WO2023125073A1 - Methods for preparing organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst - Google Patents

Methods for preparing organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst Download PDF

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WO2023125073A1
WO2023125073A1 PCT/CN2022/139608 CN2022139608W WO2023125073A1 WO 2023125073 A1 WO2023125073 A1 WO 2023125073A1 CN 2022139608 W CN2022139608 W CN 2022139608W WO 2023125073 A1 WO2023125073 A1 WO 2023125073A1
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phosphine ligand
reaction
ligand polymer
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Chinese (zh)
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杨春基
杨勇
赵光辉
王召战
高萌
刘金成
周薪
曾群英
陈谦
李琛
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中国石油天然气股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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

Definitions

  • the invention relates to a preparation method of an organic phosphine ligand polymer and a bidentate phosphine ligand copolymer catalyst, belonging to the field of fine chemicals.
  • Hydroformylation reaction also known as oxo reaction, is an important reaction for converting olefins into aldehydes in industry. It can convert olefins into aldehydes with one more carbon, not only can increase the carbon chain, but also the product can be further converted into alcohols , carboxylic acids, amines, esters and other valuable chemical substances.
  • aldehydes There are many products of hydroformylation reaction, mainly aldehydes, isomerized olefins and alkanes generated by hydrogenation. And aldehydes are also divided into straight-chain aldehydes and branched-chain aldehydes. Therefore, improving the selectivity of the aldehyde in the hydroformylation reaction and the normal isomerization ratio (l/b value) is an important technical problem that needs to be solved urgently, and the key to solving this problem is the selection of the phosphine ligand used for the catalyst.
  • the phosphorus ligands mainly include monodentate ligands, bidentate ligands, tridentate ligands and tetradentate ligands.
  • the patent document CN1857776A discloses a substituted bidentate phosphoramidite ligand with a binaphthol skeleton
  • olefin hydroformylation reaction after the ligand and Rh salt are reacted in an organic solvent to obtain the ligand I/Rh catalyst, under an inert gas or N2 gas atmosphere, add the ligand I/Rh catalyst to the solution
  • Add olefin substrates (C2-C50 olefins) into the mixture respectively charge CO and H 2 , and react to produce hydroformylation products
  • CN101768060A discloses the application of a class of bisphosphine ligands in olefin hydroformylation reactions, The ligand is reacted with Rh, Ru, Ir, Pd, Pt, Ni, Ag, Cu, Co, Mn, Zn or Fe salt to form a catalyst to catalyze the reaction of alkenes (C2-C50 terminal or internal alkenes
  • the catalyst introducing the above-mentioned phosphine ligand has a certain catalytic effect on mono-olefin hydroformylation, it is basically a homogeneous catalytic reaction, and the ligand and catalyst cannot be recycled, especially the expensive rhodium metal is not easy to recycle, thus This increases the cost of the reaction, which is unfavorable for industrial applications.
  • CN110343209A discloses a bidentate phosphorus ligand polymer and its preparation method and application in olefin hydroformylation reaction, the bidentate phosphorus ligand polymer, dicarbonyl acetyl Carry out olefin hydroformylation reaction in the autoclave after rhodium of inner ketone and olefin compound are mixed, and olefin selects 1-hexene, 1-heptene, 2-heptene and styrene; CN109942750A discloses a kind of containing bidentate phosphorous Porous organic polymer with amide ligand and its preparation method and application, after
  • a water-oil two-phase catalyst is usually used.
  • a surfactant to the reaction system , and this will cause emulsification of the reaction system, increasing the difficulty of separation of subsequent products, resulting in low yield and poor selectivity of the target product. Therefore, it is urgent to develop new hydroformylation catalysts and their preparation processes.
  • the invention provides an organic phosphine ligand polymer and a bidentate phosphine ligand copolymer catalyst, which can prepare a highly active bidentate phosphine ligand copolymer catalyst that can be used as a heterogeneous catalyst for hydroformylation reaction, and increase the hydrogen
  • the target product yield and selectivity of the formylation reaction effectively overcome the defects in the prior art.
  • One aspect of the present invention provides a method for preparing an organophosphine ligand polymer, comprising: polymerizing a bidentate phosphine ligand and a vinyl-containing comonomer to obtain the organophosphine ligand polymer; wherein,
  • the bidentate phosphine ligands include compounds shown in formula 3;
  • R 1 and R 2 are each independently a phosphine-containing group.
  • R 1 and R 2 are each independently selected from the following substituents:
  • the vinyl-containing comonomer includes at least one of the following compounds:
  • the molar ratio of the bidentate phosphine ligand to the vinyl-containing comonomer is 1:(1-10).
  • the conditions of the polymerization reaction are: the temperature is 60-100° C., and the time is 2-6 hours; and/or, the process of the polymerization reaction includes: making the compound represented by formula 3, containing The third mixed system of vinyl comonomer and third solvent is polymerized under an inert gas atmosphere. After the reaction, the temperature of the system is controlled to be room temperature, methanol is added thereto for precipitation, and then filtered, and the obtained solid product is passed through methanol After washing, vacuum drying is carried out to obtain the organophosphine ligand polymer; wherein, the third solvent includes at least one of tetrahydrofuran, 2-methyltetrahydrofuran and toluene.
  • it also includes:
  • X in formula 1 is a halogen
  • step (1) the first mixed system containing the compound shown in formula 1, the vinylating agent, and the first solvent is subjected to a reflux reaction under an inert gas atmosphere; after the reaction is completed, the system is cooled to room temperature, remove the solvent by distillation under reduced pressure, and then carry out column chromatography purification to obtain the compound shown in formula 2; and/or, in step (2), under an inert gas atmosphere, control the compound containing the phosphine chloride and The temperature of the second mixed system of the second solvent is 0-30°C, add the mixed solution containing the compound shown in formula 2 and triethylamine to it, and then rise to room temperature for reaction; after the reaction is completed, add water to the system to quench react, and then add ethyl acetate for extraction to obtain an organic phase and an aqueous phase respectively; after drying the organic phase, separate by column chromatography to obtain the compound shown in formula 3.
  • the first solvent includes at least one of toluene, tetrahydrofuran and 1,4-dioxane; and/or, the vinylating agent includes and/or, the first mixed system also includes a catalyst, and the catalyst includes at least one of tetrakis (triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 and/or, the second solvent includes at least one of tetrahydrofuran, toluene and N,N-dimethylformamide.
  • the catalyst includes at least one of tetrakis (triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2
  • the second solvent includes at least one of tetrahydrofuran, toluene and N,N-dimethylformamide.
  • Another aspect of the present invention provides a method for preparing a bidentate phosphine ligand copolymer catalyst, comprising: preparing an organic phosphine ligand polymer according to the above-mentioned preparation method of an organic phosphine ligand polymer; mixing a rhodium compound and the The organic phosphine ligand polymer is dispersed in the fourth solvent, and reacted in a stirring state to obtain the bidentate phosphine ligand copolymer catalyst.
  • the fourth solvent includes one or more of n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran and dioxane; and/or, the rhodium compound Including Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh(CO) 2 Cl] 2 , RhH(CO) At least one of (PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (cod) 2 ], [Rh(cod) 2 ]BF 4 ; and/or, the rhodium compound is coordinated with the organophosphine
  • the mass ratio of the bulk polymer is 1:1 to 1:50; and/or, the reaction temperature for the reaction under stirring is 50°C to 200°C; and/or, the reaction for the reaction
  • the organophosphine ligand polymer is formed by copolymerizing the bidentate phosphine ligand shown in formula 3 with a vinyl-containing comonomer, and the organophosphine ligand polymer is coordinated with rhodium to form the bidentate phosphine ligand Copolymer catalyst
  • the bidentate phosphine ligand copolymer catalyst can be used as a heterogeneous catalyst for the hydroformylation reaction of olefins, especially for the hydroformylation reaction of C 4 -C 10 higher carbon olefins, to achieve heterogeneous Catalytic olefin hydroformylation reaction
  • the catalyst is easy to separate from the reaction product, which is beneficial to the recycling of the catalyst, maintains the high activity and long service life of the catalyst during recycling, and effectively improves the yield and selectivity of the target product of the hydroformylation reaction.
  • the technological process is simplified, and the production cost is greatly reduced.
  • Fig. 1 is the proton nuclear magnetic spectrum ( 1H -NMR) figure of the compound shown in formula 2 prepared in embodiment 1;
  • Fig. 2 is the 1 H-NMR figure of the compound shown in formula 3-1a prepared in embodiment 1;
  • Fig. 3 is the nuclear magnetic phosphine spectrum ( 31 P-NMR) figure of the compound shown in formula 3-1a prepared in Example 1;
  • Fig. 4 is the 1 H-NMR figure of the organophosphine ligand polymer L1 that embodiment 1 makes;
  • Fig. 5 is the 31 P-NMR figure of the organophosphine ligand polymer L1 that embodiment 1 makes;
  • Example 6 is a 31 P-NMR chart of the organophosphine ligand polymer L2 prepared in Example 2.
  • the preparation method of the organic phosphine ligand polymer provided by the present invention comprises: polymerizing the bidentate phosphine ligand and the vinyl-containing comonomer to obtain the organic phosphine ligand polymer; wherein the bidentate phosphine ligand includes the formula 3 Compounds shown:
  • R 1 and R 2 are each independently a phosphine-containing group.
  • the bidentate phosphorus ligand may include a bidentate phosphorus ligand having a phosphite structure.
  • R 1 and R 2 are each independently selected from the following substituents:
  • R 1 and R 2 are each independently selected from the following substituents:
  • R 1 and R 2 may be the same or different.
  • the vinyl-containing comonomer includes at least one of the following four compounds:
  • the molar ratio of the bidentate phosphine ligand to the vinyl-containing comonomer can be 1:(1-10), for example, 1:1, 1:2, 1:3, 1:4, 1: 5.
  • the molar ratio of ligand-forming groups to vinyl-containing comonomer-forming groups is substantially equal to the molar ratio of bidentate phosphorus ligand to vinyl-containing comonomer used in the preparation.
  • the organophosphine ligand polymer (or organic phosphine ligand copolymer) prepared by the present invention contains a phosphite structure.
  • the vinyl-containing comonomer is The obtained organophosphorus ligand polymer is shown in formula 4-1:
  • the vinyl-containing comonomer is The obtained organophosphorus ligand polymer is shown in formula 4-2:
  • the molecular weight of the obtained organic phosphine ligand polymer can generally be 70000g/mol ⁇ 100000g/mol, such as 70000g/mol, 75000g/mol, 80000g/mol, 85000g/mol, 90000g/mol, 95000g/mol, 100,000 g/mol or any combination thereof, the degree of polymerization of the organophosphine ligand polymer is 35-55.
  • the conditions of the polymerization reaction can be: the temperature is 60-100°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C or any of them
  • the time is 2 to 6h, such as 2h, 3h, 4h, 5h, 6h or the range of any combination of the two.
  • the above-mentioned polymerization reaction can be carried out under an inert gas atmosphere.
  • the process of the polymerization reaction includes: making a third mixture containing a compound shown in formula 3, a vinyl-containing comonomer, and a third solvent The system is polymerized under an inert gas atmosphere.
  • the temperature of the system is controlled at room temperature, methanol is added to it for precipitation, and then filtered, and the obtained solid product is washed with methanol, and then vacuum-dried to obtain an organic phosphine ligand polymer;
  • the third solvent includes an organic solvent, such as a furan solvent and/or toluene, preferably at least one of tetrahydrofuran, 2-methyltetrahydrofuran and toluene.
  • the above-mentioned third mixing system may further include an initiator to facilitate the polymerization reaction, and the initiator used may specifically include azoisobutyronitrile (AIBN), but is not limited thereto.
  • AIBN azoisobutyronitrile
  • the compound shown in formula 3 can be added in the third reactor, and then add vinyl-containing comonomer, initiator and third solvent therein to form the third mixed system, and then carry out polymerization under the protection of inert gas reaction.
  • bidentate phosphorus ligands can be purchased commercially or made by themselves, and specifically can be formed from anthraquinone derivatives.
  • the compound shown in formula 3 can be prepared by reacting the compound shown in formula 2 with phosphorus chloride compound. During the reaction, the phosphine chloride compound is dechlorinated, and then replaces the compound shown in formula 2 Hydrogen (H) on the hydroxyl group (-OH), thereby generating the compound shown in formula 3.
  • the general formula of phosphine chloride compounds is RCl, R is an organic group containing phosphorus, specifically R 1 or R 2 above, and the phosphine chloride compounds include R 1 Cl and R 2 Cl (when R 1 and R 2 are the same, R 1 Cl and R 2 Cl are the same compound).
  • the compound shown in formula 2 can be prepared by reacting the compound shown in formula 1 with vinylating reagent:
  • X in Formula 1 is halogen, preferably Br.
  • the compound shown in formula 1 can be prepared from an anthraquinone compound shown in formula 5, for example, by referring to the method in patent document CN113004326A, but not limited thereto.
  • the vinyl group generated by the vinylating reagent replaces X in the compound shown in Formula 1, so as to prepare the compound shown in Formula 2.
  • vinylating agents can include Vinyl tri-n-butyltin at least one of the
  • the above preparation process may also include: (1) making the compound shown in formula 1 contact and react with vinylating reagent to generate the compound shown in formula 2; (2) making the compound shown in formula 2 contact and react with phosphine chloride compounds , generating the compound shown in formula 3.
  • the first mixed system containing the compound shown in formula 1, the vinylating agent, and the first solvent is subjected to a reflux reaction under an inert gas atmosphere; after the reaction, the system is cooled to room temperature , the solvent was removed by distillation under reduced pressure, and then purified by column chromatography to obtain the compound shown in formula 2.
  • the first solvent includes an organic solvent, preferably at least one of toluene, tetrahydrofuran and 1,4-dioxane.
  • the first mixed system can also include a catalyst, which includes a palladium-based catalyst, preferably including at least one of tetrakis(triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 kind.
  • a catalyst which includes a palladium-based catalyst, preferably including at least one of tetrakis(triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 kind.
  • the compound shown in Formula 1 and the first solvent can be added to the first reactor, and then the vinylating agent and the catalyst are added thereto to obtain the first mixed system, which is then refluxed and reacted overnight under an inert gas atmosphere, and then The system was cooled to room temperature, and the solvent was distilled off under reduced pressure, followed by purification by column chromatography, and the compound represented by formula 2 was isolated and obtained.
  • the eluent used in the column chromatography process can be formed by mixing petroleum ether and ethyl acetate at a volume ratio of 2:1, which is beneficial to the separation of the compound shown in formula 2.
  • step (2) under an inert gas atmosphere, the temperature of the second mixed system containing the phosphine chloride compound and the second solvent is controlled to be 0-30°C, such as 0°C, 5°C, 10°C °C, 15 °C, 20 °C, 25 °C, 30 °C or any two of them, then add the compound shown in formula 2 to it, and then rise to room temperature for reaction, the reaction time can generally be 5-10h; After completion, add water to the system to quench the reaction, and then add ethyl acetate for extraction to obtain an organic phase and an aqueous phase, respectively, and dry the organic phase, then perform column chromatography separation to obtain the compound shown in formula 3.
  • the second solvent includes an organic solvent, such as at least one of furan solvents, formamide solvents, and toluene, preferably at least one of tetrahydrofuran, toluene, and N,N-dimethylformamide.
  • organic solvent such as at least one of furan solvents, formamide solvents, and toluene, preferably at least one of tetrahydrofuran, toluene, and N,N-dimethylformamide.
  • the phosphine chloride compound and the second solvent can be added to the second reactor first, then the temperature is lowered to 0°C, and the compound containing the formula 2 is added dropwise to it under the condition of maintaining 0°C. After the mixed solution of the compound and triethylamine was added dropwise completely, the temperature was naturally raised to room temperature for reaction.
  • the compound shown in formula 2 and triethylamine can be dissolved in a solvent (such as the second solvent) to form a mixed solution containing the compound shown in formula 2 and triethylamine.
  • the preparation method of the bidentate phosphine ligand copolymer catalyst provided by the present invention comprises: preparing the organic phosphine ligand polymer according to the preparation method of the above-mentioned organic phosphine ligand polymer; dispersing the rhodium compound and the organic phosphine ligand polymer in In the fourth solvent, the reaction is carried out in a stirring state to obtain a bidentate phosphine ligand copolymer catalyst.
  • the aforementioned rhodium compound may include rhodium salts, preferably including Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh At least one of (CO) 2 Cl] 2 , RhH(CO)(PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (cod) 2 ], [Rh(cod) 2 ]BF 4 , more preferably Includes Rh(CO) 2 (acac).
  • rhodium salts preferably including Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh At least one of (CO) 2 Cl] 2 , RhH(CO)(PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (co
  • the fourth solvent includes an organic solvent, such as at least one of alkanes, benzenes, furans, and dioxane, preferably including n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, and dioxane.
  • organic solvent such as at least one of alkanes, benzenes, furans, and dioxane, preferably including n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, and dioxane.
  • One or more of the six rings more preferably at least one of n-hexane, tetrahydrofuran, and toluene.
  • the mass ratio of the rhodium compound to the organophosphine ligand polymer can be 1:1 to 1:50, such as 1:1, 1:5, 1:10, 1:15, 1:20, 1 :25, 1:30, 1:35, 1:40, 1:45, 1:50 or any two of them.
  • reaction of the rhodium compound and the organic phosphine ligand polymer can be carried out under an inert gas atmosphere, and the reaction temperature can be 50°C to 200°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 150°C , 180°C, 200°C or any two of them, the reaction time can be 1h to 24h, such as 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 24h or any two of them range of composition.
  • the inert gas atmosphere may include nitrogen, but is not limited thereto.
  • the organophosphine ligand polymer coordinates with rhodium to form a complex to generate a bidentate phosphine ligand copolymer catalyst with a phosphite structure, and its general formula can be expressed as Rh/CPOL -(AQBP&VFC), where Rh represents the active rhodium metal, CPOL represents "copolymer", VFC represents vinyl-functionalized compounds (i.e., vinyl-containing comonomers), AQBP represents the bidentate phosphine ligand, Rh/CPOL- (AQBP&VFC) means a copolymer rhodium agent catalyst formed by the coordination of bidentate phosphorus ligands and vinyl-containing comonomers (CPOL-(AQBP&VFC)) and rhodium (Rh). bidentate phosphine ligand copolymer catalyst).
  • Rh represents the active rhodium metal
  • CPOL represents "copolymer”
  • the system after the reaction can be directly applied to the hydroformylation reaction of olefins, or the system after the reaction can be purified to obtain a high-purity bidentate phosphine ligand copolymer catalyst, which can then be applied to Hydroformylation of alkenes.
  • the purification process includes: centrifuging the reacted system to obtain the separated solid phase product, washing the solid phase product with toluene, and then vacuum drying to obtain bidentate phosphine ligand copolymerization material catalyst.
  • a bidentate phosphine ligand copolymer containing a phosphite structure can be generated in one step (ie, an organic phosphine ligand polymer), and then a bidentate phosphine ligand copolymer containing a phosphite structure can be generated.
  • the material catalyst, the raw materials such as vinyl-containing comonomers used are cheap and easy to obtain, can significantly reduce the preparation cost of organic phosphine ligands and bidentate phosphine ligand copolymer catalysts, and the preparation process is simple, time-consuming, and the product yield is high.
  • the yield of the bidentate phosphine ligand copolymer catalyst is higher than 95%, which can realize the large-scale preparation of the catalyst, that is, several grams to hundreds of grams of the bidentate phosphine ligand copolymer catalyst can be prepared at one time , and the product has high purity and does not require operations such as recrystallization.
  • the prepared catalyst can be used for olefin hydroformylation, especially for the hydroformylation of C 4 -C 10 higher olefins, and the bidentate phosphine complex
  • the bulk copolymer catalyst is easy to separate hydromethylation products, fundamentally solves the difficult problem of difficult separation of reaction products and catalysts in the hydroformylation reaction process of olefins (especially high-carbon olefins), and improves the conversion rate of olefins and the selectivity of aldehyde products.
  • organophosphine ligand polymer L1 is a compound represented by formula 4-1a, and its synthetic route is shown as follows:
  • organophosphine ligand polymer L2 is a compound shown in formula 4-2, and its synthetic route is shown as follows:
  • Formula 3-1a was prepared according to steps (1) to (3) in Example 1;
  • organophosphine ligand polymer L1 Take 500mg of organophosphine ligand polymer L1, add it to the reactor, add 50mg Rh(acac)(CO) 2 , 5mL tetrahydrofuran to it, stir and react at 80°C for 2h under the protection of nitrogen; then cool the system to room temperature , add 30mL toluene, centrifuge, the separated solid phase product is washed 3 times with toluene, and then carry out vacuum drying, obtain bidentate phosphine ligand copolymer catalyst A.
  • organophosphine ligand polymer L2 Take 500mg of organophosphine ligand polymer L2, add it to the reactor, add 25mg Rh(acac)(CO) 2 , 5mL tetrahydrofuran to it, stir and react at 80°C for 2h under nitrogen protection; then cool the system to room temperature, Add 30 mL of toluene, centrifuge, wash the separated solid phase product with toluene 3 times, and then vacuum-dry to obtain bidentate phosphine ligand copolymer catalyst B.
  • 1,6- Adipaldehyde The conversion rate of 1,3-butadiene is 99.8% and the selectivity of 1,6-hexanedial is 57.9% as measured by the internal standard method of gas chromatography.
  • 1,6-hexyl Dialdehyde The conversion rate of 1,3-butadiene is 99.5% and the selectivity of 1,6-hexanedialdehyde is 53.4% as measured by the internal standard method of gas chromatography.

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Abstract

The present invention provides methods for preparing an organic phosphine ligand polymer and a bidentate phosphine ligand copolymer catalyst. The method for preparing an organic phosphine ligand polymer comprises: subjecting a bidentate phosphine ligand and a vinyl-containing comonomer to a polymerization reaction to obtain an organic phosphine ligand polymer, wherein the bidentate phosphine ligand comprises a compound as represented by formula 3, and R1 and R2 in formula 3 are each independently a phosphine-containing group. In the present invention, a high-activity bidentate phosphine ligand copolymer catalyst capable of serving as a heterogeneous catalyst for a hydroformylation reaction can be prepared, so as to improve the target product yield and selectivity of the hydroformylation reaction.

Description

有机膦配体聚合物及二齿膦配体共聚物催化剂的制备方法Preparation method of organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst 技术领域technical field
本发明涉及一种有机膦配体聚合物及二齿膦配体共聚物催化剂的制备方法，属于精细化工领域。The invention relates to a preparation method of an organic phosphine ligand polymer and a bidentate phosphine ligand copolymer catalyst, belonging to the field of fine chemicals.
背景技术Background technique
氢甲酰化反应又称羰基合成反应，是工业上将烯烃转化为醛的重要反应，其可以将烯烃转化为多一个碳的醛，不仅可以使碳链增长，而且产物还可以进一步转化为醇、羧酸、胺、酯等极具价值的化学物质。Hydroformylation reaction, also known as oxo reaction, is an important reaction for converting olefins into aldehydes in industry. It can convert olefins into aldehydes with one more carbon, not only can increase the carbon chain, but also the product can be further converted into alcohols , carboxylic acids, amines, esters and other valuable chemical substances.
氢甲酰化反应的产物较多，主要有醛、异构化的烯烃以及氢化生成的烷烃。而且醛也有直链醛和支链醛之分。因此，提高氢甲酰化反应醛的选择性以及正异构比(l/b值)是急需解决的重要技术问题，而解决这一问题的关键是用于催化剂的膦配体的选择，常用的磷配体主要包括单齿配体、二齿配体、三齿配体以及四齿配体，举例来说，专利文献CN1857776A公开了一种联萘酚骨架的取代双齿亚磷酰胺配体在烯烃氢甲酰化反应中的应用，将配体与Rh盐在有机溶剂中反应得到配体I/Rh催化剂后，在惰性气体或N 2气气氛下，向配体I/Rh催化剂的溶液中加入烯烃底物(C2～C50的烯烃)，分别充入CO和H 2，反应制得氢甲酰化产物；CN101768060A公开了一类双膦配体在烯烃氢甲酰化反应中的应用，将配体与Rh、Ru、Ir、Pd、Pt、Ni、Ag、Cu、Co、Mn、Zn或Fe盐作用形成催化剂，催化烯烃(C2～C50的端烯烃或内烯烃)与CO和H 2发生氢甲酰化反应；CN102746338A公开了一类螺缩酮骨架的双齿亚磷酰胺配体，与过渡金属盐形成配合物后，应用于端烯烃的氢甲酰化反应或内烯烃的异构化-氢甲酰化反应；CN108525704A公开了一种用于烯烃氢甲酰化反应的催化剂及其制备方法和应用，该催化剂由铑络合物和含吲哚环的双齿或多齿亚膦酰胺配体制得，具体还公开了一类四齿膦配体，该催化剂用于催化C2-C18烯烃与CO和H2发生氢甲酰化反应。 There are many products of hydroformylation reaction, mainly aldehydes, isomerized olefins and alkanes generated by hydrogenation. And aldehydes are also divided into straight-chain aldehydes and branched-chain aldehydes. Therefore, improving the selectivity of the aldehyde in the hydroformylation reaction and the normal isomerization ratio (l/b value) is an important technical problem that needs to be solved urgently, and the key to solving this problem is the selection of the phosphine ligand used for the catalyst. The phosphorus ligands mainly include monodentate ligands, bidentate ligands, tridentate ligands and tetradentate ligands. For example, the patent document CN1857776A discloses a substituted bidentate phosphoramidite ligand with a binaphthol skeleton In the application of olefin hydroformylation reaction, after the ligand and Rh salt are reacted in an organic solvent to obtain the ligand I/Rh catalyst, under an inert gas or N2 gas atmosphere, add the ligand I/Rh catalyst to the solution Add olefin substrates (C2-C50 olefins) into the mixture, respectively charge CO and H 2 , and react to produce hydroformylation products; CN101768060A discloses the application of a class of bisphosphine ligands in olefin hydroformylation reactions, The ligand is reacted with Rh, Ru, Ir, Pd, Pt, Ni, Ag, Cu, Co, Mn, Zn or Fe salt to form a catalyst to catalyze the reaction of alkenes (C2-C50 terminal or internal alkenes) with CO and H2 A hydroformylation reaction occurs; CN102746338A discloses a class of bidentate phosphoramidite ligands with a spirketal skeleton, which is applied to the hydroformylation reaction of terminal olefins or the isomerization of internal olefins after forming a complex with a transition metal salt Hydroformylation-hydroformylation; CN108525704A discloses a catalyst for olefin hydroformylation and its preparation method and application, the catalyst consists of rhodium complex and bidentate or polydentate phosphine containing indole ring The amide ligand is prepared, and a class of tetradentate phosphine ligand is specifically disclosed. The catalyst is used to catalyze the hydroformylation reaction of C2-C18 olefins with CO and H2.
虽然引入上述膦配体的催化剂对单烯烃氢甲酰化反应具有一定的催 化效果，但基本均是均相催化反应，配体和催化剂无法循环使用，尤其是昂贵的铑金属不易回收利用，从而增加了反应的成本，不利于工业化应用。Although the catalyst introducing the above-mentioned phosphine ligand has a certain catalytic effect on mono-olefin hydroformylation, it is basically a homogeneous catalytic reaction, and the ligand and catalyst cannot be recycled, especially the expensive rhodium metal is not easy to recycle, thus This increases the cost of the reaction, which is unfavorable for industrial applications.
基于此，有研究提出设计膦配体聚合物，将其与过渡金属(如铑)配位形成膦配体聚合物催化剂，将该催化剂应用于氢甲酰化反应，通过非均相催化来实现配体和催化剂的循环利用，例如，CN110343209A公开了一种二齿磷配体聚合物及其制备方法和在烯烃氢甲酰化反应中的应用，将二齿磷配体聚合物、二羰基乙酰内酮铑和烯烃化合物混合后在高压釜中进行烯烃氢甲酰化反应，烯烃选择1-己烯、1-庚烯、2-庚烯和苯乙烯；CN109942750A公开了一种含有双齿亚磷酰胺配体的多孔有机聚合物及其制备方法和应用，将该多孔有机聚合物与过渡金属盐形成催化剂后，催化端烯烃的氢甲酰化反应或内烯烃的异构化-氢甲酰化反应，烯烃是C2～C50的端烯烃或内烯烃；CN109836318A公开了一种烯烃氢甲酰化反应制备醛的方法，以C3-C20的烯烃为原料，在催化剂作用下进行烯烃氢甲酰化反应，催化剂为聚合物自负载型催化剂以及含膦有机聚合物作为载体，以金属Rh、Co、Ir、Pd、Pt中的至少一种作为活性组分，含膦有机聚合物载体是由烯烃基官能团化单齿有机膦配体和/或多齿有机膦配体共聚或自聚而成的。然而，由膦配体聚合物与过渡金属配位形成磷配体聚合物催化剂的催化性能比均相反应低了许多。Based on this, some studies have proposed to design a phosphine ligand polymer, coordinate it with a transition metal (such as rhodium) to form a phosphine ligand polymer catalyst, apply the catalyst to the hydroformylation reaction, and achieve Recycling of ligands and catalysts, for example, CN110343209A discloses a bidentate phosphorus ligand polymer and its preparation method and application in olefin hydroformylation reaction, the bidentate phosphorus ligand polymer, dicarbonyl acetyl Carry out olefin hydroformylation reaction in the autoclave after rhodium of inner ketone and olefin compound are mixed, and olefin selects 1-hexene, 1-heptene, 2-heptene and styrene; CN109942750A discloses a kind of containing bidentate phosphorous Porous organic polymer with amide ligand and its preparation method and application, after the porous organic polymer and transition metal salt form a catalyst, catalyze the hydroformylation reaction of terminal olefins or the isomerization-hydroformylation of internal olefins Reaction, olefins are C2-C50 terminal olefins or internal olefins; CN109836318A discloses a method for preparing aldehydes by hydroformylation of olefins, using C3-C20 olefins as raw materials, and performing olefin hydroformylation under the action of a catalyst , the catalyst is a polymer self-supporting catalyst and a phosphine-containing organic polymer as a carrier, and at least one of metal Rh, Co, Ir, Pd, and Pt is used as an active component, and the phosphine-containing organic polymer carrier is composed of an olefin-based functional group Copolymerized or self-polymerized monodentate organic phosphine ligands and/or multidentate organic phosphine ligands. However, the catalytic performance of phosphorus-ligand polymer catalysts formed by coordination of phosphine-ligand polymers with transition metals is much lower than that of homogeneous reactions.
此外，为了克服催化剂与氢甲酰化反应产物难以分离的问题，通常采用水油两相催化剂，为了提高水油两相的互溶性，以提高反应效率，通常需要在反应体系中加入表面活性剂，而由此会造成反应体系的乳化，增大后续产品的分离难度，导致目标产品收率低和选择性差。因此，亟待开发新型氢甲酰化反应催化剂及其制备工艺。In addition, in order to overcome the problem that the catalyst is difficult to separate from the hydroformylation reaction product, a water-oil two-phase catalyst is usually used. In order to improve the mutual solubility of the water-oil two-phase to improve the reaction efficiency, it is usually necessary to add a surfactant to the reaction system , and this will cause emulsification of the reaction system, increasing the difficulty of separation of subsequent products, resulting in low yield and poor selectivity of the target product. Therefore, it is urgent to develop new hydroformylation catalysts and their preparation processes.
发明内容Contents of the invention
本发明提供一种有机膦配体聚合物及二齿膦配体共聚物催化剂，能够制得高活性的可作为氢甲酰化反应非均相催化剂的二齿膦配体共聚物催化剂，提高氢甲酰化反应的目标产品收率和选择性，有效克服现有技术存在的缺陷。The invention provides an organic phosphine ligand polymer and a bidentate phosphine ligand copolymer catalyst, which can prepare a highly active bidentate phosphine ligand copolymer catalyst that can be used as a heterogeneous catalyst for hydroformylation reaction, and increase the hydrogen The target product yield and selectivity of the formylation reaction effectively overcome the defects in the prior art.
本发明的一方面，提供一种有机膦配体聚合物的制备方法，包括：使二齿膦配体与含乙烯基共聚单体进行聚合反应，得到所述有机膦配体聚合物； 其中，所述二齿膦配体包括式3所示化合物；One aspect of the present invention provides a method for preparing an organophosphine ligand polymer, comprising: polymerizing a bidentate phosphine ligand and a vinyl-containing comonomer to obtain the organophosphine ligand polymer; wherein, The bidentate phosphine ligands include compounds shown in formula 3;
Figure PCTCN2022139608-appb-000001
Figure PCTCN2022139608-appb-000001
其中，R 1和R 2各自独立地为含膦基团。 Wherein, R 1 and R 2 are each independently a phosphine-containing group.
根据本发明的一实施方式，式3中，R 1和R 2各自独立地选自如下取代基： According to one embodiment of the present invention, in formula 3, R 1 and R 2 are each independently selected from the following substituents:
Figure PCTCN2022139608-appb-000002
Figure PCTCN2022139608-appb-000002
根据本发明的一实施方式，所述含乙烯基共聚单体包括如下化合物中的至少一种：According to one embodiment of the present invention, the vinyl-containing comonomer includes at least one of the following compounds:
Figure PCTCN2022139608-appb-000003
Figure PCTCN2022139608-appb-000003
根据本发明的一实施方式，所述二齿膦配体与所述含乙烯基共聚单体的摩尔比为1:(1～10)。According to one embodiment of the present invention, the molar ratio of the bidentate phosphine ligand to the vinyl-containing comonomer is 1:(1-10).
根据本发明的一实施方式，所述聚合反应的条件为：温度为60～100℃，时间为2～6h；和/或，所述聚合反应的过程包括：使含有式3所示化合物、含乙烯基共聚单体、第三溶剂的第三混合体系在惰性气体氛围下进行聚合反应， 反应结束后，控制体系温度为室温，向其中加入甲醇进行沉淀，然后过滤，将得到的固体产物经甲醇洗涤后，再进行真空干燥，得到所述有机膦配体聚合物；其中，所述第三溶剂包括四氢呋喃、2-甲基四氢呋喃和甲苯中的至少一种。According to an embodiment of the present invention, the conditions of the polymerization reaction are: the temperature is 60-100° C., and the time is 2-6 hours; and/or, the process of the polymerization reaction includes: making the compound represented by formula 3, containing The third mixed system of vinyl comonomer and third solvent is polymerized under an inert gas atmosphere. After the reaction, the temperature of the system is controlled to be room temperature, methanol is added thereto for precipitation, and then filtered, and the obtained solid product is passed through methanol After washing, vacuum drying is carried out to obtain the organophosphine ligand polymer; wherein, the third solvent includes at least one of tetrahydrofuran, 2-methyltetrahydrofuran and toluene.
根据本发明的一实施方式，还包括：According to one embodiment of the present invention, it also includes:
(1)使式1所示化合物与乙烯化试剂接触反应，生成式2所示化合物；(1) making the compound shown in formula 1 contact and react with vinylating reagent to generate the compound shown in formula 2;
Figure PCTCN2022139608-appb-000004
Figure PCTCN2022139608-appb-000004
其中，式1中的X为卤素；Wherein, X in formula 1 is a halogen;
(2)使式2所示化合物与氯化膦类化合物接触反应，生成所述式3所示化合物；(2) making the compound shown in formula 2 contact with the phosphine chloride compound to generate the compound shown in formula 3;
Figure PCTCN2022139608-appb-000005
Figure PCTCN2022139608-appb-000005
根据本发明的一实施方式，步骤(1)中，使含有式1所示化合物、乙烯化试剂、第一溶剂的第一混合体系在惰性气体氛围下进行回流反应；反应结束后，将体系冷却至室温，通过减压蒸馏除去溶剂，再进行柱层析纯化，得到式2所示化合物；和/或，步骤(2)中，在惰性气体氛围下，控制含有所述氯化膦类化合物和第二溶剂的第二混合体系的温度为0～30℃，向其中加入含有式2所示化合物和三乙胺的混合液，然后升至室温进行反应；反应结束后，向体系中加水淬灭反应，然后加乙酸乙酯进行萃取，分别得到有机相和水相，将有机相进行干燥后，再进行柱层析分离，得到式3所示化合物。According to one embodiment of the present invention, in step (1), the first mixed system containing the compound shown in formula 1, the vinylating agent, and the first solvent is subjected to a reflux reaction under an inert gas atmosphere; after the reaction is completed, the system is cooled to room temperature, remove the solvent by distillation under reduced pressure, and then carry out column chromatography purification to obtain the compound shown in formula 2; and/or, in step (2), under an inert gas atmosphere, control the compound containing the phosphine chloride and The temperature of the second mixed system of the second solvent is 0-30°C, add the mixed solution containing the compound shown in formula 2 and triethylamine to it, and then rise to room temperature for reaction; after the reaction is completed, add water to the system to quench react, and then add ethyl acetate for extraction to obtain an organic phase and an aqueous phase respectively; after drying the organic phase, separate by column chromatography to obtain the compound shown in formula 3.
根据本发明的一实施方式，所述第一溶剂包括甲苯、四氢呋喃和1，4-二氧六环中的至少一种；和/或，所述乙烯化试剂包括
Figure PCTCN2022139608-appb-000006
Figure PCTCN2022139608-appb-000007
中的至少一种；和/或，所述第一混合体系还包含催化剂，所述催化剂包括四(三苯基膦)钯、PdCl 2(dppf)、PdCl 2(PPh 3) 2中的至少一种；和/或，所述第二溶剂包括四氢呋喃、甲苯和N,N-二甲基甲酰胺中的至少一种。 According to an embodiment of the present invention, the first solvent includes at least one of toluene, tetrahydrofuran and 1,4-dioxane; and/or, the vinylating agent includes
Figure PCTCN2022139608-appb-000006
Figure PCTCN2022139608-appb-000007
and/or, the first mixed system also includes a catalyst, and the catalyst includes at least one of tetrakis (triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 and/or, the second solvent includes at least one of tetrahydrofuran, toluene and N,N-dimethylformamide.
本发明的另一方面，提供一种二齿膦配体共聚物催化剂的制备方法，包括：按照上述有机膦配体聚合物的制备方法制得有机膦配体聚合物；将铑化合物和所述有机膦配体聚合物分散于第四溶剂中，在搅拌状态下进行反应，得到所述二齿膦配体共聚物催化剂。Another aspect of the present invention provides a method for preparing a bidentate phosphine ligand copolymer catalyst, comprising: preparing an organic phosphine ligand polymer according to the above-mentioned preparation method of an organic phosphine ligand polymer; mixing a rhodium compound and the The organic phosphine ligand polymer is dispersed in the fourth solvent, and reacted in a stirring state to obtain the bidentate phosphine ligand copolymer catalyst.
根据本发明的一实施方式，所述第四溶剂包括正己烷、环己烷、苯、甲苯、二甲苯、四氢呋喃和二氧六环中的一种或多种；和/或，所述铑化合物包括Rh(acac)(CO) 2、Rh(AcO) 2、RhCl 3、Rh(NO 3) 3、RhH(CO)(PPh 3) 3、[Rh(CO) 2Cl] 2、RhH(CO)(PPh 3) 3、[Rh 2(m-Cl) 2(cod) 2]、[Rh(cod) 2]BF 4中的至少一种；和/或，所述铑化合物与所述有机膦配体聚合物的质量比为1:1～1:50；和/或，所述在搅拌状态下进行反应的反应温度为50℃～200℃；和/或，所述在搅拌状态下进行反应的反应时间为1h～24h。 According to an embodiment of the present invention, the fourth solvent includes one or more of n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran and dioxane; and/or, the rhodium compound Including Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh(CO) 2 Cl] 2 , RhH(CO) At least one of (PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (cod) 2 ], [Rh(cod) 2 ]BF 4 ; and/or, the rhodium compound is coordinated with the organophosphine The mass ratio of the bulk polymer is 1:1 to 1:50; and/or, the reaction temperature for the reaction under stirring is 50°C to 200°C; and/or, the reaction for the reaction under stirring The reaction time is 1h～24h.
本发明中，采用式3所示的二齿膦配体与含乙烯基共聚单体共聚而成有机磷配体聚合物，使该有机膦配体聚合物与铑配位形成二齿膦配体共聚物催化剂，该二齿膦配体共聚物催化剂可作为烯烃氢甲酰化反应的非均相催化剂，尤其可用于C 4-C 10的高碳烯烃的氢甲酰化反应，实现非均相催化烯烃氢甲酰化反应，催化剂容易与反应产物分离，利于催化剂回收利用，保持催化剂循环使用过程中的高活性和长使用寿命，有效提高氢甲酰化反应的目标产品收率和选择性，且简化工艺流程，大幅降低生产成本。此外，本发明的制备过程还具有原料易得、操作简单、条件温和、成本低、效率高等优点，利于工业化应用。 In the present invention, the organophosphine ligand polymer is formed by copolymerizing the bidentate phosphine ligand shown in formula 3 with a vinyl-containing comonomer, and the organophosphine ligand polymer is coordinated with rhodium to form the bidentate phosphine ligand Copolymer catalyst, the bidentate phosphine ligand copolymer catalyst can be used as a heterogeneous catalyst for the hydroformylation reaction of olefins, especially for the hydroformylation reaction of C 4 -C 10 higher carbon olefins, to achieve heterogeneous Catalytic olefin hydroformylation reaction, the catalyst is easy to separate from the reaction product, which is beneficial to the recycling of the catalyst, maintains the high activity and long service life of the catalyst during recycling, and effectively improves the yield and selectivity of the target product of the hydroformylation reaction. Moreover, the technological process is simplified, and the production cost is greatly reduced. In addition, the preparation process of the present invention also has the advantages of readily available raw materials, simple operation, mild conditions, low cost, high efficiency, etc., which is beneficial to industrial application.
附图说明Description of drawings
图1为实施例1制得的式2所示化合物的核磁氢谱( 1H-NMR)图； Fig. 1 is the proton nuclear magnetic spectrum ( 1H -NMR) figure of the compound shown in formula 2 prepared in embodiment 1;
图2为实施例1制得的式3-1a所示化合物的 1H-NMR图； Fig. 2 is the 1 H-NMR figure of the compound shown in formula 3-1a prepared in embodiment 1;
图3为实施例1制得的式3-1a所示化合物的核磁膦谱( 31P-NMR)图； Fig. 3 is the nuclear magnetic phosphine spectrum ( 31 P-NMR) figure of the compound shown in formula 3-1a prepared in Example 1;
图4为实施例1制得的有机膦配体聚合物L1的 1H-NMR图； Fig. 4 is the 1 H-NMR figure of the organophosphine ligand polymer L1 that embodiment 1 makes;
图5为实施例1制得的有机膦配体聚合物L1的 31P-NMR图； Fig. 5 is the 31 P-NMR figure of the organophosphine ligand polymer L1 that embodiment 1 makes;
图6为实施例2制得的有机膦配体聚合物L2的 31P-NMR图。 6 is a 31 P-NMR chart of the organophosphine ligand polymer L2 prepared in Example 2.
具体实施方式Detailed ways
为使本领域技术人员更好地理解本发明的方案，下面对本发明作进一步地详细说明。以下所列举具体实施方式只是对本发明的原理和特征进行描述，所举实例仅用于解释本发明，并非限定本发明的范围。基于本发明实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本发明保护的范围。In order to enable those skilled in the art to better understand the solution of the present invention, the present invention will be further described in detail below. The specific embodiments listed below are only to describe the principles and features of the present invention, and the examples are only used to explain the present invention, not to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementations obtained by persons of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.
本发明提供的有机膦配体聚合物的制备方法，包括：使二齿膦配体与含乙烯基共聚单体进行聚合反应，得到有机膦配体聚合物；其中，二齿膦配体包括式3所示化合物：The preparation method of the organic phosphine ligand polymer provided by the present invention comprises: polymerizing the bidentate phosphine ligand and the vinyl-containing comonomer to obtain the organic phosphine ligand polymer; wherein the bidentate phosphine ligand includes the formula 3 Compounds shown:
Figure PCTCN2022139608-appb-000008
Figure PCTCN2022139608-appb-000008
其中，R 1和R 2各自独立地为含膦基团。 Wherein, R 1 and R 2 are each independently a phosphine-containing group.
本发明中，二齿磷配体可以包括具有亚磷酸酯结构的二齿磷配体，在一些具体实施例中，式3中，R 1和R 2各自独立地选自如下取代基： In the present invention, the bidentate phosphorus ligand may include a bidentate phosphorus ligand having a phosphite structure. In some specific embodiments, in formula 3, R 1 and R 2 are each independently selected from the following substituents:
Figure PCTCN2022139608-appb-000009
Figure PCTCN2022139608-appb-000009
优选地，式3中，R 1和R 2各自独立地选自如下取代基： Preferably, in formula 3, R 1 and R 2 are each independently selected from the following substituents:
Figure PCTCN2022139608-appb-000010
Figure PCTCN2022139608-appb-000010
其中，“.”表示R 1和R 2基团与式3中的氧原子(O)的连接位置，即式3中的O分别与R 1和R 2中的P形成化学键。R 1和R 2可相同或不同。 Among them, "." indicates the connection position of the R1 and R2 groups and the oxygen atom (O) in Formula 3, that is, O in Formula 3 forms a chemical bond with P in R1 and R2 , respectively. R 1 and R 2 may be the same or different.
本发明中，含乙烯基共聚单体中乙烯基(-HC＝CH 2)的数量为1～3，即其可以是含有一个乙烯基的化合物
Figure PCTCN2022139608-appb-000011
含有两个乙烯基的化合物、含有三个乙烯基的化合物中的至少一种。例如，在一些优选实施例中，含乙烯基共聚单体包括如下四种化合物中的至少一种： In the present invention, the number of vinyl groups (-HC=CH 2 ) in the vinyl group-containing comonomer is 1 to 3, that is, it can be a compound containing one vinyl group
Figure PCTCN2022139608-appb-000011
At least one of compounds containing two vinyl groups and compounds containing three vinyl groups. For example, in some preferred embodiments, the vinyl-containing comonomer includes at least one of the following four compounds:
Figure PCTCN2022139608-appb-000012
Figure PCTCN2022139608-appb-000012
优选地，含乙烯基(-HC＝CH 2)共聚单体选自如下两种化合物中的至少一种： Preferably, the vinyl group-containing (-HC=CH 2 ) comonomer is selected from at least one of the following two compounds:
Figure PCTCN2022139608-appb-000013
Figure PCTCN2022139608-appb-000013
上述制备过程中，二齿膦配体与含乙烯基共聚单体的摩尔比可以为1:(1～10)，例如为1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9、1：10或其中的任意两者组成的范围，一般情况下，所制得的有机膦配体聚合物中，二齿磷配体形成的基团与含乙烯基共聚单体形成的基团的摩尔比与制备过程中所用的二齿磷配体与含乙烯基共聚单体的摩尔比基本相等。In the above preparation process, the molar ratio of the bidentate phosphine ligand to the vinyl-containing comonomer can be 1:(1-10), for example, 1:1, 1:2, 1:3, 1:4, 1: 5. The range of 1:6, 1:7, 1:8, 1:9, 1:10 or any two of them, in general, in the prepared organophosphine ligand polymer, bidentate phosphorus The molar ratio of ligand-forming groups to vinyl-containing comonomer-forming groups is substantially equal to the molar ratio of bidentate phosphorus ligand to vinyl-containing comonomer used in the preparation.
本发明所制得的有机膦配体聚合物(或称有机膦配体共聚物)含有亚磷酸酯结构，举例来说，在一些实施例中，含乙烯基共聚单体为
Figure PCTCN2022139608-appb-000014
所制得的 有机磷配体聚合物如式4-1所示： The organophosphine ligand polymer (or organic phosphine ligand copolymer) prepared by the present invention contains a phosphite structure. For example, in some embodiments, the vinyl-containing comonomer is
Figure PCTCN2022139608-appb-000014
The obtained organophosphorus ligand polymer is shown in formula 4-1:
Figure PCTCN2022139608-appb-000015
Figure PCTCN2022139608-appb-000015
例如，含乙烯基共聚单体为
Figure PCTCN2022139608-appb-000016
(即
Figure PCTCN2022139608-appb-000017
中的R 3为苯基)，所制得的有机磷配体聚合物如式4-1a所示： For example, vinyl-containing comonomers are
Figure PCTCN2022139608-appb-000016
(Right now
Figure PCTCN2022139608-appb-000017
In R 3 is phenyl), the obtained organophosphorus ligand polymer is shown in formula 4-1a:
Figure PCTCN2022139608-appb-000018
Figure PCTCN2022139608-appb-000018
在另一些实施例中，含乙烯基共聚单体为
Figure PCTCN2022139608-appb-000019
所制得的有机磷配体聚合物如式4-2所示： In other embodiments, the vinyl-containing comonomer is
Figure PCTCN2022139608-appb-000019
The obtained organophosphorus ligand polymer is shown in formula 4-2:
Figure PCTCN2022139608-appb-000020
Figure PCTCN2022139608-appb-000020
上述式4-1、式4-1a、式4-2中，m与n的比值基本等于其制备过程中所用的二齿膦配体与含乙烯基共聚单体的摩尔比，即m：n＝1:(1-10)，例如为1：1、1：2、1：3、1：4、1：5、1：6、1：7、1：8、1：9、1：10或其中的任意两者组成的范围。In the above formula 4-1, formula 4-1a, and formula 4-2, the ratio of m to n is basically equal to the molar ratio of the bidentate phosphine ligand used in the preparation process to the vinyl-containing comonomer, that is, m:n ＝1:(1-10), such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or a range of any two of them.
此外，所制得的有机膦配体聚合物的分子量一般可以为70000g/mol～100000g/mol，例如70000g/mol、75000g/mol、80000g/mol、85000g/mol、90000g/mol、95000g/mol、100000g/mol或其中的任意两者组成的范围，该有机膦配体聚合物的聚合度为35～55。In addition, the molecular weight of the obtained organic phosphine ligand polymer can generally be 70000g/mol～100000g/mol, such as 70000g/mol, 75000g/mol, 80000g/mol, 85000g/mol, 90000g/mol, 95000g/mol, 100,000 g/mol or any combination thereof, the degree of polymerization of the organophosphine ligand polymer is 35-55.
上述制备过程中，聚合反应的条件可以为：温度为60～100℃，例如60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃或其中的任意两者组成的范围，时间为2～6h，例如2h、3h、4h、5h、6h或其中的任意两者组成的范围。In the above preparation process, the conditions of the polymerization reaction can be: the temperature is 60-100°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C or any of them The range of the combination of the two, the time is 2 to 6h, such as 2h, 3h, 4h, 5h, 6h or the range of any combination of the two.
一般情况下，上述聚合反应可在惰性气体氛围下进行，在一些具体实施例中，聚合反应的过程包括：使含有式3所示化合物、含乙烯基共聚单体、第三溶剂的第三混合体系在惰性气体氛围下进行聚合反应，反应结束后，控制体系温度为室温，向其中加入甲醇进行沉淀，然后过滤，将得到的固体产物经甲醇洗涤后，再进行真空干燥，得到有机膦配体聚合物；其中，第三溶剂包括有机溶剂，例如包括呋喃类溶剂和/或甲苯，优选包括四氢呋喃、2-甲基四氢呋喃和甲苯中的至少一种。Generally, the above-mentioned polymerization reaction can be carried out under an inert gas atmosphere. In some specific embodiments, the process of the polymerization reaction includes: making a third mixture containing a compound shown in formula 3, a vinyl-containing comonomer, and a third solvent The system is polymerized under an inert gas atmosphere. After the reaction, the temperature of the system is controlled at room temperature, methanol is added to it for precipitation, and then filtered, and the obtained solid product is washed with methanol, and then vacuum-dried to obtain an organic phosphine ligand polymer; wherein, the third solvent includes an organic solvent, such as a furan solvent and/or toluene, preferably at least one of tetrahydrofuran, 2-methyltetrahydrofuran and toluene.
此外，上述第三混合体系还可以包括引发剂，以利于发生聚合反应，所用引发剂具体可以包括偶氮异丁腈(AIBN)，但不局限于此。In addition, the above-mentioned third mixing system may further include an initiator to facilitate the polymerization reaction, and the initiator used may specifically include azoisobutyronitrile (AIBN), but is not limited thereto.
具体实施时，可以将式3所示化合物加入第三反应器中，然后向其中加 入含乙烯基共聚单体、引发剂和第三溶剂，形成第三混合体系，再在惰性气体保护下进行聚合反应。During specific implementation, the compound shown in formula 3 can be added in the third reactor, and then add vinyl-containing comonomer, initiator and third solvent therein to form the third mixed system, and then carry out polymerization under the protection of inert gas reaction.
本发明中，二齿磷配体可以商购或自制，其具体可以由蒽醌衍生物形成。在一些实施例中，式3所示化合物具体可以是由如下式2所示化合和氯化磷类化合物反应制得，反应过程中，氯化膦类化合物脱氯，然后取代式2所示化合物羟基(-OH)上的氢(H)，从而生成式3所示化合物。In the present invention, bidentate phosphorus ligands can be purchased commercially or made by themselves, and specifically can be formed from anthraquinone derivatives. In some embodiments, the compound shown in formula 3 can be prepared by reacting the compound shown in formula 2 with phosphorus chloride compound. During the reaction, the phosphine chloride compound is dechlorinated, and then replaces the compound shown in formula 2 Hydrogen (H) on the hydroxyl group (-OH), thereby generating the compound shown in formula 3.
Figure PCTCN2022139608-appb-000021
Figure PCTCN2022139608-appb-000021
一般情况下，氯化膦类化合物通式为RCl，R为含有磷的有机基团，具体可以是上述R 1或R 2，该氯化膦类化合物包括R 1Cl和R 2Cl(当R 1和R 2相同时，R 1Cl和R 2Cl为同一种化合物)。 In general, the general formula of phosphine chloride compounds is RCl, R is an organic group containing phosphorus, specifically R 1 or R 2 above, and the phosphine chloride compounds include R 1 Cl and R 2 Cl (when R 1 and R 2 are the same, R 1 Cl and R 2 Cl are the same compound).
此外，式2所示化合物可以是由如下式1所示化合物与乙烯化试剂反应制得：In addition, the compound shown in formula 2 can be prepared by reacting the compound shown in formula 1 with vinylating reagent:
Figure PCTCN2022139608-appb-000022
Figure PCTCN2022139608-appb-000022
其中，式1中的X为卤素，优选为Br。具体地，式1所示化合物可以是由如下式5所示的蒽醌化合物制得，例如参考专利文献CN113004326A中的方法制得，但不局限于此。Wherein, X in Formula 1 is halogen, preferably Br. Specifically, the compound shown in formula 1 can be prepared from an anthraquinone compound shown in formula 5, for example, by referring to the method in patent document CN113004326A, but not limited thereto.
Figure PCTCN2022139608-appb-000023
Figure PCTCN2022139608-appb-000023
式1所示化合物与乙烯化试剂反应过程中，乙烯化试剂产生的乙烯基取代式1所示化合物中的X，从而制得式2所示化合物。During the reaction process between the compound shown in Formula 1 and the vinylating reagent, the vinyl group generated by the vinylating reagent replaces X in the compound shown in Formula 1, so as to prepare the compound shown in Formula 2.
在一些具体实施例中，乙烯化试剂可以包括
Figure PCTCN2022139608-appb-000024
乙烯基三正丁基锡
Figure PCTCN2022139608-appb-000025
中的至少一种。 In some embodiments, vinylating agents can include
Figure PCTCN2022139608-appb-000024
Vinyl tri-n-butyltin
Figure PCTCN2022139608-appb-000025
at least one of the
由此，上述制备过程还可以包括：(1)使式1所示化合物与乙烯化试剂接触反应，生成式2所示化合物；(2)使式2所示化合物与氯化膦类化合物接触反应，生成式3所示化合物。Thus, the above preparation process may also include: (1) making the compound shown in formula 1 contact and react with vinylating reagent to generate the compound shown in formula 2; (2) making the compound shown in formula 2 contact and react with phosphine chloride compounds , generating the compound shown in formula 3.
以采用
Figure PCTCN2022139608-appb-000026
作为含乙烯基共聚单体为例，上述制备过程的反应式示意如下： to adopt
Figure PCTCN2022139608-appb-000026
As an example of a vinyl-containing comonomer, the reaction formula of the above-mentioned preparation process is shown as follows:
Figure PCTCN2022139608-appb-000027
Figure PCTCN2022139608-appb-000027
在一些实施例中，步骤(1)中，使含有式1所示化合物、乙烯化试剂、第一溶剂的第一混合体系在惰性气体氛围下进行回流反应；反应结束后，将体系冷却至室温，通过减压蒸馏除去溶剂，再进行柱层析纯化，得到式2所示化合物。其中，第一溶剂包括有机溶剂，优选包括甲苯、四氢呋喃和1，4-二氧六环中的至少一种。In some embodiments, in step (1), the first mixed system containing the compound shown in formula 1, the vinylating agent, and the first solvent is subjected to a reflux reaction under an inert gas atmosphere; after the reaction, the system is cooled to room temperature , the solvent was removed by distillation under reduced pressure, and then purified by column chromatography to obtain the compound shown in formula 2. Wherein, the first solvent includes an organic solvent, preferably at least one of toluene, tetrahydrofuran and 1,4-dioxane.
为进一步提高反应效率，第一混合体系还可以包含催化剂，该催化剂包括钯基催化剂，优选包括四(三苯基膦)钯、PdCl 2(dppf)、PdCl 2(PPh 3) 2中的至少一种。 In order to further improve the reaction efficiency, the first mixed system can also include a catalyst, which includes a palladium-based catalyst, preferably including at least one of tetrakis(triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 kind.
具体实施时，可以向第一反应器中加入式1所示化合物和第一溶剂，然后向其中加入乙烯化试剂和催化剂，即得到第一混合体系，然后在惰性气体氛围下回流反应过夜，然后将体系冷却至室温，通过减压蒸馏除去溶剂后，进行柱层析纯化，分离得到式2所示化合物。其中，柱层析过程中所用的洗脱剂可以是由石油醚与乙酸乙酯按照体积比2:1混合形成，利于分离出式2所示化合物。During specific implementation, the compound shown in Formula 1 and the first solvent can be added to the first reactor, and then the vinylating agent and the catalyst are added thereto to obtain the first mixed system, which is then refluxed and reacted overnight under an inert gas atmosphere, and then The system was cooled to room temperature, and the solvent was distilled off under reduced pressure, followed by purification by column chromatography, and the compound represented by formula 2 was isolated and obtained. Wherein, the eluent used in the column chromatography process can be formed by mixing petroleum ether and ethyl acetate at a volume ratio of 2:1, which is beneficial to the separation of the compound shown in formula 2.
在一些实施例中，步骤(2)中，在惰性气体氛围下，控制含有氯化膦类化合物和第二溶剂的第二混合体系的温度为0～30℃，例如0℃、5℃、10℃、15℃、20℃、25℃、30℃或其中的任意两者组成的范围，然后向其中加入式2所示化合物，然后升至室温进行反应，反应时间一般可以为5-10h；反应结束后，向体系中加水淬灭反应，然后加乙酸乙酯进行萃取，分别得到有机相 和水相，将有机相进行干燥后，再进行柱层析分离，得到式3所示化合物。其中，第二溶剂包括有机溶剂，例如包括呋喃类溶剂、甲酰胺类溶剂、甲苯中的至少一种，优选包括四氢呋喃、甲苯和N,N-二甲基甲酰胺中的至少一种。In some embodiments, in step (2), under an inert gas atmosphere, the temperature of the second mixed system containing the phosphine chloride compound and the second solvent is controlled to be 0-30°C, such as 0°C, 5°C, 10°C °C, 15 °C, 20 °C, 25 °C, 30 °C or any two of them, then add the compound shown in formula 2 to it, and then rise to room temperature for reaction, the reaction time can generally be 5-10h; After completion, add water to the system to quench the reaction, and then add ethyl acetate for extraction to obtain an organic phase and an aqueous phase, respectively, and dry the organic phase, then perform column chromatography separation to obtain the compound shown in formula 3. Wherein, the second solvent includes an organic solvent, such as at least one of furan solvents, formamide solvents, and toluene, preferably at least one of tetrahydrofuran, toluene, and N,N-dimethylformamide.
具体实施时，在惰性气体氛围下，可以先在第二反应器中加入氯化膦类化合物和第二溶剂，然后降温至0℃，维持0℃条件下，向其中滴加含有式2所示化合物和三乙胺的混合液，滴加完全后，再自然升温至室温进行反应。其中，可以将式2所示化合物和三乙胺溶于溶剂(如第二溶剂)中，形成含有式2所示化合物和三乙胺的混合液。During specific implementation, under an inert gas atmosphere, the phosphine chloride compound and the second solvent can be added to the second reactor first, then the temperature is lowered to 0°C, and the compound containing the formula 2 is added dropwise to it under the condition of maintaining 0°C. After the mixed solution of the compound and triethylamine was added dropwise completely, the temperature was naturally raised to room temperature for reaction. Wherein, the compound shown in formula 2 and triethylamine can be dissolved in a solvent (such as the second solvent) to form a mixed solution containing the compound shown in formula 2 and triethylamine.
本发明提供的二齿膦配体共聚物催化剂的制备方法，包括：按照上述有机膦配体聚合物的制备方法制得有机膦配体聚合物；将铑化合物和有机膦配体聚合物分散于第四溶剂中，在搅拌状态下进行反应，得到二齿膦配体共聚物催化剂。The preparation method of the bidentate phosphine ligand copolymer catalyst provided by the present invention comprises: preparing the organic phosphine ligand polymer according to the preparation method of the above-mentioned organic phosphine ligand polymer; dispersing the rhodium compound and the organic phosphine ligand polymer in In the fourth solvent, the reaction is carried out in a stirring state to obtain a bidentate phosphine ligand copolymer catalyst.
具体地，上述铑化合物可以包括铑盐，优选包括Rh(acac)(CO) 2、Rh(AcO) 2、RhCl 3、Rh(NO 3) 3、RhH(CO)(PPh 3) 3、[Rh(CO) 2Cl] 2、RhH(CO)(PPh 3) 3、[Rh 2(m-Cl) 2(cod) 2]、[Rh(cod) 2]BF 4中的至少一种，更优选包括Rh(CO) 2(acac)。 Specifically, the aforementioned rhodium compound may include rhodium salts, preferably including Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh At least one of (CO) 2 Cl] 2 , RhH(CO)(PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (cod) 2 ], [Rh(cod) 2 ]BF 4 , more preferably Includes Rh(CO) 2 (acac).
此外，第四溶剂包括有机溶剂，例如包括烷烃类、苯类、呋喃类、二氧六环中的至少一种，优选包括正己烷、环己烷、苯、甲苯、二甲苯、四氢呋喃和二氧六环中的一种或多种，更优选包括正己烷、四氢呋喃、甲苯中的至少一种。In addition, the fourth solvent includes an organic solvent, such as at least one of alkanes, benzenes, furans, and dioxane, preferably including n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, and dioxane. One or more of the six rings, more preferably at least one of n-hexane, tetrahydrofuran, and toluene.
在一些实施例中，铑化合物与有机膦配体聚合物的质量比可以为1:1～1:50，例如1:1、1:5、1:10、1:15、1:20、1:25、1:30、1:35、1:40、1:45、1:50或其中的任意两者组成的范围。In some embodiments, the mass ratio of the rhodium compound to the organophosphine ligand polymer can be 1:1 to 1:50, such as 1:1, 1:5, 1:10, 1:15, 1:20, 1 :25, 1:30, 1:35, 1:40, 1:45, 1:50 or any two of them.
此外，上述铑化合物与有机膦配体聚合物的反应可以在惰性气体氛围下进行，反应温度可以为50℃～200℃，例如50℃、60℃、80℃、100℃、120℃、150℃、180℃、200℃或其中的任意两者组成的范围，反应时间可以为1h～24h，例如1h、3h、5h、8h、10h、12h、15h、18h、20h、24h或其中的任意两者组成的范围。In addition, the reaction of the rhodium compound and the organic phosphine ligand polymer can be carried out under an inert gas atmosphere, and the reaction temperature can be 50°C to 200°C, such as 50°C, 60°C, 80°C, 100°C, 120°C, 150°C , 180°C, 200°C or any two of them, the reaction time can be 1h to 24h, such as 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 24h or any two of them range of composition.
本发明中，惰性气体氛围可以包括氮气，但不局限于此。In the present invention, the inert gas atmosphere may include nitrogen, but is not limited thereto.
具体地，在上述搅拌反应过程中，有机膦配体聚合物与铑发生配位，形成配合物，生成亚磷酸酯结构的二齿膦配体共聚物催化剂，其通式可表示为Rh/CPOL-(AQBP&VFC)，其中，Rh代表活性金属铑，CPOL表示“共聚物”，VFC代表乙烯基功能化的化合物(即含乙烯基共聚单体)，AQBP代表二齿膦配体，Rh/CPOL-(AQBP&VFC)表示由二齿磷配体与含乙烯基共聚单体共聚而成的有机膦配体聚合物(CPOL-(AQBP&VFC))与铑(Rh)配位形成的共聚物铑剂催化剂(即二齿膦配体共聚物催化剂)。Specifically, in the above stirring reaction process, the organophosphine ligand polymer coordinates with rhodium to form a complex to generate a bidentate phosphine ligand copolymer catalyst with a phosphite structure, and its general formula can be expressed as Rh/CPOL -(AQBP&VFC), where Rh represents the active rhodium metal, CPOL represents "copolymer", VFC represents vinyl-functionalized compounds (i.e., vinyl-containing comonomers), AQBP represents the bidentate phosphine ligand, Rh/CPOL- (AQBP&VFC) means a copolymer rhodium agent catalyst formed by the coordination of bidentate phosphorus ligands and vinyl-containing comonomers (CPOL-(AQBP&VFC)) and rhodium (Rh). bidentate phosphine ligand copolymer catalyst).
具体实施时，可以直接将反应后的体系应用于烯烃的氢甲酰化反应，或者，也可以对反应后的体系进行纯化，获得高纯度的二齿膦配体共聚物催化剂，再将其应用于烯烃的氢甲酰化反应。在一些具体实施例中，纯化过程包括：将反应后的体系进行离心分离，得到分离出的固相产物，将固相产物经甲苯洗涤后，再进行真空干燥，制得二齿膦配体共聚物催化剂。During specific implementation, the system after the reaction can be directly applied to the hydroformylation reaction of olefins, or the system after the reaction can be purified to obtain a high-purity bidentate phosphine ligand copolymer catalyst, which can then be applied to Hydroformylation of alkenes. In some specific embodiments, the purification process includes: centrifuging the reacted system to obtain the separated solid phase product, washing the solid phase product with toluene, and then vacuum drying to obtain bidentate phosphine ligand copolymerization material catalyst.
本发明中，通过上述制备过程，可一步反应生成含亚磷酸酯结构的二齿膦配体共聚物(即有机膦配体聚合物)，进而生成含亚磷酸酯结构的二齿膦配体共聚物催化剂，所用含乙烯基共聚单体等原料廉价易得，能够显著降低有机膦配体和二齿膦配体共聚物催化剂的制备成本，且制备过程简单，耗时短，产品收率高，以铑化合物中的铑计，二齿膦配体共聚物催化剂收率高于95％，可实现催化剂的规模化制备，即可以一次制备数克至数百克的二齿膦配体共聚物催化剂，且产品纯度高，不需要重结晶等操作，制得的催化剂可用于烯烃氢甲酰化反应，尤其可用于C 4-C 10的高碳烯烃的氢甲酰化反应，且二齿膦配体共聚物催化剂易于氢甲基化产物分离，从根本上解决烯烃(尤其是高碳烯烃)氢甲酰化反应工艺中反应产物与催化剂难以分离的难题，提高烯烃转化率和醛产物选择性。 In the present invention, through the above preparation process, a bidentate phosphine ligand copolymer containing a phosphite structure can be generated in one step (ie, an organic phosphine ligand polymer), and then a bidentate phosphine ligand copolymer containing a phosphite structure can be generated. The material catalyst, the raw materials such as vinyl-containing comonomers used are cheap and easy to obtain, can significantly reduce the preparation cost of organic phosphine ligands and bidentate phosphine ligand copolymer catalysts, and the preparation process is simple, time-consuming, and the product yield is high. Calculated by the rhodium in the rhodium compound, the yield of the bidentate phosphine ligand copolymer catalyst is higher than 95%, which can realize the large-scale preparation of the catalyst, that is, several grams to hundreds of grams of the bidentate phosphine ligand copolymer catalyst can be prepared at one time , and the product has high purity and does not require operations such as recrystallization. The prepared catalyst can be used for olefin hydroformylation, especially for the hydroformylation of C 4 -C 10 higher olefins, and the bidentate phosphine complex The bulk copolymer catalyst is easy to separate hydromethylation products, fundamentally solves the difficult problem of difficult separation of reaction products and catalysts in the hydroformylation reaction process of olefins (especially high-carbon olefins), and improves the conversion rate of olefins and the selectivity of aldehyde products.
为使本发明的目的、技术方案和优点更加清楚，下面将结合具体实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. Example. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1有机膦配体聚合物L1的制备The preparation of embodiment 1 organophosphine ligand polymer L1
本实施例中，有机膦配体聚合物L1为式4-1a所示化合物，其合成路线示意如下：In this example, the organophosphine ligand polymer L1 is a compound represented by formula 4-1a, and its synthetic route is shown as follows:
Figure PCTCN2022139608-appb-000028
Figure PCTCN2022139608-appb-000028
式4-1a的制备过程如下：The preparation process of formula 4-1a is as follows:
(1)参考专利文献CN113004326中的方法合成式1所示化合物；(1) Synthesize the compound shown in formula 1 with reference to the method in patent document CN113004326;
(2)取5g式1-1a所示化合物，将其加入反应器中，向其中加100mL甲苯，然后再加入12g乙烯基三正丁基锡和0.73g四(三苯基膦)钯，在氮气保护下回流反应过夜；然后将反应体系冷却至室温，通过减压蒸馏除去溶剂后，进行柱层析纯化，洗脱剂为石油醚：乙酸乙酯＝2:1，分离得到式2所示化合物(液体)，其核磁数据如下： 1H NMR(400MHz,DMSO)δ9.39(s,1H),7.16(dt,J＝11.2,8.2Hz,2H),6.60(d,J＝8.5Hz,1H),5.56(d,J＝1.4Hz,1H),5.18(dd,J＝11.0,1.4Hz,1H),5.10(d,J＝1.7Hz,1H),1.51(s,2H)， 1H NMR谱图见图1； (2) Take 5g of the compound shown in formula 1-1a, put it into the reactor, add 100mL of toluene to it, then add 12g of vinyl tri-n-butyltin and 0.73g of tetrakis (triphenylphosphine) palladium, under nitrogen protection The reaction was refluxed overnight; then the reaction system was cooled to room temperature, and after the solvent was removed by distillation under reduced pressure, column chromatography purification was carried out, and the eluent was petroleum ether: ethyl acetate=2:1, and the compound shown in formula 2 was isolated ( Liquid), its NMR data are as follows: 1 H NMR (400MHz, DMSO) δ9.39 (s, 1H), 7.16 (dt, J = 11.2, 8.2Hz, 2H), 6.60 (d, J = 8.5Hz, 1H) , 5.56(d, J=1.4Hz, 1H), 5.18(dd, J=11.0, 1.4Hz, 1H), 5.10(d, J=1.7Hz, 1H), 1.51(s, 2H), 1 H NMR spectrum See Figure 1 for the picture;
(3)取1.27g
Figure PCTCN2022139608-appb-000029
将其加入反应器中，在氮气保护下，向其中加6mL超干四氢呋喃，降温至0℃；另取400mg式2所示化合物和 418mg三乙胺溶于2mL超干四氢呋喃中，得到混合液，在0℃下将该混合液滴加到反应器中，然后自然升至室温，反应5～6h；再加入20mL水中淬灭，然后加入20mL乙酸乙酯进行萃取，经萃取得到的有机相经无水硫酸钠干燥后，再进行柱层析分离，得到式3-1a所示化合物(液体)，其核磁数据如下： 1H NMR(400MHz,CDCl 3)δ7.22(d,J＝8.5Hz,2H),7.14(dd,J＝17.4,11.0Hz,2H),7.03(d,J＝3.8Hz,5H),6.97(d,J＝8.5Hz,2H),6.92(d,J＝8.3Hz,5H),5.61(dd,J＝17.4,1.2Hz,2H),5.42(s,1H),5.34(dd,J＝11.0,1.2Hz,2H),5.15(s,0H),2.31(d,J＝7.2Hz,12H),2.21(d,J＝3.6Hz,12H),1.67(q,J＝9.1Hz,4H)， 1H-NMR谱图见图2， 31P-NMR谱图见图3； (3) Take 1.27g
Figure PCTCN2022139608-appb-000029
Add it into the reactor, add 6mL of ultra-dry tetrahydrofuran to it under the protection of nitrogen, and cool down to 0°C; another 400mg of the compound shown in formula 2 and 418mg of triethylamine are dissolved in 2mL of ultra-dry tetrahydrofuran to obtain a mixed solution. Add the mixture dropwise to the reactor at 0°C, then naturally rise to room temperature, and react for 5-6 hours; then add 20mL of water to quench, and then add 20mL of ethyl acetate for extraction, and the organic phase obtained by extraction is washed without After drying with sodium sulfate, column chromatography separation was carried out to obtain the compound (liquid) represented by formula 3-1a, and its NMR data is as follows: 1 H NMR (400MHz, CDCl 3 ) δ7.22 (d, J=8.5Hz, 2H), 7.14(dd, J=17.4, 11.0Hz, 2H), 7.03(d, J=3.8Hz, 5H), 6.97(d, J=8.5Hz, 2H), 6.92(d, J=8.3Hz, 5H), 5.61(dd, J=17.4, 1.2Hz, 2H), 5.42(s, 1H), 5.34(dd, J=11.0, 1.2Hz, 2H), 5.15(s, 0H), 2.31(d, J =7.2Hz, 12H), 2.21(d, J=3.6Hz, 12H), 1.67(q, J=9.1Hz, 4H), see Figure 2 for 1 H-NMR spectrum, see Figure 3 for 31 P-NMR spectrum ;
(4)取400mg式3-1a所示化合物，将其加入反应器中，向其中加500mg苯乙烯、45mg AIBN、9mL超干四氢呋喃，在氮气保护下于100℃反应24h；然后将体系温度冷却至室温，加20mL甲醇沉淀，然后过滤，将得到的固体产物经甲醇洗涤后，再进行真空干燥，得到式4-1a所示的有机膦配体聚合物L1，该有机膦配体共聚物L1的分子量为85000g/mol，式4-1a中，m＝40，n＝50，m:n＝1:1.25，该有机膦配体共聚物L1的 1H-NMR谱图见图4， 31P-NMR谱图见图5。 (4) Take 400mg of the compound shown in formula 3-1a, put it into the reactor, add 500mg of styrene, 45mg of AIBN, and 9mL of ultra-dry tetrahydrofuran to it, and react at 100°C for 24h under the protection of nitrogen; then cool the system temperature to room temperature, add 20 mL of methanol to precipitate, then filter, wash the obtained solid product with methanol, and then vacuum-dry to obtain the organophosphine ligand polymer L1 shown in formula 4-1a, the organophosphine ligand copolymer L1 The molecular weight is 85000g/mol, in formula 4-1a, m=40, n=50, m:n=1:1.25, the 1 H-NMR spectrum of this organophosphine ligand copolymer L1 is shown in Figure 4, 31 P -NMR spectrum is shown in Figure 5.
实施例2有机膦配体聚合物L2的制备The preparation of embodiment 2 organophosphine ligand polymer L2
本实施例中，有机膦配体聚合物L2为式4-2所示化合物，其合成路线示意如下：In this example, the organophosphine ligand polymer L2 is a compound shown in formula 4-2, and its synthetic route is shown as follows:
Figure PCTCN2022139608-appb-000030
Figure PCTCN2022139608-appb-000030
式4-2的制备过程如下：The preparation process of formula 4-2 is as follows:
按照实施例1中的步骤(1)～(3)制得式3-1a；Formula 3-1a was prepared according to steps (1) to (3) in Example 1;
取300mg式3-1a所示化合物，将其加入反应器中，向其中加1.22g三(4-乙烯基苯基)膦、35mg AIBN、15ml超干四氢呋喃，在氮气保护下于100℃反应24h；然后将体系温度冷却至室温，加30mL甲醇沉淀，然后过滤，将得到的固体产物经甲醇洗涤后，再进行真空干燥，得到式4-2所示的有机膦配体聚合物L2，该有机膦配体共聚物L2的分子量为91000g/mol，式4-2中，m＝36，n＝52，m:n＝1:1.44，该有机膦配体共聚物L2的 31P-NMR谱图见图6。 Take 300mg of the compound shown in formula 3-1a, put it into the reactor, add 1.22g of tris(4-vinylphenyl)phosphine, 35mg of AIBN, 15ml of ultra-dry tetrahydrofuran, and react at 100°C for 24h under the protection of nitrogen Then the system temperature is cooled to room temperature, add 30mL methanol precipitation, then filter, after the solid product that obtains is washed with methanol, carry out vacuum drying again, obtain the organic phosphine ligand polymer L2 shown in formula 4-2, this organic The molecular weight of the phosphine ligand copolymer L2 is 91000g/mol, in formula 4-2, m=36, n=52, m:n=1:1.44, the 31 P-NMR spectrum of the organophosphine ligand copolymer L2 See Figure 6.
实施例3二齿膦配体共聚物催化剂A的制备The preparation of embodiment 3 bidentate phosphine ligand copolymer catalyst A
取500mg有机膦配体聚合物L1，将其加入反应器中，向其中加50mg Rh(acac)(CO) 2、5mL四氢呋喃，在氮气保护下于80℃搅拌反应2h；然后将体系冷却至室温，加30mL甲苯，离心分离，将分离出的固相产物经甲苯洗涤3次后，再进行真空干燥，得到二齿膦配体共聚物催化剂A。 Take 500mg of organophosphine ligand polymer L1, add it to the reactor, add 50mg Rh(acac)(CO) 2 , 5mL tetrahydrofuran to it, stir and react at 80°C for 2h under the protection of nitrogen; then cool the system to room temperature , add 30mL toluene, centrifuge, the separated solid phase product is washed 3 times with toluene, and then carry out vacuum drying, obtain bidentate phosphine ligand copolymer catalyst A.
实施例4二齿膦配体共聚物催化剂B的制备The preparation of embodiment 4 bidentate phosphine ligand copolymer catalyst B
取500mg有机膦配体聚合物L2，将其加入反应器中，向其中加25mg Rh(acac)(CO) 2、5mL四氢呋喃，在氮气保护下80℃搅拌反应2h；然后将体系冷却至室温，加30mL甲苯，离心分离，将分离出的固相产物经甲苯洗涤3次后，再真空干燥，得到二齿膦配体共聚物催化剂B。 Take 500mg of organophosphine ligand polymer L2, add it to the reactor, add 25mg Rh(acac)(CO) 2 , 5mL tetrahydrofuran to it, stir and react at 80°C for 2h under nitrogen protection; then cool the system to room temperature, Add 30 mL of toluene, centrifuge, wash the separated solid phase product with toluene 3 times, and then vacuum-dry to obtain bidentate phosphine ligand copolymer catalyst B.
应用实施例1Application Example 1
向反应釜中加入8.5mg催化剂A和1mL浓度为3mol/L的1,3-丁二烯甲苯溶液，通入合成气加压至6MPa，在80℃下搅拌反应12h，制备得到1,6-己二醛；通过气相色谱内标法测得1,3-丁二烯的转化率为99.8％，1,6-己二醛的选择性为57.9％。Add 8.5 mg of Catalyst A and 1 mL of 1,3-butadiene toluene solution with a concentration of 3 mol/L into the reaction kettle, feed in synthesis gas and pressurize to 6 MPa, and stir and react at 80°C for 12 hours to prepare 1,6- Adipaldehyde: The conversion rate of 1,3-butadiene is 99.8% and the selectivity of 1,6-hexanedial is 57.9% as measured by the internal standard method of gas chromatography.
应用实施例2Application Example 2
向反应釜中加入20mg催化剂B和1ml浓度为3mol/L的1,3-丁二烯甲苯溶液，通入合成气加压至4MPa，在80℃下搅拌反应12h，制备得到1,6-己二醛；通过气相色谱内标法测得1,3-丁二烯的转化率为99.5％，1,6-己二醛的选择性为53.4％。Add 20 mg of Catalyst B and 1 ml of 1,3-butadiene toluene solution with a concentration of 3 mol/L into the reaction kettle, feed synthesis gas and pressurize to 4 MPa, and stir and react at 80°C for 12 hours to prepare 1,6-hexyl Dialdehyde: The conversion rate of 1,3-butadiene is 99.5% and the selectivity of 1,6-hexanedialdehyde is 53.4% as measured by the internal standard method of gas chromatography.
以上对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种有机膦配体聚合物的制备方法，其特征在于，包括：A preparation method of an organic phosphine ligand polymer, characterized in that, comprising:
    使二齿膦配体与含乙烯基共聚单体进行聚合反应，得到所述有机膦配体聚合物；其中，所述二齿膦配体包括式3所示化合物；The bidentate phosphine ligand is polymerized with a vinyl-containing comonomer to obtain the organic phosphine ligand polymer; wherein the bidentate phosphine ligand includes a compound shown in formula 3;
    Figure PCTCN2022139608-appb-100001
    Figure PCTCN2022139608-appb-100001
    其中，R 1和R 2各自独立地为含膦基团。 Wherein, R 1 and R 2 are each independently a phosphine-containing group.
  2. 根据权利要求1所述的有机膦配体聚合物的制备方法，其特征在于，式3中，R 1和R 2各自独立地选自如下取代基： The preparation method of organophosphine ligand polymer according to claim 1, is characterized in that, in formula 3, R 1 and R 2 are each independently selected from the following substituents:
    Figure PCTCN2022139608-appb-100002
    Figure PCTCN2022139608-appb-100002
  3. 根据权利要求1所述的有机膦配体聚合物的制备方法，其特征在于，所述含乙烯基共聚单体包括如下化合物中的至少一种：The preparation method of the organophosphine ligand polymer according to claim 1, wherein the vinyl-containing comonomer comprises at least one of the following compounds:
    Figure PCTCN2022139608-appb-100003
    Figure PCTCN2022139608-appb-100003
  4. 根据权利要求1所述的有机膦配体聚合物的制备方法，其特征在于， 所述二齿膦配体与所述含乙烯基共聚单体的摩尔比为1:(1～10)。The method for preparing an organophosphine ligand polymer according to claim 1, characterized in that, the molar ratio of the bidentate phosphine ligand to the vinyl-containing comonomer is 1:(1-10).
  5. 根据权利要求1所述的有机膦配体聚合物的制备方法，其特征在于，The preparation method of organophosphine ligand polymer according to claim 1, is characterized in that,
    所述聚合反应的条件为：温度为60～100℃，时间为2～6h；和/或，The conditions of the polymerization reaction are: the temperature is 60-100° C., and the time is 2-6 hours; and/or,
    所述聚合反应的过程包括：使含有式3所示化合物、含乙烯基共聚单体、第三溶剂的第三混合体系在惰性气体氛围下进行聚合反应，反应结束后，控制体系温度为室温，向其中加入甲醇进行沉淀，然后过滤，将得到的固体产物经甲醇洗涤后，再进行真空干燥，得到所述有机膦配体聚合物；其中，所述第三溶剂包括四氢呋喃、2-甲基四氢呋喃和甲苯中的至少一种。The process of the polymerization reaction includes: making the third mixed system containing the compound shown in formula 3, the vinyl-containing comonomer, and the third solvent carry out the polymerization reaction under an inert gas atmosphere. After the reaction is completed, the temperature of the control system is room temperature, Adding methanol to it for precipitation, then filtering, washing the obtained solid product with methanol, and then vacuum-drying to obtain the organic phosphine ligand polymer; wherein, the third solvent includes tetrahydrofuran, 2-methyltetrahydrofuran and at least one of toluene.
  6. 根据权利要求1所述的有机膦配体聚合物的制备方法，其特征在于，还包括：The preparation method of organophosphine ligand polymer according to claim 1, is characterized in that, also comprises:
    (1)使式1所示化合物与乙烯化试剂接触反应，生成式2所示化合物；(1) making the compound shown in formula 1 contact and react with vinylating reagent to generate the compound shown in formula 2;
    Figure PCTCN2022139608-appb-100004
    Figure PCTCN2022139608-appb-100004
    其中，式1中的X为卤素；Wherein, X in formula 1 is a halogen;
    (2)使式2所示化合物与氯化膦类化合物接触反应，生成所述式3所示化合物；(2) making the compound shown in formula 2 contact with the phosphine chloride compound to generate the compound shown in formula 3;
    Figure PCTCN2022139608-appb-100005
    Figure PCTCN2022139608-appb-100005
  7. 根据权利要求6所述的有机膦配体聚合物的制备方法，其特征在于，The preparation method of organophosphine ligand polymer according to claim 6, is characterized in that,
    步骤(1)中，使含有式1所示化合物、乙烯化试剂、第一溶剂的第一混合体系在惰性气体氛围下进行回流反应；反应结束后，将体系冷却至室温，通过减压蒸馏除去溶剂，再进行柱层析纯化，得到式2所示化合物；和/或，In step (1), the first mixed system containing the compound shown in formula 1, the vinylating agent, and the first solvent is subjected to reflux reaction under an inert gas atmosphere; after the reaction is completed, the system is cooled to room temperature and removed by distillation under reduced pressure. Solvent, then carry out column chromatography purification, obtain the compound shown in formula 2; And/or,
    步骤(2)中，在惰性气体氛围下，控制含有所述氯化膦类化合物和第二溶剂的第二混合体系的温度为0～30℃，向其中加入含有式2所示化合物和三乙胺的混合液，然后升至室温进行反应；反应结束后，向体系中加水淬灭反应，然后加乙酸乙酯进行萃取，分别得到有机相和水相，将有机相进行干燥 后，再进行柱层析分离，得到式3所示化合物。In step (2), under an inert gas atmosphere, the temperature of the second mixed system containing the phosphine chloride compound and the second solvent is controlled to be 0-30° C. After the reaction, add water to the system to quench the reaction, and then add ethyl acetate for extraction to obtain an organic phase and an aqueous phase respectively. After the organic phase is dried, the column Separated by chromatography, the compound shown in formula 3 was obtained.
  8. 根据权利要求7所述的有机膦配体聚合物的制备方法，其特征在于，The preparation method of organophosphine ligand polymer according to claim 7, is characterized in that,
    所述第一溶剂包括甲苯、四氢呋喃和1，4-二氧六环中的至少一种；和/或，The first solvent includes at least one of toluene, tetrahydrofuran and 1,4-dioxane; and/or,
    所述乙烯化试剂包括
    Figure PCTCN2022139608-appb-100006
    中的至少一种；和/或，     The vinylating reagents include
    Figure PCTCN2022139608-appb-100006
    at least one of; and/or,
    所述第一混合体系还包含催化剂，所述催化剂包括四(三苯基膦)钯、PdCl 2(dppf)、PdCl 2(PPh 3) 2中的至少一种；和/或， The first mixed system also includes a catalyst, the catalyst includes at least one of tetrakis(triphenylphosphine) palladium, PdCl 2 (dppf), PdCl 2 (PPh 3 ) 2 ; and/or,
    所述第二溶剂包括四氢呋喃、甲苯和N,N-二甲基甲酰胺中的至少一种。The second solvent includes at least one of tetrahydrofuran, toluene and N,N-dimethylformamide.
  9. 一种二齿膦配体共聚物催化剂的制备方法，其特征在于，包括：A preparation method of a bidentate phosphine ligand copolymer catalyst, characterized in that it comprises:
    按照权利要求1-8任一项所述的有机膦配体聚合物的制备方法制得有机膦配体聚合物；According to the preparation method of the organophosphine ligand polymer described in any one of claims 1-8, an organophosphine ligand polymer is obtained;
    将铑化合物和所述有机膦配体聚合物分散于第四溶剂中，在搅拌状态下进行反应，得到所述二齿膦配体共聚物催化剂。Dispersing the rhodium compound and the organic phosphine ligand polymer in the fourth solvent and reacting in a stirring state to obtain the bidentate phosphine ligand copolymer catalyst.
  10. 根据权利要求9所述的二齿膦配体共聚物催化剂的制备方法，其特征在于，The preparation method of bidentate phosphine ligand copolymer catalyst according to claim 9, is characterized in that,
    所述第四溶剂包括正己烷、环己烷、苯、甲苯、二甲苯、四氢呋喃和二氧六环中的一种或多种；和/或，The fourth solvent includes one or more of n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran and dioxane; and/or,
    所述铑化合物包括Rh(acac)(CO) 2、Rh(AcO) 2、RhCl 3、Rh(NO 3) 3、RhH(CO)(PPh 3) 3、[Rh(CO) 2Cl] 2、RhH(CO)(PPh 3) 3、[Rh 2(m-Cl) 2(cod) 2]、[Rh(cod) 2]BF 4中的至少一种；和/或， The rhodium compound includes Rh(acac)(CO) 2 , Rh(AcO) 2 , RhCl 3 , Rh(NO 3 ) 3 , RhH(CO)(PPh 3 ) 3 , [Rh(CO) 2 Cl] 2 , At least one of RhH(CO)(PPh 3 ) 3 , [Rh 2 (m-Cl) 2 (cod) 2 ], [Rh(cod) 2 ]BF 4 ; and/or,
    所述铑化合物与所述有机膦配体聚合物的质量比为1:1～1:50；和/或，The mass ratio of the rhodium compound to the organophosphine ligand polymer is 1:1 to 1:50; and/or,
    所述在搅拌状态下进行反应的反应温度为50℃～200℃；和/或，The reaction temperature for the reaction under stirring is 50°C to 200°C; and/or,
    所述在搅拌状态下进行反应的反应时间为1h～24h。The reaction time for the reaction under stirring state is 1h-24h.
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