CN116178623A - Phosphine ligand organic polymer and application thereof - Google Patents

Phosphine ligand organic polymer and application thereof Download PDF

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CN116178623A
CN116178623A CN202111421292.2A CN202111421292A CN116178623A CN 116178623 A CN116178623 A CN 116178623A CN 202111421292 A CN202111421292 A CN 202111421292A CN 116178623 A CN116178623 A CN 116178623A
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phosphine ligand
organic
ligand
organic polymer
polymerization
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李存耀
严丽
丁云杰
钱磊磊
姜淼
马雷
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a phosphine ligand organic polymer, a preparation method and application thereof, wherein the phosphine ligand organic polymer is obtained by olefine group functionalized multi-tooth organic phosphine ligand self-polymerization or single-tooth organic phosphine ligand mixed polymerization with olefine group functionalized multi-tooth organic phosphine ligand. The multi-tooth organic phosphine ligand in the phosphine ligand organic polymer skeleton has stronger steric hindrance effect and adjustable electronic effect, so that the prepared phosphine ligand organic polymer can be used as an excellent carrier for preparing a heterogeneous reaction catalyst. In the prepared metal supported catalyst, the metal components are highly dispersed in the organic polymer in a single-point mode, so that the utilization efficiency of metal is greatly improved; the catalyst prepared by taking the polymer as a carrier has higher regioselectivity of a product due to the stereo effect of the immobilized diphosphine ligand. The domain-limiting effect of the carrier skeleton is such that the ligands embedded in the carrier skeleton have a stronger steric effect than the homogeneous ligands.

Description

Phosphine ligand organic polymer and application thereof
Technical Field
The invention belongs to the field of material preparation and heterogeneous catalysis, and particularly relates to a phosphine ligand organic polymer, and a preparation method and application thereof.
Background
Porous organic polymers (porous organic polymers, POPs) are a new class of materials with high specific surface area, abundant pore structure, low skeletal density and good thermal stability, emerging in recent years from purely organic molecular building blocks connected by covalent bonds (Chem Soc Rev,2012, 41, 2083-2094). The diversity of the organic chemical synthesis method provides rich synthesis paths and construction modes for the construction of organic molecular building block precursors and molecular networks, the final material can have corresponding properties by purposefully introducing functionalized organic molecular building blocks, and the pore properties of the material can be regulated and controlled by regulating the structures of the precursors. The organic microporous polymers are all connected through covalent bonds, so that the molecular network structure is more stable while the pore properties of the material are maintained. Porous organic materials can be generally divided into four types according to different construction ideas: super cross-linked polymers (Hyper-CrosslinkedPolymers, HCPs), inherently microporous polymers (Polymers of Intrinsic Microporosity, PIMs), conjugated microporous polymers (Conjugated Microporous Polymers, CMPs), covalent organic frameworks (Covalent Organic Frameworks, COFs).
Phosphine ligands, especially multidentate phosphine ligands, have important application in reactions such as homogeneous transition metal catalyzed hydroformylation reaction, coupling reaction, hydrogenation reaction, hydrosilylation reaction, CO2 cycloaddition reaction and the like, and the yield and selectivity of target products can be effectively regulated and controlled through reasonable design and modification of the electronic effect and the three-dimensional structure of the phosphine ligands. Patent CN1319580a describes several homogeneous bidentate phosphite ligands with large steric hindrance, and the homogeneous catalysts obtained after coordination of these ligands with Rh, co, etc. achieve good stereoselectivity (better product ortho-iso) in hydroformylation of higher olefins. However, the homogeneous reaction catalyst is not easy to recycle and the production cost is high. In the patent CN102911021A, a composite catalytic system consisting of rhodium complex and biphosphine ligand with biphenyl skeleton or binaphthyl skeleton and triphenylphosphine or phosphite triphenyl ester monophosphine ligand is used as a catalyst, and normal aldehyde has higher selectivity in the hydroformylation of linear olefins, so that the consumption of expensive biphosphine ligand is reduced, but the catalytic system is still homogeneous, and the catalyst is not reused. The patent CN1986055A also utilizes the coordination of bisphosphite and triphenylphosphine with Rh to form a catalytic system, the molar ratio of n-butyraldehyde to isobutyraldehyde in the hydroformylation reaction of propylene is more than 20, the service life of bisphosphite ligand is obviously prolonged, the dosage of triarylphosphine is obviously reduced, but the reaction is essentially homogeneous, and the problem of difficult recycling of the catalyst is also faced.
In 2014, shore-harvest, ding Yunjie et al (chem. Commun.,2014,50,11844) polymerized tris (4-vinylbenzene) phosphine by solvothermal polymerization, named POLs, the catalyst prepared from the organic polymer had good activity in olefin hydroformylation, and the active components were not easily lost, but the catalyst prepared from the polymer as a carrier did not have good stereoselectivity in high-carbon olefin hydroformylation due to polymerization of the monophosphine ligand. The applicant synthesizes a vinyl functionalized Biphephos diphosphine ligand for the first time in the early stage, and copolymerizes the vinyl functionalized Biphephos ligand and PPh3 ligand, so as to prepare the copolymer self-supported multiphase Rh/CPOL-bp & PPh3 catalyst. The catalyst can convert low-cost internal olefin into normal aldehyde with higher added value in high regioselectivity (the normal-iso ratio of the product is close to 98:2). And through fine adjustment of catalyst preparation parameters such as copolymerization proportion, the catalyst can efficiently catalyze the hydroformylation of propylene to prepare n-butyraldehyde (Catal. Sci. Technology., 2016,6,2143-2149; green Chem.,2016,18,2995-3005). However, the synthesis procedure of the vinyllbiphos ligand is too complicated, and the total yield of seven parts is about 15%. How to obtain functionalized phosphine ligands more simply still faces a great challenge. On the other hand, the porous organic polymer has wide application prospect in the field of homogeneous catalysis multiphase, however, the porous organic matter is used as a carrier of multiphase reaction, and the problems to be solved and overcome are also exposed, such as poor thermal stability of polymer materials, complicated material synthesis process and the like, which are sensitive to air and water, and the organic polymer is not high enough in reaction selectivity as a carrier, and is difficult to commonly and simply introduce target monomers and the like.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a phosphine ligand organic polymer, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a phosphine ligand organic polymer, a preparation method and application thereof, wherein the phosphine ligand organic polymer carrier is obtained by self-polymerizing or compounding with an olefin group functionalized monodentate organic phosphine ligand through a method of bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization.
The functional group olefin group in the phosphine ligand used for polymerization is vinyl functional group; the alkene-based functionalized monodentate organic phosphine ligand is a triphenylphosphine ligand containing vinyl, and the alkene-based functionalized multidentate organic phosphine ligand is a bidentate organic phosphine ligand containing vinyl.
The multi-tooth organic phosphine ligand (one or more than two of A-J) containing olefin groups and one or more than two of the following synthetic routes are provided:
Figure BDA0003377548560000031
/>
Figure BDA0003377548560000041
the single-tooth organic phosphine ligand containing olefin is selected from one or more than two of the following:
Figure BDA0003377548560000042
/>
Figure BDA0003377548560000051
/>
Figure BDA0003377548560000061
/>
Figure BDA0003377548560000071
the phosphine ligand organic polymer has a hierarchical pore structure, and the specific surface area is 10-3000 m 2 Preferably in the range of 100 to 1000m per gram 2 Per gram, the pore volume is 0.1-10.0 cm 3 Preferably 0.5 to 2.0cm per gram 3 Per g, pore size distribution is in the range of 0.01 to 100.0nm, preferably 0.1 to 10.0nm;
the preparation method of the phosphine ligand organic polymer comprises the following steps: fully dissolving and mixing a multidentate organic phosphine ligand and/or a monodentate organic phosphine ligand, and initiating an olefin group in the organic phosphine ligand to generate a polymerization reaction by a free radical initiator by adopting a solvothermal polymerization method to generate a phosphine-containing organic polymer with a multistage pore structure;
the preparation method comprises the following specific steps:
a) Adding a multidentate organic phosphine ligand and/or a monodentate organic phosphine ligand, adding or not adding a cross-linking agent and then adding a free radical initiator into a solvent under the atmosphere of 273-473K of inert gas, 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 synthesis autoclave, standing or stirring for 1-100 hours under the inert gas atmosphere of 273-473K for polymerization reaction to obtain a phosphine-containing organic polymer;
c) Vacuum pumping the solvent of the phosphine-containing organic polymer obtained in the step b) at room temperature to obtain a phosphine ligand organic polymer with a multistage pore structure;
the solvent in the step a) is one or more than two of water, methanol, ethanol, methylene dichloride, chloroform, benzene, toluene, xylene or tetrahydrofuran; the cross-linking agent in the step a) is one or more than two of styrene, divinylbenzene, stilbene, ethylene, propylene or butadiene; the free radical initiator is one or more than two of tert-butyl hydroperoxide, azodiisobutyronitrile, azodiisoheptonitrile, cyclohexanone peroxide and dibenzoyl peroxide.
The molar ratio of the monodentate organic phosphine ligand to the multidentate organic phosphine ligand in step a) is 0.01:1-100:1, preferably 1:1-100:1, and the molar ratio of the monodentate organic phosphine ligand to the crosslinking agent is 0.01:1-10:1, preferably 0.1:1-1:1, and the molar ratio of the monodentate organic phosphine ligand to the free radical initiator is 300:1-10:1, preferably 100:1-10:1 when the crosslinking agent is added. The concentration of the monodentate organophosphine ligand in the solvent prior to polymerization into the organic polymer is in the range of 0.01-1000g/L, preferably 0.1-10g/L; the inert gas in steps a) and b) is selected from Ar, he, N 2 And CO 2 One or two or more of them.
The phosphine ligand polymer obtained by the method can be selected from bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, the polymerization operation temperature range is 273-473K, and the phosphine ligand polymer after polymerization can be used as a carrier of a heterogeneous catalyst for preparing catalysts for reactions such as olefin hydroformylation/amination, suzuki coupling, heck coupling, stille coupling, negishi coupling, hydrogenation or ammoniation.
The preparation method of the hydromethylamine catalyst comprises the following steps: preparing an active metal precursor into an impregnating solution, adding the impregnating solution into a carrier, adopting an equal volume impregnating or excessive solution impregnating method, and finally preparing a catalyst suitable for olefin hydroformylation reaction through drying;
the active component is one or more than two of Rh, co, ir, pd or Pt, wherein RhThe precursor of (C) is RhH (CO) (PPh) 3 ) 3 、Rh(CO) 2 (acac)、RhCl 3 、Rh(CH 3 COO) 2 One or two or more of them; the precursor of Co is Co (CH 3 COO) 2 、Co(CO) 2 (acac)、Co(acac) 2 、CoCl 2 One or two or more of them; the precursor of Ir is Ir (CO) 3 (acac)、Ir(CH 3 COO) 3 、Ir(acac) 3 、IrCl 4 One or two or more of them; the precursor of Pd is Pd (CH) 3 COO) 2 、Pd(acac) 2 、PdCl2、Pd(PPh 3 ) 4 、PdCl 2 (CH 3 CN) 2 One or two or more of them; the precursor of Pt is Pt (acac) 2 、PtCl 4 、PtCl 2 (NH 3 ) 2 One or two or more of them; the metal loading in the catalyst ranges from 0.01 to 10wt%, preferably from 0.1 to 2wt%.
The solvent used for preparing the impregnating solution is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform;
the impregnation operation temperature is 243-373K, the catalyst is dried by spray drying or vacuum drying, the drying operation temperature is 303-403K, the spray drying adopts N2 and/or Ar gas as working gas, and the absolute pressure of operation is maintained below 10kPa during vacuum drying.
The reaction principle of the invention:
the vinyl functional multidentate phosphine ligand designed by the invention has a stronger steric hindrance effect, and meanwhile, the electron withdrawing group connected with P enables the multidentate ligand to have proper electron and steric effect, and a large amount of exposed P with lone pair electrons is contained in an organic polymer skeleton formed by self-polymerization or copolymerization of the vinyl multidentate phosphine ligand and the vinyl monodentate phosphine ligand. The multi-tooth organic phosphine ligand in the phosphine ligand organic polymer skeleton has stronger steric hindrance effect and adjustable electronic effect, so that the prepared phosphine ligand organic polymer can be used as an excellent carrier for preparing a heterogeneous reaction catalyst. In the prepared metal supported catalyst, the metal components are highly dispersed in the organic polymer in a single-point mode, so that the utilization efficiency of metal is greatly improved; the catalyst prepared by taking the polymer as a carrier has higher regioselectivity of a product due to the stereo effect of the immobilized diphosphine ligand. The domain-limiting effect of the carrier skeleton is such that the ligands embedded in the carrier skeleton have a stronger steric effect than the homogeneous ligands. The prepared catalyst can obviously improve the regioselectivity of aldehyde which is a hydroformylation/amination reaction product, and the proportion of normal aldehyde in the product is higher.
The phosphine ligand organic polymer prepared by the invention has a developed hierarchical pore structure, a high specific surface area and a large pore volume, and the skeleton contains rich P functional sites, so that the polymer has good application prospects in the fields of gas storage and adsorption, photoelectric conversion, catalysis and the like. The multi-tooth organic phosphine ligand in the phosphine ligand organic polymer skeleton has stronger steric hindrance effect and adjustable electronic effect, so that the prepared phosphine ligand organic polymer can be used as an excellent carrier for preparing a heterogeneous reaction catalyst. In the prepared metal supported catalyst, the metal components are highly dispersed in the organic polymer in a single-point mode, so that the utilization efficiency of metal is greatly improved; the catalyst prepared by taking the polymer as a carrier has higher regioselectivity of a product due to the stereo effect of the immobilized diphosphine ligand. The domain-limiting effect of the carrier skeleton is such that the ligands embedded in the carrier skeleton have a stronger steric effect than the homogeneous ligands.
The beneficial effects of the invention are as follows:
the invention provides a phosphine ligand organic polymer and a preparation method thereof, wherein 10 vinyl multidentate phosphine ligands are designed in the claims, the upper half parts of olefin groups of A-E are the same, the industrial preparation steps are already completed, the upper half parts of F-J are the same, and the phosphine ligand organic polymer can be produced in factories. Thus, compared with the earlier applied patent of the subject group, the 10 key vinyl polydentate ligands related to the subject group have obvious cost advantages, and the synthetic route is relatively simple, and the yield is obviously higher than that of the previous scheme.
The heterogeneous catalyst prepared by taking the phosphine ligand organic polymer as the carrier can solve the problems of poor stability and selectivity, serious loss of metal components and the like in the heterogeneous process of certain reaction homogeneous catalysts for a long time. For example, the prepared heterogeneous hydroformylation catalyst is suitable for reaction processes such as bubbling beds, slurry beds, fixed beds, trickle beds and the like, has high catalyst activity and good stability, has the most outstanding advantage of high selectivity of normal aldehyde in product aldehyde, and can provide a new industrialized technology for olefin hydroformylation.
Drawings
The synthetic route pattern of 10 vinyl multidentate phosphine ligands referred to in the claims in figure 1.
FIG. 2 is a schematic representation of the technical route for the self-polymerization of F multidentate phosphine ligands in FIG. 1.
FIG. 3 is a schematic representation of a typical cross-linking agent used in the polymerization.
FIG. 4 is a plot of N2 physisorption of the phosphine ligand organic polymer catalyst obtained in example 1.
FIG. 5 is a pore size distribution diagram of the phosphine ligand organic polymer catalyst obtained in example 1.
Detailed Description
The following examples are given to better illustrate the invention but do not limit the scope of the invention.
The specific synthesis steps and yields of the A-E monomers are as follows:
Figure BDA0003377548560000101
intermediate 1 can be prepared according to the procedure of document (Tetrahedron Letters,2010,51,27 2497-2499):
Figure BDA0003377548560000102
8g of intermediate 1 was added to freshly prepared phosphorus ylide reagent (13.4 g of potassium tert-butoxide was added to a mixture of 42g of p-methyltriphenylphosphine bromide and 400ml of tetrahydrofuran under argon at 10 ℃ C., stirred for 3 hours) to give key intermediate 2: />
Figure BDA0003377548560000111
10mmol of intermediate 2 (29.8 g) and 30g of triethylamine in 1L of tetrahydrofuran are added dropwise under argon at-5 ℃
Figure BDA0003377548560000112
(see, for details, catal. Sci. Technology. 2016,6 (7): 2143-2149), and the reaction was continued for 5 hours after completion of the dropwise addition. Adding 200mL of saturated ammonium chloride solution at 0 ℃ for annihilation reaction, concentrating an oil layer, passing through a silica gel column, eluting with a 20:1 eluent to obtain a monomer A (the product is confirmed by nuclear magnetism and high-resolution mass spectrum), and the total yield of five steps is 40%.
By the same mole number
Figure BDA0003377548560000113
Substitute for->
Figure BDA0003377548560000114
Monomers B-E (the products are confirmed by nuclear magnetism and high-resolution mass spectrum) can be obtained respectively, and the yields are 45%,37%,43% and 35% respectively.
The specific synthesis steps and yields of F-J monomers are as follows:
Figure BDA0003377548560000115
55.5mmol of K3Fe (CN) 6 and 198mmol of KOH were dissolved in 300mL of water at 25℃to form a mixture, and the mixture was added dropwise to 55.5mmol of 4-bromo-3-tert-butylphenol (CAS No. 103114-68-2) dissolved therein and reacted at room temperature for 5 hours. After the reaction, 500ml of ethyl acetate was used to extract the reaction mixture 5 times, and the mixture was distilled under reduced pressure to obtain a coupling product for use.
Under the protection of argon at 0 ℃, 4.2mmol of the coupling product, 4.2mmol of triethylamine, 10mmol of tri-tert-butyl vinyl tin and 0.1mmol of triphenylphosphine palladium are dissolved in 50ml of normal propyl alcohol, the temperature is raised to 100 ℃ and stirred for 5 hours, 50ml of diethyl ether is used for extracting the product after the reaction is finished, and the key intermediate is obtained by column chromatography separation3：
Figure BDA0003377548560000121
30mmol of intermediate 3 (10.5 g) and 300mmol of triethylamine are dissolved in 500mL of toluene at-5℃under argon, 60mmol of which are added dropwise
Figure BDA0003377548560000122
The reaction was continued for 5 hours after completion of the dropwise addition. 400mL of saturated ammonium chloride solution is added at 0 ℃ for annihilation reaction, an oil layer is concentrated and passes through a silica gel column, and the monomer F (the product is confirmed by nuclear magnetism and high-resolution mass spectrum) can be obtained after eluting with 40:1 eluent, and the total yield of three steps is 30%.
By the same mole number
Figure BDA0003377548560000123
Substitute for->
Figure BDA0003377548560000124
The monomer G-J can be obtained (the product is confirmed by nuclear magnetism and high-resolution mass spectrum) with the yields of 32%,26%,28% and 23% respectively.
Example 1
Preparation of phosphine ligand organic polymer: under 298K and inert gas Ar atmosphere, 1.0g of a vinyl diphosphine ligand (product F in the drawing, the product is confirmed by nuclear magnetism and high resolution mass spectrum) and 50g of a monodentate ligand tris (4-vinylbenzene) phosphine are dissolved in 500.0ml of tetrahydrofuran solvent, 0.01 g of a radical initiator azodiisobutyronitrile is added to the solution, and the mixture is stirred for 2 hours to obtain a prepolymer. The prepolymer was transferred to an autoclave and polymerized for 24 hours by solvothermal polymerization under 373K and inert gas Ar atmosphere. And (3) cooling the polymerization kettle to room temperature, and vacuum-pumping the solvent at room temperature to obtain the phosphine-containing organic polymer carrier (specific surface 1315m < 2 >/g, pore size distribution 0.1-10 nm) copolymerized by the diphosphine ligand and the tri (4-vinylbenzene) phosphine organic monomer.
Preparation of a hydroformylation catalyst: 3.13 mg of rhodium acetylacetonato carbonyl (Rh (CO) was weighed out 2 (acac)) was dissolved in 10.0ml of tetrahydrofuran solvent, and 1.0g of the above-obtained mixture was addedAnd (3) stirring the mixture for 15 hours under the protection atmosphere of 298K and inert gas Ar, and vacuum pumping the solvent at room temperature to obtain the solid phase catalyst, wherein the catalyst is a multiple coordination bond type solid phase catalyst.
Example 2
In example 2, the procedure for the preparation of the polymer support was the same as in example 1, except that 50.0 g of the vinyl diphosphine ligand (product F in the drawing) was weighed out, and no comonomer tris (4-vinylbenzene) phosphine was added, and FIG. 2 is a schematic diagram of the autopolymerization route of the diphosphine ligand F.
Example 3
In example 3, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1 except that 0.005 g of the radical initiator azobisisobutyronitrile was weighed out instead of 0.01 g of the radical initiator azobisisobutyronitrile.
Example 4
In example 4, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1, except that 50.0ml of tetrahydrofuran solvent was used instead of 500.0ml of tetrahydrofuran solvent.
Example 5
In example 5, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1, except that 500.0ml of dichloromethane solvent was used instead of 500.0ml of tetrahydrofuran solvent.
Example 6
In example 6, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1, except that 353K polymerization temperature was used instead of 373K polymerization temperature.
Example 7
In example 7, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1, except that the polymerization time of 6 hours was used instead of the polymerization time of 24 hours.
Example 8
In example 8, the phosphine ligand organic polymer and catalyst preparation procedure was the same as in example 1, except that 10.0 g of styrene was further added as a crosslinking agent.
Example 9
In example 9, the phosphine ligand organic polymer and catalyst synthesis procedure were the same as in example 1, except that the same number of moles of cobalt acetylacetonate dicarbonyl instead of rhodium acetylacetonate carbonyl was weighed out and dissolved in 10.0ml of tetrahydrofuran solvent.
Example 10
In example 10, the phosphine ligand organic polymer and catalyst synthesis procedure were the same as in example 1, except that the same number of moles of iridium acetylacetonate tricarbonyl instead of rhodium acetylacetonate carbonyl was weighed out and dissolved in 10.0ml of tetrahydrofuran solvent.
Example 11
In example 11, the phosphine ligand organic polymer and catalyst synthesis procedure were the same as in example 1, except that the same molar number of palladium dichloride was weighed out in place of rhodium acetylacetonate carbonyl and dissolved in 10.0ml of tetrahydrofuran solvent.
Example 12
In example 12, 1.0g of A in FIG. 1 was weighed out to replace the diphosphine ligand in example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 13
In example 13, 1.0g of the diphosphine ligand of example 1 was replaced with B of FIG. 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 14
In example 14, 1.0g of C in FIG. 1 was weighed out in place of the diphosphine ligand in example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 15
In example 15, 1.0g of the D of FIG. 1 was weighed out to replace the diphosphine ligand of example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 16
In example 16, 1.0g of E in FIG. 1 was weighed out to replace the diphosphine ligand in example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 17
In example 17, 1.0G of G of FIG. 1 was weighed out to replace the diphosphine ligand of example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 18
In example 18, 1.0g of H in FIG. 1 was weighed out in place of the diphosphine ligand in example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 19
In example 19, 1.0g of the diphosphine ligand of example 1 was replaced with I of FIG. 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 20
In example 20, 1.0g of J in FIG. 1 was weighed out to replace the diphosphine ligand in example 1, and the rest of the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1.
Example 21
In example 21, the phosphine ligand organic polymer and catalyst synthesis procedure was the same as in example 1, except that the suspension polymerization method was used instead of the bulk polymerization method.
Example 22
1g of the catalyst synthesized in examples 1 to 21 was placed in a 500ml reaction vessel, 4g of N-methylpyrrolidone was added as a reaction solvent, 25mmol of ammonium chloride, 25mmol of 1-hexene was added as a reactant, 3MPaCO was charged, and the reaction was carried out at 130℃for 24 hours. The product was analyzed by HP-7890N gas chromatography, using an HP-5 capillary column and an FID detector, using N-propanol as an internal standard. The reaction results are shown in Table 1.
TABLE 1 specific surface area of the catalysts synthesized in examples 1-21 and the results of the hexenehydromethylamine reaction
Figure BDA0003377548560000141
Figure BDA0003377548560000151
/>

Claims (8)

1. A phosphine ligand organic polymer characterized in that:
phosphine ligand organic polymer is obtained by self-polymerization of olefin group functionalized multidentate organic phosphine ligand through a method of bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization; or, the polymer is obtained by mixing polymerization of an olefine-based functionalized multidentate organic phosphine ligand and an olefine-based functionalized monodentate organic phosphine ligand by a solution polymerization, suspension polymerization or emulsion polymerization method; the functional group olefin group in the olefin group functionalized multi-tooth organic phosphine ligand is a vinyl functional group, and the olefin group functionalized multi-tooth organic phosphine ligand is a bidentate organic phosphine ligand containing vinyl;
the olefine group functionalized monodentate organic phosphine ligand is a triphenylphosphine ligand containing vinyl.
2. Phosphine ligand polymer according to claim 1, characterized in that: the multi-tooth organic phosphine ligand containing olefin group is one or more than two of the following structural formulas A-J;
their synthetic routes are respectively as follows:
Figure FDA0003377548550000021
/>
Figure FDA0003377548550000031
3. phosphine ligand polymer according to claim 1, characterized in that: the single-tooth organic phosphine ligand containing olefin is selected from one or more than two of the following:
Figure FDA0003377548550000032
/>
Figure FDA0003377548550000041
/>
Figure FDA0003377548550000051
/>
Figure FDA0003377548550000061
the molar ratio of the monodentate organic phosphine ligand to the multidentate organic phosphine ligand is 0.01:1-100:1, preferably 1:1-100:1.
4. The phosphine ligand organic polymer of claim 1 wherein:
the preparation method of the phosphine ligand organic polymer comprises the following steps: dissolving and mixing the polydentate organic phosphine ligand or dissolving and mixing the polydentate organic phosphine ligand and the monodentate organic phosphine ligand, and initiating olefin groups in the organic phosphine ligand to generate polymerization reaction by a free radical initiator by adopting a solvothermal polymerization method to generate a phosphine-containing organic polymer with a multistage pore structure;
the preparation method comprises the following specific steps:
a) Adding a multidentate organic phosphine ligand or a multidentate organic phosphine ligand and a monodentate organic phosphine ligand into a solvent under the inert atmosphere of 273-473K, adding or not adding a cross-linking agent, adding a free radical initiator, 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 synthesis autoclave, and standing or stirring for 1-100 hours under the inert atmosphere of 273-473K to perform polymerization reaction to obtain a phosphine-containing organic polymer;
c) And b) pumping out the solvent of the phosphine-containing organic polymer obtained in the step b) to obtain the phosphine ligand organic polymer with the multistage pore structure.
5. The method of manufacturing according to claim 4, wherein: the solvent in the step a) is one or more than two of water, methanol, ethanol, methylene dichloride, chloroform, benzene, toluene, xylene or tetrahydrofuran; the cross-linking agent in the step a) is one or more than two of styrene, divinylbenzene, stilbene, ethylene, propylene or butadiene; the free radical initiator is one or more than two of tert-butyl hydroperoxide, azodiisobutyronitrile, azodiisoheptonitrile, cyclohexanone peroxide and dibenzoyl peroxide.
6. The method of claim 4 or 5, wherein: the molar ratio of monodentate organophosphine ligand to multidentate organophosphine ligand in step a) is from 0.01:1 to 100:1, preferably from 1:1 to 100:1,
in the case of crosslinker addition, the molar ratio of multidentate organophosphine ligand to crosslinker is from 0.01:1 to 10:1, preferably from 0.1:1 to 1:1, and the molar ratio of multidentate organophosphine ligand to free radical initiator is from 300:1 to 10:1, preferably from 100:1 to 10:1;
the concentration of the multidentate organophosphine ligand in the solvent prior to polymerization into the organic polymer ranges from 0.01 to 1000g/L, preferably from 0.1 to 10g/L;
the inert atmosphere gas in step a) or b) is selected from Ar, he, N 2 And CO 2 One or two or more of them.
7. Phosphine ligand organic polymer according to any of claims 1-6, characterized in that: the organic polymer has a hierarchical pore structure, and the specific surface area is 10-3000 m 2 Preferably in the range of 100 to 1000m per gram 2 Per gram, the pore volume is 0.1-10.0 cm 3 Preferably 0.5 to 2.0cm per gram 3 The pore size distribution is 0.01 to 100.0nm, preferably 0.1 to 10.0nm.
8. Use of a phosphine ligand organic polymer as defined in claims 1-7, characterized in that:
the phosphine ligand organic polymer can be used as a carrier of a heterogeneous catalyst for preparing catalysts for reactions such as olefin hydroformylation/methylamination, suzuki coupling, heck coupling, stille coupling, negishi coupling, hydrogenation or ammoniation.
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