A method for directly preparing alcohol by catalytic reduction hydroformylation of olefins

Abstract

The invention discloses a method for directly preparing alcohols with high selectivity by olefin reduction hydroformylation reaction. The method adopts a phosphine-containing porous organic polymer supported ruthenium catalyst for catalytic reaction. The method is to take a proper amount of catalyst and add it to an autoclave under the protection of inert gas, add olefin and solvent, seal the autoclave, introduce a mixture of hydrogen and carbon monoxide, react at temperature T1 for t1 hour, heat to temperature T2, and react at temperature T2 for t2 hours. Cool to room temperature. Take out the reaction solution and centrifuge, wash the solid with methanol 3 times, and vacuum dry at 50°C for 5 hours, and the catalyst can be regenerated. The preparation method according to the invention adopts a specific catalyst and realizes the high-activity and high-selectivity preparation of olefins directly to alcohols through a segmented temperature control mode.

Description

Technical Field

[0001] The present invention belongs to the fields of catalysis and fine chemical engineering. Specifically, it relates to a method for directly preparing alcohols by the reductive hydroformylation of olefins, and the method uses a class of ruthenium-based catalysts of phosphine-containing porous organic polymers for the catalytic reaction. Background Art

[0002] The hydroformylation reaction, also known as the oxo synthesis reaction, is a reaction in which olefins react with syngas under the catalysis of transition metals to form aldehydes with one more carbon atom. Due to the high atom economy of the hydroformylation reaction, it can not only increase the carbon chain length but also the products can be further converted into fine chemicals with higher added values such as alcohols, carboxylic acids, amines, esters, etc. Therefore, the hydroformylation reaction has become one of the catalytic processes with the largest production scale.

[0003] Alcohols are very important chemical products, especially higher alcohols, which are widely used in the fields of food, pharmaceutical chemistry, cosmetics, detergents, surfactants, etc. The main production methods for synthesizing higher alcohols include the oxo synthesis method, the Ziegler method, and the oxidation method of normal paraffins. The Ziegler method uses ethylene as the raw material and, under the catalysis of triethylaluminum, prepares higher alcohols through a series of high-energy-consuming and highly polluting processes such as oxidation, hydrolysis, and rectification. Its process flow is complex and the requirements for equipment are high, and it has gradually been replaced by the oxo synthesis method. The oxo synthesis method uses petrochemical products such as α-olefins as raw materials. First, aldehydes are prepared through the hydroformylation reaction, and then alcohols can be obtained through reduction. The oxidation method of normal paraffins is a process in which normal paraffins are oxidized with air under atmospheric pressure in the presence of a boric acid catalyst, resulting in a large amount of chain scission to form various alcohols. This method has high energy consumption, poor selectivity for single alcohols, and is difficult to separate. Therefore, the oxo synthesis method is currently the most advanced process for producing higher alcohols.

[0004] In the hydroformylation process, an aldehyde is first generated through a hydroformylation reaction and then reduced to obtain an alcohol. The drawback of this method is that it requires two-step operations, which is a cumbersome process. Moreover, the activity of the precious metal rhodium in the first step is the best. Due to the sharp increase in the price of rhodium in recent years, the cost of this process has been continuously increasing. Therefore, the development of a new process is an urgent problem to be solved at present. The one-step reductive hydroformylation reaction of olefins to directly prepare alcohols can perfectly solve this problem. Firstly, only one step is required in this process to obtain the desired alcohol, and the process is simple. Secondly, ruthenium is used as the catalyst in this process, and its price is much lower than that of rhodium, resulting in a low overall cost. Thirdly, the desired alcohol can also be obtained by changing different raw material olefins in this process, and the selectivity for linear alcohols is very high. Although this process has many advantages, there are also obvious problems. At present, some progress has been made by Beller et al. in Germany in the homogeneous catalytic reductive hydroformylation of olefins to directly prepare alcohols (Angew. Chem. Int. Ed. 2013, 52, 2949–2953; J. Am. Chem. Soc. 2013, 135, 14306-14312; ChemSusChem 2018, 11, 2310–2314; Chem. Eur. J. 2022, 28, e202104012), but the process is not yet mature. The disadvantages of homogeneous catalysis are the difficult separation of the catalyst from the product after the reaction, the poor stability of the ligand, the poor recyclability of the catalyst, and the high cost. These are the main factors restricting the industrialization of precious metal homogeneous catalysis. If a breakthrough can be made in heterogeneous catalysis, it will accelerate the industrialization process of this process.

[0005] Porous organic polymer materials (POPs) are a class of porous network materials with two-dimensional or three-dimensional structures, which have advantages such as a large specific surface area, porous structure, and high thermal stability, and are widely used in various fields such as gas storage, gas separation, heterogeneous catalysis, and optoelectronic materials. In recent years, the construction of phosphine-containing organic porous polymers by polymerizing functionalized phosphine ligand monomers has received extensive attention in the research of olefin hydroformylation, and the research has become increasingly mature, but there has been no research on directly catalyzing the formation of alcohols. Summary of the Invention

[0006] In view of the above problems in the prior art, the present application has successfully developed a ruthenium catalyst supported on a phosphine-containing porous organic polymer, which can not only efficiently catalyze olefins to carry out reductive hydroformylation reactions to directly prepare linear alcohols with higher added value with high selectivity, but also can be recycled after the reaction and has good cyclic catalytic performance, which can greatly reduce the production cost. The catalyst has shown very good activity, selectivity, and cyclic stability in the reaction of directly preparing alcohols by the reductive hydroformylation of olefins, laying a foundation for the industrialization of this process.

[0007] According to one aspect of the present invention, an object of the present invention is to provide a method for directly and highly selectively preparing alcohol by the reductive hydroformylation reaction of olefins. The method uses a ruthenium catalyst supported on a phosphine-containing porous organic polymer to catalyze the reaction, and the method is carried out as follows:

[0008] Under the protection of an inert gas, an appropriate amount of catalyst is added to an autoclave, olefins and a solvent are added, the autoclave is sealed, a mixture of hydrogen and carbon monoxide is introduced, and the reaction is carried out at a temperature of T1 for t1 hours. Then the temperature is raised to T2, and the reaction is carried out at T2 for t2 hours. The temperature is lowered to room temperature, n-decane is added as an internal standard, and the sample is taken for gas chromatography analysis. The reaction solution is taken out and centrifuged, and the solid is washed 3 times with methanol and dried in vacuo at 50 °C for 5 hours, and the catalyst can be regenerated.

[0009] Preferably, the olefins are selected from terminal olefins or internal olefins of ethylene, propylene, 1-butene, 2-butene, mixed butenes, 1-pentene, 1-hexene, 1-octene, 2-octene, 4-octene, 1-decene, diisobutylene, triisobutylene, isododecene, and styrene.

[0010] Preferably, the solvent is selected from n-hexane, benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide. Toluene, tetrahydrofuran, and N-methylpyrrolidone are preferred.

[0011] Preferably, the amount of the catalyst used is 0.01% to 5% of the molar amount of the olefins, and more preferably 0.1% to 1%.

[0012] Preferably, the reaction concentration of the olefins is 0.1 mmol / L - 10 mmol / L, or no solvent is added.

[0013] Preferably, the ratio of hydrogen to carbon monoxide is 10:1 - 1:1.

[0014] Preferably, the pressure of the mixed gas is 0.1 MPa - 10 MPa.

[0015] Preferably, the temperature T1 is 50 °C - 100 °C, and more preferably the temperature T1 is 60 °C - 90 °C.

[0016] Preferably, the temperature T2 is 100 °C - 200 °C, and more preferably the temperature T2 is 120 °C - 160 °C.

[0017] Preferably, the time t1 is 12 hours - 36 hours, and more preferably the time t1 is 18 hours - 30 hours.

[0018] Preferably, the time t2 is 12 hours - 36 hours, and more preferably the time t2 is 18 hours - 30 hours.

[0019] In the method for preparing an alcohol according to the present invention, the phosphine-containing porous organic polymer-supported ruthenium catalyst is prepared by an impregnation method using a Ru precursor and a phosphine-containing porous organic polymer ligand, and the loading amount of Ru is 0.1% - 10% by mass fraction. Among them, the Ru precursor can be selected from Ru 3 (CO) 12 、RuH 2 (CO)(PPh 3 ) 3 、RuCl 2 (PPh 3 ) 3 、Ru 2 Cl 4 (CO) 6 、[CpRu(CO) 2 2 、RuCl 3 、[Ru(COD)Cl 2 n 、Ru(allylmethyl) 2 (COD)、[Ru(COD) 2 BF 4 or one or more of them, preferably Ru 3 (CO) 12 . The phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by the general formula I:

[0020]

[0021] wherein

[0022] R is selected from or one or more of them, where * represents the polymerization link position.

[0023] R 1 and R 2 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C14 cycloalkyl, C6-C14 aryl, 3-10 membered heteroaryl containing 1 to 3 heteroatoms selected from N, O and S.

[0024] Preferably, R 1 and R 2 are each independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, 5-10 membered heteroaryl containing 1 or 2 heteroatoms selected from N and O.

[0025] More preferably, R 1 and R 2 ​​Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, cyclopentyl, cyclohexyl, 1-adamantyl, phenyl, 1-naphthyl, 2-furyl, 2-pyrrolyl, pyranyl, pyridyl respectively.

[0026] R 3 and R 4 Each independently selected from hydrogen, halogen, cyano, amino, C1-C6 alkyl, C1-C6 alkoxy.

[0027] Preferably, R 3 and R 4 Each independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkyl, C1-C4 alkoxy.

[0028] More preferably, R 3 and R 4 Each independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl, cyano, etc.

[0029] R 5 、R 6 、R 7 and R 8 Each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, cyano.

[0030] Preferably, R 5 、R 6 、R 7 and R 8 Each independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, cyano.

[0031] More preferably, R 5 、R 6 、R 7 and R 8 Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, dimethylamino, cyano, etc.

[0032] Preferably, in the general formula I, the subscript m represents the molar content of the phosphine-containing polymerizable monomer, the subscript n represents the molar content of the comonomer, and m:n is 1:0 to 1:100, but the subscripts m and n do not represent the linking order of each monomer, and the linking order of each monomer can be not fixed, being a random polymer.

[0033] Preferably, m:n is 1:1 to 1:20.

[0034] The preparation method of the phosphine-containing porous organic polymer supported ruthenium catalyst is as follows: Under the protection of an inert gas, a certain amount of Ru precursor and a phosphine-containing porous organic polymer ligand are taken in proportion, and the Ru precursor is deposited on the phosphine-containing porous organic polymer ligand by stirring in a solvent at a certain temperature for a certain time, and then the solvent is removed under reduced pressure to obtain the catalyst.

[0035] Preferably, the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, toluene, and preferably tetrahydrofuran and toluene.

[0036] Preferably, the temperature is 0°C - 100°C, and preferably 10°C - 50°C.

[0037] Preferably, the stirring time is 2 - 48 hours, and preferably 12 - 36 hours.

[0038] Preferably, the inert gas is argon or nitrogen, and preferably argon.

[0039] The preparation method of the phosphine-containing porous organic polymer ligand is as follows: Under the protection of an inert gas, a certain amount of vinyl-functionalized phosphine-containing polymerization monomer and a certain amount of comonomer based on substituent R are dissolved in tetrahydrofuran, a certain amount of free radical initiator azobisisobutyronitrile is added, and the reaction is stirred at a certain temperature for 24 - 48 hours.

[0040] Preferably, the molar ratio of the phosphine-containing polymerization monomer to the comonomer based on substituent R is 1:0 - 1:100, and preferably 1:5 - 1:20.

[0041] Preferably, the dosage of the initiator azobisisobutyronitrile is 0.1% - 5% of the molar amount of vinyl in the raw materials.

[0042] Preferably, the comonomer based on substituent R is selected from one or more of them.

[0043] Preferably, the reaction temperature is 60°C - 150°C, and preferably 80°C - 100°C.

[0044] Preferably, the inert gas is argon or nitrogen, and preferably argon.

[0045] The preparation method of the vinyl-functionalized phosphine-containing polymerization monomer is as follows:

[0046]

[0047] Among them, the definitions of substituents R1 to R8 are the same as those in General Formula I.

[0048] Step 1: Add Compound 1, trimethyl orthoformate, and tetrabutylammonium tribromide into a reactor, dissolve them in methanol, stir and react at 80 °C for 3 hours, remove the solvent under reduced pressure, and separate by column chromatography to obtain Compound 2.

[0049] Step 2: Add sodium hydride and DMF into a reactor, and add the imidazole compound in batches Stir and react at room temperature for half an hour, add copper powder and Compound 2, stir and react at 150 °C for 3 hours, cool down, quench with water, extract with ethyl acetate, and purify by column chromatography to obtain Compound 3.

[0050] Step 3: Under the protection of inert gas, add Compound 3 into a reactor, dissolve it in tetrahydrofuran, cool down to -78 °C, dropwise add n-butyllithium, stir and react at -78 °C for 1 hour, and then add the phosphine chloride compound React at room temperature for 1 hour, add dilute hydrochloric acid and continue to react for 2 hours. Add sodium bicarbonate to dissolve and adjust the pH value to weakly alkaline, extract with ethyl acetate, and separate by column chromatography to obtain Compound 4.

[0051] Step 4: Under the protection of inert gas, add methyltriphenylphosphonium bromide into a reaction flask, disperse it in tetrahydrofuran, add potassium tert-butoxide in batches, stir and react at room temperature for half an hour, add Compound 4, and stir and react at room temperature for 3 hours. Quench with water, extract with ethyl acetate, and separate by column chromatography to obtain Compound 5, which is the vinyl-functionalized phosphine-containing polymer monomer.

[0052] Beneficial Effects

[0053] The biggest feature of the preparation method according to the present invention is that a specific catalyst is used and high-activity and high-selectivity preparation of olefins directly to alcohols is achieved through a segmented temperature control mode.

[0054] 1. For the first time, a phosphine-containing porous organic polymer-supported Ru catalyst is applied to the direct preparation of alcohols by the reductive hydroformylation reaction of olefins. Both the reaction activity and regioselectivity are very high. Among them, the selectivity of alcohols is nearly 95% at most, and the ratio of linear alcohols to branched-chain alcohols is as high as 40.

[0055] 2. The catalytic process is carried out in a segmented temperature control process mode. The first stage is carried out at a low temperature, mainly the hydroformylation reaction occurs, and the product is mainly aldehyde (high chemical selectivity and regioselectivity); the second stage is carried out at a higher temperature, mainly the hydroformylation of internal olefins and the reaction of aldehyde reduction to alcohol occur, and the product is mainly alcohol. Therefore, by adopting the segmented temperature control mode, not only aldehydes can be prepared but also alcohols with higher added value can be obtained by selecting different reaction temperatures. Moreover, both the chemical selectivity and regioselectivity of aldehydes and alcohols are very high.

[0056] 3. This heterogeneous catalyst has good stability and recycling performance, and still has good catalytic activity and selectivity after being recycled many times.

[0057] 4. The catalyst is a solid catalyst. After the reaction, the catalyst and the product can be easily separated by centrifugation or filtration. This not only simplifies the operation but also enables the recycling of the catalyst, greatly reducing the production cost. Detailed Embodiments

[0058] Hereinafter, the present invention will be described in detail. Before the description, it should be understood that the terms used in this specification and the appended claims should not be construed as being limited to their ordinary and dictionary meanings, but should be interpreted based on the principle that allows the inventor to appropriately define the terms for the best interpretation, in accordance with the meanings and concepts corresponding to the technical aspects of the present invention. Therefore, the description presented here is merely a preferred example for illustrative purposes and is not intended to limit the scope of the present invention. Thus, it should be understood that other equivalent ways or improved ways can be obtained without departing from the spirit and scope of the present invention.

[0059] Definitions

[0060] In the present application, the term "cycloalkyl" refers to a group of non-aromatic cyclic hydrocarbon groups. For example, it has 3 to 14 ring carbon atoms ("C3-14 cycloalkyl") and zero heteroatoms in a non-aromatic ring system. The cycloalkyl group can be monocyclic ("monocyclic cycloalkyl") or contain a fused, bridged or spiro ring system, such as a bicyclic system ("bicyclic cycloalkyl"), and can be saturated or can be partially unsaturated. "Cycloalkyl" also includes such a ring system in which a carbocyclic ring as defined above is fused to one or more aryl or heteroaryl groups, where the point of attachment is on the cycloalkyl ring, and in this case, the carbon number continues to represent the number of carbon atoms in the cycloalkyl ring system. Non-limiting exemplary cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, decalin, adamantyl, cyclopentenyl, and cyclohexenyl. In a preferred embodiment, the term "cycloalkyl" refers to a monocyclic saturated group having 3 to 10, more preferably 3 to 6, ring carbon atoms.

[0061] "Heterocycloalkyl" refers to a group of 3- to 10-membered non-aromatic ring systems having ring carbon atoms and 1 to 4 ring heteroatoms, where each heteroatom is independently selected from N, O, and S ("3–10-membered heterocyclic group"). In heterocyclic groups containing one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom where valence allows. The heterocyclic group can be monocyclic ("monocyclic heterocyclic group") or a fused, bridged, or spiro ring system, such as a bicyclic system ("bicyclic heterocyclic group"), and can be saturated or can be partially unsaturated. The bicyclic heterocyclic group system can contain one or more heteroatoms in one or both rings. "Heterocyclic group" also includes a ring system in which the above-defined heterocycle is fused to one or more cycloalkyl groups, where the point of attachment is on the cycloalkyl or heterocycle, or a ring system in which the above-defined heterocycle is fused to one or more aryl or heteroaryl groups, where the point of attachment is on the heterocycle, in which case the number of ring members continues to represent the number of ring members in the heterocyclic system.

[0062] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of a numerical range or percentage range should be considered to have covered and specifically disclosed all possible sub-ranges and individual numerical values within the range, especially integer numerical values. For example, the description of the range "1 to 8" should be considered to have specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially the sub-ranges defined by all integer numerical values, and should be considered to have specifically disclosed individual numerical values such as 1, 2, 3, 4, 5, 6, 7, 8, etc. within the range. Unless otherwise specified, the foregoing method of interpretation applies to all contents of the present invention, regardless of the breadth of the range.

[0063] If a quantity or other numerical value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that all ranges formed by any pair of the upper limit or preferred value of the range and the lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are separately disclosed. In addition, when a numerical range is mentioned in this document, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0064] In this document, on the premise that the object of the invention can be achieved, a numerical value should be understood to have the precision of the significant digits of that numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0065] In the method for preparing an alcohol according to the present invention, the temperature T1 is 50°C - 100°C, and more preferably the temperature T1 is 60°C - 90°C. If the temperature is too low, the reaction is too slow; if the temperature is too high, side hydrogenation reactions are likely to occur, the amount of reduction products increases, and the amount of target products decreases.

[0066] The temperature T2 is 100°C - 200°C, and more preferably the temperature T2 is 120°C - 160°C. If the temperature is too low, the hydrogenation reaction is too slow; if the temperature is too high, the equipment requirements are high and more by-products will be generated.

[0067] In the method for preparing alcohol according to the present invention, it cannot be carried out at only one temperature. Because when the temperature is higher than 100°C, on the one hand, the proportion of direct hydrogenation of olefins to alkanes will increase significantly, and on the other hand, the regioselectivity of the obtained aldehyde or alcohol will be very low (i.e., the ratio of linear alcohol to branched-chain alcohol is very small); while when the temperature is lower than 100°C, the hydrogenation of aldehyde to alcohol is very slow, and no hydrogenation reaction occurs if the temperature is too low. Therefore, two-stage program temperature control is very important for the present invention.

[0068] The following examples are only listed as examples of the embodiments of the present invention and do not constitute any limitation to the present invention. Those skilled in the art can understand that modifications within the scope not departing from the essence and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are all commercially available products. The gas phase uses GC-2030 of Shimadzu.

[0069] Preparation Example 1: Preparation of phosphine-containing porous organic polymer PL1

[0070] Step 1: Preparation of compound 2a

[0071]

[0072] Take 10 g of compound 1a, 6.9 g of trimethyl orthoformate, and 1.3 g of tetrabutylammonium tribromide and add them to a reaction flask. Add 20 mL of methanol to dissolve, stir and react at 80°C for 3 hours, remove the solvent under reduced pressure, and separate by column chromatography to obtain 12.57 g of compound 2a. The NMR data is as follows: 1 H NMR(400MHz,CDCl 3 )δ7.49(d,J=8.3Hz,2H),7.32(d,J=8.4Hz,2H),5.35(s,1H),3.30(s,6H).

[0073] Step 2: Preparation of compound 3a

[0074]

[0075] Add 4.4 g of sodium hydride and 38 mL of DMF to a reaction flask, add 7.4 g of imidazole in batches, stir and react at room temperature for half an hour, then add 0.69 g of copper powder and 12.57 g of compound 2a, and stir and react at 150°C for 3 hours. Cool down, quench with water, extract with ethyl acetate, and purify by column chromatography to obtain 7 g of compound 3a. The NMR data is as follows: 11H NMR (400 MHz, DMSO) δ 8.30 (s, 1H), 7.78 (s, 1H), 7.73–7.64 (m, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.14 (s, 1H), 5.45 (s, 1H), 3.28 (s, 6H).

[0076] Step 3: Preparation of Compound 4a

[0077]

[0078] Under argon protection, 5 g of Compound 3a was added to a reaction flask, dissolved in 50 mL of tetrahydrofuran, cooled to -78 °C, 10 mL of 1.6 mol / L n-butyllithium was added dropwise, and the mixture was stirred at -78 °C for 1 hour. Then 5.32 g of dicyclohexylphosphine chloride was added, and the reaction was stirred at room temperature for 1 hour. 25 mL of 2.4 mol / L dilute hydrochloric acid was added and the reaction continued for 2 hours. Sodium bicarbonate was added to dissolve and the pH value was adjusted to weakly alkaline, then extracted with ethyl acetate and separated by column chromatography to obtain 2 g of Compound 4a. The NMR data are as follows: 1 1H NMR (400 MHz, CDCl 3 ) δ 10.08 (s, 1H), 7.99 (d, J = 8.3 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 1.0 Hz, 1H), 7.24–7.20 (m, 1H), 2.15 (dd, J = 16.9, 6.6 Hz, 2H), 1.77–1.54 (m, 10H), 1.35–0.92 (m, 10H). 31 31P NMR (162 MHz, CDCl 3 ) δ -23.37.

[0079] Step 4: Preparation of Compound 5a

[0080]

[0081] Under argon protection, 4.4 g of methyltriphenylphosphonium bromide was added to a reaction flask, dispersed in 40 ml of tetrahydrofuran, 1.4 g of potassium tert-butoxide was added in batches, and the mixture was stirred at room temperature for half an hour. Then 2 g of Compound 4a was added, and the reaction was stirred at room temperature for 3 hours. The reaction was quenched with water, extracted with ethyl acetate, and separated by column chromatography to obtain 1.9 g of Compound 5a, the vinyl-functionalized phosphine-containing polymerization monomer. The NMR data are as follows: 1 1H NMR (400 MHz, CDCl 3) δ 7.48 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 0.8 Hz, 1H), 7.26 (d, J = 7.5 Hz, 3H), 7.16 (dd, J = 2.2, 1.1 Hz, 1H), 6.75 (dd, J = 17.6, 10.9 Hz, 1H), 5.80 (d, J = 17.6 Hz, 1H), 5.33 (d, J = 11.0 Hz, 1H), 2.13 (dd, J = 17.0, 6.4 Hz, 2H), 1.75–1.54 (m, 10H), 1.31–0.98 (m, 10H). 31 P NMR (162 MHz, CDCl 3 ) δ -24.03.

[0082] Step 5: Preparation of phosphine-containing porous organic polymer PL1 (m:n = 1:5)

[0083]

[0084] Under argon protection, 1 g of compound 5a obtained in Example 1, 1.77 g of divinylbenzene and 49 mg of azobisisobutyronitrile (AIBN) were added to a reaction flask, dissolved in 30 ml of THF, stirred at room temperature for half an hour, transferred to a hydrothermal autoclave, and reacted at 100 °C for 24 h. After cooling to room temperature, it was dispersed with methanol, centrifuged and separated, and washed with methanol three times to obtain 2.7 g of phosphine-containing porous organic polymer (PL1). The BET specific surface area of this polymer is 350 m 2 / g, mainly existing in the form of micropores and mesopores.

[0085] Step 6: Preparation of ruthenium catalyst Ru@PL1 supported on phosphine porous organic polymer

[0086] Under argon protection, 500 mg of phosphine-containing porous organic polymer PL1 was dispersed in 30 ml of tetrahydrofuran, and 52.5 mg of Ru 3 (CO) 12 was added, stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst supported on phosphine-containing porous organic polymer (Ru@PL1). The BET specific surface area of this polymer is 330 m 2 / g, mainly existing in the form of micropores and mesopores. (m:n = 1:5, Ru loading is 4.7%)

[0087] Examples 1 - 3: Influence of the molar ratio (m:n) of the phosphine-containing monomer to the comonomer in the phosphine-containing porous organic polymer ligand in the catalyst

[0088] Example 1:

[0089] Under the protection of inert gas, 57 mg of the catalyst Ru@PL1 prepared in Preparation Example 1 was taken and added into an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, the reaction solution was taken out and centrifuged. The solid was washed with methanol three times and dried in vacuum at 50 °C for 5 hours, and the catalyst could be regenerated. 1.25 mmol of n-decane was added to the reaction solution. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 83%, and the ratio of linear heptanol to branched heptanol (l / b) was 24.

[0090] Example 2:

[0091] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 was taken and added into an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, the reaction solution was taken out and centrifuged. The precipitate was washed with methanol three times and dried in vacuum at 50 °C for 5 hours, and the catalyst could be regenerated. 1.25 mmol of n-decane was added to the reaction solution. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 88%, and the ratio of linear heptanol to branched heptanol (l / b) was 26.

[0092] The catalyst Ru@PL2 was prepared in a similar manner to Preparation Example 1. In the catalyst Ru@PL2, m:n = 1:10 and the Ru loading was 2.9%.

[0093] Example 3:

[0094] Under the protection of inert gas, 166 mg of the catalyst Ru@PL3 was taken and added into an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, the reaction solution was taken out and centrifuged. The precipitate was washed with methanol three times and dried in vacuum at 50 °C for 5 hours, and the catalyst could be regenerated. 1.25 mmol of n-decane was added to the reaction solution. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 70%, and the ratio of linear heptanol to branched heptanol (l / b) was 31.

[0095] The catalyst Ru@PL3 was prepared in a similar manner to Preparation Example 1. In the catalyst Ru@PL3, m:n = 1:20 and the Ru loading was 1.6%.

[0096] Example m:n Conversion rate % Selectivity of heptanol % l / b 1 1:5 99％ 83％ 24 2 1:10 99％ 88％ 26 3 1:20 99％ 70％ 31

[0097] Examples 3 - 5: Influence of Ru loading

[0098] Example 4:

[0099] Under the protection of inert gas, 83 mg of the catalyst Ru@PL4 was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 89%, and the ratio of linear heptanol to branched heptanol (l / b) was 23.

[0100] The catalyst Ru@PL4 was prepared in a similar manner to that of Preparation Example 1. In the catalyst Ru@PL4, m:n = 1:20 and the Ru loading was 3.2%.

[0101] Example 5:

[0102] Under the protection of inert gas, 48 mg of the catalyst Ru@PL5 was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 62%, and the ratio of linear heptanol to branched heptanol (l / b) was 18.

[0103] The catalyst Ru@PL5 was prepared in a similar manner to that of Preparation Example 1. In the catalyst Ru@PL5, m:n = 1:20 and the Ru loading was 6.0%.

[0104] Example m:n Ru content Conversion rate % Selectivity of heptanol % l / b 3 1:20 1.6％ 99％ 70％ 31 4 1:20 3.2％ 99％ 89％ 23 5 1:20 6.0％ 99％ 62％ 18

[0105] Examples 2, 6 - 7: Influence of temperature T1

[0106] Example 6:

[0107] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading 2.9%) was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 70 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 81%, and the ratio of linear heptanol to branched heptanol (l / b) was 28.

[0108] Example 7:

[0109] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the reaction was stirred at 60 °C for 24 hours, and then at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The gas chromatography analysis results were as follows: the conversion rate was 95%, the selectivity for heptanol was 83%, and the ratio of linear heptanol to branched heptanol (l / b) was 27.

[0110] Example T1 Conversion rate % Selectivity of heptanol % l / b 2 80℃ 99％ 88％ 26 6 70℃ 99％ 85％ 28 7 60℃ 95％ 83％ 27

[0111] Examples 2, 8 - 9: Influence of reaction time t1

[0112] Example 8:

[0113] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the reaction was stirred at 80 °C for 20 hours, and then at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The gas chromatography analysis results were as follows: the conversion rate was 99%, the selectivity for heptanol was 80%, and the ratio of linear heptanol to branched heptanol (l / b) was 15.

[0114] Example 9:

[0115] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added into an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the reaction was stirred at 80 °C for 28 hours, and then at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The gas chromatography analysis results were as follows: the conversion rate was 99%, the selectivity for heptanol was 88%, and the ratio of linear heptanol to branched heptanol (l / b) was 25.

[0116]

[0117]

[0118] Examples 2, 10 - 11: Influence of temperature T2

[0119] Example 10:

[0120] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 70 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 70%, and the ratio of linear heptanol to branched heptanol (l / b) was 25.

[0121] Example 11:

[0122] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 60 °C for 24 hours, and then reacted at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 43%, and the ratio of linear heptanol to branched heptanol (l / b) was 26.

[0123] Example T2 Conversion rate % Selectivity of heptanol % l / b 2 150℃ 99％ 88％ 26 10 130℃ 99％ 70％ 25 11 110℃ 99％ 43％ 26

[0124] Examples 2, 12 - 13: Influence of reaction time t2

[0125] Example 12:

[0126] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 28 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 90%, and the ratio of linear heptanol to branched heptanol (l / b) was 17.

[0127] Example 13:

[0128] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of toluene were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 36 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 90%, and the ratio of linear heptanol to branched heptanol (l / b) was 17.

[0129] Example t2 Conversion rate % Selectivity of heptanol % l / b 2 24 99％ 88％ 26 12 28 99％ 90％ 17 13 36 99％ 90％ 17

[0130] Examples 2, 14 - 15: Influence of solvent

[0131] Example 14:

[0132] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of tetrahydrofuran were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 28 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 92%, and the ratio of linear heptanol to branched heptanol (l / b) was 17.

[0133] Example 15:

[0134] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave. 5 mmol of 1-hexene and 3 ml of N-methylpyrrolidone were added. The autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the mixture was stirred and reacted at 80 °C for 24 hours, and then reacted at 150 °C for 28 h. After cooling to room temperature, 1.25 mmol of n-decane was added. The results of gas chromatography analysis were as follows: the conversion rate was 99%, the selectivity for heptanol was 94%, and the ratio of linear heptanol to branched heptanol (l / b) was 40.

[0135] Example Solvent Conversion rate % Selectivity of heptanol % l / b 2 Toluene 99％ 88％ 26 14 Tetrahydrofuran 99％ 92％ 17 15 N - Methylpyrrolidone 99％ 94％ 40

[0136] Examples 8, 16 - 19: Recycling performance of catalyst

[0137] Under the protection of inert gas, 100 mg of the catalyst Ru@PL2 (m:n = 1:10, Ru loading is 2.9%) was added to an autoclave, 5 mmol of 1-hexene and 3 ml of toluene were added, the autoclave was sealed, 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced, and the reaction was stirred at 80 °C for 24 hours, and then reacted at 150 °C for 28 h. It was cooled to room temperature, 1.25 mmol of n-decane was added, and the sample was taken for gas chromatography analysis. The reaction solution was taken out for centrifugation, washed with methanol three times, and dried in vacuo at 50 °C for 5 hours. The dried recovered catalyst was added to the autoclave, and the above operation was repeated 5 times to test the stability and recycling performance of the catalyst. The gas phase results are as follows:

[0138] Example Number of times of catalyst use Conversion rate % Selectivity of heptanol % l / b 8 1 99％ 90％ 17 16 2 99％ 90％ 18 17 3 99％ 89％ 17 18 4 98％ 88％ 16 19 5 97％ 88％ 17

[0139] As described above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, and all of them should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for directly and selectively preparing alcohols by reductive hydroformylation of olefins, the method using a phosphine-containing porous organic polymer supported ruthenium catalyst to catalyze the reaction, the method being carried out as follows: Under the protection of inert gas, add the catalyst into the autoclave, add olefin and solvent, seal the autoclave, introduce a mixture of hydrogen and carbon monoxide, react at temperature T1 for t1 hour, heat to temperature T2, react at temperature T2 for t2 hours, cool to room temperature, add n-decane as internal standard, take a sample for gas chromatography analysis, take out the reaction liquid and centrifuge, wash the precipitate with methanol for 3 times, dry it in vacuum at 50°C for 5 hours, and the catalyst can be regenerated; The olefin is 1-hexene; The solvent is selected from the group consisting of n-hexane, benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, acetonitrile, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide; The catalyst is used in an amount of 0.01% to 5% of the molar amount of the olefin; The reaction concentration of olefin is 0.1mmol / L-10mmol / L, or no solvent is added; The ratio of hydrogen to carbon monoxide is 10:1-1:1; the pressure of the mixed gas is 0.1MPa-10MPa; Temperature T1 is 50°C-100°C; Temperature T2 is 100°C-200°C; Time t1 is 12 hours to 36 hours; Time t2 is 12 hours to 36 hours; in, The phosphine-containing porous organic polymer supported ruthenium catalyst is prepared by an impregnation method of a Ru precursor and a phosphine-containing porous organic polymer ligand, and the mass fraction of Ru loading is 0.1%-10%; wherein the Ru precursor is selected from Ru3(CO) 12 , RuH2(CO)(PPh3)3, RuCl2(PPh3)3, Ru2Cl4(CO)6, [CpRu(CO)2]2, RuCl3, [Ru(COD)Cl2] n , Ru(methallyl)2(COD), [Ru(COD)2]BF4, wherein the phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by the general formula I: in R is selected from One or more of the following, where * indicates the aggregation link location; R 1 and R 2 is cyclohexyl; R 3 To R 8 All are hydrogen; The subscript m represents the molar content of the phosphine-containing polymerized monomer, the subscript n represents the molar content of the comonomer, and m:n is 1:5 to 1:

20.

2. The method for preparing alcohol according to claim 1, characterized in that The Ru precursor in the phosphine-containing porous organic polymer-supported ruthenium catalyst is Ru3(CO) 12 .

3. The method for preparing alcohol according to claim 1, characterized in that The solvent is selected from toluene, tetrahydrofuran and N-methylpyrrolidone.

4. The method for preparing alcohol according to claim 1, characterized in that The amount of the catalyst used is 0.1% to 1% of the molar amount of the olefin.

5. The method for preparing alcohol according to claim 1, characterized in that: Temperature T1 is 60°C-90°C; temperature T2 is 120°C-160°C; time t1 is 18 hours-30 hours; time t2 is 18 hours-30 hours.

Images