Supported double metal cyanide complex catalyst, preparation method thereof and preparation method of polycarbonate

Abstract

The invention relates to a supported double metal cyanide complex catalyst, a preparation method thereof and a preparation method of polycarbonate. The supported double metal cyanide complex catalyst comprises a resin carrier and a double metal cyanide complex supported on the resin carrier, the resin carrier is polystyrene resin containing a terminal hydroxyl group and a quaternary ammonium salt group. The supported double-metal cyanide complex catalyst has high catalytic activity, is particularly applied to the process of preparing polycarbonate by catalyzing copolymerization of CO2 and epoxide, can improve the CO2 insertion rate and reduce the proportion of a cyclic byproduct propylene carbonate in the product, has low metal residue in the product, does not need further post-treatment, and can greatly reduce the post-treatment cost. More importantly, the catalyst can be recycled for multiple times, and the catalytic activity and selectivity are basically not influenced.

Description

Technical Field

[0001] This application relates to the field of catalytic synthesis technology, and in particular to a supported bimetallic cyanide complex catalyst, its preparation method, and a method for preparing polycarbonate. Background Technology

[0002] Since the concept of the "greenhouse effect" was proposed, the conversion of CO2, a cheap resource, into useful chemicals has been a hot research topic in the field of chemistry. In 1969, Japanese scientist Shohei Inoue discovered the reaction in which CO2 copolymerizes with epoxides to form polymers that possess both good biocompatibility and biodegradability. However, due to serious problems with the activity and selectivity of the catalyst, industrial production has not yet been achieved.

[0003] Bimetallic cyanide complex (DMC) catalysts were first discovered and applied by General Tire & Rubber Company in the 1960s to catalyze the preparation of polyether polyols from epoxides. Subsequent studies found that DMC catalysts could also be used to catalyze the copolymerization of CO2 and epoxides to prepare polycarbonates; however, the catalytic activity was generally low. These traditional methods often suffer from low CO2 insertion rates leading to low CO2 utilization, and the resulting polycarbonate products contain a high proportion of cyclic byproduct propylene carbonate and are prone to metal residues. Summary of the Invention

[0004] Based on this, this application provides a supported bimetallic cyanide complex catalyst, its preparation method, and a method for preparing polycarbonate. This supported bimetallic cyanide complex catalyst exhibits high catalytic activity, particularly in the process of catalyzing the copolymerization of CO2 and epoxides to prepare polycarbonate. It can improve the CO2 insertion rate, and the proportion of cyclic byproduct propylene carbonate and metal residue in the product are both low.

[0005] A first aspect of this application provides a supported bimetallic cyanide complex catalyst, comprising a resin support and a bimetallic cyanide complex supported on the resin support.

[0006] The resin carrier is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

[0007] In some embodiments, the bimetallic cyanide complex includes one or more of zinc hexacyanocobaltate, zinc hexacyanoferrate, zinc tetracyanonitrile, and zinc hexacyaniridiumate, and the complex includes one or two of tert-butanol and glycol dimethyl ether.

[0008] Optionally, the bimetallic cyanide in the bimetallic cyanide complex includes zinc hexacyanocobaltate, and the complex includes tert-butanol.

[0009] In some embodiments, the resin carrier comprises polystyrene resin, an amine compound grafted onto the polystyrene resin, and an epoxy compound grafted onto the amine compound;

[0010] The amine compound contains at least two amine groups, and at least one amine group is quaternized to form the quaternary ammonium salt group;

[0011] The amine compound is grafted onto the polystyrene resin via the amine group;

[0012] The epoxy compound is grafted onto the amine compound via the amino group, and the epoxy compound undergoes ring-opening to form the terminal hydroxyl group.

[0013] In some embodiments, the amine compound includes a diamine compound, optionally one or more of ethylenediamine, 1,2-propanediamine, and 1,4-butanediamine; and / or,

[0014] The epoxy compound includes one or both of ethylene oxide and propylene oxide.

[0015] In some embodiments, the resin carrier has the structural features shown in formula (I):

[0016] Formula (I),

[0017] Where n is an integer from 2 to 4, and L is a C2 to C5 alkylene group.

[0018] A second aspect of this application provides a method for preparing a supported bimetallic cyanide complex catalyst, comprising the following steps:

[0019] The supported bimetallic cyanide complex catalyst is prepared by reacting a first metal salt with a complex, a resin support, and a cyanide of a second metal in a solvent.

[0020] The resin carrier is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

[0021] In some embodiments, the method for preparing the supported bimetallic cyanide complex catalyst has one or more of the following features:

[0022] (1) The reaction conditions include: temperature of 30℃~50℃ and time of 2h~5h;

[0023] (2) The first metal salt includes zinc chloride;

[0024] (3) The complex comprises one or both of tert-butanol and glycol dimethyl ether;

[0025] (4) The cyanide of the second metal includes one or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium tetracyanonitrile and potassium hexacyaniridiumate;

[0026] (5) The total mass ratio of the first metal salt, the complex and the cyanide of the second metal to the mass ratio of the resin carrier is (0.2~1):1;

[0027] (6) The mass ratio of the first metal salt, the complex and the cyanide of the second metal is (5~15):(2.5~12.5):1.

[0028] In some embodiments, the method for preparing the resin carrier includes:

[0029] Chloromethyl polystyrene microspheres were mixed with a first organic solvent and swollen to prepare a swelling solution.

[0030] The swelling solution is mixed with an amine compound to carry out a first reaction to prepare an amine resin; the amine compound contains at least two amine groups.

[0031] The amine resin is mixed with an acid and a second organic solvent to carry out a second reaction, and then an epoxy compound is added to carry out a third reaction to prepare the resin carrier.

[0032] In some embodiments, the method for preparing the resin carrier has one or more of the following features:

[0033] (1) The first organic solvent includes one or more of methanol, ethanol, n-hexane, dichloromethane and toluene, and may be toluene;

[0034] (2) Based on the amount of the first organic solvent, the concentration of the chloromethyl polystyrene microspheres is 0.1 g / mL to 0.3 g / mL;

[0035] (3) The particle size of the chloromethyl polystyrene microspheres is 40 μm to 50 μm;

[0036] (4) The mass ratio of the amine compound to the chloromethyl polystyrene microspheres is (5~10):1;

[0037] (5) The conditions for the first reaction include: temperature of 50℃~80℃ and time of 4h~36h;

[0038] (6) The second organic solvent includes one or more of n-hexane, dichloromethane and toluene, and may be dichloromethane;

[0039] (7) Based on the amount of the second organic solvent, the concentration of the amine resin is 0.4 g / mL to 0.6 g / mL;

[0040] (8) The acid includes one or more of hydrochloric acid, sulfuric acid, and phosphoric acid;

[0041] (9) Based on the amount of the amine resin, the mass percentage of the acid is 0.1% to 1%;

[0042] (10) Based on the amount of the amine resin, the epoxy compound has a mass percentage of 5% to 10%;

[0043] (11) The conditions for the third reaction include: temperature of 100℃~120℃ and time of 1h~3h.

[0044] A third aspect of this application provides a method for preparing polycarbonate, which uses a catalyst to catalyze the polymerization reaction of CO2 and epoxide, wherein the catalyst includes the supported bimetallic cyanide complex catalyst described in the first aspect or the supported bimetallic cyanide complex catalyst prepared by the method described in the second aspect.

[0045] In some embodiments, the polymerization reaction includes the following steps:

[0046] In an inert gas atmosphere, the catalyst is filled into a reactor, then an initiator is added to the reactor, the temperature is raised to 60°C~100°C, CO2 is introduced, and then an epoxide is added to carry out the reaction.

[0047] Optionally, the initiator includes one or both of polyether PPG230 and polyether C2020;

[0048] Optionally, the mass percentage of the catalyst is 30% to 80% based on the mass of the initiator.

[0049] The above-mentioned supported bimetallic cyanide complex catalyst, by using polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups to support the bimetallic cyanide complex, exhibits a synergistic effect with the resin support, significantly enhancing catalytic activity compared to traditional bimetallic cyanide complexes or resin supports. In particular, it effectively catalyzes the polymerization of CO2 with epoxides to prepare polycarbonate, offering the following advantages:

[0050] (1) It has high catalytic activity and can react under relatively mild conditions;

[0051] (2) The high insertion rate of CO2 is conducive to the resource conversion and utilization of CO2;

[0052] (3) The low proportion of cyclic byproduct propylene carbonate in polycarbonate products is beneficial to improving product quality;

[0053] (4) Polycarbonate products have low metal residue and do not require additional post-processing, simplifying the production process;

[0054] (5) Forming a supported catalyst is beneficial for the reuse of the catalyst and it still has high catalytic activity after multiple cycles, thus reducing production costs. Attached Figure Description

[0055] Figure 1 The NMR spectrum of polycarbonate prepared in one example is shown. Detailed Implementation

[0056] The supported bimetallic cyanide complex catalyst and its preparation method, as well as the polycarbonate preparation method of this application, are described in further detail below with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0057] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0058] As used herein, the terms “and / or,” “or / and,” and “and / or” may include any one of two or more of the related listed items, as well as any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all the related listed items.

[0059] In this article, "one or more" refers to any one, two or more of the listed items.

[0060] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0061] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0062] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0063] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0064] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0065] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0066] In this application, room temperature generally refers to 4℃~30℃, and preferably 20±5℃.

[0067] In this application, "alkylene" refers to a divalent residue formed by the loss of two hydrogen atoms from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C2-C5 alkylene," refer to alkylenes containing 2-5 carbon atoms, and each occurrence can independently be C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, or C5 alkylene. Suitable examples include, but are not limited to: ethylene, 1-propylene, 2-propylene, 1-butylene, 2-methyl-1-propylene, 2-butylene, 2-methyl-2-propylene, 1-pentylene, 2-pentylene, 3-pentylene, 2-methyl-2-butylene, 3-methyl-2-butylene, 3-methyl-1-butylene, and 2-methyl-1-butylene.

[0068] Some embodiments of this application provide a supported bimetallic cyanide complex catalyst, comprising a resin support and a bimetallic cyanide complex supported on the resin support; the resin support is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

[0069] In some embodiments, the bimetallic cyanide complex comprises one or more of zinc hexacyanocobaltate, zinc hexacyanoferrate, zinc tetracyanonitrile, and zinc hexacyaniridiumate, and the complex comprises one or two of tert-butanol and glycol dimethyl ether. Further, the bimetallic cyanide complex comprises zinc hexacyanocobaltate, and the complex comprises tert-butanol.

[0070] In some embodiments, the resin carrier comprises a polystyrene resin, an amine compound grafted onto the polystyrene resin, and an epoxy compound grafted onto the amine compound; the amine compound comprises at least two amino groups, and at least one amino group is quaternized to form the quaternary ammonium salt group; the amine compound is grafted onto the polystyrene resin via the amino groups; the epoxy compound is grafted onto the amine compound via the amino groups, and the epoxy compound undergoes ring-opening to form the terminal hydroxyl group.

[0071] Understandably, the amine groups grafted onto the polystyrene resin and the epoxy compound may be the same or different.

[0072] In some embodiments, the amine compound includes a diamine compound. Further, the amine compound includes one or more of ethylenediamine, 1,2-propanediamine, and 1,4-butanediamine.

[0073] In some embodiments, the epoxy compound includes one or both of ethylene oxide and propylene oxide.

[0074] In some embodiments, the resin carrier has the structural features shown in formula (I):

[0075] Formula (I),

[0076] Where n is an integer from 2 to 4, and L is a C2 to C5 alkylene group.

[0077] In other embodiments of this application, a method for preparing a supported bimetallic cyanide complex catalyst is provided, comprising the following steps:

[0078] The supported bimetallic cyanide complex catalyst is prepared by reacting a first metal salt with a complex, a resin support, and a cyanide of a second metal in a solvent.

[0079] The resin carrier is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

[0080] Understandably, the bimetallic cyanide complex is generated by the reaction of the first metal salt with the complex and the cyanide of the second metal, and is simultaneously loaded onto the resin support during the reaction. The bimetallic cyanide complex, amine compound, and epoxide compound have similar schemes and advantages to the aforementioned catalysts, and will not be elaborated further here.

[0081] Without limitation, the solvent is water.

[0082] In some embodiments, the first metal salt is first mixed with the complex and the resin carrier in a solvent, and then the cyanide of the second metal is added to the resulting mixture for reaction.

[0083] In some embodiments, the reaction conditions include a temperature of 30°C to 50°C and a time of 2 hours to 5 hours. Specifically, the temperature includes, but is not limited to, 30°C, 35°C, 40°C, 45°C, 50°C, or any two of the foregoing; the time includes, but is not limited to, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or any two of the foregoing.

[0084] In some embodiments, the first metal salt comprises zinc chloride.

[0085] In some embodiments, the complex comprises one or both of tert-butanol and glycol dimethyl ether.

[0086] In some embodiments, the cyanide of the second metal includes one or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium tetracyanonitrile, and potassium hexacyaniridiumate.

[0087] In some embodiments, the mass ratio of the first metal salt, the complex, and the cyanide of the second metal is (5~15):(2.5~12.5):1. Specifically, this mass ratio includes, but is not limited to: 5:12.5:1, 15:2.5:1, 8:10:1, 12:5:1, 10:7.5:1, or any range between the foregoing.

[0088] In some embodiments, the total mass ratio of the first metal salt, the complex, and the cyanide of the second metal to the resin carrier is (0.2~1):1. Specifically, this mass ratio includes, but is not limited to: 0.2:1, 0.4:1, 0.6:1, 0.67:1, 0.7:1, 0.8:1, 0.95:1, 1:1, or any range between the foregoing.

[0089] Without limitation, the step of mixing the first metal salt with the complex and the resin carrier in water includes:

[0090] First, the first metal salt is mixed with water to prepare the first material;

[0091] A complex and a resin carrier are added to the first mixture.

[0092] Furthermore, in the first material, the mass percentage of the first metal salt is 20% to 25%. Specifically, the mass percentage of the first metal salt includes, but is not limited to: 20%, 21%, 22%, 23%, 24%, 25%, or any range between the two mentioned above.

[0093] Without limitation, the step of adding a second metal cyanide to the resulting mixture includes:

[0094] First, the cyanide of the second metal is mixed with water to prepare the second material;

[0095] The second material is added to the mixture.

[0096] Furthermore, in the second material, the mass percentage of cyanide of the second metal is 5% to 10%. Specifically, the mass percentage of cyanide of the second metal includes, but is not limited to: 5%, 6%, 7%, 8%, 9%, 10%, or any range between the foregoing.

[0097] In some embodiments, after the reaction is completed, a washing step is also included, in which a mixed solvent of water and tert-butanol is used for washing, with a mass ratio of 1:(1~1.5).

[0098] In some embodiments, the method for preparing the resin carrier includes:

[0099] S1: Chloromethyl polystyrene microspheres are mixed with a first organic solvent and swollen to prepare a swelling solution;

[0100] S2: The swelling solution is mixed with an amine compound to carry out a first reaction to prepare an amine resin; the amine compound contains at least two amine groups;

[0101] S3: The amine resin is mixed with an acid and a second organic solvent to carry out a second reaction, and then an epoxy compound is added to carry out a third reaction to prepare the resin carrier.

[0102] Specifically, in step S1:

[0103] In some embodiments, the first organic solvent includes one or more of methanol, ethanol, n-hexane, dichloromethane, and toluene, optionally toluene.

[0104] In some embodiments, the concentration of the chloromethyl polystyrene microspheres is 0.1 g / mL to 0.3 g / mL, based on the amount of the first organic solvent. Specifically, the concentration of the chloromethyl polystyrene microspheres includes, but is not limited to, 0.1 g / mL, 0.15 g / mL, 0.2 g / mL, 0.25 g / mL, 0.3 g / mL, or a range between any two of the foregoing.

[0105] In some embodiments, the chloromethyl polystyrene (i.e., chloromethylated styrene-divinylbenzene copolymer) microspheres have a particle size of 40 μm to 50 μm. Specifically, the particle size of the chloromethyl polystyrene microspheres includes, but is not limited to, 40 μm, 42 μm, 45 μm, 47 μm, 50 μm, or any range between the foregoing.

[0106] Without limitation, the purpose of swelling is to fully swell the microspheres. This can be carried out at room temperature for 4 to 8 hours.

[0107] Without limitation, the chloromethyl polystyrene microspheres have the structural features shown in formula (II):

[0108] Equation (II).

[0109] Specifically, in step S2:

[0110] In some embodiments, the mass ratio of the amine compound to the chloromethyl polystyrene microspheres is (5~10):1. Specifically, this mass ratio includes, but is not limited to: 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, or any range between the foregoing.

[0111] In some embodiments, the conditions for the first reaction include a temperature of 50°C to 80°C and a time of 4 hours to 36 hours. Specifically, the temperature includes, but is not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or any range between the two; the time includes, but is not limited to, 4 hours, 8 hours, 10 hours, 12 hours, 15 hours, 17 hours, 20 hours, 20 hours, 24 hours, 26 hours, 28 hours, 30 hours, 34 hours, 36 hours, or any range between the two. Without limitation, the first reaction is carried out under reflux conditions.

[0112] Without limitation, the amine resin has the structural features shown in formula (III):

[0113] Formula (III).

[0114] Specifically, in step S3:

[0115] In some embodiments, the second organic solvent includes one or more of n-hexane, dichloromethane, and toluene, with dichloromethane being an option.

[0116] In some embodiments, the concentration of the amine resin is 0.4 g / mL to 0.6 g / mL, based on the amount of the second organic solvent. Specifically, the concentration of the amine resin includes, but is not limited to, 0.4 g / mL, 0.45 g / mL, 0.5 g / mL, 0.55 g / mL, 0.6 g / mL, or any range between the foregoing.

[0117] In some embodiments, the acid includes one or more of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0118] In some embodiments, the mass percentage of the acid is 0.1% to 1% based on the amount of the amine resin. Specifically, the mass percentage of the acid includes, but is not limited to, 0.1%, 0.3%, 0.5%, 0.7%, 1%, or any range between the foregoing.

[0119] In some embodiments, the epoxy compound is 5% to 10% by mass, based on the amount of the amine resin. Specifically, the epoxy compound by mass percentage includes, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, or any range between the foregoing.

[0120] In some embodiments, the conditions for the third reaction include a temperature of 100°C to 120°C and a time of 1 hour to 3 hours. Specifically, the temperature includes, but is not limited to, 100°C, 105°C, 110°C, 115°C, 120°C, or any two of the foregoing; the time includes, but is not limited to, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any two of the foregoing.

[0121] Without limitation, the second reaction, involving the addition of an acid and a second organic solvent to the amine resin, comprises the following steps:

[0122] First, the amine resin is mixed with the second organic solvent to swell, and then the acid is added to carry out the second reaction.

[0123] Without limitation, the swelling conditions include: room temperature and time of 4 to 8 hours.

[0124] Without limitation, the third reaction may include washing and drying steps. Washing may be performed with water or ethanol until the pH reaches 6-8; drying conditions may include a temperature of 80-100°C and a time of 5-10 hours.

[0125] In other embodiments of this application, a method for preparing polycarbonate is also provided, which uses a catalyst to catalyze the polymerization reaction of CO2 and epoxide, wherein the catalyst includes the supported bimetallic cyanide complex catalyst as described above or the supported bimetallic cyanide complex catalyst prepared by the method described above.

[0126] In some embodiments, the polymerization reaction includes the following steps:

[0127] In an inert gas atmosphere, the catalyst is filled into the reactor, then an initiator is introduced into the reactor, the temperature is raised to 60°C~100°C, CO2 is introduced, and then epoxide is introduced to carry out the reaction.

[0128] Specifically, the temperature reached includes, but is not limited to: 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or any range between the two mentioned above.

[0129] Furthermore, the initiator includes one or more of polyether PPG230 and polyether C2020.

[0130] Furthermore, based on the mass of the initiator, the mass percentage of the catalyst is 30% to 80%. Specifically, this mass percentage includes, but is not limited to: 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any range between the foregoing.

[0131] Furthermore, the epoxide includes propylene oxide.

[0132] Furthermore, the pressure of CO2 introduced into the reactor is 2MPa~4MPa.

[0133] Furthermore, the mass ratio of the initiator to the epoxide is (1~1.5):(3~4).

[0134] Furthermore, the reaction conditions include: after the epoxide is added, maintaining the temperature reached during the heating process for 1 to 2 hours. Without limitation, the epoxide is added for 0.5 to 1 hour.

[0135] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0136] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0137] Chloromethyl polystyrene resin, purchased from Tianmen Hengchang Chemical Co., Ltd., with a particle size of 40μm~50μm, product number HC2253.

[0138] Example 1-1

[0139] This example describes the preparation of amine resin A, and the steps are as follows:

[0140] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene microspheres were added and swollen in 100 mL of toluene at room temperature for 4 hours. Then, 150 g of ethylenediamine was added, and the mixture was stirred and refluxed at 80 °C for 10 hours. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The effluent was then vacuum dried at 80 °C for 5 hours to obtain amine resin A.

[0141] Examples 1-2

[0142] This example describes the preparation of amine resin B, and the steps are as follows:

[0143] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene microspheres were added and swollen in 100 mL of anhydrous ethanol at room temperature for 8 h. Then, 100 g of 1,2-propanediamine was added, and the mixture was stirred and refluxed at 80 °C for 36 h. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The resin was then dried under vacuum at 100 °C for 10 h to obtain amine resin B.

[0144] Examples 1-3

[0145] This example describes the preparation of amine resin C, and the steps are as follows:

[0146] In a 500 mL three-necked flask, 20.0 g of chloromethyl polystyrene microspheres were added and swollen in 100 mL of dichloromethane at room temperature for 6 hours. Then, 200 g of 1,4-butanediamine was added, and the mixture was stirred and refluxed at 80 °C for 24 hours. After the reaction was completed, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The resin was then dried under vacuum at 90 °C for 8 hours to obtain amine resin C.

[0147] The elemental analysis results of the amine resin (using Vario MICRO elemental analyzer, Elementar GmbH, Germany) are shown in Table 1 below:

[0148] Table 1

[0149]

[0150] As shown in Table 1, the nitrogen content of amino resins A, B, and C is significantly higher than that of the initial polystyrene resin, indicating that the amino groups were successfully grafted onto the polystyrene resin.

[0151] Example 2-1

[0152] This embodiment describes the preparation of hydroxyl-terminated quaternary ammonium salt resin A, and the steps are as follows:

[0153] In a 500mL three-necked flask, 20.0g of amine resin A was added and swollen in 50mL of dichloromethane for 6 hours at room temperature. The mixture was stirred at room temperature and 0.2g of hydrochloric acid was added dropwise. The temperature was raised to 100℃, and 2g of ethylene oxide was added dropwise. After reacting for 1 hour, the resin was filtered off and washed successively with water, ethanol, and water until the pH of the effluent was 6-8. The resin was then dried under vacuum at 90℃ for 8 hours to obtain hydroxyl-terminated quaternary ammonium salt resin A.

[0154] Hydroxyl-terminated quaternary ammonium salt resin A:

[0155] n is 2, m is 2.

[0156] Example 2-2

[0157] This embodiment describes the preparation of hydroxyl-terminated quaternary ammonium salt resin B. The steps are the same as in Example 2-1, except that amine resin B is used to replace amine resin A by the same mass.

[0158] Hydroxyl-terminated quaternary ammonium salt resin B:

[0159] n is 3 and m is 2.

[0160] Example 2-3

[0161] This embodiment describes the preparation of hydroxyl-terminated quaternary ammonium salt resin C. The steps are the same as in Example 2-1, except that amine resin C is used to replace amine resin A by the same mass.

[0162] Hydroxyl-terminated quaternary ammonium salt resin C:

[0163] n is 4 and m is 2.

[0164] Example 3-1

[0165] This embodiment describes the preparation of supported bimetallic cyanide complex catalyst A, and the steps are as follows:

[0166] 40g of zinc chloride was dissolved in 150g of water, and 30g of tert-butanol and 110g of hydroxyl-terminated quaternary ammonium salt resin A were added. Then, 4g of potassium hexacyanocobaltate was dissolved in 50g of water. The potassium hexacyanocobaltate solution was added dropwise to the zinc chloride solution. After the reaction was completed, the mixture was filtered and washed with a mixture of 100g of water (50g) and tert-butanol (50g) to obtain the supported bimetallic cyanide complex (tert-butanol complex of zinc hexacyanocobaltate) catalyst A.

[0167] Example 3-2

[0168] This embodiment describes the preparation of supported bimetallic cyanide complex catalyst B. The steps are the same as in Example 3-1, except that hydroxyl-terminated quaternary ammonium salt resin B is used to replace hydroxyl-terminated quaternary ammonium salt resin A by the same mass.

[0169] Example 3-3

[0170] This embodiment describes the preparation of a supported bimetallic cyanide complex catalyst C. The steps are the same as in Example 3-1, except that the hydroxyl-terminated quaternary ammonium salt resin C is used to replace the hydroxyl-terminated quaternary ammonium salt resin A by the same mass.

[0171] Examples 3-4

[0172] This embodiment describes the preparation of supported bimetallic cyanide complex catalyst D. The steps are the same as in Example 3-1, except that the bimetallic cyanide complex is changed to a zinc hexacyanoferrate glycol dimethyl ether complex. The steps are as follows:

[0173] 40g of zinc chloride was dissolved in 150g of water, 30g of glycol dimethyl ether and 110g of hydroxyl-terminated quaternary ammonium salt resin A were added, and then 4g of potassium hexacyanocobaltate was dissolved in 50g of water. The potassium hexacyanoferrate solution was added dropwise to the zinc chloride solution. After the reaction was completed, the mixture was filtered and washed with a mixture of 100g of water (50g) and glycol dimethyl ether (50g) to obtain the supported bimetallic cyanide complex (glycol dimethyl ether complex of zinc hexacyanoferrate) catalyst A.

[0174] Examples 3-5

[0175] This embodiment describes the preparation of a supported bimetallic cyanide complex catalyst E. The steps are the same as in Example 3-1, except that the total mass ratio of the first metal salt (zinc chloride), the complex (tert-butanol), and the second metal cyanide (potassium hexacyanocobaltate) to the resin support (hydroxyl-terminated quaternary ammonium salt resin A) is adjusted to 0.95:1. The steps are as follows:

[0176] Dissolve 50g of zinc chloride in 180g of water, add 40g of tert-butanol and 100g of hydroxyl-terminated quaternary ammonium salt resin A, then dissolve 5g of potassium hexacyanocobaltate in 50g of water, add the potassium hexacyanocobaltate solution dropwise into the zinc chloride solution, filter after the reaction is complete, and wash with a mixture of 100g of water (50g) and tert-butanol (50g) to obtain supported bimetallic cyanide complex (tert-butanol complex of zinc hexacyanocobaltate) catalyst A.

[0177] Examples 3-6

[0178] This embodiment describes the preparation of a supported bimetallic cyanide complex catalyst F. The steps are the same as in Example 3-1, except that the total mass ratio of the first metal salt (zinc chloride), the complex (tert-butanol), and the second metal cyanide (potassium hexacyanocobaltate) to the resin support (hydroxyl-terminated quaternary ammonium salt resin A) is adjusted to 0.6:1. The steps are as follows:

[0179] 40g of zinc chloride was dissolved in 150g of water, and 30g of tert-butanol and 120g of hydroxyl-terminated quaternary ammonium salt resin A were added. Then, 4g of potassium hexacyanocobaltate was dissolved in 50g of water. The potassium hexacyanocobaltate solution was added dropwise to the zinc chloride solution. After the reaction was completed, the mixture was filtered and washed with a mixture of 100g of water (50g) and tert-butanol (50g) to obtain the supported bimetallic cyanide complex (tert-butanol complex of zinc hexacyanocobaltate) catalyst A.

[0180] Example 4-1

[0181] This example describes the preparation of polycarbonate, and the steps are as follows:

[0182] Under an inert gas atmosphere, 200g of polyether (brand name C2020, Wanhua, molecular weight 2000) was added to a reactor, along with 100g of supported bimetallic cyanide complex catalyst A. The temperature was raised to 60℃, CO2 was introduced at a pressure of 4MPa, and then 400g of propylene oxide was slowly introduced over a period of 1 hour. After the addition was completed, the mixture was aged for 1 hour. The reaction was then complete, yielding a polycarbonate product, the NMR spectrum of which is shown below. Figure 1 As shown.

[0183] Example 4-2

[0184] This embodiment describes the preparation of polycarbonate, following the same steps as in Example 4-1, except that supported bimetallic cyanide complex catalyst B is used to replace supported bimetallic cyanide complex catalyst A by the same mass.

[0185] Example 4-3

[0186] This embodiment describes the preparation of polycarbonate, following the same steps as in Example 4-1, except that the supported bimetallic cyanide complex catalyst C is used to replace the supported bimetallic cyanide complex catalyst A by the same mass.

[0187] Example 4-4

[0188] This embodiment describes the preparation of polycarbonate, following the same steps as in Example 4-1, except that the supported bimetallic cyanide complex catalyst D is used to replace the supported bimetallic cyanide complex catalyst A by the same mass.

[0189] Examples 4-5

[0190] This embodiment describes the preparation of polycarbonate, following the same steps as in Example 4-1, except that the supported bimetallic cyanide complex catalyst E is used to replace the supported bimetallic cyanide complex catalyst A by the same mass.

[0191] Examples 4-6

[0192] This embodiment describes the preparation of polycarbonate, following the same steps as in Example 4-1, except that the supported bimetallic cyanide complex catalyst F is used to replace the supported bimetallic cyanide complex catalyst A by the same mass.

[0193] Comparative Example 1

[0194] This comparative example is the preparation of polycarbonate, and the steps are the same as in Example 4-1, except that the supported bimetallic cyanide complex catalyst A is replaced by an equal amount of hydroxyl-terminated quaternary ammonium salt resin A.

[0195] Comparative Example 2

[0196] This comparative example is the preparation of polycarbonate, and the steps are the same as in Example 4-1, except that the supported bimetallic cyanide complex catalyst A is replaced by an equal mass of amine resin A.

[0197] Comparative Example 3

[0198] This comparative example is for the preparation of polycarbonate, with the same steps as in Example 4-1, except that the supported bimetallic cyanide complex catalyst A is replaced by a zinc hexacyanocobaltate tert-butanol complex at an equal mass, with a catalyst mass of 0.2g.

[0199] Test case

[0200] The polycarbonate products prepared in the examples and comparative examples were subjected to NMR detection and elemental analysis to detect the carbon dioxide insertion rate, cyclic carbonate content, and residual metal elements in the polycarbonate products.

[0201] Nuclear magnetic resonance spectrometers: Bruker-400 MHz, Varian INOVA-400 MHz, Bruker-600 MHz. 1 H-NMR testing was performed using TMS as an internal standard (0 ppm). Elemental analyzer: Vario:MICRO, Elementar GmbH, Germany.

[0202] The results are shown in Table 2 below:

[0203] Table 2

[0204]

[0205] (2) The supported bimetallic cyanide complex catalyst A was used 10 times as described in Example 4-1, and the performance of the polycarbonate products prepared in each cycle was tested. The results are shown in Table 3 below:

[0206] Table 3

[0207]

[0208] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0209] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A supported bimetallic cyanide complex catalyst, characterized in that, Includes a resin carrier and a bimetallic cyanide complex loaded on the resin carrier; The resin carrier is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

2. The supported bimetallic cyanide complex catalyst according to claim 1, characterized in that, The bimetallic cyanide complex includes one or more of zinc hexacyanocobaltate, zinc hexacyanoferrate, zinc tetracyanonitrile, and zinc hexacyaniridiumate, and the complex includes one or two of tert-butanol and glycol dimethyl ether. Optionally, the bimetallic cyanide in the bimetallic cyanide complex includes zinc hexacyanocobaltate, and the complex includes tert-butanol.

3. The supported bimetallic cyanide complex catalyst according to claim 1 or 2, characterized in that, The resin carrier includes polystyrene resin, an amine compound grafted onto the polystyrene resin, and an epoxy compound grafted onto the amine compound; The amine compound contains at least two amine groups, and at least one amine group is quaternized to form the quaternary ammonium salt group; The amine compound is grafted onto the polystyrene resin via the amine group; The epoxy compound is grafted onto the amine compound via the amino group, and the epoxy compound undergoes ring-opening to form the terminal hydroxyl group.

4. The supported bimetallic cyanide complex catalyst according to claim 3, characterized in that, The amine compounds include diamine compounds, optionally one or more selected from ethylenediamine, 1,2-propanediamine, and 1,4-butanediamine; and / or, The epoxy compound includes one or both of ethylene oxide and propylene oxide.

5. The supported bimetallic cyanide complex catalyst according to claim 3, characterized in that, The resin carrier has the structural features shown in formula (I): Formula (I), Where n is an integer from 2 to 4, and L is a C2 to C5 alkylene group.

6. A method for preparing a supported bimetallic cyanide complex catalyst, characterized in that, Includes the following steps: The supported bimetallic cyanide complex catalyst is prepared by reacting a first metal salt with a complex, a resin support, and a cyanide of a second metal in a solvent. The resin carrier is a polystyrene resin containing terminal hydroxyl groups and quaternary ammonium salt groups.

7. The method for preparing the supported bimetallic cyanide complex catalyst according to claim 6, characterized in that, It has one or more of the following characteristics: (1) The reaction conditions include: temperature of 30℃~50℃ and time of 2h~5h; (2) The first metal salt includes zinc chloride; (3) The complex comprises one or both of tert-butanol and glycol dimethyl ether; (4) The cyanide of the second metal includes one or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium tetracyanonitrile and potassium hexacyaniridiumate; (5) The total mass ratio of the first metal salt, the complex and the cyanide of the second metal to the mass ratio of the resin carrier is (0.2~1):1; (6) The mass ratio of the first metal salt, the complex and the cyanide of the second metal is (5~15):(2.5~12.5):

1.

8. The method for preparing the supported bimetallic cyanide complex catalyst according to claim 6 or 7, characterized in that, The method for preparing the resin carrier includes: Chloromethyl polystyrene microspheres were mixed with a first organic solvent and swollen to prepare a swelling solution. The swelling solution is mixed with an amine compound to carry out a first reaction to prepare an amine resin; the amine compound contains at least two amine groups. The amine resin is mixed with an acid and a second organic solvent to carry out a second reaction, and then an epoxy compound is added to carry out a third reaction to prepare the resin carrier.

9. The method for preparing the supported bimetallic cyanide complex catalyst according to claim 8, characterized in that, The method for preparing the resin carrier has one or more of the following features: (1) The first organic solvent includes one or more of methanol, ethanol, n-hexane, dichloromethane and toluene, and may be toluene; (2) Based on the amount of the first organic solvent, the concentration of the chloromethyl polystyrene microspheres is 0.1 g / mL to 0.3 g / mL; (3) The particle size of the chloromethyl polystyrene microspheres is 40 μm to 50 μm; (4) The mass ratio of the amine compound to the chloromethyl polystyrene microspheres is (5~10):1; (5) The conditions for the first reaction include: temperature of 50℃~80℃ and time of 4h~36h; (6) The second organic solvent includes one or more of n-hexane, dichloromethane and toluene, and may be dichloromethane; (7) Based on the amount of the second organic solvent, the concentration of the amine resin is 0.4 g / mL to 0.6 g / mL; (8) The acid includes one or more of hydrochloric acid, sulfuric acid, and phosphoric acid; (9) Based on the amount of the amine resin, the mass percentage of the acid is 0.1% to 1%; (10) Based on the amount of the amine resin, the epoxy compound has a mass percentage of 5% to 10%; (11) The conditions for the third reaction include: temperature of 100℃~120℃ and time of 1h~3h.

10. A method for preparing polycarbonate, characterized in that, The polymerization reaction of CO2 and epoxide is catalyzed by a catalyst, wherein the catalyst comprises the supported bimetallic cyanide complex catalyst according to any one of claims 1 to 5 or the supported bimetallic cyanide complex catalyst prepared by the preparation method according to any one of claims 6 to 9.

11. The method for preparing polycarbonate according to claim 10, characterized in that, The polymerization reaction includes the following steps: In an inert gas atmosphere, the catalyst is filled into a reactor, then an initiator is added to the reactor, the temperature is raised to 60°C~100°C, CO2 is introduced, and then an epoxide is added to carry out the reaction. Optionally, the initiator includes one or both of polyether PPG230 and polyether C2020; Optionally, the mass percentage of the catalyst is 30% to 80% based on the mass of the initiator.

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