Ionic carbonyl cobalt-phosphine complex as well as synthesis method and application thereof

Abstract

The invention relates to an ionic carbonyl cobalt-phosphine complex. The complex has a structure as shown in a formula I, wherein R1 to R8 are respectively any one of independently aryl, benzyl or cycloalkylene formed in pairs; x is an integer of 1-3; y is a counter anion; the xanthene ligand is any one of phenyl, diphenyl ether group, xanthene group, biphenyl group, dinaphthyl group, silyl group and cyclosiloxy / nitrogen alkyl ligand skeleton; and the dotted line part only represents a complex structure composed of tridentate or more phosphine compounds and cobalt. Meanwhile, the invention also discloses a synthesis method and application of the complex. The synthesis method is simple and high in yield, and the obtained ionic carbonyl cobalt-phosphine complex has more excellent stability and oxidation resistance, is more convenient to store, transport and use in long-period hydroformylation reaction, has the advantages of being capable of being separated, recycled and reused and the like, and is more suitable for industrial amplification application.

Description

Technical Field

[0001] This invention relates to the field of organometallic complex synthesis technology, and in particular to an ionic carbonyl cobalt-phosphine complex, its synthesis method, and its application. Background Technology

[0002] Hydroformylation is a chemical reaction process that converts olefins with CO / H2 into aldehydes with one more carbon atom. The product has linearity and branching regioselectivity (as shown in Formula II). Side reactions include the isomerization of olefin double bonds to internal olefins and direct hydrogenation to alkanes.

[0003]

[0004] HCo(CO)4 is the earliest discovered and considered the most active cobalt catalyst known, and it remains the primary catalyst technology used by ExxonMobil and BASF. Due to insufficient coordination strength between CO and Co in the HCo(CO)4 molecule, the catalyst readily decomposes into metallic cobalt. To stabilize HCo(CO)4 as much as possible, the reaction pressure used industrially with this catalyst is extremely high (>20 MPa), a technology known in the industry as high-pressure or unmodified cobalt technology.

[0005] To enable hydroformylation reactions to operate at lower pressures, companies such as Shell and Sasol have developed electron-rich organophosphine ligands to modify HCo(CO)4, obtaining phosphine-modified carbonyl cobalt hydrogen (HCo(CO)3(PR3)). Representative ligands include PBu3, Phobanes, Lims, and VCH. Phosphine ligand modification significantly improves catalyst stability and regioselectivity for straight-chain products, and allows for one-step production of alcohols. However, because phosphine modification strengthens the binding affinity between the cobalt center and the carbonyl group, catalytic activity is reduced, requiring reaction temperatures above 190°C, accompanied by a significant increase in by-product alkanes. Phosphine-modified cobalt catalysts typically operate at pressures below 10 MPa; this technology is known as low-pressure cobalt technology.

[0006] Both of these catalyst systems have been in industrial application for over 50 years, during which time substantial breakthroughs have been difficult to achieve. Until 2020, Professor George G. Stanley's research group at Louisiana State University innovatively developed a [cobalt(II)-bisphosphine] catalyst with ultra-high activity and stability. + [BF4] -The complex (Science 2020, 367, 542–548) represents a milestone in cobalt-catalyzed hydroformylation. Although this catalyst exhibits excellent hydroformylation performance, its synthesis is extremely complex, yields are very low, and operating conditions are demanding, for example, in the synthesis of [Co(acac)(dioxane)] from cobalt acetylacetonate. x In the (BF4) step, the freshness of the raw material diethyl tetrafluoroborate is critical, the yield is only 35-45%, and the product is highly hygroscopic. Subsequent steps of complexation with phosphine ligands and catalyst activation are also required (WO 2019 / 237090A1; US ​​2021 / 0291156A1). Therefore, researchers are continuously optimizing the catalyst synthesis process (Science 2022, 377, 1223–1227; J.Am.Chem.Soc.2024, 146, 19183-19192; CN 202111282349.5; CN202310653435.5). The optimized synthesis method is an improvement over the first report, and the yield can be further increased to 55-63% (J. Am. Chem. Soc. 2024, 146, 19183-19192). However, the overall synthesis process has not been simplified and still requires three steps: Co(acac)2→[Co(acac)(dioxane)4]BF4v[Co(acac)(dppBz)]BF4→[HCo(CO) x Only by obtaining (DPPBz)]BF4 can an active catalyst be obtained. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide an ionic carbonyl cobalt-phosphine complex with strong antioxidant properties and good stability.

[0008] Another technical problem to be solved by the present invention is to provide a method for synthesizing the ionic carbonyl cobalt-phosphine complex.

[0009] The third technical problem to be solved by the present invention is to provide the application of this ionic carbonyl cobalt-phosphine complex.

[0010] To address the above problems, the present invention provides an ionic carbonyl cobalt-phosphine complex, characterized in that the complex has a structure as shown in Formula I:

[0011]

[0012] Wherein: R1 to R8 are any one of aryl, benzyl, or paired cycloalkylene groups; x is an integer from 1 to 3; Y is a counter anion; It can be any one of the following ligand skeletons: phenyl, diphenyl ether, ketolyl, biphenyl, naphthyl, silyl, or cyclosiloxane / nitroalkyl; the dashed part only represents the structure of complexes composed of tridentate or higher phosphine compounds and cobalt.

[0013] The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described above is characterized by: adding a cobalt precursor, a phosphine ligand, and a solvent into a high-pressure reaction vessel and mixing them uniformly to form a first mixed reaction system, and reacting at 100–170°C for 0.5–30 h in a reducing atmosphere, during which the pressure of the high-pressure reaction vessel is maintained at 3–8 MPa, and then obtaining the ionic carbonyl cobalt-phosphine complex solid through post-treatment.

[0014] Its synthetic route is shown in equation (III):

[0015]

[0016] The cobalt precursor refers to Co(BF4)2·6H2O, [Co(acac)(dioxane]... x The cobalt precursor is selected from the following: Co(NO3)2·6H2O, CoCl2·6H2O, CoCO3, Co(OH)2, Co5(CO3)2(OH)6, CoSO4·7H2O, cobalt acetate tetrahydrate, cobalt(II) 2-ethylhexanoate, and cobalt(II) naphthenate; the molar mass ratio of the cobalt precursor to the phosphine ligand is 1:0.8 to 1.2, and the weight percentage concentration of the cobalt precursor in the first mixed reaction system is 1% to 25%.

[0017] The phosphine ligand refers to any one of bisphosphine, triphosphine, and tetraphosphine compounds, and its weight percentage concentration in the first mixed reaction system is 0.6% to 20%.

[0018] The phosphine ligands mentioned refer to 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,2-(bis(diphenylphosphino)benzene), 4,6-bis(diphenylphosphino)-10H-phenoxazine, 1,2-bis((di-tert-butylphosphino)methyl)benzene, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,5-bis(diphenylphosphine)pentane, 1,6-bis(diphenylphosphine)hexane, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, bis[2-(diphenylphosphino)phenyl]ether, 1,1'-bis(diphenylphosphine)ferrocene, 2,2',5,5'-tetra[(diphenylphosphino)methyl]-1,1 The following is an example of '-biphenyl, tetra(2-(diphenylphosphine)ethyl)silane, tri(2-(diphenylphosphine)ethyl)methylsilane, bis(2-(diphenylphosphine)ethyl)dimethylsilane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasiloxane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisiloxane, bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsiloxane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisilazane, and bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsilazane.

[0019] The solvent refers to any one or a combination of two or more of the following: n-octane, petroleum ether, n-hexane, toluene, methyl tert-butyl ether, and ethylene glycol dimethyl ether.

[0020] The reducing atmosphere refers to a mixed atmosphere composed of H2 and CO in a volume ratio of 1:1 to 3.

[0021] The application of the ionic carbonyl cobalt-phosphine complex described above is characterized in that: the ionic carbonyl cobalt-phosphine complex acts as a catalyst for hydroformylation reaction, chemically transforming olefins to prepare mixed higher alcohol / aldehyde products.

[0022] In an H2 / CO mixed atmosphere consisting of H2 and CO in a volume ratio of 1 to 2:1, a second mixed system containing alkyl olefins, a reaction solvent, and an ionic carbonyl cobalt-phosphine complex is reacted for 2 to 40 hours under a gas pressure of 3 to 9 MPa and a temperature of 90 to 170 °C to obtain a mixed higher alcohol / aldehyde product.

[0023] The molar ratio of the ionic carbonyl cobalt-phosphine complex to the polyolefin is 1:20 to 500.

[0024] The composite olefins include oligomers of low-carbon-number olefins derived from propylene or butene.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] 1. This invention provides a one-step method for the direct synthesis of cobalt-phosphine complexes containing carbonyl groups in their molecular structure. These complexes can be directly used as active catalysts for hydroformylation reactions, completely simplifying the cumbersome synthetic route of intermediate synthesis, ligand complexation, and catalyst activation.

[0027] 2. This invention utilizes the polarity difference between ionic carbonyl cobalt-phosphine complexes and nonpolar solvents to significantly improve the synthesis yield and cobalt metal utilization efficiency.

[0028] 3. The ionic carbonyl cobalt-phosphine complex obtained by the method of the present invention has better stability and antioxidant properties than the traditional single phosphine ligand modified carbonyl cobalt hydrogen (HCo(CO)3(PR3). It can be stored, transported and used for long-term hydroformylation reactions more conveniently. It also has the advantages of being separable, recyclable and reusable, making it more suitable for industrial scale-up applications. Attached Figure Description

[0029] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0030] Figure 1 The infrared spectra of the ionic carbonyl cobalt-phosphine complexes synthesized in Examples 1-4, 7-9, and 11 of this invention are shown. Detailed Implementation

[0031] An ionic carbonyl cobalt-phosphine complex having the structure shown in Formula I:

[0032]

[0033] Wherein: R1 to R8 are any one of aryl, benzyl, or paired cycloalkylene groups; x is an integer from 1 to 3; Y is a counter anion; It can be any one of the following ligand skeletons: phenyl, diphenyl ether, ketolyl, biphenyl, naphthyl, silyl, or cyclosiloxane / nitroalkyl; the dashed part only represents the structure of complexes composed of tridentate or higher phosphine compounds and cobalt.

[0034] A method for synthesizing an ionic carbonyl cobalt-phosphine complex: A cobalt precursor, a phosphine ligand, and a solvent are added to a high-pressure reaction vessel and mixed uniformly to form a first mixed reaction system. The mixture is then reacted in a reducing atmosphere at 100–170°C for 0.5–30 h, preferably at 90–160°C for 1–26 h. During the reaction, the pressure in the high-pressure reaction vessel is maintained at 3–8 MPa, preferably 4–8 MPa. The mixture is then post-processed to obtain the ionic carbonyl cobalt-phosphine complex solid.

[0035] Wherein: cobalt precursors refer to Co(BF4)2·6H2O, [Co(acac)(dioxane]... x The cobalt precursor is selected from any one of the following: Co(NO3)2·6H2O, CoCl2·6H2O, CoCO3, Co(OH)2, Co5(CO3)2(OH)6, CoSO4·7H2O, cobalt acetate tetrahydrate, cobalt(II) 2-ethylhexanoate, and cobalt(II) naphthenate; the molar mass ratio of the cobalt precursor to the phosphine ligand is 1:0.8 to 1.2, and the weight percentage concentration of the cobalt precursor in the first mixed reaction system is 1% to 25%.

[0036] Phosphine ligands refer to any one of bisphosphine, triphosphine, and tetraphosphine compounds, with a weight percentage concentration of 0.6% to 20% in the first mixed reaction system. The phosphine ligands are specifically selected from 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,2-(bis(diphenylphosphine)benzene), 4,6-bis(diphenylphosphine)-10H-phenoxazine, 1,2-bis((di-tert-butylphosphine)methyl)benzene, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,5-bis(diphenylphosphine)pentane, 1,6-bis(diphenylphosphine)hexane, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, bis[2-(diphenylphosphine)phenyl]ether, 1,1'-bis(diphenylphosphine)ferrocene, 2,2',5,5'-tetra[(diphenylphosphine)methyl]-1,1 The following is an example of '-biphenyl, tetra(2-(diphenylphosphine)ethyl)silane, tri(2-(diphenylphosphine)ethyl)methylsilane, bis(2-(diphenylphosphine)ethyl)dimethylsilane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasiloxane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisiloxane, bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsiloxane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisilazane, and bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsilazane.

[0037] The solvent refers to any one or a combination of two or more of the following: n-octane, petroleum ether, n-hexane, toluene, methyl tert-butyl ether, and ethylene glycol dimethyl ether, preferably n-octane and n-hexane.

[0038] A reducing atmosphere is a mixed atmosphere consisting of H2 and CO in a volume ratio of 1:1 to 3 (mL / mL).

[0039] Post-treatment refers to the sequential solid-liquid separation, washing, and drying of the mixture obtained from the reaction under an inert atmosphere. Solid-liquid separation methods include filtration or centrifugation; the washing liquid used is the reaction solvent; and the drying method is vacuum drying or direct air drying.

[0040] An application of an ionic cobalt-phosphine carbonyl complex, which acts as a catalyst for hydroformylation, chemically transforms olefins to prepare mixed higher alcohols / aldehydes. The specific process is as follows:

[0041] In an H2 / CO mixed atmosphere (composed of H2 and CO at a volume ratio of 1–2:1, mL / mL), a second mixed system containing a complexed olefin, a reaction solvent, and an ionic cobalt carbonyl phosphine complex is reacted at a gas pressure of 3–9 MPa and a temperature of 90–170 °C for 2–40 h. Preferably, the reaction temperature is 90–160 °C, the reaction time is 3–32 h, and the gas pressure is 3.5–8.5 MPa. After the reaction, a mixed higher alcohol / aldehyde product is obtained.

[0042] Wherein, the molar ratio of the ionic carbonyl cobalt-phosphine complex to the composite olefin is 1:20 to 500, preferably 1:40 to 400.

[0043] Polyolefins include oligomers of low-carbon olefins derived from propylene or butene, such as polyhexene, polyoctaene, polynonene, polydodecene, polypentadene, polyhexadecene, etc.

[0044] This invention can also separate and recover ionic carbonyl cobalt-phosphine complexes from the mixture obtained after the reaction of the second mixing system. Specifically, the separation and recovery process is carried out under an inert atmosphere using heating and vacuum distillation.

[0045] Unless otherwise specified, the experimental materials used in the embodiments described below can be purchased from conventional biochemical reagent manufacturers.

[0046] The synthesis method of the ionic carbonyl cobalt-phosphine complex of the present invention is shown in Examples 1-12:

[0047] Example 1

[0048] 150 g of petroleum ether, 28.9 g of Co(BF4)2·6H2O, and 37.8 g of 1,2-(bis(diphenylphosphine)benzene) were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 6 MPa, and the reactor was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (DPPBz)](BF4) y .

[0049] Example 2

[0050] 200 g of petroleum ether, 7.9 g of Co(OH)₂, and 35.3 g of 1,2-(bis(diphenylphosphine)benzene) were added to a high-pressure reactor. A 1:1 H₂ / CO mixture was introduced at 6 MPa, and the mixture was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (DPPBz)](OH) y .

[0051] Example 3

[0052] 200 g of petroleum ether, 10.9 g of Co(CO)3, and 39.1 g of 1,2-(bis(diphenylphosphine)benzene) were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 6 MPa, and the mixture was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO)3]. x (DPPBz)](CO3) y .

[0053] Example 4

[0054] 300 g of ethylene glycol dimethyl ether, 20.2 g of CoCl2·6H2O, and 37.8 g of 1,2-(bis(diphenylphosphine)benzene) were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 6 MPa, and the reactor was heated to 110 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO)]. x (DPPBz)]Cl y .

[0055] Example 5

[0056] 150 g of petroleum ether, 21.1 g of cobalt acetate tetrahydrate, and 37.8 g of tetra(2-(diphenylphosphino)ethyl)-1,3,5,7-tetramethylcyclotetrasiloxane were added to a high-pressure reactor. A 1:1 H₂ / CO mixture was introduced at 6 MPa, and the reactor was heated to 130 °C and reacted for 26 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO)]. x (V4-4Ph2P)](Ac) y .

[0057] Example 6

[0058] 130 g of petroleum ether, 4.9 g of Co(NO3)2·6H2O, and 7.6 g of tris(2-(diphenylphosphino)ethyl)-1,3,5-trimethylcyclotrisilazane were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 6 MPa, and the reactor was heated to 150 °C and reacted for 1 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (N3-3Ph2P)](NO3) y .

[0059] Example 7

[0060] 150 g of petroleum ether, 28.9 g of Co(BF4)2·6H2O, and 28.8 g of 1,2-bis(diphenylphosphine)ethane were added to a high-pressure reactor. A 1:3 H2 / CO mixture was introduced at 6 MPa, and the reactor was heated to 170 °C and reacted for 3 hours. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (DPPE)](BF4) y .

[0061] Example 8

[0062] 150 g of n-hexane, 17.3 g of Co(BF4)2·6H2O, and 20.3 g of 1,3-bis(diphenylphosphine)propane were added to a high-pressure reactor. A 1:2 H2 / CO mixture was introduced at 4 MPa, and the reactor was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (DPPP)](BF4) y .

[0063] Example 9

[0064] 150 g of petroleum ether, 28.9 g of Co(BF4)2·6H2O, and 36.2 g of 1,4-bis(diphenylphosphine)butane were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 5 MPa, and the reactor was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (DPPB)](BF4) y .

[0065] Example 10

[0066] 190 g of n-octane, 28.9 g of Co(BF4)2·6H2O, and 38.5 g of tetrakis(2-(diphenylphosphine)ethyl)silane were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 6 MPa, and the reactor was heated to 150 °C and reacted for 16 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x [(Si-4Ph2P)](BF4) y .

[0067] Example 11

[0068] 200 g of methyl tert-butyl ether, 28.9 g of Co(BF4)2·6H2O, and 49.0 g of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene were added to a high-pressure reactor. A 1:1 H2 / CO mixture was introduced at 7 MPa, and the reactor was heated to 150 °C and reacted for 20 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (Xantphos)](BF4) y .

[0069] Example 12

[0070] Toluene (220 g), Co(BF4)2·6H2O (28.9 g), and 2,2'-bis(diphenylphosphine)-1,1'-binaphthylene (52.8 g) were added to a high-pressure reactor. A 1:2 H2 / CO mixture was introduced at 8 MPa, and the reactor was heated to 150 °C and reacted for 14 h. After cooling, the mixture was filtered, and the solid phase was washed three times with petroleum ether and then dried under vacuum to obtain a solid named [Co(CO]. x (BINAP)](BF4) y .

[0071] The ionic carbonyl cobalt-phosphine complexes synthesized in Examples 1-4, 7-9, and 11 were characterized by infrared spectroscopy after being pressed into KBr pellets, with wavenumbers ranging from 1600 to 2200 cm⁻¹. -1 Infrared absorption situation as follows Figure 1 As shown in the figure, all complexes exhibit a distinct carbonyl (C=O) absorption peak, indicating that their molecular structures contain a carbonyl group. The position of the carbonyl absorption peak changes depending on the type of counter anion and phosphine ligand, suggesting that the complexes likely exhibit hydroformylation reactivity.

[0072] The method for using the hydroformylation reaction of the ionic carbonyl cobalt-bisphosphine complex of the present invention is shown in Examples 13-27:

[0073] Example 13

[0074] Add 200g of dioxane and [Co(CO)] to the autoclave. x (DPPBz)](BF4) y 2.0 g of H2 / CO mixture was introduced at 4 MPa (ratio 1:1), and the temperature was raised to 90 °C. Then, 40 g of fused C6ene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 3 h and then cooled. The system was then quantitatively analyzed by GC.

[0075] Example 14

[0076] Add 100g of ethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPBz)](BF4) y 1.0 g of H2 / CO mixture was introduced at 5 MPa (ratio 1:1), and the temperature was raised to 100 °C. Then, 40 g of fused C99ene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 5 h and then cooled. The system was then quantitatively analyzed by GC.

[0077] Example 15

[0078] Add 200g of tetrahydrofuran and [Co(CO)] to the autoclave. x [(Si-4Ph2P)](BF4) y 1.0 g of H2 / CO mixture was introduced at 5 MPa (ratio 1:1), and the temperature was raised to 110 °C. Then, 60 g of fused C80 was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 6 h and then cooled. The system was then quantitatively analyzed by GC.

[0079] Example 16

[0080] Add 200g of methyl tert-butyl ether and [Co(CO)] to the autoclave. x (N3-3Ph2P)](NO3) y 2.0 g of H2 / CO mixture (2:1 ratio) was charged into the mixture at 6 MPa. The mixture was heated to 120 °C and then 60 g of polycarbododecene was rapidly charged into the mixture using a high-pressure metering pump. The reaction was maintained for 8 h and then cooled. The system was then quantitatively analyzed by GC.

[0081] Example 17

[0082] Add 160g of diethylhexanol and [Co(CO)] to the autoclave. x (DPPBz)](BF4) y 4.0 g of H2 / CO mixture (1:1 ratio) was introduced at 6 MPa, and the temperature was raised to 130 °C. Then, 80 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 6 h and then cooled. The system was then quantitatively analyzed by GC.

[0083] Example 18

[0084] Add 160g of diethylhexanol and [Co(CO)] to the autoclave. x (DPPBz)](BF4) y 4.0 g of H2 / CO mixture (2:1 ratio) was introduced at 7 MPa, and the temperature was raised to 130 °C. Then, 80 g of polyvinyl chloride was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 20 h and then cooled. The system after the reaction was quantitatively analyzed by GC.

[0085] Example 19

[0086] Add 120g of tetraethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (V4-4Ph2P)](Ac) y 6.0 g of H2 / CO mixture (1:1 ratio) was introduced at 8 MPa, and the temperature was raised to 160 °C. Then, 80 g of hexadecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 30 h and then cooled. The system was then quantitatively analyzed by GC.

[0087] Example 20

[0088] Add 140g of triethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPP)](BF4) y 6.0 g of H2 / CO mixture (1:1 ratio) was introduced at 6 MPa, and the temperature was raised to 160 °C. Then, 60 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 18 h and then cooled. The system was then quantitatively analyzed by GC.

[0089] Example 21

[0090] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPE)](BF4) y 6.0 g of H2 / CO mixture (1:1 ratio) was introduced at 6 MPa, and the temperature was raised to 150 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 26 h and then cooled. The system was then quantitatively analyzed by GC.

[0091] Example 22

[0092] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (Xantphos)](BF4) y7.0 g of H2 / CO mixture (1:1 ratio) was introduced at 6 MPa, and the temperature was raised to 150 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 22 h and then cooled. The system was then quantitatively analyzed by GC.

[0093] Example 23

[0094] Add 200g of diethylhexanol and [Co(CO)] to the autoclave. x (BINAP)](BF4) y 8.0 g of H2 / CO mixture (1:1 ratio) was introduced at 8 MPa, and the temperature was raised to 160 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 19 h and then cooled. The system after the reaction was quantitatively analyzed by GC.

[0095] Example 24

[0096] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPBz)](OH) y 3.0 g of H2 / CO mixture (1:1 ratio) was charged into the mixture at 6 MPa. The mixture was heated to 160 °C and then 50 g of polycarbododecene was rapidly charged into the mixture using a high-pressure metering pump. The reaction was maintained for 18 h and then cooled. The system was then quantitatively analyzed by GC.

[0097] Example 25

[0098] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPBz)](CO3) y 7.0 g of H2 / CO mixture (1:1 ratio) was introduced at 8 MPa, and the temperature was raised to 140 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 22 h and then cooled. The system was then quantitatively analyzed by GC.

[0099] Example 26

[0100] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (DPPBz)]Cl y 7.0 g of H2 / CO mixture (1:1 ratio) was introduced at 7 MPa, and the temperature was raised to 150 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 12 h and then cooled. The system after the reaction was quantitatively analyzed by GC.

[0101] Example 27

[0102] Add 150g of diethylene glycol dimethyl ether and [Co(CO)] to the autoclave. x (N3-3Ph2P)](NO3) y 7.0 g of H2 / CO mixture (1:1 ratio) was introduced at 6 MPa, and the temperature was raised to 160 °C. Then, 50 g of polycarbododecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 25 h and then cooled. The system after the reaction was quantitatively analyzed by GC.

[0103] The results of the hydroformylation reactions in Examples 13–27 are shown in Table 1.

[0104] Table 1 Summary of the results of hydroformylation reactions in Examples 13-27

[0105]

[0106] Note: Isomerized olefins are classified as unconverted olefin feedstocks.

[0107] Comparative Example 1

[0108] The catalyst preparation method of Example 1 and the catalyst application method of Example 20 were adopted, using triphenylphosphine (PPh3), tributylphosphine (PBu3), and tri-tert-butylphosphine (P) from the prior art. t Bu3, as an organophosphorus ligand, has lower olefin conversion and selectivity for alcohol / aldehyde products than the present invention (as shown in Table 2).

[0109] Table 2 Results of the reaction in Comparative Example 1

[0110]

[0111] Note: Isomerized olefins are classified as unconverted olefin feedstocks.

[0112] Comparative Example 2

[0113] Using Co2(CO)8 without phosphine ligand modification from the prior art as a catalyst precursor, and adopting the catalyst application method of Example 20, although the olefin conversion rate reached 93.1% after the reaction, which was higher than that of Example 20, a large amount of cobalt black was found deposited on the reactor wall after the reaction, and the organic phase was almost colorless, indicating that the catalyst was almost completely deactivated and the stability of the Co2(CO)8 catalyst without phosphine ligand modification was extremely poor.

[0114] Comparative Example 3

[0115] [HCo(CO)] was prepared using the three-step synthesis method reported in Science 2020, 367, 542–548. xUsing the catalyst application method of Example 20 with (DPPBz)BF4 solution, the conversion rate of olefins and the selectivity of products after the reaction were not significantly different from the results of Example 20 in Table 1. This further illustrates that the synthesis method of the cobalt-phosphine complex of the present invention has a simple preparation process and good hydroformylation reaction performance.

[0116] Example 28

[0117] After the reaction in Example 15 was completed, the unreacted olefins, alkanes, and alcohols / aldehydes were removed by vacuum distillation to recover the catalyst. The catalyst was then added back into the autoclave and purged with syngas. The temperature was raised to 160°C, and 80g of hexadecene was rapidly introduced using a high-pressure metering pump. The reaction was maintained for 30 hours and then cooled. This method was repeated five times, and the catalytic activity and product selectivity remained consistent, indicating that the catalyst has good stability and reusability.

[0118] In summary, the synthesis method of the ionic carbonyl cobalt-phosphine complex of the present invention is simple, has a short process route, and high yield. It has high reactivity as a catalyst for hydroformylation reaction, and the catalyst is easy to separate, recover and recycle after the reaction. It also has stable reaction performance and is suitable for industrial use.

[0119] In addition, the present invention has also conducted experiments with other raw materials, process operating conditions, reaction parameters, etc., as shown in the foregoing embodiments, and all of them have yielded relatively ideal results.

[0120] It should be understood that the technical solutions of the present invention are not limited to the specific examples described above. Any technical modifications made to the technical solutions of the present invention, or equivalent substitutions of some of the technical features, without departing from the spirit and scope of the claims, shall fall within the protection scope of the present invention.

Claims

1. An ionic carbonyl cobalt-phosphine complex, characterized in that: The complex has the structure shown in Formula I: Wherein: R1 to R8 are any one of aryl, benzyl, or paired cycloalkylene groups; x is an integer from 1 to 3; Y is a counter anion; It can be any one of the following ligand skeletons: phenyl, diphenyl ether, ketolyl, biphenyl, naphthyl, silyl, or cyclosiloxane / nitroalkyl; the dashed part only represents the structure of complexes composed of tridentate or higher phosphine compounds and cobalt.

2. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 1, characterized in that: The cobalt precursor, phosphine ligand, and solvent are added to a high-pressure reaction vessel and mixed evenly to form a first mixed reaction system. The system is then reacted at 100–170 °C for 0.5–30 h in a reducing atmosphere, during which the pressure of the high-pressure reaction vessel is maintained at 3–8 MPa. After post-processing, an ionic carbonyl cobalt-phosphine complex solid is obtained.

3. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 2, characterized in that: The cobalt precursor refers to Co(BF4)2·6H2O, [Co(acac)(dioxane]... x The cobalt precursor is selected from the following: Co(NO3)2·6H2O, CoCl2·6H2O, CoCO3, Co(OH)2, Co5(CO3)2(OH)6, CoSO4·7H2O, cobalt acetate tetrahydrate, cobalt(II) 2-ethylhexanoate, and cobalt(II) naphthenate; the molar mass ratio of the cobalt precursor to the phosphine ligand is 1:0.8 to 1.2, and the weight percentage concentration of the cobalt precursor in the first mixed reaction system is 1% to 25%.

4. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 2, characterized in that: The phosphine ligand refers to any one of bisphosphine, triphosphine, and tetraphosphine compounds, and its weight percentage concentration in the first mixed reaction system is 0.6% to 20%.

5. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 4, characterized in that: The phosphine ligands mentioned refer to 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 1,2-(bis(diphenylphosphino)benzene), 4,6-bis(diphenylphosphino)-10H-phenoxazine, 1,2-bis((di-tert-butylphosphino)methyl)benzene, bis(diphenylphosphine)methane, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,5-bis(diphenylphosphine)pentane, 1,6-bis(diphenylphosphine)hexane, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, bis[2-(diphenylphosphino)phenyl]ether, 1,1'-bis(diphenylphosphine)ferrocene, 2,2',5,5'-tetra[(diphenylphosphino)methyl]-1,1 The following is an example of '-biphenyl, tetra(2-(diphenylphosphine)ethyl)silane, tri(2-(diphenylphosphine)ethyl)methylsilane, bis(2-(diphenylphosphine)ethyl)dimethylsilane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasiloxane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisiloxane, bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsiloxane, tetra(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5,7-tetramethylcyclotetrasilazane, tri(2-(diphenylphosphine)ethyl)-1,3,5-trimethylcyclotrisilazane, and bis(2-(diphenylphosphine)ethyl)-1,3-dimethylsilazane.

6. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 2, characterized in that: The solvent refers to any one or a combination of two or more of the following: n-octane, petroleum ether, n-hexane, toluene, methyl tert-butyl ether, and ethylene glycol dimethyl ether.

7. The method for synthesizing an ionic carbonyl cobalt-phosphine complex as described in claim 2, characterized in that: The reducing atmosphere refers to a mixed atmosphere composed of H2 and CO in a volume ratio of 1:1 to 3.

8. The application of the ionic carbonyl cobalt-phosphine complex as described in claim 1, characterized in that: This ionic carbonyl cobalt-phosphine complex acts as a catalyst for hydroformylation, chemically transforming olefins to prepare mixed higher alcohol / aldehyde products.

9. The application of the ionic carbonyl cobalt-phosphine complex as described in claim 8, characterized in that: In an H2 / CO mixed atmosphere consisting of H2 and CO in a volume ratio of 1 to 2:1, a second mixed system containing alkyl olefins, a reaction solvent, and an ionic carbonyl cobalt-phosphine complex is reacted for 2 to 40 hours under a gas pressure of 3 to 9 MPa and a temperature of 90 to 170 °C to obtain a mixed higher alcohol / aldehyde product.

10. The application of the ionic carbonyl cobalt-phosphine complex as described in claim 9, characterized in that: The molar ratio of the ionic carbonyl cobalt-phosphine complex to the polyolefin is 1:20 to 500.

11. The application of the ionic carbonyl cobalt-phosphine complex as described in claim 10, characterized in that: The composite olefins include oligomers of low-carbon-number olefins derived from propylene or butene.

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