CN1915496A - Application of load type catalyst in synthesizing N phenyl maleimide - Google Patents
Application of load type catalyst in synthesizing N phenyl maleimide Download PDFInfo
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- CN1915496A CN1915496A CNA2005101367837A CN200510136783A CN1915496A CN 1915496 A CN1915496 A CN 1915496A CN A2005101367837 A CNA2005101367837 A CN A2005101367837A CN 200510136783 A CN200510136783 A CN 200510136783A CN 1915496 A CN1915496 A CN 1915496A
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- loaded catalyst
- phenylmaleimide
- application
- synthetic
- catalyst
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Abstract
An application of a carried catalyst in synthesizing the N-phenyl maleimide from N-phenyl maleamidic acid by cyclizing reaction is disclosed. Said carried catalyst is prepared through immersing the carrier chosen from metallic oxide, zeolite molecular sieve, and their mixture in the aquatic solution containing the salt of Fe, Ni, Co, or Cu, drying and calcining.
Description
Technical field
The invention belongs to the application of loaded catalyst in the special fine chemical product, particularly a kind of loaded catalyst is in the application of synthetic N-phenylmaleimide.
Background technology
N-phenylmaleimide is a kind of important fine chemical product, modifier such as heat-resisting, wear-resisting, withstand voltage mainly as acrylonitrile-butadiene-styrene (ABS) (ABS), polyvinyl chloride (PVC), methyl methacrylate resins such as (MMA), reaching the intermediate of medicine, agricultural chemicals etc., is a kind of very important compound therefore.
The preparation of N-phenylmaleimide, usually adopt maleic anhydride and amino benzenes compounds in dehydrating agent, to carry out ring-closure reaction and obtain target product, course of reaction as narration in the U.S. Pat 2444536, used acetic anhydride in large quantities in the method that is adopted in the dehydrating agent, produced a large amount of acetic acid wastewaters thus, as the preparation of industry, this method exists significantly not enough.In Japan Patent JP53-68770, said method is improved, in ring-closure reaction, adopted non-protonic solvent and dehydration under inorganic acid (as: phosphoric acid, the concentrated sulfuric acid, p-methyl benzenesulfonic acid and phosphorus pentoxide) catalysis, this method shortcoming has been to use high price and the poisonous non-proton property polar solvent as dimethyl formamide, and production cost is improved.Owing to used acid catalyst, make the loss of solvent bigger, and in product, thoroughly remove very difficulty owing to higher boiling makes.Having narrated in Japan Patent JP60-11465 with the strong-acid ion exchange resin is the preparation method of the N-phenylmaleimide of catalyst, and the use amount of catalyst is bigger in this method, and catalyst itself costs an arm and a leg.In U.S. Pat 4400521, put down in writing oxide (as zinc oxide, magnesia, cobalt oxide, nickel oxide, cupric oxide) with metal and its esters (as: organic acid, inorganic acid salt) report as catalyst, the use of high boiling solvent has been avoided in the use of this catalyst, reduced reaction temperature, but the use amount of catalyst is bigger, is difficult to reclaim.In U.S. Pat 4705866 and the flat 4-295462 of Japan Patent JP, reported recently with organic tin compound (as: SnX
2, SnAc
2Deng) prepare the report of N-phenylmaleimide as new catalyst, but this kind catalyst costliness and toxicity are very big, and the source difficulty is unfavorable for large-scale production.
Summary of the invention
The object of the present invention is to provide a kind of easy and simple to handlely, be easy to control, raw material is convenient to obtain, reclaim, and the loaded catalyst of compliance with environmental protection requirements and suitability for scale production is in the application of synthetic N-phenylmaleimide.
Technical solution of the present invention can realize according to following mode:
A kind of loaded catalyst is in the application of synthetic N-phenylmaleimide, and it is the raw material thing with the acid of N-phenyl maleimide, adopts loaded catalyst to carry out cyclization and makes target compound; Described loaded catalyst system as carrier, is that maceration extract make with the aqueous solution that contains molysite, nickel salt, cobalt salt or mantoquita with the mixture of metal oxide, zeolite molecular sieve or metal oxide and zeolite molecular sieve.
The preparation process of above-mentioned loaded catalyst is carried out according to the following steps:
1) described carrier is carried out 6～12 hours dipping;
2) with soaked carrier 60～150 ℃ dry 3～8 hours down, 300～700 ℃ of following roasts 4～12 hours, obtain catalyst again.
Metal oxide of the present invention is Al
2O
3, MgO, TiO
2Or ZnO.
Metal oxide of the present invention is Al
2O
3, MgO, TiO
2And the mixture of ZnO or the mixture of wherein any two kinds of described metal oxides.
Zeolite molecular sieve of the present invention can adopt Na type zeolite, H type zeolite, X type zeolite, y-type zeolite, zeolite beta or A type zeolite or be the mixture of two or more described zeolite.
As a kind of preferred version, when the present invention adopted molysite, the mass concentration of described molysite was 0.1～5%, and its optimal values scope is 0.3～3%; When adopting nickel salt, the mass concentration of described nickel salt is 10～50%, and its optimal values scope is 5～40%; When adopting cobalt salt, the mass concentration of described cobalt salt is 10～50%, and its optimal values scope is 5～40%; When adopting mantoquita, the mass concentration of described mantoquita is 1～30%, and its optimal values scope is 3～25%.。
As another kind of preferred version, carrier of the present invention and maceration extract weight ratio are 1: 1～20, and its optimal values scope is 1: 5～20.
The consumption that is used for cyclization process loaded catalyst of the present invention accounts for 0.5～25% of N-phenyl maleimide acid, and its optimal values scope is 1～15%.
The prepared target product yield height of the present invention, purity height, production cost is low, and environmental pollution is little, and recyclable utilization is suitable for suitability for industrialized production.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
At room temperature, by weight with 3 parts of Fe (NO
3)
3.6H
2O, 35 parts of Co (NO
3)
2.4H
2O and 62 parts of water are hybridly prepared into maceration extract.5 gram 4A type molecular sieve carriers were joined in the maceration extract that 25 grams prepare dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the Muffle furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains novel catalyst, is designated as 1
#Catalyst.
Embodiment 2
At room temperature, by weight with 3 parts of Fe (NO
3)
3.6H
2O, 35 parts of Ni (NO
3)
2.4H
2O and 62 parts of water are hybridly prepared into maceration extract.5 gram 4A type molecular sieve carriers were joined in the maceration extract that 25 grams prepare dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the Muffle furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains novel catalyst, is designated as 2
#Catalyst.
Embodiment 3:
At room temperature, by weight with 3 parts of Fe (NO
3)
3.6H
2O, 20 parts of Co (NO
3)
2.4H
2O, 20 parts of Ni (NO
3)
2.4H
2O, 10 parts of Cu (NO
3)
2.6H
2O and 47 parts of water are hybridly prepared into maceration extract.5 gram 4A type molecular sieve carriers were joined in the maceration extract that 25 grams prepare dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the Muffle furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains novel catalyst, is designated as 3
#Catalyst.
Embodiment 4:
At room temperature, by weight with 3 parts of Fe (NO
3)
3.6H
2O, 20 parts of Co (NO
3)
2.4H
2O, 20 parts of Ni (NO
3)
2.4H
2O, 10 parts of Cu (NO
3)
2.6H
2O and 47 parts of water are hybridly prepared into maceration extract.With 5 gram α-Al
2O
3Carrier joined in 25 maceration extracts that prepare of gram dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the Muffle furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains novel catalyst, is designated as 4
#Catalyst.
Embodiment 5:
At room temperature, by weight with 3 parts of Fe (NO
3)
3.6H
2O, 20 parts of Co (NO
3)
2.4H
2O, 20 parts of Ni (NO
3)
2.4H
2O, 10 parts of Cu (NO
3)
2.6H
2O and 47 parts of water are hybridly prepared into maceration extract.With 5 gram TiO
2Carrier joined in 25 maceration extracts that prepare of gram dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the Muffle furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains novel catalyst, is designated as 5
#Catalyst.
Embodiment 6:
The catalyst that the present invention is obtained is applied in the cyclization process of N-phenylmaleimide, and wherein the acid of N-phenyl maleimide is easy to make by prior art.
(190g 1mol) with homemade above-mentioned loaded catalyst (9g), adds hydroquinones (0.5g) in this mixed liquor to add the acid of N-phenyl maleimide in dimethylbenzene (650ml), add about 140 ℃ insulations of thermal agitation, continue reaction 3 hours, stop reaction, filter, tell catalyst, decompression distillation obtains yellow solid 159g, and yield is 92%, through liquid chromatographic detection, the purity of thick product is 94%.Obtain yellow needle-like N-phenylmaleimide behind the recrystallization, product is through liquid chromatographic detection, and purity is 99.5%.
Embodiment 7
According to above course of reaction, select dissimilar catalyst, other conditions remain unchanged, and the result who obtains is as follows:
The N-phenylmaleimide for preparing under the table different catalysts
| Catalyst type | The catalyst addition * | Conversion ratio % | Yield % | Selectivity % |
| 1 # | 9 | 96 | 85 | 88 |
| 2 # | 9 | 97 | 87 | 90 |
| 3 # | 9 | 98 | 92 | 94 |
| 4 # | 9 | 98 | 91 | 93 |
| 5 # | 9 | 97 | 90 | 93 |
*The addition of catalyst is 5% of a N-phenyl maleimide acid quality
Comparative example
To dimethylbenzene, dimethyl formamide (650ml, volume ratio 20: 1) (190g 1mol) and sulfuric acid (5ml), adds hydroquinones (0.5g) in this mixed liquor to add the acid of N-phenyl maleimide in the mixed solvent, add about 110 ℃ insulations of thermal agitation, continue reaction 3 hours, stop reaction, decompression distillation removes and desolvates, obtain yellow solid 145g, yield is 81%, and through liquid chromatographic detection, the purity of thick product is 77%.
Protection scope of the present invention will not only be confined to above-mentioned specific embodiment; in the building-up process of N-phenylmaleimide, this loaded catalyst of any employing carries out the process route that cyclization prepares N-phenylmaleimide and is within protection scope of the present invention.
Claims (8)
1, a kind of loaded catalyst is in the application of synthetic N-phenylmaleimide, and it is characterized in that: with the acid of N-phenyl maleimide is the raw material thing, adopts loaded catalyst to carry out cyclization and makes target compound; Described loaded catalyst system as carrier, is that maceration extract make with the aqueous solution that contains molysite, nickel salt, cobalt salt or mantoquita with the mixture of metal oxide, zeolite molecular sieve or metal oxide and zeolite molecular sieve.
2, according to the application of the described loaded catalyst of claim 1 at synthetic N-phenylmaleimide, it is characterized in that: this Preparation of catalysts process is carried out according to the following steps:
1) described carrier is carried out 6～12 hours dipping;
2) with soaked carrier 60～150 ℃ dry 3～8 hours down, 300～700 ℃ of following roasts 4～12 hours, obtain catalyst again.
3, according to the application of the described loaded catalyst of claim 2 at synthetic N-phenylmaleimide, it is characterized in that: described metal oxide is Al
2O
3, MgO, TiO
2Or ZnO.
4, according to the application of the described loaded catalyst of claim 2 at synthetic N-phenylmaleimide, it is characterized in that: described metal oxide is Al
2O
3, MgO, TiO
2And the mixture of ZnO or the mixture of wherein any two kinds of described metal oxides.
5, according to the application at synthetic N-phenylmaleimide of the arbitrary described loaded catalyst of claim 2～4, it is characterized in that: described zeolite molecular sieve is Na type zeolite, H type zeolite, X type zeolite, y-type zeolite, zeolite beta or A type zeolite or is the mixture of two or more described zeolite.
6, according to the application at synthetic N-phenylmaleimide of the arbitrary described loaded catalyst of claim 2～4, it is characterized in that: when adopting molysite, the mass concentration of described molysite is 0.1～5%, is preferably 0.3～3%; When adopting nickel salt, the mass concentration of described nickel salt is 10～50%, is preferably 5～40%; When adopting cobalt salt, the mass concentration of described cobalt salt is 10～50%, is preferably 5～40%; When adopting mantoquita, the mass concentration of described mantoquita is 1～30%, is preferably 3～25%.。
7, according to the application at synthetic N-phenylmaleimide of the arbitrary described loaded catalyst of claim 2～4, it is characterized in that: described carrier and maceration extract weight ratio are 1: 1～20, be preferably 1: 5～and 20.
8, according to of the application of the described loaded catalyst of claim 1～2 at synthetic N-phenylmaleimide, it is characterized in that: the described consumption that is used for cyclization process loaded catalyst accounts for 0.5～25% of N-phenyl maleimide acid, is preferably 1～15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101367837A CN100509151C (en) | 2005-12-31 | 2005-12-31 | Application of load type catalyst in synthesizing N phenyl maleimide |
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|---|---|---|---|
| CNB2005101367837A CN100509151C (en) | 2005-12-31 | 2005-12-31 | Application of load type catalyst in synthesizing N phenyl maleimide |
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| Publication Number | Publication Date |
|---|---|
| CN1915496A true CN1915496A (en) | 2007-02-21 |
| CN100509151C CN100509151C (en) | 2009-07-08 |
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ID=37736646
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
| CN102350349A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalyst for diphenylguanidine (DPG) serving as accelerating agent in oxygen oxidation synthesis production process, and preparation method thereof |
| CN102350350A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalysts used in production of promoter 2,2'-dithiobisbenzothiazole, and preparation method thereof |
| CN102380404A (en) * | 2011-08-29 | 2012-03-21 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-cyclohexyl benzothiazole sulfonamide and its preparation method |
| CN102909074A (en) * | 2012-10-24 | 2013-02-06 | 武汉新概念化工有限公司 | Immobilized type non-toxic catalyst and method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2683404B2 (en) * | 1989-02-27 | 1997-11-26 | 三井東圧化学株式会社 | Method for producing N-phenylmaleimide compound |
| GB9012453D0 (en) * | 1990-06-05 | 1990-07-25 | Ucb Sa | Process for the manufacture of n-phenylmaleimide |
| JP2951696B2 (en) * | 1990-06-14 | 1999-09-20 | 三井化学株式会社 | 4- (Hydroxyphenoxy) phenylmaleimide and method for producing the same |
-
2005
- 2005-12-31 CN CNB2005101367837A patent/CN100509151C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309986A (en) * | 2011-08-29 | 2012-01-11 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method |
| CN102350349A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalyst for diphenylguanidine (DPG) serving as accelerating agent in oxygen oxidation synthesis production process, and preparation method thereof |
| CN102350350A (en) * | 2011-08-29 | 2012-02-15 | 科迈化工股份有限公司 | Catalysts used in production of promoter 2,2'-dithiobisbenzothiazole, and preparation method thereof |
| CN102380404A (en) * | 2011-08-29 | 2012-03-21 | 科迈化工股份有限公司 | Catalyst used for producing promoter N-cyclohexyl benzothiazole sulfonamide and its preparation method |
| CN102909074A (en) * | 2012-10-24 | 2013-02-06 | 武汉新概念化工有限公司 | Immobilized type non-toxic catalyst and method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide |
| CN102909074B (en) * | 2012-10-24 | 2014-04-16 | 武汉新概念化工有限公司 | Immobilized type non-toxic catalyst and method for synthesizing N-phenylmaleimide and N-substitutional phenylmaleimide |
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|---|---|
| CN100509151C (en) | 2009-07-08 |
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Granted publication date: 20090708 Termination date: 20121231 |