CN104326853A - Selective side chain alkylation method of alkyl aromatic compound - Google Patents
Selective side chain alkylation method of alkyl aromatic compound Download PDFInfo
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- CN104326853A CN104326853A CN201410454235.8A CN201410454235A CN104326853A CN 104326853 A CN104326853 A CN 104326853A CN 201410454235 A CN201410454235 A CN 201410454235A CN 104326853 A CN104326853 A CN 104326853A
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Abstract
The invention relates to a selective side chain alkylation method of an alkyl aromatic compound. The method is characterized in that the alkyl aromatic compound undergoes a side chain alkylation reaction by unsaturated hydrocarbon with an aromatic halide as a cocatalyst and alkyl ether and an alkali metal catalyst as catalysts, wherein the aromatic halide is halide of naphthalene, biphenyl, terphenyl, pyrene or phenanthrene, and the addition amount of the aromatic halide is 0.1-1.0 time the mole of the alkali metal. The method greatly improves the selectivity of 1:1 additives and allows the catalysts to well and evenly perform only through using a small amount of the alkali metal catalyst, so compared with previous known methods, the method has the advantages of very easy reaction operation and very large industrialization values.
Description
Technical field
The present invention relates to a kind of side chain alkylation method of alkylation selectivity aromatics, belong to the method field of alkyl aromatic compound side chain alkylation.
Background technology
The pendant alkyl group compound of alkyl aromatic compound, the intermediate raw material tool as interfacial agent raw material, alkylnaphthalene, alkyl phenanthrene and alkyl anthracene etc. has been widely used.As: intermediate raw material 1, the 5-dimethylnaphthalene preparing the alkylation of o-Xylol and 1,3-butadiene, cyclisation, dehydrogen substance, or intermediate raw material 2, the 6-dimethylnaphthalene preparing NDA, paid close attention to all widely.
To there is the method that side chain alkylation reacts in alkyl aromatic compound and unsaturated hydrocarbon widely known very early under the catalysis of base metal catalysts.As:
JP51-17539 publication discloses the catalyzer with potassium metal and biphenyl or alkyl biphenyl generation, makes the method that the alkyl aromatic compound containing benzylic hydrogens and ethene react.
JP 51-17540 publication discloses the catalyzer generated with sodium Metal 99.5 and pyrene, makes the method that the alkyl aromatic hydrocarbon containing benzylic hydrogens and ethene react.
It is catalyzer that JP 51-8930 publication discloses with potassium metal, and naphthalene or alkylnaphthalene are promotor, make the method that alkylbenzene and 1,3-butadiene react.
EP0575081 discloses alkyl oxide as solvent, makes the method that alkyl aromatic compound generation side chain alkylation reacts.
J.org.chem., vol.30,280 (1965); J.Am.chem.Soc., vol.82.4912 (1960) discloses alkylbenzene, alkylnaphthalene and with isoprene, propylene, ethene, the reaction of side chain alkylation occurs under alkali-metal catalysis respectively.
J.org.chem., vol.30,280 (1965) disclose alkyl aromatic compound and 1,3-butadiene reacts under alkali-metal catalysis, and particularly the two generates the reaction of 1: 1 mixture.
Having 1: 1 compound tense of the aromatics of multiple alkyl hydrogen and unsaturated hydrocarbon, selectivity is poor; And when the annexation synthesis of the carbon element toward alpha-position, need excess alkali metal very many compared with object resultant, operationally then need to make basic metal disperse to make it reaction, complex operation; And it is low that object resultant obtains yield.
As o-Xylol/butadiene process produces the reaction of 2,6-DMN, in the reaction of its side chain alkylation under base metal catalysts exists, when the mol ratio of o-Xylol and divinyl is 5: 1, reacts and carry out at 145 DEG C.First in order to reduce the generation of diene affixture, reaction needed o-Xylol is greatly excessive, causes the waste of material, and needs higher temperature of reaction.
Goal of the invention
Technical problem solved by the invention is to provide one can improve selectivity when benzylic hydrogens aromatics and unsaturated hydrocarbon 1: 1 react, and can simplify the operation simultaneously and improve the side chain alkylation method of the alkylation selectivity aromatics of target product yield.
In order to realize foregoing invention object, the technical solution adopted in the present invention is:
The present invention is using aromatic halide as promotor, with alkyl oxide and base metal catalysts for catalyzer, with unsaturated hydrocarbon, alkyl aromatic compound generation side chain alkylation is reacted, wherein said aromatic halide is the halogenide of naphthalene, biphenyl, terphenyl, pyrene or phenanthrene, and the add-on of described aromatic halide is alkali-metal 0.1 ~ 1.0 times of molar weight.
Further, aromatic halide of the present invention is the bromide of the muriate of naphthalene, the bromide of naphthalene, the muriate of biphenyl or biphenyl.
Further, aromatic halide add-on of the present invention is alkali-metal 0.3 ~ 0.6 times of molar weight.
Further, alkyl oxide of the present invention is one or more in diethyl ether, diisopropyl ether, glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methyltetrahydrofuran, dioxan or phenyl ether; Described base metal catalysts is the complex compound of the hydride of alkali metal or alkali metal, alkyl alkali compound, aromatic base compound or alkali metal and alkyl oxide; Described alkali metal is sodium, potassium, lithium or caesium; Described unsaturated hydrocarbon is C
2~ C
20chain or the unsaturated hydrocarbon of ring-type; Described alkyl aromatic compound is benzene compound, alkylnaphthalene compounds, alkyl biphenyl compounds, alkyl anthracene compounds or alkyl biphenyl ether compound.
Further, alkyl aromatic compound of the present invention is toluene, dimethylbenzene, Three methyl Benzene, ethylbenzene, ethyltoluene compounds, ethylxylenes compounds, diethylbenzene compounds, propylbenzene; Methylnaphthalene compounds, ethyl naphthalene compounds or dimethylnaphthalene.
Further, the consumption of alkyl oxide of the present invention is 0.1 ~ 5 times of alkyl aromatic quality.
Further, the usage quantity of base metal catalysts of the present invention is 0.1 ~ 3 mol% for alkyl aromatic hydrocarbon.
Further, unsaturated hydrocarbon of the present invention is ethene, vinylbenzene, propylene, butylene, 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, pentadiene class, hexadiene class, tetrahydrobenzene or acenaphthene.
Further, operation steps of the present invention is: add alkyl oxide, alkyl aromatic compound, base metal catalysts and aromatic halide in a reservoir, be heated to 30 ~ 100 DEG C, stir at this temperature, and unsaturated hydrocarbon gases is slowly passed in said mixture.
Further, the consumption of unsaturated hydrocarbon of the present invention is 0.3 ~ 0.7 times of molar weight of alkyl aromatic compound.
Alkyl aromatic compound of the present invention, main finger has the aromatics that benzylic hydrogens replaces, see chemical formula (1 ~ 3), but be not restricted to the alkylnaphthalene class, alkyl biphenyl class, alkyl anthracene class, alkyl biphenyl ether etc. of the alkyl benzene, methylnaphthalene class, ethyl naphthalene class, dimethylnaphthalene class etc. of toluene, dimethylbenzene, Three methyl Benzene, ethylbenzene, ethyltoluene class, ethylxylenes class, diethylbenzene class, propylbenzene class etc.
Chemical formula (1) chemical formula (2) chemical formula (3)
Wherein R
1for methyl, ethyl, propyl group, hydrogen, sec.-propyl; R
2for being methyl, ethyl, propyl group, hydrogen, sec.-propyl.
Alkyl oxide of the present invention, see chemical formula (4 ~ 6), base metal catalysts is dissolved in its effect, as long as the alkyl oxide that therefore can realize above-mentioned effect all can be applied to the present invention and realize object of the present invention, can select but one or more the composition be not restricted in diethyl ether, diisopropyl ether, glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methyltetrahydrofuran, dioxan or phenyl ether.Be preferably wherein tetrahydrofuran (THF), when the solvent selecting tetrahydrofuran (THF) as dissolving base metal catalysts, higher reaction preference can be obtained.The consumption of alkyl oxide is preferably for making the consoluet amount of base metal catalysts, but it is also operable for not dissolving alkali-metal consumption completely, 0.1 ~ 10 times of general is alkyl aromatic.If the usage quantity of alkyl oxide is very few, then reaction preference can be caused to decline, and volumetric efficiency excessively can be caused at most to worsen and make industrialness be worth reduction.
Chemical formula (4) chemical formula (5) chemical formula (6)
Wherein n=1,2 or 3; R
1=CH
3, CH
3cH
2, CH
3cH (CH
3) CH
2, phenyl or H; R
2=CH
3, CH
3cH
2or CH
3cH (CH
3) CH
2.
Base metal catalysts of the present invention is as anionic catalyst, can be the complex compound (as sodium glycol dinitrate ether complexes) etc. of sodium Metal 99.5, potassium, lithium, the annexation (as toluene and sodium) of caesium and above-mentioned alkali-metal hydride (as sodium hydride, potassium hydride KH) or alkyl alkali compound (as sodium methyl, potassium ethide), basic metal and aromatics, basic metal and alkyl oxide, can separately or mixing make it for reaction.The usage quantity of base metal catalysts is 0.05 ~ 50mol%, preferably 0.5 ~ 15mol% for alkyl aromatic hydrocarbon.Base metal catalysts usage quantity crosses the addition speed of unsaturated compound at least will be slow, easily plays side reaction.And though contrary usage quantity is crossed the accrete selectivity of 1:1 at most and is improved and to talk and uneconomical.
Aromatic series halogen compound of the present invention uses as promotor, sees chemical formula (7 ~ 10).Common, those skilled in the art only use the composition of basic metal and alkyl oxide to use as catalyzer, and think that the two is very effective catalyzer.The present invention finds that under great many of experiments and research aromatic halide coexists at alkyl oxide can promote that the side chain alkylation selectivity of alkyl aromatic compound occurs efficiently down.As the aromatic halide that promotor uses, can for but be not restricted to the halogenide of naphthalene, biphenyl, terphenyl, pyrene or phenanthrene.Iodine, chlorine, bromine, fluorine etc. are then had as halogen.This muriate wherein easily obtained, bromide are proper.The usage quantity of the aromatic chlorinated thing of promotor is 0.001 ~ 1 times of molar weight to base metal catalysts, normally 0.01 ~ 0.5 times of molar weight.It is just little that the usage quantity of the aromatics of promotor crosses effect at least, otherwise and cross in uneconomical or operation at most and can be restricted and not advise.
Chemical formula (7) chemical formula (8) chemical formula (9) chemical formula (10)
Wherein X=F, Cl, Br or I.
Unsaturated hydrocarbon of the present invention can be the unsaturated hydrocarbon of chain or ring-type, is preferably the C such as ethene, vinylbenzene, propylene, butylene class
2~ C
20unsaturated compound; Diolefinic compounds, as 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, pentadiene class, hexadiene class; The unsaturated hydrocarbon of ring-type, as tetrahydrobenzene, acenaphthene etc.When using unsaturated hydrocarbon to promote reaction, need the speed taking into account side reaction to determine interpolation speed.Generalized case is that the slower accelerated energy that adds obtains good result.And because unsaturated hydrocarbon has very large solubleness, so coexisting of alkyl ether is also effective on operation in alkyl oxide.
In the present invention, under the existence of alkyl oxide and base metal catalysts, making alkyl aromatic compound carry out alkylated reaction by adding unsaturated hydrocarbons, the selectivity of main reaction can be increased significantly.As unsaturated hydrocarbons and alkyl aromatic compound carry out 1: 1 addition reaction time, use reactive system of the present invention, secondary adduct is if diolefine adduct is lower than detectability.Therefore method of the present invention is particularly suitable for the reactive system of side reaction as secondary addition reaction easily occurs.
Method of the present invention is particularly useful for the reactive system of complicated alkyl aromatic compound, as dimethylbenzene, Three methyl Benzene and ethyltoluene class or have the aromatics containing two or more alkyl such as ethyl-p-dimethylbenzene and unsaturated hydrocarbons to carry out the addition reaction of 1:1, method of the present invention can improve selectivity significantly, obtain single target product, there is significant advantage.
The present invention is equally applicable to the reaction that complicated unsaturated hydrocarbons participates in, as 1,3-divinyl etc. carry out the addition reaction of 1: 1 containing the compound of two or more unsaturated link(age) and alkyl aromatic compound, method of the present invention can improve selectivity significantly, obtain single target product, there is significant advantage.
Alkylated reaction of the present invention is generally in the mixing system of alkyl aromatic compound, alkyl oxide and base metal catalysts, add unsaturated hydrocarbon, but does not consider order of addition.The addition of unsaturated hydrocarbon, reduces its addition and can increase by 1: 1 accrete selectivity; And if increase its addition, then easily can generate secondary affixture, and the consumption of raw material is increased.Therefore, different according to reactive system, below waiting alkyl aromatic compound mole, particularly in general about 0.3 ~ 0.7mol is more appropriate.Temperature of reaction, need not more than alkali-metal fusing point as method in the past, because more cryogenically can make it reaction, so within more suitable scope, be often adopted near 30 ~ 100 DEG C.Alkylated reaction pressurization, decompression so normal pressure under, interval or can implement continuously, importantly carry out under the state eliminating water as far as possible.Reaction makes catalyst deactivation after ending, or does not carry out inactivation but also can be separated object by well-known means such as distillation, partial crystallizations.
Technique effect of the present invention:
Method of the present invention is compared with known method:
One is be a significant increase 1: 1 accrete synthesis of selective, decreases the incidence of the side reactions such as secondary addition, the single more easily separated purifying of the target product therefore obtained.
Two is that the unsaturated hydrocarbon of reaction raw materials and alkyl aromatic compound are reacted under more balanced material proportion, the material ratio of the two gets final product the generation goal response of highly selective under the mol ratio of 0.3 ~ 0.7, and in existing method, for obtaining higher selectivity, the material ratio of the two is less than 0.2 usually, therefore method of the present invention can improve material ratio, thus saves material.
Three is reduce temperature of reaction significantly, temperature of reaction of the present invention used alkali-metal fusing point or lower than the temperature of basic metal fusing point under all can occur, be generally 30 ~ 100 DEG C, and the temperature of reaction in existing method is higher than used alkali-metal fusing point usually, and it is common at 150 DEG C, therefore method of the present invention can reduce operation easier, saves power consumption.
Four is to reduce alkali-metal consumption, and existing alkali-metal consumption is generally 0.1mol%, and method of the present invention, when using existing basic metal consumption, can improve the selectivity of reaction further; And when reducing basic metal consumption, during as used the basic metal consumption of 0.05mol%, the selectivity of reaction is significantly higher than existing reaction system.
Therefore with known Measures compare, method of the present invention not only significantly improves in 1: 1 accrete selectivity, and only use extremely a small amount of base metal catalysts just can well and catalyzer can very balancedly play a role again, thus operation is very easy to, industrial value is very large.
Embodiment
Embodiment 1 ~ 5 and comparative example 1,2
In the beaker of 300ml with agitator, add the aromatic halide 0.0040 mole of tetrahydrofuran (THF) 89.0g, ethyl-p-dimethylbenzene 134.2g, sodium Metal 99.5 0.010 mole, promotor, the kind of aromatic halide is as shown in table 1.The promotor of comparative example 1 and 2 uses polycyclc aromatic compound 0.0040 mole, and the kind of polycyclc aromatic compound is as shown in table 1.Be heated to 60 DEG C of stirrings 5 minutes at this temperature, at this temperature the speed of 1,3-butadiene by 0.10mol/ hour ventilated 6 hours.Add after water makes catalyst deactivation, as shown in table 1 according to the result that gc analysis goes out.Wherein transformation efficiency represents with the analytical data (area percentage) of reacted matrix (ethyl ester-p-dimethylbenzene), and selection rate represents with the ratio (area percentage) of the object resultant (5-p-hexadiene) in divinyl annexation.
Table 1
Compared by above-mentioned test-results, compared with polycyclc aromatic compound, using aromatic halide as promotor, transformation efficiency and the selection rate of side chain alkylation reaction can be significantly improved.
Embodiment 6 ~ 9
The usage quantity of further change promotor, specifically in table 2, its operation and unclassified stores add-on same as described above, experimental result is as follows:
Table 2
Embodiment 10
Be used as alkali-metal potassium metal 0.0040mol, 4-bromo biphenyl 0.0040 mole as promotor, carry out the experiment same with case study on implementation 1, obtain that 5-p-hexadiene transformation efficiency is 57%, selection rate is 71.0%.
Embodiment 11 ~ 15
Change the usage quantity of alkyl oxide, its operation and unclassified stores add-on identical with embodiment 1, experimental result is as follows.
Embodiment 16 ~ 21
Change alkali-metal usage quantity, its operation and unclassified stores add-on identical with case study on implementation 1, experimental result is as follows.
Claims (10)
1. the side chain alkylation method of an alkylation selectivity aromatics, it is characterized in that it is using aromatic halide as promotor, with alkyl oxide and base metal catalysts for catalyzer, with unsaturated hydrocarbon, alkyl aromatic compound generation side chain alkylation is reacted
Wherein said aromatic halide is the halogenide of naphthalene, biphenyl, terphenyl, pyrene or phenanthrene,
The add-on of described aromatic halide is alkali-metal 0.1 ~ 1.0 times of molar weight.
2. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1, is characterized in that described aromatic halide is the bromide of the muriate of naphthalene, the bromide of naphthalene, the muriate of biphenyl or biphenyl.
3. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1, is characterized in that described aromatic halide add-on is alkali-metal 0.3 ~ 0.6 times of molar weight.
4. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1, is characterized in that described alkyl oxide is one or more in diethyl ether, diisopropyl ether, glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methyltetrahydrofuran, dioxan or phenyl ether;
Described base metal catalysts is the complex compound of the hydride of alkali metal or alkali metal, alkyl alkali compound, aromatic base compound or alkali metal and alkyl oxide; Described alkali metal is sodium, potassium, lithium or caesium;
Described unsaturated hydrocarbon is C
2~ C
20chain or the unsaturated hydrocarbon of ring-type;
Described alkyl aromatic compound is benzene compound, alkylnaphthalene compounds, alkyl biphenyl compounds, alkyl anthracene compounds or alkyl biphenyl ether compound.
5. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 4, is characterized in that described alkyl aromatic compound is toluene, dimethylbenzene, Three methyl Benzene, ethylbenzene, ethyltoluene compounds, ethylxylenes compounds, diethylbenzene compounds, propylbenzene; Methylnaphthalene compounds, ethyl naphthalene compounds or dimethylnaphthalene.
6. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1, is characterized in that the consumption of described alkyl oxide is 0.1 ~ 5 times of alkyl aromatic quality.
7. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1, is characterized in that the usage quantity of described base metal catalysts is 0.1 ~ 3 mol% for alkyl aromatic hydrocarbon.
8. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 4, it is characterized in that described unsaturated hydrocarbon is ethene, vinylbenzene, propylene, butylene, 1,3-divinyl, 2-methyl isophthalic acid, 3-divinyl, pentadiene class, hexadiene class, tetrahydrobenzene or acenaphthene.
9., according to the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 1 ~ 8 any one, it is characterized in that its operation steps is:
Add alkyl oxide, alkyl aromatic compound, base metal catalysts and aromatic halide in a reservoir, be heated to 30 ~ 100 DEG C, stir at this temperature, and unsaturated hydrocarbon gases is slowly passed in said mixture.
10. the side chain alkylation method of a kind of alkylation selectivity aromatics according to claim 9, is characterized in that the consumption of described unsaturated hydrocarbon is 0.3 ~ 0.7 times of molar weight of alkyl aromatic compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582844A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation catalyst composition and applications thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0439679A2 (en) * | 1990-01-30 | 1991-08-07 | Sumitomo Chemical Company, Limited | Process for alkylating alkylaromatic hydrocarbons |
| EP0575081A2 (en) * | 1992-06-05 | 1993-12-22 | Sumikin Chemical Co., Ltd. | Side-chain alkylation method |
-
2014
- 2014-09-09 CN CN201410454235.8A patent/CN104326853B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0439679A2 (en) * | 1990-01-30 | 1991-08-07 | Sumitomo Chemical Company, Limited | Process for alkylating alkylaromatic hydrocarbons |
| EP0575081A2 (en) * | 1992-06-05 | 1993-12-22 | Sumikin Chemical Co., Ltd. | Side-chain alkylation method |
| US5414174A (en) * | 1992-06-05 | 1995-05-09 | Sumikin Chemical Co., Ltd. | Side-chain alkylation method |
| EP0575081B1 (en) * | 1992-06-05 | 1997-08-20 | Sumikin Chemical Co., Ltd. | Side-chain alkylation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582844A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation catalyst composition and applications thereof |
| CN106582844B (en) * | 2015-10-19 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of aromatic alkylation catalysts composition and application |
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