CN106431927A - Preparing method of 3-hydroxypropionic acid ester - Google Patents
Preparing method of 3-hydroxypropionic acid ester Download PDFInfo
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- CN106431927A CN106431927A CN201510493328.6A CN201510493328A CN106431927A CN 106431927 A CN106431927 A CN 106431927A CN 201510493328 A CN201510493328 A CN 201510493328A CN 106431927 A CN106431927 A CN 106431927A
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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
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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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
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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
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention relates to a preparing method of 3-hydroxypropionic acid ester, and aims to solve the problem that a catalyst under a homogeneous system is difficult to separate in the prior art. The preparing method of the 3-hydroxypropionic acid ester comprises the steps of making ligand and cobalt carbonyl conduct coordination reaction in a solvent to obtain catalyst solution, wherein the solvent is alcohol or a solvent containing the alcohol, the ligand comprises a crosslinked polystyrene skeleton and -CH2XR perssad which is connected to benzene ring in the crosslinked polystyrene skeleton, wherein X is chosen from one of O atom, S atom and NH radical, R is chosen from one of 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; adding ethylene oxide and carbon monoxide into the catalyst solution to conduct reaction so as to obtain the 3-hydroxypropionic acid. According to the technical scheme, technical problems are favorably solved, and the preparing method can be applicable to the industrial production of 3-hydroxypropionic acid ester.
Description
Technical field
The present invention relates to the preparation method of 3- hydroxy propionate.
Background technology
1,3-PD is a kind of important organic fine chemicals, can be used as producing antifreezing agent, plasticizer, preservative
With the raw material of emulsifying agent, also it is widely used in the industries such as food, cosmetics and pharmacy, its most important application is conduct
Monomer synthesizes PTT (PTT) polyester fiber, with conventional polyethylene terephthalate
(PET) fiber is compared, ptt fiber both had light resistance, water suction less, the premium properties such as good stability, have simultaneously again
There is resilience good, the advantages of easily biological-degradable and environmental pollution are little, be with a wide range of applications, be current research
Focus with exploitation.At present, the technical process of 1,3-PD mainly has 3 kinds：Industrialized U.S. Shell in 1996
The oxirane hydroformylation hydrogenation method of company；The nineteen ninety-five acrolein hydration hydrogen succeeded in developing of Degussa company of Germany
Change method；Microbe fermentation method with DuPont as representative.Three of the above method has no substantially poor in production capacity
Not, but have their own characteristics each：Acrolein hydration hydrogenization method process conditions are gentle, and less, hydrogenation technique is ripe for technical difficulty,
Not high to equipment requirements, but this route raw material acrylic aldehyde hypertoxic and inflammable and explosive it is difficult to storage and transport, cost simultaneously
Higher.Microbe fermentation method is characterized with " Green Chemistry ", and using Renewable resource, production environment cleans, reaction
Mild condition, easy and simple to handle, pollution is little, but product design is low, and production efficiency is difficult to improve.Oxirane has
Abundance, cheap advantage, epoxyethane method enjoys favor, the centre of its ethylene oxide hydroformylation method
Body 3-HPA extremely unstable, catalytic separation technical sophistication and need to be using autoclave more than 10MPa, equipment
Have high demands, complex art difficulty is big, cost of investment is high.Comparatively speaking, oxirane hydroesterification method is due to intermediate
3- hydroxy propionate stable in properties and there is obvious advantage.
Oxirane hydroesterification method synthesizes 3- hydroxy propionate, taking synthesize 3- hydroxy methyl propionate as a example, reaction principle
It is expressed as follows：
This field prior art is mainly as follows：
Nineteen ninety, US4973741 discloses using Noble Metal Rhodium catalyst and triphenylphosphine ligand, oxirane hydrogen methyl ester
Base is combined to 3- hydroxy methyl propionate, but reaction needs the high pressure of 14MPa, and oxirane conversion ratio and target
The selectivity of product is relatively low.
Calendar year 2001, US6191321 discloses and uses Co2(CO)8The catalyst system of/1,10- adjacent phenanthrene quinoline, methyl- tert fourth
Base ether is solvent, at 90 DEG C, reacts 18 hours, oxirane conversion ratio is only 11% under conditions of 1125psi,
The selectivity of target product 3- hydroxy methyl propionate is 74%.
2002, EP1179524A1 disclosed with cobalt salt as catalyst, and N- alkyl azole compounds are part, and methanol is
The method that solvent synthesizes 3- hydroxy methyl propionate, wherein target product selectivity reaches as high as 90%.
2003, US6521801 disclosed with cobalt salt as catalyst, and nitrogen-containing heterocycle compound is part, in carbon monoxide
Pressure is 6MPa, and reaction temperature is under 75 DEG C of reaction condition, and oxirane conversion ratio is 94%, target product 3-
The selectivity of hydroxy methyl propionate is 78%.
2007, CN101020635A disclosed with cobalt salt as catalyst, and pyridine, quinoline and its respective derivant are to join
Body, alkaline or alkaline-earth salts are accelerator, and pressure is 3.0MPa～7.0MPa, and reaction temperature is 50 DEG C～100 DEG C,
Reaction 3 hours～5 hours, the selectivity of target product 3- hydroxy methyl propionate is up to 90%.
2011, CN101973881A disclosed with carbonyl cobalt functionalized ion liquid as catalyst, with nitrogen-containing hetero cyclisation
Compound or organic phosphine are part, and the pressure of carbon monoxide is 3.0MPa～7.0MPa, and reaction temperature is 50 DEG C～100 DEG C,
Response time be 6 hours～18 hours, the conversion ratio of oxirane up to 98.1%, target product 3- hydroxy methyl propionate
Yield up to 90.8%.
But the catalyst of homogeneous system is difficult to separate in prior art.
Content of the invention
To be solved by this invention is that the catalyst of homogeneous system in prior art is difficult to detached problem, provides a kind of new
The preparation method of 3- hydroxy propionate, the method has the advantages that catalyst system is easily separated from reaction system.
For solving above-mentioned technical problem, technical scheme is as follows：The preparation method of 3- hydroxy propionate, including
Following steps：
I, part and carbonyl cobalt is made to carry out complexation reaction in a solvent and obtain catalyst solution, described solvent is alcohol or contains
The solvent of alcohol；
Described part has crosslinked polystyrene skeleton and the-CH being connected with the phenyl ring in crosslinked polystyrene skeleton2XR
Group, wherein X are selected from one of O atom, S atom, NH base, and R is selected from 2- pyridine radicals, 3- pyridine radicals, 4-
Pyridine radicals, 5- quinolyl, 6- quinolyl, 7- quinolyl, one of 8- quinolyl；
Ii, in above-mentioned catalyst solution, add oxirane and carbon monoxide, reaction obtains described 3- hydracrylic acid
Ester.
In technique scheme, in terms of the molal quantity of the monomeric unit forming crosslinked polystyrene skeleton, described crosslinked poly-
In styrene skeleton containing 0.5～10% crosslinker module.Described crosslinker module is more preferably divinylbenzene units.
Described crosslinked polystyrene skeleton can also be able to be macroporous type crosslinked polystyrene skeleton for gel-type.The present invention is implemented
In mode in terms of the molal quantity of the monomeric unit forming crosslinked polystyrene skeleton, contain in described crosslinked polystyrene skeleton
There is 1% crosslinker module, the cross-linking agent of employing is divinylbenzene.
In technique scheme, described alcohol be preferably C1～C5 straight or branched alcohol, such as but not limited to be selected from methanol,
At least one in ethanol and propanol.
In technique scheme, described part nitrogen content is preferably 0.9-8.0mmol/g.
In technique scheme, in part, contained nitrogen and the mol ratio of carbonyl cobalt are preferably (1～5):1.
In technique scheme, described alcohol is preferably (2～25) with the mol ratio of oxirane:1.
In technique scheme, reaction pressure is preferably 3MPa～8MPa.
In technique scheme, reaction temperature is preferably 45～100 DEG C.
In technique scheme, the response time is preferably 3～10 hours.
Technical barrier to be solved by this invention is that the homogeneous catalyst of oxirane hydroesterification reaction is difficult to recycle
Key issue, provide a kind of short-cut method of the Immobilized homogenous catalyst based on resinamines to be easy to so as to have
The advantage recycling.
The present invention can specifically be carried out as follows：
I resin part and Co2(CO)8Complexation reaction in the solvent of containing alcohol, obtains the solution of catalyst, and this solution is turned
Move in reactor；
Ii nitrogen purging reactor three times, adds oxirane and CO to be reacted；
Iii reaction terminates, and kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, purges reactor three with nitrogen
Secondary；
Iv sample analysis, the conversion ratio of oxirane, the yield of 3- hydroxy propionate use gas chromatogram quantitative.
Co2(CO)8There is toxicity and easy decomposition, the therefore preparation of catalyst are preferably entered under the protection of the argon of glove box
OK.
The present invention does part using the polystyrene resins that pyridine or quinoline are modified, and can obtain stable solid catalyst,
After reaction, easy filtrations is recyclable, efficiently solves homogeneous catalyst separation difficulty used in conventional art
Problem, and gained solid catalyst has gentle, the active high remarkable advantage of catalytic reaction condition.
Give further instruction below by example to the present invention, but do not limit present disclosure.
Specific embodiment
Embodiment 1
1st, synthetic ligands A
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 2 hydroxy pyrimidine of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part A (nitrogen content is 2.0mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, adds the part A of 1g, stir under room temperature
2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds 50mmol
Oxirane, carbon monoxide, make system pressure be 6.0MPa, at 65 DEG C react 5 hours.Kettle is through fully
It is cooled to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result shows：Epoxy
The conversion ratio of ethane is the selectivity of 28%, 3- hydroxy methyl propionate is 76%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 2
1st, synthetic ligands B
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 3- pyridone of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part B (nitrogen content is 2.2mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part B of 0.91g, under room temperature
Stirring 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds
The oxirane of 50mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle
Body is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result table
Bright：The conversion ratio of oxirane is the selectivity of 35%, 3- hydroxy methyl propionate is 80%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 3
1st, synthetic ligands C
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 4- pyridone of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part C (nitrogen content is 2.5mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part C of 0.8g, stir under room temperature
Mix 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds 50
The oxirane of mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle warp
It is sufficiently cooled to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result shows：
The conversion ratio of oxirane is the selectivity of 42%, 3- hydroxy methyl propionate is 85%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 4
1st, synthetic ligands D
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the PA of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part D (nitrogen content is 3.6mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part D of 0.56g, under room temperature
Stirring 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds
The oxirane of 50mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle
Body is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result table
Bright：The conversion ratio of oxirane is the selectivity of 39%, 3- hydroxy methyl propionate is 87%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 5
1st, synthetic ligands E
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 2- mercaptopyridine of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part E (nitrogen content is 2.1mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part E of 0.95g, under room temperature
Stirring 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds
The oxirane of 50mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle
Body is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result table
Bright：The conversion ratio of oxirane is the selectivity of 32%, 3- hydroxy methyl propionate is 71%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 6
1st, synthetic ligands F
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 5- hydroxyquinoline of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part F (nitrogen content is 2.4mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part F of 0.83g, under room temperature
Stirring 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds
The oxirane of 50mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle
Body is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result table
Bright：The conversion ratio of oxirane is the selectivity of 40%, 3- hydroxy methyl propionate is 86%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
Embodiment 7
1st, synthetic ligands G
(1% divinylbenzene is handed over to add 5.0g gel-type chloromethylated polystyrene resin in 100mL round-bottomed flask
Connection, chlorinity is 4.0mmol/g), the 8- quinolin-2-ylamine of 0.2mol, the cesium carbonate of 0.2mol and 200mL bis-
Oxygen six ring, the lower reaction of backflow 72 hours.Reaction terminates, sucking filtration, washs solid with 20mL dioxane repeatedly, then
With 20mL deionized water wash solid repeatedly, finally wash solid respectively with 20mL ethanol, 20mL ether repeatedly,
Vacuum drying obtains 5.87g light yellow solid and is part G (nitrogen content is 3.0mmol/g).
2nd, 3- hydroxy methyl propionate synthesis
Co by 1.0mmol2(CO)8It is dissolved in 740mmol methanol, add the part G of 0.67g, under room temperature
Stirring 2 hours.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times, adds
The oxirane of 50mmol, carbon monoxide, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.Kettle
Body is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result table
Bright：The conversion ratio of oxirane is the selectivity of 43%, 3- hydroxy methyl propionate is 93%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 1】
In addition to replacing part A using pyridine, 3- hydroxy methyl propionate synthesis condition is same as Example 1, specifically
For：
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, add the pyridine of 2.0mmol,
Stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times,
Add oxirane, the carbon monoxide of 50mmol, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.
Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result
Show：The conversion ratio of oxirane is the selectivity of 80%, 3- hydroxy methyl propionate is 83%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
【Comparative example 2】
In addition to replacing part A using quinoline, 3- hydroxy methyl propionate synthesis condition is same as Example 1, specifically
For：
Co by 342mg (1.0mmol)2(CO)8It is dissolved in 740mmol methanol, add the quinoline of 2.0mmol,
Stir 2 hours under room temperature.Catalyst solution is transferred in the reactor of 100mL, with nitrogen purging reactor three times,
Add oxirane, the carbon monoxide of 50mmol, make system pressure be 6.0MPa, react 5 hours at 65 DEG C.
Kettle is cooled sufficiently to 0 DEG C, slow pressure release to normal pressure, with nitrogen purging reactor three times, sample analysis, result
Show：The conversion ratio of oxirane is the selectivity of 82%, 3- hydroxy methyl propionate is 77%.
For ease of comparing, by 3- hydroxy methyl propionate synthetic reaction, the results are shown in Table 1.
After data from table is it was found that be linked to crosslinked polystyrene skeleton by part, though the activity of catalyst
Decline, but selectivity has significantly improved, achieved unforeseeable technique effect.
Table 1
| Part | EO conversion ratio, % | 3- hydroxy methyl propionate selectivity, % | |
| Embodiment 1 | Part A | 28 | 76 |
| Embodiment 2 | Part B | 35 | 80 |
| Embodiment 3 | Part C | 42 | 85 |
| Embodiment 4 | Part D | 39 | 87 |
| Embodiment 5 | Part E | 32 | 71 |
| Embodiment 6 | Part F | 40 | 86 |
| Embodiment 7 | Part G | 43 | 93 |
| Comparative example 1 | Pyridine | 80 | 83 |
| Comparative example 2 | Quinoline | 82 | 77 |
Claims (9)
1. a kind of preparation method of 3- hydroxy propionate, comprises the steps：
I, part and carbonyl cobalt is made to carry out complexation reaction in a solvent and obtain catalyst solution, described solvent is alcohol or contains
The solvent of alcohol；
Described part has crosslinked polystyrene skeleton and the-CH being connected with the phenyl ring in crosslinked polystyrene skeleton2XR
Group, wherein X are selected from one of O atom, S atom, NH base, and R is selected from 2- pyridine radicals, 3- pyridine radicals, 4-
Pyridine radicals, 5- quinolyl, 6- quinolyl, 7- quinolyl, one of 8- quinolyl；
Ii, in above-mentioned catalyst solution, add oxirane and carbon monoxide, reaction obtains described 3- hydracrylic acid
Ester.
2. preparation method according to claim 1 it is characterised in that with form crosslinked polystyrene skeleton monomer
The molal quantity meter of unit, in described crosslinked polystyrene skeleton containing 0.5～10% crosslinker module.
3. preparation method according to claim 1 is it is characterised in that alcohol is the straight or branched alcohol of C1～C5.
4. preparation method according to claim 1 is it is characterised in that described part nitrogen content is 0.9-8.0
mmol/g.
5. preparation method according to claim 1 is it is characterised in that nitrogen contained in described part and carbonyl cobalt
Mol ratio is (1～5):1.
6. preparation method according to claim 1 is it is characterised in that the mol ratio of described alcohol and oxirane
For (2～25):1.
7. preparation method according to claim 1 is it is characterised in that reaction pressure is 3MPa～8MPa.
8. preparation method according to claim 1 is it is characterised in that reaction temperature is 45 DEG C～100 DEG C.
9. preparation method according to claim 1 is it is characterised in that the response time is 3 hours～10 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126879A (en) * | 2018-07-19 | 2019-01-04 | 厦门大学 | The method that nitrogen phosphorus coordination type metal catalyst and catalysis prepare 3- hydroxy propionate |
| CN115569669A (en) * | 2021-06-21 | 2023-01-06 | 惠生工程（中国）有限公司 | Solid heterogeneous catalyst for ethylene oxide methyl hydrogen esterification reaction, preparation method and application |
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| CN1186796A (en) * | 1996-12-30 | 1998-07-08 | 千代田化工建设株式会社 | Method for preparing carbonyl compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126879A (en) * | 2018-07-19 | 2019-01-04 | 厦门大学 | The method that nitrogen phosphorus coordination type metal catalyst and catalysis prepare 3- hydroxy propionate |
| CN109126879B (en) * | 2018-07-19 | 2020-09-25 | 厦门大学 | Nitrogen-phosphorus coordination metal catalyst and method for preparing 3-hydroxy propionate through catalysis |
| CN115569669A (en) * | 2021-06-21 | 2023-01-06 | 惠生工程（中国）有限公司 | Solid heterogeneous catalyst for ethylene oxide methyl hydrogen esterification reaction, preparation method and application |
| CN115569669B (en) * | 2021-06-21 | 2024-03-08 | 惠生工程（中国）有限公司 | Solid heterogeneous catalyst for ethylene oxide hydro-methyl esterification reaction, preparation method and application |
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Application publication date: 20170222 |