Monophosphine polymer embedded catalyst for olefin hydroformylation as well as preparation method and application of monophosphine polymer embedded catalyst

Abstract

The invention discloses a monophosphine polymer embedded catalyst for olefin hydroformylation as well as a preparation method and application of the monophosphine polymer embedded catalyst. The monophosphine polymer embedded catalyst is obtained by solvothermal polymerization of a monophosphine ligand containing vinyl functionalization and an active metal precursor in one step. The prepared catalyst is composed of the active metal and the monophosphine copolymer, the active metal can be embedded by the catalyst, and olefin hydroformylation reaction with CO as a carbonyl source can be efficiently and highly selectively achieved under the mild condition. The catalyst retains the advantages of high catalytic activity and good chemical selectivity of a homogeneous catalyst, and is relatively simple in synthetic route, relatively low in production cost, easy to separate from a product and suitable for olefin hydroformylation reaction, so that industrial application of the olefin hydroformylation reaction can be met, and the catalyst has a wide application prospect. Moreover, controllable synthesis of aldehyde or alcohol can be realized by controlling the temperature.

Description

Technical Field

[0001] The invention belongs to the field of catalytic materials, and in particular relates to a monophosphine polymer embedded catalyst for olefin hydroformylation and a preparation method and application thereof. Background Art

[0002] Currently, the industrial production of alcohols is based on a multi-step process involving hydroformylation of olefins to aldehydes, which are purified and then hydrogenated to alcohols. Reductive hydroformylation of readily available olefins and synthesis gas in a one-pot hydroformylation reaction is a simple and atom-economical process for producing homologous alcohols. This process eliminates the need for energy-intensive aldehyde separation, simplifies the overall operation and reduces energy consumption, ultimately improving process economics and reducing environmental impact.

[0003] Direct conversion of readily available olefins into high-value-added alcohols is an important and challenging task in organic synthesis and industry. The one-pot hydroformylation of olefins by temperature regulation provides a simple and atom-economical method for the synthesis of homologous alcohols and homologous aldehydes. However, the use of stable and efficient heterogeneous catalysts to catalyze this reaction is not well-developed. Therefore, it is urgent to develop a new type of highly efficient porous organophosphorus ligand polymer catalytic material that can be effectively recycled while improving the activity of the hydroformylation reaction and the universality of the substrate, thereby realizing the one-pot reductive hydroformylation of olefins to controllably synthesize alcohols or aldehydes.

[0004] It should be noted that the information disclosed in the above background technology section is only used to enhance the understanding of the background of the present disclosure, and therefore may include information that does not constitute the prior art known to ordinary technicians in the field. Summary of the invention

[0005] The purpose of the present invention is to provide a monophosphine polymer embedded catalyst for olefin hydroformylation and a preparation method and application thereof, which can realize a one-pot reduction hydroformylation reaction of olefins and controllably synthesize alcohols or aldehydes.

[0006] In order to achieve the above object, the present invention provides a monophosphine polymer embedded catalyst for olefin hydroformylation, wherein the monophosphine polymer embedded catalyst is obtained by solvent thermal polymerization of a monophosphine ligand containing a vinyl functional group and an active metal precursor in one step; the weight of the active metal in the active metal precursor accounts for 0.1 to 10.0% of the total weight of the monophosphine polymer embedded catalyst; wherein the structure of the monophosphine ligand containing a vinyl functional group is selected from any one or more of the following:

[0007]

[0008] Preferably, the active metal precursor is any one or more precursors of metal cobalt, ruthenium or platinum.

[0009] The second object of the present invention is to provide a method for preparing the monophosphine polymer embedded catalyst, the method comprising:

[0010] (1) under an inert gas atmosphere, dissolving the monophosphine ligand containing a vinyl functional group and the active metal precursor in a molar ratio of 10 to 1000:1 in a first organic solvent, stirring and reacting at 20 to 80° C. for 1 to 4 hours to obtain a coordination product;

[0011] (2) Under an inert gas atmosphere, the coordination product and the free radical initiator are co-dissolved in a second organic solvent, and the polymerization reaction is carried out in an autoclave at 40 to 150° C. for 20 to 25 hours, followed by washing, and the organic solvent is removed under reduced pressure at 20 to 50° C. to obtain a catalyst embedded in a monophosphine ligand polymer.

[0012] Preferably, the active metal precursor is selected from any one or more of cobalt acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetylacetonate, cobalt oxalate, bis(pentamethylcyclopentadienyl)cobalt, hexaamminecobalt trichloride, dicobalt octacarbonyl, ruthenium trichloride, ruthenium acetate, bis(triphenylphosphine)dicarbonylruthenium(II) chloride and platinum nitrate.

[0013] Preferably, the molar ratio of the monophosphine ligand containing vinyl functional group to the free radical initiator is (10-100):1.

[0014] Preferably, the free radical initiator is selected from any one of azobisisobutyronitrile, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide and methyl ethyl ketone peroxide; or / and, the first organic solvent and the second organic solvent are each independently selected from any one or more of ethanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, n-hexane, toluene, anisole, dichloromethane and chloroform.

[0015] Preferably, for three monophosphine ligands having the same substitution, the method for preparing the monophosphine ligand containing vinyl functional group comprises:

[0016] At -78°C under an inert gas environment, a n-hexane solution of n-butyl lithium is added dropwise to a solution of bromovinylbenzene in anhydrous tetrahydrofuran, the solution is stirred, and then a solution of phosphorus trichloride in anhydrous tetrahydrofuran is added dropwise, the mixture is stirred continuously at -78°C, and then the system is returned to room temperature and the reaction is allowed to proceed overnight to obtain a monophosphine ligand containing a vinyl functional group;

[0017] Alternatively, at -50°C and in an inert gas environment, a n-hexane solution of n-butyl lithium is added dropwise to a tetrahydrofuran solution of methyltriphenylphosphine bromide, the solution is stirred, and then a tetrahydrofuran solution of 3-bromo-4-substituted benzaldehyde is slowly added dropwise, and the mixture is continuously stirred at 0°C. After the reaction is completed, post-treatment is performed, the obtained product is dissolved in tetrahydrofuran, and the solution is added dropwise to magnesium chips for reaction to obtain a monophosphine ligand containing a vinyl functional group.

[0018] More preferably, the 3-bromo-4-substituted benzaldehyde is selected from 3-bromo-4-fluorobenzaldehyde, 3-bromo-4-methylbenzaldehyde or 3-bromo-4-methoxybenzaldehyde.

[0019] Preferably, for monophosphine ligands with different substitutions, the method for preparing the monophosphine ligand containing vinyl functional groups comprises:

[0020] At -78°C and in an inert gas environment, a n-hexane solution of n-butyl lithium is added dropwise to a solution of bromovinylbenzene in anhydrous tetrahydrofuran, the solution is stirred, and then a solution of phosphorus trichloride in anhydrous tetrahydrofuran is added dropwise, the mixture is stirred continuously at -78°C, the system is then returned to room temperature, and the reaction is allowed to proceed overnight, a n-hexane solution of n-butyl lithium is added dropwise to the above solution, the solution is stirred, and then a solution of bromobenzene in anhydrous tetrahydrofuran is added dropwise, the mixture is stirred continuously at -78°C, the system is then returned to room temperature, and the reaction is allowed to proceed overnight to obtain a vinyl-functionalized monophosphine ligand containing different groups substituted on the benzene ring.

[0021] The third object of the present invention is to provide the use of the monophosphine polymer embedded catalyst in the hydroformylation reaction of medium-chain α-olefins to prepare high-carbon alcohols and high-carbon aldehydes, wherein the medium-chain α-olefins are olefins with a total carbon number of more than 5.

[0022] Preferably, the medium-long chain α-olefin is selected from olefins with a carbon chain length of 5 to 15 or olefins with a five- to eight-membered ring. Specifically, the olefin with a carbon chain length of 5 to 15 can be selected from 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene or 1-pentadecene.

[0023] Preferably, the carbon chain of the olefin having a total of 5 or more carbon atoms contains an ester group or a silane group.

[0024] Preferably, the reaction conditions for preparing high-carbon alcohols and high-carbon aldehydes by the hydroformylation reaction are as follows: in a kettle reactor, the volume ratio of synthesis gas is CO:H2=1-3:1, the reaction pressure is 0.1-10.0 MPa, the reaction temperature is 40-200°C, the reaction solvent is selected from any one or more of cyclohexane, toluene, 1,4-dioxane, tetrahydrofuran or p-xylene, and olefins and synthesis gas undergo a hydroformylation reaction under the catalytic action of the monophosphine polymer-encapsulated catalyst to generate aldehydes or alcohols having one more carbon than medium-chain α-olefins; when the reaction temperature is above 160°C, alcohols having one more carbon than medium-chain α-olefins are generated; when the reaction temperature is less than 160°C, aldehydes having one more carbon than medium-chain α-olefins are generated.

[0025] More preferably, when the reaction temperature is between 160 and 200° C., alcohols having one more carbon than the medium-chain α-olefins are generated; when the reaction temperature is between 40 and 150° C., aldehydes having one more carbon than the medium-chain α-olefins are generated.

[0026] The monophosphine polymer embedded catalyst for olefin hydroformylation of the present invention and its preparation method and application have the following advantages:

[0027] The catalyst prepared by the present invention is composed of an active metal and a monophosphine copolymer, and the catalyst can not only embed the active metal, but also efficiently and highly selectively realize an olefin hydroformylation reaction using CO as a carbonyl source under mild conditions. The active metal component forms a chemical coordination bond with P in the polymer so that the active component exists in a highly dispersed state, and the catalyst has high activity and high stability. The catalyst of the present invention retains the advantages of high catalytic activity and good chemical selectivity of a homogeneous catalyst, and the synthesis route is relatively simple, the production cost is relatively low, the catalyst and the product are easy to separate, and it is suitable for olefin hydroformylation reaction, thereby being able to meet the industrial application of olefin hydroformylation reaction, and can realize controllable synthesis of aldehydes or alcohols by controlling the temperature.

[0028] The monophosphine copolymer of the present invention is a vinyl functionalized monophosphine ligand monomer, one or more of which are polymerized by regulating the input ratio through solvent thermal polymerization to generate a copolymer with a large specific surface area (355.270 m 2 ·g -1 ) and copolymers with pore structures of various types and sizes. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the BET characterization diagram of catalyst A in Example 1.

[0030] Figure 2 This is the TGA characterization chart of catalyst A in Example 1.

[0031] Figure 3(a) HR-TEM characterization image and (b) EDX maps characterization image of catalyst A in Example 1.

[0032] Figure 4 XRD characterization diagram of catalyst A in Example 1. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] It should be noted that if the specific conditions are not specified in the examples, the experiments were carried out according to conventional conditions or the conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased from the market.

[0035] In the present invention, all features defined in the form of numerical ranges or percentage ranges, such as values, quantities, contents and concentrations, are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0036] The features mentioned in the present invention can be combined arbitrarily, as long as there is no contradiction in the combination of these features, all possible combinations should be considered as the scope of this specification. Each feature disclosed in the specification can be replaced by any alternative feature that can provide the same, equal or similar purpose. Therefore, unless otherwise specified, the disclosed features are only general examples of equal or similar features.

[0037] In the present invention, unless otherwise specified, the term "medium-chain α-olefin" refers to an olefin having a total carbon number of 5 or more, preferably an olefin having a total carbon number of 5 to 15.

[0038] Example 1

[0039] A monophosphine polymer embedded catalyst for olefin hydroformylation, the preparation method of which is as follows:

[0040] At -78°C under argon, a solution of n-butyl lithium in n-hexane (2.5M, 12.6mL, 31.5mmol) was added dropwise to a solution of p-bromovinylbenzene (6.04g, 33mmol) in anhydrous tetrahydrofuran (40ml) over 20 minutes. The solution was stirred for 1h, and then phosphorus trichloride (1.37g, 10mmol) dissolved in anhydrous tetrahydrofuran (5mL) was added dropwise over 5min. The mixture was stirred at -78°C for 1h, and then the system was returned to room temperature and the reaction was allowed to proceed overnight.

[0041] After the reaction was completed, the mixture was quenched with 2M HCl solution, extracted with ethyl acetate and water three times, and the combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel using an ethyl acetate-petroleum ether mixture as eluent to obtain the desired monophosphine ligand L1 as a white solid.

[0042] Under an inert atmosphere, the monophosphine ligand L1 (340.0 mg, 1 mmol) and dicobalt octacarbonyl (34.1 mg, 0.1 mmol) were dissolved in 10 mL of tetrahydrofuran (THF) and stirred at room temperature for 2 h to obtain a coordination product. Under an inert atmosphere, the coordination product and azobisisobutyronitrile (16.4 mg, 0.1 mmol), a free radical initiator, were added to 10 mL of tetrahydrofuran, and the resulting reaction solution was transferred to a hydrothermal autoclave, stirred at room temperature for 0.5 h, and then heated to 100° C. in a forced air drying oven and allowed to react for 24 h.

[0043] After the polymerization reaction was completed, the obtained brown solid was filtered, washed with tetrahydrofuran (20 mL×3), and dried under vacuum at 60° C. for 12 h to obtain a monophosphine ligand polymer-embedded cobalt-based catalytic material, which was recorded as catalyst A.

[0044]

[0045] Example 2

[0046] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0047] 340 mg of monophosphine ligand L2 was weighed to replace 340 mg of L1, 3.41 mg of dicobalt octacarbonyl was weighed to replace 34.1 mg of dicobalt octacarbonyl, and 1.64 mg of azobisisobutyronitrile was weighed to replace 16.4 mg of azobisisobutyronitrile.

[0048] The rest is the same as Example 1. The obtained monophosphine ligand polymer encapsulates the cobalt-based catalytic material and is recorded as Catalyst B.

[0049]

[0050] The preparation method of the monophosphine ligand L2 is substantially the same as the preparation method of the monophosphine ligand L1 in Example 1, except that:

[0051] m-bromovinylbenzene was used instead of p-bromovinylbenzene.

[0052] Example 3

[0053] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0054] 409 mg of monophosphine ligand L3 was weighed to replace 340 mg of L1. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst C.

[0055]

[0056] The preparation method of the monophosphine ligand L3 is as follows:

[0057] First, at -50 ° C, under argon, a solution of n-butyl lithium in hexane (2.5M, 8.4 mL, 31.5 mmol) was added dropwise to a solution of methyl triphenylphosphine bromide (4.06 g, 20 mmol) in anhydrous tetrahydrofuran (100 mL) over 60 minutes. The solution was stirred for 1 hour, and then 3-bromo-4-fluorobenzaldehyde (4.06 g, 20 mmol) dissolved in anhydrous tetrahydrofuran (100 mL) was slowly added dropwise. The mixture was stirred for 1 hour at 0 ° C. After the reaction was completed, 50 mL of NH4Cl solution was added. The organic phase was extracted three times with ethyl acetate. Then filtered and purified by silica gel chromatography (eluent was petroleum ether).

[0058] The above product was dissolved in 60 mL THF, magnesium turnings (0.51 g, 21 mmol) were added dropwise within 1 h, and the mixture was reacted for 4 h. The residue was purified by flash column chromatography on silica gel using an ethyl acetate-petroleum ether mixture as the eluent to obtain the desired monophosphine ligand L3 as a white solid.

[0059] Example 4

[0060] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0061] 51.8 mg (0.20 mmol) of cobalt acetylacetonate was weighed to replace 34.1 mg of dicobalt octacarbonyl, and the rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst D.

[0062] Example 5

[0063] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0064] 113.7 mg of dicobalt octacarbonyl was weighed to replace 34.1 mg of dicobalt octacarbonyl. The polymerization temperature was 40° C., and the rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst E.

[0065] Example 6

[0066] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0067] The stirring temperature of the coordination process was 80° C. for 1 h, and the solvent N,N-dimethylformamide (DMF) was used instead of tetrahydrofuran. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-encapsulated cobalt-based catalytic material was recorded as Catalyst F.

[0068] Example 7

[0069] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0070] The stirring temperature of the coordination process was 20°C. During the polymerization process, the hydrothermal autoclave was heated to 140°C in a forced air drying oven and allowed to react for 24 hours. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst G.

[0071] Example 8

[0072] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0073] 26.0 mg of cobalt chloride was weighed to replace 34.1 mg of dicobalt octacarbonyl, hydrogen peroxide was selected as the free radical initiator to replace azobisisobutyronitrile, and the rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as catalyst H.

[0074] Example 9

[0075] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0076] 36.6 mg of cobalt nitrate was weighed to replace 34.1 mg of dicobalt octacarbonyl, and the solvent ethanol was used instead of tetrahydrofuran. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst I.

[0077] Example 10

[0078] 41.4 mg of ruthenium trichloride was weighed to replace 34.1 mg of dicobalt octacarbonyl. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst J.

[0079] Embodiment 11

[0080] A monophosphine polymer embedded catalyst for olefin hydroformylation, which differs from Example 1 only in that:

[0081] 73.8 mg of platinum nitrate was weighed to replace 34.1 mg of dicobalt octacarbonyl. The rest was the same as in Example 1. The obtained monophosphine ligand polymer-embedded cobalt-based catalytic material was recorded as Catalyst K.

[0082] Experimental Example 1 Structural Characterization

[0083] 1. BET characterization

[0084] The structural characteristics of catalyst A in Example 1 were evaluated by nitrogen adsorption isotherm at 77 K, showing a reversible type IV adsorption isotherm and the presence of a mesoporous structure with pore sizes mainly distributed in the range of 3 to 10 nm.

[0085] 2. TGA characterization

[0086] The TGA analysis curve shows that the catalyst A in Example 1 exhibits good thermal stability and only loses 3.28% of its weight at a high temperature of 372°C.

[0087] 3. HR-TEM and EDX maps characterization

[0088] TEM showed that the catalyst A used in Example 1 was porous and amorphous, while no Co nanoparticles were detected in the HR-TEM image, indicating that the Co species were highly dispersed in the polymer. In addition, the EDX spectrum showed that the C, P and Co elements were evenly distributed in the catalyst A used in Example 1, and the presence of the Co element indicated that encapsulated isolated Co species were formed in the polymer.

[0089] 4. XRD characterization

[0090] XRD showed that no characteristic peak of Co was detected in the XRD pattern of catalyst A used in Example 1, indicating that the Co species was highly dispersed in the polymer.

[0091] Experimental Example 2 Performance Evaluation

[0092] The catalysts A to K and the hydroformylation reaction conditions prepared in Examples 1 to 11 above were used in the hydroformylation reaction of medium- and long-chain α-olefins to illustrate the catalytic performance of different catalysts and different reaction conditions in catalyzing the hydroformylation reaction of medium- and long-chain α-olefins to produce high-carbon alcohols and high-carbon aldehydes by regulating temperature.

[0093] 1. Catalytic performance

[0094] 1) Effects of different monophosphine ligands, metal precursors and temperatures on the catalytic performance of the hydroformylation reaction to alcohols

[0095] 50 mg of the catalyst prepared in the examples of the present invention (catalyst A to catalyst K), 0.5 mmol 1-octene, and 3 mL tetrahydrofuran (THF) were placed in a 100 mL autoclave reactor, and the gas in the autoclave was replaced three times with 1 MPa synthesis gas (CO / H2=1:1), and 4 MPa synthesis gas (CO / H2=1:1) was introduced, and the reaction was stirred at 170°C for 12 hours.

[0096] After the reaction, the reactor was cooled to room temperature, biphenyl was added as an internal standard, and the reaction solution was analyzed by gas chromatography using HP-7890N equipped with an HP-5 capillary column and a FID detector. The results are shown in Table 1.

[0097] Table 1 The results of the reaction of 1-octene hydroformylation to alcohol catalyzed by the catalyst in the example at 170°C

[0098]

[0099] 2) The effect of different hydroformylation reaction conditions on the catalytic performance of hydroformylation to synthesize aldehydes is basically the same as the hydroformylation reaction in 1) above, except that:

[0100] a) hydroformylating different catalysts A to I at different temperatures;

[0101] b) Catalyst A was hydroformylated in different solvents.

[0102] The test results are shown in Table 2 and Table 3.

[0103] Table 2 Results of catalytic hydroformylation of 1-octene to synthesize aldehydes at different temperatures and solvents

[0104] catalyst Reaction temperature Reaction solvent Conversion rate (%) Aldehyde selectivity (%) Aldehyde yield (%) A 40℃ THF 15 89 13 A 150℃ THF 96 55 53 A 140℃ THF 91 79 72 A 140℃ Toluene 79 45 36 B 140℃ THF 93 77 72 C 140℃ THF 79 79 62 D 140℃ THF 13 5 7 E 140℃ THF 53 35 19 F 140℃ THF 69 66 46 G 140℃ THF 89 79 70 H 140℃ THF 59 73 43 I 140℃ THF 55 69 40 G 140℃ THF 90 78 70 K 140℃ THF 88 66 58

[0105] Table 3 Results of catalytic 1-octene hydroformylation to alcohol at different solvents and temperatures

[0106] catalyst Reaction temperature Reaction solvent Conversion rate (%) Alcohol selectivity (%) Alcohol yield (%) A 160℃ THF 96 79 76 A 170℃ THF 98 91 89 A 170℃ Toluene 44 53 47 A 200℃ THF 99 85 84

[0107] As can be seen from Tables 1 to 3, the catalyst provided by the present invention has good catalytic performance in controlling the reaction of hydroformylation of long-chain α-olefins to generate higher alcohols and higher aldehydes by changing the temperature.

[0108] 2. Cycle stability

[0109] Taking the catalyst A prepared in Example 1 as an example, the reusability of the cobalt-based catalyst embedded with a monophosphine ligand polymer in catalyzing the hydroformylation reaction of 1-octene is illustrated.

[0110] The same as the hydroformylation reaction in 1) above, the reaction data of the catalyst reuse is shown in Table 4.

[0111] Table 4 Reusability of Catalyst A in Example 1

[0112] Number of times of reuse Conversion rate (%) Alcohol yield (%) first 98 87 Second time 97 85 The third time 99 83 Fourth 99 85

[0113] It can be seen from Table 4 that the catalyst prepared by the present invention can be reused at least four times, and the catalytic activity can still be maintained at a high level.

[0114] 3. Substrate adaptability

[0115] Taking the catalyst A prepared in Example 1 as an example, the catalytic performance of the cobalt-based catalyst embedded with a monophosphine ligand polymer in catalyzing the hydroformylation reaction of different olefins is illustrated.

[0116] The hydroformylation reaction is basically the same as in the above 1), except that 0.5 mmol of a different olefin substrate is used instead of 0.5 mmol of 1-octene during the reaction. The rest is the same as the 1-octene reaction. The structures are shown in Tables 5 and 6 below.

[0117] Table 5 Catalytic performance of catalyst A for the hydroformylation of different olefins to produce alcohols at 170°C

[0118]

[0119] Note: l / b in the table indicates the generated positive difference ratio, which is the same in the following table.

[0120] Table 6 Catalytic performance of catalyst A for hydroformylation of different olefins to form aldehydes at 140°C

[0121]

[0122] It can be seen from Table 5 and Table 6 that the catalytic materials prepared by the present invention are applied to the hydroformylation reactions of different aliphatic olefins, and all exhibit excellent catalytic activity and good applicability.

[0123] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as a limitation of the present invention. After reading the above content, it will be apparent to those skilled in the art that various modifications and substitutions of the present invention will occur. Therefore, the protection scope of the present invention should be limited by the appended claims.

Claims

1. A monophosphine polymer embedded catalyst for olefin hydroformylation, characterized in that: The monophosphine polymer embedded catalyst is obtained by solvent thermal polymerization of a vinyl functionalized monophosphine ligand and an active metal precursor in one step; the weight of the active metal in the active metal precursor accounts for 0.1 to 10.0% of the total weight of the monophosphine polymer embedded catalyst; Wherein, the structure of the monophosphine ligand containing vinyl functional group is selected from any one or more of the following:

2. The monophosphine polymer embedded catalyst according to claim 1, characterized in that: The active metal precursor is any one or more precursors of metal cobalt, ruthenium or platinum.

3. The method for preparing the monophosphine polymer embedded catalyst according to claim 1 or 2, characterized in that: The method includes: (1) under an inert gas atmosphere, dissolving the monophosphine ligand containing a vinyl functional group and the active metal precursor in a molar ratio of 10 to 100:1 in a first organic solvent, stirring and reacting at 20 to 80° C. for 1 to 4 hours to obtain a coordination product; (2) Under an inert gas atmosphere, the coordination product and the free radical initiator are co-dissolved in a second organic solvent, and the polymerization reaction is carried out in an autoclave at 40 to 150° C. for 20 to 25 hours, followed by washing, and the organic solvent is removed under reduced pressure at 20 to 50° C. to obtain a catalyst embedded in a monophosphine ligand polymer.

4. The preparation method according to claim 3, characterized in that: The active metal precursor is selected from any one or more of cobalt acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetylacetonate, cobalt oxalate, bis(pentamethylcyclopentadienyl)cobalt, hexaamminecobalt trichloride, dicobalt octacarbonyl, ruthenium trichloride, ruthenium acetate, bis(triphenylphosphine)dicarbonylruthenium(II) chloride and platinum nitrate.

5. The preparation method according to claim 3, characterized in that: The molar ratio of the monophosphine ligand containing vinyl functional group to the free radical initiator is (10-100):

1.

6. The preparation method according to claim 3, characterized in that: The free radical initiator is selected from any one of azobisisobutyronitrile, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide and methyl ethyl ketone peroxide; Or / and, the first organic solvent and the second organic solvent are each independently selected from any one or more of ethanol, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, n-hexane, toluene, anisole, dichloromethane and chloroform.

7. Use of the monophosphine polymer embedded catalyst as claimed in claim 1 or 2 in the hydroformylation reaction of medium and long chain α-olefins to prepare higher alcohols and higher carbon aldehydes, characterized in that: The medium- and long-chain α-olefins are olefins with a total carbon number of 5 or more.

8. The use according to claim 7, characterized in that: The medium- and long-chain α-olefins are selected from olefins with a carbon chain length of 5 to 15 or olefins with five to eight-membered rings.

9. The use according to claim 7, characterized in that: The olefin having a total of 5 or more carbon atoms contains an ester group or a silane group on its carbon chain.

10. The use according to claim 7, characterized in that: The reaction conditions for preparing higher alcohols and higher aldehydes by hydroformylation are: In a tank reactor, the volume ratio of synthesis gas is CO:H2=1-3:1, the reaction pressure is 0.1-10.0MPa, the reaction temperature is 40-200°C, the reaction solvent is selected from any one or more of cyclohexane, toluene, 1,4-dioxane, tetrahydrofuran or p-xylene, and olefins and synthesis gas undergo a hydroformylation reaction under the catalytic action of the monophosphine polymer embedded catalyst to generate an aldehyde or alcohol having one more carbon than the medium- and long-chain α-olefin; When the reaction temperature is above 160°C, an alcohol having one more carbon than the medium- and long-chain α-olefin is generated; When the reaction temperature is less than 160° C., an aldehyde having one more carbon than the medium-chain α-olefin is generated.

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