CN103433071B - IPN supported palladium nanocatalyst and Synthesis and applications thereof - Google Patents
IPN supported palladium nanocatalyst and Synthesis and applications thereof Download PDFInfo
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Abstract
The invention discloses a kind of interpenetrating polymer network (IPN) supported palladium nanocatalyst, preparation and application thereof, the catalytic activity of this IPN supported palladium nanocatalyst is high, and the product yield obtained when being applied to catalysis Suzuki coupling reaction is high; Simultaneously because the most of solvent in Suzuki coupling reaction is water, thus be conducive to protection of the environment; In addition, palladium exists with the form of nano particle in IPN supported palladium nanocatalyst, thus can disperse uniformly, further enhances catalytic performance; Moreover, the carrier of supported palladium is interpenetrating polymer network, the high molecular hydrophily forming this interpenetrating polymer network is strong, thus more applicablely to react in aqueous, hydrogel is formed in water, and constraint palladium nano metal is effective, thus extend the service life of IPN supported palladium nanocatalyst; When repeatedly using, before catalyst complete deactivation, the cost performance that IPN supported palladium nanocatalyst is applied to Suzuki coupling reaction is good, thus is more suitable for industrial application.
Description
Technical field
The present invention relates to a kind of catalyst and Synthesis and applications thereof, particularly relate to a kind of IPN supported palladium nanocatalyst and Synthesis and applications thereof.
Background technology
In transition metal-catalyzed aryl coupling reaction, at the Pd (PPh of the exploitations in 1981 such as Suzuki
3)
4under catalysis, aryl boric acid and bromine or iodine are called as Suzuki aryl coupling reaction for the cross-coupling reaction of aromatic hydrocarbons.This reaction has reaction condition gentleness, tolerable various active functional group, little by steric interference, productive rate is high and aryl boric acid economy is easy to get and become blanket C-C key coupling method to the superiority such as moisture is insensitive, it is widely used in the fields such as pharmacy, electronics industry and advanced material, complicated organic molecule can be synthesized, so favor that is extremely organic and Polymer Synthesizing worker.And for the choosing of catalyst of Suzuki coupling reaction, be the challenging field of most, the catalyst of Suzuki coupling reaction experienced by the evolution from palladium salt homogeneous catalyst to load type palladium salt heterogeneous catalysis.
Chinese patent (application number: 201210264089.3) disclose a kind of palladium catalyst of catalysis Suzuki coupling reaction, synthetic method, application and ligand, its chemical structural formula is Pd
6(L
11)
8(NO
3)
12.Synthetic method step is as follows: A, with the SOCl of 2,4,6-triethyl group-1,3,5-trimesic acid and backflow volume
2, heating reflux reaction is clarified to system; B, in reaction system, add 5-(4-pyridine radicals) tetrazolium, back flow reaction 2 ~ 3 hours in anhydrous pyridine, separation and purification obtains ligand L; C, ligand L and palladium nitrate heat 60 ~ 70 DEG C of back flow reaction 2 ~ 3 hours in DMSO, and separation and purification obtains catalyst P d
6(L
11)
8(NO
3)
12.The application of above-mentioned palladium catalyst in catalysis Suzuki coupling reaction, also provides a kind of ligand.
The palladium catalyst that this invention provides does not need oxygen free operation, avoids the larger reagent of the toxicity such as toluene, and reaction temperature and time also reduce greatly, and catalyst activity is higher.This invention is expected to be widely used in the cleaner production of the Medicine small molecule and ligand that need employing Suzuki coupling technology.But the palladium catalyst that this invention provides is owing to being a kind of palladium salt homogeneous catalyst, palladium salt homogeneous catalyst not easily separation and recovery, palladium runs off serious, not only use cost is high, and also unfavorable to environment, the palladium black of generation can pollute product, and therefore application is in the industry restricted.Especially in daily chemical products and pharmaceutical synthesis, very strict to the content requirement of kish in product, further application is in the industry restricted.
In order to overcome the shortcoming of homogeneous catalytic reaction, exploitation out-phase palladium catalyst becomes the focus of this area research work, has obtained in recent years and has developed rapidly.Wherein, macromolecular material metal supported catalyst becomes the focus of people's research owing to having higher catalytic activity and stereoselectivity, preferably stability and reusability.And the post processing of macromolecule loading heterogeneous catalysis is fairly simple: after completion of the reaction can easily by solid-liquid separating method by other Component seperation in polymer catalyst and reaction system, regenerate and reuse, can reduce costs and reduce environmental pollution.
Summary of the invention
For above-mentioned Problems existing, the invention provides a kind of interpenetrating polymer network (IPN) supported palladium nanocatalyst and Synthesis and applications thereof, to overcome in prior art, be applied to the palladium salt homogeneous catalyst not easily separation and recovery of Suzuki coupling reaction, Metal Palladium runs off serious, not only use cost is high, and to the disadvantageous problem of environment, thus it is higher to obtain a kind of catalytic activity, the product yield that catalysis Suzuki coupling reaction obtains is higher, repeatedly can repeat to reclaim and use, be conducive to the IPN supported palladium nanocatalyst of protection of the environment, and service life is longer.
To achieve these goals, the technical scheme that the present invention takes is:
A kind of IPN supported palladium nanocatalyst, wherein, active component is palladium, and carrier is interpenetrating polymer network, and described palladium is nanostructured;
Wherein, the relative amount of described palladium in described IPN supported palladium nanocatalyst is 0.1 × 10
-6mol/g ~ 6 × 10
-6mol/g.
Above-mentioned IPN supported palladium nanocatalyst, wherein, described carrier is that cross-linking polyvinyl alcohol and crosslinked PVP carry out the interpenetrating polymer network after being cross-linked;
Wherein, described cross-linking polyvinyl alcohol is the network of self of polyvinyl alcohol crosslinked rear formation; Described crosslinked PVP is that N-vinylpyrrolidone is polymerized and is cross-linked the rear network of self formed.
The preparation method of above-mentioned IPN supported palladium nanocatalyst, wherein, described preparation method comprises the following steps:
1) polyvinyl alcohol, absolute ethyl alcohol, distilled water, palladium bichloride-hydrogen chloride solution, sulfuric acid solution, acetic acid solution and glutaraldehyde solution are provided;
2) the described distilled water of the described absolute ethyl alcohol of 30ml and 25ml is mixed to form mixed solution;
3) by the degree of polymerization of 5g be 1750 described polyvinyl alcohol join in described mixed solution, after carrying out condensing reflux, carry out 95 DEG C of oil baths heating 2h and obtain polyvinyl alcohol colourless transparent solution;
4) the described palladium bichloride-hydrogen chloride solution of 2ml, 2.82mmol/L is joined in described polyvinyl alcohol colourless transparent solution, under 95 DEG C of oil baths, carry out condensing reflux 5h obtain dark solution;
5) after described dark solution being cooled, by 0.2ml, 10% described sulfuric acid solution, 0.6ml,
The described acetic acid solution of 10% and 1.0ml, 25% described glutaraldehyde solution join in described dark solution,
Obtain polyvinyl alcohol-palladium complex solution;
6) N-vinylpyrrolidone, N, N are provided '-methylene-bisacrylamide, potassium peroxydisulfate and distilled water;
7) by the described N-vinylpyrrolidone of 6.14g, the described N of 0.31g, the described potassium peroxydisulfate of N '-methylene-bisacrylamide, 0.15g to join in the described distilled water of 20ml and stirs, make described N-vinylpyrrolidone, described N, N '-methylene-bisacrylamide, described potassium peroxydisulfate are dissolved in described distilled water, obtain N-vinylpyrrolidone solution;
8) by after described polyvinyl alcohol-palladium complex solution and the mixing of described N-vinylpyrrolidone solution, carry out stirring 30min, then in baking oven, carry out heating 3h under the condition of 70 DEG C, obtain black transparent solid gel;
9) outwell after adding black transparent solid gel 5h described in distilled water immersion, and repeat 2 ~ 3 times;
10) after described black transparent solid gel being dried under the condition of 60 DEG C, pulverize, to obtain described IPN supported palladium nanocatalyst.
The application of above-mentioned IPN supported palladium nanocatalyst, wherein, described catalyst is used for halogen for the Suzuki coupling reaction between benzene and phenyl boric acid.
Above-mentioned application, wherein, comprises the following steps:
1) be 2:3:4:2.5 × 10 for benzene, phenyl boric acid, potash, TBAB and IPN supported palladium nanocatalyst according to mol ratio by halogen
-3: 0.25 × 10
-3mixing, and join in the mixed solvent of 1ml dimethylacetylamide and 20ml distilled water;
2) after being heated to 100 DEG C, backflow 4h;
3) after being filtered by described IPN supported palladium nanocatalyst, in filtrate, add distilled water, produce white precipitate;
4) after centrifugal, filtration, separation, washing, dry 6h in vacuum drying chamber, thus complete described halogen for the Suzuki coupling reaction between benzene and described phenyl boric acid.
Above-mentioned application, wherein, described halogen is iodobenzene or bromobenzene for benzene.
Above-mentioned application, wherein, described IPN supported palladium nanocatalyst first Application is in described halogen for the Suzuki coupling reaction between benzene and phenyl boric acid, and the yield of its product biphenyl is 90%.
Above-mentioned application, wherein, in step 3): after being filtered by described IPN supported palladium nanocatalyst, fully wash described IPN supported palladium nanocatalyst 3 times, then carry out drying, to reuse with water and ethanol.
Above-mentioned application, wherein, after described IPN supported palladium nanocatalyst circulation uses 6 times continuously, be applied to described halogen for the 7th time for the Suzuki coupling reaction between benzene and phenyl boric acid, the yield of product is 77%.
Technique scheme tool has the following advantages or beneficial effect:
The product yield that the catalytic activity of IPN supported palladium nanocatalyst provided by the invention is higher, catalysis Suzuki coupling reaction obtains is high; This IPN supported palladium nanocatalyst repeatedly can repeat to reclaim and use simultaneously, and due to the most of solvent in Suzuki coupling reaction be water, thus be conducive to protection of the environment; In addition, palladium exists with the form of nano particle in IPN supported palladium nanocatalyst, thus can disperse more uniformly, also just further enhances catalytic performance; Moreover, the carrier of supported palladium is interpenetrating polymer network, the high molecular hydrophily forming this interpenetrating polymer network is strong, thus more applicablely to react in aqueous, hydrogel is formed in water, and constraint palladium nano metal is effective, thus extend the service life of IPN supported palladium nanocatalyst.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that IPN supported palladium nanocatalyst provided by the invention is applied to Suzuki coupling reaction;
Fig. 2 is temperature 90 DEG C, and under the condition of cosolvent acetonitrile/water=3/1, in the Suzuki coupling reaction between iodobenzene and phenyl boric acid, the fluorescence intensity of biphenyl is along with time variations spectrogram;
Fig. 3 is under different temperatures T, and product biphenyl is at the fluorescence peak area schematic diagram over time of 290nm-375nm;
Fig. 4 is the graph of a relation of logarithm lnk and the 1/T of initial rate constant;
Fig. 5 is the graph of a relation of ln (k/T) and 1/T;
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but not as limiting to the invention.
Embodiment:
The active component of the IPN supported palladium nanocatalyst that the embodiment of the present invention provides is palladium, and carrier is interpenetrating polymer network, and palladium is nanostructured; Meanwhile, the relative amount of palladium in IPN supported palladium nanocatalyst is 0.1 × 10
-6mol/g ~ 6 × 10
-6mol/g, as 0.1 × 10
-6mol/g, 0.3 × 10
-6mol/g, 0.7 × 10
-6mol/g, 1 × 10
-6mol/g, 2.5 × 10
-6mol/g, 3.5 × 10
-6mol/g, 4.9 × 10
-6mol/g, 5 × 10
-6mol/g etc.
Wherein, carrier is that cross-linking polyvinyl alcohol and crosslinked PVP carry out the interpenetrating polymer network after being cross-linked, this cross-linking polyvinyl alcohol is the network of self of polyvinyl alcohol crosslinked rear formation, and this crosslinked PVP to be N-vinylpyrrolidone be polymerized and the network of self formed after being cross-linked.
The embodiment of the present invention also provides a kind of preparation method of IPN supported palladium nanocatalyst, comprise three large steps: the preparation of 1) polyvinyl alcohol-palladium complex solution: by the 5g degree of polymerization be 1750 polyvinyl alcohol join in the round-bottomed flask with 30ml absolute ethyl alcohol and 25ml distilled water mixed solution, carry out condensing reflux; Then under the temperature conditions of 95 DEG C, carry out oil bath, heat 2 hours, just can obtain polyvinyl alcohol colourless transparent solution; Again by the PdCl of good for configured in advance 2.0ml, 2.82mmol/L
2-HCl solution joins in above-mentioned polyvinyl alcohol colourless transparent solution, continues to carry out oil bath at the temperature of 95 DEG C, then condensing reflux 5 hours, thus obtains dark solution; Cool again, in dark solution, add 10% sulfuric acid solution 0.2ml, 10% acetic acid solution 0.6ml, 25% glutaraldehyde solution 1.0ml, thus prepare polyvinyl alcohol-palladium complex solution.
2) preparation of N-vinylpyrrolidone solution: by the N-vinylpyrrolidone of 6.14g, the N of 0.31g, the potassium peroxydisulfate of N '-methylene-bisacrylamide and 0.15g joins in 20ml distilled water solvent, carrying out stirring makes it dissolve, thus prepares N-vinylpyrrolidone solution.
3) rapidly above-mentioned polyvinyl alcohol-palladium complex solution of preparing and N-vinylpyrrolidone solution are mixed in beaker, stir and make it fully to mix half an hour, heating 3 hours in the baking oven putting it into 70 DEG C after mixing, just black transparent solid gel can be obtained, then add distilled water immersion and pour out distilled water again after 5 hours, repeat this soaking step 2 ~ 3 times, finally carry out drying, pulverizing under the temperature conditions of 60 DEG C, thus obtain IPN supported palladium nanocatalyst (representing with PdIPN (PVA-PVP)).
Wherein, above-mentioned PdCl is changed
2-HCl(palladium bichloride-hydrogen chloride) solution volume used or concentration, just can regulate Pd(palladium) relative amount in IPN supported palladium nanocatalyst; And change the consumption of N-vinylpyrrolidone, just can regulate IPN(carrier: interpenetrating polymer network) in PVA(polyvinyl alcohol) and PVP(polyvinylpyrrolidone) between ratio.
In addition, the embodiment of the present invention also provides a kind of and IPN supported palladium nanocatalyst is applied to halogen for the Suzuki coupling reaction between benzene and phenyl boric acid, and Fig. 1 is the schematic flow sheet that IPN supported palladium nanocatalyst provided by the invention is applied to Suzuki coupling reaction; As shown in the figure, concrete steps are as follows: be 2:3:4:2.5 × 10 for benzene, phenyl boric acid, potash, TBAB and IPN supported palladium nanocatalyst according to mol ratio by halogen
-3: 0.25 × 10
-3mixing, and join in the mixed solvent of 1ml dimethylacetylamide and 20ml distilled water; After being heated to 100 DEG C, backflow 4h; After being filtered by IPN supported palladium nanocatalyst, in filtrate, add distilled water, produce white precipitate; After centrifugal, filtration, separation, washing, dry 6h in vacuum drying chamber, thus complete halogen for the Suzuki coupling reaction between benzene and phenyl boric acid, simultaneously, this IPN supported palladium nanocatalyst first Application is in Suzuki coupling reaction, and the yield of its product biphenyl is 90%.This Suzuki coupling reaction is as follows:
Wherein, above-mentioned halogen is iodobenzene or bromobenzene for benzene, meanwhile, after being filtered by above-mentioned IP N supported palladium nanocatalyst, fully washs 3 times, then carries out drying, just can reuse with water and ethanol.
Application examples 1:
The IPN supported palladium nanocatalyst provided by above-described embodiment is applied in the Suzuki coupling reaction between iodobenzene and phenyl boric acid, wherein, iodobenzene is 2.0mmol, and phenyl boric acid is 3.0mmol, and potash is 4.0mmol, phase transfer catalyst TBAB TBAB is 2.5 μm of ol, dimethylacetylamide DMAC is 1ml, and distilled water is 20ml, and reaction temperature is 100 DEG C, reaction time is 4h, thus makes the yield of the product biphenyl of Suzuki coupling reaction be 90%.
Application examples 2:
The IPN supported palladium nanocatalyst provided by above-described embodiment is applied in the Suzuki coupling reaction between iodobenzene and phenyl boric acid, wherein, iodobenzene is 2.0mmol, and phenyl boric acid is 3.0mmol, and potash is 4.0mmol, phase transfer catalyst TBAB TBAB is 0 μm of ol, dimethylacetylamide DMAC is 10ml, and distilled water is 10ml, and reaction temperature is 100 DEG C, reaction time is 4h, thus makes the yield of the product biphenyl of Suzuki coupling reaction be 90%.
Application examples 2 shows, under the catalytic condition of the IPN supported palladium nanocatalyst provided in the embodiment of the present invention, even if the product biphenyl that phase transfer catalyst TBAB TBAB is 0mmol, Suzuki coupling reaction also can reach the yield of 90%.That is, use IPN supported palladium nanocatalyst catalysis Suzuki coupling reaction provided by the invention, can save and use TBAB TBAB, because TBAB TBAB has certain toxicity, thus also just avoid the potential safety hazard that TBAB TBAB brings.
Application examples 3:
The IPN supported palladium nanocatalyst provided by above-described embodiment is applied in the Suzuki coupling reaction between iodobenzene and phenyl boric acid, wherein, iodobenzene is 2.0mmol, phenyl boric acid is 3.0mmol, and potash is 4.0mmol, and phase transfer catalyst TBAB TBAB is 0 μm of ol, acetonitrile and water are mixed to form solvent 20ml according to volume ratio 3:1, reaction temperature is 100 DEG C, and the reaction time is 4h, thus makes the yield of the product biphenyl of Suzuki coupling reaction be 88%.
Application examples 3 shows, under the catalytic condition of the IPN supported palladium nanocatalyst provided in the embodiment of the present invention, the product biphenyl that phase transfer catalyst TBAB TBAB is 0mmol, Suzuki coupling reaction uses the solvent that acetonitrile and water are formed, even if also can reach the yield of 88%.That is, use IPN supported palladium nanocatalyst catalysis Suzuki coupling reaction provided by the invention, under the solvent using acetonitrile and water to be formed, just can save and use TBAB TBAB, because TBAB TBAB has certain toxicity, thus avoid the potential safety hazard using TBAB TBAB to bring.
Contrast application examples 2 and application examples 3 can be learnt, omitting under the condition using TBAB TBAB, the solvent that no matter solvent is dimethylacetylamide and distilled water to be formed or the solvent of acetonitrile and water formation, under the catalytic condition of IPN supported palladium nanocatalyst provided by the invention, the product biphenyl that Suzuki coupling reaction obtains all can have higher yield.
Application examples 4:
The IPN supported palladium nanocatalyst provided by above-described embodiment is applied in the Suzuki coupling reaction between bromobenzene and phenyl boric acid, wherein, bromobenzene is 2.0mmol, and phenyl boric acid is 3.0mmol, and potash is 4.0mmol, phase transfer catalyst TBAB TBAB is 0mmol, dimethylacetylamide DMAC is 10ml, and distilled water is 10ml, and reaction temperature is 100 DEG C, reaction time is 4h, thus completes Suzuki coupling reaction; After each Suzuki coupled catalytic reaction, all by catalyst filtration out, after fully washing 3 times with water and ethanol, dry in atmosphere, for the Suzuki coupled catalytic reaction of next time.IPN supported palladium nanocatalyst is applied to the Suzuki coupling reaction of bromobenzene and phenyl boric acid, and after using seven times continuously, the yield of product biphenyl is 77% after the 7th secondary response.
Can learn from application examples 4, when using IPN supported palladium nanocatalyst provided by the invention to carry out Suzuki coupling reaction, this IPN supported palladium nanocatalyst activity is comparatively strong, and can repeatedly use, when reusing continuously to the 7th time, the yield of biphenyl still can reach 77%; And in the prior art, the catalyst of palladium load in hydrotalcite, after recycling three times, the yield of product is 20%, and when using the 4th time, the yield of product is that 10%[is see Tetrahedron62 (2006) 2922-2926; J.ColloidInterfaceSci.302 (2006) 568-575]; The Pd nano particle of carbon load is after five uses, and catalytic activity is down to 71%[see J.Catal.234 (2005) 348-355]; The Pd nano particle that polystyrene-poly ethylene glycol resin is fixed can recycle six times [see J.Am.Chem.Soc.128 (2006) 6276-6277].
As can be seen here, IPN supported palladium nanocatalyst provided by the invention is applied to Suzuki coupling reaction, not only can obtain higher product yield, and reuse often, there is longer serviceability, that is: before catalyst complete deactivation, the cost performance that IPN supported palladium nanocatalyst is applied to Suzuki coupling reaction is better, thus is more suitable for industrial application.
So the product yield that the catalytic activity of the IPN supported palladium nanocatalyst that the embodiment of the present invention provides is higher, catalysis Suzuki coupling reaction obtains is high; This IPN supported palladium nanocatalyst repeatedly can repeat to reclaim and use simultaneously, and due to the most of solvent in Suzuki coupling reaction be water, thus be conducive to protection of the environment; In addition, palladium exists with the form of nano particle in IPN supported palladium nanocatalyst, thus can disperse more uniformly, also just further enhances catalytic performance; Moreover, the carrier of supported palladium is interpenetrating polymer network, the high molecular hydrophily forming this interpenetrating polymer network is strong, thus more applicablely to react in aqueous, hydrogel is formed in water, and constraint palladium nano metal is effective, thus extend the service life of IPN supported palladium nanocatalyst.
In addition, IPN supported palladium nanocatalyst provided by the invention, learnt by transmission electron microscope observation analysis, palladium nano-particles is high degree of dispersion in the polymer, the average grain diameter of this IPN supported palladium nanocatalyst is 37.38 ± 13.64nm, as can be seen here, the average grain diameter of the palladium in IPN supported palladium nanocatalyst provided by the invention is larger, and be uniformly distributed in IPN supported palladium nanocatalyst due to palladium, thus the surface area of the reactant making palladium touch is larger, and then enhance the catalytic activity of IPN supported palladium nanocatalyst, improve the yield of product, accelerate reaction rate simultaneously.
For further instruction, the activity of IPN supported palladium nanocatalyst provided by the invention, the present invention further detects the rate of catalysis reaction of the Suzuki coupling reaction of the iodobenzene under different temperatures and phenyl boric acid, synthetic product biphenyl fluorescent spectrometry is followed the tracks of, and calculates activation energy, the enthalpy change of reaction and Entropy Changes.
Fig. 2 is temperature 90 DEG C, and under the condition of cosolvent acetonitrile/water=3/1, in the Suzuki coupling reaction between iodobenzene and phenyl boric acid, the fluorescence intensity of biphenyl is along with time variations spectrogram; Fig. 3 is under different temperatures T, and product biphenyl is at the fluorescence peak area schematic diagram over time of 290nm-375nm; Wherein, ◆ 90 DEG C; 85 DEG C; ▲ 80 DEG C; △ 70 DEG C; ■ 65 DEG C; And the slope of straight line in Fig. 3 representative reaction initial rate constant k; Fig. 4 is the graph of a relation of logarithm lnk and the 1/T of initial rate constant; Fig. 5 is the graph of a relation of ln (k/T) and 1/T.As shown in Figure 2-5, at 65 ~ 90 DEG C, because the peak area of fluorescence spectrum can monitor the generating rate of product biphenyl under different temperatures, so, can according to the peak area in the fluorogram of product biphenyl in Fig. 3 along with the straight slope of time variations obtains coupling reaction speed constant under different temperatures.Then lnk ~ 1/T curve is made respectively and ln (k/T) ~ 1/T curve obtains Fig. 4 and Fig. 5.
lnk=-E
a/(RT)+lnA(1)
Obtaining activation energy according to the slope of above-mentioned two formula (1) and (2) and Fig. 4 and Fig. 5 is 47.37kJmol
-1, activation enthalpy is 44.35kJmol
-1, the entropy of activation is-62.53Jmol
-1k
-1, wherein, the activation energy numerical value of reaction is very low, and this just ensure that the higher reactivity of catalyst.By contrast, in phenyl boric acid molecule, the heterolytic fission of C-B covalent bond needs about 200kJmol when not having Pd catalyst
-1energy, so IPN supported palladium nanocatalyst catalytic activity provided by the invention is higher, simultaneously catalysis Suzuki coupling reaction can also improve product yield, can also augmenting response speed.
In sum, the catalytic activity of IPN supported palladium nanocatalyst provided by the invention product yield that is high, the acquisition of catalysis Suzuki coupling reaction is high; This IPN supported palladium nanocatalyst repeatedly can repeat to reclaim and use simultaneously, and allows use major part to be the solvent of water, thus is conducive to protection of the environment; In addition, palladium exists with the form of nano particle in IPN supported palladium nanocatalyst, thus can disperse more uniformly, also just further enhances catalytic performance; Moreover the carrier of supported palladium is interpenetrating polymer network, the high molecular hydrophily forming this interpenetrating polymer network is strong, thus more applicablely reacts in aqueous; The hydrogel carrier constraint palladium nano metal formed in water is effective, thus extends the service life of IPN supported palladium nanocatalyst.
It should be appreciated by those skilled in the art that those skilled in the art can realize described change case in conjunction with prior art and above-described embodiment, do not repeat them here.Such change case does not affect flesh and blood of the present invention, does not repeat them here.
Above preferred embodiment of the present invention is described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, to be construed as in this area common is implemented for the equipment wherein do not described in detail to the greatest extent and structure; Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or being revised as the Equivalent embodiments of equivalent variations, this does not affect flesh and blood of the present invention.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (8)
1. an IPN supported palladium nanocatalyst, is characterized in that, active component is palladium, and carrier is interpenetrating polymer network, and described palladium is nanostructured;
Wherein, the relative amount of described palladium in described IPN supported palladium nanocatalyst is 0.1 × 10
-6mol/g ~ 6 × 10
-6mol/g; Described carrier is that cross-linking polyvinyl alcohol and crosslinked PVP carry out the interpenetrating polymer network after being cross-linked;
Wherein, described cross-linking polyvinyl alcohol is the network of self of polyvinyl alcohol crosslinked rear formation; Described crosslinked PVP is that N-vinylpyrrolidone is polymerized and is cross-linked the rear network of self formed.
2. a preparation method for IPN supported palladium nanocatalyst as claimed in claim 1, it is characterized in that, described preparation method comprises the following steps:
1) polyvinyl alcohol, absolute ethyl alcohol, distilled water, palladium bichloride-hydrogen chloride solution, sulfuric acid solution, acetic acid solution and glutaraldehyde solution are provided;
2) the described distilled water of the described absolute ethyl alcohol of 30ml and 25ml is mixed to form mixed solution;
3) by the degree of polymerization of 5g be 1750 described polyvinyl alcohol join in described mixed solution, after carrying out condensing reflux, carry out 95 DEG C of oil baths heating 2h and obtain polyvinyl alcohol colourless transparent solution;
4) the described palladium bichloride-hydrogen chloride solution of 2ml, 2.82mmol/L is joined in described polyvinyl alcohol colourless transparent solution, under 95 DEG C of oil baths, carry out condensing reflux 5h obtain dark solution;
5) after described dark solution being cooled, by 0.2ml, 10% described sulfuric acid solution, 0.6ml, 10% described acetic acid solution and 1.0ml, 25% described glutaraldehyde solution join in described dark solution, obtain polyvinyl alcohol-palladium complex solution;
6) N-vinylpyrrolidone, N, N are provided '-methylene-bisacrylamide, potassium peroxydisulfate and distilled water;
7) by the described N-vinylpyrrolidone of 6.14g, the described N of 0.31g, the described potassium peroxydisulfate of N '-methylene-bisacrylamide, 0.15g to join in the described distilled water of 20ml and stirs, make described N-vinylpyrrolidone, described N, N '-methylene-bisacrylamide, described potassium peroxydisulfate are dissolved in described distilled water, obtain N-vinylpyrrolidone solution;
8) by after described polyvinyl alcohol-palladium complex solution and the mixing of described N-vinylpyrrolidone solution, carry out stirring 30min, then in baking oven, carry out heating 3h under the condition of 70 DEG C, obtain black transparent solid gel;
9) outwell after adding black transparent solid gel 5h described in distilled water immersion, and repeat 2 ~ 3 times;
10) after described black transparent solid gel being dried under the condition of 60 DEG C, pulverize, to obtain described IPN supported palladium nanocatalyst.
3. the application of IPN supported palladium nanocatalyst as claimed in claim 1, is characterized in that, described catalyst is used for halogen for the Suzuki coupling reaction between benzene and phenyl boric acid.
4. apply as claimed in claim 3, it is characterized in that, comprise the following steps:
1) be 2mmol:3mmol:4mmol:2.5 × 10 for benzene, phenyl boric acid, potash, TBAB and IPN supported palladium nanocatalyst according to mol ratio by halogen
-3mmol:0.25 × 10
-3mmol mixes, and joins in the mixed solvent of 1ml dimethylacetylamide and 20ml distilled water;
2) after being heated to 100 DEG C, backflow 4h;
3) after being filtered by described IPN supported palladium nanocatalyst, in filtrate, add distilled water, produce white precipitate;
4) after centrifugal, filtration, separation, washing, dry 6h in vacuum drying chamber, thus complete described halogen for the Suzuki coupling reaction between benzene and described phenyl boric acid.
5. the application as described in claim 3 or 4, is characterized in that, described halogen is iodobenzene or bromobenzene for benzene.
6. the application as described in claim 3 or 4, is characterized in that, described IPN supported palladium nanocatalyst first Application is in described halogen for the Suzuki coupling reaction between benzene and phenyl boric acid, and the yield of its product biphenyl is 90%.
7. apply as claimed in claim 4, it is characterized in that, step 3) in: after described IPN supported palladium nanocatalyst is filtered, fully wash described IPN supported palladium nanocatalyst 3 times with water and ethanol, then carry out drying, to reuse.
8. apply as claimed in claim 3, it is characterized in that, after described IPN supported palladium nanocatalyst circulation uses 6 times continuously, be applied to described halogen for the 7th time for the Suzuki coupling reaction between benzene and phenyl boric acid, the yield of product is 77%.
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| CN106513051A (en) * | 2016-10-26 | 2017-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Load type visible light photocatalyst and preparation method thereof |
| CN108283936A (en) * | 2018-01-11 | 2018-07-17 | 安徽大学 | A kind of preparation method and applications of the recyclable palladium catalyst of water soluble polymer load |
| CN110394190B (en) * | 2019-07-09 | 2022-04-01 | 上海应用技术大学 | Nitrogen-rich triazine-based calix [4] arene polymer supported palladium catalyst, and preparation method and application thereof |
| CN110327921A (en) * | 2019-07-18 | 2019-10-15 | 武汉理工大学 | Loading type nano Pd/MgO catalyst and the method for using the catalyst preparation biphenyl compound |
| CN110327974B (en) * | 2019-07-26 | 2022-03-15 | 湖北工程学院 | Cross-linked norbornene copolymer/carbon black three-dimensional network supported palladium nano catalyst and preparation method and application thereof |
| CN112756012B (en) * | 2019-11-05 | 2023-03-10 | 六盘水师范学院 | Hydrophilic organic porous polymer supported palladium catalyst, and preparation method and application thereof |
| CN113956231A (en) * | 2021-09-27 | 2022-01-21 | 哈尔滨工业大学（深圳） | Preparation method of biaryl compound based on continuous flow reactor |
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