CN108057459A - 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
- Publication number
- CN108057459A CN108057459A CN201610986344.3A CN201610986344A CN108057459A CN 108057459 A CN108057459 A CN 108057459A CN 201610986344 A CN201610986344 A CN 201610986344A CN 108057459 A CN108057459 A CN 108057459A
- Authority
- CN
- China
- Prior art keywords
- acid
- palladium
- formula
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C*(C)(N)[Si](**)(O*)O* Chemical compound C*(C)(N)[Si](**)(O*)O* 0.000 description 5
Classifications
-
- 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
- B01J31/16—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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
-
- 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
- B01J2231/49—Esterification or transesterification
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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) double-tooth chelate ligand containing N of the functional group containing trialkoxy silane is prepared first；(2) one or more in the double-tooth chelate ligand containing N that step (1) is prepared carry out complexation reaction with palladium inorganic salts, generate palladium complex；(3) reaction is hydrolyzed with tetraalkyl orthosilicate in the palladium complex that step (2) is prepared, and generates the silica gel load coordination palladium catalyst.The preparation method easily carries out, and the reaction was complete, and Metal Palladium utilization rate is high；It is controlled by the rate of charge to reaction raw materials, the load capacity of Metal Palladium in prepared silica gel supported palladium catalyst can be controlled within the specific limits.The catalyst can effectively be catalyzed 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 is used
Silica gel load coordination palladium catalyst and its preparation method and application.
Background technology
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, because of its active double bond structure, be often used as the monomer of synthetic organic polymer, homopolymer or altogether
Polymers is widely used in the preparation of adhesive, coating, antirust agent etc., and the vinyl acetate of wherein unsaturated carboxylic acid may be additionally used for conduct
Crosslinking agent or the 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.
At present, 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 be catalyzed the hair of vinyl interchange reaction
It is raw.Patent US4425277 is reported in vinyl interchange reaction, using palladium or palladium bichloride as major catalyst, is added in simultaneously
Lithium acetate and copper bromide are as co-catalyst.In vinyl interchange reaction, when with the palladiums inorganic salts such as palladium or palladium bichloride
During as major catalyst, often need to add in alkali metal ion, halide ion or copper ion (such as lithium chloride, lithium acetate, copper bromide
Etc. compounds) as co-catalyst, to improve the activity of palladium catalyst and slow down the generation of palladium black as far as possible.Patent
The reports 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 '-bipyridyl or both) generation complex when, such composition catalyst can effectively be catalyzed 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
It is distilled under part or distillation operation could separate catalyst from reaction system.However, in high temperature, reduced pressure
Under, Pd (II) is easily reduced to Pd (0), and then generation palladium black of reuniting, and causes catalyst inactivation, the palladium after recycling is so caused to be urged
Agent cannot continue directly to use in the reaction, substantially increase manufacture cost.
Silica gel load coordination palladium catalyst is related in the prior art in catalysis Heck reactions, Suzuki reactions, 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, is introduced in silica gel inorganic skeleton structure double containing N with good coordination ability
Tooth cheland (substituted pyridine-imines or pyridine-secondary amine), then combined by organic ligand and 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
Chemical bond is connected in carrier silica gel, is not easy to be eluted, and shows good catalytic activity and catalytic stability.
James H.Clark seminars, pyridine-imines-palladium out-phase that silica gel load has been prepared by anchor titration are urged
(for the structure of the catalyst as shown in formula a, wherein R is H or methyl to agent；X is chlorion or acetate ion), preparation side
Method is specially：(1) hydrolysis is occurred by the hydroxyl and 3- aminopropyl trimethoxysilanes of Silica Surface, modification is prepared
There is-CH2-CH2-CH2-NH2The silica gel of organic group；(2) silica gel of aminopropyl and 2- pyridine carboxaldehydes or 2- acetyl will be modified with
Pyridine reacts, and prepares silica gel-imines；(3) silica gel-imines is combined with palladium bichloride or palladium coordination, completes palladium on silica gel
Load.Such catalyst can effectively be catalyzed Heck reaction, Suzuki reaction, and show good catalytic activity and
Catalytic stability, it is ensured that the repetitive cycling of 10 times or more 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 bichloride of silica gel load has been prepared by sol-gel method for Pietro Moggi seminars
Catalyst (structure of the catalyst is as shown in formula b), preparation method is specially：(1) 2- acetylpyridines and three ethoxy of 3- aminopropyls
Base silane reaction prepares silane-imines；(2) NaBH is passed through4It is silane-secondary amine by silane-imine reduction；(3) 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 reactions and iodobenzene, and the TON values of catalysis are respectively
4100mmol products/mmolPd and 2300mmol products/mmolPd (Journal of Molecular Catalysis A,
2002,182:61~72).
The research of the emerging seminars of Li Guang shows 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 in into reaction system2O and tetrahydrofuran, can be with
Improve catalyst activity and stability (Appl.Organometal.Chem, 2006,20:656~662).
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 as to which palladium functional unit be born
It is downloaded on silica gel.But after containing N double-tooth chelate ligands and being connected in carrier silica gel, no longer it is small molecule state, causes organic match somebody with somebody
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 when small (be typically larger than 24), it just can guarantee palladium inorganic salts and have 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.
The content 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 within the specific limits.Specifically, the present invention is by chemical grafting method,
In the inorganic skeleton structure of silica gel, the functional unit of coordination palladium is introduced to get to the coordination palladium catalyst of silica gel load.It and 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, after catalytic reaction, can be separated and recovered by simple filter operation, to reuse.
Specifically, it is contemplated that by being loaded to solve urging in existing vinyl interchange reaction 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 particularly 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 R4The five-membered ring with double bond, hexatomic ring or heptatomic ring can be formed, alkyl, alkenyl, alkynes can also be independently from each other
One kind in base, cycloalkyl, aryl or two kinds；
(2) one or more in the double-tooth chelate ligand containing N that step (1) is prepared are coordinated with palladium inorganic salts
Reaction generates palladium complex；
(3) reaction is hydrolyzed with tetraalkyl orthosilicate in the palladium complex that step (2) is prepared, and generates 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 R4The five-membered ring with double bond, hexatomic ring or heptatomic ring can be formed, C can also be independently from each other1-6Alkyl, C2-6
Alkenyl, C2-6Alkynyl, C3-10Cycloalkyl, C3-10Cycloalkenyl group, C6-14One kind in 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 carry
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 carries 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), the preparation method of ligand shown in Formulas I is：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), the preparation method of ligand shown in Formula II is：By formula III compound represented and formula
IV compounds represented are reacted, and ligand shown in Formulas I is prepared；By the 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, chlorion, 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, palladium bichloride, palladium bromide, palladium iodide, nitre
One or more of sour palladium.Preferably one or more of palladium or palladium bichloride.
According to the present invention, in step (2), one or more summations and palladium in ligand shown in the Formulas I or Formula II
The molar feed ratio of inorganic salts is 1:0.8~1.2, it is 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, it is described organic
One or more of the solvent in acetone, methanol, ethyl alcohol.
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 or more in ester, positive isopropyl silicate.
According to the present invention, in step (3), the molar feed ratio of the palladium complex and tetraalkyl orthosilicate is 1:1
~1:100, it is 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 for 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, is preferably 8
~9.
According to the present invention, in step (3), the one kind of the pH adjusting agent in triethylamine, ammonium hydroxide, sodium hydroxide
It is or a variety of.
In the present invention, in step (3), by mole throwing for controlling palladium complex and tetraalkyl orthosilicate in hydrolytic process
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
The purpose of product and catalytic activity.
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, first, by palladium inorganic salts with carrying three alkane
The organic ligand containing N (ligand shown in Formulas I or Formula II) of oxysilane functional group is coordinated generation palladium cooperation according to molar ratio
Object.The complexation reaction is very easy to carry out, and almost the reaction was complete, this ensure that in the preparation of loaded catalyst
Cheng Zhong, palladium have high utilization rate.Then, then the siloxy group in preparation-obtained palladium complex molecular structure is passed through
With tetraalkyl orthosilicate (hydrolysis occurs for positive quanmethyl silicate or (and) tetraethyl orthosilicate), generates silica gel structure, and then
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 within the specific limits.
The present invention also provides the applications of the silica gel load coordination palladium catalyst 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, the preparation applied to vinyl carboxylates.
The present invention further provides the applications of the silica gel load coordination palladium catalyst 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 methods of vinyl carboxylates, are included in the silica gel load shown in Formula VII
It is coordinated under palladium catalyst catalysis, starting carboxylic acid is made to carry out vinyl interchange reaction with starting carboxylic acid's vinyl acetate；
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 fourths
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 acids, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitic acid, stearic acid or benzoic acid, naphthoic acid
One or more in (ring) race or aromatic carboxylic acid.
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 acids, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitic acid, stearic acid or benzoic acid, naphthoic acid
The vinyl acetate of fat (ring) race or aromatic carboxylic acid is waited, is 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, it is preferably 1:0.3~15.
According to the present invention, the vinyl interchange reaction temperature is 40~120 DEG C, is preferably 60~100 DEG C, during reaction
Between for 5~35h, be 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 easily carries out, and reacts
Completely, Metal Palladium utilization rate is high；It is controlled, can controlled within the specific limits prepared by the rate of charge to reaction raw materials
Silica gel supported palladium catalyst in Metal Palladium load capacity.
2. the present invention also provides a kind of vinyl interchange reaction silica gel load palladium catalyst, the catalyst is a kind of silicon
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 by simple filter operation, can be completed, to reuse.
3. the present invention furthermore provides a kind of application of silica gel load palladium catalyst, vinyl can be effectively catalyzed
Exchange reaction is used to prepare vinyl carboxylates.
Description of the drawings
Fig. 1 is the infrared spectrogram of ligand shown in 1 preparation-obtained Formulas I -1 of embodiment.
Fig. 2 is the infrared spectrogram of ligand shown in 2 preparation-obtained Formula II -1 of embodiment.
Fig. 3 is the infrared spectrogram of palladium complex shown in 3 preparation-obtained Formula V -1 of embodiment.
Fig. 4 is the photoelectron spectroscopy figure of palladium catalyst shown in 5 preparation-obtained Formula VII -1 of embodiment.
Fig. 5 is the infrared spectrogram of palladium complex shown in 7 preparation-obtained Formula IV -1 of embodiment.
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 formula I-1 first and/or Formula II -1；
(2) one or more in ligand shown in the Formulas I -1 and/or Formula II -1 step (1) being prepared are inorganic with palladium
Salt carries out complexation reaction, palladium complex shown in production V-1 and/or VI-1；
(3) palladium complex shown in Formula V -1 and/or VI-1 step (2) being prepared is carried out with tetraalkyl orthosilicate
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 ligand shown in Formulas I -1, the formula III -1
Molar feed ratio with compound shown in formula IV -1 is 0.5~2:1, it is preferably 0.8~1.5:1, further preferably 0.9~
1.2:1.The reaction time is related to reaction temperature, is preferably that reaction temperature is 25~50 DEG C, 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
Reaction carries out under the conditions of existing for 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 system of ligand shown in Formula II -1 is reduced in ligand shown in Formulas I -1
During standby, ligand and NaBH shown in the Formulas I -14Molar feed ratio be 1:1~4.The reaction temperature for 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 formula I-1 and Formula II -1
Ligand shown in formula I-1：By 3- aminopropyl trimethoxysilanes or 3- aminopropyl triethoxysilanes, with 2-
Either 2- acetylpyridines or the acyl pyridine class compound of arbitrary two substitutions press molar feed ratio as 0.5~2 to pyridine carboxaldehyde:
1 is dissolved in organic solvent, in ethyl alcohol, toluene, and adds in a certain amount ofMolecular sieve at 25~100 DEG C, is reacted 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 formula II-1：It is 1 by molar feed ratio:Ligand and NaBH shown in 1~4 Formulas I -14It is dissolved in water removal
Organic solvent (for example, except water methanol or except 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 room temperature, adds in a certain amount of water and reacts remaining NaBH4.Again with dichloromethane,
The organic solvents such as chloroform or toluene extract reaction solution, anhydrous sodium sulfate drying organic phase, 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 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, palladium bichloride, palladium nitrate, by close
1:1 molar ratio is dissolved in a certain amount of organic solvent, in acetone, methanol, ethyl alcohol or its mixed liquor, stirs at room temperature,
It is clarified when reaction solution starts, it is then quick muddiness occur, continue 0.5~3h of stir about, obtain palladium shown in Formula V -1 or Formula IV -1 and match somebody with somebody
Close object.
(3) silica gel load coordination palladium catalyst is prepared
In the case of being stirred at room temperature, into the turbid solution of palladium complex shown in above-mentioned Formula V -1 or Formula IV -1, add in 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 in, reaction solution becomes clarifying again, adds a certain amount of three second
Amine or ammonium hydroxide, the pH value for adjusting reaction system are 8~9.Continue stirring 4~for 24 hours at room temperature, reaction solution is gradually become by clarifying
It is muddy.Then stand, until there is gel generation, filtering, solvent washing, 60~80 DEG C of vacuum drying obtain solid powder.Gained
Product is Formula VII -1 or the silica gel load coordination palladium catalyst shown in 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- acetylpyridines, 3- aminopropyl triethoxysilanes, 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, reaction is measured by gas chromatography and is terminated
The mass concentration of product vinyl carboxylate afterwards.
Wherein, GC conditions are：GC9790 type gas chromatographs, flame ionization ditector, capillary chromatograph
For FFAP types 30m × 0.32mm × 0.5 μm.
The detection method of Pd mass fractions in catalyst：Plasma emlssion spectrometry.
Wherein, testing conditions are：Ultima2 type plasma emission spectrometers, 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- acetylpyridines of the 3- aminopropyl triethoxysilanes of 2.11g (10mmoL) and 1.21g (10mmoL) are dissolved in
About 25mL's removes in alcoholic solvent, and adds in a certain amount ofMolecular sieve, in the case that nitrogen is protected, 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.
Reaction is 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 1 preparation-obtained Formulas I -1 of embodiment.
Wherein, FT-IR (KBr, cm-1)：3052cm-1Locate as pyridine ring C-H absworption peaks；2972cm-1、2925cm-1、
2884cm-1Locate as alkyl C-H absworption peaks；1640cm-1Locate as C=N double bond absorption peaks in imines；1585cm-1、1565cm-1Locate be
Pyridine ring bending vibration absworption peak；1103cm-1、1079cm-1Locate as Si-O-C absworption peaks in silicon ethyoxyl；And raw material 2- second
1699cm in acyl pyridine-1Locate C=O double bond absorption peaks 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 reacts about 1h for 40 DEG C, until former
The reaction was complete for material.It is cooled to room temperature, adds in about 10mL water and react away remaining NaBH4, then the dichloromethane of about 20mL is used respectively
Solvent extraction 3 times, anhydrous sodium sulfate drying organic phase, then evaporated under reduced pressure solvent, obtains brown viscous liquid.
Reaction process is schematically as follows：
The infrared structure of the compound confirms that data are as follows：
Fig. 2 is the infrared spectrogram of ligand shown in 2 preparation-obtained Formula II -1 of embodiment.
Wherein, FT-IR (KBr, cm-1)：3050cm-1Locate as pyridine ring C-H absworption peaks；2966cm-1、2926cm-1、
2864cm-1Locate as alkyl C-H absworption peaks；1590cm-1、1570cm-1Locate as pyridine ring bending vibration absworption peak；1050~
1120cm-1Locate as Si-O-C absworption peaks in silicon ethyoxyl；And 1640cm in ligand shown in starting materials of formulae I-1-1Locate C=N double bonds to absorb
Peak disappears.
Embodiment 3
(palladium complex shown in Formula V -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:2)
Ligand and 1.12g (5mmoL) palladium shown in Formulas I -1 prepared in 1.62g (5mmoL) embodiment 1 are dissolved in
In the acetone solvent of about 40mL, stir about 1h, is clarified when reaction solution starts at room temperature, then gradually appears muddiness, is finally had big
Amount precipitation generation.It is palladium complex of the palladium shown in the Formula V -1 of the generation of ligand shown in Formulas I -1 to generate precipitation.
The infrared structure of the compound confirms that data are as follows：
Fig. 3 is the infrared spectrogram of palladium complex shown in 3 preparation-obtained Formula V -1 of embodiment.
Wherein, FT-IR (KBr, cm-1)：2976cm-1、2930cm-1Locate as C-H absworption peaks in alkyl；1594cm-1Locate as vinegar
C=O double bond absorption peaks in acid group；1050~1100cm-1Locate as Si-O-C absworption peaks in silicon ethyoxyl.
Then the tetraethyl orthosilicate of 2.08g (10mmoL) is added in into reaction solution, continues stir about 10 minutes, is added
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, soon
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 the palladium catalyst shown in Formula VII -1.
Reaction process is schematically as follows：
Pd mass percentage contents are 15.92% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 4
(palladium complex shown in Formula V -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:4)
It is similar to Example 3, simply the dosage of tetraethyl orthosilicate is changed to add in the positive silicic acid tetrems of 4.16g (20mmoL)
Ester, subsequent aqueous solvent dosage are 120mL.Final products therefrom is still yellow solid powder.
Pd mass percentage contents are 11.94% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 5
(palladium complex shown in Formula V -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:6)
Similar to Example 3, the dosage for simply improving tetraethyl orthosilicate is changed to add in the positive silicic acid four of 6.24g (30mmoL)
Ethyl ester, subsequent aqueous solvent dosage are 140mL.Final products therefrom is still yellow solid powder.
Pd mass percentage contents are 8.85% in using plasma emission spectrographic determination prepared catalyst.
Fig. 4 is the photoelectron spectroscopy figure of palladium catalyst shown in 5 preparation-obtained Formula VII -1 of embodiment.Wherein, C1sFor
284.7eV；N1sFor 399.5eV；Pd3dFor 337.7eV.
Embodiment 6
(palladium complex shown in Formula V -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:8)
Similar to Example 3, the dosage for simply improving tetraethyl orthosilicate is changed to add in the positive silicic acid four of 8.32g (40mmoL)
Ethyl ester, subsequent aqueous solvent dosage are 160mL.Final products therefrom is still yellow solid powder.
Pd mass percentage contents are 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, can be by controlling the molar ratio of palladium complex shown in Formula V -1 and silicon source, to control from 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 more than 85%.
Embodiment 7
(palladium complex shown in Formula IV -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:2)
Ligand shown in Formula II -1 prepared in 1.62g (5mmoL) embodiment 2 and 1.12g (5mmoL) palladium is molten
In the acetone solvent of about 40mL, stir about 1h, is clarified when reaction solution starts at room temperature, then gradually appears muddiness, finally has
A large amount of precipitation generations.It is shown in the Formula IV -1 that palladium is generated with the ligand shown in prepared Formula II -1 to generate precipitation
Complex.
The infrared structure of the compound confirms that data are as follows：
Fig. 5 is the infrared spectrogram of palladium complex shown in 7 preparation-obtained Formula IV -1 of embodiment.
Wherein, FT-IR (KBr, cm-1)：2926cm-1Locate as C-H absworption peaks in alkyl；1587cm-1Locate as C in acetate
=O double bond absorption peaks；1125cm-1Locate as Si-O-C absworption peaks in silicon ethyoxyl.
Then the tetraethyl orthosilicate of 2.08g (10mmoL) is added in into reaction solution, continues stir about 10 minutes, is added
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, soon
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 the palladium catalyst shown in Formula VIII -1.
Reaction process is schematically as follows：
Pd mass percentage contents are 16.15% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 8
(palladium complex shown in Formula IV -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:4)
Similar to Example 7, the dosage for simply improving tetraethyl orthosilicate is changed to add in the positive silicic acid four of 4.16g (20mmoL)
Ethyl ester, subsequent aqueous solvent dosage are 120mL.Final products therefrom is still khaki solid powder.
Pd mass percentage contents are 12.06% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 9
(palladium complex shown in Formula IV -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:6)
Similar to Example 7, the dosage for simply improving tetraethyl orthosilicate is changed to add in the positive silicic acid four of 6.24g (30mmoL)
Ethyl ester, subsequent aqueous solvent dosage are 140mL.Final products therefrom is still khaki solid powder.
Pd mass percentage contents are 8.46% in using plasma emission spectrographic determination prepared catalyst.
Embodiment 10
(palladium complex shown in Formula IV -1 is 1 with silicon source molar ratio for the preparation of the palladium catalyst of silica gel load:8)
Similar to Example 7, the dosage for simply improving tetraethyl orthosilicate is changed to add in the positive silicic acid four of 8.32g (40mmoL)
Ethyl ester, subsequent aqueous solvent dosage are 160mL.Final products therefrom is still khaki solid powder.
Pd mass percentage contents are 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, can be by controlling the molar ratio of palladium complex shown in Formula IV -1 and silicon source, to control from 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 more 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.
Reaction is schematically as follows：
The silica gel load for recycling gained is coordinated palladium catalyst, is placed in the three-necked flask of 100mL, adds in 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 such as following table：
| 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.
Reaction is schematically as follows：
Wherein R1、R2For saturated alkyl, R1+R2The total number of carbon atoms be 7.
The silica gel load for recycling gained is coordinated palladium catalyst, is placed in the three-necked flask of 100mL, adds in 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 such as following table：
| 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 there was only a small amount of vinyl benzoate generation.Catalyst is recovered by filtration, gained palladium catalyst is in aterrimus, may
It is that Pd (II) in former loaded catalyst has at least partly been reduced to caused by Pd (0).Since secondary amine group has in itself
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 reactions, Suzuki reactions etc..
The foregoing is only a preferred embodiment of the present invention, protection scope of the present invention is without being limited thereto, it is any ripe
Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical solution that can be become apparent to
Altered or equivalence replacement are each fallen in protection scope of the present invention.
Claims (10)
1. 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 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 R4
The five-membered ring with double bond, hexatomic ring or heptatomic ring can be formed, alkyl, alkenyl, alkynyl, ring can also be independently from each other
One kind in alkyl, aryl or two kinds；
(2) one or more in the double-tooth chelate ligand containing N that step (1) is prepared with palladium inorganic salts be coordinated anti-
Should, generate palladium complex；
(3) reaction is hydrolyzed with tetraalkyl orthosilicate in the palladium complex that step (2) is prepared, and generates the silica gel and bears
Carry coordination palladium catalyst.
2. preparation method according to claim 1, which is characterized in that in Formulas I or Formula II, R1Selected from alkyl；R2Selected from H,
C1-6Alkyl, C6-14Aromatic radical；R3And R4The five-membered ring with double bond, hexatomic ring or heptatomic ring can be formed, it can also each other solely
On the spot it is selected from C1-6Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-10Cycloalkyl, C3-10Cycloalkenyl group, C6-14One kind in 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 with double bond
Five-membered ring, hexatomic ring or heptatomic ring.
It is further preferred that R1Selected from methyl, ethyl；R2Selected from H, methyl, ethyl, phenyl；R3And R4Five with double bond can be formed
Yuan of rings or hexatomic ring.
It is more preferred still that R1Selected from methyl, ethyl；R2Selected from H, methyl, ethyl, phenyl；R3And R4Composition is hexa-atomic with double bond
Ring.
Preferably, in Formulas I or Formula II, 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.
3. preparation method according to claim 1 or 2, which is characterized in that the step of the preparation method in (1), Formulas I institute
The preparation method for showing ligand is：Compound shown in formula III and formula IV compound represented are reacted, Formulas I institute is prepared
Show ligand：
Wherein, n, R1、R2、R3And R4Definition it is as claimed in claim 1 or 2.
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.
4. according to the preparation method described in any one of claim 1-3 claim, which is characterized in that in step (2), institute
The structural formula for the palladium complex stated is as shown in Formula V or Formula IV：
Wherein, n, R1、R2、R3And R4Definition it is as claimed in claim 1 or 2, X ' for acetate, chlorion, bromide ion, iodine from
Son, nitrate anion or other anion.
Most preferably, the palladium complex is as shown in Formula V -1 or Formula IV -1：
Wherein, R1And R2Definition it is as claimed in claim 1 or 2, X ' is defined as described above.
Preferably, in step (2), the palladium inorganic salts are in palladium, palladium bichloride, palladium bromide, palladium iodide, palladium nitrate
It is one or more of.Preferably palladium, palladium bichloride.
Preferably, in step (2), the molar feed ratio of ligand shown in the Formulas I or Formula II and palladium inorganic salts is 1:0.8~
1.2, it is preferably 1:0.9~1.1, further preferably 1:1.
Preferably, in step (2), the complexation reaction carries out in organic solvent.Preferably, the organic solvent is selected from
One or more in acetone, methanol, ethyl alcohol.
Preferably, in step (2), the complexation reaction time is 0.5~5h, and reaction temperature is room temperature；Preferably, it is described to match somebody with somebody
The position reaction time is 0.5~3h.
5. according to the preparation method described in any one of claim 1-4 claim, which is characterized in that in step (3), institute
The tetraalkyl orthosilicate stated is preferably positive silicic acid tetraalkyl ester.
Preferably, the Arrcostab 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, four n-propyl of positive silicic acid, just
One or more in isopropyl silicate.
Preferably, 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.
Preferably, in step (3), the progress at room temperature of the hydrolysis, the reaction time is 2~48h, is preferably
4~for 24 hours.
Preferably, in step (3), in the hydrolysis reaction, the pH of reaction system is 7~10, is preferably 8~9.
Preferably, in step (3), one or more of the pH adjusting agent in triethylamine, ammonium hydroxide, sodium hydroxide.
6. according to the preparation method described in any one of claim 1-5 claim, which is characterized in that the method is prepared into
The silica gel load arrived is coordinated palladium catalyst as shown in Formula VII or Formula VIII：
Wherein, n, R2、R3And R4Definition it is as claimed in claim 1 or 2, the definition of X ' is as claimed in claim 4.
Most preferably, the catalyst is as shown in Formula VII -1 or Formula VIII -1：
Wherein, R2Definition it is as claimed in claim 1 or 2, X ' is defined as described above.
7. according to the preparation method described in any one of claim 1-6 claim, which is characterized in that the preparation method,
Specifically comprise the following steps：
(1) ligand shown in formula I-1 and Formula II -1
Ligand shown in formula I-1：By 3- aminopropyl trimethoxysilanes or 3- aminopropyl triethoxysilanes, with 2- pyridines
Either 2- acetylpyridines or the acyl pyridine class compound of arbitrary two substitutions press molar feed ratio as 0.5~2 to formaldehyde:1 is molten
In organic solvent, in ethyl alcohol, toluene, and add in a certain amount ofMolecular sieve at 25~100 DEG C, reacts basic to raw material
The reaction was 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 formula II-1：It is 1 by molar feed ratio:Ligand and NaBH shown in 1~4 Formulas I -14Be dissolved in water removal has
Solvent (for example, except water methanol or except water-ethanol) at a temperature of 20~60 DEG C, reacts 0.5~3h, until shown in Formulas I -1
Ligand reaction is complete.It is then cooled to room temperature, adds in a certain amount of water and reacts remaining NaBH4.Again with dichloromethane, trichlorine
The organic solvents such as methane or toluene extract reaction solution, anhydrous sodium sulfate drying organic phase, and evaporated under reduced pressure solvent obtains viscous brown
Ligand shown in the Formula II -1 is prepared in liquid.
(2) palladium complex shown in formula V-1 or Formula IV -1
By gained Formulas I -1 or Formula II -1 and palladium inorganic salts, such as palladium, palladium bichloride, palladium nitrate, by close to 1:1 molar ratio
Example is dissolved in a certain amount of organic solvent, in acetone, methanol, ethyl alcohol or its mixed liquor, stirs at room temperature, when reaction solution starts
Clarification, it is then quick muddiness occur, continue 0.5~3h of stir about, obtain palladium complex shown in Formula V -1 or Formula IV -1.
(3) silica gel load coordination palladium catalyst is prepared
In the case of being stirred at room temperature, into the turbid solution of palladium complex shown in above-mentioned Formula V -1 or Formula IV -1, certain proportion is added in
Positive quanmethyl silicate or (and) tetraethyl orthosilicate, palladium complex and positive quanmethyl silicate or (and) tetraethyl orthosilicate rubs
Your ratio is 1:1~20, then add in a certain amount of water, reaction solution becomes clarifying again, add a certain amount of triethylamine or
Person's ammonium hydroxide, the pH value for adjusting reaction system are 8~9.Continue stirring 4~for 24 hours at room temperature, reaction solution gradually becomes muddy by clarifying
It is turbid.Then stand, until there is gel generation, filtering, solvent washing, 60~80 DEG C of vacuum drying obtain solid powder.Gained produces
Object is Formula VII -1 or the silica gel load coordination palladium catalyst shown in Formula VIII -1.
Preferably, the synthesis of the catalyst is carried out according to following reaction equations：
Preferably, the synthesis of the catalyst is carried out according to following reaction equations：
8. the silica gel load coordination palladium catalyst being prepared using any one of claim 1-7 the method, which is characterized in that
The structural formula of the catalyst is as shown in Formula VII or Formula VIII：
Wherein, n, R2、R3And R4Definition it is as claimed in claim 1 or 2, the definition of X ' is as claimed in claim 4；
In the palladium catalyst Metal Palladium account for the mass percent of prepared silica gel load coordination palladium catalyst for 0.05~
20wt%.
Preferably, the catalyst is as shown in Formula VII -1 or Formula VIII -1：
Wherein, R2Definition it is as claimed in claim 1 or 2, X ' is defined as described above.
9. the silica gel load described in prepared by any one of claim 1-7 the method or claim 8 is coordinated palladium catalyst
Using, can be applied to catalysis vinyl interchange reaction or its can be applied to catalysis vinethene synthesis；
The structural formula of the catalyst is as shown in Formula VII：
Wherein, n, R2、R3And R4Definition it is as claimed in claim 1 or 2, the definition of X ' is as claimed in claim 4.
Preferably, the preparation applied to vinyl carboxylates.
10. a kind of preparation method of vinyl carboxylates, which is characterized in that it is any that the preparation method is included in claim 1-7
Under silica gel load coordination palladium catalyst catalysis described in prepared by item the method or claim 8, make starting carboxylic acid and raw material
Vinyl carboxylates carry out vinyl interchange reaction；
The structural formula of the catalyst is as shown in Formula VII：
Wherein, n, R2、R3And R4Definition it is as claimed in claim 1 or 2, the definition of X ' is as claimed in claim 4.
Preferably, the starting carboxylic acid is selected from propionic acid, acrylic acid, butyric acid, isobutyric acid, positive valeric acid, 2-Methyl Butyric Acid, 3- methyl
Butyric acid, pivalic acid, positive enanthic acid, 2 methyl caproic acid, 2 ethyl hexanoic acid, caprylic acid, pelargonic acid, new n-nonanoic acid, n-capric acid, 2- propyl heptan
Acid, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitic acid, the stearic acid either fat such as benzoic acid, naphthoic acid (ring) race or virtue
It is in fragrant race's carboxylic acid and one or more.
Preferably, starting carboxylic acid's vinyl acetate is selected from acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, positive valeric acid, 2- methyl fourths
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 acids, neodecanoic acid, dodecanoic acid, tridecanoic acid, palmitic acid, stearic acid or benzoic acid, naphthoic acid
(ring) race or the vinyl acetate of aromatic carboxylic acid are preferably vinylacetate.
Preferably, 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.
Preferably, the vinyl interchange reaction temperature is 40~120 DEG C, is preferably 60~100 DEG C, the reaction time for 5~
35h is preferably 10~30h；Reaction pressure can be normal pressure, high pressure or negative pressure.
Preferably, the vinyl after reaction, recycle catalyst, then pass through the operations such as distillation, rectifying point by cooling, filtering
From unreacted raw material, product vinyl carboxylate and product carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610986344.3A CN108057459B (en) | 2016-11-09 | 2016-11-09 | A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610986344.3A CN108057459B (en) | 2016-11-09 | 2016-11-09 | A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108057459A true CN108057459A (en) | 2018-05-22 |
| CN108057459B CN108057459B (en) | 2019-09-20 |
Family
ID=62137833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610986344.3A Active CN108057459B (en) | 2016-11-09 | 2016-11-09 | A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108057459B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590715A (en) * | 2018-06-12 | 2019-12-20 | 中科合成油技术有限公司 | Surface-modified Pd-based catalyst and preparation method and application thereof |
| CN116139928A (en) * | 2022-11-28 | 2023-05-23 | 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 |
|---|
| MOREAU JJE ET AL.: ""The design of selective catalysts from hybrid silica-based materials"", 《COORDINATION CHEMISTRY REVIEWS》 * |
| SATYA PAUL ET AL.: ""A highly active and reusable heterogeneous catalyst for the Suzuki reaction: synthesis of biaryls and polyaryls"", 《GREEN CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590715A (en) * | 2018-06-12 | 2019-12-20 | 中科合成油技术有限公司 | Surface-modified Pd-based catalyst and preparation method and application thereof |
| CN116139928A (en) * | 2022-11-28 | 2023-05-23 | 上海巧坤化工科技有限公司 | Composite 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108057459B (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yun et al. | Titanocene-catalyzed asymmetric ketone hydrosilylation: the effect of catalyst activation protocol and additives on the reaction rate and enantioselectivity | |
| US11884639B2 (en) | Preparation method for high optical indoxacarb intermediate | |
| CN111054443B (en) | Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof | |
| CN108057459B (en) | A kind of vinyl interchange reaction silica gel load coordination palladium catalyst and its preparation method and application | |
| CN105753700A (en) | Method of synthesizing methyl acetate through acetylene carbonylation | |
| Li et al. | Redox Chemistry between Europium (III) Amide and Pyrrolyl-Functionalized Secondary Amines. Synthesis and Structural Characterization of Lithium and Novel Lanthanide Complexes Incorporating Functionalized Pyrrolyl Ligands | |
| CN105294646A (en) | Method for preparing nitrile by alcohol oxidation | |
| CN101270113A (en) | Preparation of multi-chiral catalyst, preparation and application of cyclic carbonates with optical activity | |
| CN105618136A (en) | Iodine-containing polymer-loaded rhodium-based catalyst for methanol carbonylation | |
| CN113004326A (en) | Phosphine ligand for butadiene hydroformylation reaction and preparation method thereof | |
| CN102500418B (en) | Preparation method of magnetic bidentate imide palladium ligand catalyst | |
| CN109553633B (en) | Preparation method of phenylacetic acid type aryne | |
| CN113527373A (en) | Catalyst for synthesizing benzenediol, preparation method and application thereof | |
| CN103896753B (en) | A kind of synthetic method of three grades of alpha-hydroxy carbonyl compounds | |
| CN107915653B (en) | Method for preparing amide by catalyzing ester and amine to react | |
| CN102993129A (en) | Method for preparing 1,2-epoxyoctane | |
| CN113087740B (en) | Preparation method and application of organotin ionic liquid catalyst | |
| CN102838469A (en) | Preparation method for palladium acetylacetonate | |
| CN106694049B (en) | A kind of methyl acetate catalysis agent system and application | |
| CN114920648A (en) | Synthesis method and catalyst of 3- (3-oxo-2-pentyl) cyclopentyl malonic acid dimethyl ester | |
| CN104860980A (en) | Ezetimibe synthesis intermediate and preparation method and application thereof | |
| CN102040487B (en) | Method for preparing 3,4-dimethoxy toluene under catalysis | |
| CN112979714A (en) | Triplecene carbene tridentate metal complex and application thereof | |
| CN102942548A (en) | Delta-dodecalactone synthesis method | |
| CN103787302B (en) | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |