CN114591159B - Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst - Google Patents

Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst Download PDF

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CN114591159B
CN114591159B CN202210231431.3A CN202210231431A CN114591159B CN 114591159 B CN114591159 B CN 114591159B CN 202210231431 A CN202210231431 A CN 202210231431A CN 114591159 B CN114591159 B CN 114591159B
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phosphine oxide
hydroformylation
oxide polymer
olefin
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李存耀
严丽
丁云杰
丁玉龙
姜淼
马雷
姬广军
钱磊磊
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a method for carrying out internal olefin hydroformylation reaction by utilizing a phosphine oxide polymer supported catalyst, wherein the catalyst takes one, two or more than two of metals Rh, co, ir, ru, pt, pd and Fe as active components, and phosphine oxide polymer as a carrier. The heterogeneous catalyst provided by the invention has good performance in the hydroformylation reaction of internal olefin, after the secondary phosphine oxide monomer in the catalyst body is coordinated with metal, a hydroxyl functional group connected with P can be formed, the acidity of the hydroxyl functional group is favorable for isomerization of the internal olefin, the proportion of normal aldehyde and isomeric aldehyde in a hydroformylation product is flexible and adjustable and can be between 0.2 and 40, and the alkane content in the product is lower than 1 percent. The phosphine oxide polymer supported catalyst provided by the patent is simple and efficient to separate from reactants and products, greatly reduces the production cost of high-carbon aldehyde, and provides a new industrialized technology for hydroformylation of internal olefins.

Description

Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst
Technical Field
The invention belongs to the field of heterogeneous catalysis and fine chemical engineering, and particularly relates to a method for carrying out internal olefin hydroformylation reaction by utilizing a phosphine oxide polymer supported catalyst.
Background
The product aldehydes from the hydroformylation of olefins are very useful intermediates, and the subsequent conversion products alcohols, acids, esters, and amines, etc. have a wide range of applications. At present, the olefin hydroformylation reaction is mainly carried out under homogeneous phase conditions in industry, and the used catalyst is mainly a homogeneous Rh and Co metal complex catalyst which is mutually soluble with a reaction system, and various problems of metal and ligand loss, complex operation and the like are faced. Today, the green chemistry concept is more and more emphasized, and the development of a green and environment-friendly heterogeneous process and a catalyst is urgently needed.
Internal olefins are relatively inexpensive and commercially available, for example, the product olefins produced by alkane dehydrogenation processes are mainly internal olefins, but the hydroformylation of internal olefins has been a difficult problem in the research field of hydroformylation, mainly because internal olefins have low activity and are difficult to convert. Currently, no heterogeneous catalyst and process specially aiming at the hydroformylation of internal olefins are available in the industry.
Secondary Phosphine Oxide (SPO) ligands are stronger electron donating ligands, SPO ligands exist in the equilibrium of pentavalent phosphine oxide and trivalent phosphorous acid. When the SPO is coordinated to the metal, it is converted to the state of trivalent phosphorous acid (formula 1).
Figure BDA0003540696360000011
Two Presence states of SPO
Phosphine oxide monomers in trivalent phosphorous acid state have hydroxyl functional groups that can function as acid functional sites (cat. Sci. Technol.2011,1,401), targeting effector groups (org. Lett.2003,5,1503), or modifiable sites (Organometallics 2010,29,5953) to generate a synergistic effect between ligand and metal.
Disclosure of Invention
In order to develop a green and environment-friendly internal olefin hydroformylation process, the invention aims to provide a method for performing internal olefin hydroformylation reaction by using a phosphine oxide polymer supported catalyst.
The technical scheme of the invention is as follows:
a method for internal olefin hydroformylation reaction by using a phosphine oxide polymer supported catalyst is characterized in that:
introducing internal olefin and synthesis gas to carry out hydroformylation reaction in the presence of a phosphine oxide polymer supported catalyst;
the phosphine oxide supported catalyst takes one or more than two of metals Rh, co, ir, ru, pt, pd and Fe as active components, and takes phosphine oxide polymer as a carrier;
the phosphine oxide polymer is formed by self-polymerization of a secondary phosphine oxide ligand containing alkylene, or is formed by copolymerization of the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene;
the structural formula of the internal olefin is as follows:
Figure BDA0003540696360000021
the internal olefin of the raw material is C4-C30 (preferably C4-C20) olefin, and the double bond can be positioned at the No. 2-15 position of the carbon chain.
The reaction process is that the prepared catalyst is loaded into a reactor, reaction raw materials and synthesis gas are introduced, the reaction temperature is 333-573K (preferably 333-473K),the reaction pressure is 0.5-12.0 MPa (preferably 0.5-7.0 MPa), and the space velocity of the gas (synthetic gas) is 100-20000 h -1 (preferably 500 to 10000 h) -1 ) The space velocity of liquid (internal olefin) is 0.01 to 10.0h -1 (preferably 0.05 to 8.0 hours) -1 ) (ii) a The main component of the reaction raw material synthesis gas is H 2 And CO, (H) 2 + CO) in a volume content of 20 to 100% (preferably 50 to 100%) H 2 The volume ratio of/CO is 0.5-5.0 (preferably 0.5-2.0), and the rest gas components are one or more than two of CO2, N2, he and Ar gas; the purity of the internal olefin raw material is 20-100% (preferably 50-100%), and the rest is C4-C30 alkane.
The loading range of the metal active component in the catalyst is 0.01-10wt%, and preferably 0.01-2wt%.
The secondary phosphine oxide ligand containing alkylene is one or more than two of the following:
Figure BDA0003540696360000022
the second component containing olefin group is selected from one or more than two of the following components:
Figure BDA0003540696360000031
Figure BDA0003540696360000041
Figure BDA0003540696360000051
the secondary phosphine oxide ligand containing an alkylene group and/or the second component alkylene group containing an alkylene group used for the polymerization are preferably vinyl functional materials.
The phosphine oxide polymer carrier has a hierarchical pore structure and a specific surface area of 10-2000m 2 A preferred range is 100 to 1000 m/g 2 Per g, pore volume of 0.1-10.0cm 3 In terms of/g, preferably from 0.2 to 2.0cm 3 A pore size distribution in the range from 0.01 to 100.0nm, preferably from 0.1 to 5.0nm,/g;
the metal loading amount of the active component in the catalyst is in the range of 0.01-10wt%, and the preferable range is 0.1-2wt%. The phosphine oxide polymer is prepared by the following steps:
after a secondary phosphine oxide ligand containing alkylene is dissolved or after the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene are dissolved and mixed, initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate a phosphine oxide polymer carrier with a hierarchical pore structure;
the preparation process of the phosphine oxide polymer supported catalyst comprises the following steps: and fully stirring and coordinating a precursor of the active metal component and the phosphine oxide polymer carrier in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the phosphine oxide polymer supported catalyst.
The specific preparation steps of the phosphine oxide supported catalyst are as follows:
a) Under the inert gas atmosphere 273-473K (preferably 298K-433K), adding a secondary phosphine oxide ligand containing alkylene or adding the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene into a solvent, then adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution, wherein the preferable stirring time range is 0.1-20 hours;
b) Transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting one or more methods of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like to obtain a phosphine oxide polymer;
c) Removing the solvent from the phosphine oxide polymer obtained in the step b) under 273-403K (preferably 298K-333K) to obtain the phosphine oxide polymer with a hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) Adding into solvent containing active metal component precursor under inert gas atmosphere 273-473K (preferably 298K-333K)Adding the phosphine oxide polymer carrier obtained in the step c), stirring for 0.1-100 hours, preferably for 0.1-20 hours, and then removing the solvent under 273-403K (preferably 298K-333K) to obtain a phosphine oxide polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.001-1mol L -1 (preferably 0.01-1mol L) -1 )。
The solvent in the steps a) and d) is one or more than two of methanol, ethanol, dichloromethane, trichloromethane, benzene, toluene, xylene, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide.
The molar ratio of secondary phosphine oxide ligand containing alkylene group and second component containing alkylene group in step a) is from 0.01 to 1, preferably from 1:1-1, the molar ratio of secondary phosphine oxide ligand containing alkylene group to free radical initiator is from 500 to 1, preferably from 100 to 1; the concentration of the secondary phosphine oxide containing an alkylene group in the solvent before polymerization to an organic polymer is in the range of 0.01 to 1000g/L, preferably 0.1 to 10g/L; the inert gases in the steps a), b) and d) are respectively selected from one or more than two of Ar, he, N2 and CO 2.
The active component is one or more than two of Rh, co, ir, ru, pt, pd or Fe, wherein the precursor of Rh is one or more than two of RhH (CO) (PPh 3) 3, rh (CO) 2 (acac), rhCl3 and Rh (CH 3 COO) 2; the precursor of Co is one or more than two of Co (CH 3 COO) 2, co (CO) 2 (acac), co (acac) 2 and CoCl 2; the precursor of Ir is one or more of Ir (CO) 3 (acac), ir (CH 3 COO) 3, ir (acac) 3 and IrCl 4; precursors of Ru are dichloro (cyclooctyl-1,5-diene) ruthenium (II), ruCl3, ru (acac) 3, dodecacarbonyl triruthenium, [ RuAr2 (bezene) ]2, [ RuAr2 (p-cymene) ]2, [ RuAr2 (mesitylene) ]2, [ (Pi-ally) Ru (cod) ]2, [ (Pi-ally) Ru (nbd) ]2; the precursor of Pt is one or more than two of Pt (acac) 2, ptCl4 and PtCl2 (NH 3) 2; the precursor of Pd is one or more than two of Pd (CH 3 COO) 2, pd (acac) 2, pdCl2, pd (PPh 3) 4 and PdCl2 (CH 3 CN) 2; the precursor of Fe is one or more than two of Fe (acac) 3, feCl2, feS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10wt%, preferably 0.1-2wt%.
The reaction principle of the invention is as follows:
secondary phosphine oxides, when coordinated to the metal, form hydroxyl functional groups attached to the P atom, which groups can serve as acidic functional sites, facilitating isomerization reactions of internal olefins, and "activating" internal olefins. The invention creatively introduces alkylene to the secondary phosphine oxide organic monomer and utilizes the polymerization reaction of the alkylene on the monomer molecule to prepare the functional polymer carrier with developed pores. P in the phosphine oxide polymer bulk phase can form a high-performance catalyst suitable for internal olefin hydroformylation reaction after being coordinated with metal, and the catalyst prepared by crosslinking vinyl phosphine oxide, divinyl benzene, vinyl monodentate phosphine ligand, vinyl polydentate phosphine ligand and the like has flexible and adjustable proportion of normal aldehyde and isomeric aldehyde in a hydroformylation product due to the unique electronic effect and stereoscopic effect of secondary phosphine oxide and the synergistic effect of hydroxyl functional sites. The active metal component can be dispersed in the phosphine oxide supported catalyst in a monatomic or ionic manner, so that the metal utilization efficiency is greatly improved. The carrier phosphine oxide polymer skeleton has higher P concentration, is easy to form double or multiple metal-P coordination bonds with the active metal component, and the coordination bonds have stronger bonding capability, so that the active component is not easy to lose, and the catalyst has long-range stability and is suitable for industrial application.
The invention has the beneficial effects that:
the heterogeneous catalyst provided by the invention has good performance in the hydroformylation reaction of internal olefin, after a secondary phosphine oxide monomer in a catalyst body is coordinated with metal, a hydroxyl functional group connected with P can be formed, the acidity of the hydroxyl functional group is favorable for isomerization of the internal olefin, the proportion of normal aldehyde and isomeric aldehyde in a hydroformylation product is flexible and adjustable and can be between 0.2 and 40, and the alkane content in the product is lower than 1 percent. The supported catalyst is suitable for reactors such as fixed beds, slurry beds, kettle reactors, trickle beds and the like. Compared with the traditional hydroformylation catalyst with triphenylphosphine as a ligand, the catalyst has higher catalytic activity; the catalyst is stable to air and moisture, and the operation conditions are not required to be harsh. The phosphine oxide polymer supported catalyst provided by the patent is simple and efficient to separate from reactants and products, greatly reduces the production cost of high-carbon aldehyde, and provides a new industrialized technology for hydroformylation of internal olefins. The method for carrying out internal olefin hydroformylation on the basis of the phosphine oxide supported catalyst is green and environment-friendly, the pollutant emission is less, the price of the internal olefin is low, and the technical scheme for producing the high-carbon aldehyde provided by the patent has obvious cost advantage.
Detailed Description
The following examples illustrate the invention better without limiting its scope.
Example 1
The specific preparation step of the monomer B: at 5 ℃, under the protection of Ar gas, 12.8g of 1-bromo-2-methyl-4-vinylbenzene (CAS number: 90560-53-5) is dissolved in 50ml of tetrahydrofuran, and the mixture is uniformly stirred for standby. 2.0g of Mg scrap is put into a flask, the temperature of the flask is raised to 65 ℃,5 ml of mixed solution of 1-bromo-2-methyl-4-vinyl benzene and tetrahydrofuran is dripped, after the Grignard reagent is initiated (the color of the reaction solution is changed into dark green, and the reaction solution is vigorously boiled), the rest mixed solution is continuously dripped, and the dripping temperature is maintained at 60 ℃. After the dropwise addition, the temperature is kept for 1 hour to obtain a Grignard reagent solution. Then, the temperature is reduced to 0 ℃, a mixed solution of 4.5 g of diethyl phosphite and 50ml of 2-methyltetrahydrofuran is added, and the reaction is continued for 1 hour after the dropwise addition is finished. Adding 10ml of saturated ammonium chloride solution for annihilation reaction, separating the mixed solution into two layers, taking out the upper oil layer, distilling at 65 ℃ to remove the solvent to obtain light yellow oily liquid, adding 10ml of n-heptane to heat the mixed solvent to 65 ℃ for full dissolution, then cooling to 0 ℃ for recrystallization and drying to obtain 3.91 g of distyrylphosphine oxide (secondary phosphine oxide ligand B) (the yield is about 43%, and the product is confirmed by nuclear magnetic and high resolution mass spectrometry).
Preparation of porous organic polymers of distyrylphosphine oxide: 5.0g of distyrylphosphine oxide monomer B and 50.0g of a second component divinylbenzene (ligand L1, CAS number: 1321-74-0) were dissolved in 550.0 ml of tetrahydrofuran solvent at 25 ℃ under the protection of inert gas Ar, 0.01g of azobisisobutyronitrile, a radical initiator, was added to the above solution, and stirred for 2 hours to obtain a prepolymer. And transferring the prepolymer into an autoclave, and polymerizing for 24 hours by a bulk polymerization method under the protection of 363K and inert gas argon. When the polymerization kettle is cooled to 25 ℃, the solvent is removed in vacuum at room temperature, and the polymer CPOL-1SPO10DVB copolymerized by the distyrylphosphine oxide and the divinylbenzene is obtained with the yield of 100%. The adsorption curve of the CPOL-1SPO10DVB in a hierarchical pore structure can be seen from the nitrogen physical adsorption curve and the pore diameter distribution diagram of the CPOL-1SPO10DVB, the specific surface area is 905m < 2 >/g, and the pore diameter is mainly distributed at 0.4-5nm through calculation.
Preparation of highly dispersed Rh metal catalyst: weighing 7.8mg of acetylacetonatocarbonylrhodium (CAS No. 14874-82-9) and dissolving in 10.0 ml of tetrahydrofuran solvent, adding 1.0g of the prepared CPOL-1SPO10DVB polymer, stirring at 25 ℃ for 5 hours, continuing stirring for 5 hours under the protection of 298K, ar gas, and vacuumizing under 318K to remove the solvent, thus obtaining the phosphine oxide polymer self-supported high-dispersion rhodium-based catalyst Rh/CPOL-1SPO10DVB, actually measuring the loading of rhodium to be 0.29%, and observing the metal rhodium in a monodispersed state by a high-resolution transmission electron microscope. The thermogravimetric curve of the Rh/CPOL-1SPO10DVB catalyst shows that the catalyst is stable and basically has no weight loss before 440 ℃ under the nitrogen atmosphere, and the weight loss peak of decomposition occurs before 440 ℃.
Example 2
In example 2, the synthesis process and conditions were the same as in example 1 except that 50.0g of the second component divinylbenzene was not added.
Example 3
In example 3, the synthesis procedure and conditions were the same as in example 1 except that 50.0g of a second component, tristyrylbenzene (ligand L3 in claim 3) was used in place of divinylbenzene (ligand L1).
Example 4
In example 4, the procedure and catalyst synthesis conditions were the same as in example 1 except that the same molar amount of dibenzoyl peroxide was used instead of azobisisobutyronitrile as the radical initiator.
Example 5
In example 5, a highly dispersed Co-based catalyst was obtained by following the same synthesis procedure and conditions as in example 1, except that the same molar amount of cobalt dichloride was used instead of rhodium acetylacetonate carbonyl.
Example 6
In example 6, the highly dispersed Ir-based catalyst was obtained by following the same synthesis procedure and conditions as in example 1, except that the same molar amount of iridium acetylacetonate dicarbonyl was used instead of rhodium acetylacetonate carbonyls.
Example 7
In example 7, the synthesis procedure and conditions were the same as in example 1 except that rhodium acetylacetonate carbonyl was replaced with the same number of moles of ruthenium chloride.
Example 8
In example 8, the synthesis procedure and conditions were the same as in example 1 except that the same molar amount of nonacarbonyl diiron was used instead of rhodium acetylacetonate carbonyl.
Example 9
In example 9, a comparative catalyst Rh/CPOL-10DVB1PPh3 was obtained using the same synthesis procedure and conditions as in example 1 except that the same molar amount of tris (4-vinylphenyl) phosphine was used in place of the distyrylphosphine oxide monomer B.
Example 10
In example 10, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligand C was used in place of the distyrylphosphine oxide monomer B.
Example 11
In example 11, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand E was used in place of distyrylphosphine oxide monomer B.
Example 12
In example 12, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligand G was used in place of the distyrylphosphine oxide monomer B.
Example 13
In example 13, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligand I was used in place of the distyrylphosphine oxide monomer B.
Example 14
In example 14, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligand J was used in place of the distyrylphosphine oxide monomer B.
Example 15
In example 15, the synthesis procedure and conditions were the same as in example 1 except that the same number of moles of ligand K was used in place of distyrylphosphine oxide monomer B.
Example 16
In example 16, the synthesis procedure and conditions were the same as in example 1 except that the same molar number of ligands L was used in place of the distyrylphosphine oxide monomer B.
Example 17
In example 17, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component, vinyl monodentate phosphine ligand L25.
Example 18
In example 18, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component, vinylmonodentate phosphine ligand L27.
Example 19
In example 19, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component vinylmonodentate phosphine ligand L37.
Example 20
In example 20, the synthesis procedure and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component vinylbidentate phosphine ligand L7.
Example 21
In example 21, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component vinylbidentate phosphine ligand L11.
Example 22
In example 22, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component vinylbidentate phosphine ligand L18.
Example 23
In example 23, the synthesis procedures and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced with the same number of moles of the second component vinylbidentate phosphine ligand L24.
Example 24
0.5g of the prepared catalyst was placed in a fixed bed reactor, and quartz sand was charged into both ends. The micro-feed pump maintains the flow of 2-hexene at 0.8ml/min, and the mass flowmeter controls the synthesis gas (H) 2 CO =1 -1 The hydroformylation reaction was carried out under the conditions of 373K and 1MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as an internal standard. The off-gas from the collection tank was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
TABLE 1 data on specific surface area, pore size distribution and hydroformylation of 2-hexene for the catalysts synthesized in examples 1 to 24
Figure BDA0003540696360000101
Figure BDA0003540696360000111
Example 9 prepared was a triphenylphosphine complex Rh catalyst (comparative example) and example 1 prepared was a phosphine oxide complex Rh catalyst, and from the reaction data for 2-hexene hydroformylation, it can be seen that the phosphine oxide complex Rh catalyst is more active in hydroformylation and has a low ratio of normal aldehyde to iso-aldehyde. In examples 5, 6, 7 and 8, the active metal components were Co, ir, ru and Fe, respectively, and the reactivity was lower than that of the catalyst in which the active metal was Rh. When the active center is Rh, the data in the table show that the 2-hexene hydroformylation activity of the Rh catalyst coordinated with phosphine oxide is higher than that of the Rh catalyst coordinated with triphenylphosphine, and the selectivity of aldehyde is better. The proportion of normal aldehyde and isomeric aldehyde in the hydroformylation catalyst product formed by the copolymerization of phosphine oxide ligand, cross-linking agent, monophosphine ligand and multidentate ligand is flexible and adjustable. The proportion of normal aldehyde and isomeric aldehyde in the catalyst prepared by copolymerization with the cross-linking agent is basically below 1 or 1-2, the normal-to-iso ratio of the final catalyst prepared by copolymerization of different phosphine oxide monomers and divinyl benzene is slightly different, when the periphery of P contains large steric hindrance groups, the normal-to-iso ratio of aldehyde can be between 1 and 2, the normal-to-iso ratio of the catalyst prepared by phosphine oxide monomer R in example 14 is the highest and can reach 1.63, and the normal-to-iso ratio of the catalyst prepared by phosphine oxide monomer R in example 3 is the lowest and is 0.66. The catalyst prepared by copolymerization of phosphine oxide with vinyl monophosphine ligand has aldehyde positive-to-positive ratio of 2-10 (examples 17-19). The catalyst prepared by copolymerization of phosphine oxide with vinyl bidentate ligand had an aldehyde number of essentially 10 or more (examples 20-23).
Example 25
0.5g of the catalyst prepared in example 20 was charged into a 50 ml-capacity slurry bed reactor, 30ml of valeraldehyde was added as a slurry, and a reaction mixture gas (H) was introduced 2 CO = 1:1) and 3-octene at 393K,1.0MPa, reaction mixture space velocity of 2000h -1 3-octene liquid hourly speed 8h -1 The hydroformylation was carried out at a stirring rate of 750 revolutions per minute.
3-octene TOF value of 401.5h -1 The aldehyde selectivity was 96.6%, and the aldehyde normal to iso ratio was 23.10.
Example 26
0.5g of the catalyst prepared in example 16 was charged in a 50 ml-capacity slurry bed reactor, 30ml of valeraldehyde was added as a slurry, and a reaction mixture gas (H) was introduced 2 CO = 1:1) and 3-octene at 393K,1.0MPa, reaction mixture space velocity of 2000h -1 The hydroformylation reaction is carried out under the conditions that the speed of 3-octene liquid per hour is 8h < -1 > and the stirring speed is 750 r/min.
3-octene TOF value of 794.2h -1 Aldehyde selectivity 95.8%, aldehydeThe positive to negative ratio is 1.28.
Example 27
0.5g of the catalyst prepared in example 23 was charged into a fixed bed reactor, and both ends were charged with quartz sand. The micro-feed pump maintains the flow of the internal olefin at 0.8ml/min, and the mass flow meter controls the synthesis gas (H) 2 CO = 1:1) airspeed 1000h -1 The hydroformylation reaction was carried out at 373K and 1MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as an internal standard. The off-gas from the collection tank was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 2.
TABLE 2 hydroformylation results of different substrates over the catalyst of example 23
Figure BDA0003540696360000121
As can be seen from the table, the catalyst prepared by copolymerizing the vinylphosphine oxide ligand prepared in example 23 with the vinylbidentate phosphine ligand L24 has good applicability to different olefin substrates, the highest activity is towards the terminal olefin, and the lower the activity is towards the middle of the molecular chain.
Example 28
5g of each of the catalysts prepared in the example 1 and the example 9 are respectively put into a quartz tube and treated for 5 hours at 80 ℃, the air pressure of 1.1bar and the space velocity of 1000h-1 to obtain the treated catalysts. 0.5g of the treated catalyst was placed in a fixed bed reactor, and quartz sand was charged into both ends. The micro-feed pump maintains the flow of 2-hexene at 0.8ml/min, and the mass flowmeter controls the synthesis gas (H) 2 CO = 1:1) airspeed 1000h -1 The hydroformylation reaction was carried out under the conditions of 373K and 1MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as an internal standard. The tail gas from the collection tank is subjected to on-line gas chromatography by HP-7890N gas chromatography provided with Porapak-QS column and TCD detectorAnd (6) analyzing. The reaction results are shown in Table 3.
TABLE 3 specific surface area of catalyst and 2-hexene reaction data after air treatment in examples 1 and 9
Figure BDA0003540696360000131
Example 9 prepared is a triphenylphosphine complex Rh catalyst (comparative example), example 1 prepared is a phosphine oxide complex Rh catalyst, and after air treatment, the 2-hexene hydroformylation performance of example 9 significantly decreased (compare with data in table 1), probably due to the ease of oxidative instability in triphenylphosphine air, while the hydroformylation performance of example 1 catalyst treated did not significantly change, which indicates that the phosphine oxide catalyst is stable to air and moisture, the catalyst stability is better, the operating conditions do not need to be too harsh, and the industrial production is more facilitated.
Comparative example 1
In comparative example 1, the synthesis was the same as in example 1 except that divinylbenzene (ligand L1) was replaced with 4-vinylphenol (CAS number: 2628-17-3), which is a crosslinking agent, in the same molar amount.
Comparative example 2
In comparative example 2, except that the same molar amount of vinyl monodentate phosphine ligand was used
Figure BDA0003540696360000132
The rest of the synthesis procedure and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced.
Comparative example 3
In comparative example 3, except that the same number of moles of vinyl monodentate phosphine ligand was used
Figure BDA0003540696360000141
The rest of the synthesis procedure and conditions were the same as in example 1 except that divinylbenzene (ligand L1) was replaced.
Comparative example 4
In comparative example 4, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000142
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
Comparative example 5
In comparative example 5, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000143
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
Comparative example 6
In comparative example 6, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000144
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
Comparative example 7
In comparative example 7, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000151
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
Comparative example 8
In comparative example 8, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000152
The synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
Comparative example 9
In comparative example 9, except that the same molar number of vinyl secondary phosphine oxide monomers were used
Figure BDA0003540696360000153
The rest of the synthesis procedure was the same as in example 1 except that the distyrylphosphine oxide monomer B was replaced.
0.5g of the catalyst prepared in the comparative example was placed in a fixed bed reactor, and quartz sand was charged into both ends. The micro-feed pump maintains the flow of 2-hexene at 0.8ml/min, and the mass flowmeter controls the synthesis gas (H) 2 CO = 1:1) airspeed 1000h -1 The hydroformylation reaction was carried out at 373K and 1MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as an internal standard. The off-gas from the collection tank was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 4.
TABLE 4 specific surface area of catalyst synthesized in comparative examples 1-3 and data on 2-hexene reaction
Figure BDA0003540696360000154
Figure BDA0003540696360000161
As can be seen from the table, when the second component was 4-vinylphenol in the polymerization, the TOF of 2-hexene was only 123.1h-1, which is significantly lower than the data for the second component, divinylbenzene, although the catalyst prepared also had a specific surface area of 463m2/g (example 1). Whereas, when only one vinyl group is present and the position of the ortho position of triphenylphosphine is present, the specific surface area of the catalyst prepared after copolymerization with the secondary phosphine oxide A monomer is only 185m2/g, and the activity of 2-hexene is not satisfactory (comparative example 2). The hydroformylation performance of 2-hexene in the prepared catalyst is also significantly affected when the triphenylphosphine has a bulky steric hindrance group in the ortho position (comparative example 3). And when the secondary phosphine oxide monomer has the structure in comparative examples 4 to 9, the normal aldehyde in the product aldehyde is as follows: the isomeric aldehyde ratios are all greater than 1, but since internal olefin hydroformylation has a specific selectivity for ligand structure, the TOF values of 2-hexene are all lower compared to example 1, and thus the catalysts prepared from the secondary phosphine oxide ligands of comparative examples 4-9 are not suitable for the hydroformylation of internal olefins.

Claims (13)

1. A method for internal olefin hydroformylation reaction by using a phosphine oxide polymer supported catalyst is characterized in that:
introducing internal olefin and synthesis gas to carry out hydroformylation reaction in the presence of a phosphine oxide polymer supported catalyst;
the phosphine oxide polymer supported catalyst takes one or more than two of metals Rh, co, ir, ru, pt, pd and Fe as active components, and takes phosphine oxide polymer as a carrier;
the phosphine oxide polymer is formed by self-polymerization of secondary phosphine oxide ligand containing alkylene, or is formed by copolymerization of secondary phosphine oxide ligand containing alkylene and second component containing alkylene;
the structural formula of the internal olefin is as follows:
Figure QLYQS_1
，
the internal olefin of the raw material is C4-C30 olefin, and the double bond can be positioned at No. 2-15 positions of a carbon chain;
the secondary phosphine oxide ligand containing alkylene is one or more than two of the following:
Figure QLYQS_2
；
the second component containing olefin group is selected from one or more than two of the following components:
Figure QLYQS_3
Figure QLYQS_4
Figure QLYQS_5
Figure QLYQS_6
。/>
2. a process for the hydroformylation of internal olefins according to claim 1, wherein:
the reaction process is that the prepared catalyst is loaded into a reactor, reaction raw materials and synthesis gas are introduced, the reaction temperature is 333 to 573K, the reaction pressure is 0.5 to 12.0MPa, and the space velocity of the synthesis gas is 100 to 20000h -1 The hourly space velocity of the internal olefin liquid is 0.01 to 10.0h -1 (ii) a The main component of the reaction raw material synthesis gas is H 2 And CO, (H) 2 + CO) volume content of 20 to 100 percent, H 2 The volume ratio of the gas to the CO is 0.5 to 5.0, and the rest gas component is CO 2 、N 2 One or more than two of He and Ar gas; the purity of the internal olefin raw material is 20 to 100 percent, and the rest substances are C 4 -C 30 Of (a) an alkane.
3. A process for the hydroformylation of internal olefins as claimed in claim 1 or 2, wherein:
the reaction temperature is 333 to 473K, the reaction pressure is 0.5 to 7.0MPa, and the space velocity of the synthesis gas is 500 to 10000h -1 The hourly space velocity of the internal olefin liquid is 0.05 to 8.0h -1 (ii) a The main component of the reaction raw material synthesis gas is H 2 And CO, (H) 2 + CO) volume content of 50 to 100%, H 2 The volume ratio of the gas to the CO is 0.5 to 2.0, and the rest gas component is CO 2 、N 2 One or more than two of He and Ar gas; the internal olefin is C4-C20 olefin, the purity of the internal olefin is 50-100%, and the rest is C 4 -C 30 Of an alkane.
4. A process for the hydroformylation of internal olefins according to claim 1, wherein: the loading range of the metal active component in the catalyst is 0.01-10wt%.
5. An internal olefin hydroformylation reaction process according to claim 1, wherein:
the second phosphine oxide ligand containing olefin group and/or the substance of which the olefin group as the second component is a vinyl functional group are used for polymerization.
6. A process for the hydroformylation of internal olefins as claimed in claim 1, wherein: the phosphine oxide polymer carrier has a hierarchical pore structure and a specific surface area of 10-2000m 2 Per g, pore volume of 0.1-10.0cm 3 The pore size distribution is 0.01-100.0nm;
the metal loading range of the active component in the catalyst is 0.1-2wt%.
7. A process for the hydroformylation of internal olefins as claimed in claim 1, wherein:
the loading range of the metal active component in the catalyst is 0.01-2wt%;
the phosphine oxide polymer carrier has a hierarchical pore structure and a specific surface area of 100-1000m 2 Per g, pore volume of 0.2-2.0cm 3 (ii)/g, pore size distribution of 0.1-5.0nm.
8. A process for the hydroformylation of internal olefins according to claim 1, wherein:
the phosphine oxide polymer is prepared by the following steps:
after a secondary phosphine oxide ligand containing alkylene is dissolved or after the secondary phosphine oxide ligand containing alkylene and a second component containing alkylene are dissolved and mixed, initiating the alkylene in the organic phosphine ligand to carry out polymerization reaction by a free radical initiator to generate a phosphine oxide polymer carrier with a hierarchical pore structure;
the preparation process of the phosphine oxide polymer supported catalyst comprises the following steps: and fully stirring and coordinating a precursor of the active metal component and the phosphine oxide polymer carrier in a solvent, forming a firm chemical bond between the active metal component and the exposed P in the phosphine oxide polymer carrier, and evaporating the solvent to obtain the phosphine oxide polymer supported catalyst.
9. A process for the hydroformylation of internal olefins as claimed in claim 1, wherein:
the specific preparation steps of the phosphine oxide supported catalyst are as follows:
a) Under the inert gas atmosphere of 273-473K, adding a secondary phosphine oxide ligand containing alkylene into a solvent, or adding a secondary phosphine oxide ligand containing alkylene and a second component containing alkylene into the solvent, adding a free radical initiator, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution;
b) Transferring the prepolymer mixed solution prepared in the step a) into a polymerization reactor, and carrying out polymerization reaction for 1-100 hours by adopting one or more of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization methods to obtain a phosphine oxide polymer;
c) Removing the solvent from the phosphine oxide polymer obtained in the step b) at 273-403K to obtain the phosphine oxide polymer with a hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) Under the inert gas atmosphere of 273-473K, adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor, stirring for 0.1-100 hours, and then removing the solvent under 273-403K to obtain a phosphine oxide polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.001-1mol L -1 。
10. A process for the hydroformylation of internal olefins according to claim 9, wherein: the solvent in the steps a) and d) is one or more than two of methanol, ethanol, dichloromethane, trichloromethane, benzene, toluene, xylene, water or tetrahydrofuran;
the free radical initiator in the step a) is one or more than two of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide or dibenzoyl peroxide.
11. A process for the hydroformylation of internal olefins according to claim 9, wherein: the molar ratio of the secondary phosphine oxide ligand containing an olefin group and the second component containing an olefin group in step a) is from 0.01 to 100, the molar ratio of the secondary phosphine oxide ligand containing an olefin group to the radical initiator is from 500 to 1; before the polymerization into the organic polymer, the concentration range of the secondary phosphine oxide containing alkylene in the solvent is 0.01-1000g/L; the inert gas in steps a), b) and d) is selected from Ar, he, N 2 And CO 2 One or more than two of them.
12. A process for the hydroformylation of internal olefins according to claim 9, wherein: the active component is one or more than two of Rh, co, ir, ru, pt, pd or Fe, wherein the precursor of Rh is RhH (CO) (PPh) 3 ) 3 、Rh(CO) 2 (acac)、RhCl3、Rh(CH3COO) 2 One or more than two of the above; the precursor of Co is Co (CH) 3 COO) 2 、Co(CO) 2 (acac)、Co (acac) 2 、CoCl 2 One or more than two of the above; ir precursor is Ir (CO) 3 (acac)、Ir(CH3COO) 3 、Ir(acac) 3 、IrCl 4 One or more than two of (a); the precursor of Ru is dichloro (cyclooctyl-1,5-diene) ruthenium (II) and RuCl 3 、Ru(acac) 3 Dodecacarbonyltriruthenium, [ RuAr ] 2 (benzene)] 2 、[RuAr 2 (p-cymene)] 2 , [RuAr 2 (mesitylene)] 2 、[(π-ally)Ru(cod)] 2 、[(π-ally)Ru(nbd)] 2 One or more than two of the above; the precursor of Pt is Pt (acac) 2 、PtCl 4 、PtCl 2 (NH 3 ) 2 One or more than two of the above; the precursor of Pd is Pd (CH) 3 COO) 2 、Pd(acac) 2 、PdCl 2 、Pd(PPh 3 ) 4 、PdCl 2 (CH 3 CN) 2 One or more than two of (a); precursor of FeIs Fe (acac) 3 、FeCl 3 、FeCl 2 One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10wt%.
13. A process for the hydroformylation of internal olefins according to claim 9, wherein:
in the step a), the atmosphere of inert gas is 298K-433K, and the stirring time of the mixture is 0.1-20 hours;
the molar ratio of the secondary phosphine oxide ligand containing olefin groups to the second component containing olefin groups is 1:1-1, and the molar ratio of the secondary phosphine oxide ligand containing olefin groups to the free radical initiator is 100; before the polymerization into the organic polymer, the concentration of the secondary phosphine oxide containing olefin groups in the solvent is in the range of 0.1-10g/L;
the temperature of the solvent removal in the step c) is 298K-333K;
adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor under the inert gas atmosphere of 298K-333K in the step d), stirring for 0.1-20 hours, and then removing the solvent under 298K-333K to obtain a phosphine oxide polymer supported catalyst; the concentration of the active metal in the precursor solution is in the range of 0.01-1mol L -1 。
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CN106140303B (en) * 2015-04-03 2018-11-27 中国科学院大连化学物理研究所 One kind is containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation and application
CN107793304B (en) * 2016-09-07 2021-03-16 中国科学院大连化学物理研究所 Method for preparing aldehyde by olefin with high selectivity
CN107790188B (en) * 2016-09-07 2020-09-04 中国科学院大连化学物理研究所 Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof
CN108069842B (en) * 2016-11-15 2021-06-08 中国科学院大连化学物理研究所 Method for synthesizing valeraldehyde by hydroformylation of butene
CN109806911B (en) * 2017-11-21 2022-01-21 中国科学院大连化学物理研究所 Catalyst for preparing straight-chain aldehyde with high selectivity and preparation and application thereof
CN109836318B (en) * 2017-11-27 2022-09-30 中国科学院大连化学物理研究所 Method for preparing aldehyde through olefin hydroformylation reaction
CN113713862B (en) * 2020-05-26 2023-04-11 中国科学院大连化学物理研究所 Co-based multi-phase catalyst for olefin hydroformylation reaction, preparation and application thereof

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