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB827638A (en) * | 1957-07-29 | 1960-02-10 | Pfizer & Co C | Preparation of citraconic anhydride |
| US2966498A (en) * | 1958-04-23 | 1960-12-27 | Pfizer & Co C | Preparation of citraconic anhydride |
| CN1077563C (en) * | 1995-06-21 | 2002-01-09 | 罗纳·布朗克化学公司 | Process for preparation of citraconic anhydride |
| CN103739539A (en) * | 2013-12-24 | 2014-04-23 | 武汉径河化工有限公司 | Method for preparing anti-vulcanization reversion agent 1,3-bis(citraconimidomethyl)benzene |
| CN104387347A (en) * | 2014-11-19 | 2015-03-04 | 山东阳谷华泰化工股份有限公司 | Preparation method of 2-methyl maleic anhydride and 1,3-bis(citraconoyl formimino)-benzene |
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| CN105017186A (en) | 2015-11-04 |
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