CN113198538A - Preparation method of superstrong fiber-loaded Schiff base palladium catalyst - Google Patents
Preparation method of superstrong fiber-loaded Schiff base palladium catalyst Download PDFInfo
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- CN113198538A CN113198538A CN202110515279.7A CN202110515279A CN113198538A CN 113198538 A CN113198538 A CN 113198538A CN 202110515279 A CN202110515279 A CN 202110515279A CN 113198538 A CN113198538 A CN 113198538A
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- 239000000835 fiber Substances 0.000 title claims abstract description 84
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002262 Schiff base Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 37
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 37
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 7
- OVZQVGZERAFSPI-UHFFFAOYSA-N quinoline-8-carbaldehyde Chemical compound C1=CN=C2C(C=O)=CC=CC2=C1 OVZQVGZERAFSPI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000001035 drying Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- -1 quinoline Schiff base Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 abstract description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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Abstract
The invention relates to a preparation method of a super-strong fiber-loaded Schiff base palladium catalyst; taking polyether-ether-ketone super strong fibers as a matrix, grafting and neutralizing chloromethyl functionalized polyether-ether-ketone fibers and diamine, reacting the obtained diamine functionalized super strong fibers with quinoline-8-formaldehyde to prepare Schiff base loaded by super strong fibers, and coordinating and chelating the Schiff base loaded by the fibers and palladium acetate to obtain a polyether-ether-ketone fiber loaded Schiff base type palladium complex catalyst; the polyether-ether-ketone fiber supported Schiff base palladium catalyst is simple to prepare, shows excellent catalytic performance in Suzuki and Heck reactions, is convenient to separate, recover and circularly apply, and provides a new way for industrial catalytic synthesis by virtue of higher mechanical strength and flexibility and convenience for secondary processing.
Description
Technical Field
The invention relates to a preparation method of a super-strong fiber-loaded Schiff base palladium catalyst, which can efficiently and circularly catalyze reactions such as Suzuki, Heck and the like, and belongs to the technical field of green catalysis.
Background
Fourteen five is the key period of realizing carbon peak reaching and promoting carbon neutralization starting period, and the Chinese union of petroleum and chemical industries compiles and issues opinions on promoting energy conservation and emission reduction of petroleum and chemical industries for many times. The method adopts technically feasible and economically reasonable measures to develop energy conservation and emission reduction, and is a necessary way for enterprises to seek development. In recent years, the green catalytic technology has received wide attention of chemists all over the world as the leading edge of international chemical science research, and has also played a significant promoting role in the sustainable development of economy and society. However, the fine chemical catalytic technology mainly used for synthesizing the drug intermediate is relatively lagged behind, the development is slow, the level of clean production and comprehensive utilization is far away from the requirement of ecological civilization construction, and the sustainable development of the industry faces a plurality of challenges. Advanced catalytic technology will certainly promote significant advances in production processes, and improvements in catalytic technology are generally subject to innovation of catalysts or catalytic materials. Therefore, designing and developing efficient and environment-friendly catalytic materials will be a hotspot and a key point in the chemical and chemical research field in a future period, and will also be a basic way for implementing energy conservation and emission reduction in the chemical industry in China during the fourteen-five period.
In the fields of fine chemical engineering and pharmaceutical synthetic chemistry, reactions such as Suzuki and Heck coupling catalyzed by palladium are the most effective methods for constructing carbon-carbon bonds, wherein the type of palladium ligand has a crucial influence on the yield and selectivity of products.
At present, commonly used ligands are mainly phosphine ligands with high steric hindrance and strong electron supply capacity, N-heterocyclic carbene, Schiff bases and the like, and the Schiff bases are favored by people due to the advantages of simple preparation, good coordination capacity, diversified structures and the like. However, the homogeneous schiff base palladium catalyst is not easy to separate and recover and is difficult to recycle, so that the load of the homogeneous schiff base palladium catalyst has very important significance. Bhunia and the like design and prepare a supported Schiff base palladium catalyst by taking MCM-41 as a matrix, Koner and the like prepare a MOF supported Schiff base palladium catalyst by taking a modified organic metal framework (MOF) as a carrier, and graphene oxide supported Schiff base palladium catalyst is reported in Yuanqian and the like. However, the supported schiff base palladium catalyst is not high in active component proportion under most conditions, easy to aggregate and run off and inconvenient to operate, and in addition, part of the novel carrier is high in use cost due to the fact that the preparation process of the novel carrier is complicated, and is difficult to reprocess and utilize due to the limitation of a specific structure of a carrier material, so that the industrial scale application of the novel carrier is severely limited. The polyether-ether-ketone fiber is used as a novel super-strong fiber material, and has unique advantages in reprocessing performance and circulating operation when being used as a Schiff base palladium catalyst carrier by virtue of higher mechanical properties.
Disclosure of Invention
The invention aims to provide a preparation method of a superstrong fiber supported Schiff base palladium catalyst, which takes commercial polyether-ether-ketone as a substrate and is characterized in that a quinoline Schiff base palladium complex is covalently bonded on the substrate. The functional fiber catalyst can efficiently catalyze the reaction constructed by a series of carbon-carbon bonds, and can be recycled at least for more than 10 times.
The technical scheme of the invention is as follows:
a super strong fiber load Schiff base palladium catalyst takes commercial polyether-ether-ketone super strong fiber as a matrix, and a functional fiber catalytic material with an active site of quinoline palladium complex is prepared in a top-down mode.
The preparation method of the super-strong fiber supported Schiff base palladium catalyst disclosed by the invention preferably comprises the following steps of:
1) blending polyether-ether-ketone fibers with the weight increased by 15% in the chloromethyl functionalization and diamine in toluene according to the mass ratio of 1: 15-25, stirring at a specific temperature, cooling to room temperature after reaction, taking out the super-strong fibers, and sequentially removing the super-strong fibers with alkali liquorRinsing with water until the filtrate is neutral, and then 80-85% of the filtrateoC, drying to constant weight to obtain diamine functionalized polyether-ether-ketone fibers;
2) blending the obtained diamine functionalized polyether ether ketone fiber and quinoline-8-formaldehyde in ethanol according to the mass ratio of 1: 10-20, stirring at a specific temperature, cooling to room temperature after reaction, taking out the super-strong fiber, washing with ethanol, and then 80-85oDrying to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fiber;
3) blending the obtained polyether-ether-ketone fiber-loaded Schiff base and palladium acetate in ethanol according to the mass ratio of 1: 2-5, taking out the super-strong fiber and washing the super-strong fiber with ethanol after the reaction at room temperature under the stirring condition, and then 80-85oAnd C, drying to constant weight to obtain the polyether-ether-ketone fiber-loaded quinoline Schiff base type palladium complex catalyst.
The preferable diamine in the step 1) is 1, 3-propane diamine, 1, 4-butane diamine or 1, 6-hexane diamine, and the reaction temperature is 105-110oAnd C, the reaction time is 12-24 h.
The preferable reaction temperature in the step 2) is 75-80 DEG CoAnd C, the reaction time is 12-36 h.
The preferable reaction time in the step 3) is 24-48 h.
The method has the advantages that the quinoline Schiff base palladium complex is grafted and bonded on the surface layer of the super-strong fiber polyether-ether-ketone, and efficient catalysis in carbon-carbon bond construction processes such as Suzuki and Heck reactions and convenient circulation of a system are realized by utilizing the excellent active site of the palladium complex and various advantages of fiber materials.
Drawings
FIG. 1: the structure diagram of the super-strong fiber load Schiff base palladium catalyst;
FIG. 2: a circulating catalysis effect diagram of the superstrong fiber loaded Schiff base palladium catalyst in the Suzuki reaction;
FIG. 3: the circulating catalysis effect of the super-strong fiber supported Schiff base palladium catalyst in the Heck reaction is shown.
Detailed Description
The specific examples further illustrate the practice of the invention.
Example 1
At 100 mL three-necked flask was charged with 1.0 g of dry chloromethyl-functionalized polyetheretherketone fiber, 15.0 g of 1, 3-propanediamine and 50 mL of acetonitrile, 110oC, stirring and reacting for 12 hours, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then, at the temperature of 85 ℃, washing with deionized wateroC, drying in a drying box in vacuum to constant weight to obtain the 1, 3-propylenediamine functional super-strong fiber;
adding the dried 1, 3-propanediol functionalized super-strong fiber, 12 g of quinoline-8-formaldehyde, 50 mL of ethanol and 80 mL of ethanol into a 100 mL three-neck flaskoC, stirring and reacting for 24 hours, cooling to room temperature, taking out the super-strong fiber, washing with ethanol, and then reacting at 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fibers.
Adding the dried quinoline Schiff base loaded by the polyether-ether-ketone fiber, 2.5 g of palladium acetate and 50 mL of ethanol into a 100 mL three-neck flask, stirring at room temperature for reaction for 48 hours, washing with ethanol after the reaction is finished, and then washing at the temperature of 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber supported Schiff base palladium catalyst.
Example 2
A100 mL three-necked flask was charged with 1.0 g of dry chloromethyl-functionalized polyetheretherketone fiber, 20.0 g of 1, 4-butanediamine and 50 mL of acetonitrile, 110oC, stirring and reacting for 18 h, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then, at the temperature of 85 DEG, washing with deionized wateroC, drying in a drying box in vacuum to constant weight to obtain the 1, 4-butanediamine functional super-strong fiber;
adding the dried 1, 4-butanediamine functionalized super-strong fiber, 15 g of quinoline-8-formaldehyde and 50 mL of ethanol, and 80 percent of ethanol into a 100 mL three-neck flaskoC, stirring and reacting for 24 hours, cooling to room temperature, taking out the super-strong fiber, washing with ethanol, and then reacting at 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fibers.
The dried quinoline Schiff base supported by the polyether-ether-ketone fiber, 4.0 g of palladium acetate and 50 mL of ethanol are added into a 100 mL three-neck flask, and the mixture is cooled to room temperatureStirring for reaction for 36 h, washing with ethanol, and reacting at 85 deg.CoAnd C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber supported Schiff base palladium catalyst.
Example 3
A100 mL three-necked flask was charged with 1.0 g of dry chloromethyl-functionalized polyetheretherketone fiber, 25.0 g of 1, 6-hexanediamine and 50 mL of acetonitrile, 110oC, stirring and reacting for 24 hours, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then, at the temperature of 85 ℃, washing with deionized wateroC, drying in a drying box in vacuum to constant weight to obtain the 1, 6-butanediamine functional super-strong fiber;
adding the dried 1, 6-hexamethylene diamine functional super-strong fiber, 20 g of quinoline-8-formaldehyde and 50 mL of ethanol, 80 mL of ethanol into a 100 mL three-neck flaskoC, stirring and reacting for 12 h, cooling to room temperature, taking out the super-strong fibers, washing with ethanol, and then reacting at 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fibers.
Adding the dried quinoline Schiff base loaded by the polyether-ether-ketone fiber, 5.0 g of palladium acetate and 50 mL of ethanol into a 100 mL three-neck flask, stirring at room temperature for reaction for 24 hours, washing with ethanol after the reaction is finished, and then washing at the temperature of 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber supported Schiff base palladium catalyst.
Example 4
A100 mL three-necked flask was charged with 1.0 g of dry chloromethyl-functionalized polyetheretherketone fiber, 25.0 g of 1, 4-butanediamine and 50 mL of acetonitrile, 105 mL of 105oC, stirring and reacting for 20 hours, cooling to room temperature, taking out the super-strong fiber, sequentially washing with 5% sodium carbonate solution and deionized water until the filtrate is neutral, and then, at the temperature of 85 DEG, washing with deionized wateroC, drying in a drying box in vacuum to constant weight to obtain the 1, 4-butanediamine functional super-strong fiber;
adding the dried 1, 4-butanediamine functionalized super-strong fiber, 20 g of quinoline-8-formaldehyde and 50 mL of ethanol, 78oC, stirring and reacting for 16 h, cooling to room temperature, taking out the super-strong fibers, washing with ethanol, and then reacting at 85 DEG CoDrying of CAnd (5) drying in a box in vacuum to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fiber.
Adding the dried quinoline Schiff base loaded by the polyether-ether-ketone fiber, 4.0 g of palladium acetate and 50 mL of ethanol into a 100 mL three-neck flask, stirring at room temperature for reaction for 30 h, washing with ethanol after the reaction is finished, and then washing at the temperature of 85 DEG CoAnd C, drying in a drying box in vacuum to constant weight to obtain the polyether-ether-ketone fiber supported Schiff base palladium catalyst.
0.1 g of the super-strong fiber-supported Schiff base palladium catalyst in example 4 is used for Suzuki coupling reaction of bromobenzene and phenylboronic acid (reaction conditions are that 10.0 mmol of bromobenzene, 10.5 mmol of phenylboronic acid, 15.0 mmol of potassium carbonate, 10 mL of ethanol and 5 mL of water are mixed as a solvent, and the mixture is subjected to reflux reaction for 2.5 h in air atmosphere). After the reaction, the super-strong fiber catalyst is taken out by tweezers and washed clean by ethanol, 1.51 g of biphenyl is obtained by post-treatment of the reaction liquid, and the yield of the product reaches 98%. According to the operation, the catalyst is circularly catalyzed for 10 times, the strength of the super fiber catalyst is hardly changed, and the yield of the product is not obviously reduced (figure 2).
0.1 g of the super-strong fiber supported Schiff base palladium catalyst in example 4 is used for Heck reaction of iodobenzene and acrylic acid (reaction conditions: 10.0 mmol of iodobenzene, 12.5 mmol of methyl acrylate, 20.0 mmol of triethylamine, 15 mL of DMF as solvent, 90 mL of DMF as solvent)oC, reacting for 1.0 h). After the reaction, the super-strong fiber catalyst is taken out by tweezers and washed clean by DMF, and the reaction solution is post-treated to obtain 1.52 g of methyl cinnamate, and the product yield reaches 94%. According to the operation, the catalyst is circularly catalyzed for 10 times, the strength of the super fiber catalyst is hardly changed, and the yield of the product is not obviously reduced (figure 3).
The invention discloses and provides a preparation method of a super-strong fiber-loaded Schiff base palladium catalyst, which can be realized by appropriately changing links such as raw materials, process parameters, structural design and the like by referring to the contents in the text. While the methods and techniques of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and techniques described herein may be made and equivalents employed to practice the techniques of this invention without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (5)
1. A preparation method of a superstrong fiber supported Schiff base palladium catalyst is characterized in that a supported quinoline Schiff base palladium complex functional fiber catalytic material is prepared by taking polyether-ether-ketone superstrong fibers as a matrix in a top-down manner; the preparation method comprises the following specific steps:
1) blending polyether-ether-ketone fibers with the weight increased by 15% through chloromethyl functionalization and diamine in toluene according to the mass ratio of 1: 15-25, stirring at a specific temperature, cooling to room temperature after reaction, taking out super-strong fibers, sequentially washing with alkali liquor and deionized water until filtrate is neutral, and then washing with 80-85% of filtrateoC, drying to constant weight to obtain diamine functionalized polyether-ether-ketone fibers;
2) blending the obtained diamine functionalized polyether ether ketone fiber and quinoline-8-formaldehyde in ethanol according to the mass ratio of 1: 10-20, stirring at a specific temperature, cooling to room temperature after reaction, taking out the super-strong fiber, washing with ethanol, and then 80-85oDrying to constant weight to obtain the quinoline Schiff base loaded by the polyether-ether-ketone fiber;
3) blending the obtained polyether-ether-ketone fiber-loaded Schiff base and palladium acetate in ethanol according to the mass ratio of 1: 2-5, taking out the super-strong fiber and washing the super-strong fiber with ethanol after the reaction at room temperature under the stirring condition, and then 80-85oAnd C, drying to constant weight to obtain the polyether-ether-ketone fiber-loaded quinoline Schiff base type palladium complex catalyst.
2. The method according to claim 1, wherein the diamine in step 1) is 1, 3-propanediamine, 1, 4-butanediamine or 1, 6-hexanediamine.
3. The method according to claim 1, wherein the reaction temperature in step 1) is 105 to 110%oAnd C, the reaction time is 12-24 h.
4. The method of claim 1, wherein the step of preparing the composition comprisesThe reaction temperature in the step 2) is 75-80 DEG CoAnd C, the reaction time is 12-36 h.
5. The preparation method according to claim 1, wherein the reaction time in step 3) is 24-48 h.
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