CN113976175A - Ionic liquid catalyst for preparing primary amine and application thereof - Google Patents

Ionic liquid catalyst for preparing primary amine and application thereof Download PDF

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CN113976175A
CN113976175A CN202111201507.XA CN202111201507A CN113976175A CN 113976175 A CN113976175 A CN 113976175A CN 202111201507 A CN202111201507 A CN 202111201507A CN 113976175 A CN113976175 A CN 113976175A
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ionic liquid
primary amine
liquid catalyst
hydrocarbon
reaction
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黄小兵
刘北平
申有名
张向阳
丁祥
靳俊玲
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Hunan Yadevance Chemical Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/068—Polyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups

Abstract

The invention provides an ionic liquid catalyst for preparing primary amine and application thereof, the ionic liquid catalyst is polyethylene glycol type gemini ionic liquid, and can form an ionic liquid catalytic system with high-temperature homogeneous phase and low-temperature two-phase with an organic hydrocarbon solvent, polyethylene glycol with proper polymerization degree is selected to synthesize the gemini ionic liquid, and a catalytic ionic liquid system with high-temperature two-phase and low-temperature homogeneous phase can be formed with water. Can be used for ammonolysis of halogenated hydrocarbon in organic solution or aqueous solution by using cheap ammonia source to obtain high-purity primary amine product easy to separate. The loss of the ionic liquid catalyst is small in the production and synthesis process, the reaction rate is high in the ammonolysis process, and the product purity and the yield are high. The ionic liquid catalyst has the advantages of simple synthesis process, easy recovery and recycling, and small loss. The ionic liquid catalyst is used for aminolysis of halogenated hydrocarbon to produce primary amine, and the three wastes are less, so that the ionic liquid catalyst is green and environment-friendly, and has remarkable economic benefit.

Description

Ionic liquid catalyst for preparing primary amine and application thereof
Technical Field
The invention mainly relates to a technology for ammonolysis of halogenated hydrocarbon (or hydrocarbyl alcohol sulfonate), belongs to the field of chemical industry, and relates to a novel ionic liquid catalyst for preparing primary amine by using halogenated hydrocarbon (or hydrocarbyl alcohol sulfonate) and ammonia (or formamide) solution as raw materials.
Background
The primary amine compound is an important organic raw material and has wide application in the fields of medicines, pesticides, fine chemical industry and the like. The traditional method for preparing primary amine mainly comprises the following steps of (1) Gaberial reaction, (2) Hoffmann degradation reaction, (3) nitrile hydrogenolysis, (4) ammonium acetate heating decomposition (5), leucokart reaction, (6) curtius rearrangement reaction, (7) schmidt reaction, (8) Delipine reaction, and (9) ammonia direct substitution. However, none of these methods is entirely satisfactory from the industrial point of view, since these processes require the use of expensive aminating agents, there are complicated decomposition processes, and a large number of "three wastes" are produced which are difficult to handle.
In view of economic benefits of industrial production, halogenated hydrocarbon and hydrocarbon-based alcohol sulfonate have wide sources, convenient preparation and low price, so halogenated hydrocarbon or hydrocarbon-based alcohol sulfonate is mostly used as a raw material in industrial production, cheap ammonia is used as an N source, and a method of directly substituting ammonia is adopted to produce primary amine. However, this process produces a large amount of by-products, secondary and tertiary amines, resulting in low yields (< 50%) of the desired product, while typically 20-fold or even more ammonia is required to increase the yield of primary amines. The Delipine method, the Gabriel method and the like have good selectivity on the generation of primary amine, but a large amount of byproducts are left in the Delipine method and the Gabriel method, so that the products are difficult to separate and purify, and the treatment cost of three wastes is increased. In order to use cheap halogenated hydrocarbon or hydrocarbon alcohol sulfonate and ammonia as the starting materials for synthesizing primary amine, CN102718673 and CN103804108 propose adding catalysts, and CN101346345, CN101370765 and US005210303A propose adding side reaction inhibitors and the like, so as to achieve the purpose of improving the product yield. However, the additives added in these methods are either difficult to recover or difficult to separate and purify the product, and thus are not satisfactory.
In summary, these methods have not achieved the desired results, but the fundamental reasons are that these "additives" have no controllability, do not allow quantitative aminolysis to primary amines, are not stable enough in chemical properties, are homogeneous throughout the reaction, and are not easy to separate the product, "additives" and solvent at the end of the reaction. And the ionic liquid can be used for eliminating the defects. The invention provides a novel ionic liquid catalyst for preparing primary amine by taking halohydrocarbon and ammonia water as raw materials through ammonolysis, and the process for preparing the primary amine by taking the ionic liquid which is easy to separate and has specificity for generating the primary amine as the catalyst is prepared.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a high-efficiency catalyst for directly substituting ammonia for aminolysis of halogenated hydrocarbon to generate primary amine, which can improve reaction selectivity, has strong specificity, does not generate side reaction, and can solve the problem of environmental pollution in the production process of primary amine.
The invention aims to provide a new process method for preparing primary amine by taking halohydrocarbon (or hydrocarbon alcohol sulfonate) and ammonia water (or formamide) as raw materials and carrying out catalytic ammonolysis reaction temperature-controlled separation under the condition of the ionic liquid catalyst.
The ionic liquid catalyst for preparing primary amine by ammonolysis of halogenated hydrocarbon is polyethylene glycol type gemini (or single branching, and the gemini is taken as an example for illustration) ionic liquid, and the structure of the ionic liquid catalyst is as follows:
Figure BDA0003305111490000021
substituents R on maleic anhydride at both ends of its molecular chain1Can be used forIs hydrogen, or RnGroup (R)nPhenyl, naphthyl, halogen, nitro, cyano, mercapto, amino, N-monoalkyl (or aryl) amino, N-dialkyl (or aryl) amino, amido, alkyl, alkoxy, carboxyl, haloalkyl, 3-to 6-membered N, O, S heterocyclic group). The aromatic hydrocarbon is aromatic hydrocarbon below 9 carbon atoms, the alkane is alkane below 7 carbon atoms, and all the alkane comprises isomers and derivatives of the aromatic hydrocarbon and the alkane, and when the alkane is phenyl or naphthyl, 0-5 same or different R can be arranged on the groupnA radical substituent. The phenyl substituents on the maleic anhydride can be naphthyl, 5-or 6-membered N, O, S heterocyclic groups, and these substituents can also have one or more identical or different RnA substituent group.
The specific synthesis process of the ionic liquid catalyst comprises the following steps: (taking 3-alkyl-4-p-methylbenzene maleic anhydride as an example)
(1) Chloridizing 3-alkyl-4-p-methyl benzene maleic anhydride in a proper solvent to obtain 3-alkyl-4-p-chloromethyl benzene maleic anhydride;
Figure BDA0003305111490000031
(2) reacting polyethylene glycol (PEG) with thionyl chloride in a proper solvent under the nitrogen protection anhydrous condition to obtain polyethylene glycol (Cl-PEG) with two chlorinated endsn-Cl)；
Figure BDA0003305111490000032
(3) And (2) adding equimolar imidazole into a sodium alkoxide solution, heating for reaction, adding the polyethylene glycol with two chlorinated ends in the step (2) for continuous reaction, reacting with the 3-alkyl-4-p-chloromethyl benzene maleic anhydride synthesized in the step (1), and refining and purifying to obtain the required polyethylene glycol type gemini ionic liquid catalyst.
Figure BDA0003305111490000033
Further, polyethylene glycol (PEG) in the molecular chain of the polyethylene glycol type gemini ionic liquid catalystn) The polymerization degree n of (A) is 100 to 4000, preferably 200 to 2000. When the kind of the solvent is not specifically described, the organic solvent may be an alcohol, aldehyde, ether, ketone, ester, carboxylic acid, amide, amine having 8 or less carbon atoms, 3 to 6-membered cycloalkane having 11 or less carbon atoms, heterocyclic hydrocarbon having 5 or 6-membered N, O, S carbon atoms, aromatic hydrocarbon having 11 or less carbon atoms, and these organic substances include isomers and derivatives thereof. One of chlorobenzene, toluene, cyclohexane, ethanol and isopropanol is preferred.
The polyethylene glycol type gemini ionic liquid catalyst provided by the invention has the following characteristics in structure:
(1) maleic anhydride with 1 or 2 substituent groups at two ends of a molecular chain is grafted on imidazole groups at two ends of the gemini ionic liquid through one of the maleic anhydride (such as a benzene ring);
(2) imidazole groups are respectively grafted at two ends of polyethylene glycol with proper polymerization degree in the middle of a molecular chain to form gemini ionic liquid (PEG)nDIL) to give it a higher thermal stability;
(3) by changing the polymerization degree and R of polyethylene glycol in the middle of molecular chain1The structure of (2) can change the dissolution characteristics of the ionic liquid with water and certain organic solvents; the ionic liquid catalyst is polyethylene glycol type gemini ionic liquid, which can form an ionic liquid catalytic system with high-temperature homogeneous phase and low-temperature two-phase with an organic hydrocarbon solvent, and polyethylene glycol with proper polymerization degree is selected to synthesize the gemini ionic liquid, and can also form a catalytic ionic liquid system with high-temperature two-phase and low-temperature homogeneous phase with water.
The polyethylene glycol type gemini ionic liquid catalyst provided by the invention can complete the cycle process shown in figure 1 when being used for preparing primary amine by ammonolysis of halogenated hydrocarbon or hydrocarbon alcohol sulfonate. The method comprises the steps of reacting polyethylene glycol type gemini ionic liquid with a solution dissolved with ammonia or formamide to form a polyethylene glycol type gemini ionic liquid aminolysis agent with an imide structure, and further carrying out aminolysis reaction with halogenated hydrocarbon or hydrocarbyl alcohol sulfonate to prepare primary amine.
The new technological process of preparing primary amine with halohydrocarbon and ammonia water or formamide as material and through catalytic ammonolysis reaction in the presence of the ionic liquid catalyst and temperature controlling separation;
the method specifically comprises the following steps:
(1) dissolving hydrocarbon raw material into one or more organic solvents (hydrocarbon is in flowing state or not adding solvent), halogenating or sulfonating, and controlling low conversion rate to obtain reaction liquid containing product halohydrocarbon or hydrocarbon alcohol sulfonate and unreacted hydrocarbon raw material (or its solution dissolved in one or more organic solvents), namely hydrocarbon raw material phase.
Carrying out ammonolysis (or heating or pressurizing) on the ionic liquid compound (I) and ammonia or formamide (or a solution of the ionic liquid compound (I) dissolved in water and one or more organic solvents) to obtain a solution of polyethylene glycol type gemini ionic liquid (II) with an imide structure (or a solution of the ionic liquid compound (I) dissolved in water and one or more organic solvents), namely an ammonolysis agent phase;
Figure BDA0003305111490000051
further, step (1) may be carried out by dissolving ammonia in water and then adding a hydrocarbon maleic anhydride to react to convert it into an imide structure. The ammonia can also be replaced by formamide, and when formamide is used, the reactant formamide can also be directly used as a solvent.
The solvent used in step (1) may also be an organic solvent, or a mixture thereof. The organic solvent is alcohol, aldehyde, ether, ketone, ester, carboxylic acid, amide and amine with less than 8C atoms, 3-6 membered cyclic alkane with less than 11C atoms, heterocyclic hydrocarbon with 5 or 6 membered N, O, S, and aromatic hydrocarbon with less than 11C atoms, and all the organic substances comprise isomers and derivatives thereof. One of chlorobenzene, toluene, cyclohexane, ethanol and isopropanol is preferred.
Further, the heating manner in step (1) is not limited, and if the heating manner is conventional heating, microwave heating may also be used. The reaction pressure in the step (1) can be controlled to be 0-1 MPa, the reaction time is 0.01-12 hours, and the reaction temperature is 10-120 ℃.
(2) Adding an aminolysis agent phase (II) into a reaction kettle, heating and increasing the pressure to the temperature and the pressure of the aminolysis reaction, then gradually adding a hydrocarbon raw material phase (halohydrocarbon or hydrocarbyl alcohol sulfonate), carrying out the aminolysis reaction in an ionic liquid catalysis aminolysis system with high-temperature homogeneous phase and low-temperature two-phase, controlling the ratio of the hydrocarbon raw material phase to the aminolysis agent phase to be 1: 0.01-100 (V), keeping the reaction liquid in homogeneous phase by controlling the temperature of the reaction kettle so as to rapidly carry out the aminolysis process similar to the Gabriel reaction [ such as a reaction (2) in the circulation process of figure 1 ], and cooling and standing for layering under normal pressure after the halohydrocarbon or the hydrocarbyl alcohol sulfonate is completely converted into the N-alkyl polyethylene glycol type gemini ionic liquid (III) to obtain the aminolysis product phase and the hydrocarbon raw material phase of the non-halogenated or sulfonated completely hydrocarbon raw material (or the solution thereof dissolved in one or more organic solvents). The hydrocarbon raw material phase of the hydrocarbon raw material which is not halogenated or sulfonated completely (or the solution of the hydrocarbon raw material dissolved in one or more organic solvents) is distilled and dehydrated, then returned to the halogenation (or sulfonation) reactor, and is supplemented with new raw material to continue halogenation or sulfonation.
Figure BDA0003305111490000061
Further, the reaction pressure in the step (2) can be controlled to be 0-2 MPa; the reaction time is 0.01 to 24 hours;
further, in the halogenated hydrocarbon or hydrocarbon-based alcohol sulfonate in the step (2), the hydrocarbon group is a hydrocarbon having 10 or less carbon atoms, or a O, S, N hydrocarbon containing one or more of the same or different hydrocarbon, and may be a hydrocarbon in which one or more of the hydrocarbon is substituted with one or more of the same or different halogen, nitro, amino, hydroxyl, carboxyl, cyano or mercapto.
Further, the base of step (2) is a hydroxide of an alkali metal or an alkaline earth metal, and may be a mixed base of one or more of these bases. The amount of the alkali is 1-1.5 equivalent;
(3) adding acid, alkali or hydrazine into the N-alkyl imide structure ionic liquid (III) under the heating condition for acidolysis, alkaline hydrolysis or hydrazinolysis to generate reaction liquid containing primary amine (or primary amine salt), adjusting the pH value to the isoelectric point of the primary amine by using the alkali or the acid, precipitating the primary amine in a solid state, and separating to obtain the target product of the primary amine. Simultaneously generating an ionic liquid with a maleic anhydride structure, adding acid to enable the pH value of the solution to be 4-9, and automatically closing the ring of the maleic acid to form internal anhydride, namely the ionic liquid (I) with the maleic anhydride structure; and when the temperature is properly reduced, the ionic liquid (I) with the maleic anhydride structure becomes solid and is separated out from the reaction liquid.
Figure BDA0003305111490000062
Figure BDA0003305111490000072
Further, the heating mode of the reaction (3) is not limited, and if the reaction is carried out by conventional heating or microwave heating, the hydrolysis temperature is controlled to be 15-180 ℃.
The obtained maleic anhydride structure ionic liquid catalyst (I) is directly used for the imidization and N-alkylation reactions to realize cyclic utilization.
Figure BDA0003305111490000071
The ionic liquid catalyst can adjust the dissolution characteristic of the polyethylene glycol in a water phase, an organic phase or a mixed phase of the polyethylene glycol and the organic phase through the polymerization degree of the polyethylene glycol, so that various ionic liquid catalysts suitable for different ammonolysis environments can be designed to form an ionic liquid catalytic system with high-temperature homogeneous phase and low-temperature homogeneous phase or high-temperature homogeneous phase and low-temperature homogeneous phase, so that the homogeneous phase is converted into two phases or multiple phases when the ammonolysis reaction is finished, the method is favorable for the ammonolysis reaction, and the products, the solvent and the catalyst are separated, purified and recovered.
Meanwhile, maleic anhydride groups are grafted, so that the interconversion of an anhydride structure and an amide structure can be completed, the process similar to the Gabriel reaction for synthesizing primary amine can be completed, and the high selectivity of the synthesized primary amine is ensured. The ionic liquid catalyst is symmetrically grafted with two imidazole groups to form a gemini ionic liquid, so that the synthesized ionic liquid catalyst has high thermal stability and little loss when being used for recycling. It is apparent that the ionic liquid catalyst of the present invention is an ideal solvent and catalyst for the ammonolysis of halogenated hydrocarbons to produce primary amines. Therefore, the method is economical and environment-friendly.
Drawings
FIG. 1 is a diagram of an ionic liquid catalyzed ammonolysis cycle.
Detailed Description
The following provides a more detailed description of the present invention. The above and other objects, features and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the present invention.
The ammonolysis of halogenated hydrocarbons is an important class of reactions in organic synthesis. When the ammonolysis reaction occurs, a large amount of byproducts, namely secondary amine and tertiary amine, are generated due to serial reactions, and the purer primary amine is difficult to obtain in industrial production. The polyethylene glycol gemini ionic liquid is used in the ammonolysis reaction process of halogenated hydrocarbon, is a solvent and a catalyst, and is an ideal ionic liquid catalyst for ammonolysis of the halogenated hydrocarbon to synthesize primary amine. It has the following structure:
Figure BDA0003305111490000081
example 1 preparation of a polyethylene glycol type Gemini Ionic liquid catalyst (degree of polymerization n 1000)
(1) Weighing 100g of the compound 1, adding the compound into 100mL of chlorobenzene, magnetically stirring the mixture to fully dissolve the compound, introducing chlorine, and reacting the mixture for 2 hours at 40 ℃ under the condition of illumination; after removal of the solvent by rotary evaporation, a crude product of this material was obtained, which was recrystallized from ethyl acetate to obtain 98g of 3-methyl-4-p-chloromethylbenzene maleic anhydride (Compound 2). (reaction formula 1)
Figure BDA0003305111490000091
(2) 186g of double-end-chlorinated polyethylene glycol (with a polymerization degree N of 1000), 136g of imidazole and 112g of potassium hydroxide are weighed, added into 100ml of N-dimethylformamide, and reacted for 10 hours at 25 ℃ after being sufficiently dissolved by magnetic stirring; after the solvent is removed by rotary evaporation, a crude product of the substance is obtained, and after recrystallization by ethanol, 190g of the double-end-chlorinated polyethylene glycol derivative is obtained. (reaction formula 2)
Figure BDA0003305111490000092
(3) Weighing 125g of double-end-chlorinated polyethylene glycol derivative, 236g of compound 2 and 56g of potassium hydroxide, adding into 100mL of acetonitrile solvent, magnetically stirring for full dissolution, and reacting at 25 ℃ for 10 hours; after the solvent was removed by rotary evaporation, a crude product of the substance was obtained, and after recrystallization with diethyl ether, 300g of a polyethylene glycol type gemini ionic liquid catalyst (degree of polymerization n 1000) was obtained. (reaction formula 3)
Figure BDA0003305111490000093
Example 2 preparation of polyethylene glycol type Gemini Ionic liquid catalyst (degree of polymerization n 2000)
(1) Preparation of Compound 2 As in example 1
(2) 225g of double-end-chlorinated polyethylene glycol (with a polymerization degree N of 2000,) 136g of imidazole and 112g of potassium hydroxide are weighed, added into 100mL of N, N-dimethylformamide, and reacted for 10 hours at 25 ℃ after being sufficiently dissolved by magnetic stirring; after the solvent is removed by rotary evaporation, a crude product of the substance is obtained, and after recrystallization by ethanol, 290g of the double-end-chlorinated polyethylene glycol derivative is obtained.
Figure BDA0003305111490000101
(3) Weighing 125g of polyethylene glycol derivative (with the polymerization degree n of 2000), 118g of compound 2 and 28g of potassium hydroxide, adding into 100mL of acetonitrile solvent, magnetically stirring for full dissolution, and reacting at 25 ℃ for 10 hours; after the solvent was removed by rotary evaporation, a crude product of the substance was obtained, and after recrystallization with diethyl ether, 310g of a polyethylene glycol type gemini ionic liquid catalyst (degree of polymerization n of 2000) was obtained.
Figure BDA0003305111490000102
Example 3: process for preparing primary amine by using ionic liquid catalyst
650L of polyethylene glycol (n is 1000) gemini ionic liquid (I) and 25 percent (wt) of ammonia water (the volume ratio of the ionic liquid to the ammonia water is 6.5:1) are put into a 1000L stirring reaction kettle, the mixture is heated to 50 ℃ by microwave and reacts for 20min, then the mixture is cooled and layered, the lower layer is separated and added into the 1000L ammonolysis reaction kettle at one time, and the liquid is an ammonolysis agent phase. Gradually adding p-chloromethylbenzoic acid (hydrocarbon raw material phase) into the 1000L ammonolysis reaction kettle with ammonolysis agent phase under stirring, microwave heating to 100 deg.C after adding hydrocarbon raw material phase, controlling constant temperature reaction for 50min, reducing the temperature of reaction liquid to 35 deg.C, standing and layering. The p-methyl benzoic acid is enriched in hydrocarbon raw material phase due to high solubility in chlorobenzene, and is enriched in lower layer. As the hydrocarbon raw material phase contains a certain amount of HCl generated by chlorination reaction, and reacts with the alkylated ionic liquid to generate hydrochloride, the solubility in the water phase is increased, and the alkylated ionic liquid is almost completely enriched in the upper ammonolysis agent phase. And (3) transferring the upper-layer aminolysis agent phase into a hydrolysis tank, adding 36% HCl to pH 5 at the natural temperature, adjusting the pH to 7.5 isoelectric point of the aminomethylbenzoic acid by using 30% NaOH after the hydrocarbonized liquid hydrochloride is completely hydrolyzed into the aminomethylbenzoic acid hydrochloride, and cooling, crystallizing and separating to obtain the product aminomethylbenzoic acid. And meanwhile, the liquid phase after the product is separated is further layered, the upper layer is a water phase containing a very small amount of product, the lower layer is an ionic liquid phase, and the ionic liquid is imidized into the ionic liquid with the imide structure and recycled.
The ammonolysis agent phase is recycled for 10 times, the ionic liquid loss is 10 percent (wt), and the actual yield of the product aminomethylbenzoic acid is 95 percent of the theoretical yield.
Example 4
700L of polyethylene glycol (n is 2000) gemini ionic liquid (II) and 25 percent (wt) of ammonia water (the volume ratio of the ionic liquid to the ammonia water is 7:1) are stirred and reacted in 1000L, the kettle is heated to 50 ℃ by microwave for 20min, then cooled and layered, and the lower layer is separated and added into the 1000L ammonolysis reaction kettle at one time. Gradually adding 200kg p-chloromethylbenzoic acid into the 1000L ammonolysis reaction kettle with ammonolysis agent phase under stirring, adding hydrocarbon material phase, microwave heating to 100 deg.C, reacting at constant temperature for 50min, cooling to 35 deg.C, standing, and layering. The subsequent process steps and parameters are essentially the same as in example 4. The ammonolysis agent phase is recycled for 10 times, the ionic liquid loss is 10 percent (wt), and the actual yield of the product aminomethylbenzoic acid is 90 percent of the theoretical yield.
It should also be understood that although the present invention has been clearly illustrated by the foregoing examples, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.

Claims (7)

1. An ionic liquid catalyst for the preparation of a primary amine, characterized by: the structure of the ionic liquid catalyst is as follows:
Figure FDA0003305111480000011
wherein R is1Is hydrogen or RnGroup, RnOne or more of phenyl, naphthyl, halogen, nitro, cyano, mercapto, amino, N-monoalkylamino, N-dialkylamino, amido, alkyl, alkoxy, carboxyl, haloalkyl, and a 3-to 6-membered N, O, S heterocyclic group; the polymerization degree n is 100 to 4000.
2. The ionic liquid catalyst for the ammonolysis of halogenated hydrocarbons to produce primary amines according to claim 1, wherein: the alkyl is alkane with 7 or less carbon atoms or isomers and derivatives thereof; rnThe number of the groups may be 0 to 5Identical or different RnA substituent group; the polymerization degree n is 200 to 2000.
3. Use of an ionic liquid catalyst according to claim 1 or 2 for the preparation of a primary amine, characterized in that: the application steps are as follows:
(1) mixing an ionic liquid catalyst with a solution dissolved with ammonia or formamide to form an aminolysis agent, stirring and heating to the aminolysis reaction temperature, wherein the maleic anhydride structure ionic liquid (I) is converted into an imide structure ionic liquid compound (II);
Figure FDA0003305111480000012
(2) carrying out N-alkylation reaction on an imide structure ionic liquid compound (II) and halohydrocarbon or hydrocarbyl alcohol sulfonate under the condition of adding alkali to generate an N-hydrocarbyl imide structure compound (III);
Figure FDA0003305111480000021
(3) adding N-alkyl imide structure ionic liquid (III) into alkali, heating and hydrolyzing to generate primary amine or primary amine salt, and separating to obtain a product; simultaneously generating an ionic liquid with a maleic anhydride structure, adding acid to enable the pH value of the solution to be 4-9, and automatically closing the ring of the maleic acid to form internal anhydride, namely the ionic liquid (I) with the maleic anhydride structure; cooling to enable the ionic liquid (I) with the maleic anhydride structure to become solid, and separating out the solid from the reaction liquid for recycling;
Figure FDA0003305111480000022
4. use of an ionic liquid catalyst according to claim 3 for the preparation of a primary amine, characterized in that: the reaction temperature of the step (1) is 10-120 ℃; the reaction pressure is controlled to be 0-1 MPa, and the reaction time is 0.01-12 hours.
5. Use of an ionic liquid catalyst according to claim 3 for the preparation of a primary amine, characterized in that: the reaction pressure in the step (2) can be controlled to be 0-2 MPa; the reaction time is 0.01-24 hours; in the halogenated hydrocarbon or hydrocarbon alcohol sulfonate in the step (2), the hydrocarbon group is a hydrocarbon with 10 carbon atoms or less, or is a O, S, N hydrocarbon containing one or more same or different hydrocarbons, or is a hydrocarbon in which one or more same or different halogens, nitro groups, amino groups, hydroxyl groups, carboxyl groups, cyano groups or mercapto groups are substituted.
6. Use of an ionic liquid catalyst according to claim 3 for the preparation of a primary amine, characterized in that: the alkali in the step (2) is mixed alkali of one or more of hydroxides of alkali metals and alkaline earth metals; the amount of base used is 1-1.5 equivalents.
7. Use of an ionic liquid catalyst according to claim 3 for the preparation of a primary amine, characterized in that: and (3) controlling the hydrolysis temperature to be 15-180 ℃.
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