CN110483293A - A kind of method that acetylene double carbonylation prepares succinate - Google Patents
A kind of method that acetylene double carbonylation prepares succinate Download PDFInfo
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- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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Abstract
The present invention provides a kind of methods that acetylene double carbonylation prepares succinate, carry out double carbonylation through catalyst in a solvent as raw material using acetylene, carbon monoxide and alcohol compound and react to obtain succinic acid ester type compound；Wherein catalyst is made of palladium compound, lithium halide/acid assistant and nitrogen oxygen ligand, and nitrogen oxygen ligand is one of 2 hydroxy pyrimidine, 3- pyridone and 2- pyridine carboxylic acid or a variety of, and the dosage of catalyst is the 0.0001-1.0% of reaction system total weight；In reaction system, the molar ratio of acetylene and alcohol compound is 1:2-16, and the molar ratio of alcohol compound and solvent is 1:7-35.The method of acetylene double carbonylation synthesizing succinic acid ester provided by the invention can be realized one kettle way production succinic acid ester type compound, and simple process, industrialized unit cost of investment is low；And the reaction condition of production process is mild, catalyst activity is strong, and stability is high, and service life is high, and yield has higher technology competition advantage up to 90% or more.
Description
Technical field
The invention belongs to technical field of chemical synthesis, specifically, being related to a kind of acetylene double carbonylation prepares succinate
Method.
Background technique
Two acid esters of fourth (alkene) is a kind of important Organic Chemicals and intermediate, is widely present in human body, animal, plant
In object and microorganism.Two acid esters of fourth (alkene) is industrial in synthetic plastic, rubber, dyestuff, fragrance, coating, medicine, pesticide and food etc.
Middle application is very extensive, it is the primary raw material of biodegradable plastic poly butylene succinate (PBS), and PBS material has excellent
Different mechanical property and heat resistance, the guidance and development of the highly compliant world and country to environment-friendly degradable policy, therefore,
Two acid esters of synthesis material fourth (alkene) similarly has huge market prospects.
Currently, the synthesis of two acid esters of fourth (alkene) is that first esterification occurs for synthesis fourth (alkene) diacid, subsequent succinic acid and alcohol instead
Two acid esters of fourth (alkene) should be generated.
The chemical synthesis process of existing succinic acid includes two major classes, and one kind is one-step method, that is, uses acetylene, carbon monoxide
And water is in [Co (CO)4] it is catalyzed lower synthesizing succinic acid, the reaction condition control of this reaction process is harsh, and reaction temperature is
80-250 DEG C, reaction pressure 2.9-49.0MPa, there is very big risk, and reaction yield is low；Another kind of is two-step method,
That is acetylene double carbonylation method, specifically: the first step, it is double that acetylene, carbon monoxide and water carry out acetylene under the effect of the catalyst
Carbonylation；Second step obtains succinic acid, the method for this synthesizing succinic acid using the further hydrogenation synthesis of acetylene carbonylation product
Reaction condition is mild and reaction yield is high, and there is good development prospect still to be found by the analysis to the prior art, existing
Have in technology and meeting the needs of actual production is difficult to the study on the synthesis of succinic acid using acetylene double carbonylation method.
Existing acetylene double carbonylation reaction synthesizing succinic acid is studied mainly around palladium-based catalyst, Bruk etc.
[Journal of Molecular Catalysis A:Chemical, 1995,104 (1): 9-16] use PdBr2-LiBr-
CH3CN catalyst system, under conditions of 40 DEG C and 101Kpa, acetylene carbonyl compound is at succinic anhydride, and the conversion ratio of acetylene is about
70%, but such method has the generation of the by-products such as 2,5- furanone, ethylene, and later separation processing is more difficult；Jinheng Li et al.
[Tetrahedron Letters, 2001,42 (39): 6923-6924] make solvent with dioxanes and water mixing, with PdCl2With
CuCl2Carbonylation is carried out to terminal alkyne for catalyst system, the yield of maleic anhydride is 98% or so, but reaction terminates
Afterwards, catalyst becomes black solid powder, and X-ray crystallography shows that the black powder is the Pd simple substance of black, is unfavorable for being catalyzed
Agent is recycled.
To sum up, existing acetylene double carbonylation prepares succinate there are two main problems: (1) needing first to synthesize fourth two
Acid, then reacted with alcohol esterification and generate succinate, reaction process is complicated, and industrialized unit cost of investment is high；(2) conjunction of succinic acid
The problems such as harsh, catalyst is difficult to be recycled, reaction yield is low at there are reaction conditions.
Summary of the invention
For deficiency above-mentioned in the prior art, the present invention provides the side that a kind of acetylene double carbonylation prepares succinate
Method can be realized one kettle way production succinic acid ester type compound, and simple process, industrialized unit cost of investment is low；And it produced
The reaction condition of journey is mild, and catalyst activity is strong, and catalyst stability is high, and service life is high, yield up to 90% or more,
With higher technology competition advantage.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
A kind of method that acetylene double carbonylation prepares succinate, using acetylene, carbon monoxide and alcohol compound as raw material
Double carbonylation is carried out through catalyst in a solvent to react to obtain succinic acid ester type compound；Wherein the catalyst is by palladium
Object, lithium halide/acid assistant and nitrogen oxygen ligand composition are closed, nitrogen oxygen ligand is 2 hydroxy pyrimidine, 3- pyridone and 2- pyridine carboxylic acid
One of or it is a variety of, the dosage of catalyst is the 0.0001-1.0% of reaction system total weight；In reaction system, acetylene and alcohol
The molar ratio of class compound is 1:2-16, and the molar ratio of alcohol compound and solvent is 1:7-35.
When reaction, alcohol compound, solvent and catalyst are added in a kettle, fixed proportion is passed through into reaction kettle
Acetylene and carbon mono oxide mixture react certain time in certain temperature and pressure limit, obtain succinic acid ester type compound,
The reaction has an advantage that
(1) reaction uses carbon monoxide, acetylene and alcohol compound for reaction raw materials, and in reaction process, acetylene is first sent out
Raw double carbonylation, the acetylene of subsequent double carbonylation react synthesizing succinic acid ester type compound with alcohol compound, and entire reaction exists
It is carried out in same reaction kettle, directly generates product from raw material one kettle way, it is not necessary that even three-step reaction, reaction process are simple in two steps
Single, industrialized unit cost of investment is low.
(2) in addition, in above-mentioned reaction, alcohol compound not only can be used as reactant but also can be used as solvent, Ke Yiyou
Effect reduces the solvent usage in reaction system.
(3) above-mentioned reacting middle catalyst is using palladium compound, the caltalyst of lithium halide/acid assistant and nitrogen oxygen ligand composition
System.Under normal conditions, with palladium compound (halogenation palladium) for major catalyst, metal salt is that the catalyst system of auxiliary agent can make C2H2With
Double carbonylation reaction occurs for CO, and in this reaction process, catalyst is in homogeneous reaction state in system, and precious metal palladium is with+2
Valence or+1 valence exist, and due to there is a small amount of hydrogen to generate in reaction process, other factors (match by unstripped gas in hydrogen and reaction system
Than, the dosage of alcohol, reaction temperature etc.) under the influence of, Metal Palladium is easy to be reduced into 0 valence state, and the palladium of 0 valence state can be with black precipitate
Form be precipitated, not only substantially reduce catalytic activity, reduce catalyst life, increase reaction cost, and give the separation of product
Increase difficulty with purifying.Nitrogen oxygen ligand is added in the present invention in catalyst system, can make nitrogen oxygen ligand and Pd2+Complex is formed,
Containing n-donor ligand has stronger coordination ability, and especially nitrogen ligand is mostly the bidentate containing two or more nitrogen-atoms or more
Tooth nitrogen ligand, and form bidentate or multiple tooth chelate containing other hetero atoms, due to the effect of bidentate and multiple tooth chelate, it
With transition metal formed complex have stronger stability；Meanwhile the electron cloud in nitrogen oxygen ligand on N and hydroxyl O is close
Degree has adjustment effect to the effect of catalyst, when closing on electrophilic on N and hydroxyl O or have aromatic radical, favorably
It is converted in carbonyl-complexes to acyl group complex, to improve catalyst activity, increases the yield of product；Acid assistant is added can be into
One step effectively avoids Pd2+It is reduced, further increases the stability of catalyst, extend the service life of catalyst.
Preferably, the molar ratio of acetylene and carbon monoxide is 1:0.5-5 in reaction system of the invention.Reaction temperature
Degree is 30~80 DEG C, and reaction pressure is 0.1~5MPa, and the reaction time is 30~2000min.
Its reaction condition of preparation method of the invention is mild, and the reaction time is reasonable, and reaction can directly obtain succinate
Class compound, simple process are suitable for promoting.
Specifically, in catalyst of the invention palladium compound be palladium bromide, palladium chloride, palladium iodide it is one or more；Halogen
Change lithium is one of lithium bromide, lithium chloride, lithium iodide or a variety of；Acid assistant is the concentrated sulfuric acid, concentrated hydrochloric acid, methane sulfonic acid, hydrogen bromine
One of acid is a variety of.
Preferably, pd in catalyst system of the invention2+With Li+Molar ratio be 1:6-14, palladium compound (halogenation
Palladium) it with the molar ratio of nitrogen oxygen ligand is 1:0.3-1, the molar ratio of palladium compound (halogenation palladium) and acid assistant is 1:10-50.This
The stability and activity for the palladium-based catalyst that catalyst system is formed are best.
Preferably, alcohol compound is one of methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol and octanol.
Preferably, solvent is one of toluene, acetone, acetonitrile, tetrahydrofuran, dioxanes and acetylacetone,2,4-pentanedione.
Specifically, succinic acid ester type compound of the present invention includes succinate, maleate and anti-butylene
Two acid esters.Wherein, the yield for the succinate for using preparation method of the invention to prepare is 30%-65%, maleate
Yield be 0.5%-4%, the yield of fumarate is 13%-25%, and the yield of total succinic acid ester type compound can
Up to 90% or more.
The beneficial effects of the present invention are:
(1) present invention uses carbon monoxide, acetylene and alcohol compound for reaction raw materials, and direct one kettle way generates product fourth
Two acid esters compounds are not necessarily in two steps even three-step reaction, and reaction process is simple, and industrialized unit cost of investment is low, competition
Advantage is strong；
(2) in the reaction of the present invention, alcohol compound not only can be used as reactant but also can be used as solvent, can be effective
Reduce the solvent usage in reaction system；
(3) catalyst of the invention is made of palladium compound, lithium halide/acid assistant and nitrogen oxygen ligand, which has
The advantage that stability is high, catalytic activity is high, so that the service life height of catalyst and the high income of reaction product.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It is specifically described below with reference to the method that embodiment prepares succinate to acetylene double carbonylation of the invention.
Embodiment 1
Weigh PdBr20.052g, LiBr 0.107g, methane sulfonic acid 0.2mL, 2 hydroxy pyrimidine 0.019g, n-butanol
2mL is dissolved in 30mL acetonitrile, is filled with acetylene 500mL and carbon monoxide 1000mL into storage cylinder respectively.Connection storage cylinder and anti-
Device is answered, is warming up to 40 DEG C, reacts 180min, pressure 0.1MPa.The yield of dibutyl succinate is 46.08% in product, along fourth
The yield of enedioic acid dibutyl ester is 7.36%, and the yield of dibutyl fumarate is 29.47%, and succinic acid ester type compound is total
Yield is 82.91%.
Embodiment 2
Weigh PdBr20.052g, LiBr 0.107g, methane sulfonic acid 0.2mL, 2 hydroxy pyrimidine 0.019g, n-butanol
2mL is dissolved in 30mL acetonitrile, is filled with acetylene 500mL and carbon monoxide 1000mL into storage cylinder respectively.Connection storage cylinder and anti-
Device is answered, is warming up to 40 DEG C, reacts 240min, pressure 0.1MPa.The yield of dibutyl succinate is 57.03% in product, along fourth
The yield of enedioic acid dibutyl ester is 2.81%, and the yield of dibutyl fumarate is 30.26%, and succinic acid ester type compound is total
Yield is 90.1%.
Embodiment 3
Supplement n-butanol 1.8ml, acetonitrile 1ml every time in the reaction solution of embodiment 2.Acetylene is filled with into storage cylinder respectively
500mL and carbon monoxide 1000mL.Connection storage cylinder and reactor investigate catalyst and reuse number, be warming up to 40 DEG C, instead
Answer 240min, pressure 0.1MPa.The yield of product dibutyl succinate is in reaction solution after catalyst repetition applies 10 times
58.63%, the yield of dibutyl maleate is 7.26%, and the yield of dibutyl fumarate is 22.45%, succinic acid
Ester type compound total recovery is 88.34%.
Embodiment 4
Weigh PdCl20.048g, LiI 0.106g, the concentrated sulfuric acid 0.2mL, 3- pyridone 0.0075g, n-butanol 2mL,
It is dissolved in 30mL acetonitrile, is filled with acetylene 500mL and carbon monoxide 1000mL into storage cylinder respectively.Connection storage cylinder with react
Device is warming up to 40 DEG C, reacts 180min, pressure 0.1MPa.The yield of dibutyl succinate is 46.63% in product, maleic
The yield of adipate is 1.15%, and the yield of dibutyl fumarate is 20.36%, and succinic acid ester type compound is always received
Rate is 68.14%.
Embodiment 5
Weigh PdBr20.175g, LiCl 0.370g, concentrated hydrochloric acid 0.1mL, 2 hydroxy pyrimidine 0.094g, n-butanol 2mL,
It is dissolved in 30mL acetonitrile, is filled with acetylene 500mL and carbon monoxide 1000mL into storage cylinder respectively.Connection storage cylinder with react
Device is warming up to 40 DEG C, reacts 180min, pressure 0.1MPa.The yield of dibutyl succinate is 45.30% in product, maleic
The yield of adipate is 2.83%, and the yield of dibutyl fumarate is 19.66%, and succinic acid ester type compound is always received
Rate is 67.79%.
Comparative example 1
Weigh PdBr20.052g, LiBr 0.107g, methane sulfonic acid 0.2mL, n-butanol 2mL are dissolved in 30mL acetonitrile,
Acetylene 500mL and carbon monoxide 1000mL are filled with into storage cylinder respectively.Connection storage cylinder and reactor are warming up to 40 DEG C, instead
Answer 180min, pressure 0.1MPa.The yield of dibutyl succinate is 41.84% in product, the yield of dibutyl maleate
It is 3.51%, the yield of dibutyl fumarate is 21.00%, and succinic acid ester type compound total recovery is 66.35%.
Above-described embodiment is all made of one kettle way and prepares succinic acid ester type compound, and preparation process is simple；And it is real by comparison
Example 1 is applied with the product yield of comparative example 1 it is known that when other reaction conditions are identical, in caltalyst of the invention
Under system, reaction product yield is significantly improved；By embodiment 3 also it is known that catalyst of the invention produces after multiplicating
Object yield is still higher, illustrates that the service life of catalyst of the invention is high.
To sum up, it is known that the method that acetylene carbonylation of the invention prepares succinate, can be realized one kettle way production
The reaction condition of succinate, simple process, and production process is mild, and catalyst activity is high, and catalyst service life is high, product
High income has very strong technology competition advantage.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of method that acetylene double carbonylation prepares succinate, which is characterized in that with acetylene, carbon monoxide and alcohols chemical combination
Object is that raw material reacts to obtain succinic acid ester type compound through catalyst progress double carbonylation in a solvent；
Wherein the catalyst is made of palladium compound, lithium halide/acid assistant and nitrogen oxygen ligand, and the nitrogen oxygen ligand is 2- hydroxyl
One of pyridine, 3- pyridone and 2- pyridine carboxylic acid are a variety of, and the dosage of the catalyst is reaction system total weight
0.0001-1.0%；
In reaction system, the molar ratio of acetylene and alcohol compound is 1:2-16, and the molar ratio of alcohol compound and solvent is 1:
7-35。
2. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that reaction system
In, the molar ratio of acetylene and carbon monoxide is 1:0.5-5.
3. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that reaction temperature is
30~80 DEG C, reaction pressure is 0.1~5MPa, and the reaction time is 30~2000min.
4. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that the catalyst
Middle palladium compound be palladium bromide, palladium chloride, palladium iodide it is one or more；Lithium halide is lithium bromide, in lithium chloride, lithium iodide
It is one or more；Acid assistant is one of the concentrated sulfuric acid, concentrated hydrochloric acid, methane sulfonic acid, hydrobromic acid or a variety of.
5. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that the catalytic body
Pd in system2+With Li+Molar ratio be 1:6-14, the molar ratio of palladium compound and nitrogen oxygen ligand is 1:0.3-1, palladium compound and acid
The molar ratio of auxiliary agent is 1:10-50.
6. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that the alcohols
Conjunction object is one of methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol and octanol.
7. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that the solvent is
One of toluene, acetone, acetonitrile, tetrahydrofuran, dioxanes and acetylacetone,2,4-pentanedione.
8. the method that acetylene double carbonylation according to claim 1 prepares succinate, which is characterized in that the succinic acid
Ester type compound includes succinate, maleate and fumarate.
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| CN112724007A (en) * | 2020-12-17 | 2021-04-30 | 中国成达工程有限公司 | System and method for producing succinic acid and PBS (Poly Butylene succinate) by using natural gas |
| CN113816839A (en) * | 2021-09-23 | 2021-12-21 | 中国成达工程有限公司 | Method for synthesizing butanedialdehyde by acetylene double-hydrogen formyl |
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| CN113816839B (en) * | 2021-09-23 | 2024-02-02 | 中国成达工程有限公司 | Method for synthesizing glyoxal through acetylene double hydroformylation |
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Application publication date: 20191122 |