CN108057459B - A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application - Google Patents
A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application Download PDFInfo
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- CN108057459B CN108057459B CN201610986344.3A CN201610986344A CN108057459B CN 108057459 B CN108057459 B CN 108057459B CN 201610986344 A CN201610986344 A CN 201610986344A CN 108057459 B CN108057459 B CN 108057459B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
The invention discloses a kind of vinyl interchange reaction silica gel load palladium catalysts and its preparation method and application, and described method includes following steps: (1) preparing the double-tooth chelate ligand containing N of the functional group containing trialkoxy silane first；(2) one of double-tooth chelate ligand containing N that step (1) is prepared or a variety of and palladium inorganic salts carry out complexation reaction, generate palladium complex；(3) palladium complex that step (2) is prepared is hydrolyzed with tetraalkyl orthosilicate and is reacted, generate the silica gel load coordination palladium catalyst.The preparation method is easy to carry out, fully reacting, and Metal Palladium utilization rate is high；It is controlled by the feed ratio to reaction raw materials, the load capacity of Metal Palladium in prepared silica gel supported palladium catalyst can be controlled in a certain range.The catalyst can effectively catalyze vinyl interchange reaction, be used to prepare vinyl carboxylates.
Description
Technical field
The invention belongs to vinyl interchange reaction catalyst technical fields, and in particular to a kind of vinyl interchange reaction use
Silica gel load is coordinated palladium catalyst and its preparation method and application.
Background technique
The intermolecular transfer of vinyl occurs for the vinyl acetate of vinyl interchange reaction, i.e., a kind of carboxylic acid and another carboxylic acid
Reaction.Reaction equation is as follows, wherein R1、R2Respectively different fat (ring) races or aromatic alkyl.
Industrially, vinyl interchange reaction is widely used in preparing vinyl carboxylates.Vinyl carboxylates are a kind of common
Industrial chemicals be often used as the monomer of synthetic organic polymer because of its active double bond structure, homopolymer or altogether
Polymers is widely used in the preparation of adhesive, coating, antirust agent etc., and wherein the vinyl acetate of unsaturated carboxylic acid may be additionally used for conduct
Crosslinking agent or preparation for photosensitive resin.
Vinyl interchange reaction must can be effectively performed under the catalytic action of catalyst.Compared with reporting
Catalyst for such vinyl interchange reaction is mainly mercury salt, such as mercuric sulfate.But due to mercury metal environmental pollution compared with
Greatly, and it is volatile, be difficult to administer, so such mercury catalyst is abandoned substantially.
Currently, the catalyst that be used to be catalyzed such vinyl interchange reaction is mainly palladium catalyst.Patent US318829
Report metal palladium catalyst PdCl2LiCl or PdCl2NaCl can effectively catalyze the hair of vinyl interchange reaction
It is raw.Patent US4425277 is reported in vinyl interchange reaction, using palladium acetate or palladium chloride as major catalyst, is added simultaneously
Lithium acetate and copper bromide are as co-catalyst.In vinyl interchange reaction, when with the palladiums inorganic salts such as palladium acetate or palladium chloride
When as major catalyst, often need that alkali metal ion, halide ion or copper ion (such as lithium chloride, lithium acetate, copper bromide is added
Equal compounds) it is used as co-catalyst, to improve the activity of palladium catalyst and the generation for slowing down palladium black as far as possible.Patent
The report such as US5214172, US5741925 and US0275852, palladium inorganic salts with double-tooth chelate ligand containing N (cough up by such as 1,10- neighbour's phenanthrene
Quinoline, 2, the derivative of 2 '-bipyridyls or both) generate complex when, such composition catalyst can effectively catalyze second
The generation of alkenyl exchange reaction, while the generation of palladium black is slowed down to a certain extent.
But in existing disclosed document, the palladium catalyst for vinyl interchange reaction is homogeneous catalyst, it should
Class catalyst is dissolved in reaction system, and catalyst is difficult to separate, recycle after the completion of reaction, it usually needs in high temperature, decompression item
Distillation or distillation operation are carried out under part to separate catalyst from reaction system.However, in high temperature, reduced pressure
Under, Pd (II) is easily reduced to Pd (0), and then is reunited and generated palladium black, causes catalyst inactivation, palladium after the recovery is caused to be urged in this way
Agent cannot continue directly to use in the reaction, substantially increase manufacturing cost.
In the prior art about silica gel load coordination palladium catalyst in catalysis Heck reaction, Suzuki reaction, iodobenzene
Carbonylation, phenol carbonylation etc. in application, there are mainly two types of the preparation methods of such catalyst: (1) table
Face Graft Method, also referred to as anchor titration；(2) cohydrolysis polymerization, also referred to as sol-gel method.The basic ideas of two kinds of preparation methods
It is by being chemically modified to silica gel structure, introducing in silica gel inorganic skeleton structure has the bis- containing N of good coordination ability
Tooth cheland (substituted pyridine-imines or pyridine-secondary amine), then combined by organic ligand with the coordination of palladium inorganic salts, it can
To be prepared using silica gel as carrier, load has the different-phase catalyst of coordination palladium.In such catalyst, palladium functional motif passes through
Chemistry is keyed in carrier silica gel, is not easy to be eluted, and shows good catalytic activity and catalytic stability.
James H.Clark seminar is urged by pyridine-imines-palladium out-phase that silica gel load has been prepared in anchor titration
(for the structure of the catalyst as shown in formula a, wherein R is H or methyl to agent；X is chloride ion or acetate ion), preparation side
Method specifically: (1) hydrolysis is occurred by the hydroxyl of Silica Surface and 3- aminopropyl trimethoxysilane, modification is prepared
There is-CH2-CH2-CH2-NH2The silica gel of organic group；(2) silica gel and 2- pyridine carboxaldehyde or 2- acetyl of aminopropyl will be modified with
Pyridine reaction, prepares silica gel-imines；(3) silica gel-imines is combined with palladium chloride or palladium acetate coordination, completes palladium on silica gel
Load.Such catalyst can effectively catalyze Heck reaction, Suzuki reaction, and show good catalytic activity and
Catalytic stability, it is ensured that 10 times or more repetitive cyclings use (Green Chemistry, 2000,2:53~55 Hes
Green Chemistry, 2001,3:23~25 and Green Chemistry, 2003,5:635~638).
Pyridine-secondary amine-palladium chloride of silica gel load has been prepared by sol-gel method for Pietro Moggi seminar
Catalyst (structure of the catalyst is as shown in formula b), preparation method specifically: (1) 2- acetylpyridine and three ethoxy of 3- aminopropyl
Base silane reaction prepares silane-imines；(2) pass through NaBH4It is silane-secondary amine by silane-imine reduction；(3) it is provided in ammonium hydroxide
Alkaline environment under, cohydrolysis reaction occurs for silane-imines and a certain proportion of tetraethyl orthosilicate, is prepared and has been modified with
The silica gel of machine group；(4) and PdCl2(PhCN)2Coordination combines, and finally obtains pyridine-secondary amine-chlorination palladium chtalyst of silica gel load
Agent.This loaded catalyst can efficiently be catalyzed the carbonylation of Heck reaction and iodobenzene, and the TON value of catalysis is respectively
4100mmol product/mmolPd and 2300mmol product/mmolPd (Journal of Molecular Catalysis A,
2002,182:61~72).
Li Guangxing seminar studies have shown that pyridine-secondary amine-palladium chloride catalyst of such silica gel load can be effectively
The carbonylation of catalysis of phenol, prepares diphenyl carbonate.Moreover, Cu is added into reaction system2O and tetrahydrofuran, can be with
Improve activity and stability (Appl.Organometal.Chem, 2006,20:656~662) of catalyst.
The preparation process of above-mentioned silica gel load coordination palladium catalyst, is all to prepare to have modified double-tooth chelate ligand containing N first
Silica gel, be then coordinated and combined by the metal center of organic ligand unit and palladium inorganic salts again, so that palladium functional unit be born
It is downloaded on silica gel.But after containing N double-tooth chelate ligand and being connected in carrier silica gel, no longer it is small molecule state, causes organic match
The more difficult abundant progress of complexation reaction of body unit and palladium inorganic salts.In order to complete this complexation process, often require to use excessive
Palladium inorganic salts and longer reaction time (typically larger than 24 hours) just can guarantee palladium inorganic salts and has been coupled to carrier silicon
Organic ligand on glue can be coordinated combination well.As a result cause in the preparation process of entire catalyst, the utilization rate of palladium
It is not high, the waste of palladium resource is caused to a certain extent.
Summary of the invention
For overcome the deficiencies in the prior art, an object of the present invention is to provide a kind of silica gel load coordination palladium catalyst
Preparation method；Method of the present invention is modified with the silica gel of organic ligand and then completes again with disclosed first prepare
The method of the coordination load of palladium is different, and method of the invention can effectively improve the utilization rate of palladium in catalyst preparation process,
And the load capacity of palladium can be efficiently controlled in a certain range.Specifically, the present invention passes through chemical grafting method,
In the inorganic skeleton structure of silica gel, the functional unit of coordination palladium is introduced to get the coordination palladium catalyst for arriving silica gel load.And it can
To construct the hole of different pore size size or regular texture by being selectively added suitable template, to improve load
The specific surface area and catalytic activity of type catalyst.Such loaded catalyst, Metal Palladium center is not easy to be eluted, and shows
Good catalytic activity and catalytic stability.
The second object of the present invention is to provide a kind of vinyl interchange reaction silica gel load coordination palladium catalyst, the catalysis
Agent is different-phase catalyst, is being catalyzed after reaction, can separated and recovered by simple filter operation, to reuse.
Specifically, the present invention is directed to solve urging in existing vinyl interchange reaction by being loaded to homogeneous palladium catalysts
The problems of agent.
The third object of the present invention is to provide a kind of application of silica gel load coordination palladium catalyst, is used to be catalyzed vinyl
The progress of exchange reaction, is especially used to prepare vinyl carboxylates.
The object of the invention can be achieved through the following technical solutions:
A kind of preparation method of silica gel load coordination palladium catalyst, described method includes following steps:
(1) double-tooth chelate ligand containing N of the functional group containing trialkoxy silane as shown in Formulas I or Formula II is prepared first；
Wherein, n is the integer of 2-6；R1Selected from alkyl；R2Selected from H, alkyl or derivatives thereof, aromatic radical or derivatives thereof；
R3And R4Five-membered ring, hexatomic ring or heptatomic ring with double bond can be formed, alkyl, alkenyl, alkynes can also be independently from each other
One of base, naphthenic base, aryl or two kinds；
(2) it a variety of is coordinated one of double-tooth chelate ligand containing N that step (1) is prepared or with palladium inorganic salts
Reaction generates palladium complex；
(3) palladium complex that step (2) is prepared is hydrolyzed with tetraalkyl orthosilicate and is reacted, generate the silicon
Glue load coordination palladium catalyst.
According to the present invention, in Formulas I or Formula II, it is preferable that R1Selected from alkyl；R2Selected from H, C1-6Alkyl, C6-14Aromatic radical；
R3And R4Five-membered ring, hexatomic ring or heptatomic ring with double bond can be formed, C can also be independently from each other1-6Alkyl, C2-6
Alkenyl, C2-6Alkynyl, C3-10Naphthenic base, C3-10Cycloalkenyl, C6-14One of aryl or two kinds.
It is highly preferred that R1Selected from methyl, ethyl；R2Selected from H, C1-6Alkyl, C6-14Aromatic radical；R3And R4It can form and have
Five-membered ring, hexatomic ring or the heptatomic ring of double bond.
It is further preferred that R1Selected from methyl, ethyl；R2Selected from H, methyl, ethyl, phenyl；R3And R4It can form with double bond
Five-membered ring or hexatomic ring.
It is more preferred still that R1Selected from methyl, ethyl；R2Selected from H, methyl, ethyl, phenyl；R3And R4Composition is with double bond
Hexatomic ring.
According to the present invention, in Formulas I or Formula II, it is preferable that n 3-5；It is further preferred that n is 3.
Most preferably, the ligand is as shown in Formulas I -1 or Formula II -1:
Wherein, R1And R2It is defined as described above.
According to the present invention, in step (1), ligand shown in Formulas I the preparation method comprises the following steps: by compound shown in formula III and formula IV
Compound represented is reacted, and ligand shown in Formulas I is prepared:
Wherein, n, R1、R2、R3And R4It is defined as described above.
Preferably, formula III compound represented is as shown in formula III -1, and compound is as shown in formula IV -1 shown in formula IV:
Wherein, R1、R2It is defined as described above.
According to the present invention, in step (1), ligand shown in Formula II the preparation method comprises the following steps: by formula III compound represented and formula
IV compound represented is reacted, and ligand shown in Formulas I is prepared；By ligand shown in the Formulas I being prepared, after reduction,
Ligand shown in Formula II is prepared.
According to the present invention, in step (2), the structural formula of the palladium complex is as shown in Formula V or Formula IV:
Wherein, n, R1、R2、R3And R4Defined as described above, X ' is acetate, chloride ion, bromide ion, iodide ion, nitric acid
Root or other anion.
Preferably, the palladium complex is as shown in Formula V -1 or Formula IV -1:
Wherein, R1、R2, X ' it is defined as described above.
According to the present invention, in step (2), the palladium inorganic salts are selected from palladium acetate, palladium chloride, palladium bromide, palladium iodide, nitre
One or more of sour palladium.Preferably one or more of palladium acetate or palladium chloride.
According to the present invention, in step (2), one of ligand shown in the Formulas I or Formula II or a variety of summations and palladium
The molar feed ratio of inorganic salts is 1:0.8~1.2, preferably 1:0.9~1.1, further preferably 1:1.
According to the present invention, in step (2), the complexation reaction carries out in organic solvent.Preferably, described organic
Solvent is selected from one of acetone, methanol, ethyl alcohol or a variety of.
According to the present invention, in step (2), the complexation reaction time is 0.5~5h, and reaction temperature is room temperature；It is preferred that
Ground, the complexation reaction time are 0.5~3h.
According to the present invention, in step (3), the tetraalkyl orthosilicate is preferably positive silicic acid tetraalkyl ester.
Preferably, the alkyl in the positive silicic acid tetraalkyl ester is selected from C1-6Alkyl.
Preferably, the positive silicic acid tetraalkyl ester is selected from positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four positive third
One of ester, positive isopropyl silicate are a variety of.
According to the present invention, in step (3), the molar feed ratio of the palladium complex and tetraalkyl orthosilicate is 1:1
~1:100, preferably 1:1~1:30, further preferably 1:1~1:20.
According to the present invention, in step (3), the progress at room temperature of the hydrolysis, the reaction time be 2~
48h, preferably 4~for 24 hours.
According to the present invention, in step (3), in the hydrolysis reaction, the pH of reaction system is 7~10, preferably 8
~9.
According to the present invention, in step (3), the pH adjusting agent is selected from one of triethylamine, ammonium hydroxide, sodium hydroxide
Or it is a variety of.
In the present invention, in step (3), pass through mole throwing of palladium complex in control hydrolytic process and tetraalkyl orthosilicate
Material can efficiently control the palladium load capacity in final gained loaded catalyst.Further, it is also possible to by using specific mould
Plate agent, to obtain the hole with certain pore size size or regular texture, to reach the specific surface for improving loaded catalyst
Long-pending and catalytic activity purpose.
The present invention also provides the silica gel loads being prepared using the above method to be coordinated palladium catalyst, structural formula such as formula
Shown in VII or Formula VIII:
Wherein, n, R2、R3、R4And X ' is defined as described above；
The mass percent that Metal Palladium accounts for prepared silica gel load coordination palladium catalyst in the palladium catalyst is 0.05
~20wt%.
Most preferably, the catalyst such as Formula VII -1, shown in Formula VIII -1:
Wherein, R2And X ' is defined as described above.
In the present invention, the preparation method of the silica gel load coordination palladium catalyst, firstly, by palladium inorganic salts and having three alkane
The organic ligand containing N (ligand shown in Formulas I or Formula II) of oxysilane functional group is coordinated according to molar ratio and generates palladium cooperation
Object.The complexation reaction is very easy to carry out, and almost fully reacting, this ensure that in the preparation of loaded catalyst
Cheng Zhong, palladium have high utilization rate.Then, then pass through the siloxy group in preparation-obtained palladium complex molecular structure
(hydrolysis occurs for positive quanmethyl silicate or (and) tetraethyl orthosilicate), generates silica gel structure, in turn with tetraalkyl orthosilicate
Silica gel load coordination palladium catalyst is prepared.In the hydrolysis, can by control participate in reaction palladium complex and
The molar ratio of silicon source controls the load capacity of palladium in gained loaded catalyst in a certain range.
The present invention also provides the applications of the coordination palladium catalyst of silica gel load shown in Formula VII, can be applied to catalysis ethylene
Base exchange reaction；
Wherein, n, R2、R3、R4And X ' is defined as described above.
Preferably, applied to the preparation of vinyl carboxylates.
The present invention further provides the applications of the coordination palladium catalyst of silica gel load shown in Formula VII, can be applied to be catalyzed
The synthesis of vinethene；
Wherein, n, R2、R3、R4And X ' is defined as described above.
Invention further provides a kind of preparation method of vinyl carboxylates, it is included in silica gel load shown in Formula VII
It is coordinated under palladium catalyst catalysis, starting carboxylic acid and starting carboxylic acid's vinyl acetate is made to carry out vinyl interchange reaction；
Wherein, n, R2、R3、R4And X ' is defined as described above.
According to the present invention, the starting carboxylic acid is selected from propionic acid, acrylic acid, butyric acid, isobutyric acid, positive valeric acid, 2- methyl fourth
Acid, 3 Methylbutanoic acid, pivalic acid, positive enanthic acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, caprylic acid, pelargonic acid, new n-nonanoic acid, the positive last of the ten Heavenly stems
The fat such as acid, 2- propylheptanoic acid, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitinic acid, stearic acid or benzoic acid, naphthoic acid
(ring) one of race or aromatic carboxylic acid is a variety of.
According to the present invention, starting carboxylic acid's vinyl acetate be selected from acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, positive valeric acid,
2-Methyl Butyric Acid, 3 Methylbutanoic acid, pivalic acid, positive enanthic acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, caprylic acid, pelargonic acid, new nonyl
Acid, n-capric acid, 2- propylheptanoic acid, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitinic acid, stearic acid or benzoic acid, naphthoic acid
The vinyl acetate of equal fat (ring) race or aromatic carboxylic acid, preferably vinylacetate.
According to the present invention, the molar feed ratio of the vinyl interchange reaction starting carboxylic acid and starting carboxylic acid's vinyl acetate is 1:
0.1~30, preferably 1:0.3~15.
According to the present invention, the vinyl interchange reaction temperature is 40~120 DEG C, preferably 60~100 DEG C, when reaction
Between be 5~35h, preferably 10~30h；Reaction pressure can be normal pressure, high pressure or negative pressure.
According to the present invention, after the vinyl interchange reaction, cooling, filtering, recycling catalyst, then pass through steaming
It evaporates, the operations such as rectifying separate unreacted raw material, product vinyl carboxylate and product carboxylic acid.
Beneficial effects of the present invention:
1. the present invention provides a kind of preparation method of silica gel load palladium catalyst, the preparation method is easy to carry out, reaction
Completely, Metal Palladium utilization rate is high；It is controlled, can be controlled in a certain range prepared by the feed ratio to reaction raw materials
Silica gel supported palladium catalyst in Metal Palladium load capacity.
2. the catalyst is a kind of silicon the present invention also provides a kind of vinyl interchange reaction silica gel load palladium catalyst
The different-phase catalyst of glue load, and palladium functional unit is connected by chemical bond with carrier silica gel, is not easy to be eluted.It is in ethylene
After base exchange reaction, the separation and recovery of catalyst can be completed, to reuse by simple filter operation.
3. the present invention furthermore provides a kind of application of silica gel load palladium catalyst, vinyl can effectively catalyze
Exchange reaction is used to prepare vinyl carboxylates.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of ligand shown in the preparation-obtained Formulas I -1 of embodiment 1.
Fig. 2 is the infrared spectrogram of ligand shown in the preparation-obtained Formula II -1 of embodiment 2.
Fig. 3 is the infrared spectrogram of palladium complex shown in the preparation-obtained Formula V -1 of embodiment 3.
Fig. 4 is the photoelectron spectroscopy figure of palladium catalyst shown in the preparation-obtained Formula VII -1 of embodiment 5.
Fig. 5 is the infrared spectrogram of palladium complex shown in the preparation-obtained Formula IV -1 of embodiment 7.
Specific embodiment
In a preferred embodiment of the present invention, the present invention provides a kind of preparation of silica gel load coordination palladium catalyst
Method, the preparation method include the following steps:
(1) ligand shown in preparation formula I-1 first and/or Formula II -1；
(2) one of ligand shown in the Formulas I -1 and/or Formula II -1 that step (1) is prepared or a variety of inorganic with palladium
Salt carries out complexation reaction, palladium complex shown in production V-1 and/or VI-1；
(3) palladium complex shown in the Formula V -1 and/or VI-1 step (2) being prepared and tetraalkyl orthosilicate carry out
Hydrolysis generates silica gel structure, that is, the silica gel load coordination palladium catalyst is prepared.
In a preferred embodiment of the present invention, in the preparation process of the ligand shown in Formulas I -1, the formula III -1
With the molar feed ratio of compound shown in formula IV -1 be 0.5~2:1, preferably 0.8~1.5:1, further preferably 0.9~
1.2:1.The reaction time is related to reaction temperature, and preferably reaction temperature is 25~50 DEG C, and the reaction time is 5~7d；Or
Person's reaction temperature is 50~80 DEG C, and the reaction time is 20~30h, is entirely to react ending standard with raw material fundamental reaction.It is described
It being carried out under the conditions of reaction is existing for the organic solvent and molecular sieve, it is preferable that the organic solvent is ethyl alcohol, toluene, described point
Son sievesMolecular sieve.
In a preferred embodiment of the present invention, the ligand shown in Formulas I -1 is reduced to the system of ligand shown in Formula II -1
During standby, ligand shown in the Formulas I -1 and NaBH4Molar feed ratio be 1:1~4.The reaction temperature be 20~
60 DEG C, the reaction time is 0.5~3h.The reaction carries out in except aqueous organic solvent, preferably except water methanol, except water-ethanol.
Remaining NaBH in the reaction4After being removed with water, reaction solution is extracted with organic solvent, organic solvent is preferably dichloro
It is a kind of in methane, chloroform or toluene.
In a preferred embodiment of the present invention, the preparation side of the catalyst of a kind of silica gel load coordination palladium
Method specifically comprises the following steps:
(1) ligand shown in preparation formula I-1 and Formula II -1
Ligand shown in preparation formula I-1: by 3- aminopropyl trimethoxysilane or 3- aminopropyl triethoxysilane, with 2-
It is 0.5~2 that pyridine carboxaldehyde or 2- acetylpyridine or the acyl pyridine class compound of any two substitutions, which press molar feed ratio:
1 is dissolved in organic solvent, in ethyl alcohol, toluene, and is added a certain amount ofMolecular sieve, at 25~100 DEG C, reaction to raw material
Fundamental reaction is complete.Then evaporated under reduced pressure solvent obtains viscous shape, brown liquid, that is, ligand shown in the Formulas I -1 is prepared.
Ligand shown in preparation formula II-1: by molar feed ratio be 1:1~4 Formulas I -1 shown in ligand and NaBH4It is dissolved in water removal
Organic solvent (for example, except water methanol or remove water-ethanol), at a temperature of 20~60 DEG C, 0.5~3h is reacted, until Formulas I -1
Shown ligand reaction is complete.It is then cooled to which room temperature, is added a certain amount of water and reacts remaining NaBH4.Again with methylene chloride,
The organic solvents such as chloroform or toluene extract reaction solution, the dry organic phase of anhydrous sodium sulfate, and evaporated under reduced pressure solvent obtains brown
Ligand shown in the Formula II -1 is prepared in thick liquid.
(2) palladium complex shown in preparation formula V-1 or Formula IV -1
By ligand shown in gained Formulas I -1 or Formula II -1 and palladium inorganic salts, such as palladium acetate, palladium chloride, palladium nitrate, by close
The molar ratio of 1:1 is dissolved in a certain amount of organic solvent, in acetone, methanol, ethyl alcohol or its mixed liquor, stirs at room temperature,
Then quickly there is muddiness in clarification when reaction solution starts, continue 0.5~3h of stir about, obtain palladium shown in Formula V -1 or Formula IV -1 and match
Close object.
(3) silica gel load coordination palladium catalyst is prepared
In the case where being stirred at room temperature, in the turbid solution of palladium complex shown in Xiang Shangshu Formula V -1 or Formula IV -1, it is added certain
The positive quanmethyl silicate of ratio or (and) tetraethyl orthosilicate, palladium complex and positive quanmethyl silicate or (and) tetraethyl orthosilicate
Molar ratio be 1:1~20, a certain amount of water is then added, reaction solution becomes clarifying again, adds a certain amount of three second
Amine or ammonium hydroxide, the pH value for adjusting reaction system is 8~9.Continue stirring 4~for 24 hours at room temperature, reaction solution is gradually become by clarifying
It is muddy.It is then allowed to stand, until there is gel generation, filtering, solvent washing, 60~80 DEG C of vacuum drying obtain solid powder.Gained
Product is the coordination palladium catalyst of silica gel load shown in Formula VII -1 or Formula VIII -1.
In a preferred embodiment of the present invention, the synthesis of the catalyst is carried out according to following reaction equations:
In a preferred embodiment of the present invention, the synthesis of the catalyst is carried out according to following reaction equations:
The embodiment of the present invention is raw materials used: 2- acetylpyridine, 3- aminopropyl triethoxysilane, tetraethyl orthosilicate, vinegar
Sour palladium is market purchasing, and benzoic acid, neodecanoic acid and vinylacetate are all technical grade.
During catalysis vinyl interchange reaction prepares vinyl carboxylates, terminated by gas chromatography measurement reaction
The mass concentration of product vinyl carboxylate afterwards.
Wherein, GC conditions are as follows: GC9790 type gas chromatograph, flame ionization ditector, capillary chromatograph
For FFAP type 30m × 0.32mm × 0.5 μm.
The detection method of Pd mass fraction in catalyst: plasma emlssion spectrometry.
Wherein, testing conditions are as follows: Ultima2 type plasma emission spectrometer, incident power 1kW, carrier gas flux 0.98L/
min。
The yield of product vinyl carboxylate is calculated as follows in embodiment: wherein the amount of the substance of starting carboxylic acid is according to reaction
In the Mass Calculation of input starting carboxylic acid obtain；The amount of the substance of product vinyl carboxylate is according to after reaction, product
The mass concentration of vinyl carboxylates is calculated.
Embodiment 1
The preparation of ligand shown in Formulas I -1, wherein R1For ethyl, R2For methyl
The 2- acetylpyridine of the 3- aminopropyl triethoxysilane of 2.11g (10mmoL) and 1.21g (10mmoL) is dissolved in
About 25mL's removes in alcoholic solvent, and is added a certain amount ofMolecular sieve, in the case where nitrogen protection, 70 DEG C of reflux are about
For 24 hours, until reactant fundamental reaction is complete.Then solvent is removed under reduced pressure, obtains brown and glues shape liquid.
It reacts schematically as follows:
The structure confirmation datas such as the nuclear-magnetism of the compound, infrared are as follows:
1H NMR (300MHz, CDCl3): δ=0.76-0.80 (t, 2H), 1.24 (t, 9H), 1.87-1.91 (m, 2H),
2.36(s,3H),3.52(t,2H),3.85(q,6H),7.27(t,1H),7.67-7.71(t,1H),8.07(d,1H),8.58
(d,1H)。
Fig. 1 is the infrared spectrogram of ligand shown in the preparation-obtained Formulas I -1 of embodiment 1.
Wherein, FT-IR (KBr, cm-1): 3052cm-1Place is pyridine ring C-H absorption peak；2972cm-1、2925cm-1、
2884cm-1Place is alkyl C-H absorption peak；1640cm-1Place is C=N double bond absorption peak in imines；1585cm-1、1565cm-1Place is
Pyridine ring bending vibration absorption peak；1103cm-1、1079cm-1Place is Si-O-C absorption peak in silicon ethyoxyl；And raw material 2- second
1699cm in acyl pyridine-1Locate C=O double bond absorption peak to disappear.Embodiment 2
The preparation of ligand shown in Formula II -1, wherein R1For ethyl, R2For methyl
By ligand shown in Formulas I -1 prepared in 1.62g (5mmoL) embodiment 1 be dissolved in about 20mL except in water methanol, room
20mL is added dropwise under temperature thereto dissolved with 0.38gNaBH4The water removal methanol solution of (10mmoL), then 40 DEG C of reaction about 1h, until former
Expect fully reacting.It is cooled to room temperature, about 10mL water is added and reacts away remaining NaBH4, then the methylene chloride of about 20mL is used respectively
Solvent extraction 3 times, the dry organic phase of anhydrous sodium sulfate, then evaporated under reduced pressure solvent, obtains brown viscous liquid.
Reaction process is schematically as follows:
The infrared structure confirmation data of the compound are as follows:
Fig. 2 is the infrared spectrogram of ligand shown in the preparation-obtained Formula II -1 of embodiment 2.
Wherein, FT-IR (KBr, cm-1): 3050cm-1Place is pyridine ring C-H absorption peak；2966cm-1、2926cm-1、
2864cm-1Place is alkyl C-H absorption peak；1590cm-1、1570cm-1Place is pyridine ring bending vibration absorption peak；1050~
1120cm-1Place is Si-O-C absorption peak in silicon ethyoxyl；And 1640cm in ligand shown in starting materials of formulae I-1-1Locate C=N double bond to absorb
Peak disappears.
Embodiment 3
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula V -1 is 1:2 with silicon source molar ratio)
Ligand shown in Formulas I -1 prepared in 1.62g (5mmoL) embodiment 1 and 1.12g (5mmoL) palladium acetate are dissolved in
In the acetone solvent of about 40mL, stir about 1h, clarification when reaction solution starts, then gradually appear muddiness at room temperature, finally have big
Amount precipitating generates.Generate palladium complex shown in the Formula V -1 that precipitating is the generation of ligand shown in palladium acetate and Formulas I -1.
The infrared structure confirmation data of the compound are as follows:
Fig. 3 is the infrared spectrogram of palladium complex shown in the preparation-obtained Formula V -1 of embodiment 3.
Wherein, FT-IR (KBr, cm-1): 2976cm-1、2930cm-1Place is C-H absorption peak in alkyl；1594cm-1Place is vinegar
C=O double bond absorption peak in acid group；1050~1100cm-1Place is Si-O-C absorption peak in silicon ethyoxyl.
Then the tetraethyl orthosilicate of 2.08g (10mmoL) is added into reaction solution, continues stir about 10 minutes, adds
The water of about 100mL, reaction solution become clarifying again.Then triethylamine is added dropwise into reaction solution, until pH is 8~9.At room temperature, fastly
Speed is stirred to react about 6h, a large amount of muddinesses occurs, stands until there is gel generation.Filtering, acetone solvent washing, 60 DEG C of vacuum drying
Overnight, yellow solid powder is obtained.Products therefrom is palladium catalyst shown in Formula VII -1.
Reaction process is schematically as follows:
Pd mass percentage content is 15.92% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 4
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula V -1 is 1:4 with silicon source molar ratio)
It is similar to Example 3, only the dosage of tetraethyl orthosilicate is changed to 4.16g (20mmoL) positive silicic acid tetrem is added
Ester, subsequent aqueous solvent dosage are 120mL.Final products therefrom is still yellow solid powder.
Pd mass percentage content is 11.94% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 5
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula V -1 is 1:6 with silicon source molar ratio)
Similar to Example 3, the dosage for only improving tetraethyl orthosilicate is changed to that 6.24g (30mmoL) positive silicic acid four is added
Ethyl ester, subsequent aqueous solvent dosage are 140mL.Final products therefrom is still yellow solid powder.
Pd mass percentage content is 8.85% in using plasma emission spectrographic determination prepared catalyst.
Fig. 4 is the photoelectron spectroscopy figure of palladium catalyst shown in the preparation-obtained Formula VII -1 of embodiment 5.Wherein, C1sFor
284.7eV；N1sFor 399.5eV；Pd3dFor 337.7eV.
Embodiment 6
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula V -1 is 1:8 with silicon source molar ratio)
Similar to Example 3, the dosage for only improving tetraethyl orthosilicate is changed to that 8.32g (40mmoL) positive silicic acid four is added
Ethyl ester, subsequent aqueous solvent dosage are 160mL.Final products therefrom is still yellow solid powder.
Pd mass percentage content is 6.84% in using plasma emission spectrographic determination prepared catalyst.
The data obtained in above-described embodiment 3~6 is analyzed, is listed in Table 1 below.
The performance parameter of palladium catalyst shown in 1 embodiment 3~6 of table
It is found that it can be by the molar ratio of palladium complex and silicon source shown in control Formula V -1, to control as the data obtained
The content of Pd in loaded catalyst is obtained, and in the preparation process of entire catalyst, the utilization rate of Pd is greater than 85%.
Embodiment 7
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula IV -1 is 1:2 with silicon source molar ratio)
Ligand shown in Formula II -1 prepared in 1.62g (5mmoL) embodiment 2 and 1.12g (5mmoL) palladium acetate is molten
In the acetone solvent of about 40mL, at room temperature then stir about 1h, clarification when reaction solution starts gradually appear muddiness, finally have
A large amount of precipitatings generate.Generating precipitating is shown in the Formula IV -1 of ligand generation shown in palladium acetate and prepared Formula II -1
Complex.
The infrared structure confirmation data of the compound are as follows:
Fig. 5 is the infrared spectrogram of palladium complex shown in the preparation-obtained Formula IV -1 of embodiment 7.
Wherein, FT-IR (KBr, cm-1): 2926cm-1Place is C-H absorption peak in alkyl；1587cm-1Place is C in acetate
=O double bond absorption peak；1125cm-1Place is Si-O-C absorption peak in silicon ethyoxyl.
Then the tetraethyl orthosilicate of 2.08g (10mmoL) is added into reaction solution, continues stir about 10 minutes, adds
The water of about 100mL, reaction solution become clarifying again.Then triethylamine is added dropwise into reaction solution, until pH is 8~9.At room temperature, fastly
Speed is stirred to react about 6h, a large amount of muddinesses occurs, stands until there is gel generation.Filtering, acetone solvent washing, 60 DEG C of vacuum drying
Overnight, khaki solid powder is obtained.Products therefrom is palladium catalyst shown in Formula VIII -1.
Reaction process is schematically as follows:
Pd mass percentage content is 16.15% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 8
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula IV -1 is 1:4 with silicon source molar ratio)
Similar to Example 7, the dosage for only improving tetraethyl orthosilicate is changed to that 4.16g (20mmoL) positive silicic acid four is added
Ethyl ester, subsequent aqueous solvent dosage are 120mL.Final products therefrom is still khaki solid powder.
Pd mass percentage content is 12.06% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 9
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula IV -1 is 1:6 with silicon source molar ratio)
Similar to Example 7, the dosage for only improving tetraethyl orthosilicate is changed to that 6.24g (30mmoL) positive silicic acid four is added
Ethyl ester, subsequent aqueous solvent dosage are 140mL.Final products therefrom is still khaki solid powder.
Pd mass percentage content is 8.46% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 10
The preparation of the palladium catalyst of silica gel load (palladium complex shown in Formula IV -1 is 1:8 with silicon source molar ratio)
Similar to Example 7, the dosage for only improving tetraethyl orthosilicate is changed to that 8.32g (40mmoL) positive silicic acid four is added
Ethyl ester, subsequent aqueous solvent dosage are 160mL.Final products therefrom is still khaki solid powder.
Pd mass percentage content is 6.69% in using plasma emission spectrographic determination prepared catalyst.
The data obtained in above-described embodiment 7~10 is analyzed, is listed in Table 2 below.
The performance parameter of palladium catalyst shown in 2 embodiment 7~10 of table
It is found that it can be by the molar ratio of palladium complex and silicon source shown in control Formula IV -1, to control as the data obtained
The content of Pd in gained loaded catalyst, and in the preparation process of entire catalyst, the utilization rate of Pd is greater than 85%.
Embodiment 11
Silica gel load coordination palladium catalyst (shown in Formula VII -1) catalysis prepares vinyl benzoate
The formula that benzoic acid 4.88g (0.04moL), vinylacetate 17.22g (0.2moL) and embodiment 5 are prepared
Palladium catalyst 0.50g shown in VII-1 is placed in the three-necked flask of 100mL, and flow back about 20h at 70 DEG C.It is subsequently cooled to room
Temperature, filtering, recycling catalyst.Weigh filtrate weight, and in gas Chromatographic Determination filtrate vinyl benzoate mass concentration.
It reacts schematically as follows:
Resulting silica gel load coordination palladium catalyst will be recycled, is placed in the three-necked flask of 100mL, is added as described above
Benzoic acid, the vinylacetate of amount repeat above-mentioned vinyl interchange reaction.So repeat coreaction 3 times.
The quality of reaction solution after separating catalyst, and the concentration of gas Chromatographic Determination vinyl benzoate are weighed, is calculated
It obtains in 3 secondary responses, vinyl benzoate yield is respectively 64.77%, 63.02%, 61.55%.Data used are as follows:
| Number | Vinyl benzoate mass concentration | Reaction solution gross mass | Vinyl benzoate yield |
| For the first time | 18.27% | 21.01g | 64.77% |
| Second | 17.87% | 20.90g | 63.02% |
| For the third time | 17.19% | 21.22g | 61.55% |
Embodiment 12
Silica gel load coordination palladium catalyst (shown in Formula VII -1) catalysis prepares vinyl neodecanoate
Neodecanoic acid 6.89g (0.04moL), vinylacetate 17.22g (0.2moL) and embodiment 5 is preparation-obtained
Palladium catalyst 0.50g shown in Formula VII -1 (is placed in the three-necked flask of 100mL, flow back about 20h at 70 DEG C.It is subsequently cooled to
Room temperature, filtering, recycling catalyst.Weigh filtrate weight, and in gas Chromatographic Determination filtrate vinyl neodecanoate quality it is dense
Degree.
It reacts schematically as follows:
Wherein R1、R2For saturated alkyl, R1+R2The total number of carbon atoms be 7.
Resulting silica gel load coordination palladium catalyst will be recycled, is placed in the three-necked flask of 100mL, is added as described above
Neodecanoic acid, the vinylacetate of amount repeat above-mentioned vinyl interchange reaction.So repeat coreaction 3 times.
The quality of reaction solution after separating catalyst, and the concentration of gas Chromatographic Determination vinyl neodecanoate are weighed, is calculated
It obtains in 3 secondary responses, vinyl neodecanoate yield is respectively 60.76%, 57.62%, 56.93%.Data used are as follows:
| Number | Vinyl neodecanoate mass concentration | Reaction solution gross mass | Vinyl neodecanoate yield |
| For the first time | 21.12% | 22.82g | 60.76% |
| Second | 20.09% | 22.75g | 57.62% |
| For the third time | 19.83% | 22.77g | 56.93% |
Comparative example 1
Silica gel load coordination palladium catalyst (shown in Formula VIII -1) catalysis prepares vinyl benzoate
The formula that benzoic acid 4.88g (0.04moL), vinylacetate 17.22g (0.2moL) and embodiment 9 are prepared
Palladium catalyst 0.50g shown in VIII-1 is placed in the three-necked flask of 100mL, and flow back about 20h at 70 DEG C.
As a result a small amount of vinyl benzoate generates.Catalyst is recovered by filtration, gained palladium catalyst is in aterrimus, may
It is that Pd (II) in former loaded catalyst has at least partially been reduced to caused by Pd (0).Since secondary amine group itself has
There is certain reducing power, this may accelerate the reduction that Pd (II) arrives Pd (0).
The above result shows that such palladium catalyst as shown in Formula VIII -1 is not suitable for catalysis second under the reaction conditions
Alkenyl exchange reaction.But the reaction for thering is the such palladium catalyst of document report to be more suitable for Pd (0) for catalytic active center, such as
Heck reaction, Suzuki reaction etc..
The foregoing is only a preferred embodiment of the present invention, the scope of protection of the present invention is not limited to this, it is any ripe
Know those skilled in the art within the technical scope of the present disclosure, the letter for the technical solution that can be become apparent to
Altered or equivalence replacement are fallen within the protection scope of the present invention.
Claims (24)
1. a kind of preparation method of vinyl carboxylates, which is characterized in that the preparation method is that the silica gel shown in Formula VII -1 is negative
Under the catalysis for carrying coordination palladium catalyst, starting carboxylic acid and starting carboxylic acid's vinyl acetate is made to carry out vinyl interchange reaction；
The structural formula of the catalyst is as shown in Formula VII -1:
Wherein, R2Selected from one of H, alkyl or derivatives thereof, aromatic radical or derivatives thereof；X ' is acetate, chloride ion, bromine
Ion, iodide ion or nitrate anion；
The preparation method of the catalyst includes the following steps:
(1) double-tooth chelate ligand containing N of the functional group containing trialkoxy silane as shown in Formulas I -1 is prepared first；
Wherein, R1Selected from methyl or ethyl；R2Selected from one of H, alkyl or derivatives thereof, aromatic radical or derivatives thereof；
Wherein, the method for ligand shown in preparation formula I-1 includes:
By 3- aminopropyl trimethoxysilane perhaps 3- aminopropyl triethoxysilane and 2- pyridine carboxaldehyde or 2- acetylpyridine
Or the acyl pyridine class compound of any two substitutions is that 0.5~2:1 is dissolved in the organic solvent of water removal by molar feed ratio,
And it is added a certain amount ofMolecular sieve reacts complete to raw material fundamental reaction, then evaporated under reduced pressure is molten at 25~100 DEG C
Agent obtains viscous shape, brown liquid, that is, ligand shown in the Formulas I -1 is prepared；
(2) by one of double-tooth chelate ligand containing N that step (1) is prepared or it is a variety of with palladium inorganic salts be coordinated it is anti-
It answers, generates palladium complex；
(3) palladium complex that step (2) is prepared is hydrolyzed with tetraalkyl orthosilicate and is reacted, it is negative to generate the silica gel
Carry coordination palladium catalyst.
2. preparation method according to claim 1, which is characterized in that R1Selected from methyl or ethyl；R2Selected from H, C1-6Alkyl,
C6-14One of aromatic radical.
3. preparation method according to claim 2, which is characterized in that R1Selected from methyl or ethyl；R2Selected from H, methyl, second
One of base, phenyl.
4. preparation method according to claim 1, which is characterized in that the starting carboxylic acid is selected from propionic acid, acrylic acid, fourth
Acid, isobutyric acid, positive valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, pivalic acid, positive enanthic acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, just
Octanoic acid, pelargonic acid, new n-nonanoic acid, n-capric acid, 2- propylheptanoic acid, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitinic acid, stearic acid,
One of benzoic acid, naphthoic acid are a variety of.
5. preparation method according to claim 1, which is characterized in that starting carboxylic acid's vinyl acetate be selected from acetic acid, propionic acid,
Acrylic acid, butyric acid, isobutyric acid, positive valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, pivalic acid, positive enanthic acid, 2 methyl caproic acid, 2- second
Base caproic acid, caprylic acid, pelargonic acid, new n-nonanoic acid, n-capric acid, 2- propylheptanoic acid, neodecanoic acid, dodecanoic acid, tridecanoic acid, palm
One of vinyl acetate of acid, stearic acid, benzoic acid, naphthoic acid is a variety of.
6. preparation method according to claim 1, which is characterized in that the vinyl interchange reaction starting carboxylic acid and raw material
The molar feed ratio of vinyl carboxylates is 1:0.1~30.
7. preparation method according to claim 1, which is characterized in that the vinyl interchange reaction temperature is 40~120
DEG C, the reaction time is 5~35h；Reaction pressure is normal pressure, high pressure or negative pressure.
8. preparation method according to claim 1, which is characterized in that the vinyl after reaction, cooling, filtering,
Catalyst is recycled, then unreacted raw material, product vinyl carboxylate and product carboxylic acid are separated by the operation of distillation, rectifying.
9. a kind of preparation method of silica gel load coordination palladium catalyst, which is characterized in that described method includes following steps:
(1) double-tooth chelate ligand containing N of the functional group containing trialkoxy silane as shown in Formulas I -1 or Formula II -1 is prepared first；
Wherein, R1Selected from one of methyl, ethyl；R2One in H, alkyl or derivatives thereof, aromatic radical or derivatives thereof
Kind；
Wherein, the method for ligand shown in preparation formula I-1 includes:
By 3- aminopropyl trimethoxysilane perhaps 3- aminopropyl triethoxysilane and 2- pyridine carboxaldehyde or 2- acetylpyridine
Or the acyl pyridine class compound of any two substitutions is that 0.5~2:1 is dissolved in the organic solvent of water removal by molar feed ratio,
And it is added a certain amount ofMolecular sieve reacts complete to raw material fundamental reaction, then evaporated under reduced pressure is molten at 25~100 DEG C
Agent obtains viscous shape, brown liquid, that is, ligand shown in the Formulas I -1 is prepared；
The method of ligand shown in preparation formula II-1 includes:
By ligand and NaBH shown in Formulas I -1 of the molar feed ratio for 1:1~44It is dissolved in the organic solvent of water removal, in 20~60 DEG C of temperature
Under degree, 0.5~3h is reacted, until ligand reaction shown in Formulas I -1 is complete；It is then cooled to which room temperature, is added a certain amount of water reaction
Remaining NaBH4；Reaction solution, the dry organic phase of anhydrous sodium sulfate are extracted with organic solvent again, it is viscous to obtain brown for evaporated under reduced pressure solvent
Ligand shown in the Formula II -1 is prepared in thick liquid；
(2) by one of double-tooth chelate ligand containing N that step (1) is prepared or it is a variety of with palladium inorganic salts be coordinated it is anti-
It answers, generates palladium complex；
(3) palladium complex that step (2) is prepared is hydrolyzed with tetraalkyl orthosilicate and is reacted, it is negative to generate the silica gel
Carry coordination palladium catalyst.
10. preparation method according to claim 9, which is characterized in that in Formulas I -1 or Formula II -1, R1Selected from methyl, second
One of base；R2Selected from H, C1-6Alkyl, C6-14One of aromatic radical.
11. preparation method according to claim 10, which is characterized in that R1Selected from one of methyl, ethyl；R2It is selected from
H, one of methyl, ethyl, phenyl.
12. preparation method according to claim 9, which is characterized in that in step (2), the palladium complex such as formula
Shown in V-1 or Formula IV -1:
Wherein, R1Selected from one of methyl, ethyl；R2One in H, alkyl or derivatives thereof, aromatic radical or derivatives thereof
Kind, X ' is acetate, chloride ion, bromide ion, iodide ion or nitrate anion.
13. preparation method according to claim 9, which is characterized in that in step (2), the palladium inorganic salts are selected from vinegar
One or more of sour palladium, palladium chloride, palladium bromide, palladium iodide, palladium nitrate.
14. preparation method according to claim 9, which is characterized in that in step (2), -1 institute of the Formulas I -1 or Formula II
The molar feed ratio for showing ligand and palladium inorganic salts is 1:0.8~1.2.
15. preparation method according to claim 9, which is characterized in that in step (2), the complexation reaction is organic
It is carried out in solvent；The organic solvent is selected from one of acetone, methanol, ethyl alcohol or a variety of.
16. preparation method according to claim 9, which is characterized in that in step (2), the complexation reaction time is
0.5~5h, reaction temperature are room temperature.
17. preparation method according to claim 9, which is characterized in that in step (3), the tetraalkyl orthosilicate
Be positive silicic acid tetraalkyl ester, and the Arrcostab in the positive silicic acid tetraalkyl ester is selected from C1-6Alkyl.
18. preparation method according to claim 17, which is characterized in that the positive silicic acid tetraalkyl ester is selected from positive silicic acid four
One of methyl esters, tetraethyl orthosilicate, four n-propyl of positive silicic acid, positive isopropyl silicate are a variety of.
19. preparation method according to claim 9, which is characterized in that in step (3), the palladium complex with just
The molar feed ratio of alkyl silicate is 1:1~1:100.
20. preparation method according to claim 9, which is characterized in that in step (3), the hydrolysis is in room temperature
Lower progress, the reaction time are 2~48h.
21. preparation method according to claim 9, which is characterized in that in step (3), in the hydrolysis reaction,
The pH of reaction system is 7~10.
22. preparation method according to claim 21, which is characterized in that in step (3), use triethylamine, ammonium hydroxide, hydrogen
One of sodium oxide molybdena or a variety of pH for adjusting reaction system.
23. according to preparation method described in any one of claim 9-22 claim, which is characterized in that the method preparation
Obtained silica gel load coordination palladium catalyst is as shown in Formula VII -1 or Formula VIII -1:
Wherein, R2It is acetate, chloride ion, bromine selected from one of H, alkyl or derivatives thereof, aromatic radical or derivatives thereof, X '
Ion, iodide ion or nitrate anion.
24. the preparation method according to any one of claim 9-22, which is characterized in that the preparation method is specific to wrap
Include following steps:
(1) ligand shown in preparation formula I-1 and Formula II -1
Ligand shown in preparation formula I-1: by 3- aminopropyl trimethoxysilane or 3- aminopropyl triethoxysilane, with 2- pyridine
Formaldehyde or 2- acetylpyridine or the acyl pyridine class compound of any two substitutions are molten for 0.5~2:1 by molar feed ratio
In the organic solvent of water removal, and it is added a certain amount ofMolecular sieve reacts complete to raw material fundamental reaction at 25~100 DEG C
Entirely；Then evaporated under reduced pressure solvent obtains viscous shape, brown liquid, that is, ligand shown in the Formulas I -1 is prepared；
Ligand shown in preparation formula II-1: by molar feed ratio be 1:1~4 Formulas I -1 shown in ligand and NaBH4Be dissolved in water removal has
Solvent reacts 0.5~3h at a temperature of 20~60 DEG C, until ligand reaction shown in Formulas I -1 is complete；It is then cooled to room
Temperature is added a certain amount of water and reacts remaining NaBH4；Methylene chloride, chloroform or Toluene extractive reaction liquid are used again, it is anhydrous
Sodium sulphate dries organic phase, and evaporated under reduced pressure solvent obtains brown viscous liquid, that is, ligand shown in the Formula II -1 is prepared；
(2) palladium complex shown in preparation formula V-1 or Formula IV -1
By gained Formulas I -1 or Formula II -1 and palladium inorganic salts, it is dissolved in a certain amount of organic solvent by the molar ratio of 1:1, room temperature
Then quickly there is muddiness, continue 0.5~3h of stirring, obtain -1 institute of Formula V -1 or Formula IV in lower stirring, clarification when reaction solution starts
Show palladium complex；
(3) silica gel load coordination palladium catalyst is prepared
In the case where being stirred at room temperature, in the turbid solution of palladium complex shown in Xiang Shangshu Formula V -1 or Formula IV -1, certain proportion is added
Positive quanmethyl silicate or/and tetraethyl orthosilicate, mole of palladium complex and positive quanmethyl silicate or/and tetraethyl orthosilicate
Ratio be 1:1~20, a certain amount of water is then added, reaction solution becomes clarifying again, add a certain amount of triethylamine or
Ammonium hydroxide, the pH value for adjusting reaction system is 8~9；Continue stirring 4~for 24 hours at room temperature, reaction solution gradually becomes muddy by clarifying；
It is then allowed to stand, until there is gel generation, filtering, solvent washing, 60~80 DEG C of vacuum drying obtain solid powder；Products therefrom
As silica gel load shown in Formula VII -1 or Formula VIII -1 is coordinated palladium catalyst；
The synthesis of the catalyst is carried out according to following reaction equations:
Alternatively, the synthesis of the catalyst is carried out according to following reaction equations:
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| CN110590715B (en) * | 2018-06-12 | 2021-05-14 | 中科合成油技术有限公司 | Surface-modified Pd-based catalyst and preparation method and application thereof |
| CN116139928B (en) * | 2022-11-28 | 2024-02-13 | 上海巧坤化工科技有限公司 | Composite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5214172A (en) * | 1991-05-06 | 1993-05-25 | Air Products And Chemicals, Inc. | Catalytic transvinylation of vinyl esters |
| US5741925A (en) * | 1997-01-13 | 1998-04-21 | Air Products And Chemicals, Inc. | Transvinylation of naphthenic acids |
| CN104487411A (en) * | 2012-02-06 | 2015-04-01 | Oxea有限责任公司 | Method for producing vinyl esters |
-
2016
- 2016-11-09 CN CN201610986344.3A patent/CN108057459B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5214172A (en) * | 1991-05-06 | 1993-05-25 | Air Products And Chemicals, Inc. | Catalytic transvinylation of vinyl esters |
| US5741925A (en) * | 1997-01-13 | 1998-04-21 | Air Products And Chemicals, Inc. | Transvinylation of naphthenic acids |
| CN104487411A (en) * | 2012-02-06 | 2015-04-01 | Oxea有限责任公司 | Method for producing vinyl esters |
Non-Patent Citations (2)
| Title |
|---|
| "A highly active and reusable heterogeneous catalyst for the Suzuki reaction: synthesis of biaryls and polyaryls";Satya Paul et al.;《GREEN CHEMISTRY》;20030812;第5卷(第5期);第636-638页 * |
| "The design of selective catalysts from hybrid silica-based materials";Moreau JJE et al.;《COORDINATION CHEMISTRY REVIEWS》;19981231;第178卷;第1075页 * |
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