CN106278867A - A kind of preparation method and applications containing fluorocarbon chain palladium catalyst - Google Patents
A kind of preparation method and applications containing fluorocarbon chain palladium catalyst Download PDFInfo
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- CN106278867A CN106278867A CN201610557173.2A CN201610557173A CN106278867A CN 106278867 A CN106278867 A CN 106278867A CN 201610557173 A CN201610557173 A CN 201610557173A CN 106278867 A CN106278867 A CN 106278867A
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- fluorocarbon chain
- palladium catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of preparation method containing fluorocarbon chain palladium catalyst, palladium-containing precursor is reacted with perfluorocarboxylic acid 1:2 3 in molar ratio, described reaction temperature is 60 100 DEG C, response time is 2 24h, and reaction cools down after terminating, filters, washs, is dried to obtain containing fluorocarbon chain palladium catalyst product.The invention also discloses the application in preparing vinyl carboxylates of this catalyst, this catalyst is used for preparing vinyl carboxylates, has technique simple, and yield is high, and catalyst system and catalyzing is easily separated, low cost, the advantage of safety and environmental protection.
Description
Technical field
The present invention relates to catalyst technical field, be specifically related to a kind of preparation method containing fluorocarbon chain palladium catalyst and
Application in synthesis of carboxylic acid vinyl acetate.
Background technology
Traditionally, acrylic ester compound is widely used in macromolecular material as polymer monomer.But acrylic acid
Compounds often has strong impulse and high volatility, and has carcinogenesis, and some countries have limited use.Carboxylic acid
Vinyl acetate is a kind of new polymer monomer, is the succedaneum of acrylate.Vinyl benzoate is a kind of important carboxylic acid second
Alkene ester, vinyl benzoate is the basic chemical raw materials of synthesis modification macromolecular material, at paint, binding agent, coating, water
Mud compound is used widely.Finding economy, easy vinyl carboxylates synthetic method is always the mesh of chemical research
One of mark.
At present, the synthesis of vinyl benzoate has acetylene method (WO2007060176), ethylene process (EP648734) and acetic acid
Vinyl acetate and benzoic ester-interchange method (CN102381978B).During the reaction of ethylene process gas phase, conversion ratio is low, rotten during liquid phase reactor
Erosion property is big, has the danger of blast simultaneously；Acetylene method also has bigger security risk, uses noble metal catalyst, shadow simultaneously
Ring its economy.Ester-interchange method is simple, and reaction condition is gentle, is vinyl benzoate synthetic method currently mainly.
In ester-interchange method, vinylacetate and benzoic acid occur ester exchange reaction to generate benzoic acid second under noble metal catalyst effect
Alkene ester (WO2013117294), reaction is generally carried out under mercury salt or palladium salt are catalyzed.Mercury salt is due to its toxicity and the shadow to environment
Ring and be no longer influenced by favoring (US2997494).Palladous chloride. is carried on activated carbon catalysis synthesizing benzoic acids by patent CN102381978B
Vinyl acetate, reaches the conversion ratio of 95% and the selectivity of 98%.Pd/C as catalyst, is used for synthesizing by CN201110362536
Vinyl benzoate, but actual production showing, its catalytic efficiency is more much lower than Palladous chloride. system.Celanese company uses all
Phase catalyst Pd (OAc)2Synthesizing benzoic acids vinyl acetate, obtains the conversion ratio of about 75%.
Above-mentioned technology commonly used palladium salt catalyst, weak point is the easy seepage of catalyst, affects the recovery of catalyst.
Utilizing Pd/C to make catalyst and can overcome above-mentioned difficulties, catalyst easily reclaims, but catalysis activity is far below palladium salt catalyst.
Therefore, find more efficiently palladio catalyst system and catalyzing, improve yield and the selectivity of reaction further, reduce production cost, be
The problem that research worker is in the urgent need to address.
Summary of the invention
It is an object of the invention to the defect for prior art, it is provided that a kind of technique is simple, and yield is high, and catalyst system and catalyzing easily divides
From, low cost, the preparation method and applications containing fluorocarbon chain palladium catalyst of safety and environmental protection.
The present invention solves the scheme of above-mentioned technical problem employing: a kind of preparation method containing fluorocarbon chain palladium catalyst, will
Palladium-containing precursor and perfluorocarboxylic acid 1:2-3 in molar ratio reacts, and described reaction temperature is 60-100 DEG C, and the response time is 2-
24h, reaction cools down after terminating, filters, washs, is dried to obtain containing fluorocarbon chain palladium catalyst product.
Described palladium-containing precursor is preferably the one in palladium, Palladous chloride., palladium dydroxide, Palladous nitrate..
Described perfluorocarboxylic acid is preferably perfluor caproic acid or perfluoro caprylic acid.
Preferably, described reaction is carried out in a solvent, and described palladium-containing precursor molar concentration in a solvent is 0.02-
0.1mol/L.Described solvent is preferably N-Methyl pyrrolidone (NMP).
The invention also discloses the above-mentioned application containing fluorocarbon chain palladium catalyst in synthesis of carboxylic acid vinyl acetate, containing fluorocarbon chain
Under the catalyst system and catalyzing catalysis of palladium catalyst and part composition, vinylacetate and carboxylic acid carry out ester exchange reaction and generate generating vinyl carboxylate
Ester, described carboxylic acid and vinylacetate mass ratio are 1:2-10, and the described palladium catalyst consumption containing fluorocarbon chain is carboxylic acid quality
0.03-3.2%, reaction temperature 80-140 DEG C, the response time is 2-20h.
Described carboxylic acid is preferably benzoic acid, ten dicarboxylic acids, the one in trifluoracetic acid.
It is luxuriant and rich with fragrance that described part is preferably adjacent two.
Present invention perfluorocarboxylic acid replaces two acetyl group in palladium-containing precursor palladium and urges to change catalyst acetic acid palladium
Change activity.Wherein, with palladium (X=OAc) as raw material, react with perfluor caproic acid or perfluoro caprylic acid and obtain perfluor caproic acid palladium or complete
The chemical equation of fluorine octanoic acid palladium is as follows:
X=NO2, OH, Cl, OAc
Wherein, n=2-17, as n=5, product is perfluor caproic acid palladium；As n=7, product is perfluoro caprylic acid palladium.
Under the catalyst system and catalyzing catalysis formed containing fluorocarbon chain palladium catalyst and part of the present invention, vinylacetate and carboxylic acid
Carrying out ester exchange reaction and generate vinyl carboxylates, catalysis activity is good, and the conversion ratio of carboxylic acid can reach more than 80%, and selectivity is
100%.The wherein chemical reaction of the ester exchange reaction of the benzoic acid of perfluor caproic acid or perfluoro caprylic acid palladium chtalyst and vinylacetate
Formula is as follows:
Compared with prior art, the invention have the advantages that
1, catalyst efficiency high, under the catalyst system and catalyzing catalysis formed containing fluorocarbon chain palladium catalyst and part of the present invention,
Vinylacetate and carboxylic acid carry out ester exchange reaction and generate vinyl carboxylates, and catalysis activity is good, and the conversion ratio of carboxylic acid can be
More than 80%, selectivity is 100%；
2, low cost, safety and environmental protection, the present invention hands over for the ester of vinylacetate and carboxylic acid containing fluorocarbon chain palladium catalyst
Changing reaction and prepare corresponding vinyl carboxylates, consumption is few, and consumption is less than the 3.2% of carboxylic acid quality, and recyclable repeatedly utilizes,
Significantly reduce production cost；
3, catalyst preparation process is simple, low cost, and the present invention's is simple containing fluorocarbon chain palladium catalyst preparation method, condition
Gentleness, greatly reduces cost.
Detailed description of the invention
Being described in more detail the method for the present invention below in conjunction with specific embodiment, following instance is only into one
The step explanation present invention, is not to limit the scope of protection of the invention.
Embodiment 1. perfluor caproic acid palladium (Pd (OCOC5F11)2) preparation
Under nitrogen atmosphere, palladium 100mg (0.446mmol) is added burning with perfluor caproic acid 420mg (1.33mmol)
In Ping, at 60 DEG C of stirring reaction 24h, it is cooled to room temperature, is filtered to remove the perfluor caproic acid of excess, obtains gray solid, use oil
Ether washing, be dried to obtain 150mg product, yield 46%.
Embodiment 2. perfluor caproic acid palladium (Pd (OCOC5F11)2) preparation
Under nitrogen atmosphere, palladium 100mg (0.446mmol) is added burning with perfluor caproic acid 420mg (1.33mmol)
In Ping, add NMP 5mL, at 60 DEG C of stirring reaction 24h, be cooled to room temperature, remove volatile matter, obtain gray solid, use oil
Ether washing, be dried to obtain 200mg product, yield 61%.
Embodiment 3. perfluor caproic acid palladium (Pd (OCOC5F11)2) preparation
Under nitrogen atmosphere, Palladous nitrate. 100mg (0.43mmol) is added flask with perfluor caproic acid 420mg (1.33mmol)
In, 80 DEG C of stirring reactions 12 hours, it is cooled to room temperature, is filtered to remove the perfluor caproic acid of excess, obtains gray solid, use oil
Ether washing, be dried to obtain 180mg product, yield 57%.
Embodiment 4. perfluor caproic acid palladium (Pd (OCOC5F11)2) preparation
Under nitrogen atmosphere, Palladous chloride. 100mg (0.56mmol) is added flask with perfluor caproic acid 420mg (1.33mmol)
In, at 100 DEG C, stirring reaction 2 hours, it is cooled to room temperature, has a small amount of solid to separate out, be filtered to remove the perfluor caproic acid of excess,
To gray solid, by petroleum ether, it is dried to obtain 190mg product, yield 46%.
Embodiment 5. perfluor caproic acid palladium (Pd (OCOC5F11)2) preparation
Under nitrogen atmosphere, palladium dydroxide 80mg (0.57mmol) is added burning with perfluor caproic acid 420mg (1.33mmol)
In Ping, 80 DEG C of stirring reactions 12 hours, it is cooled to room temperature, is filtered to remove the perfluor caproic acid of excess, obtains gray solid, use stone
Oil ether washing, be dried to obtain 175mg product, yield 42%.
Embodiment 6.
Perfluoro caprylic acid palladium (Pd (OCOC7F13)2) preparation
Under nitrogen atmosphere, by palladium 100mg (0.446mmol), perfluoro caprylic acid (HOCOC7F13)370mg
(0.893mmol), NMP (N-Methyl pyrrolidone) 10ml add in flask, 90 DEG C of stirring reactions 20 hours, be cooled to room
Temperature, filters the solid of precipitation, after washing with a small amount of NMP, by petroleum ether, is dried to obtain gray solid 250mg, yield
55%.
Embodiment 7.
Perfluoro caprylic acid palladium (Pd (OCOC7F13)2) preparation
Under nitrogen atmosphere, by palladium 100mg (0.446mmol), perfluoro caprylic acid (HOCOC7F13)370mg
(0.893mmol), NMP (N-Methyl pyrrolidone) 15ml add in flask, 100 DEG C of stirring reactions 8 hours, be cooled to room
Temperature, filters the solid of precipitation, after washing with a small amount of NMP, by petroleum ether, is dried to obtain gray solid 275mg, yield
60.5%.
Embodiment 8.
Perfluoro caprylic acid palladium (Pd (OCOC7F13)2) preparation
Under nitrogen atmosphere, by palladium 100mg (0.446mmol), perfluoro caprylic acid (HOCOC7F13)555mg
(1.34mmol), adding in flask, 100 DEG C of stirring reactions 12 hours, be cooled to room temperature, the solid of precipitation filters, and uses
After a small amount of NMP washing, by petroleum ether, it is dried to obtain gray solid 280mg, yield 62%.
Embodiment 9-14
Containing fluorocarbon chain palladium catalyst application experiment in synthesis of carboxylic acid vinyl acetate:
In reaction bulb add vinylacetate, carboxylic acid, containing fluorocarbon chain palladium catalyst and part, be warmed up to reaction temperature and enter
Row reaction, reaction cools and isolates palladium-carbon catalyst after terminating, and it is quantitative that reactant liquor carries out chromatography, the results are shown in Table 1.
Table 1 is used for experiment condition and the implementation result of synthesis of carboxylic acid vinyl acetate containing fluorocarbon chain palladium catalyst
Claims (8)
1. the preparation method containing fluorocarbon chain palladium catalyst, it is characterised in that by palladium-containing precursor and perfluorocarboxylic acid in molar ratio 1:
2-3 reacts, and described reaction temperature is 60-100 DEG C, and the response time is 2-24h, reaction cools down, filters, washs after terminating,
It is dried to obtain containing fluorocarbon chain palladium catalyst product.
Preparation method containing fluorocarbon chain palladium catalyst the most according to claim 1, it is characterised in that described palladium-containing precursor is
One in palladium, Palladous chloride., palladium dydroxide, Palladous nitrate..
Preparation method containing fluorocarbon chain palladium catalyst the most according to claim 1, it is characterised in that described perfluorocarboxylic acid is
Perfluor caproic acid or perfluoro caprylic acid.
Preparation method containing fluorocarbon chain palladium catalyst the most according to claim 1, it is characterised in that described reaction is at solvent
In carry out, described palladium-containing precursor molar concentration in a solvent is 0.02-0.1mol/L.
Preparation method containing fluorocarbon chain palladium catalyst the most according to claim 4, it is characterised in that described solvent is N-first
Base ketopyrrolidine.
6. described in claim 1 containing the application in synthesis of carboxylic acid vinyl acetate of the fluorocarbon chain palladium catalyst, it is characterised in that containing
Under the catalyst system and catalyzing catalysis of fluorocarbon chain palladium catalyst and part composition, vinylacetate and carboxylic acid carry out ester exchange reaction and generate carboxylic
Vinyl acetate, described carboxylic acid and vinylacetate mass ratio are 1:2-10, and the described palladium catalyst consumption containing fluorocarbon chain is carboxylic acid matter
The 0.03-3.2% of amount, the described mass ratio containing fluorocarbon chain palladium catalyst Yu part is 0.2-4:1, reaction temperature 80-140 DEG C,
Response time is 2-20h.
Application containing fluorocarbon chain palladium catalyst in synthesis of carboxylic acid vinyl acetate the most according to claim 6, it is characterised in that
Described carboxylic acid is benzoic acid, ten dicarboxylic acids, the one in trifluoracetic acid.
Application containing fluorocarbon chain palladium catalyst in synthesis of carboxylic acid vinyl acetate the most according to claim 6, it is characterised in that
Described part is adjacent two phenanthrene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807948A (en) * | 2019-11-11 | 2020-10-23 | 西安凯立新材料股份有限公司 | Preparation method of palladium pivalate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627558A (en) * | 2012-03-22 | 2012-08-08 | 江苏怡达化工有限公司 | Preparation method of vinyl carboxylate |
| CN102958899A (en) * | 2010-05-04 | 2013-03-06 | 塞拉尼斯国际公司 | Process for the semi-continuous transvinylation of carboxylic acids with vinyl acetate |
-
2016
- 2016-07-12 CN CN201610557173.2A patent/CN106278867A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102958899A (en) * | 2010-05-04 | 2013-03-06 | 塞拉尼斯国际公司 | Process for the semi-continuous transvinylation of carboxylic acids with vinyl acetate |
| CN102627558A (en) * | 2012-03-22 | 2012-08-08 | 江苏怡达化工有限公司 | Preparation method of vinyl carboxylate |
Non-Patent Citations (2)
| Title |
|---|
| SCARSO, A. ET AL: "Product class 4: salts of alkyl hydroperoxides", 《SCIENCE OF SYNTHESIS》 * |
| 李渭鹏: "钯盐化工产品的研制探讨", 《新疆有色金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807948A (en) * | 2019-11-11 | 2020-10-23 | 西安凯立新材料股份有限公司 | Preparation method of palladium pivalate |
| CN111807948B (en) * | 2019-11-11 | 2023-05-02 | 西安凯立新材料股份有限公司 | Preparation method of palladium pivalate |
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