CN107382712A - A kind of preparation method of 1,10 decanedioic acid - Google Patents
A kind of preparation method of 1,10 decanedioic acid Download PDFInfo
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- CN107382712A CN107382712A CN201710768995.XA CN201710768995A CN107382712A CN 107382712 A CN107382712 A CN 107382712A CN 201710768995 A CN201710768995 A CN 201710768995A CN 107382712 A CN107382712 A CN 107382712A
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Abstract
The invention discloses a kind of preparation method of 1,10 decanedioic acid, comprise the following steps：By substance A, hydrolysis obtain the decanedioic acid of 4,7 diketone 1,10 in sour environment；The decanedioic acid of 4,7 diketone 1,10 obtains 1,10 decanedioic acid with hydrogen, fluoroform sulphonate, hydrogenation catalyst hydrogenation deoxidation.Atom economy of the present invention is good, product yield high, and product purity is high, and environmental pollution is small, and process route is simple, easy to operate, and raw material is cheap and easy to get, is adapted to industrialization large-scale production.
Description
Technical field
The present invention relates to chemical substance preparing technical field, more particularly to the preparation method of one kind 1,10- decanedioic acid.
Background technology
1,10- decanedioic acid is widely used, is mainly used to produce the esters of decanedioic acid, and its esters is widely used, such as decanedioic acid
Dibutyl ester, di-n-octyl sebacate, Plexol 201.These esters can make the plasticizer of plastics, arctic rubber；It can also be used for
Produce polyamide, polyurethane, alkyd resin, synthetic lubricant fluid, lube oil additive and spices, coating, cosmetics etc.；Also may be used
As production nylon 10,10, nylon 9,10, nylon 8,10, nylon 6,10, the raw material of nylon 9 and high temperature resistant luboil diethyl
The raw material of own ester；And production alkyd resin (be used as surface coating, plasticising cellulose nitrate coating and urea resin varnish) and
Polyurethane rubber, celluosic resin, the plasticizer of vinylite and synthetic rubber, the raw material of softening agent and solvent.
1,10- decanedioic acid is to add alkali destructive distillation to obtain with castor oil earliest, follow-up developments synthetic method.It is currently being deployed
The variation route of oil n-alkane fermentation 1,10- decanedioic acid processed.Another production method of 1,10- decanedioic acid is Japanese Asahi Chemical Industry
The adipic acid electrolytic oxidation of industrial group's exploitation, but either source is limited or used the raw material that uses of the above method
It is non-renewable petroleum resources.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes the preparation method of one kind 1,10- decanedioic acid, this hair
Bright raw material is cheap and easy to get, and Atom economy is good, product yield high, and product purity is high, and environmental pollution is small, and process route is simple,
It is easy to operate, it is adapted to industrialization large-scale production.
A kind of preparation method of 1,10- decanedioic acid proposed by the present invention, comprises the following steps：By substance A in sour environment
Middle hydrolysis obtain 4,7- diketone -1,10- decanedioic acid；4,7- diketone -1,10- decanedioic acid and hydrogen, fluoroform sulphonate, add
Hydrogen catalyst hydrogenation deoxidation obtains 1,10- decanedioic acid, wherein, the chemical structural formula of substance A is as follows：
Wherein, R is hydrogen atom or alkyl.
Preferably, R is the alkyl that hydrogen atom or carbon number are less than 5.
Preferably, the pH of sour environment is less than 1.
Preferably, fluoroform sulphonate is the metal salts of trifluoromethane sulphonic acid of+3 to+6 valencys.
Preferably, 4,7- diketone -1,10- decanedioic acid, the mol ratio of fluoroform sulphonate are 10-100：1.
Above-mentioned fluoroform sulphonate includes W (OTf)6、Hf(OTf)4、Al(OTf)3、Ta(OTf)5、Nb(OTf)5、Zr
(OTf)4Deng the metal salts of trifluoromethane sulphonic acid of+3 to+6 valencys.
Preferably, hydrogenation catalyst is the catalyst containing the VIIIth group 4 transition metal element.
Preferably, the metallic element and 4 in catalyst containing the VIIIth group 4 transition metal element, 7- diketone -1,10- last of the ten Heavenly stems two
The mol ratio of acid is 1：10-1000.
Above-mentioned hydrogenation catalyst refers to compound and the catalyst used during hydrogen addition, such as：VIIIth group 4 transition metal, contains
The metal oxide of VIIIth group 4 transition metal element, metal complex etc.；The carrier of metal complex is generally aluminum oxide or work
Property carbon；Specific hydrogenation catalyst includes：Palladium carbon, platinum carbon etc..
Preferably, the reaction dissolvent of hydrogenation deoxidation is carboxylic acid.
Preferably, the reaction dissolvent of hydrogenation deoxidation is acetic acid.
Preferably, sour environment is maintained with acidic materials.
Preferably, acidic materials are inorganic acid.
Above-mentioned inorganic acid includes the general inorganic strong acid such as hydrochloric acid, sulfuric acid.
Preferably, Hydrogen Vapor Pressure 3-100atm.
Preferably, Hydrogen Vapor Pressure 3-50atm.
Preferably, the reaction temperature of hydrogenation deoxidation is 120-250 DEG C.
Preferably, the reaction temperature of hydrogenation deoxidation is 160-200 DEG C.
Preferably, the reaction time of hydrogenation deoxidation is 1-24h.
Preferably, hydrolysis concretely comprise the following steps：Methanol, substance A are mixed, regulation pH is less than 1, backflow, is spin-dried for
It is 4,7- diketone -1,10- decanedioic acid to solid.
Preferably, during hydrolysis, it is less than 1 with acidic materials aqueous solution regulation pH.
Preferably, the mass fraction of the acidic materials aqueous solution is 20-50wt%.
Preferably, during hydrolysis, flow back 10-24h.
Preferably, during hydrolysis, after being spin-dried for, repurity obtains 4,7- diketone -1,10- decanedioic acid.
Preferably, purifying concretely comprises the following steps：Solid is dissolved in alkaline aqueous solution, adds decolorizing with activated carbon, filters to take filter
Liquid, regulation pH are less than 1, and crystallization obtains 4,7- diketone -1,10- decanedioic acid.
Preferably, hydrogenation deoxidation concretely comprises the following steps：By 4,7- diketone -1,10- decanedioic acid, hydrogenation catalyst, fluoroform
Sulfonate, reaction dissolvent mix, and in atmosphere of hydrogen, stirring heating, insulated and stirred obtains 1,10- decanedioic acid.
Preferably, during hydrogenation deoxidation, after insulated and stirred, repurity obtains 1,10- decanedioic acid.
Preferably, purifying concretely comprises the following steps：Filtrate is filtered to take, vacuum distillation obtains solid；Solid is decolourized to obtain 1,
10- decanedioic acid.
Preferably, decolouring concretely comprises the following steps：Solid is dissolved in sodium hydrate aqueous solution, adds activated carbon decolorizing, mistake
Leaching filtrate, it is less than 2 with salt acid for adjusting pH, filters to take filter cake, drying obtains 1,10- decanedioic acid.
Preferably, furfural and substance B obtain substance A through alkaline matter catalyzing and condensing, wherein, the chemical structural formula of substance B
It is as follows：
Wherein, substance B is identical with the R in substance A.
Substance A is obtained through alkaline matter catalyzing and condensing with furfural and substance B, is conventional aldol condensation reactions, it is synthesized
Route is as follows：
The preparation method of aldol condensation reactions is quite perfect, and those skilled in the art can be conventional according to this area
Prepared by method, can also be prepared according to content as defined below：
Preferably, when R is hydrogen atom, alkaline matter is the alkaline matter containing metallic element.
The above-mentioned alkaline matter containing metallic element includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, caustic alcohol, uncle
The conventional alkaline matter containing metallic element such as butanol potassium.
Preferably, when R is hydrogen atom, the mol ratio of alkaline matter and substance B is more than 1.
Preferably, when R is alkyl, alkaline matter is organic base.
Preferably, when R is alkyl, alkaline matter is organic base, wherein, in organic base containing primary amine group, secondary amine group,
At least one of tertiary amine group group.
Above-mentioned organic base includes the Conventional organic bases such as pyrroles, triethylamine, morpholine, pyridine.
Preferably, when R is hydrogen atom, after condensation, acidified processing is needed to obtain substance A.
Preferably, when R is hydrogen atom, condensation concretely comprises the following steps：Alkaline matter and substance B solution are mixed, are heated to
Backflow, furfuryl aldehyde solution is added dropwise, flow back 1-24h, and acidifying obtains substance A.
Preferably, when R is hydrogen atom, in the condensation process, the solvent of substance B solution is water.
Preferably, when R is hydrogen atom, in the condensation process, the solvent of furfuryl aldehyde solution is methanol.
Preferably, when R is hydrogen atom, in the condensation process, it is acidified with acidic aqueous solution.
Preferably, acidic aqueous solution is that mass fraction is 5-10wt% aqueous hydrochloric acid solutions.
Preferably, when R is hydrogen atom, in the condensation process, after acidifying, repurity obtains substance A.
Preferably, purifying concretely comprises the following steps：Filter cake, frozen water washing are filtered to take, hot water is recrystallized to give substance A.
Preferably, when R is hydrogen atom, in the condensation process, substance B, the mol ratio of furfural are 5：1-3.
Preferably, when R is alkyl, condensation concretely comprises the following steps：Alkaline matter, substance B, furfural are mixed, are stirred at room temperature
1-24h obtains substance A.
Preferably, when R is alkyl, in the condensation process, after being stirred at room temperature, repurity obtains substance A.
Preferably, purifying concretely comprises the following steps：Filtrate is filtered to take, is concentrated to give concentrate；Dissolved and concentrated with ethyl acetate
Thing, with silicagel column elution, it is spin-dried for obtaining substance A.
Preferably, when R is alkyl, in the condensation process, alkaline matter, substance B, the mol ratio of furfural are 1：1-10：1-
10。
During above-mentioned hydrolysis, the dosage of methanol is not provided, and its dosage is determined according to concrete operations；Do not provide to flow back
Temperature, maintain the reflux for state.
During above-mentioned hydrogenation deoxidation, the dosage of reaction dissolvent is not provided, and its dosage is determined according to concrete operations.
In condensation course when above-mentioned R is hydrogen atom, the concentration of substance A solution, furfuryl aldehyde solution is not provided, according to specific behaviour
Make to determine its concentration；Reflux temperature is not provided, maintains the reflux for state.
During above-mentioned hydrogenation deoxidation, condensation, hydrolysis, thin-layer chromatography auxiliary monitoring can be used whether complete to react.
The synthetic route of the present invention is as follows：
The present inventor has found that substance A (δ-furfuryl group levulic acid or its ester) hydrolyzes in sour environment by further investigation
Open loop obtains 4,7- diketone -1,10- decanedioic acid, and the ketone carbonyl in 4,7- diketone -1,10- decanedioic acid, which is hydrogenated, is changed into secondary alcohol hydroxyl
After base, under fluoroform sulphonate promotion, secondary hydroxyl group is easily and carboxylic acid acts on obtaining secondary alcohol ester；And secondary alcohol ester is in fluoroform sulphur
Under hydrochlorate promotes, hydroxyl-removal can be gone with hydrogenolysis, so that 4,7- diketone -1,10- decanedioic acid are in hydrogenation catalyst and fluoroform
Selective hydrogenation deoxidation obtains 1,10- decanedioic acid under the common catalyst system and catalyzing of sulfonate；Atom economy of the present invention is good, product yield
Height, product purity is high, and environmental pollution is small, and process route is simple, easy to operate, is adapted to industrialization to mass produce, product 1,
The application field of 10- decanedioic acid is extensive, and market prospects are good, and the added value of product is high, before the present invention has potential commercial Application
Scape；And substance A is prepared for raw material from furfural and substance B (levulic acid or its ester), furfural can be obtained using hydrolysis of hemicellulose
Arrive, substance B can utilize cellulose hydrolysis or alcoholysis to obtain, and wide material sources, be reproducible biomass resource, cheap and easy to get, behaviour
Make simple, reduction production cost, suitable industrialized production.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure for the 1,10- decanedioic acid that the present invention is prepared.
Fig. 2 is the nuclear-magnetism carbon spectrogram for the 1,10- decanedioic acid that the present invention is prepared.
Fig. 3 is the nucleus magnetic hydrogen spectrum figure for the 4,7- diketone -1,10- decanedioic acid that the present invention is prepared.
Fig. 4 is the nuclear-magnetism carbon spectrogram for the 4,7- diketone -1,10- decanedioic acid that the present invention is prepared.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：By substance A, hydrolysis obtain in sour environment
To 4,7- diketone -1,10- decanedioic acid；4,7- diketone -1,10- decanedioic acid is hydrogenated with hydrogen, fluoroform sulphonate, hydrogenation catalyst
Deoxidation obtains 1,10- decanedioic acid
Embodiment 2
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：Methanol, δ-furfuryl group methyl ester levulinate are mixed,
It is that 37wt% aqueous hydrochloric acid solutions regulation pH is less than 1 with mass fraction, flow back 17h, is spin-dried for obtaining solid；Solid is dissolved in hydroxide
In sodium water solution, adding activated carbon heating to decolourize, filter to take filtrate, be less than 1 with salt acid for adjusting pH, crystallization obtains 4,7- diketone -1,
10- decanedioic acid；
By 4,7- diketone -1,10- decanedioic acid, palladium carbon, Al (OTf)3, acetic acid mix, in atmosphere of hydrogen, adjust hydrogen pressure
Power is 80atm, and stirring is warming up to 140 DEG C, insulated and stirred 20h, filters to take filtrate, and vacuum distillation obtains solid；Solid is dissolved in
In sodium hydrate aqueous solution, activated carbon decolorizing is added, filters to take filtrate, be less than 2 with salt acid for adjusting pH, filter to take filter cake, dry
1,10- decanedioic acid is obtained, wherein, 4,7- diketone -1,10- decanedioic acid, W (OTf)6Mol ratio be 55：1, the palladium member in palladium carbon
The mol ratio of element and 4,7- diketone -1,10- decanedioic acid is 1：500.
Embodiment 3
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Sodium hydroxide and the levulic acid aqueous solution are mixed, are heated to flowing back, furfural-methanol solution is added dropwise, flow back 1h, uses
Mass fraction is acidified for 5wt% aqueous hydrochloric acid solutions, filters to take filter cake, frozen water washing, and hot water is recrystallized to give δ-furfuryl group levulinic
Acid, wherein, levulic acid, the mol ratio of furfural are 5：3, the mol ratio of sodium hydroxide and levulic acid is 1.05：1；
Methanol, δ-furfuryl group levulic acid are mixed, is that 20wt% aqueous hydrochloric acid solutions regulation pH is less than 1 with mass fraction, returns
10h is flowed, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon heating de-
Color, filtrate is filtered to take, be less than 1 with salt acid for adjusting pH, crystallization obtains 4,7- diketone -1,10- decanedioic acid；
By 4,7- diketone -1,10- decanedioic acid, platinum carbon, Zr (OTf)4, acetic acid mix, in atmosphere of hydrogen, adjust hydrogen pressure
Power is 100atm, and stirring is warming up to 120 DEG C, insulated and stirred 24h, filters to take filtrate, and vacuum distillation obtains solid；Solid is dissolved in
In sodium hydrate aqueous solution, activated carbon decolorizing is added, filters to take filtrate, be less than 2 with salt acid for adjusting pH, filter to take filter cake, dry
1,10- decanedioic acid is obtained, wherein, 4,7- diketone -1,10- decanedioic acid, Zr (OTf)4Mol ratio be 100：1, the platinum in platinum carbon
The mol ratio of element and 4,7- diketone -1,10- decanedioic acid is 1：10.
Embodiment 4
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Caustic alcohol and the levulic acid aqueous solution are mixed, are heated to flowing back, furfural-methanol solution is added dropwise, flow back 24h, uses matter
Measure fraction to be acidified for 10wt% aqueous hydrochloric acid solutions, filter to take filter cake, frozen water washing, hot water is recrystallized to give δ-furfuryl group levulinic
Acid, wherein, levulic acid, the mol ratio of furfural are 5：1, the mol ratio of caustic alcohol and levulic acid is 1.05：1；
Methanol, δ-furfuryl group levulic acid are mixed, is that 50wt% aqueous sulfuric acids regulation pH is less than 1 with mass fraction, returns
24h is flowed, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon heating de-
Color, filtrate is filtered to take, be less than 1 with salt acid for adjusting pH, cooling crystallization obtains 4,7- diketone -1,10- decanedioic acid；
By 4,7- diketone -1,10- decanedioic acid, palladium carbon, Hf (OTf)4, acetic acid mix, in atmosphere of hydrogen, adjust hydrogen pressure
Power is 3atm, with 600r/min speed, is stirred in 30min and is warming up to 250 DEG C, insulated and stirred 1h, filter to take filtrate, depressurized
Distillation obtains solid；Solid is dissolved in sodium hydrate aqueous solution, activated carbon decolorizing is added, filters to take filtrate, adjusted with hydrochloric acid
PH is less than 2, filters to take filter cake, and drying obtains 1,10- decanedioic acid, wherein, 4,7- diketone -1,10- decanedioic acid, Hf (OTf)4Rub
You are than being 10：1, the mol ratio of palladium element and 4,7- diketone -1,10- decanedioic acid in palladium carbon is 1：1000.
Embodiment 5
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Triethylamine, ethyl levulinate, furfural are mixed, 1h is stirred at room temperature, filters to take filtrate, is concentrated to give concentrate；
Concentrate is dissolved with ethyl acetate, with silicagel column elution, is spin-dried for obtaining δ-furfuryl group ethyl levulinate, wherein, triethylamine, acetyl
Ethyl propionate, the mol ratio of furfural are 1：1：1；
Methanol, δ-furfuryl group ethyl levulinate are mixed, are that 30wt% aqueous hydrochloric acid solutions regulation pH is less than with mass fraction
1, flow back 12h, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon to add
Heat decoloring, filtrate is filtered to take, be less than 1 with salt acid for adjusting pH, be cooled to 0 DEG C, crystallization 10h obtains 4,7- diketone -1,10- last of the ten Heavenly stems two
Acid；
By 4,7- diketone -1,10- decanedioic acid, platinum carbon, Ta (OTf)5, acetic acid mix, in atmosphere of hydrogen, adjust hydrogen pressure
Power is 10atm, with 700r/min speed, is stirred in 30min and is warming up to 200 DEG C, insulated and stirred 12h, filtered to take filtrate, subtract
Pressure distillation obtains solid；Solid is dissolved in sodium hydrate aqueous solution, activated carbon decolorizing is added, filters to take filtrate, adjusted with hydrochloric acid
Saving pH and be less than 2, filter to take filter cake, drying obtains 1,10- decanedioic acid, wherein, 4,7- diketone -1,10- decanedioic acid, Ta (OTf)5's
Mol ratio is 80：1, the mol ratio of platinum element and 4,7- diketone -1,10- decanedioic acid in platinum carbon is 1：700.
Embodiment 6
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Pyridine, Butyl acetylpropanoate, furfural are mixed, 24h is stirred at room temperature, filters to take filtrate, is concentrated to give concentrate；With
Ethyl acetate dissolves concentrate, with silicagel column elution, is spin-dried for obtaining δ-furfuryl group Butyl acetylpropanoate, wherein, pyridine, levulic acid
Butyl ester, the mol ratio of furfural are 1：10：10；
Methanol, δ-furfuryl group Butyl acetylpropanoate are mixed, are that 35wt% aqueous sulfuric acids regulation pH is less than with mass fraction
1, flow back 20h, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon to add
Heat decoloring, filtrate is filtered to take, be less than 1 with salt acid for adjusting pH, be cooled to 0 DEG C, crystallization 10h obtains 4,7- diketone -1,10- last of the ten Heavenly stems two
Acid；
By 4,7- diketone -1,10- decanedioic acid, palladium carbon, Nb (OTf)5, acetic acid mix, in atmosphere of hydrogen, adjust hydrogen pressure
Power is 60atm, with 650r/min speed, is stirred in 30min and is warming up to 220 DEG C, insulated and stirred 8h, filtered to take filtrate, subtract
Pressure distillation obtains solid；Solid is dissolved in sodium hydrate aqueous solution, activated carbon decolorizing is added, filters to take filtrate, adjusted with hydrochloric acid
Saving pH and be less than 2, filter to take filter cake, drying obtains 1,10- decanedioic acid, wherein, 4,7- diketone -1,10- decanedioic acid, Nb (OTf)5's
Mol ratio is 40：1, the mol ratio of palladium element and 4,7- diketone -1,10- decanedioic acid in palladium carbon is 1：100.
Embodiment 7
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Pyrroles, methyl ester levulinate, furfural are mixed, 8h is stirred at room temperature, filters to take filtrate, is concentrated to give concentrate；With
Ethyl acetate dissolves concentrate, with silicagel column elution, is spin-dried for obtaining δ-furfuryl group methyl ester levulinate, wherein, pyrroles, levulic acid
Methyl esters, the mol ratio of furfural are 1：8：8；
Methanol, δ-furfuryl group methyl ester levulinate are mixed, are that 40wt% aqueous sulfuric acids regulation pH is less than with mass fraction
1, flow back 15h, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon to add
Heat decoloring, filtrate is filtered to take, be less than 1 with salt acid for adjusting pH, be cooled to 0 DEG C, crystallization 10h obtains 4,7- diketone -1,10- last of the ten Heavenly stems two
Acid, wherein, the mol ratio of δ-furfuryl group methyl ester levulinate and sulfuric acid is 1：2.8, δ-furfuryl group methyl ester levulinate and methanol rub
Your volume (mol/l) ratio is 1：1；
It is 5wt% palladium carbon, Hf (OTf) by 4,7- diketone -1,10- decanedioic acid, palladium content3, acetic acid mix, logical hydrogen puts
After changing four gases, it is 50atm to be flushed with hydrogen gas to Hydrogen Vapor Pressure at room temperature, and with 800r/min speed, heating is stirred in 30min
To 160 DEG C, insulated and stirred 15h, filtrate is filtered to take in cooling, pressure release, and vacuum distillation obtains solid；Solid is dissolved in mass fraction
In 10wt% sodium hydrate aqueous solutions, to add activated carbon heating decolouring 30min, filtrate is filtered to take, is less than with salt acid for adjusting pH
2, filter cake is filtered to take, drying obtains 1,10- decanedioic acid, wherein, 4,7- diketone -1,10- decanedioic acid, Al (OTf)3Mol ratio be
50：3, the mol ratio of palladium element and 4,7- diketone -1,10- decanedioic acid in palladium carbon is 1：50,4,7- diketone -1,10- decanedioic acid
Molal volume (mol/l) with acetic acid is than being 1：15.
Embodiment 8
The preparation method of one kind 1,10- decanedioic acid, comprises the following steps：
Concentration is added portionwise to be mixed in the 1.55mol/l levulic acid aqueous solution in sodium carbonate, is heated to flowing back, is added dropwise dense
Spend for 5.81mol/l furfural-methanol solution, flow back 1h, is that 7.5wt% aqueous hydrochloric acid solutions are acidified with mass fraction, filters to take filter
Cake, frozen water washing, hot water are recrystallized to give δ-furfuryl group levulic acid, wherein, levulic acid, the mol ratio of furfural are 1：0.6, carbon
The mol ratio of sour sodium and levulic acid is 1.46：1；
Methanol, δ-furfuryl group levulic acid are mixed, is that 37wt% aqueous hydrochloric acid solutions regulation pH is less than 1 with mass fraction, returns
15h is flowed, is spin-dried for obtaining solid；Solid is dissolved in mass fraction in 10wt% sodium hydrate aqueous solutions, to add activated carbon heating de-
Color, filtrate being filtered to take, be less than 1 with salt acid for adjusting pH, be cooled to 0 DEG C, crystallization 10h obtains 4,7- diketone -1,10- decanedioic acid, its
In, the mol ratio of δ-furfuryl group levulic acid and hydrochloric acid is 1：The molal volume of 7.2, δ-furfuryl group levulic acid and methanol (mol/l)
Than for 3：4；
It is 10wt% palladium carbon, W (OTf) by 4,7- diketone -1,10- decanedioic acid, palladium content6, acetic acid mix, logical hydrogen puts
After changing four gases, it is 30atm to be flushed with hydrogen gas to Hydrogen Vapor Pressure at room temperature, and with 500r/min speed, heating is stirred in 30min
To 180 DEG C, insulated and stirred 10h, filtrate is filtered to take in cooling, pressure release, and vacuum distillation obtains solid；Solid is dissolved in mass fraction
In 10wt% sodium hydrate aqueous solutions, to add activated carbon heating decolouring 30min, filtrate is filtered to take, is less than with salt acid for adjusting pH
2, filter cake is filtered to take, drying obtains 1,10- decanedioic acid, wherein, 4,7- diketone -1,10- decanedioic acid, W (OTf)6Mol ratio be
50：3, the mol ratio of palladium element and 4,7- diketone -1,10- decanedioic acid in palladium carbon is 1：50,4,7- diketone -1,10- decanedioic acid
Molal volume (mol/l) with acetic acid is than being 1：10.
4,7- diketone -1,10- decanedioic acid, 1, the 10- decanedioic acid that embodiment 8 is prepared carry out nuclear-magnetism detection, as a result
Reference picture 1-4.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 1,10- decanedioic acid that the present invention is prepared, as a result for1H NMR(400MHz,
DMSO):δ=11.98 (s, 2H), 2.18 (t, J=7.4Hz, 4H), 1.55-1.40 (m, 4H), 1.25 (s, 8H)；
Fig. 2 is the nuclear-magnetism carbon spectrogram of 1,10- decanedioic acid that the present invention is prepared, as a result for13C NMR(101MHz,
DMSO):δ=174.97,34.12,29.03 (d, J=11.7Hz), 24.94；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of 4,7- diketone -1,10- decanedioic acid that the present invention is prepared, as a result for1H-NMR
(400MHz,DMSO):δ=12.10 (s, 2H), 2.66 (dd, J=11.4,4.6Hz, 8H), 2.38 (t, J=6.5Hz, 4H)；
Fig. 4 is the nuclear-magnetism carbon spectrogram of 4,7- diketone -1,10- decanedioic acid that the present invention is prepared, as a result for13C-NMR
(101MHz,DMSO):δ=208.30,174.17,37.04,36.06,28.12；
Can be seen that the present invention is prepared by above-mentioned testing result is 4,7- diketone -1,10- decanedioic acid, the 1,10- last of the ten Heavenly stems two
Acid.
The yield of Statistics Implementation example 7,8, detection δ-furfuryl group levulic acid, δ-furfuryl group methyl ester levulinate, 4,7- diketone -1,
The purity of 10- decanedioic acid and 1,10- decanedioic acid is as a result as follows：
High income of the invention, 1, the 10- decanedioic acid purity being prepared are good as can be seen from the above table.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. one kind 1, the preparation method of 10- decanedioic acid, it is characterised in that comprise the following steps：By substance A in sour environment reclaimed water
Solution open loop obtains 4,7- diketone -1,10- decanedioic acid；4,7- diketone -1,10- decanedioic acid is urged with hydrogen, fluoroform sulphonate, hydrogenation
Agent hydrogenation deoxidation obtains 1,10- decanedioic acid, wherein, the chemical structural formula of substance A is as follows：
Wherein, R is hydrogen atom or alkyl.
2. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that R is that hydrogen atom or carbon number are small
In 5 alkyl；Preferably, the pH of sour environment is less than 1.
3. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that fluoroform sulphonate is+3 to+6
The metal salts of trifluoromethane sulphonic acid of valency.
4. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that hydrogenation catalyst is to contain the VIIIth
The catalyst of group 4 transition metal element.
5. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that the reaction dissolvent of hydrogenation deoxidation is
Carboxylic acid；Preferably, the reaction dissolvent of hydrogenation deoxidation is acetic acid.
6. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that maintain acyclic acidic with acidic materials
Border；Preferably, acidic materials are inorganic acid.
7. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that Hydrogen Vapor Pressure 3-100atm；It is excellent
Selection of land, Hydrogen Vapor Pressure 3-50atm；Preferably, the reaction temperature of hydrogenation deoxidation is 120-250 DEG C；Preferably, hydrogenation deoxidation
Reaction temperature is 160-200 DEG C；Preferably, the reaction time of hydrogenation deoxidation is 1-24h.
8. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that hydrolysis concretely comprise the following steps：
Methanol, substance A are mixed, regulation pH is less than 1, and backflow, it is 4,7- diketone -1,10- decanedioic acid to be spin-dried for obtaining solid；It is preferred that
Ground, during hydrolysis, it is less than 1 with acidic materials aqueous solution regulation pH；Preferably, during hydrolysis,
Flow back 10-24h；Preferably, during hydrolysis, after being spin-dried for, repurity obtains 4,7- diketone -1,10- decanedioic acid；It is excellent
Selection of land, purifying concretely comprise the following steps：Solid is dissolved in alkaline aqueous solution, adds decolorizing with activated carbon, filters to take filtrate, regulation pH is small
In 1, crystallization obtains 4,7- diketone -1,10- decanedioic acid.
9. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that hydrogenation deoxidation concretely comprises the following steps：
4,7- diketone -1,10- decanedioic acid, hydrogenation catalyst, fluoroform sulphonate, reaction dissolvent are mixed, in atmosphere of hydrogen, stirring
Heating, insulated and stirred obtain 1,10- decanedioic acid；Preferably, during hydrogenation deoxidation, after insulated and stirred, repurity obtains 1,
10- decanedioic acid；Preferably, purifying concretely comprises the following steps：Filtrate is filtered to take, vacuum distillation obtains solid；Solid is decolourized to obtain
1,10- decanedioic acid；Preferably, decolouring concretely comprises the following steps：Solid is dissolved in sodium hydrate aqueous solution, activated carbon is added and takes off
Color, filtrate is filtered to take, be less than 2 with salt acid for adjusting pH, filter to take filter cake, drying obtains 1,10- decanedioic acid.
10. the preparation method of 1,10- decanedioic acid according to claim 1, it is characterised in that furfural and substance B are through basic species
Matter catalyzing and condensing obtains substance A, wherein, the chemical structural formula of substance B is as follows：
Wherein, substance B is identical with the R in substance A.
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| CN111187161B (en) * | 2020-01-20 | 2021-10-01 | 中国科学技术大学 | Preparation method of dihydrocapsaicin and dihydrocapsaicin ester |
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