CN114591159A - 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

Info

Publication number
CN114591159A
CN114591159A CN202210231431.3A CN202210231431A CN114591159A CN 114591159 A CN114591159 A CN 114591159A CN 202210231431 A CN202210231431 A CN 202210231431A CN 114591159 A CN114591159 A CN 114591159A
Authority
CN
China
Prior art keywords
phosphine oxide
oxide polymer
hydroformylation
catalyst
alkylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210231431.3A
Other languages
Chinese (zh)
Other versions
CN114591159B (en
Inventor
李存耀
严丽
丁云杰
丁玉龙
姜淼
马雷
姬广军
钱磊磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202210231431.3A priority Critical patent/CN114591159B/en
Publication of CN114591159A publication Critical patent/CN114591159A/en
Application granted granted Critical
Publication of CN114591159B publication Critical patent/CN114591159B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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, olefin hydroformylation reaction is mainly carried out under homogeneous phase condition 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 cheap olefins in industry and are also relatively available in industry, for example, the product olefins produced by the alkane dehydrogenation process are mainly internal olefins, but the hydroformylation of the internal olefins is always a difficult point in the research field of hydroformylation, and is mainly due to the low activity and poor conversion of the internal olefins. At present, no heterogeneous catalyst and process specially aiming at the hydroformylation reaction of the internal olefin exist in the industry.
Secondary Phosphine Oxide (SPO) ligands are stronger electron donating ligands, and the SPO ligands have the balance 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 the trivalent phosphorous acid state present hydroxyl functional groups that can function as acid functional sites (cat al. sci. technol.2011,1,401), site-directed effector groups (org. lett.2003,5,1503), or modifiable sites (Organometallics 2010,29,5953), which in turn lead to a synergistic effect between the ligand and the 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 utilizing 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 secondary phosphine oxide ligand containing alkylene or copolymerization of secondary phosphine oxide ligand containing alkylene and 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), and the double bond can be positioned at the No. 2-15 position of the carbon chain.
The reaction process comprises the steps of loading the prepared catalyst into a reactor, introducing reaction raw materials and synthesis gas, wherein 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 (synthesis 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 H2And CO, (H)2+ CO) in a volume content of 20-100% (preferably 50-100%), H2The 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 0.01-10 wt%, and preferably 0.01-2 wt%.
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 10-2000m2A preferred range is 100-2Per g, pore volume of 0.1-10.0cm3In g, preferably 0.2 to 2.0cm3(ii)/g, pore size distribution is 0.01-100.0nm, preferably 0.1-5.0 nm;
the metal loading amount of the active component in the catalyst is in the range of 0.01-10 wt%, and the preferable range is 0.1-2 wt%. 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 an alkylene group into a solvent, or adding a secondary phosphine oxide ligand containing an alkylene group and a second component containing an alkylene group into the 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 the hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere 273-473K (preferably 298K-333K), stirring for 0.1-100 hours, preferably within a stirring time range of 0.1-20 hours, and then removing the solvent under 273-403K (preferably 298K-333K) to obtain the 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 alkylene-containing phosphine oxide ligand to second alkylene-containing component in step a) is 0.01:1 to 100:1, preferably 1:1 to 1:10, and the molar ratio of secondary alkylene-containing phosphine oxide ligand to free radical initiator is 500:1 to 10:1, preferably 100:1 to 10: 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 10 g/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) (PPh3)3, Rh (CO)2(acac), RhCl3 and Rh (CH3COO) 2; the precursor of Co is one or more than two of Co (CH3COO)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 (CH3COO)3, Ir (acac)3 and IrCl 4; precursors of Ru are dichloro (cyclooctyl-1, 5-diene) ruthenium (II), RuCl3, Ru (acac)3, dodecacarbonyltriruthenium, [ 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(NH3) 2; the precursor of Pd is one or more than two of Pd (CH3COO)2, Pd (acac)2, PdCl2, Pd (PPh3)4 and PdCl2(CH3CN) 2; the precursor of Fe is one or more than two of Fe (acac)3, FeCl3, FeCl2, FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-2 wt%.
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 monoatomic 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 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 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 stirred uniformly 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 ℃. And preserving the temperature for 1 hour after the dropwise addition is finished to obtain the 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%. From the nitrogen physical adsorption curve and the pore size distribution diagram of the CPOL-1SPO10DVB, the adsorption curve of the CPOL-1SPO10DVB with a hierarchical pore structure is shown, and the specific surface area is calculated to be 905m2/g, and the pore size is mainly distributed in the range of 0.4-5 nm.
Preparation of highly dispersed Rh metal catalyst: weighing 7.8mg of acetylacetonatocarbonylrhodium (CAS number 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 removing the solvent under vacuum at 318K to obtain the phosphine oxide polymer self-supported high-dispersion rhodium-based catalyst Rh/CPOL-1SPO10DVB, wherein the loading of rhodium is actually measured to be 0.29%, and the metal rhodium is observed to be in a monodisperse 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 the 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, a highly dispersed Ir-based catalyst was obtained in the same manner 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 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
The synthesis procedure and conditions were the same as in example 1 except that tris (4-vinylphenyl) phosphine was used in the same molar amount in place of distyrylphosphine oxide monomer B in example 9, to give a comparative catalyst of Rh/CPOL-10DVB1PPh 3.
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 molar number of ligands E was used in place of the 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 molar number of ligand K was used in place of the 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 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, vinyl monodentate phosphine ligand L27.
Example 19
In example 19, 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, vinyl monodentate 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 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 L11.
Example 22
In example 22, 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 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)2CO is 1:1, V/V) space velocity of 1000h-1The hydroformylation is carried out under the condition of 373K and 1 MPa. The reaction was collected via an ice-cooled collection tank. The obtained liquid product was analyzed by HP-7890N gas chromatography using HP-5 capillary column and FID detector, using N-propanol as the solventAn 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 of the catalyst prepared by copolymerization with the cross-linking agent is basically less than 1 or 1-2, the normal-to-iso ratio of the catalyst prepared by copolymerization of different phosphine oxide monomers and divinylbenzene is slightly different, when P contains large steric hindrance groups around P, 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 introduced2CO 1:1) and 3-octene at 393K, 1.0MPa with a reaction mixture air speed of 2000h-13-octene liquid hourly speed 8h-1The hydroformylation was carried out at a stirring rate of 750 revolutions per minute.
The TOF value of 3-octene is 401.5h-1The aldehyde selectivity was 96.6%, and the aldehyde normal ratio was 23.10.
Example 26
0.5g of the catalyst prepared in example 16 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 introduced2CO 1:1) and 3-octene at 393K, 1.0MPa with a reaction mixture air speed of 2000h-1The 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.
The TOF value of 3-octene is 794.2h-1The aldehyde selectivity was 95.8%, and the aldehyde normal to iso ratio was 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 flowmeter controls the synthesis gas (H)2CO is 1:1) space velocity of 1000h-1The hydroformylation is carried out under the condition of 373K and 1 MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as 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 for the terminal olefin, and the lower the activity is the closer the olefin is to 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)2CO is 1:1) space velocity of 1000h-1The hydroformylation is carried out under the condition of 373K and 1 MPa. The reaction was collected via an ice-bath cooled collection tank. The liquid product obtained was analysed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using N-propanol as 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 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 molar amount 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
In place of the distyrylphosphine oxide monomer B, the remainderThe synthesis procedure of (2) was the same as in example 1.
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 rest of 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 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 charged into a fixed bed reactor, and both ends were charged with quartz sand. The micro-feed pump maintains the flow of 2-hexene at 0.8ml/min, and the mass flowmeter controls the synthesis gas (H)2CO is 1:1) space velocity of 1000h-1The hydroformylation is carried out under the condition of 373K and 1 MPa. 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, significantly lower than that of divinylbenzene as the second component (example 1), although the catalyst prepared also had a 463m2/g specific surface area. While the specific surface area of the catalyst prepared after copolymerization with the secondary phosphine oxide A monomer was 185m2/g only with only one vinyl group and ortho to the triphenylphosphine, the activity of 2-hexene was also 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 (10)

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 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 copolymerization of secondary phosphine oxide ligand containing alkylene and second component containing alkylene;
the structural formula of the internal olefin is as follows:
Figure FDA0003540696350000011
the internal olefin of the raw material is C4-C30 (preferably C4-C20), and the double bond can be positioned at the No. 2-15 position of the carbon chain.
2. A process for the hydroformylation of internal olefins as claimed in claim 1, wherein:
the reaction process comprises the steps of loading the prepared catalyst into a reactor, introducing reaction raw materials and synthesis gas, wherein 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 (synthesis 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 H2And CO, (H)2+ CO) in a volume content of 20-100% (preferably 50-100%), H2The volume ratio of/CO is 0.5-5.0 (preferably 0.5-2.0), and the rest gas component is CO2、N2One or more than two of He and Ar gas; the purity of the internal olefin raw material is 20-100% (preferably 50-100%), and the rest is C4-C30Of an alkane.
3. 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 0.01-10 wt%, and preferably 0.01-2 wt%. The secondary phosphine oxide ligand containing alkylene is one or more than two of the following:
Figure FDA0003540696350000021
the second component containing olefin group is selected from one or more than two of the following components:
Figure FDA0003540696350000022
Figure FDA0003540696350000031
Figure FDA0003540696350000041
Figure FDA0003540696350000051
4. a method according to claim 3, characterized by:
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.
5. 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 10-2000m2A preferred range is 100-1000m2Per g, pore volume of 0.1-10.0cm3In g, preferably 0.2 to 2.0cm3(ii)/g, pore size distribution is 0.01-100.0nm, preferably 0.1-5.0 nm;
the metal loading amount of the active component in the catalyst is in the range of 0.01-10 wt%, and the preferable range is 0.1-2 wt%.
6. A process for the hydroformylation of internal olefins as claimed in 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.
7. 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 273-473K (preferably 298K-433K), adding a secondary phosphine oxide ligand containing an alkylene group into a solvent, or adding a secondary phosphine oxide ligand containing an alkylene group and a second component containing an alkylene group into the 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 the hierarchical pore structure, namely the carrier of the phosphine oxide polymer supported catalyst;
d) adding the phosphine oxide polymer carrier obtained in the step c) into a solvent containing an active metal component precursor under an inert gas atmosphere 273-473K (preferably 298K-333K), stirring for 0.1-100 hours, preferably within a stirring time range of 0.1-20 hours, and then removing the solvent under 273-403K (preferably 298K-333K) to obtain the 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)。
8. A process for the hydroformylation of internal olefins as claimed in claim 7, 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.
9. A process for the hydroformylation of internal olefins as claimed in claim 7, wherein: the molar ratio of the secondary alkylene-containing phosphine oxide ligand to the second alkylene-containing component of step a) is from 0.01:1 to 100:1, preferably from 1:1 to 1:10, and the molar ratio of the secondary alkylene-containing phosphine oxide ligand to the radical initiator is from 500:1 to 10:1, preferably from 100:1 to 10: 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 10 g/L; the inert gas in steps a), b) and d) is selected from Ar, He and N2And CO2One or more than two of them.
10. A process for the hydroformylation of internal olefins as claimed in claim 7, 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)2One or more than two of the above; the precursor of Co is Co (CH)3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2One or more than two of the above; the precursor of Ir is Ir (CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4One or more than two of the above; the precursor of Ru is dichloro (cyclooctyl-1, 5-diene) ruthenium (II) and RuCl3、Ru(acac)3Dodecacarbonyl groupTri-ruthenium, [ RuAr ]2(benzene)]2、[RuAr2(p-cymene)]2,[RuAr2(mesitylene)]2、[(π-ally)Ru(cod)]2、[(π-ally)Ru(nbd)]2One or more than two of the above; the precursor of Pt is Pt (acac)2、PtCl4、PtCl2(NH3)2One or more than two of the above; the precursor of Pd is Pd (CH)3COO)2、Pd(acac)2、PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2One or more than two of the above; the precursor of Fe is Fe (acac)3、FeCl3、FeCl2One or more than two of FeS, ferrocene and nonacarbonyl diiron, and the metal loading range in the catalyst is 0.01-10 wt%, preferably 0.1-2 wt%.
CN202210231431.3A 2022-03-10 2022-03-10 Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst Active CN114591159B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210231431.3A CN114591159B (en) 2022-03-10 2022-03-10 Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210231431.3A CN114591159B (en) 2022-03-10 2022-03-10 Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst

Publications (2)

Publication Number Publication Date
CN114591159A true CN114591159A (en) 2022-06-07
CN114591159B CN114591159B (en) 2023-04-07

Family

ID=81808895

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210231431.3A Active CN114591159B (en) 2022-03-10 2022-03-10 Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst

Country Status (1)

Country Link
CN (1) CN114591159B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115041232A (en) * 2022-06-19 2022-09-13 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application in preparation of aldehyde from mixed olefin

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2922757A1 (en) * 1978-06-05 1979-12-06 Kuraray Co PROCESS FOR THE HYDROFORMYLATION OF OLEFINIC COMPOUNDS
CN1174197A (en) * 1996-08-13 1998-02-25 赫彻斯特股份公司 Method for separating phosphine oxide and alkylaryl phosphine from homogeneous hydrogen formylation reaction mixture
CN106140302A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 A kind of containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and methods and applications thereof
CN106140303A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 One contains the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and application
CN106140301A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 Containing organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation method and application
CN107790188A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application
CN107793304A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of method that alkene high selectivity prepares aldehyde
CN108069842A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 A kind of method of butene hydroformylation synthesis valeral
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
CN109836318A (en) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 A kind of method that hydroformylation of olefin prepares aldehyde
CN113713862A (en) * 2020-05-26 2021-11-30 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

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2922757A1 (en) * 1978-06-05 1979-12-06 Kuraray Co PROCESS FOR THE HYDROFORMYLATION OF OLEFINIC COMPOUNDS
US4238419A (en) * 1978-06-05 1980-12-09 Kuraray Co., Ltd. Hydroformylation of olefinic compounds
CN1174197A (en) * 1996-08-13 1998-02-25 赫彻斯特股份公司 Method for separating phosphine oxide and alkylaryl phosphine from homogeneous hydrogen formylation reaction mixture
US5932770A (en) * 1996-08-13 1999-08-03 Hoechst Aktiengesellschaft Process for recovery of phosphine oxides and alklylsarylphosphines from reaction mixtures of a homogeneous hydroformylation
CN106140302A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 A kind of containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and methods and applications thereof
CN106140303A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 One contains the organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation thereof and application
CN106140301A (en) * 2015-04-03 2016-11-23 中国科学院大连化学物理研究所 Containing organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation method and application
CN107790188A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application
CN107793304A (en) * 2016-09-07 2018-03-13 中国科学院大连化学物理研究所 A kind of method that alkene high selectivity prepares aldehyde
CN108069842A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 A kind of method of butene hydroformylation synthesis valeral
CN109806911A (en) * 2017-11-21 2019-05-28 中国科学院大连化学物理研究所 A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application
CN109836318A (en) * 2017-11-27 2019-06-04 中国科学院大连化学物理研究所 A kind of method that hydroformylation of olefin prepares aldehyde
CN113713862A (en) * 2020-05-26 2021-11-30 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115041232A (en) * 2022-06-19 2022-09-13 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application in preparation of aldehyde from mixed olefin
CN115041232B (en) * 2022-06-19 2023-12-12 中海油天津化工研究设计院有限公司 Hydroformylation catalyst, preparation method and application thereof in aldehyde preparation from mixed olefins

Also Published As

Publication number Publication date
CN114591159B (en) 2023-04-07

Similar Documents

Publication Publication Date Title
CN109806911B (en) Catalyst for preparing straight-chain aldehyde with high selectivity and preparation and application thereof
CN107790188B (en) Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof
Nomura Transition metal catalyzed hydrogenation or reduction in water
CN107793304B (en) Method for preparing aldehyde by olefin with high selectivity
US4578496A (en) Polymeric metal-amine complex compounds, processes for their preparation and use
CN112892602B (en) Phosphine-containing porous organic polymer supported catalyst and preparation method and application thereof
WO2016155337A1 (en) Internal olefin hydroformylation process for producing high normal/iso ratio aldehydes
CN109836318B (en) Method for preparing aldehyde through olefin hydroformylation reaction
Spogliarich et al. Asymmetric transfer hydrogenation of ketones catalyzed by phosphine-rhodium (I) and-iridium (I) complexes
CN114588949A (en) Eggshell type catalyst for olefin hydroformylation reaction and preparation and application thereof
CN106140302A (en) A kind of containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and methods and applications thereof
CN113713862B (en) Co-based multi-phase catalyst for olefin hydroformylation reaction, preparation and application thereof
CN114591159B (en) Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst
CN114522740B (en) Method for preparing 3-acetoxypropanol from vinyl acetate
Pruchnik et al. New rhodium (I) water‐soluble complexes with 1‐alkyl‐1‐azonia‐3, 5‐diaza‐7‐phospha‐adamantane iodides and their catalytic activity
CN114797975B (en) Method for carrying out propylene hydroformylation reaction by adopting eggshell type catalyst
CN114773171B (en) Method for propylene hydroformylation reaction by using phosphine oxide polymer supported catalyst
CN114700115B (en) Phosphine oxide polymer supported catalyst and preparation method and application thereof
Luo et al. Enantioselective Carbonyl‐Ene Reactions of Arylglyoxals with a Chiral Palladium (II)‐BINAP Catalyst
CN116174050A (en) P-containing porous organic polymer self-supported heterogeneous catalyst and preparation and application thereof
Mirzoeva et al. Catalytic hydrogenation properties of Pd-and Rh-containing polymers immobilized on Al2O3
CN116178609A (en) Phosphine oxide porous organic polymer and application thereof
WO2023125073A1 (en) Methods for preparing organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst
CN114985002B (en) Biphosphine polymer catalyst for olefin hydroformylation, preparation method and application thereof
CN117899943A (en) Biphosphine copolymer supported catalyst for olefin hydroformylation, and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant