CN112853751B - Phenanthroline palladium functionalized fiber and preparation method and application thereof - Google Patents

Phenanthroline palladium functionalized fiber and preparation method and application thereof Download PDF

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CN112853751B
CN112853751B CN202110048228.8A CN202110048228A CN112853751B CN 112853751 B CN112853751 B CN 112853751B CN 202110048228 A CN202110048228 A CN 202110048228A CN 112853751 B CN112853751 B CN 112853751B
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phenanthroline
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陶敏莉
肖剑
马宁
张文勤
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Tianjin University
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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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
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    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Abstract

The invention is applicable to the technical field of materials, and provides a phenanthroline palladium functionalized fiber, and a preparation method and application thereof, wherein the phenanthroline palladium functionalized fiber is obtained by loading phenanthroline onto the surface of an acrylic fiber, complexing palladium chloride, and reducing in situ under the action of hydrazine hydrate. The palladium nanoparticles in the phenanthroline palladium functionalized fiber obtained by the invention have good dispersion degree and uniform particle size, the particle diameter is distributed about 3nm, the phenanthroline palladium functionalized fiber can efficiently catalyze Heck reaction under the solvent-free condition, and after the phenanthroline palladium functionalized fiber is repeatedly used for 6 times in the reaction of catalyzing iodobenzene and acrylic acid, the activity of the catalyst is not obviously reduced, and the HPLC yield is only reduced from 96% to 87%.

Description

Phenanthroline palladium functionalized fiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to phenanthroline palladium functionalized fiber and a preparation method and application thereof.
Background
The Heck reaction is an important approach to achieving C-C bond coupling, which provides a new avenue for the synthesis of many drugs, such as montelukast (anti-asthmatics), naproxen (anti-inflammatory agents), eletriptan (anti-migraine agents), and rilpivirine (anti-aids), among others. Organometallic catalysts are reported in the literature as the most commonly used catalysts for catalyzing Heck reactions, such as copper, nickel, cobalt, palladium catalysts, and the like. Of these, palladium catalysis is the most efficient method and is therefore of great interest to researchers.
However, palladium is expensive and difficult to recycle in homogeneous reaction systems; in addition, palladium is used as a heavy metal element, has high toxicity, and is easy to cause a series of environmental problems if being randomly discharged. Based on the starting points of green production and environmental affinity, the preparation of the novel heterogeneous palladium catalyst has important significance. In recent years, palladium catalysts loaded on different carriers are developed successively, and the carriers mainly applied comprise silicon dioxide, graphene oxide, organic polymers and magnetic Fe3O4MOF, carbon nanotubes, and composites, etc., which have good catalytic performance, most of them still have difficulty in achieving the cycleThe ring is used, and most of the toxic solvents are needed.
Therefore, the existing palladium catalyst has the problems that the catalyst cannot be recycled and the toxic solvent cannot be used.
Disclosure of Invention
The embodiment of the invention aims to provide a phenanthroline palladium functionalized fiber, and aims to solve the problems that an existing palladium catalyst cannot be recycled and cannot be used without a toxic solvent.
The embodiment of the invention is realized by taking aluminum trifluoromethanesulfonate as a catalyst, loading phenanthroline on the surface of an acrylic fiber, complexing palladium chloride, and reducing in situ under the action of hydrazine hydrate to obtain the phenanthroline palladium functionalized fiber.
Another object of the embodiments of the present invention is to provide a method for preparing the phenanthroline palladium functionalized fiber, including:
placing acrylic fiber, water and organic amine in a reaction vessel for reflux reaction, and washing and drying to obtain secondary amine functional fiber;
placing the secondary amine functional fiber, aluminum trifluoromethanesulfonate and epoxy-substituted phenanthroline in a reaction container, performing reflux reaction under the action of acetonitrile, and washing and drying to obtain phenanthroline functional fiber;
placing phenanthroline functionalized fiber, palladium chloride, acetone and water in a reaction container for reflux reaction, and washing and drying to obtain palladium chloride functionalized fiber;
and (3) placing the palladium chloride functionalized fiber in a hydrazine hydrate solution for in-situ reduction reaction to obtain the phenanthroline palladium functionalized fiber.
The embodiment of the invention also aims to provide application of the phenanthroline palladium functionalized fiber in a Heck reaction.
The phenanthroline palladium functionalized fiber provided by the embodiment of the invention is prepared by loading phenanthroline on the surface of an acrylic fiber, efficiently complexing palladium chloride and then carrying out in-situ reduction under the action of hydrazine hydrate, wherein the loading method is efficient, palladium nanoparticles in the obtained phenanthroline palladium functionalized fiber are good in dispersion degree and uniform in particle size, and the particle diameter is distributed about 3 nm; the invention can efficiently catalyze the Heck reaction under the condition of no solvent, and can be used for catalyzing the reaction of iodobenzene and acrylic acid to be repeatedly used for 6 times, the activity of the catalyst is not obviously reduced, and the HPLC yield is only reduced from 96% to 87%.
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FIG. 1 is a transmission electron microscope image of a phenanthroline palladium functionalized fiber provided in an embodiment of the present invention;
fig. 2 is a graph of cycle performance test results of the phenanthroline palladium-functionalized fiber provided by the embodiment of the invention for catalyzing the reaction between iodobenzene and acrylic acid Heck.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to solve the problems that the existing palladium catalyst cannot be recycled and toxic solvents cannot be used, the embodiment of the invention provides the phenanthroline palladium functionalized fiber which is prepared by loading phenanthroline to the surface of an acrylic fiber, efficiently complexing palladium chloride and then carrying out in-situ reduction under the action of hydrazine hydrate, wherein the loading method is efficient, palladium nanoparticles in the obtained phenanthroline palladium functionalized fiber are good in dispersion degree and uniform in particle size, and the particle diameter is distributed about 3 nm; the invention can efficiently catalyze the Heck reaction under the condition of no solvent, and can be used for catalyzing the reaction of iodobenzene and acrylic acid to be repeatedly used for 6 times, the activity of the catalyst is not obviously reduced, and the HPLC yield is only reduced from 96% to 87%.
The phenanthroline palladium functionalized fiber provided by the embodiment of the invention is obtained by loading phenanthroline on the surface of an acrylic fiber, complexing palladium chloride and carrying out in-situ reduction under the action of hydrazine hydrate. Because the organic ligand type in the carrier determines the dispersibility and stability of the Pd (0) nano particles and the catalytic activity of the heterogeneous catalyst, the invention stabilizes the palladium nano particles by loading phenanthroline on the surface of the acrylic fiber as the ligand, the palladium nano particles in the obtained phenanthroline palladium functionalized fiber have good dispersion degree and uniform particle size, and the particle diameter is distributed at about 3 nm.
In the embodiment of the invention, the structural general formula of the phenanthroline palladium functionalized fiber is as follows:
Figure BDA0002898237380000041
the preparation method of the phenanthroline palladium functionalized fiber provided by the embodiment of the invention has the following synthetic route:
Figure BDA0002898237380000042
in the embodiment of the invention, the preparation method of the phenanthroline palladium functionalized fiber comprises the following steps:
step S1: placing the acrylic fiber, water and organic amine into a reaction vessel for reflux reaction, and washing and drying to obtain the secondary amine functional fiber.
In the embodiment of the invention, the mass-volume ratio of the acrylic fiber to the organic amine is 1: (60-70).
In the embodiment of the present invention, the volume ratio of the water to the organic amine is 3: (6-7).
In the embodiment of the present invention, the organic amine may be one or more of N, N '-dimethyl-propane-1, 3-diamine, N' -dimethylethylenediamine, ethylenediamine, propylenediamine, N '-dimethyl-butane-1, 3-diamine, butylenediamine, N' -dimethyl-pentane-1, 3-diamine, and pentylenediamine.
In the embodiment of the present invention, the step S1 may specifically be: adding 1g of dried acrylic fiber and 60-70mL of organic amine into a single-diameter flask, adding deionized water, carrying out reflux reaction for 6-7h, washing with warm water at 60 ℃, and drying in an oven at 60 ℃ for 12h to obtain the secondary amine functionalized fiber.
Step S2: and (3) placing the secondary amine functional fiber, aluminum trifluoromethanesulfonate and epoxy-substituted phenanthroline in a reaction container, performing reflux reaction under the action of acetonitrile, and washing and drying to obtain the phenanthroline functional fiber.
In the embodiment of the present invention, the epoxy-substituted phenanthroline may be one of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 3-epoxy-1, 10-phenanthroline, and 5-epoxy-1, 10-phenanthroline.
In a preferred embodiment of the present invention, the step S2 includes:
and (2) placing 1g of the secondary amine functionalized fiber, 1-3 mol% of aluminum trifluoromethanesulfonate, 2-4g of epoxy-substituted phenanthroline and 30-40mL of acetonitrile in a reaction container for reflux reaction for 20-48h, and washing and drying to obtain the phenanthroline functionalized fiber.
In the embodiment of the present invention, the step S2 may specifically be: adding 1g of the dried secondary amine functionalized fiber, 1-3 mol% of aluminum trifluoromethanesulfonate and 2-4g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline into a single-diameter flask, adding 30-40mL of acetonitrile, carrying out reflux reaction for 20-48h, washing with ethanol, and drying in an oven at 60 ℃ for 12h to obtain the phenanthroline functionalized fiber.
It is worth noting that in the process of supporting phenanthroline, the functional group grafting is achieved through the ring-opening reaction of amine groups in secondary amine functional fibers and epoxy groups in grafting molecules, but due to low reaction activity, the functional group grafting rate is low.
Step S3: and (3) placing the phenanthroline functionalized fiber, palladium chloride, acetone and water in a reaction container for reflux reaction, and washing and drying to obtain the palladium chloride functionalized fiber.
In a preferred embodiment of the present invention, the step S3 includes:
1g of phenanthroline functionalized fiber, 0.1-0.8g of palladium chloride, 15mL of acetone and water are placed in a reaction container for reflux reaction for 1-6h, and washing and drying treatment are carried out to obtain the palladium chloride functionalized fiber.
In the embodiment of the present invention, the volume ratio of acetone to water is 3: 1.
in the embodiment of the present invention, the step S3 may specifically be: and (2) adding 1g of the dried phenanthroline functionalized fiber, 0.1-0.8g of palladium chloride and 15mL of acetone into a single-diameter flask, then adding deionized water, carrying out reflux reaction for 1-6h, taking out the fiber, washing the fiber by using a Soxhlet extractor filled with acetonitrile, and then drying the fiber in an oven at 60 ℃ for 12h to obtain the palladium chloride functionalized fiber.
Step S4: and (3) placing the palladium chloride functionalized fiber in a hydrazine hydrate solution for in-situ reduction reaction to obtain the phenanthroline palladium functionalized fiber.
In the embodiment of the invention, the hydrazine hydrate is used in an amount of 5-10 equivalents of the palladium content in the palladium chloride functionalized fiber, wherein the palladium content in the palladium chloride functionalized fiber can be tested by ICP-AES.
In the embodiment of the present invention, the step S4 may specifically be: and (2) placing the palladium chloride functionalized fiber in a hydrazine hydrate solution, stirring at room temperature for 10-30min, washing the fiber with normal-temperature water after the reaction is finished, and then placing the fiber in a 60 ℃ drying oven for drying for 12h to obtain the phenanthroline stable palladium nanoparticle functionalized fiber.
In the embodiment of the present invention, the hydrazine hydrate solution can be prepared by adding 5 equivalents of commercially available 80% mass fraction hydrazine hydrate into 5-20mL of water and mixing.
The embodiment of the invention provides application of the phenanthroline palladium functionalized fiber in a Heck reaction.
In an embodiment of the present invention, the step of the Heck reaction may be: adding 1mmol of iodo aromatic hydrocarbon, 1.5mmol of olefin, 1.5mmol of alkali and 0.1 mol% of the phenanthroline palladium functionalized fiber into a thick-wall pressure-resistant pipe, and reacting for 3 hours in an oil bath at the temperature of 110 ℃; after the reaction was completed, the yield was calculated by HPLC or recrystallization, respectively.
In embodiments of the invention, the organic base mayIs one or more of sodium hydroxide, potassium carbonate, cesium carbonate, triethylamine, tri-n-butylamine or triethanolamine, and HPLC conditions can be ultraviolet wavelength of 254nm and flow rate of 0.8mL min-1The mobile phase may be methanol: water 3: 1.
Examples of certain embodiments of the invention are given below, which are not intended to limit the scope of the invention.
In addition, it should be noted that the numerical values given in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be understood as a divisor rather than an absolutely exact numerical value due to measurement errors and experimental operational problems that cannot be avoided. For example, due to errors in the weighing apparatus, it should be understood that the weight values of the raw materials for preparing the phenanthroline palladium-functionalized fiber according to the examples may have errors of ± 2% or ± 1%.
Example 1
Adding 1g of dried polyacrylonitrile fiber, 70mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 250mL single-diameter flask, stirring and refluxing for 6h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 2g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 1 mol% of aluminum trifluoromethanesulfonate and 30mL of acetonitrile into a 50mL single-diameter flask, stirring and refluxing for 24h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.4g of palladium chloride, 15mL of acetone and 5mL of water into a 50mL single-diameter flask, stirring and refluxing for 6h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 5eq hydrazine hydrate and 20mL of water into a 50mL single-neck flask, stirring the system at room temperature for 10min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Example 2
Adding 1g of dried polyacrylonitrile fiber, 60mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 250mL single-diameter flask, stirring and refluxing for 7h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
1g of dried secondary amine fiber, 4g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 2 mol% of aluminum trifluoromethanesulfonate and 40mL of acetonitrile are added into a 100mL single-diameter flask, the mixture is stirred and refluxed for 20h, the fiber is taken out after the reaction is finished, the fiber is repeatedly washed by ethanol until the washing liquid does not show fluorescence any more through a TLC method, and the mixture is dried in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.8g of palladium chloride, 15mL of acetone and 5mL of water into a 50mL single-diameter flask, stirring and refluxing for 6h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 10eq hydrazine hydrate and 5mL of water into a 25mL single-neck flask, stirring the system at room temperature for 10min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Example 3
Adding 1g of dried polyacrylonitrile fiber, 60mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 250mL single-diameter flask, stirring and refluxing for 6.5h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 3g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 3 mol% of aluminum trifluoromethanesulfonate and 30mL of acetonitrile into a 50mL single-diameter flask, stirring and refluxing for 24h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.3g of palladium chloride, 15mL of acetone and 5mL of water into a 50mL single-diameter flask, stirring and refluxing for 3h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 8eq hydrazine hydrate and 10mL of water into a 25mL single-neck flask, stirring the system at room temperature for 10min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Example 4
Adding 1g of dried polyacrylonitrile fiber, 70mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 250mL single-diameter flask, stirring and refluxing for 6.5h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 2g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 2 mol% of aluminum trifluoromethanesulfonate and 40mL of acetonitrile into a 100mL single-diameter flask, stirring and refluxing for 36h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.2g of palladium chloride, 15mL of acetone and 5mL of water into a 50mL single-diameter flask, stirring and refluxing for 3h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 10eq hydrazine hydrate and 5mL of water into a 25mL single-neck flask, stirring the system at room temperature for 20min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Example 5
Adding 1g of dried polyacrylonitrile fiber, 70mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 250mL single-diameter flask, stirring and refluxing for 6h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 2g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 1 mol% of aluminum trifluoromethanesulfonate and 30mL of acetonitrile into a 100mL single-diameter flask, stirring and refluxing for 48h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.1g of palladium chloride, 15mL of acetone and 5mL of water into a 100mL single-diameter flask, stirring and refluxing for 1h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 5eq hydrazine hydrate and 10mL of water into a 25mL single-neck flask, stirring the system at room temperature for 30min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Comparative example 1
Adding 1g of dried polyacrylonitrile fiber, 50mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 100mL single-diameter flask, stirring and refluxing for 5h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 2g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 1 mol% of aluminum trifluoromethanesulfonate and 40mL of acetonitrile into a 100mL single-diameter flask, stirring and refluxing for 12h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.8g of palladium chloride, 20mL of acetone and 5mL of water into a 50mL single-diameter flask, stirring and refluxing for 4h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 5eq hydrazine hydrate and 5mL of water into a 25mL single-neck flask, stirring the system at room temperature for 10min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Comparative example 2
Adding 1g of dried polyacrylonitrile fiber, 5mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 50mL single-diameter flask, stirring and refluxing for 12h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 3g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 0.1 mol% of aluminum trifluoromethanesulfonate and 10mL of acetonitrile into a 25mL single-diameter flask, stirring and refluxing for 48h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through TLC (thin layer chromatography), and drying in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.1g of palladium chloride, 15mL of acetone and 5mL of water into a 25mL single-diameter flask, stirring and refluxing for 4h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 10eq hydrazine hydrate and 20mL of water into a 50mL single-neck flask, stirring the system at room temperature for 2min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
Comparative example 3
Adding 1g of dried polyacrylonitrile fiber, 5mL of N, N' -propane-1, 3-diamine and 30mL of deionized water into a 50mL single-diameter flask, stirring and refluxing for 12h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with warm water at 60 ℃ until the water solution is neutral after washing, and drying the fiber in an oven at 60 ℃ overnight to obtain the light yellow secondary amine functionalized fiber.
Adding 1g of dried secondary amine fiber, 4g of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 10 mol% of aluminum trifluoromethanesulfonate and 40mL of acetonitrile into a 100mL single-diameter flask, stirring and refluxing for 2h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid does not show fluorescence any more through a TLC method, and drying the fiber in an oven at 60 ℃ overnight to obtain the yellow phenanthroline functionalized fiber.
Adding 1g of dried secondary amine fiber, 0.2g of palladium chloride, 50mL of acetone and 10mL of water into a 100mL single-diameter flask, stirring and refluxing for 2h, taking out the fiber after the reaction is finished, washing the fiber for 3h under the reflux of acetonitrile by using a Soxhlet extractor, and drying the fiber in an oven at 60 ℃ overnight to obtain the brown phenanthroline complex palladium chloride functionalized fiber.
Adding 1g of phenanthroline complexed palladium chloride functionalized fiber, 5eq hydrazine hydrate and 5mL of water into a 25mL single-neck flask, stirring the system at room temperature for 10min, taking out the fiber after the reaction is finished, washing the fiber with 1L of deionized water at room temperature, and drying the fiber in an oven at 60 ℃ overnight to obtain the black phenanthroline palladium functionalized fiber.
By observing the morphology of the phenanthroline palladium functionalized fiber prepared in the embodiment 1 of the invention, as shown in a transmission electron microscope image of the phenanthroline palladium functionalized fiber shown in fig. 1, it can be known that the dispersion degree of palladium nanoparticles in the phenanthroline palladium functionalized fiber is good, the particle size is uniform, and the particle diameter is distributed at about 3 nm.
Further, an appropriate amount of the phenanthroline palladium functionalized fiber prepared in the invention in example 1 is added into a thick-walled pressure-resistant pipe which is pre-filled with 1mmol of iodobenzene, an appropriate amount of acrylic acid and 1.5 equivalents of tri-n-butylamine to perform reaction activity tests under different conditions, after the reaction is finished, samples are respectively taken for HPLC detection, as shown in the following table 1,
TABLE 1
Figure BDA0002898237380000121
Figure BDA0002898237380000131
As can be seen from table 1, the catalytic activity is significantly improved with the increase of the usage amount of the phenanthroline palladium functionalized fiber catalyst, but the catalytic activity is not significantly improved when the usage amount is increased to a certain value; the reduction of the content of acrylic acid is not beneficial to the high-efficiency conversion of iodobenzene; in addition, too short a reaction time also leads to a decrease in reaction yield; that is, the reaction activity is influenced by the amount of catalyst, the reaction time and the amount of substrate, the optimal conditions determined by screening are that the amount of fiber is 0.1 mol%, 1.5eq of acrylic acid, 1.5eq of tri-n-butylamine, 1mmol of iodobenzene and oil bath are controlled at 110 ℃ for reaction for 3 hours, and the yield and the TON value under the optimal conditions are 97% and 970 respectively.
The phenanthroline palladium functionalized fiber prepared in the embodiments 1-5 and the comparative examples 1-3 is added into a thick-wall pressure-resistant pipe which is pre-filled with 1mmol of iodobenzene, 1.5eq of acrylic acid and 1.5eq of tri-n-butylamine according to the dosage of 0.1 mol%, the reaction is carried out for 3 hours under the condition that the temperature of the oil bath is controlled to be 110 ℃, and samples are respectively taken for HPLC detection after the reaction is finished. The results are shown in Table 2.
TABLE 2
Figure BDA0002898237380000132
Figure BDA0002898237380000141
As can be seen from Table 2, the phenanthroline palladium functionalized fibers prepared in the embodiments 1-5 of the invention can efficiently catalyze the Heck reaction in the absence of solvent. Meanwhile, according to examples 1 to 5 and comparative examples 1 to 3 of the present invention, it can be seen that the catalytic activity of the phenanthroline palladium functionalized fiber prepared in comparative examples 1 to 3 is not as good as that of examples 1 to 5 of the present invention, and the main reason is that changing the fiber preparation conditions will affect the fiber weight gain rate in each step, so that the phenanthroline ligand cannot be efficiently loaded on the fiber, and the grafting rate of palladium is further affected, thereby affecting the reaction activity.
Further, the phenanthroline palladium functionalized fiber prepared in the embodiment 1 of the invention is repeatedly used, and the fiber catalyst is found to have good recycling performance, after a single catalytic process is finished, the fiber catalyst can be separated by a filtering method, and can be applied to the next reaction after being simply cleaned, as shown in fig. 2, 0.1 mol% of the fiber catalyst can be repeatedly used for 6 times, the activity of the catalyst is not obviously reduced, the HPLC yield is only reduced from 96% to 87%, and the good recycling performance is proved.
To sum up, the phenanthroline palladium functionalized fiber provided by the embodiment of the invention is prepared by loading phenanthroline on the surface of an acrylic fiber, complexing palladium chloride efficiently and then reducing in situ under the action of hydrazine hydrate, the loading method is efficient, the palladium nanoparticles in the obtained phenanthroline palladium functionalized fiber have good dispersion degree and uniform particle size, and the particle diameter is distributed about 3 nm; the invention can efficiently catalyze the Heck reaction under the condition of no solvent, and can be used for catalyzing the reaction of iodobenzene and acrylic acid to be repeatedly used for 6 times, the activity of the catalyst is not obviously reduced, and the HPLC yield is only reduced from 96% to 87%.
Further, in the prior research and development process, relevant experimental researches are carried out on the influence of various process parameters related in the phenanthroline loading process on the loading condition, and the research and development process is specifically shown in the following comparative experiment groups 1-4.
The specific experimental process is as follows: a50 mL single diameter flask was charged with 1g of dry secondary amine functionalized fiber, 2g of 5, 6-epoxy-5, 6-dihydro- [1, 10%]Phenanthroline, catalysts of different contents (0.5-3 mol%) (zinc triflateAluminum trifluoromethanesulfonate (CTF), 30mL of organic solvent (acetonitrile, ethylene glycol, absolute ethyl alcohol and 50% ethanol solution), stirring and refluxing for 12-48h, taking out the fiber after the reaction is finished, repeatedly washing the fiber with ethanol until the washing liquid is monitored by a TLC method and does not show fluorescence any more, drying the fiber in an oven at 60 ℃ overnight to obtain yellow phenanthroline functionalized fiber, and calculating the fiber weight gain (the mass of the fiber before grafting is m)1The mass of the grafted fiber is m2The fiber weight gain (%) (m)2-m1)/m1×100)。
Comparative experimental group 1: only the kind of the organic solvent used in the step of preparing the phenanthroline functionalized fiber was adjusted, and the obtained fiber weight gain ratio was as shown in table 3.
TABLE 3
Kind of organic solvent Type/amount of catalyst Reflux time (h) Fiber weight gain (%)
Acetonitrile Aluminum triflate/1 mol% 24 23.1
Ethylene glycol Aluminum triflate/1 mol% 24 2.5
Anhydrous ethanol Aluminum triflate/1 mol% 24 1.8
Ethanol solution (50%) Aluminum triflate/1 mol% 24 2.1
It can be seen from table 3 that when the organic solvent is acetonitrile, the fiber weight gain is significantly higher than that of other ethanol or ethylene glycol solvents, mainly because the fiber has different swellability in different solvents and the grafted molecules have different solubility in different solvents, so that the organic solvent has an important effect on the fiber weight gain.
Comparative experiment group 2: only the kind of the catalyst used in the step of preparing the phenanthroline functionalized fiber was adjusted, and the obtained fiber weight gain ratio was as shown in table 4.
TABLE 4
Type/amount of catalyst Kind of organic solvent Reflux time (h) Fiber weight gain (%)
Zinc trifluoromethanesulfonate 1 mol% Acetonitrile 24 4.9
Aluminum triflate/1 mol% Acetonitrile 24 23.1
It can be seen from table 4 that when the catalyst type is selected to be aluminum trifluoromethanesulfonate, the obtained fiber weight gain rate is much higher than that when the catalyst type is zinc trifluoromethanesulfonate, mainly because different catalysts have different activities for catalyzing ring opening reactions of primary amines and epoxy groups of grafted molecules in the fibers, thereby causing some differences in fiber weight gain rate.
Comparative experiment group 3: only the amount of catalyst used in the step of preparing phenanthroline functionalized fibers was adjusted, and the fiber weight gain was as shown in table 5.
TABLE 5
Type/amount of catalyst Kind of organic solvent Reflux time (h) Fiber weight gain (%)
Aluminum trifluoromethanesulfonate 0.5 mol% Acetonitrile 24 15.2
Aluminum triflate/1 mol% Acetonitrile 24 23.1
Aluminum triflate/2 mol% Acetonitrile 24 20.4
Aluminum triflate/3 mol% Acetonitrile 24 22.9
Comparative experiment group 4: only the reflux time in the step of preparing phenanthroline functionalized fibers was adjusted, and the obtained fiber weight gain was as shown in table 6.
TABLE 6
Reflux time (h) Type/amount of catalyst Kind of organic solvent Fiber weight gain (%)
12 Aluminum triflate/1 mol% Acetonitrile 11.2
24 Aluminum triflate/1 mol% Acetonitrile 23.1
48 Aluminum triflate/1 mol% Acetonitrile 24.8
From tables 5-6, it can be seen that the catalyst amount and the reaction time affect the reaction process of the fiber modification process, and the increase of the catalyst amount or the extension of the reaction time in a certain range is beneficial to the increase of the fiber weight gain rate, but the fiber grafting rate is not increased any more after the optimum value is exceeded.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A preparation method of phenanthroline palladium functionalized fiber is characterized by comprising the following steps:
placing acrylic fiber, water and organic amine in a reaction vessel for reflux reaction, and washing and drying to obtain secondary amine functional fiber; the mass volume ratio of the acrylic fiber to the organic amine is 1: (60-70); the volume ratio of the organic amine to the water is (6-7): 3;
placing the secondary amine functional fiber, aluminum trifluoromethanesulfonate and epoxy-substituted phenanthroline in a reaction container, performing reflux reaction under the action of acetonitrile, and washing and drying to obtain phenanthroline functional fiber;
placing phenanthroline functionalized fiber, palladium chloride, acetone and water in a reaction container for reflux reaction, and washing and drying to obtain palladium chloride functionalized fiber;
and (3) placing the palladium chloride functionalized fiber in a hydrazine hydrate solution for in-situ reduction reaction to obtain the phenanthroline palladium functionalized fiber.
2. The method for preparing phenanthroline palladium functionalized fiber according to claim 1, wherein the step of placing the secondary amine functionalized fiber, the aluminum trifluoromethanesulfonate and the epoxy-substituted phenanthroline in a reaction vessel, performing reflux reaction under the action of acetonitrile, and performing washing and drying treatment to obtain the phenanthroline functionalized fiber comprises the following steps:
and (2) placing 1g of the secondary amine functionalized fiber, 1-3 mol% of aluminum trifluoromethanesulfonate, 2-4g of epoxy-substituted phenanthroline and 30-40mL of acetonitrile in a reaction container for reflux reaction for 20-48h, and washing and drying to obtain the phenanthroline functionalized fiber.
3. The method for preparing phenanthroline palladium functionalized fiber according to claim 1, wherein the step of placing phenanthroline functionalized fiber, palladium chloride, acetone and water in a reaction vessel for reflux reaction, washing and drying to obtain the palladium chloride functionalized fiber comprises:
1g of phenanthroline functionalized fiber, 0.1-0.8g of palladium chloride, 15mL of acetone and water are placed in a reaction container for reflux reaction for 1-6h, and washing and drying treatment are carried out to obtain the palladium chloride functionalized fiber.
4. The method for preparing phenanthroline palladium-functionalized fiber according to claim 1 or 3, wherein the volume ratio of acetone to water is 3: 1.
5. the method for preparing phenanthroline palladium functionalized fiber according to claim 1, wherein the amount of hydrazine hydrate is 5-10 equivalents of palladium content in the palladium chloride functionalized fiber.
6. The method for preparing phenanthroline palladium-functionalized fiber according to claim 1, wherein the organic amine is one or more of N, N '-dimethyl-propane-1, 3-diamine, N' -dimethylethylenediamine, ethylenediamine, propylenediamine, N '-dimethyl-butane-1, 3-diamine, butylenediamine, N' -dimethyl-pentane-1, 3-diamine, and pentylenediamine; the epoxy-substituted phenanthroline is one of 5, 6-epoxy-5, 6-dihydro- [1,10] phenanthroline, 3-epoxy-1, 10-phenanthroline and 5-epoxy-1, 10-phenanthroline.
7. A phenanthroline palladium functionalized fiber, characterized in that the phenanthroline palladium functionalized fiber is prepared by the preparation method of the phenanthroline palladium functionalized fiber according to any one of claims 1 to 6.
8. Use of the phenanthroline palladium-functionalized fiber according to claim 7 in a Heck reaction.
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