CN106215957A - A kind of heterogeneous catalytic system for preparing vinyl carboxylates and using method thereof - Google Patents
A kind of heterogeneous catalytic system for preparing vinyl carboxylates and using method thereof Download PDFInfo
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- CN106215957A CN106215957A CN201610556220.1A CN201610556220A CN106215957A CN 106215957 A CN106215957 A CN 106215957A CN 201610556220 A CN201610556220 A CN 201610556220A CN 106215957 A CN106215957 A CN 106215957A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of heterogeneous catalytic system for preparing vinyl carboxylates, including catalyst and catalyst promoter, it is characterized in that, described catalyst be palladium weight/mass percentage composition be the palladium-carbon catalyst of 3.5% 10%, described catalyst promoter is at least one in alkali halide and quaternary ammonium salt, and described catalyst and catalyst promoter mass ratio are 0.5 5:1.This catalyst system and catalyzing is used for preparing vinyl carboxylates, has technique simple, and catalyst system and catalyzing is easily separated, and yield is high, low cost, the advantage of safety and environmental protection.
Description
Technical field
The present invention relates to heterogeneous catalytic system and using method thereof, specifically, the present invention relates to a kind of for preparing carboxylic
The heterogeneous catalytic system of vinyl acetate and using method thereof.
Background technology
Vinyl carboxylates is the industrial chemicals that a class is important, because of in molecule containing active function group-double bond, can with ethylene,
Acrylate, styrene etc. have the monomer of double bond to carry out copolymerization and improves the performance of its copolymer, widens its range of application, is one
The modified monomer that class is excellent.Its homopolymer or copolymer all have application at aspects such as binding agent, coating, antirust agent.
The performance of carboxylic acid vinyl ester polymer, different by acid kind, and difference is the biggest.And if then become copolymer, then plant
Class is more, performance difference is bigger and purposes widely.Various vinyl carboxylates polymerizing powers, different according to its hydrocarbyl carboxylic,
The vinyl acetate of representative examples of saturated aliphatic carboxylic, increases with the carbon number of alkyl, and polymerizing power reduces.Ethylene aromatic dicarboxylate ester, as
Vinyl benzoate, owing to free benzene nucleus is stable, polymerizing power is lower than aliphatic carboxylic acid vinyl acetate.Unsaturated carboxylic acid vinyl acetate is also
Can be used as cross-linking agent, photosensitive resin material.
At present, the method for synthesis of carboxylic acid vinyl acetate mainly has acetylene method, ethylene process and vinyl exchange process.Ethylene process gas phase
During reaction, conversion ratio is low, and during liquid phase reactor, corrosivity is big, has the danger of blast simultaneously;Acetylene method also has bigger safety wind
Danger, uses noble metal catalyst simultaneously, have impact on its economy.Ester-interchange method is simple, and reaction condition is gentle, is the most main
The vinyl carboxylates synthetic method wanted.Vinyl exchange process is typically, with vinylacetate and carboxylic acid, under metal catalytic, to carry out
The transfer of vinyl, prepares the vinyl esters of corresponding carboxylic acid.Owing to the double bond activity in raw material and product is the highest, it is susceptible to add
Become the side reactions such as polymerization, so the screening of catalytic condition and optimization are the most crucial.The most typical catalyst of this method be mercuric by force
Hydrochlorate.As US2997494 reports the catalyst system and catalyzing being made up of mercuric salt and strong acid.Bivalent mercury can be mercury oxide, sulfuration
Hydrargyrum, mercuric acetate, mercuric stearte etc., strong acid can be sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, trifluoracetic acid etc..Mercury salt and strong acid catalyst
System is because containing substantial amounts of mercury ion and spent acid in waste liquid, and post processing cost is high, and effect on environment is big, is the most gradually washed in a pan
Eliminate.
United States Patent (USP) US4981973 describes ruthenium-based catalyst application in vinyl interchange reaction.There is use metal
The report of platinum catalysis vinyl interchange reaction, and very satisfied result can be given, although platinum group metal catalyzed is functional, but
It is that it is expensive, and highly active homogeneous catalyst easily produces side reaction, limit the extensive application of this kind of catalyst.
Palladium-carbon catalyst is a kind of industrial application noble metal heterogeneous catalyst widely, has highly developed system
Standby process technology and market system.Palladium metal catalyst can catalyzed ethylene base exchange reaction effectively, but urge with homogeneous palladium salt
Agent is compared, and heterogeneous palladium catalyst activity reduces, and easily separates from reaction system so that precious metal palladium can easily reclaim and repeat
Use, so can be substantially reduced the probability that side reaction occurs, there is higher reaction selectivity.Therefore the heterogeneous palladium of general employing
Catalyst vinyl interchange reaction.Heterogeneous palladium catalyst is generally catalyst by palladium salt, with alkali halide for urging altogether
Agent, this catalyst system and catalyzing reactivity is high, and by-product is few.As United States Patent (USP) US5214172, US5741925 use palladium salt with adjacent
Phenanthroline ligand system catalyzes and synthesizes vinyl carboxylates, achieves extraordinary reaction effect, and adds strong acid in system
Reactivity can be significantly improved.Patent CN103025702A discloses use palladium and Phen system prepares generating vinyl carboxylate
Ester, carboxylic acid conversion ratio is about 70%, and after reactant liquor steams product and solvent (vinylacetate), Polycondensation Reactor and Esterification Reactor residue is still
So can be catalyzed repeatedly, carboxylic acid conversion ratio still can maintain a higher level.
But be that course of reaction easily separates out palladium black in place of above-mentioned the deficiencies in the prior art, and reaction yield and selectivity
The most relatively low, production cost is higher.Therefore, how to keep the stable of palladio catalyst system and catalyzing and easily separate from reaction system, with
Time further reduce occur side reaction probability, improve reaction yield and selectivity, to reduce production cost, be research people
The problem that member 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 catalyst system and catalyzing is easily separated, yield
Height, low cost, heterogeneous catalytic system and the using method thereof for preparing vinyl carboxylates of safety and environmental protection.
The present invention solves the scheme of above-mentioned technical problem employing: a kind of heterogeneous catalysis body for preparing vinyl carboxylates
System, including catalyst and catalyst promoter, described catalyst be palladium weight/mass percentage composition be the palladium-carbon catalyst of 3.5%-10%,
Described catalyst promoter is at least one in alkali halide and quaternary ammonium salt, described catalyst and catalyst promoter mass ratio
For 0.5-5:1.
In the present invention, alkali halide includes but not limited to sodium chloride, sodium bromide, sodium fluoride, sodium iodide, potassium chloride, bromine
Changing potassium, potassium fluoride, potassium iodide etc., described alkali halide is preferably sodium chloride, potassium chloride, potassium fluoride, sodium fluoride, bromination
One in potassium, potassium iodide.
In the present invention, quaternary ammonium salt includes but not limited to benzyltriethylammoinium chloride (TEBA), tetrabutyl ammonium bromide, the tetrabutyl
Ammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, myristyl three
Ammonio methacrylate etc..Described quaternary ammonium salt is preferably tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, trioctylphosphine
One in ammonio methacrylate.
The present invention also provides for the using method of this heterogeneous catalytic system for preparing vinyl carboxylates, by carboxylic acid, acetic acid
Vinyl acetate carries out reaction under heterogeneous catalytic system effect and prepares the mol ratio of vinyl carboxylates, described carboxylic acid and vinylacetate
For 1:3~15.5, in described heterogeneous catalyst system, catalyst amount is the 2.5-40% of carboxylic acid quality, and reaction temperature is 80-
160 DEG C, the response time is 6-48h.
Various carboxylic acid known in the art can be used in the method for the invention to form corresponding vinyl esters.It is applicable to this
The described carboxylic acid of invention may include but be not limited to following carboxylic acid: 2 ethyl hexanoic acid, benzoic acid, neodecanoic acid, propanoic acid, butanoic acid, valeric acid,
Enanthic acid, acrylic acid, methacrylic acid, trifluoracetic acid, lauric acid, stearic acid and Palmic acid.Described carboxylic acid is preferably 2-ethyl hexyl
One in acid, neodecanoic acid, trifluoracetic acid, butanoic acid, Palmic acid, benzoic acid, enanthic acid, stearic acid.
The present invention is for preparing the heterogeneous catalytic system of vinyl carboxylates based on palladium-carbon catalyst, with alkali metal halogenation
At least one in thing and quaternary ammonium salt is catalyst promoter, collectively constitutes catalyst system and catalyzing.This heterogeneous catalytic system is used for preparing carboxylic
Vinyl acetate, obtains the reactant liquor containing corresponding vinyl carboxylates, and cooled and filtered isolates palladium-carbon catalyst, repeatable makes
With;The catalyst promoter of trace is dissolved in reactant liquor, has technique simple, and equipment investment is few, and reaction condition is gentle, and energy and material consumption is low
Etc. advantage, can be effectively reduced production cost, the yield of vinyl carboxylates is high, production process safety and environmental protection.
Reaction equation is as follows:
The form that in the present invention, alkali halide adds is including but not limited to directly adding or by impregnating method
Load on palladium-carbon catalyst.Wherein, the method that alkali halide joins catalyst system and catalyzing by dipping is: add in reaction bulb
Enter palladium-carbon catalyst, alkali halide, high purity water, stir dipping at a certain temperature, filter and be dried to obtain at latter 150 DEG C
Pd/C-alkali halide catalyst.Wherein alkali halide is the 10%-50% of palladium-carbon catalyst quality, and high purity water is
The 300%-500% of palladium-carbon catalyst quality, dipping temperature is 20 DEG C-100 DEG C, and dip time is 2h-10h.Filter after dipping
It is dried, obtains Pd/C-alkali halide catalyst.
Compared with prior art, the invention have the advantages that
1, yield is high, and the heterogeneous catalytic system of the present invention is when carboxylic acid and vinylacetate prepare vinyl carboxylates, instead
Answering conversion ratio more than 70%, be up to 95%, selectivity, more than 95%, is up to 99%;
2, technique is simple, and catalyst system and catalyzing is easily separated, and this heterogeneous catalytic system is used for preparing vinyl carboxylates, and reactant liquor is through cold
Filtering to isolate palladium-carbon catalyst the most afterwards, reusable, the catalyst promoter of trace is dissolved in reactant liquor, simplifies and separated
Journey;
3, low cost, the palladium-carbon catalyst of the present invention, alkali halide and quaternary ammonium salt raw material are easy to get, and significantly reduce life
Produce cost;
4, safety and environmental protection, the heterogeneous catalytic system of the present invention when carboxylic acid and vinylacetate prepare vinyl carboxylates,
Stability is high, separates out without palladium black, and palladium metal runs off seldom, has efficiently, the advantage of environmental protection.
Detailed description of the invention
Starting carboxylic acid and vinylacetate used by the present invention are technical grade, palladium-carbon catalyst, alkali halide, quaternary ammonium
The most commercially available acquirement of salt.The concentration gas chromatograph of each material of reactant liquor carries out quantitative analysis.Gas chromatograph used is peace
Prompt human relations GC7890 type gas chromatograph, uses area normalization method to carry out quantitatively.
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
5g 2 ethyl hexanoic acid (0.035mol), 50ml vinylacetate (0.54mol), palladium quality is added in reaction bulb
Palladium-carbon catalyst 1g, the 0.4g sodium chloride of percentage composition 5%, is heated to reaction temperature 80 DEG C, after reacting 12 hours, stops anti-
Should, isolate palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 70%, and selectivity is
98%.
Embodiment 2
10g neodecanoic acid (0.058mol), 50ml vinylacetate (0.54mol), palladium percent mass is added in reaction bulb
Palladium-carbon catalyst 2g, the 0.5g lithium chloride of content 10%, is heated to reaction temperature 140 DEG C, after reacting 48 hours, and stopped reaction,
Isolating palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 85%, and selectivity is 96%.
Embodiment 3
20g trifluoracetic acid (0.175mol), 50ml vinylacetate (0.54mol), palladium quality hundred is added in reaction bulb
Divide palladium-carbon catalyst 0.5g, the 0.5g potassium iodide of content 5%, be heated to reaction temperature 80 DEG C, after reacting 20 hours, stop anti-
Should, isolate palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 82%, and selectivity is
99%.
Embodiment 4
5g butanoic acid (0.056mol), 50ml vinylacetate (0.54mol), palladium weight/mass percentage composition is added in reaction bulb
Palladium-carbon catalyst 2g, the 0.1g potassium bromide of 10%, is heated to reaction temperature 160 DEG C, after reacting 10 hours, and stopped reaction, cooling
After isolate palladium-carbon catalyst, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 86%, and selectivity is 99%.
Embodiment 5
15g Palmic acid (0.058mol), 50ml vinylacetate (0.54mol), palladium percent mass is added in reaction bulb
Palladium-carbon catalyst 1g, the 0.2g sodium fluoride of content 3.5%, 0.2g tetrabutylammonium chloride, it is heated to reaction temperature 60 DEG C, reacts 6
After hour, stopped reaction, isolate palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is
78%, selectivity is 95%.
Embodiment 6
20g benzoic acid (0.163mol), 50ml vinylacetate (0.54mol), palladium percent mass is added in reaction bulb
Palladium-carbon catalyst 0.5g, the 0.2g potassium fluoride of content 5%, is heated to reaction temperature 120 DEG C, after reacting 20 hours, and stopped reaction,
Isolating palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 95%, and selectivity is 99%.
Embodiment 7
Adding 20g enanthic acid (0.152mol) in reaction bulb, 50ml vinylacetate (0.54mol), palladium percent mass contains
Palladium-carbon catalyst 1g, the tri-n-octyl methyl ammonium chloride 0.4g of amount 10%, is heated to reaction temperature 120 DEG C, after reacting 15 hours, stops
Only reaction, isolates palladium-carbon catalyst after cooling, and it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 90%, selectivity
It is 98%.
Embodiment 8
10g stearic acid (0.035mol), 50ml vinylacetate (0.54mol), 1g palladium quality hundred is added in reaction bulb
Divide Pd/C, the 0.2g tetrabutyl ammonium bromide of content 10%, be heated to reaction temperature 120 DEG C, after reacting 12 hours, stopped reaction,
Isolating palladium-carbon catalyst after cooling, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 88%, and selectivity is 99%.
Comparative example 1
5g benzoic acid (0.040mol), 50ml vinylacetate (0.54mol), palladium quality hundred is added in reactor (bottle)
Divide the palladium-carbon catalyst 0.5g of content 5%, be heated to reaction temperature 80 DEG C, after reacting 10 hours, stopped reaction, separate after cooling
Going out palladium-carbon catalyst, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 5%, and selectivity is 98%.
Comparative example 2
5g benzoic acid (0.040mol), 50ml vinylacetate (0.54mol), palladium quality hundred is added in reactor (bottle)
Divide the palladium-carbon catalyst 1g of content 10%, be heated to reaction temperature 120 DEG C, after reacting 48 hours, stopped reaction, separate after cooling
Going out palladium-carbon catalyst, it is quantitative that reactant liquor carries out chromatography.Reaction conversion ratio is 15%, and selectivity is 96%.
Claims (5)
1. for preparing a heterogeneous catalytic system for vinyl carboxylates, including catalyst and catalyst promoter, it is characterised in that
Described catalyst be palladium weight/mass percentage composition be the palladium-carbon catalyst of 3.5%-10%, described catalyst promoter is alkali metal halogenation
At least one in thing and quaternary ammonium salt, described catalyst and catalyst promoter mass ratio are 0.5-5:1.
Heterogeneous catalytic system for preparing vinyl carboxylates the most according to claim 1, it is characterised in that described alkali gold
Genus halogenide is the one in sodium chloride, potassium chloride, potassium fluoride, sodium fluoride, potassium bromide, potassium iodide.
Heterogeneous catalytic system for preparing vinyl carboxylates the most according to claim 1, it is characterised in that described quaternary ammonium
Salt is the one in tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride.
4. the using method of the heterogeneous catalytic system for preparing vinyl carboxylates described in claim 1, it is characterised in that will
Carboxylic acid, vinylacetate carry out reaction under heterogeneous catalytic system effect and prepare vinyl carboxylates, described carboxylic acid and vinyl acetate
The mol ratio of ester is 1:3~15.5, and in described heterogeneous catalyst system, catalyst amount is the 2.5-40% of carboxylic acid quality, reaction
Temperature is 80-160 DEG C, and the response time is 6-48h.
The using method of the heterogeneous catalytic system for preparing vinyl carboxylates the most according to claim 4, its feature exists
In described carboxylic acid is 2 ethyl hexanoic acid, neodecanoic acid, trifluoracetic acid, butanoic acid, Palmic acid, benzoic acid, enanthic acid, stearic acid one
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Cited By (1)
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CN108084023A (en) * | 2017-12-06 | 2018-05-29 | 山东威高药业股份有限公司 | A kind of preparation method of 1- chloroethenes yl acetate |
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CN103025702A (en) * | 2010-05-04 | 2013-04-03 | 塞拉尼斯国际公司 | Process for the continuous transvinylation of carboxylic acids with vinyl acetate |
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2016
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WO1999059952A1 (en) * | 1998-05-15 | 1999-11-25 | Research Triangle Institute | Method of preparing alkyl carboxylic acids by carboxylation of lower alkanes methane |
CN103025702A (en) * | 2010-05-04 | 2013-04-03 | 塞拉尼斯国际公司 | Process for the continuous transvinylation of carboxylic acids with vinyl acetate |
CN102643263A (en) * | 2012-04-26 | 2012-08-22 | 陕西师范大学 | Method for preparing glycerol carbonate by liquid-phase oxidation and carbonylation of glycerol |
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CN108084023A (en) * | 2017-12-06 | 2018-05-29 | 山东威高药业股份有限公司 | A kind of preparation method of 1- chloroethenes yl acetate |
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