CN109331870A - Lignin-chitosan complexes loaded palladium catalyst and the preparation method and application thereof - Google Patents
Lignin-chitosan complexes loaded palladium catalyst and the preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
Abstract
The invention belongs to the technical fields of catalyst, disclose lignin-chitosan complexes loaded palladium catalyst and the preparation method and application thereof.Method: 1) monovalence copper catalyst under the action of, the Azide chitosan lignin modified with Terminal Acetylenes is reacted, lignin-chitosan complexes are obtained；2) in a solvent, lignin-chitosan complexes are mixed with palladium salt, heating reaction is filtered, is washed, and it is dry, obtain lignin-chitosan complexes loaded palladium catalyst.The application of catalyst of the invention in catalysis Suzuki coupling reaction.Method of the invention is simple, and reaction condition is mild, easy to operate, is easy to industrialize, and selected raw material is easy to get, and realizes the higher value application of industrial lignin；The catalyst of acquisition belongs to solid catalyst, does not introduce ligand, environment friendly and pollution-free；And catalyst catalytic activity with higher of the invention, the yield with higher in catalyzed coupling reaction.
Description
Technical field
The invention belongs to the technical fields of catalyst, and in particular to a kind of lignin-chitosan complexes load palladium catalysis
Agent and the preparation method and application thereof.The application of catalyst of the invention in catalysis Suzuki reaction.
Background technique
The synthesis of C-C key has consequence in organic molecule synthesis, is widely used in medicine, chemical industry and material
In the fields such as science.Suzuki reaction is as a kind of important method of synthesis C-C key, and with reaction condition, mild, substrate is adapted to
The advantages that property is wide, reaction rate is fast, and in acquisition Nobel chemistry Prize in 2010.Suzuki reaction usually with phenyl boric acid and its is spread out
Biology, aryl halide, alkali, solvent construct C-C key under the action of precious metals pd catalyst and form biphenyl compound.Tradition
Suzuki reaction generally use homogeneous palladium catalyst.Although reactivity is higher, palladium black is easily formed, is caused in catalyst
Poison such as is difficult to recycle at the problems.
Chitosan is the product that chitin is obtained by deacetylation.Chitin is widely present Yu Haiyang class biology such as shrimp
It is a kind of inexhaustible renewable biomass money in the shell of crab and some shellfish such as beetle
Source.Chitosan has extremely special chemical structure, is the linear polymeric polymerization arranged with regular amino (acetylamino)
Object is unique natural polysaccharide for having amino and acetylamino.These characteristics of molecular structure determine that chitosan has all
Mostly natural activity is widely used in the fields such as food, biomedicine, material, chemistry and chemical industry.By chitosan loaded Pd,
Since the crystalline texture of chitosan causes exposed active site insufficient, the catalytic performance of catalyst is poor, same reaction conditions
Under, the yield for being catalyzed reaction is only 75%.Black liquor of the industrial lignin in pulping and papermaking processes.Lignin is natural green
The important component of the cell wall of color plant widely exists in the pulping and paper-makings raw materials such as all kinds of timber, careless class.Lignin
The complicated skeleton structure of the rigidity formed is combined with ehter bond or carbon-carbon bond with a variety of phenylpropane units.And industrial lignin
Due to the processing by lye, so that its chemical structure is more complicated, it is its efficient very big challenge using proposition.
The present invention is prepared for wood using Azide chitosan and industrial lignin as raw material, using Click reaction, reduction reaction
Quality-chitosan complexes loaded palladium catalyst, realizes the higher value application of industrial lignin, turns waste into wealth.It is made simultaneously
Standby catalyst has very high catalytic performance.
Summary of the invention
In order to solve the disadvantage that the prior art and shortcoming, the primary purpose of the present invention is that providing a kind of lignin-
The preparation method of chitosan complexes loaded palladium catalyst.
Another object of the present invention is to provide lignin prepared by the above method-chitosan complexes supported palladiums
Catalyst.
A further object of the present invention is to provide above-mentioned lignin-chitosan complexes loaded palladium catalysts to be catalyzed
Application in Suzuki coupling reaction.
In order to achieve the above object, present invention employs following technical solutions:
A kind of preparation method of lignin-chitosan complexes loaded palladium catalyst, comprising the following steps:
(1) lignin-chitosan complexes preparation: under the action of monovalence copper catalyst, by Azide chitosan with
The modified lignin of Terminal Acetylenes is reacted, and lignin-chitosan complexes are obtained；What the Azide chitosan and Terminal Acetylenes were modified
The mass ratio of lignin is (25~75): (50~100)；
(2) lignin-chitosan complexes loaded palladium catalyst preparation: in a solvent, lignin-chitosan is compound
Object is mixed with palladium salt, and heating reaction is filtered, washed, dry, obtains lignin-chitosan complexes loaded palladium catalyst.
Monovalence copper catalyst described in step (1) is by sodium ascorbate and CuSO4Generation obtains；
The specific preparation step of lignin-chitosan complexes described in step (1) are as follows: Azide chitosan is dissolved in vinegar
In acid-organic solvent, Azide chitosan solution is obtained；The modified lignin of Azide chitosan solution and Terminal Acetylenes is mixed
Afterwards, sodium ascorbate and CuSO is added4Solution, reaction, subsequent processing obtain lignin-chitosan complexes.It is described organic molten
Agent is N, N- dimethyl sulfoxide or DMF；The temperature of the reaction is 20-50 DEG C, and the time of reaction is 24~48h；It is described subsequent
Processing refers to dialysis, is freeze-dried；
The mass ratio of the modified lignin of the Azide chitosan, Terminal Acetylenes, sodium ascorbate and copper sulphate be (25~
75): (50~100): (1~10): (5~15), preferably 50:75:5:8；
The volume ratio of acetic acid and organic solvent is (1~5) in the acetic acid-organic solvent: 100；
The concentration of the Azide chitosan solution is 0.005~0.05g/mL；
The CuSO4The concentration of solution is 0.1~2mol/L；
Lignin raw material is alkaline lignin in the modified lignin of the Terminal Acetylenes, and the modified lignin of Terminal Acetylenes is with solution
Form is added, solvent DMSO；Solution concentration is 20~80mg/mL.
Lignin-chitosan complexes and the mass ratio of palladium salt are 5:1~30:1 in step (2)；Preferably 20:1；
The palladium salt is palladium acetate；The solvent is dehydrated alcohol or ethanol water.
Stabilizer is added in lignin described in step (2)-chitosan complexes loaded palladium catalyst during the preparation process, i.e.,
Stabilizer is added in the reaction；The stabilizer is sodium citrate or PVP；Stabilizer and the mass ratio of palladium salt are (1~6): 1.
The temperature of the heating reaction is 30~80 DEG C, and the time for heating reaction is 4~12h.
The washing, which refers to, is successively washed with dehydrated alcohol and ether, and the drying refers to vacuum drying.
Lignin-chitosan complexes structural formula described in step (1):
Azide chitosan described in step (1) is prepared via a method which:
In organic solvent by chitosan dispersion, it is configured to chitosan dispersion；Phthalic anhydride, nitrogen atmosphere is added
6~12h of lower 120~130 DEG C of reactions, reaction product is purified to be dried to obtain phthalimide chitosan (PhCS)；Then
In organic solvent by the PhCS dispersion of preparation, triphenylphosphine (TPP) is sequentially added under condition of ice bath and N- bromo succinyl is sub-
Amine is passed through 2~5h of reaction at 60~100 DEG C of nitrogen, bromo chitosan (BrCS) is obtained after the purified drying of reaction product；Then
In organic solvent by BrCS dispersion, NaN is added3, 2~5h is reacted under nitrogen atmosphere at 60~80 DEG C, after being cooled to room temperature, is produced
Object is purified to be dried to obtain azidomethyl phenyl nitridation chitosan (N3PhCS)；Finally by N3PhCS disperses in organic solvent, hydration to be added
Hydrazine solution, 80~120 DEG C of 2~5h of reaction under nitrogen atmosphere, is cooled to room temperature, the purified drying of product, and it is poly- to obtain Azide shell
Sugar (N3CS)。
Organic solvent is n,N dimethylformamide or DMSO, the concentration of chitosan dispersion in the chitosan dispersion
For 25-50mg/mL；The organic solvent of PhCS dispersion in organic solvent is DMF or DMSO；BrCS disperses in organic solvent
Organic solvent is DMF or DMSO；N3The organic solvent of PhCS dispersion in organic solvent is DMF；The concentration of hydrazine hydrate solution is
4mol/L；
The molar ratio of the chitosan and phthalic anhydride: 1:1~1:3；The molar ratio of PhCS:TPP:NBS are as follows: 1:(1
~3): (5~10), BrCS and NaN3Molar ratio are as follows: 1:5~1:20.
The modified lignin of Terminal Acetylenes described in step (1) is prepared via a method which:
Alkaline lignin is dissolved in strong base solution, bromo propine is added, reaction adjusts reaction system to neutrality, subsequent place
Reason obtains the modified lignin of Terminal Acetylenes.
The strong base solution is sodium hydroxide or potassium hydroxide solution；The concentration of strong base solution is 1wt%~5wt%；Institute
The temperature for stating reaction is 20~90 DEG C, and the time of reaction is 0.5-4h；The adjusting reaction system to neutrality refers to sour using using
It neutralizes；The subsequent processing refers to product ethanol precipitation, washs, dry.The mass ratio of the lignin and bromo propane
For 2:1~1:2.
The alkalinity lignin is to purify to come out from the black liquor of pulping and paper-making using the method for alkali soluble solution, acid precipitating.
Application of the lignin-chitosan complexes loaded palladium catalyst in catalysis Suzuki coupling reaction；
The application includes the following steps: lignin-chitosan complexes loaded palladium catalyst, halogeno-benzene, aryl boron
Bronsted lowry acids and bases bronsted lowry is added in solvent, reaction, and after the reaction was completed, then filtering removes solvent in filtrate, purifies, is catalyzed and synthesized
Product.The condition of the reaction is that 1~6h is reacted at 20~90 DEG C；Solvent removal in filtrate is referred to and is gone by vacuum distillation
It removes, purification refers to column Chromatographic purification.The column chromatography refers to the volume ratio of petroleum ether, acetic acid ethyl ester for the mixed of 1:1~30:1
Bonding solvent is the silica gel column chromatography of solvent.
The halogeno-benzene is iodobenzene, iodobenzene derivative, bromobenzene, bromobenzene derivative, chlorobenzene or chlorobenzene derivative.
Such as: halogeno-benzene be iodobenzene, bromobenzene, chlorobenzene, paraiodoanisole, to Iodoacetophenone, to iodotoluene, to iodonitrobenzene,
Para-bromoanisole, parabromoacetophenone, parabromotoluene, p-Nitrobromobenzene etc..
The lignin-chitosan complexes loaded palladium catalyst dosage is using the molar amount of palladium as halogeno-benzene mole
0.2~1%, preferably 0.6%.
The molar ratio of the halogeno-benzene and aryl boric acid is preferably 1:1.2.
The alkali is potassium carbonate, sodium hydroxide, potassium hydroxide, more than one in sodium carbonate；The solvent is dehydrated alcohol
Or ethanol water.
The lignin-chitosan complexes loaded palladium catalyst catalyzed coupling reaction schematic diagram is as shown in Figure 1.
The present invention destroys the height of crystallization as chitosan using industrial alkaline lignin waste cheap and being difficult to be utilized
Molecular compound is advantageously implemented the high level for leading to the industrial alkaline lignin of more difficult higher value application since structure is complex
Change and utilize, while using the rigid network structure of industrial lignin, exposes chitosan more fully, realizing lower
Under conditions of the dosage of precious metals pd, higher catalytic performance has been reached (up to 99% or more).
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) catalyst of the invention combines the advantages of two kinds of natural polymers, is reacted by click by industrial lignin
It links together with chitosan, the application for industrial lignin and chitosan provides new method；
(2) catalyst of the invention belongs to solid catalyst, does not introduce ligand, environment friendly and pollution-free；
(3) preparation method simple process of the invention, reaction condition is mild, easy to operate, is easy to industrialize；
(4) good substrate applicability of catalyst of the invention in application process, applicable supplied for electronic and electron-withdrawing group
Halides；
(5) catalyst of the invention is antiacid, alkaline relatively strong, in addition to being applied to catalysis Suzuki reaction, in other respects
Also there is larger application prospect；
(6) catalyst of the invention catalytic activity with higher, the yield with higher when being catalyzed Suzuki reaction.
Detailed description of the invention
Fig. 1 is the signal that lignin of the invention-chitosan complexes loaded palladium catalyst is catalyzed suzuki coupling reaction
Figure；
Fig. 2 is the product that catalyzes and synthesizes of the embodiment of the present invention 1~51HNMR figure；
Fig. 3 is that the embodiment of the present invention 6 catalyzes and synthesizes product1HNMR figure；
Fig. 4 is that the embodiment of the present invention 7 catalyzes and synthesizes product1HNMR figure；
Fig. 5 is that the embodiment of the present invention 8 catalyzes and synthesizes product1HNMR figure；
Fig. 6 is that the embodiment of the present invention 9 catalyzes and synthesizes product1HNMR figure.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Lignin of the present invention-chitosan complexes loaded palladium catalyst catalyzed coupling reaction schematic diagram is as shown in Figure 1.
Azide chitosan used in following embodiment is prepared by the following method:
Chitosan is dispersed in, in N-N dimethylformamide (DMF), is configured to the dispersion that chitosan concentration is 25mg/mL
The phthalic anhydride for being 1.5:1 with the molar ratio of chitosan, the lower 130 DEG C of reactions 12h of nitrogen atmosphere, reaction product is added in liquid
Through precipitating, suction filtration, extracts, is dried to obtain brown ceramic powder phthaloyl chitosan (PhCS)；Then by the PhCS of preparation points
It is dispersed in DMF, is configured to dispersion liquid, triphenylphosphine (TPP) and N- bromo-succinimide are sequentially added under condition of ice bath
(NBS), wherein the molar ratio of PhCS, TPP and NBS be 1:1:10, be passed through at 80 DEG C of nitrogen and react 3h, reaction product through precipitating,
Brown ceramic powder bromo chitosan (BrCS) is obtained after centrifugation, extracting, drying；Then BrCS is dispersed in middle DMF, sufficiently dissolved,
It is configured to the dispersion liquid that concentration is 10mg/mL, NaN is added3, wherein NaN3Reaction equivalent with BrCS is that (equivalent refers to rub 10:1
Your amount), react 4h at lower 80 DEG C of nitrogen atmosphere, after being cooled to room temperature, product through precipitating, centrifugation, extract, be dried to obtain brown color
Powder azidomethyl phenyl nitrogenizes chitosan (N3PhCS), finally by N3PhCS is dispersed in DMF, is sufficiently stirred, and is configured to concentration and is
The hydrazine hydrate solution with the 4mol/L that the volume ratio of DMF is 1:1, the lower 100 DEG C of reactions of nitrogen atmosphere is added in the solution of 10mg/mL
4h is cooled to room temperature, and product is centrifuged 5min, in Soxhlet extractor through the dehydrated alcohol precipitating precipitating of three times volume, 5000rmp
12h and vacuum drying are extracted with dehydrated alcohol, obtains yellow powder Azide chitosan (N3CS)。
The modified lignin of used Terminal Acetylenesization (the modified lignin of Terminal Acetylenes) is prepared by the following method:
(1) industrial alkali lignin is added in the NaOH solution of 2wt% and is sufficiently stirred, stood overnight after dissolution；Filtering
Afterwards, sulfuric acid solution is added into filtrate, adjusts pH=2~3, stirs 2h at 70 DEG C；With A3 sand core funnel filter, and with distill
Water washing is to pH=7；Filter cake is dried at 50 DEG C to weight and is no longer changed.Finally obtain the purifying industrial that yield is about 10%
Lignin brown ceramic powder；
(2) industrial lignin of purification is dissolved in the sodium hydroxide solution of 2wt% at room temperature, bromo third is then added
Alkynes (mass ratio of industrial alkaline lignin and bromo propine is 4:3), reacts 3h at 50 DEG C, is adjusted with acid reaction system into
Property, it reaction product is added to absolute ethanol precipitating, ethyl alcohol, ether washs to freeze-drying after colourless and obtain the Terminal Acetylenes of brownish black
Lignin.
Embodiment 1
(1) preparation of industrial lignin-click- chitosan: precise 0.12g Azide chitosan is dissolved in 12mL
In glacial acetic acid-DMSO solution (v:v=1:100), it is named as solution A；In addition, weighing 0.18g Terminal Acetylenes lignin is added to 3mL
In DMSO, stirs to being completely dissolved, be named as solution B；After solution A is added dropwise in solution B, 0.012g Vitamin C is added
Sour sodium, stirs 10min at room temperature；Then, 12 μ L 1mol/L CuSO are measured4Solution is added in above-mentioned system, at room temperature
The reaction was continued 48h；After reaction, it is freeze-dried after product being dialysed in deionized water 3 days, finally obtaining yield is
89.8% industrial lignin-click- chitosan yellow powder；
(2) preparation of industrial lignin-click- chitosan@Pd catalyst: 0.06g industrial lignin-is accurately weighed
Click- Chitosan powder and 0.003g palladium acetate are dispersed in 6mL dehydrated alcohol；0.0083g is added in the above system
6h is stirred to react after sodium citrate at 60 DEG C and obtains brown color suspension, for several times, filter cake is at 60 DEG C for filtering, dehydrated alcohol washing
Lower vacuum drying for 24 hours, obtains industrial lignin-click- chitosan@Pd catalyst brownish-yellow powder.
Industrial lignin-click- chitosan@Pd catalyst obtained by the present embodiment is in catalysis Suzuki coupling reaction
Using: in 15mL pressure bottle 20mg industrial lignin-click- chitosan@Pd catalyst, 0.5mmol are sequentially added to iodobenzene
Methyl ether, 0.6mmol phenyl boric acid, 1mmol potassium carbonate and 2mL dehydrated alcohol are stirred to react 4h at 70 DEG C in nitrogen atmosphere, reaction
After the completion, above-mentioned reaction solution is cooled to room temperature, filters separation, is washed for several times with dehydrated alcohol, obtained filtrate is by subtracting
After pressure distillation, with petroleum ether: the mixed solvent that ethyl acetate is 20:1 is solvent, is purified to obtain white admittedly to product
Body；Its yield is 97.6%, product1HNMR is as shown in Figure 2.
1H NMR (600MHz, CDCl3): δ=7.57-7.54 (m, 4H), 7.41 (t, J=7.6Hz, 2H), 7.30 (t, J
=7.2Hz, 1H), 6.99 (d, J=8.8Hz, 2H), 3.86 (s, 3H)
Embodiment 2
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Application of the industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment in catalyzed coupling reaction:
Take above-mentioned catalyst 20mg (wherein Pd relative to paraiodoanisole mole be 0.6mol%), 0.5mmol paraiodoanisole,
0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, and filter cake after catalyst filtration is used nothing by 25 DEG C of reaction 4h again
Water-ethanol washs 3 times, and filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with petroleum ether:
Ethyl acetate=20:1 mixed solvent is solvent, is purified to obtain white solid to product；Its yield is 45.6%, is produced
Object1HNMR is as shown in Figure 2.
Embodiment 3
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment is in catalysis Suzuki coupling reaction
Application: take that above-mentioned catalyst 20mg (wherein Pd is 0.6mol% relative to the mole of paraiodoanisole), 0.5mmol is to iodine
Methyl phenyl ethers anisole, 0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, 90 DEG C of reaction 4h, by filter cake after catalyst filtration
It is washed 3 times with dehydrated alcohol again, filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with stone
Oily ether: ethyl acetate=20:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is
99.7%, product1HNMR is as shown in Figure 2.
Embodiment 4
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Application of the industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment in catalyzed coupling reaction:
Take above-mentioned catalyst 20mg (wherein Pd relative to paraiodoanisole mole be 0.6mol%), 0.5mmol paraiodoanisole,
0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, 70 DEG C of reaction 1h and 3h, again by filter cake after catalyst filtration
It is washed 3 times with dehydrated alcohol, filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with petroleum
Ether: ethyl acetate=20:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is 81.3%
With 93.6%, product1HNMR is as shown in Figure 2.
Embodiment 5
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment is in catalysis Suzuki coupling reaction
Application: take above-mentioned catalyst 15mg (wherein Pd relative to paraiodoanisole mole be 0.45mol%), 0.5mmol pairs
Iodanisol, 0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, and 70 DEG C of reaction 4h will be filtered after catalyst filtration
Cake is washed 3 times with dehydrated alcohol again, and filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with
Petroleum ether: ethyl acetate=20:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is
90.4%, product1HNMR is as shown in Figure 2.
Embodiment 6
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment is in catalysis Suzuki coupling reaction
Application: take that above-mentioned catalyst 20mg (wherein Pd is 0.6mol% relative to the mole to Iodoacetophenone), 0.5mmol is to iodine
Acetophenone, 0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, 70 DEG C of reaction 4h, by filter cake after catalyst filtration
It is washed 3 times with dehydrated alcohol again, filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with stone
Oily ether: ethyl acetate=10:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is
99.3%, product1HNMR is as shown in Figure 3.
1H NMR (600MHz, CDCl 3): δ=8.04 (d, J=8.8Hz, 2H), 7.69 (d, J=8.4Hz, 2H), 7.64
(d, J=7.2Hz, 2H), 7.49-7.46 (m, 2H), 7.42-7.40 (m, 1H), 2.64 (s, 3H)
Embodiment 7
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment is in catalysis Suzuki coupling reaction
Application: take above-mentioned catalyst 20mg (wherein Pd relative to the mole to iodobenzene be 0.6mol%), 0.5mmol iodobenzene,
0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, and filter cake after catalyst filtration is used nothing by 70 DEG C of reaction 4h again
Water-ethanol washs 3 times, and filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with petroleum ether:
Ethyl acetate=10:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is 85.2%, is produced
Object1HNMR is as shown in Figure 4.
1H NMR (600MHz, CDCl3): δ=7.66-764 (m, 4H), 7.50-7.48 (m, 4H), 7.41-7.38 (m,
2H)；13C NMR (150MHz, CDCl 3): δ=141.2,128.7,127.2,127.1.
Embodiment 8
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Application of the industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment in catalyzed coupling reaction:
Take above-mentioned catalyst 20mg (wherein Pd relative to the mole to iodotoluene be 0.6mol%), 0.5mmol to iodotoluene,
0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, and filter cake after catalyst filtration is used nothing by 70 DEG C of reaction 4h again
Water-ethanol washs 3 times, and filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with petroleum ether:
Ethyl acetate=10:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is 97.5%, is produced
Object1HNMR is as shown in Figure 5.
1H NMR (600MHz, CDCl 3): δ=7.65-764 (m, 2H), 7.57-756 (m, 2H), 7.50-7.47 (m,
2H),7.38-7.37(m,1H),7.32-731(m,2H),2.46(s,3H)；13C NMR (150MHz, CDCl 3): δ=
141.1,138.4,137.0,129.5,128.7,127.0,126.9,126.9,21.0.
Embodiment 9
The preparation of industrial lignin-click- chitosan@Pd catalyst is identical as embodiment 1 in this embodiment.
Industrial lignin-click- chitosan@Pd catalyst obtained by this embodiment is in catalysis Suzuki coupling reaction
Application: take that above-mentioned catalyst 20mg (wherein Pd is 0.6mol% relative to the mole to iodonitrobenzene), 0.5mmol is to iodine
Nitrobenzene, 0.6mmol phenyl boric acid, 1.0mmol potassium carbonate are added in 2mL ethyl alcohol, 70 DEG C of reaction 4h, by filter cake after catalyst filtration
It is washed 3 times with dehydrated alcohol again, filtrate removes solvent with vacuum distillation, after solvent volatilization is dry, using column chromatography silica gel, with stone
Oily ether: ethyl acetate=10:1 mixed solvent is solvent, is purified to obtain white solid to product.Its yield is
99.3%, product1HNMR is as shown in Figure 6.
1H NMR (600MZ, CDCl3): δ=8.30-8.28 (m, 2H), 7.75-7.72 (m, 2H), 7.64-7.62 (m,
2H), 7.52-7.47 (m, 2H), 7.47-7.44 (m, 1H)
Catalyst of the invention is relative to application No. is catalyst disclosed in 201510678900.6 to have the advantage that head
First, the industrial alkaline lignin that the present invention uses is the waste of common pulping and paper-making, compared to xylan base hemicellulose
It is more cheap and easy to get, and can turn waste into wealth.Secondly, the present invention using the stabilizers such as sodium citrate to the partial size of Pd nano particle into
Row regulation, further improves the catalytic activity of catalyst.Finally, in catalyst of the invention precious metals pd dosage relative to
Application No. is catalyst disclosed in 201510678900.6 under conditions of dosage reduces half again, the catalysis yield at 70 DEG C from
83% originally is promoted to 99% or more.
Claims (10)
1. a kind of lignin-chitosan complexes loaded palladium catalyst preparation method, it is characterised in that: the following steps are included:
(1) lignin-chitosan complexes preparation: under the action of monovalence copper catalyst, by Azide chitosan and Terminal Acetylenes
Modified lignin is reacted, and lignin-chitosan complexes are obtained；
(2) lignin-chitosan complexes loaded palladium catalyst preparation: in a solvent, by lignin-chitosan complexes with
Palladium salt mixing, heating reaction, is filtered, and is washed, dry, obtains lignin-chitosan complexes loaded palladium catalyst.
2. lignin-chitosan complexes loaded palladium catalyst preparation method according to claim 1, it is characterised in that:
The modified lignin of Terminal Acetylenes described in step (1) is prepared via a method which:
Alkaline lignin is dissolved in strong base solution, bromo propine is added, reaction adjusts reaction system to neutrality, and subsequent processing obtains
Obtain the modified lignin of Terminal Acetylenes；
Stabilizer is added in lignin described in step (2)-chitosan complexes loaded palladium catalyst during the preparation process, i.e., anti-
Answer middle addition stabilizer；The stabilizer is sodium citrate or PVP.
3. lignin-chitosan complexes loaded palladium catalyst preparation method according to claim 2, it is characterised in that:
In step (1) in the preparation of the modified lignin of Terminal Acetylenes, the strong base solution is sodium hydroxide or potassium hydroxide solution；It is described anti-
The temperature answered is 20~90 DEG C, and the time of reaction is 0.5~4h；The subsequent processing refers to product ethanol precipitation, washs,
It is dry；The mass ratio of the lignin and bromo propane is 2:1~1:2；
Stabilizer described in step (2) and the mass ratio of palladium salt are (1~6): 1.
4. lignin-chitosan complexes loaded palladium catalyst preparation method according to claim 1, it is characterised in that:
Monovalence copper catalyst described in step (1) is by sodium ascorbate and CuSO4Generation obtains；
The mass ratio for the lignin that Azide chitosan described in step (1) and Terminal Acetylenes are modified is (25~75): (50~100)；
Palladium salt described in step (2) is palladium acetate；
Lignin-chitosan complexes and the mass ratio of palladium salt are 5:1~30:1 in step (2)；
Solvent described in step (2) is dehydrated alcohol or ethanol water；
The temperature that reaction is heated described in step (2) is 30~80 DEG C, and the time for heating reaction is 4~12h.
5. lignin-chitosan complexes loaded palladium catalyst preparation method according to claim 1, it is characterised in that:
Azide chitosan described in step (1) is prepared via a method which:
In organic solvent by chitosan dispersion, it is configured to chitosan dispersion；Phthalic anhydride is added, under nitrogen atmosphere
120~130 DEG C of 6~12h of reaction, the purified phthalimide chitosan that is dried to obtain of reaction product are denoted as PhCS；Then
In organic solvent by the PhCS dispersion of preparation, triphenylphosphine and N- bromo-succinimide are sequentially added under condition of ice bath, is led to
Enter 2~5h of reaction at 60~100 DEG C of nitrogen, obtains bromo chitosan after the purified drying of reaction product and be denoted as BrCS；Then will
BrCS disperses in organic solvent, NaN to be added3, 2~5h, after being cooled to room temperature, product are reacted under nitrogen atmosphere at 60~80 DEG C
The purified azidomethyl phenyl nitridation chitosan that is dried to obtain is denoted as N3PhCS；Finally by N3PhCS disperses in organic solvent, hydration to be added
Hydrazine solution, 80~120 DEG C of 2~5h of reaction under nitrogen atmosphere, is cooled to room temperature, the purified drying of product, and it is poly- to obtain Azide shell
Sugar is denoted as N3CS；
The specific preparation step of lignin-chitosan complexes described in step (1) are as follows: Azide chitosan is dissolved in acetic acid-
In organic solvent, Azide chitosan solution is obtained；After the modified lignin of Azide chitosan solution and Terminal Acetylenes is mixed, add
Enter sodium ascorbate and CuSO4Solution, reaction, subsequent processing obtain lignin-chitosan complexes.
6. lignin-chitosan complexes loaded palladium catalyst preparation method according to claim 5, it is characterised in that:
In step (1) in the preparation process of Azide chitosan, organic solvent is n,N dimethylformamide in the chitosan dispersion
Or DMSO, the concentration of chitosan dispersion are 25-50mg/mL；PhCS dispersion organic solvent in organic solvent be DMF or
DMSO；The organic solvent of BrCS dispersion in organic solvent is DMF or DMSO；N3PhCS dispersion in organic solvent organic molten
Agent is DMF；The concentration of hydrazine hydrate solution is 4mol/L；
In step (1) lignin-chitosan complexes it is specific preparation in, the organic solvent be N, N- dimethyl sulfoxide or
DMF；The temperature of the reaction is 20-50 DEG C, and the time of reaction is 24~48h；The subsequent processing refers to that dialysis, freezing are dry
It is dry；
The mass ratio of the modified lignin of the Azide chitosan, Terminal Acetylenes, sodium ascorbate and copper sulphate is (25~75):
(50~100): (1~10): (5~15).
7. a kind of lignin-chitosan complexes load palladium catalysis obtained by any one of claim 1~6 preparation method
Agent.
8. lignin-chitosan complexes loaded palladium catalyst is in catalysis Suzuki coupling reaction according to claim 7
Application.
9. application according to claim 8, characterized by the following steps: bear lignin-chitosan complexes
Carried palladium catalyst, halogeno-benzene, aryl boric acid and alkali are added in solvent, reaction, and after the reaction was completed, filtering then will be molten in filtrate
Agent removal, purification obtain catalyzing and synthesizing product；The condition of the reaction is that 1~6h is reacted at 20~90 DEG C.
10. application according to claim 9, it is characterised in that:
The halogeno-benzene is iodobenzene, iodobenzene derivative, bromobenzene, bromobenzene derivative, chlorobenzene or chlorobenzene derivative；
The lignin-chitosan complexes loaded palladium catalyst dosage is using the molar amount of palladium as halogeno-benzene mole
0.2~1%；
The molar ratio of the halogeno-benzene and aryl boric acid is 1:1.2；
The alkali is potassium carbonate, sodium hydroxide, potassium hydroxide, more than one in sodium carbonate；The solvent is dehydrated alcohol or second
Alcohol solution.
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