CN115624985A - Preparation method and application of high-efficiency catalyst Pd/N-SBA-15 - Google Patents
Preparation method and application of high-efficiency catalyst Pd/N-SBA-15 Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a high-efficiency catalyst Pd/N-SBA-15, which comprises the following steps: taking a molecular sieve SBA-15 as a starting material, adding an amination reagent, reacting at a certain temperature, and obtaining a functionalized molecular sieve N-SBA-15 after complete reaction; and (2) soaking the N-SBA-15 by using an aqueous solution containing palladium ions, treating by using a reducing agent solution, filtering, washing, drying and the like to obtain the catalyst Pd/N-SBA-15 with high catalytic performance. The method for preparing the catalyst Pd/N-SBA-15 has the following beneficial effects: less reaction steps, mild reaction, simple post-treatment operation, strong catalytic performance, more repeated use times and the like.
Description
Technical Field
The invention belongs to the technical field of chemical raw material preparation, and particularly relates to a preparation method and application of a high-efficiency catalyst Pd/N-SBA-15 for synthesizing polyimide diamine monomer.
Background
Polyimides are polymers obtained by the polymerization of diamine and dianhydride monomers, containing recurring imide rings in the molecular chain. Polyimide has excellent thermal stability, chemical resistance, low dielectric constant and good processability, and thus, it is an indispensable position in various fields. The method is widely applied to the fields of aviation, aerospace, new energy, intelligent manufacturing, liquid crystal, separation membranes and the like. Polyimide is known as one of the most promising engineering plastics in the 21 st century.
The main problems existing in the synthesis of polyimide diamine monomers at present are that a large number of byproducts are generated in the synthesis process, for example, 3,4' -ODA (formula I), and II-VIII are all byproducts, because common catalysts comprise palladium carbon, raney nickel, iron powder and zinc powder, wherein the palladium carbon and the Raney nickel are expensive, the repeated utilization times are few, and the catalyst is flammable and easily leaks carbon during treatment, so that the product quality is influenced. The iron powder and the zinc powder have the problems of complex post-treatment, large discharge of three wastes, environmental pollution and the like. Therefore, the intermediate state is difficult to control during synthesis, and the purification is difficult, particularly the purity is over 99.5 percent.
Relatively few reports are reported on the preparation of molecular sieve palladium catalysts, and palladium carbon is generally prepared by using activated carbon as a carrier to serve as a catalyst. However, palladium carbon is used as a catalyst to prepare diamine monomers, the purity of crude products of target products obtained by reaction is generally 95% -99%, and a series of subsequent purification, decoloration and other treatments are required when the crude products are used as qualified polyimide monomers. The palladium-carbon is expensive, the recycling effect is poor, the production cost is high, the physical properties of different diamine monomers are different, the purification method has no certain rule and can be circulated, and the application of the diamine monomers in industrial production is limited due to the reason, so that a catalyst with high catalytic performance suitable for industrial production is urgently needed.
Disclosure of the invention
In order to solve the above problems, the present invention aims to provide a method for preparing a catalyst with high catalytic performance, and therefore we develop a novel molecular sieve palladium catalyst (the preparation process is shown below), the use of the catalyst can significantly improve the catalytic performance, and greatly reduce the residual of intermediate compounds in the reduction process of nitro compounds, so that the method has the advantages of short reaction time, mild conditions, simple post-treatment operation, high yield and high product purity.
In order to achieve the aim, the invention provides a preparation method of a high-efficiency catalyst Pd/N-SBA-15, which comprises the following steps in sequence:
adding a molecular sieve SBA-15 serving as a starting material into a solvent, uniformly stirring, dropwise adding an amination functional reagent, reacting at a certain temperature, cooling a reaction solution to room temperature after the reaction is finished, and washing, filtering and drying a solid obtained after the filtration to obtain a functionalized carrier N-SBA-15;
and (2) impregnating the N-SBA-15 by using a palladium ion-containing aqueous solution, treating by using a reducing reagent solution, filtering, washing and drying to obtain the catalyst Pd/N-SBA-15 with high catalytic performance.
Further, the solvent is one of toluene, tetrahydrofuran, acetone, dioxane, N-dimethylformamide, N-dimethylacetamide and ethanol, preferably ethanol.
Further, the amino functional reagent is at least one of 3-aminopropyltriethoxysilane and diethylenetriaminopropyltrimethoxysilane.
Further, the ratio of the mass of the solvent to the SBA-15 is 10-30:1, the mass ratio of SBA-15 to amino functional reagent is 5-10:1, the amination reaction temperature is 20-80 ℃.
Further, the solute in the palladium ion-containing aqueous solution is PdCl 2 And Pd (C) 2 H 3 O 2 ) 2 The palladium ion-containing aqueous solution Pd 2+ The concentration is 0.003-0.009mol/L, preferably 0.004-0.007mol/L.
Further, the reducing reagent is sodium borohydride, sodium borohydride and Pd 2+ In a molar ratio of 2 to 6, preferably 3; the washing solvent of the N-SBA-15 is one of tetrahydrofuran, dichloromethane, methanol, ethanol and ethyl acetate, and is preferably tetrahydrofuran.
The high-efficiency catalyst Pd/N-SBA-15 is applied to catalyzing and synthesizing a polyimide diamine monomer. Adding one of 1, 3-bis (4-nitrophenoxy) benzene, 3,4' -dinitrodiphenyl ether and 1, 3-bis (3-nitrophenoxy) benzene and Pd/N-SBA-15 into an organic solvent, uniformly stirring, introducing hydrogen, reacting for a period of time, treating to obtain a corresponding diamine monomer, polymerizing the prepared diamine monomer and commercial dianhydride 6FDA to obtain polyimide, and testing the viscosity of the polymer.
In the steps, the purity of diamine monomer prepared by reducing three nitro-compounds is 99.51-99.93%, and YI =1.2-2.7;
in the above steps, the molecular weight of the three polymers obtained by polymerization is 20-80 ten thousand.
Compared with commercial palladium carbon as a catalyst, the invention has the following beneficial effects:
few reaction steps, mild reaction, simple post-treatment operation, strong catalytic performance, more times of repeated use and the like. The diamine monomer synthesized by the catalyst has the yield of more than 97.5 percent, the purity of more than 99.5 percent, the highest purity of 99.93 percent and the chroma of less than 3.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation of the invention. In the drawings:
FIG. 1 is an SEM photograph of N-SBA-15 prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of CT-01 prepared in example 1 of the present invention.
Detailed Description
The method for preparing Pd-SBA-15 with high catalytic performance provided by the invention is explained in detail by combining specific examples.
Example 1
Adding 2g of SBA-15 and 40g of ethanol into a reaction bottle under the protection of nitrogen, heating to 60 ℃, starting to dropwise add a mixed solution of 250mg of diethylenetriaminopropyltrimethoxysilane and 2g of ethanol, controlling the temperature to 60 ℃ (± 1 ℃), continuing to perform heat preservation reaction for 15h after finishing dripping, cooling to room temperature, filtering, washing for 30min by using 20mL of tetrahydrofuran, filtering, and performing vacuum drying for 24h at 60 ℃ to obtain 1.9g of white powder, which is recorded as N (1) -SBA-15.
1.2mmol of PdCl 2 Dissolved in 200mL of deionized water to prepare 0.006mol/L Pd 2+ An aqueous solution of (a). Under the protection of nitrogen, 1g of N (1) -SBA-15 and 20mL of the prepared Pd 2+ The aqueous solution of (2) was put into a 100mL three-necked flask and immersed at PH =2 and 10 ℃ for 12 hours. After completion of the filtration, a white solid was obtained, which was further treated with 20mL of a 0.12mol/L aqueous solution of sodium borohydride at room temperature for 24 hours, filtered and then dried under vacuum at 100 ℃ for 24 hours to obtain 0.97g of a white powder, which was designated as CT-01.
100g of 1, 3-bis (4-nitrophenoxy) benzene, 0.2g of CT-01 and 800g of ethanol are added into a 2L autoclave, after uniform stirring, 0.5MPa of hydrogen is introduced, and the reaction is carried out for 18 hours at 60 ℃ after the reaction is finished. The catalyst CT-01 was filtered out, the temperature of the filtrate was reduced to 0 ℃, a large amount of white solid was precipitated, and vacuum drying was carried out at 80 ℃ for 12 hours to obtain 81.74g of 1, 3-bis (4-aminophenoxy) benzene with a molar yield of 98.5%, a purity of 99.93%, a YI =1.2, and a viscosity test of 79.8 ten thousand after polymerization with 6 FDA.
Example 2
Adding 2g of molecular sieve SBA-15 and 40g of toluene into a reaction bottle under the protection of nitrogen, heating to 60 ℃, starting to dropwise add a mixed solution of 250mg of diethylenetriaminopropyltrimethoxysilane and 2g of ethanol, controlling the temperature to 60 ℃ (± 1 ℃), continuing to perform heat preservation reaction for 15h after finishing dripping, cooling to room temperature, filtering, washing for 30min by using 20mL of tetrahydrofuran, filtering, and performing vacuum drying for 12h at 60 ℃ to obtain 1.9g of white powder, which is recorded as N (2) -SBA-15.
Under the protection of nitrogen, 1g of N (1-1) -SBA-15 and 20mL of Pd prepared in step 1 2+ The aqueous solution of (a) was placed in a 100mL three-necked flask and reacted at PH =2 and 10 ℃ for 12 hours. After the reaction, the mixture was filtered to obtain a white solid, which was further immersed in 20mL of 0.12mol/L aqueous sodium borohydride solution at room temperature for 24 hours, filtered and then vacuum-dried at 100 ℃ for 24 hours to obtain 0.97g of white powder, which was designated as CT-02.
100g of 3,4' -dinitrodiphenyl ether, 0.2g of CT-02 and 800g of ethanol are added into a 2L high-pressure autoclave, after uniform stirring, 0.5MPa of hydrogen is introduced, and the reaction is carried out for 18h at 60 ℃ after the reaction is finished. The catalyst CT-02 was filtered out, the filtrate was cooled to 0 ℃ and a large amount of white solid precipitated, and vacuum dried at 80 ℃ for 12 hours to give 75.57g of 3,4' -diaminodiphenyl ether with a purity of 99.83%, molar yield of 98.2%, YI =1.2, and viscosity test of 76.4 ten thousand after polymerization with 6 FDA.
Example 3
Adding 2g of SBA-15 and 40g of ethanol into a reaction bottle under the protection of nitrogen, heating to 60 ℃, starting to dropwise add a mixed solution of 180mg of diethylenetriaminopropyltrimethoxysilane and 2g of ethanol, controlling the temperature to 60 ℃ (± 1 ℃), continuing to perform heat preservation reaction for 15h after finishing dripping, cooling to room temperature, filtering, washing for 30min by using 20mL of methanol, filtering, and performing vacuum drying for 12h at 60 ℃ to obtain 1.93g of white powder, which is recorded as N (3) -SBA-15.
Under the protection of nitrogen, 1g of N (1-3) -SBA-15 and 20mL of prepared Pd in step 1 2+ The aqueous solution of (a) was placed in a 100mL three-necked flask and reacted at PH =2 and 10 ℃ for 12 hours. After the reaction, the mixture was filtered to obtain a white solid, which was further immersed in 20mL of 0.20mol/L aqueous sodium borohydride solution at room temperature for 24 hours, filtered and then vacuum-dried at 100 ℃ for 24 hours to obtain 0.98g of white powder, which was designated as CT-03.
100g of 1, 3-bis (3-nitrophenoxy) benzene, 0.2g of CT-03 and 800g of ethanol are added into a 2L high-pressure kettle, and after uniform stirring, 0.5MPa of hydrogen is introduced, and the reaction is carried out for 18h at 60 ℃ after the reaction is finished. The catalyst CT-03 was filtered out, the filtrate was cooled to 0 ℃ to precipitate a large amount of white solid, and vacuum-dried at 80 ℃ for 12 hours to obtain 81.24g of 1, 3-bis (3-nitrophenoxy) benzene with a purity of 99.63%, a molar yield of 97.9%, YI =2.3, and a viscosity test of 68.4 ten thousand after polymerization with 6 FDA.
Example 4
Adding 2g of SBA-15 of molecular sieve and 40g of ethanol into a reaction bottle under the protection of nitrogen, heating to 40 ℃, starting to dropwise add a mixed solution of 250mg of diethylenetriaminopropyltrimethoxysilane and 2g of ethanol, controlling the temperature to 40 ℃ (+ -1 ℃), continuing to perform heat preservation reaction for 15h, cooling to room temperature, filtering, washing for 30min by using 20mL of tetrahydrofuran, filtering, and performing vacuum drying for 12h at 60 ℃ to obtain 1.7g of white powder, which is recorded as N (4) -SBA-15.
Under the protection of nitrogen, 1g of N (4) -SBA-15 and 20mL in the step 1 are preparedGood Pd as described above 2+ The aqueous solution of (2) was placed in a 100mL three-necked flask and reacted at 10 ℃ for 12 hours at pH = 5. After the reaction, the mixture was filtered to obtain a white solid, which was further immersed in 20mL of 0.12mol/L aqueous sodium borohydride solution at room temperature for 24 hours, filtered and then vacuum-dried at 100 ℃ for 24 hours to obtain 0.97g of white powder, which was designated as CT-04.
100g of 1, 3-bis (4-nitrophenoxy) benzene, 0.2g of CT-04 and 800g of ethanol are added into a 2L autoclave, after uniform stirring, 0.5MPa of hydrogen is introduced, and the reaction is carried out for 18h at 60 ℃ after the reaction is finished. The catalyst CT-04 is filtered out, the filtrate is cooled to 0 ℃, a large amount of white solid is separated out, and vacuum drying is carried out for 12 hours at 80 ℃ to obtain 81.40g of 1, 3-bis (4-aminophenoxy) benzene, the purity is 99.53%, the molar yield is 98.1%, the YI =2.9, and the viscosity test after polymerization with 6FDA is 33.8 ten thousand.
Example 5
Adding 2g of SBA-15 and 40g of ethanol into a reaction bottle under the protection of nitrogen, heating to 60 ℃, starting to dropwise add a mixed solution of 250mg of 3-aminopropyltriethoxysilane and 2g of ethanol, controlling the temperature to 60 ℃ (± 1 ℃), continuing to perform heat preservation reaction for 15h after finishing dripping, cooling to room temperature, filtering, washing for 30min by using 20mL of tetrahydrofuran, filtering, and performing vacuum drying for 12h at 60 ℃ to obtain 1.9g of white powder, which is marked as N (5) -SBA-15.
Under the protection of nitrogen, 1g of N (5) -SBA-15 and 20mL of prepared Pd in step 1 2+ The aqueous solution of (a) was placed in a 100mL three-necked flask and reacted at PH =2 and 10 ℃ for 12 hours. After the reaction was complete, the reaction mixture was filtered to give a white solid, which was further immersed in 20mL of a 0.12mol/L aqueous solution of sodium borohydride at room temperature for 24 hours, filtered, and vacuum-dried at 100 ℃ for 24 hours to give 0.97g of a white powder, which was designated as CT-05.
100g of 1, 3-bis (4-nitrophenoxy) benzene, 0.2g of CT-04 and 800g of ethanol are added into a 2L autoclave, and after uniform stirring, 0.5MPa of hydrogen is introduced, and the reaction is carried out for 18h at 60 ℃ after the reaction is finished. The catalyst CT-04 is filtered out, the temperature of the filtrate is reduced to 0 ℃, a large amount of white solid is separated out, and 80.99g of 1, 3-bis (4-aminophenyloxy) benzene with the purity of 99.83 percent, the molar yield of 97.6 percent, the YI =1.6 and the viscosity test of 77.3 ten thousand after polymerization with 6FDA is obtained after vacuum drying for 12h at the temperature of 80 ℃.
Example 6
Adding 2g of SBA-15 of molecular sieve and 50g of acetone into a reaction bottle under the protection of nitrogen, heating to 60 ℃, starting to dropwise add a mixed solution of 250mg of 3-aminopropyltriethoxysilane and 2g of acetone, controlling the temperature to 60 ℃ (+ -1 ℃), continuing to perform heat preservation reaction for 15h after dropwise addition is finished, cooling to room temperature, filtering, washing for 30min by using 30mL of ethyl acetate, filtering, and performing vacuum drying for 12h at 60 ℃ to obtain 1.94g of white powder, which is recorded as N (6) -SBA-15.
Under the protection of nitrogen, 1g of N (6) -SBA-15 and 20mL of Pd prepared in example 1 2+ The aqueous solution of (a) was placed in a 100mL three-necked flask and reacted at 20 ℃ at pH =2 for 12 hours. After the reaction was complete, the mixture was filtered to give a white solid, which was further immersed in 20mL of a 0.12mol/L aqueous solution of sodium borohydride at room temperature for 24 hours, filtered and then dried under vacuum at 100 ℃ for 24 hours to give 0.99g of a white powder, which was designated as CT-06.
100g of 1, 3-bis (4-nitrophenoxy) benzene, 0.2g of CT-06 and 800g of ethanol are added into a 2L autoclave, and after uniform stirring, 0.5MPa of hydrogen is introduced to react for 18h at 60 ℃, and the reaction is finished. The catalyst CT-06 was filtered out, the filtrate was cooled to 0 ℃ to precipitate a large amount of white solid, and vacuum-dried at 80 ℃ for 12 hours to obtain 81.48g of 1, 3-bis (4-aminophenoxy) benzene with a purity of 99.51%, a molar yield of 98.2%, YI =2.8, and a viscosity test of 27.3 ten thousand after polymerization with 6 FDA.
Example 7
The difference from example 1 is that in the process of synthesizing 1, 3-bis (4-aminophenoxy) benzene, the catalyst utilizes the recovered catalyst CT-01 in example 1, 6 times of experiments are repeated to obtain diamine monomer, 1, 3-bis (4-aminophenoxy) benzene is white powder, the molar yield is between 96% and 99%, the purity is between 99.54% and 99.91%, the molar yield is between 97.5% and 98.5%, YI =1.3-2.4, and the viscosity test after polymerization with 6FDA is 63-70.4 ten thousand.
Example 8
The difference from example 5 is that in the process of synthesizing 1, 3-bis (4-aminophenoxy) benzene, the catalyst utilizes the recovered catalyst CT-04 in example 5, 6 times of experiments are repeated to obtain diamine monomer, 1, 3-bis (4-aminophenoxy) benzene is white powder, the molar yield is between 95% and 98%, the purity is between 99.51% and 99.81%, the molar yield is between 97.5% and 98.5%, YI =1.7-2.8, and the viscosity test after polymerization with 6FDA is between 48 and 69 ten thousand.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a high-efficiency catalyst Pd/N-SBA-15 is characterized by comprising the following steps: adding a molecular sieve SBA-15 serving as a starting material into a solvent, uniformly stirring, dropwise adding an amination functional reagent, reacting at a certain temperature, cooling a reaction solution to room temperature after the reaction is finished, and washing, filtering and drying a solid obtained after the filtration to obtain a functionalized carrier N-SBA-15;
and (2) impregnating the N-SBA-15 by using a palladium ion-containing aqueous solution, treating by using a reducing agent solution, filtering, washing and drying to obtain the catalyst Pd/N-SBA-15 with high catalytic performance.
2. The method of claim 1, wherein: the solvent is one of toluene, tetrahydrofuran, acetone, dioxane, N-dimethylformamide, N-dimethylacetamide and ethanol, and preferably ethanol.
3. The production method according to claim 1, characterized in that: the amino functional reagent is at least one of 3-aminopropyltriethoxysilane and diethylenetriaminopropyltrimethoxysilane.
4. The method of claim 1, wherein: the ratio of the mass of the solvent to the SBA-15 is 10-30:1, the mass ratio of SBA-15 to amino functional reagent is 5-10:1, the amination reaction temperature is 20-80 ℃.
5. The production method according to claim 1, characterized in that: the palladium-containing ionsThe solute in the aqueous solution is PdCl 2 And Pd (C) 2 H 3 O 2 ) 2 The palladium ion-containing aqueous solution Pd 2+ The concentration is 0.003-0.009mol/L, preferably 0.004-0.007mol/L.
6. The method of claim 1, wherein: the reducing reagent is sodium borohydride, sodium borohydride and Pd 2+ In a molar ratio of 2 to 6, preferably 3; the washing solvent of the N-SBA-15 is one of tetrahydrofuran, dichloromethane, methanol, ethanol and ethyl acetate, and is preferably tetrahydrofuran.
7. The application of the high-efficiency catalyst Pd/N-SBA-15 prepared by the preparation method of any one of claims 1-6 in the catalytic synthesis of polyimide diamine monomers.
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