Cobalt carbonyl organic ionic liquid as well as preparation method and application thereof

Abstract

The invention discloses a cobalt carbonyl organic ionic liquid as well as a preparation method and application thereof, and the cobalt carbonyl organic ionic liquid is prepared by taking a pyrazole cobalt carbonyl metal organic ionic liquid as a main catalyst and carrying out hydrogen esterification reaction in an organic alcohol solution of an epoxy compound in a carbon monoxide atmosphere to prepare beta-hydracrylate. The pyrazole carbonyl cobalt metal organic ionic liquid has the advantages that the stability is high, the catalytic activity is high, and the catalyst can be recycled, the hydrogen esterification reaction of ethylene oxide under the mild condition is realized by taking the pyrazole carbonyl cobalt metal organic ionic liquid as the catalyst, the conversion rate of the ethylene oxide can reach 95% at most, and the yield of beta-hydracrylic acid ester can reach 92% at most.

Description

Technical Field

[0001] The invention belongs to the field of fine chemicals, and specifically relates to a carbonyl cobalt metal organic ionic liquid, a preparation method thereof, and application thereof in synthesizing beta-hydroxypropionate. Background Art

[0002] 1,3-Propanediol (1,3-PDO) is an important class of fine chemicals. It can be used as a raw material for the production of antifreeze, plasticizers, preservatives and emulsifiers. It is also widely used in food, coatings, cosmetics and pharmaceutical industries, and has a huge market demand. 1,3-PDO is an important monomer for the synthesis of polyurethane. It can undergo polyesterification with terephthalic acid to obtain a new polyester fiber material, polytrimethylene terephthalate (PTT). This type of polyester material has the advantages of light resistance, low water absorption, good stability, good resilience, easy biodegradability and low environmental pollution, and has broad application prospects.

[0003] β-Hydroxypropionate is a key intermediate in the synthesis of 1,3-PDO. It is currently mainly prepared by the hydroesterification reaction of ethylene oxide. The synthesis reaction is shown as follows: The development of new catalysts is the research focus of the hydroesterification reaction of epoxides. Shell used Co2(CO)8 / 1,10-phenanthroline as a catalyst and methyl tert-butyl ether as a solvent. The ethylene oxide conversion rate was only 11%, and the selectivity of methyl 3-hydroxypropionate was 74%. Later, Samsung used Co as the main catalyst and nitrogen-containing heterocyclic compounds as ligands. The ethylene oxide conversion rate can be increased to 94%, and the selectivity of methyl 3-hydroxypropionate is 78%. There are also many scientific research institutions in China that have studied catalysts for the hydroesterification reaction of epoxides. For example, Chen Jing and others from the Lanzhou Institute of Chemical Physics of the Chinese Academy of Sciences used carbonyl cobalt as a catalyst, and the conversion rate of ethylene oxide hydroesterification reaction was 87%, and the yield of β-hydroxypropionate was 87%; Zhang Ye and others from Guangdong University of Petrochemical Technology used carbonyl cobalt as a catalyst and added imidazole as an auxiliary agent. The conversion rate of ethylene oxide hydroesterification reaction can be increased to 92%, and the yield of β-hydroxypropionate is 84%. Subsequently, research institutions such as Qingdao University of Science and Technology, China Petrochemical Corporation Shanghai Research Institute, and Taiyuan University of Technology also conducted research on the catalyst system for the hydroesterification reaction of ethylene oxide.

[0004] However, the cobalt carbonyl catalysts produced by existing technologies have disadvantages such as being sensitive to air, difficult to store, and difficult to recycle and reuse. Functionalized ionic liquids as catalysts have the advantages of high catalytic activity and good stability. Cobalt carbonyl metal organic ionic liquids as catalysts for the hydroesterification reaction of epoxy compounds provide a solution to the above problems and have attracted the attention of researchers at home and abroad.

[0005] Patent CN 106995391 A discloses a method for preparing a 1,1,3,3-tetraalkylguanidine carbonyl cobalt metal organic ionic liquid catalyst. After six cycles, the catalyst still maintains high catalytic activity and selectivity in the hydroesterification reaction of epoxide compounds.

[0006] Patent CN 107459451 A discloses the preparation of an ionic liquid catalyst containing transition metal cobalt. Under the conditions of a carbon monoxide pressure of 6.0 MPa and 75°C, the ethylene oxide conversion rate is 71% and the selectivity of β-hydroxypropionate methyl ester is 86%.

[0007] Patent CN 101973881B discloses the preparation of 1-R-3-methylimidazole tetracarbonyl cobalt ionic liquid catalyst and its application in the synthesis of 1,3-PDO. The hydroesterification reaction and hydrogenation reaction of epoxide can be completed in the same catalytic system, and the catalyst can be recycled.

[0008] The invention provides a pyrazole carbonyl cobalt metal organic ionic liquid, a preparation method thereof and an application thereof in synthesizing beta-hydroxypropionate by hydroesterification reaction of epoxy compounds. Summary of the invention

[0009] The invention develops a stable, non-toxic, highly catalytically active and recyclable pyrazole carbonyl cobalt functionalized ionic liquid catalyst. The nitrogen-hydrogen bond in the pyrazole ionic liquid can stabilize the tetracarbonyl cobalt anion and can also be used as a Bronsted acid to activate the epoxy compound. The pyrazole ionic liquid can be used as a catalyst to realize the hydrogen esterification reaction of ethylene oxide under mild conditions, and can be used for the preparation of various beta-hydroxypropionic acid esters, especially methyl 3-hydroxypropionate.

[0010] To achieve the above object, the present invention adopts the following technical solution: The first object of the present invention is to provide a pyrazolecarbonyl cobalt functionalized ionic liquid catalyst.

[0011] The general structural formula of the pyrazole carbonyl cobalt metal organic ionic liquid is as follows: , wherein R is selected from one of an alkyl group, an alkenyl group, and an aryl group.

[0012] The second object of the present invention is to provide a method for preparing the pyrazolecarbonyl cobalt functionalized ionic liquid catalyst.

[0013] The pyrazole carbonyl cobalt metal organic ionic liquid is prepared by premixing a high-valent cobalt salt and a reducing agent in an organic alcohol, and then loading the mixture into a closed reactor to react under a carbon monoxide atmosphere. After the reaction is completed, the remaining powder in the system is filtered out, and the filtrate and the pyrazole ionic liquid are stirred and reacted under an inert gas atmosphere, the precipitate is filtered out, and the solvent is removed under vacuum to obtain the pyrazole carbonyl cobalt organic ionic liquid.

[0014] Furthermore, the high-valent cobalt salt is selected from one of CoCl2, CoBr2, Co(acac)2, Co3(PO4)2, Co(OAC)2, and CoCO3.

[0015] Furthermore, the organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenol.

[0016] Furthermore, the X is selected from chlorine, bromine or iodine.

[0017] Furthermore, the pyrazole ionic liquid is one of pyrazole hydrochloride, pyrazole bromide and pyrazole iodate.

[0018] Furthermore, the reducing agent is one or more of Fe, Co, Ni, Zn, Mn, LiAlH4, NaBH4, KBH4, and Na2S2O3, and its particle size is 300~1600 mesh.

[0019] Furthermore, the reaction temperature of the reaction in a carbon monoxide atmosphere is 0-100°C, the pressure is 1-6 MPa, and the time is 1-24 h.

[0020] The third object of the present invention is to provide a method for synthesizing β-hydroxypropionate using the pyrazolecarbonyl cobalt metal organic ionic liquid.

[0021] The method uses the pyrazole carbonyl cobalt metal organic ionic liquid as a main catalyst, organic alcohol as a solvent and a substrate, and uses an epoxy compound to carry out a hydroesterification reaction in a carbon monoxide atmosphere to prepare beta-hydroxypropionic acid ester.

[0022] Furthermore, the organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenol.

[0023] Further, in the reaction system, the concentration of the epoxy compound is 0.001 mol / L to 100 mol / L, and the concentration of the pyrazole carbonyl cobalt metal organic ionic liquid catalyst is 0.0001 mol / L to 100 mol / L Furthermore, the temperature of the hydroesterification reaction is 40-80°C, the pressure is 2-6 MPa, and the time is 1-24 h.

[0024] The beneficial effects of the present invention are: (1) The preparation method of pyrazole carbonyl cobalt metal organic ionic liquid is simple, stable to water and oxygen, has high catalytic efficiency, and the catalyst can be easily separated and recovered after the reaction and can be recycled; (2) The product β-hydroxypropionate has extremely high application value, especially 3-hydroxypropionic acid methyl ester can be used in the large-scale production of 1,3-propylene glycol; (3) No need to use low-cost cobalt precursors that are air-sensitive, unstable, flammable, and inconvenient to store and transport; (4) The reaction raw materials are bulk chemicals ethylene oxide and carbon monoxide, which have a wide range of sources and mature preparation processes; (5) The conversion rate and selectivity of the ethylene oxide hydroesterification reaction can reach up to 95%, and the final yield of β-hydroxypropionate can reach up to 92%. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the infrared spectrum of [HMPz][Co(CO)4] in Example 2.

[0026] Figure 2 This is the gas chromatogram of the reaction stock solution in Example 18. DETAILED DESCRIPTION

[0027] The pyrazole carbonyl cobalt metal organic ionic liquid is prepared by premixing a high-valent cobalt salt and a reducing agent in an organic alcohol, and then loading the mixture into a closed reactor to react under a carbon monoxide atmosphere. After the reaction is completed, the remaining powder in the system is filtered out, and the filtrate and the pyrazole ionic liquid are stirred and reacted under an inert gas atmosphere, the precipitate is filtered out, and the solvent is removed under vacuum to obtain the pyrazole carbonyl cobalt organic ionic liquid.

[0028] The prepared pyrazole carbonyl cobalt metal organic ionic liquid is used as a main catalyst, organic alcohol is used as a solvent and a substrate, and an epoxy compound is used to carry out a hydroesterification reaction in a carbon monoxide atmosphere to prepare beta-hydroxypropionic acid ester.

[0029] Wherein, the high-valent cobalt salt is selected from one of CoCl2, CoBr2, Co(acac)2, Co3(PO4)2, Co(OAC)2, and CoCO3.

[0030] The organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenol.

[0031] The pyrazole ionic liquid is one of pyrazole hydrochloride, pyrazole bromide and pyrazole iodate.

[0032] The reducing agent is one or more of Fe, Co, Ni, Zn, Mn, LiAlH4, NaBH4, KBH4, and Na2S2O3, and its particle size is 300-1600 meshes.

[0033] The reaction temperature of the reaction under the carbon monoxide atmosphere is 0-100°C, the pressure is 0.1-6 MPa, and the time is 1-24 h.

[0034] In the reaction system, the concentration of the epoxy compound is 0.001 mol / L~100 mol / L, and the concentration of the pyrazolecarbonyl cobalt organic ionic liquid catalyst is 0.0001 mol / L~100 mol / L.

[0035] The temperature of the hydroesterification reaction is 40-80°C, the pressure is 2-6 MPa, and the time is 1-24 h.

[0036] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0037] Example 1 A 100 mL high-pressure reactor was selected. 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were first mixed in 20 mL methanol. Then the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then the system pressure was adjusted to 4.0 MPa and heated to 40 °C. The reaction was continued for 15 h. After the reaction was completed, the remaining powder in the system was removed by filtration. The above filtrate was mixed with 1-pentylpyrazole hydrochloride (HAPzCl) (the synthesis method of HAPzCl is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred under nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. In a 100 mL autoclave, pyrazole carbonyl cobalt organic ionic liquid [HAPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then, the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0038] Example 2 A 100 mL high-pressure reactor was selected. 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were first mixed in 20 mL methanol, and then loaded into the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then the system pressure was adjusted to 4.0 MPa and heated to 40 °C for 15 h. After the reaction was completed, the remaining powder in the system was filtered out. The above filtrate and 1-methylpyrazole hydrochloride (HMPzCl) (the synthesis method of HMPzCl is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred for 6 h under nitrogen atmosphere. After the reaction, the precipitate was filtered off and the solvent was removed under vacuum to obtain [HMPz][Co(CO)4]. [HMPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. The system pressure was then adjusted to 5.0 MPa and heated to 40 °C for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0039] Example 3 A 100 mL high-pressure reactor was selected. First, 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were mixed in 20 mL methanol. Then, the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then, the system pressure was adjusted to 4.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction was completed, the remaining powder in the system was filtered out. The above filtrate and 1-ethylpyrazole hydrochloride (HEPzCl) (the synthesis method of HEPzCl is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred for 6 h under nitrogen atmosphere. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HEPz][Co(CO)4]. [HEPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0040] Example 4 A 100 mL high-pressure reactor was selected. 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were first mixed in 20 mL methanol. Then the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then the system pressure was adjusted to 4.0 MPa and heated to 40 °C for 15 h. After the reaction was completed, the remaining powder in the system was removed by filtration. The above filtrate and 1-propylpyrazole hydrochloride (HPPzCl) (the synthesis method of HPPzCl is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred for 6 h under nitrogen atmosphere. After the reaction, the precipitate was filtered off and the solvent was removed under vacuum to obtain [HPPz][Co(CO)4]. [HPPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. The system pressure was then adjusted to 5.0 MPa and heated to 40 °C for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0041] Example 5 A 100 mL high-pressure reactor was selected. First, 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were mixed in 20 mL methanol. Then, the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then, the system pressure was adjusted to 4.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction was completed, the remaining powder in the system was filtered out. The above filtrate and 1-butylpyrazole hydrochloride (HBPzCl) (HBPzCl synthesis method reference ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred for 6 h under nitrogen atmosphere. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HBPz][Co(CO)4]. [HBPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0042] Example 6 A 100 mL high-pressure reactor was selected. First, 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were mixed in 20 mL methanol. Then, the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then, the system pressure was adjusted to 4.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction was completed, the remaining powder in the system was filtered out. The above filtrate and 1-pentylpyrazole bromide (HAPzBr) (the synthesis method of HAPzBr is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred under nitrogen atmosphere for 6 h. After the reaction, the precipitate was filtered off and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. [HAPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. The system pressure was then adjusted to 5.0 MPa and heated to 40 °C for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0043] Example 7 A 100 mL high-pressure reactor was selected. First, 1.0 mmol CoCl2 and 6 mmol reducing agent Mn powder (325 mesh) were mixed in 20 mL methanol. Then, the mixture was placed in the reactor and sealed. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then, the system pressure was adjusted to 4.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction was completed, the remaining powder in the system was filtered out. The above filtrate and 1-pentylpyrazole iodate (HAPzI) (the synthesis method of HAPzI is the same as ACSSustainableChem.Eng. 2018, 6 , 2574−2582 consistent) were stirred for 6 h under nitrogen atmosphere. After the reaction, the precipitate was filtered off and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. [HMPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added to a 100 mL autoclave. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. The system pressure was then adjusted to 5.0 MPa and heated to 40 °C for 15 h. After the reaction, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0044] Example 8 The Mn powder used in Example 1 was replaced with Fe powder, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0045] Example 9 The Mn powder used in Example 1 was replaced with Co powder, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0046] Example 10 The Mn powder used in Example 1 was replaced with Ni powder, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0047] Embodiment 11 The Mn powder used in Example 1 was replaced with Zn powder, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0048] Example 12 The Mn powder used in Example 1 was replaced with LiAlH4, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0049] Example 13 The Mn powder used in Example 1 was replaced with NaBH4, the catalyst preparation temperature was 0-5°C, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0050] Embodiment 14 The Mn powder used in Example 1 was replaced with KBH4, the catalyst preparation temperature was 0-5°C, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0051] Embodiment 15 The CoCl2 used in Example 1 was replaced with CoBr2, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0052] Example 16 The CoCl2 used in Example 1 was replaced with Co(acac)2, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0053] Embodiment 17 The CoCl2 used in Example 1 was replaced with Co3(PO4)2, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0054] Embodiment 18 The CoCl2 used in Example 1 was replaced with Co(OAc)2, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0055] Embodiment 19 The CoCl2 used in Example 1 was replaced with CoCO3, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0056] Embodiment 20 The amount of CoCl2 in Example 1 was changed from 1 mmol to 0.6 mmol, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0057] Embodiment 21 The amount of CoCl2 in Example 1 was changed from 1 mmol to 0.8 mmol, and other operating conditions remained unchanged. The reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0058] Embodiment 22 The amount of CoCl2 in Example 1 was changed from 1 mmol to 2 mmol, and other operating conditions remained unchanged. The reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0059] Embodiment 23 The hydroesterification reaction temperature in Example 1 was changed from 40° C. to 50° C., and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0060] Embodiment 24 The hydroesterification reaction temperature in Example 1 was changed from 40° C. to 70° C., and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0061] Embodiment 25 The hydroesterification reaction temperature in Example 1 was changed from 40° C. to 80° C., and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0062] Embodiment 26 The hydroesterification reaction pressure in Example 1 was changed from 5.0 MPa to 2.0 MPa, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0063] Embodiment 27 The hydroesterification reaction pressure in Example 1 was changed from 5.0 MPa to 3.0 MPa, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0064] Embodiment 28 The amount of methanol used in the hydroesterification reaction in Example 1 was changed from 20 mL to 40 mL, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0065] Embodiment 29 The hydroesterification reaction time in Example 1 was changed from 15 h to 4 h, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0066] Embodiment 30 The hydroesterification reaction time in Example 1 was changed from 15 h to 8 h, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0067] Embodiment 31 The hydroesterification reaction time in Example 1 was changed from 15 h to 12 h, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0068] Embodiment 32 The hydroesterification reaction time in Example 1 was changed from 15 h to 16 h, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0069] Embodiment 33 The hydroesterification reaction time in Example 1 was changed from 15 h to 24 h, and other operating conditions remained unchanged. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0070] Embodiment 34 After the reaction of Example 1 was completed, the reaction solution was distilled under reduced pressure to remove the solvent and β-hydroxypropionic acid methyl ester, and the remaining liquid was re-imported into a 100 mL high-pressure reactor, methanol (20 mL), ethylene oxide (200 mmol), and the gas in the reactor was replaced with CO three times to fill the reactor with CO. Then, the system pressure was adjusted to 5.0 MPa, heated to 40°C, and reacted for 15 hours. After the reaction was completed, the reaction stock solution was analyzed by GC. The results are shown in Table 1.

[0071] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A cobalt carbonyl organic ionic liquid, characterized in that: Its general structure is as follows: , wherein R is selected from one of an alkyl group, an alkenyl group, and an aryl group.

2. A method for preparing the cobalt carbonyl organic ionic liquid according to claim 1, characterized in that: The following steps are involved: The high-valent cobalt salt and the reducing agent are premixed in an organic alcohol, and then loaded into a closed reactor to react in a carbon monoxide atmosphere; after the reaction is completed, the remaining powder in the system is filtered out, the filtrate is stirred and reacted with a pyrazole ionic liquid in an inert gas atmosphere, the precipitate is filtered out, and the solvent is removed under vacuum to obtain a carbonyl cobalt organic ionic liquid.

3. The preparation method according to claim 2, characterized in that: The high-valent cobalt salt is selected from one of CoCl2, CoBr2, Co(acac)2, Co3(PO4)2, Co(OAC)2, and CoCO3.

4. The preparation method according to claim 2, characterized in that: The reducing agent is one or more of Fe, Co, Ni, Zn, Mn, LiAlH4, NaBH4, KBH4, and Na2S2O3, and its particle size is 300-1600 meshes.

5. The preparation method according to claim 2, characterized in that: The organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenol.

6. The preparation method according to claim 2, characterized in that: The reaction temperature in a carbon monoxide atmosphere is 0~100 °C, the pressure is 1~6 MPa, and the time is 1~24 h.

7. Use of the carbonyl cobalt organic ionic liquid according to claim 1 in the synthesis of β-hydroxypropionate, characterized in that: Carbonyl cobalt organic ionic liquid is used as the main catalyst, organic alcohol is used as the solvent and substrate, and epoxide is used to undergo hydrogen esterification reaction in a carbon monoxide atmosphere to prepare β-hydroxypropionate.

8. The use according to claim 7, characterized in that: In the reaction system, the concentration of the epoxy compound is 0.001 mol / L~100 mol / L; the concentration of the carbonyl cobalt organic ionic liquid catalyst is 0.0001 mol / L~100 mol / L.

9. The use according to claim 7, characterized in that: The organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol and phenol.

10. The use according to claim 7, characterized in that: The temperature of the hydroesterification reaction is 40-80°C, the pressure is 2-6 MPa, and the time is 1-24 h.

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