Cyclopropene imine efficient catalyst and preparation method and application thereof

Abstract

The invention discloses a cyclopropene imine efficient catalyst, which has the following structural formula: # imgabs0 #, in which groups on carbon chains and / or branched chains of RA and RB comprise-OH,-NH-,-N =,-O-,-S-,-Si-,-Si-O-,-(C = O)-,-C = N, an aromatic cluster group and a cyclic non-aromatic cluster group; the invention also provides a preparation method and application of the cyclopropene imine efficient catalyst. The method has the beneficial effects that CO2 can be activated under mild temperature and pressure by high catalysis, carbonation reaction is carried out, and carbonic ester or carbamate compounds are synthesized, so that CO2 is effectively converted into fine chemicals; and the synthesized carbonic ester or carbamate compound can effectively avoid the use of an unstable and highly toxic isocyanate raw material, so that CO2 is effectively converted into an advanced material, and the method is a safe and environment-friendly technology.

Description

Technical Field

[0001] The present invention relates to a cyclopropenimine catalyst and its application in activating carbon dioxide (CO 2 ), and specifically to a highly efficient cyclopropenimine catalyst, its preparation method and application. Trichloropropene and chlorine are used as the main raw materials to prepare cyclopropenimine, and cyclopropenimine is used as a highly efficient catalyst to activate carbon dioxide (CO 2 ) for carbonation reaction to produce carbonate and carbamate compounds. Background Art

[0002] Currently, the emissions of carbon dioxide (CO 2 ) in the atmosphere have exceeded the purification capacity of nature. To address this huge challenge concerning the survival of all mankind, scientists and engineers have developed a series of carbon reduction technologies. Representative ones include carbon capture, storage and utilization technologies, etc. Among them, based on the chemical conversion and utilization technology of CO 2 is the most important technical means to achieve "carbon peak and carbon neutrality". Although numerous technologies for using CO 2 have been proposed, only a few processes effectively use it for the synthesis of fine chemicals and materials. However, in most cases, the types of synthesized products are extremely limited, and usually need to be carried out under high temperature and high pressure.

[0003] The Chinese patent application with the publication number CN 102992947 A discloses a preparation method of pentachlorocyclopropane using 3,3,3-trichloropropene as a raw material, which undergoes a chlorination reaction with chlorine at a temperature of 0 - 100°C to produce pentachlorocyclopropane. Although this technology claims to have advantages such as a novel synthesis route, high product yield, simple operation, and easy industrial scale-up; in actual production, since the preparation process is that trichloropropene and water are stratified, and the lighter water floats on the top, playing a role of liquid sealing and chlorine conduction, it is not easy to scale up the industrialization of the reaction kettle, and the reaction rate is not easy to control.

[0004] The Chinese invention patent application with the publication number of CN 110746317 A discloses an n-type dopant based on a cycloallylimine skeleton and its applications. The cycloallylimine not only has good stability but also strong power supply ability. The reason for the high alkalinity of cycloallylimine lies in its protonated form, that is, the stability of cyclopropenium ions. Due to the smallest ring system that satisfies Hückel's rule, the 2π-electron cyclopropenium ion provides significant aromatic resonance stability for cyclopropenimine. Although this technical solution discloses the structural formula of the cycloallylimine compound, the technical problem it aims to solve is to provide an n-type dopant and improve aromatic resonance stability, which is a different technical field from this application using cyclopropenimine as an efficient catalyst for activating carbon dioxide, and is completely different in the preparation method and substituent groups. Therefore, this technical solution fails to give a technical inspiration for using cycloallylimine as a catalyst for activating carbon dioxide. Summary of the Invention

[0005] Based on the above-mentioned prior art, the object of the present invention is to provide an efficient cyclopropenimine catalyst.

[0006] The second object of the present invention is to provide a preparation method for the above-mentioned efficient cyclopropenimine catalyst.

[0007] The third object of the present invention is to provide the application of the above-mentioned efficient cyclopropenimine catalyst in activating CO 2 to carry out a carbonation reaction and synthesize carbonate or carbamate compounds.

[0008] To achieve the above-mentioned invention objects, the technical solution adopted by the present invention is: an efficient cyclopropenimine catalyst (collectively referred to as "high catalyst"), and its structural formula is as follows:

[0009] Structural formula 1:

[0010]

[0011] Among them, the groups on the carbon chain and / or side chain of R A can contain unsaturated bonds and various functional groups, including -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc.;

[0012] R B The groups on the carbon chain and / or side chain of can contain unsaturated bonds and various functional groups, including -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc.

[0013] Among them, R A and RB The number of carbon atoms in the carbon chain is 1 to 20, preferably, the R A carbon chain has 10 or fewer carbon atoms, and R B carbon chain has 7 or fewer carbon atoms. The high catalyst of the present invention can activate CO under mild temperature and pressure (such as normal temperature and pressure) 2 to carry out a carbonation reaction and synthesize carbonate or carbamate compounds, thereby effectively converting CO 2 into fine chemicals.

[0014] The activation performance of the cyclopropenimine-based highly efficient catalyst can be adjusted by the selection of R A and R B .

[0015] A preparation method of a cyclopropenimine-based highly efficient catalyst uses trichloropropene and chlorine as starting materials and is prepared through three-step reactions. The steps included are as follows:

[0016] (1) Using 3,3,3-trichloropropene and chlorine as raw materials and water as an auxiliary solvent for chlorine, prepare pentachlorocyclopropane;

[0017] (2) Using secondary amine (R A 2 NH) and pentachlorocyclopropane as raw materials, prepare a high-catalyst intermediate;

[0018] (3) Using the high-catalyst intermediate and primary amine (R B NH 2 ) as raw materials, prepare the high catalyst.

[0019] Among them, the groups on the carbon chain and / or side chain of R A and R B can include unsaturated bonds and various functional groups, including -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc.; among them, the number of carbon atoms in the carbon chain of R A and R B is 1 to 20, preferably, the R A carbon chain has 10 or fewer carbon atoms, and R B carbon chain has 7 or fewer carbon atoms.

[0020] In the step (1), first add 3,3,3-trichloropropene and water into a reaction kettle equipped with a mechanical stirring device, stir, control the temperature of the reaction kettle at 5 - 90°C, remove the oxygen in the reaction kettle, and then introduce chlorine for reaction.

[0021] Among them, the stirring rate should ensure that the Reynolds number based on the stirrer diameter is in the turbulent region to ensure good dispersion of water and gas in 3,3,3-trichloropropene. Preferably, the stirring rate ensures that the stirring Reynolds number based on the stirrer diameter and water is greater than 10 4 .

[0022] The method for removing oxygen in the reaction kettle is to introduce nitrogen to remove the oxygen in the reaction kettle. After the oxygen is removed, close the exhaust port of the reaction kettle, continuously introduce chlorine gas, and start the reaction. Preferably, the time for introducing nitrogen is 1 - 30 minutes and then evacuate. When the introduced chlorine gas is not evacuated, the reaction kettle operates at slightly above atmospheric pressure; the amount of chlorine gas introduced must be controlled to ensure that the temperature of the reaction kettle is within a controllable range. The amount of chlorine gas introduced at the beginning is very small so that the added amount can be completely consumed by the reaction. Then gradually increase the chlorine gas flow rate and monitor whether the temperature of the reaction kettle is controllable. Control is achieved through a control system that sets a temperature control feedback linked to the chlorine gas flow rate on the reaction kettle. When the control system finds that the chlorine gas consumption starts to decrease, it indicates that the conversion of trichloropropene is approaching completion, then close the chlorine gas and continue to operate until the remaining chlorine gas in the kettle is consumed.

[0023] The reaction can be carried out in the presence of light, but although the presence of light can promote the reaction rate, it will affect the reaction yield and make the reaction process difficult to control. Therefore, preferably, the reaction is carried out under light - shielding conditions.

[0024] Preferably, the temperature of the reaction kettle should be controlled between 10 - 50 °C.

[0025] Among them, the volume ratio of water to 3,3,3 - trichloropropene is 1∶10 - 4∶6. Preferably, the volume ratio of water to 3,3,3 - trichloropropene is 2∶10 - 3∶6.

[0026] The ultimate goal of the mechanical stirring device is to make the fluid flow in the turbulent region, which includes a stirring paddle and baffles; among them, the stirring paddle can be a general curved - blade turbine type, pitched - blade turbine type, propeller type, or straight - blade disk turbine type, etc., but not limited to these; the baffles can be uniform or non - uniform cylindrical type, plate type, or elliptical type, etc., but not limited to these. The number of baffles is 1 - 4, preferably two; regardless of the choice, the result should achieve a baffle effect of 50% - 100%, preferably, the result should achieve a baffle effect of 60% - 100%.

[0027] In the step (1), after the reaction ends, the main product in the reaction kettle is pentachlorocyclopropane, and its selectivity can reach more than 97%; in addition, the product also contains added water, a small amount of unreacted 3,3,3 - trichloropropene, and generated hydrogen chloride. The organic phase composed of pentachlorocyclopropane and 3,3,3 - trichloropropene is easily separated from the aqueous phase, and the boiling points of pentachlorocyclopropane and 3,3,3 - trichloropropene differ greatly, and they can be easily separated by distillation method.

[0028] The step (2) uses secondary amine (R A 2 NH) and pentachlorocyclopropane as raw materials to prepare the high-catalytic intermediate. The preparation steps are as follows: Add pentachlorocyclopropane and the first solvent into a reaction kettle with a stirring device, stir and control the temperature of the reaction kettle at 5 - 60 °C, slowly dropwise add the secondary amine and start the reaction for 1 - 12 hours, and then post-treat the reaction product to obtain the high-catalytic intermediate.

[0029] Among them, the dropping rate of the secondary amine should ensure that the concentration of the secondary amine in the reaction kettle is extremely low, that is, the reaction process is always in a "starvation" state. The reaction time is related to the temperature. Preferably, it is usually 5 - 10 hours. After the reaction, depending on the first solvent used, the reaction product can be the high-catalytic intermediate ((R A 2 N) 2 C 3 C1 2 ), the precipitate of the secondary amine salt (R A 2 NH 2 C1) or the coprecipitate of the high-catalytic intermediate and the secondary amine salt. If only the high-catalytic intermediate precipitates, the high-catalytic intermediate can be obtained by filtration separation. If the secondary amine salt is the precipitate, the solid secondary amine salt is removed by filtration separation to obtain a solution of the high-catalytic intermediate dissolved in the first solvent, and the high-catalytic intermediate can be obtained by extraction. If the obtained is the coprecipitate of the high-catalytic intermediate and the secondary amine salt, a second solvent is needed. The second solvent only dissolves the high-catalytic intermediate or only dissolves the secondary amine salt, and thus the high-catalytic intermediate and the secondary amine salt can be separated.

[0030] In the secondary amine (R A 2 NH), R A can be an alkyl group with branched or unbranched chains having various carbon numbers. The groups on the carbon chain and / or the branched chain of R A can include unsaturated bonds and various functional groups, including -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc. Preferably, it can be ethyl, propyl, n-butyl or cyclohexyl.

[0031] The first solvent can be any solvent that can make the high-catalytic intermediate or the secondary amine salt form a precipitate, or any solvent that can make the high-catalytic intermediate and the secondary amine salt form a coprecipitate. Considering the optimization of the preparation process, the first solvent is preferably a solvent that only dissolves the high-catalytic intermediate ((R A 2 N) 2 C 3 Cl 2) or a solvent that only dissolves secondary amine salts (R A 2 NH 2 Cl). Thus, the use of a second solvent can be avoided. Further preferably, the first solvent is ethyl acetate, phenylacetonitrile or n-butyronitrile.

[0032] The second solvent can be any solvent that only dissolves the high-catalyst intermediate or only dissolves secondary amine salts. Preferably, the second solvent is a solvent that only dissolves the high-catalyst intermediate. Further preferably, the second solvent is phenylacetonitrile or n-butyronitrile.

[0033] In addition, in order to recover the secondary amine in the solid secondary amine salt, an aqueous solution of an inorganic base (such as an aqueous NaOH solution) can be used to carry out a neutralization reaction with the solid secondary amine salt to reduce the secondary amine. For secondary amines with longer carbon chains, since they are insoluble in water, the aqueous phase and the organic phase are separated to obtain the secondary amine. If the carbon chain of the secondary amine is short (such as diethylamine and dipropylamine), the secondary amine is soluble in water, and a rectification method or an extraction method needs to be used to obtain the secondary amine.

[0034] Preferably, the temperature of the reaction kettle should be controlled between 10 - 40 °C, and usually, the reaction can be carried out at room temperature.

[0035] In the step (3), using the high-catalyst intermediate and primary amine (R B NH 2 ) as raw materials, the preparation steps for preparing the high-catalyst include the following: Add the high-catalyst intermediate and the third solvent to a reaction kettle with a stirring device, control the temperature of the reaction kettle at 5 - 60 °C. After the high-catalyst intermediate is fully dissolved, slowly add dropwise the primary amine and react for 1 - 20 hours to obtain the high-catalyst chloride ((R A 2 N) 2 C 3 (R B NHCl)), and then carry out post-treatment on the high-catalyst chloride to obtain the high-catalyst.

[0036] The reaction time after adding dropwise the primary amine is related to the temperature. Preferably, the reaction time is 5 - 18 hours.

[0037] After the reaction is completed, the high-catalyst chloride ((R A 2 N) 2 C 3 (R B NHCl)) and primary amine chloride (R B NH 3 Cl) can be obtained, wherein the structural formula of the high-catalyst chloride ((R A 2 N) 2 C 3 (R B NHCl)) is:

[0038] Structural formula II:

[0039]

[0040] The above-mentioned high-catalyst chloride and primary amine chloride have the characteristics of salts. If the third solvent is properly selected, the high-catalyst chloride and primary amine chloride will form a coprecipitate during the reaction. Subsequently, there are two options to obtain the high-catalyst. First, the coprecipitate separated by filtration is returned to the reaction kettle, and an aqueous solution of an inorganic base (such as an aqueous NaOH solution) is added to the reaction kettle. Under strong stirring, a neutralization reaction is carried out to generate the high-catalyst and primary amine. Since the generated high-catalyst has no salt characteristics and is insoluble in water, the high-catalyst will be dispersed in water in the form of solid particles, while the primary amine is soluble in water. Therefore, the high-catalyst dispersed in water is separated by filtration to obtain the high-catalyst in the form of a solid (white) powder with the structure of Structural formula I; the aqueous phase can be recovered by rectification separation of the primary amine. Second, if the primary amine used is insoluble in water, the coprecipitate of the high-catalyst chloride and primary amine chloride is not filtered and separated from the third solvent. An aqueous solution of an inorganic base (which can be an aqueous NaOH solution) is added to the reaction kettle under strong stirring, and a neutralization reaction is carried out to generate the high-catalyst and primary amine. The generated high-catalyst and primary amine will return to the third solvent. The organic phase and the aqueous phase are separated, and the organic phase is passed through a solid drying column to remove the residual water, so as to obtain the high-catalyst and primary amine dissolved in the third solvent. Then, a fourth solvent is added. The fourth solvent must dissolve only the primary amine or only the high-catalyst and be miscible with the third solvent, whereby the high-catalyst and primary amine can be separated.

[0041] In the primary amine (R B NH 2 ), R B can be an alkyl group with branched or unbranched chains having various carbon numbers. The groups on the carbon chain and branched chain of R B can include unsaturated bonds and various functional groups, including -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc.

[0042] Preferably, the primary amine is ethylamine, propylamine, cyclopropylamine or n-butylamine.

[0043] The third solvent can be any solvent that only dissolves the high-catalyst intermediate and the primary amine (R B NH 2 ), but does not dissolve the high-catalyst chloride and the primary amine chloride. Preferably, the third solvent is n-butyronitrile or phenylacetonitrile.

[0044] The fourth solvent can be any solvent that is miscible with the third solvent but cannot dissolve the high-catalyst or the primary amine used. Preferably, the fourth solvent can be ethyl acetate or acetonitrile.

[0045] The highly efficient cyclopropenimine catalyst (high catalyst) of the present invention is applied to activate CO under mild temperature and pressure (room temperature and normal pressure). 2 to carry out a carbonation reaction and prepare a carbonate compound, thereby effectively converting CO 2 into fine chemicals.

[0046] A carbonate compound is prepared by adding RX and ROH to the high catalyst and introducing CO. The reaction formula is as follows: A RX and ROH B are added to the high catalyst and CO is introduced. 2 The preparation is as follows: The reaction formula is as follows:

[0047] Reaction formula 1:

[0048]

[0049] where X represents a halogen, and X and the hydroxyl group (-OH) are respectively connected to the carbon atoms on R A and R B respectively. R A and R B can be the same or different, and R A and R B can be alkyl groups with branched or unbranched chains having various carbon numbers. The groups on the carbon chain and / or the branched chain of R A and R B can include unsaturated bonds and various functional groups, including -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc.

[0050] Among them, the number of carbon atoms on the carbon chain of R A and R B is 1-20, preferably, the number of carbon atoms on the carbon chain of R A is within 10 carbons, and the number of carbon atoms on the carbon chain of R B is within 7 carbons.

[0051] A dibutyl carbonate is synthesized by reacting n-butanol and 1-bromobutane in the presence of the high catalyst and introducing CO using n-butyronitrile as a solvent at room temperature and normal pressure. The reaction formula is as follows: 2 The reaction formula is as follows:

[0052]

[0053] The high catalyst can activate CO under mild temperature and pressure 2 and carry out the following carbonation reaction to prepare a cyclic carbonate compound.

[0054] A cyclic carbonate compound is prepared by adding OH-R-X to a high catalyst and introducing CO 2 The reaction formula is as follows:

[0055] Reaction formula II:

[0056]

[0057] Wherein X represents a halogen, and X and the hydroxyl group (-OH) are respectively connected to the carbon on R. R can be a branched or unbranched alkyl group with various carbon numbers. The carbon chain and / or the side chain of R can contain unsaturated bonds and various functional groups, including -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc. Among them, the number of carbon atoms on the carbon chain of R is 1-20.

[0058] A cyclic ethylene carbonate is synthesized by reacting 2-chloroethanol in the presence of a high catalyst and introducing CO at room temperature and atmospheric pressure using n-butyronitrile as a solvent. 2 The reaction synthesis is carried out.

[0059] A cyclic propylene carbonate is synthesized by reacting 3-chloro-1-propanol in the presence of a high catalyst and introducing CO at room temperature and atmospheric pressure using n-butyronitrile as a solvent. 2 The reaction synthesis is carried out.

[0060] The high catalyst can activate CO at mild temperature and pressure 2 and carry out the following carbonation reaction to prepare a carbamate compound.

[0061] A carbamate compound is prepared by adding R A NH 2 and R B X to a high catalyst and introducing CO 2 The reaction formula is as follows:

[0062] Reaction formula III:

[0063]

[0064] Wherein X represents a halogen, and the N of the primary amine (-NH 2 ) and the halogen (X) are respectively connected to the terminal carbon on R A and R B . R A and R B can be the same or different. R A and R B can be branched or unbranched alkyl groups with various carbon numbers. R A and R BThe carbon chain and / or the side chain may contain unsaturated bonds and various functional groups, including -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc. The R A and R B The number of carbon atoms in the carbon chain is 1-20.

[0065] A carbamate compound is prepared by reacting 1-naphthylmethylamine and 4-chloro-1-butene with high catalyst and introducing CO 2 under room temperature and atmospheric pressure using phenylacetonitrile as a solvent. The reaction formula is as follows:

[0066]

[0067] In the process of synthesizing the carbamate compound, the use of primary amine raw materials and CO 2 can effectively avoid the use of unstable and highly toxic isocyanate raw materials. Therefore, not only is CO 2 effectively converted into advanced materials, but it is also a safe and environmentally friendly technology.

[0068] The high catalyst can activate CO 2 under mild temperature and pressure and carry out the following carbonation reaction to prepare a secondary carbamate compound.

[0069] A secondary carbamate compound is prepared by adding R A NHR′ and R B X to the high catalyst and introducing CO 2 The reaction formula is as follows:

[0070] Reaction formula four:

[0071]

[0072] where X represents a halogen, and the N of the secondary amine (-NHR′) and the halogen (X) are respectively connected to the terminal carbon atoms on R A and R B . R′, R A and R B can be the same or different. R′, R A and R B can be alkyl groups with branched or unbranched chains of various carbon numbers. The groups on the carbon chain and / or side chain of R A and R B may contain unsaturated bonds and various functional groups, including -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, cyclic non-aromatic cluster groups, etc. The R′, R Aand R B The number of carbon atoms in the carbon chain is 1 - 20.

[0073] A secondary carbamate compound is prepared by using phenylacetonitrile as a solvent under mild temperature and pressure (room temperature and atmospheric pressure), with piperidine and 3 - bromo - 1 - propene in the presence of a high - catalyst and introducing CO 2 It is synthesized by a reaction, and the reaction formula is as follows:

[0074]

[0075] In the process of synthesizing the secondary carbamate compound, the use of secondary amine raw materials and CO 2 also effectively avoids the use of unstable and highly toxic isocyanate raw materials. Therefore, not only is CO 2 effectively converted into advanced materials, but it is also a safe and environmentally friendly technology.

[0076] The high - catalyst provided by this patent can activate CO under mild temperature and pressure (such as room temperature and atmospheric pressure) 2 , carry out a carbonation reaction and synthesize carbonate or carbamate compounds, so that CO 2 is effectively converted into fine chemicals and contributes to achieving "carbon peak and carbon neutrality".

[0077] Compared with the prior art, the beneficial effects of this application are: the high - catalyst can activate CO under mild temperature and pressure (such as room temperature and atmospheric pressure) 2 , carry out a carbonation reaction and synthesize carbonate or carbamate compounds, so that CO 2 is effectively converted into fine chemicals; the catalytic efficiency is high, and the synthesis of carbonate or carbamate compounds can effectively avoid the use of unstable and highly toxic isocyanate raw materials. Therefore, not only is CO 2 effectively converted into advanced materials, but it is also a safe and environmentally friendly technology. Detailed implementation manners

[0078] In order to make the purpose and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention; all possibilities covered by the claims of the present invention, including all alternative solutions, improvement solutions, and equivalent solutions.

[0079] Example 1: Preparation of pentachlorocyclopropane from 3,3,3 - trichloropropene

[0080] This example involves the preparation of pentachlorocyclopropane from 3,3,3-trichloropropene, and the specific steps are as follows: In a 2-liter glass reactor with a jacket, a stirring device is installed. The stirring device includes a pair of glass baffles with a diameter of 1.5 cm and a stainless-steel pitched-blade turbine agitator with a diameter of 4 cm. A thermometer is installed in one of the glass baffles. There is a feed inlet and a vent outlet above the reactor, and a discharge outlet below. Add 1200 grams of 3,3,3-trichloropropene and 250 grams of water to the reactor, start stirring, and set the reactor temperature control at 25 °C. The stirring rate ensures that the stirring Reynolds number based on the agitator diameter and water is greater than 10 4 ; First, introduce nitrogen gas from above the reactor for 5 minutes, and then evacuate; Keep the entire reactor away from light, close the vent outlet, and continuously introduce chlorine gas to start the reaction; Control the pressure in the reactor at 0.25 bar and react for 8 hours. After the reaction is completed, pentachlorocyclopropane and unreacted 3,3,3-trichloropropene are obtained by distillation. Among them, the corresponding reaction results are listed in Table 1 below:

[0081] Table 1 Influence of agitator Reynolds number on the yield of pentachlorocyclopropane

[0082]

[0083] Example 2 involves the preparation of a high-catalytic intermediate from di-n-butylamine or dicyclohexylamine and pentachlorocyclopropane

[0084] This example involves the preparation of a high-catalytic intermediate from di-n-butylamine or dicyclohexylamine and pentachlorocyclopropane, and the steps are as follows: In the reactor with a stirring device used in Example 1, add 200 grams of pentachlorocyclopropane (molecular weight 214.3) and 800 grams of solvent ethyl acetate, stir, set the reactor temperature control at 20 °C, introduce nitrogen gas from above the reactor for 5 minutes, and then evacuate; Then slowly dropwise add 603 grams of di-n-butylamine (molecular weight 129.24) or 846 grams of dicyclohexylamine (molecular weight 181.3) to start the reaction. The dropping rate of the secondary amine (di-n-butylamine or dicyclohexylamine) should ensure that the concentration of the secondary amine in the reactor is extremely low, so that the reaction process is always in a "starved" state, and the reaction time is 8 hours. After the reaction is completed, a coprecipitate of a high-catalytic intermediate ((R A 2 N) 2 C 3 Cl 2 ) and a secondary amine salt (R A 2 NH 2 Cl) is obtained, where R Ais a n-butyl group or a cyclohexyl group. Filter and separate, return the obtained coprecipitate to the original reaction kettle, add 600 grams of the solvent phenylacetonitrile, stir gently at room temperature for 30 minutes to dissolve the high-catalyst intermediate, filter to remove the solid secondary amine salt, and obtain the high-catalyst intermediate dissolved in phenylacetonitrile. Among them, Table 2 below lists the specific reaction results. Table 2 High-catalyst intermediate prepared from pentachlorocyclopropane and di-n-butylamine or dicyclohexylamine

[0085] Secondary amine type Di-n-butylamine <![CDATA[Dicyclohexyl Amine > Yield of highly catalytic intermediate relative to pentachlorocyclopropane 94.0％ 95.3％

[0086] In addition, add an aqueous NaOH solution to the solid secondary amine salt obtained by filtration to carry out a neutralization reaction to reduce the secondary amine. Since di-n-butylamine and dicyclohexylamine are insoluble in water at a lower temperature, the mixture solution is cooled to 5 °C, and di-n-butylamine or dicyclohexylamine forms an organic phase, which is separated from the aqueous phase, and the obtained secondary amine is recycled.

[0087] Example 3 Preparation of high-catalyst intermediate from diethylamine or dipropylamine and pentachlorocyclopropane

[0088] This example is to prepare a high-catalyst intermediate from diethylamine or dipropylamine and pentachlorocyclopropane. The steps included are as follows: In the reaction kettle with a stirring device used in Example 1, add 200 grams of pentachlorocyclopropane (molecular weight 214.3) and 800 grams of the solvent n-butyronitrile, stir, control and set the temperature of the reaction kettle at 25 °C, introduce nitrogen gas from above the reaction kettle for 5 minutes, and then evacuate; then slowly dropwise add 342 grams of diethylamine (molecular weight 73.14) or 473 grams of dipropylamine (molecular weight 101.19) to start the reaction; the dropping rate of the secondary amine (diethylamine or dipropylamine) should ensure that the concentration of the secondary amine in the reaction kettle is extremely low, that is, the reaction process is always in a "starvation" state, and the reaction lasts for 8 hours; after the reaction is completed, obtain the high-catalyst intermediate ((R A 2 N) 2 C 3 Cl 2 ) and the solid secondary amine salt (R A 2 NH 2 Cl), where R A is an ethyl group or a propyl group; filter and separate the solid secondary amine salt to obtain the high-catalyst intermediate dissolved in n-butyronitrile. Table 3 below lists the reaction results:

[0089] Table 3 High-catalyst intermediate prepared from pentachlorocyclopropane and diethylamine or dipropylamine

[0090] Secondary amine type Diethylamine Dipropylamine Yield of highly catalytic intermediate relative to pentachlorocyclopropane 93.3％ 92.7％

[0091] In addition, add an aqueous NaOH solution to the solid secondary amine salt obtained by filtration to carry out a neutralization reaction to reduce the secondary amine. Since diethylamine or dipropylamine is soluble in water, the secondary amine is obtained by distillation or extraction and recycled.

[0092] Example 4: Preparation of a highly catalytic substance from a highly catalytic intermediate based on dicyclohexylamine and n-butylamine or cyclopropylamine

[0093] In this example, a highly catalytic substance is prepared from a highly catalytic intermediate based on dicyclohexylamine and n-butylamine or cyclopropylamine. The steps are as follows: In the reaction kettle with a stirring device used in Example 1, add the highly catalytic intermediate based on dicyclohexylamine (molecular weight 467.6) dissolved in phenylacetonitrile obtained in Example 2 (total weight 1015 g, of which the highly catalytic intermediate is 415 g), stir, control the temperature of the reaction kettle at 35°C, introduce nitrogen gas from above the reaction kettle for 5 minutes, and then evacuate; then slowly dropwise add 130 g of n-butylamine (molecular weight 73.1) or 102 g of cyclopropylamine (molecular weight 57.1) to carry out the reaction for 8 hours; after the reaction, a highly catalytic chloride ((R A 2 N) 2 C 3 (R B NHCl)) and a primary amine chloride (R B NH 3 Cl) are obtained, where R A is a cyclohexyl group, and R B is an n-butyl group or a cyclopropyl group. The structure of the highly catalytic chloride is given by Structural Formula II; the molecular weights of the highly catalytic chlorides prepared using n-butylamine and cyclopropylamine are 504.2 and 488.2 respectively. During the reaction, the highly catalytic chloride and the primary amine chloride are dispersed in phenylacetonitrile in solid form. After the reaction, the co-precipitate of the highly catalytic chloride and the primary amine chloride obtained by filtration is returned to the reaction kettle, and 900 ml of a 2M NaOH aqueous solution is added, and a neutralization reaction is carried out under strong stirring. Thus, the highly catalytic chloride is converted into the highly catalytic substance. Since the highly catalytic substance is insoluble in water, it is dispersed in water in solid form. The primary amine chloride is also converted into a primary amine. Since n-butylamine and cyclopropylamine are soluble in water, the highly catalytic substance is separated from the primary amine. By filtration or centrifugal separation, a solid (white) powder of the highly catalytic substance ((R A 2 N) 2 C 3 (NR B )) is obtained. The structure of the highly catalytic substance is given by Structural Formula I, where R A is a cyclohexyl group, and R B is an n-butyl group or a cyclopropyl group. Table 4 below lists the analysis results after the reaction:

[0094] Table 4: Highly catalytic substance prepared from a highly catalytic intermediate based on dicyclohexylamine and n-butylamine or cyclopropylamine

[0095] Primary amine type n-Butylamine Cyclopropylamine Yield of highly catalytic relative to pentachlorocyclopropane 90.0％ 90.3％

[0096] n-Butylamine or cyclopropylamine dissolved in an aqueous solution can be obtained by distillation or extraction and recycled.

[0097] Example 5 involves preparing a highly catalytic substance from a highly catalytic intermediate based on dipropylamine and ethylamine or propylamine.

[0098] In this example, a highly catalytic substance is prepared from a highly catalytic intermediate based on dipropylamine and ethylamine or propylamine. The steps are as follows: In the reaction kettle with a stirring device used in Example 1, add the highly catalytic intermediate based on dipropylamine dissolved in n-butyronitrile obtained in Example 3 (molecular weight 307.3) (total weight 1066 grams, including 266 grams of the highly catalytic intermediate), stir, control and set the reaction kettle temperature at 25°C, introduce nitrogen gas from the top of the reaction kettle for 5 minutes, and then evacuate; then slowly dropwise add 78 grams of ethylamine (molecular weight 45.08) or 103 grams of propylamine (molecular weight 59.11) for reaction, with a reaction time of 8 hours; after the reaction, highly catalytic chloride ((R A 2 N) 2 C 3 (R B NHCl)) and primary amine chloride (R B NH 3 Cl) can be obtained, where R A is a propyl group, and R B is an ethyl group or a propyl group. The structure of the highly catalytic chloride is given by Structural Formula II. The molecular weights of the highly catalytic chlorides prepared using ethylamine and propylamine are 315.9 and 330.0 respectively. During the reaction, the highly catalytic chloride and the primary amine chloride are dispersed in n-butyronitrile in solid form. After the reaction, the co-precipitate of the highly catalytic chloride and the primary amine chloride obtained by filtration is returned to the reaction kettle, and 900 ml of 2M NaOH aqueous solution is added for neutralization reaction under strong stirring. Thus, the highly catalytic chloride is converted into the highly catalytic substance. Since the highly catalytic substance is insoluble in water, it is dispersed in water in solid form. The primary amine chloride is also converted into the primary amine. Since ethylamine and propylamine are soluble in water, the highly catalytic substance and the primary amine are separated. By filtration or centrifugal separation, a solid (white) powder of the highly catalytic substance ((R A 2 N) 2 C 3 (NR B )) can be obtained. The structure of the highly catalytic substance is given by Structural Formula I, where R A is a cyclohexyl group, and R B is an ethyl group or a propyl group. Table 5 below lists the analysis results after the reaction:

[0099] Table 5 Highly catalytic substance prepared from a highly catalytic intermediate based on dipropylamine and ethylamine or propylamine

[0100] Primary amine type Ethylamine Propylamine Yield of highly catalytic relative to pentachlorocyclopropane 90.5％ 90.1％

[0101] Ethylamine or propylamine dissolved in an aqueous solution can be obtained by distillation or extraction and recycled.

[0102] Example 6 Preparation of a highly catalytic substance from a highly catalytic intermediate based on diethylamine and ethylamine

[0103] In this example, a highly catalytic substance is prepared from a highly catalytic intermediate based on diethylamine and ethylamine. The steps are as follows: In the reaction kettle with a stirring device used in Example 1, add the highly catalytic intermediate based on diethylamine (molecular weight 251.2) dissolved in n-butyronitrile obtained in Example 3 (total weight 1019 grams, including 219 grams of the highly catalytic intermediate), stir, control the temperature of the reaction kettle at the set temperature, introduce nitrogen gas from the top of the reaction kettle for 5 minutes, and then evacuate; then slowly dropwise add 79 grams of ethylamine (molecular weight 45.08) and carry out the reaction for 8 hours; after the reaction, a highly catalytic chloride ((R A 2 N) 2 C 3 (R B NHCl)) and ethylamine chloride (R B NH 3 Cl) can be obtained, where R A and R B are ethyl groups. The structure of the highly catalytic chloride is given by Structural Formula II, and its molecular weight is 259.45. During the reaction, the highly catalytic chloride and ethylamine chloride are dispersed in n-butyronitrile in solid form. After the reaction, the coprecipitate of the highly catalytic chloride and ethylamine chloride obtained by filtration is returned to the reaction kettle, and 900 milliliters of a 2M NaOH aqueous solution is added, and a neutralization reaction is carried out under strong stirring. Thus, the highly catalytic chloride is converted into the highly catalytic substance. Since the highly catalytic substance is insoluble in water, it is dispersed in water in solid form. Ethylamine chloride is also converted into ethylamine. Since ethylamine is soluble in water, the highly catalytic substance and ethylamine are separated. By filtration or centrifugation, a solid (white) powder of the highly catalytic substance ((R A 2 N) 2 C 3 (NR B )) can be obtained. The structure of the highly catalytic substance is given by Structural Formula I, where R A and R B are ethyl groups. Table 6 below lists the analysis results after the reaction:

[0104] Table 6 Influence of reaction temperature on the preparation of a highly catalytic substance from a highly catalytic intermediate based on diethylamine and ethylamine:

[0105] Reaction temperature (°C) Yield of highly catalytic relative to pentachlorocyclopropane 15 90.3％ 20 91.1％ 25 90.7％ 30 90.9％

[0106] Ethylamine dissolved in an aqueous solution can be obtained by distillation or extraction and recycled.

[0107] Example 7 Preparation of a highly catalytic substance from a highly catalytic intermediate based on dibutylamine and propylamine

[0108] In this example, a highly catalytic substance is prepared from a highly catalytic intermediate based on dibutylamine and propylamine. The steps are as follows: In the reaction kettle with a stirring device used in Example 1, add the highly catalytic intermediate based on dibutylamine (molecular weight 363.4) dissolved in phenylacetonitrile obtained in Example 2 (total weight 1118 grams, of which the highly catalytic intermediate is 318 grams), stir, control the temperature of the reaction kettle at the set temperature, introduce nitrogen from the top of the reaction kettle for 5 minutes, and then evacuate; then slowly dropwise add 104 grams of propylamine (molecular weight 59.11) and carry out the reaction for 8 hours. After the reaction, a highly catalytic chloride ((R A 2 N) 2 C 3 (R B NHCl)) and propylamine chloride (R B NH 3 Cl) can be obtained, where R A is a n-butyl group and R B is a propyl group. The structure of the highly catalytic chloride is given by Structural Formula II, and its molecular weight is 385.45. During the reaction, the highly catalytic chloride and propylamine chloride are dispersed in phenylacetonitrile in solid form. After the reaction, the co-precipitate of the highly catalytic chloride and propylamine chloride obtained by filtration is returned to the reaction kettle, and 900 ml of 2M NaOH aqueous solution is added, and a neutralization reaction is carried out under strong stirring. Thus, the highly catalytic chloride is converted into the highly catalytic substance. Since the highly catalytic substance is insoluble in water, it is dispersed in water in solid form. The propylamine chloride is also converted into propylamine. Since propylamine is soluble in water, the highly catalytic substance and propylamine are separated. By filtration or centrifugal separation, a solid (white) powder of the highly catalytic substance ((R A 2 N) 2 C 3 (NR B )) can be obtained. The structure of the highly catalytic substance is given by Structural Formula I, where R A is a n-butyl group and R B is a propyl group. Table 7 below lists the analysis results after the reaction:

[0109] Table 7 Influence of reaction temperature on the preparation of the highly catalytic substance from the highly catalytic intermediate based on dibutylamine and propylamine

[0110] Reaction temperature (°C) Yield of highly catalytic relative to pentachlorocyclopropane 20 91.2％ 25 91.0％ 30 91.5％ 35 90.7％

[0111] The propylamine dissolved in the aqueous solution can be obtained by distillation or extraction and recycled.

[0112] Example 8 Activation of the highly catalytic substance for CO 2 Preparation of dibutyl carbonate

[0113] This example is about highly catalytically activating CO 2 To prepare dibutyl carbonate, the preparation method includes the following steps: In the reaction kettle with a stirring device used in Example 1, add 200 grams of the highly catalytic ((R A 2 N) 2 C 3 (NR B )) (molecular weight 467), where R A is cyclohexyl and R B is n-butyl), and 800 grams of the solvent n-butyronitrile. Control the temperature of the reaction kettle at the set temperature and start stirring; ensure that the stirring rate is based on the stirrer diameter and the Reynolds number of water is 5×10 4 ; First, introduce CO 2 gas from the top of the reaction kettle for 5 minutes and evacuate; then close the evacuation port and continue to introduce CO 2 , control the pressure in the reaction kettle to be 0.5 bar, and add 31.7 grams of n-butanol (molecular weight 74.12); after reacting for 1 hour, slowly dropwise add 58.7 grams of 1-bromobutane (molecular weight 137.02), react for 4 hours, and dibutyl carbonate is prepared. The preparation reaction equation of dibutyl carbonate is as follows:

[0114]

[0115] During the reaction, the highly catalytic agent obtains Br - and H + ions to form highly catalytic bromide, which is insoluble in n-butyronitrile and is dispersed in the liquid phase in solid form. Therefore, after the reaction, the solid highly catalytic bromide is separated by filtration, and the liquid phase is separated by distillation to obtain the above product dibutyl carbonate, the solvent n-butyronitrile, and the unreacted raw materials and highly catalytic agent. The reaction analysis results are shown in Table 8 below.

[0116] Table 8 Influence of reaction temperature on the yield of dibutyl carbonate

[0117]

[0118] The separated solid highly catalytic bromide is returned to the original reaction kettle, add 800 grams of n-butyronitrile and 250 ml of 2M NaOH aqueous solution, stir slowly, carry out a neutralization reaction to reduce the highly catalytic agent, and the generated highly catalytic agent is extracted and returned to n-butyronitrile. Separate the organic phase from the aqueous phase, and let the organic phase pass through a solid drying column to remove the residual moisture, and the highly catalytic agent dissolved in n-butyronitrile obtained is recycled.

[0119] Example 9 Highly catalytically activating CO 2 To prepare cyclic carbonate compounds

[0120] This example is about highly catalytically activating CO 2To prepare cyclic carbonate compounds, the preparation method includes the following steps: In the reaction kettle with a stirring device used in Example 1, add 200 grams of the highly catalytic agent (((R A 2 N) 2 C 3 (NR B )) (molecular weight 293), where R A and R B are propyl groups) and 800 grams of the solvent n-butyl nitrile. Set the temperature of the reaction kettle at 20 °C and start stirring; ensure that the stirring rate is based on the diameter of the stirrer and the Reynolds number of water is 5×10 4 ; First, introduce CO 2 gas from the top of the reaction kettle for 5 minutes and evacuate; then close the evacuation port, continue to introduce CO 2 , and control the pressure of the reaction kettle at the set pressure; then slowly dropwise add 55 grams of 2-chloroethanol (molecular weight 80.52) or 64.5 grams of 3-chloro-1-propanol (molecular weight 94.54), and react for 6 hours to prepare the cyclic carbonate compounds given by Reaction Formula 2, where R is ethyl or propyl; during the reaction, the highly catalytic agent gets Cl - and H + ions to form the highly catalytic chloride, which is insoluble in n-butyl nitrile and is dispersed in the liquid phase in solid form. So after the reaction, filter and separate the solid highly catalytic chloride, and the liquid phase is separated by distillation to obtain the cyclic carbonate compounds given by Reaction Formula 2, the solvent n-butyl nitrile, and the unreacted reactants. The reaction analysis results are shown in Table 9 below.

[0121] Table 9 Effect of CO 2 gas pressure on the yield of cyclic carbonate compounds

[0122]

[0123] Return the separated solid highly catalytic chloride to the original reaction kettle, add 800 grams of n-butyl nitrile and 350 ml of 2M NaOH aqueous solution, stir slowly, carry out a neutralization reaction to reduce the highly catalytic agent, and extract the generated highly catalytic agent back into n-butyl nitrile. Separate the organic phase from the aqueous phase, and let the organic phase pass through a solid drying column to remove the residual moisture, and obtain the highly catalytic agent dissolved in n-butyl nitrile for recycling.

[0124] Example 10 Activation of highly catalytic agent by CO 2 To prepare carbamate compounds

[0125] This example is about activating CO 2 by the highly catalytic agent to prepare carbamate compounds. The preparation method includes the following steps: In the reaction kettle with a stirring device used in Example 1, add 200 grams of the highly catalytic agent (((RA 2 N) 2 C 3 (NR B )) (molecular weight 223), where R A and R B are ethyl groups) and 900 g of the solvent phenylacetonitrile, the temperature of the reaction kettle is controlled and set at 55 °C, and stirring is started; the stirring rate is ensured to be 5×10 based on the stirrer diameter and the Reynolds number of water 4 ; First, CO 2 gas is introduced from above the reaction kettle for 5 minutes and then vented; subsequently, the vent is closed, and CO 2 is continuously introduced, and the pressure of the reaction kettle is controlled at the given pressure; then 141 g of 1-naphthalenemethylamine (molecular weight 157.21) is added. After reacting for 1 hour, 81.2 g of 4-chloro-1-butene (molecular weight 90.55) is slowly added, and the reaction proceeds for 8 hours to prepare a carbamate compound. The preparation reaction equation of the carbamate compound is as follows:

[0126]

[0127] During the reaction, high catalyst gives Cl - and H + ions to form high catalyst chloride, which is insoluble in phenylacetonitrile and is dispersed in the liquid phase in solid form. Therefore, after the reaction, the temperature is controlled at the reaction temperature (55 °C) to filter and separate the solid high catalyst chloride. The liquid phase is separated by distillation to obtain the carbamate compound given by the above reaction formula, the solvent phenylacetonitrile, and the unreacted reactants. The reaction analysis results are listed in Table 10.

[0128] Table 10 Effect of reaction (CO 2 ) pressure on the yield of carbamate compound

[0129] <![CDATA[Reaction (CO 2 ) Pressure (bar)]]> Yield of carbamate compounds 0.1 92.2％ 0.2 93.0％ 0.3 93.5％ 0.5 93.6％

[0130] The separated solid high catalyst chloride is returned to the original reaction kettle, 900 g of phenylacetonitrile and 250 mL of 2 M NaOH aqueous solution are added, and slow stirring is carried out for a neutralization reaction to reduce the high catalyst, and the generated high catalyst is extracted and returned to phenylacetonitrile. The organic phase and the aqueous phase are separated, and the organic phase is passed through a solid drying column to remove the residual moisture, and the high catalyst dissolved in phenylacetonitrile obtained is recycled.

[0131] Example 11 High catalyst activation of CO 2 Preparation of secondary carbamate compound

[0132] This example is the high catalyst activation of CO 2To prepare secondary carbamate compounds, the preparation method includes the following steps: In a reaction kettle with a stirring device used in Example 1, add 200 grams of high catalyst (((R A 2 N) 2 C 3 (NR B )) (molecular weight 279), where R A is propyl group, R B is ethyl group) and 900 grams of solvent phenylacetonitrile. Set the temperature of the reaction kettle at 25°C and start stirring; ensure that the stirring rate is based on the diameter of the stirrer and the Reynolds number of water is 5×10 4 ; First, introduce CO 2 gas from the top of the reaction kettle for 5 minutes and evacuate; then close the evacuation port, continue to introduce CO 2 , and control the pressure of the reaction kettle at 0.5 bar. Add 61 grams of piperidine (molecular weight 85.15) and react for 1 hour; then slowly add 86.7 grams of 3-bromo-1-propene (molecular weight 120.98), sample and analyze once per hour, and the reaction time is 8 hours to prepare secondary carbamate compounds. The preparation reaction equation of the secondary carbamate compounds is as follows:

[0133]

[0134] During the reaction, the high catalyst obtains Br - and H + ions to form high catalyst bromide, which is insoluble in phenylacetonitrile and is dispersed in the liquid phase in solid form. Therefore, after the reaction, filter and separate the solid high catalyst bromide. The liquid phase is separated by distillation to obtain the secondary carbamate compounds given by the above reaction formula, the solvent phenylacetonitrile, and the unreacted reactants. The reaction analysis results are shown in Table 11 below.

[0135] Table 11 Effect of reaction time on the yield of secondary carbamate compounds described by the above reaction formula

[0136]

[0137] Return the separated solid high catalyst bromide to the original reaction kettle, add 900 grams of phenylacetonitrile and 250 milliliters of 2M NaOH aqueous solution, stir slowly, carry out a neutralization reaction to reduce the high catalyst, and extract the generated high catalyst back into phenylacetonitrile. Separate the organic phase from the aqueous phase, and let the organic phase pass through a solid drying column to remove the residual moisture. The high catalyst dissolved in phenylacetonitrile obtained is recycled.

[0138] As described above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A cyclopropylene imine-based high-efficiency catalyst, characterized in that: The structural formula is as follows: Among them, R A and R B The number of carbon atoms in the carbon chain is 1-20, R A The carbon chain and / or branches of contain unsaturated bonds and -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups or cyclic non-aromatic cluster groups; the carbon chain and / or branches of RB contain unsaturated bonds and -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups or cyclic non-aromatic cluster groups.

2. A cyclopropylene imine high efficiency catalyst according to claim 1, characterized in that: The activation performance is determined by R A and R B to adjust the selection.

3. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 1, characterized in that: The steps involved are as follows: (1) Using 3,3,3-trichloropropene and chlorine as raw materials and water as an auxiliary solvent for chlorine to prepare pentachlorocyclopropane; (2) Using secondary amine and pentachlorocyclopropane as raw materials, preparing high-catalyst intermediates; (3) Using high-catalyst intermediates and primary amines as raw materials to prepare high-catalyst; The secondary amine molecular formula is R A 2NH, primary amine formula is R B NH2, where R A and R B The number of carbon atoms in the carbon chain is 1-20, R A and R B The carbon chain and / or branch chain contain unsaturated bonds and -OH, -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, and cyclic non-aromatic cluster groups.

4. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 3, characterized in that: In the step (1), 3,3,3-trichloropropylene and water are first added to a reactor, stirred and the reactor temperature is controlled at 5-90° C., and chlorine is introduced into the reactor for reaction after oxygen in the reactor is removed; the stirring rate is such that the stirring Reynolds number based on the stirrer diameter and the water is greater than 10 4 .

5. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 4, characterized in that: The method for removing oxygen in the reactor is to introduce nitrogen to remove the oxygen in the reactor. After the oxygen is completely removed, the exhaust port of the reactor is closed, and chlorine is continuously introduced to start the reaction.

6. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 4, characterized in that: The reaction was carried out under light protection.

7. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 4, characterized in that: The reactor temperature should be controlled at 10-50°C.

8. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 4, characterized in that: The volume ratio of water to 3,3,3-trichloropropene is 1:10-4:

6.

9. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 3, characterized in that: The step (2) uses secondary amine and pentachlorocyclopropane as raw materials to prepare a high-catalyst intermediate, and the preparation steps include the following: adding pentachlorocyclopropane and a first solvent into a reaction kettle, and controlling the temperature of the reaction kettle at 5-60°C, then dripping the secondary amine to start the reaction for 1-12 hours, and post-treating the reaction product to obtain a high-catalyst intermediate.

10. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 9, characterized in that: The secondary amine addition rate should be able to ensure that the concentration of the secondary amine in the reactor is such that the reaction process is always in a "starvation" state.

11. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 9, characterized in that: The reaction product is a precipitate of a high-catalyst intermediate, which is obtained by filtering and separating. If a secondary amine salt is a precipitate, the solid secondary amine salt is removed by filtering and separating to obtain a solution of the high-catalyst intermediate dissolved in a first solvent, wherein the high-catalyst intermediate is obtained by extraction. If a co-precipitate of the high-catalyst intermediate and the secondary amine salt is obtained, a second solvent is used to separate the high-catalyst intermediate from the secondary amine salt.

12. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 3, characterized in that: In the step (3), the high-catalyst intermediate and the primary amine are used as raw materials to prepare the high-catalyst, and the preparation steps include the following: adding the high-catalyst intermediate and the third solvent into a reaction kettle, controlling the temperature of the reaction kettle at 5-60°C, and after the high-catalyst intermediate is fully dissolved, slowly adding the primary amine dropwise to react for 1-20 hours to obtain the high-catalyst chloride, and then post-treating the high-catalyst chloride.

13. The method for preparing a cyclopropylene imine high-efficiency catalyst according to claim 12, characterized in that: After the reaction is completed, high catalyst chloride and primary amine chloride can be obtained. If the high catalyst chloride and the primary amine chloride form a co-precipitate during the reaction, they can be treated by the following two methods: first, the co-precipitate separated by filtration is returned to the reactor, and an aqueous solution of an inorganic base is added to the reactor for neutralization reaction to generate high catalyst and primary amine. The high catalyst will be dispersed in water in the form of solid particles. The high catalyst dispersed in water is filtered and separated to obtain a solid powder of high catalyst; second, if the primary amine used is insoluble in water, the co-precipitate of high catalyst chloride and primary amine chloride is not filtered and separated from the third solvent, and an aqueous solution of an inorganic base is added to the reactor for neutralization reaction to generate high catalyst and primary amine. The generated high catalyst and primary amine will be returned to the third solvent, the organic phase and the aqueous phase are separated, and the organic phase is passed through a solid drying column to remove residual water to obtain the high catalyst and primary amine dissolved in the third solvent, and then a fourth solvent is added to separate the high catalyst and the primary amine.

14. A cyclopropylene imine high efficiency catalyst according to claim 1, characterized in that: It is used to activate CO2, causing it to undergo a carbonation reaction and prepare carbonate compounds.

15. A carbonate compound, characterized in that: By R A X and R B OH is added to the cyclopropylene imine high-efficiency catalyst according to claim 1 and CO2 is introduced to prepare the catalyst. The reaction formula is as follows: Where X represents halogen, R A and R B The carbon chain and / or branch chain contains unsaturated bonds and -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, and cyclic non-aromatic cluster groups.

16. A di-n-butyl carbonate, characterized in that: The method is prepared by using n-butyronitrile as solvent, using n-butanol and 1-bromobutane, adding the cyclopropylene imine high-efficiency catalyst described in claim 1 and introducing CO2 for reaction synthesis, and the reaction formula is as follows:

17. A cyclic carbonate compound, characterized in that: The method is prepared by adding the cyclopropylene imine high-efficiency catalyst according to claim 1 to (HO)RX and introducing CO2. The reaction formula is as follows: Wherein X represents a halogen, and R contains unsaturated bonds and -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, and cyclic non-aromatic cluster groups on the carbon chain and / or branch chain.

18. A carbamate compound, characterized in that: By R A NH2 and R B X is prepared by adding the cyclopropylene imine high-efficiency catalyst according to claim 1 and introducing CO2, and the reaction formula is as follows: Where X represents halogen, R A and R B The carbon chain and branches contain unsaturated bonds and -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, and cyclic non-aromatic cluster groups.

19. A secondary carbamate compound, characterized in that: By R A NHR′ and R B X is prepared by adding the cyclopropylene imine high-efficiency catalyst according to claim 1 and introducing CO2, and the reaction formula is as follows: Where X represents a halogen, R′, R A and R B The carbon chain and / or branch chain contains unsaturated bonds and -NH-, -N=, -O-, -S-, -Si-, -Si-O-, -(C=O)-, -C≡N, aromatic cluster groups, and cyclic non-aromatic cluster groups.

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