CN107537562B - Phosphine-ionic liquid-containing organic copolymer heterogeneous catalyst, preparation and application thereof - Google Patents
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Abstract
The invention provides a phosphine-ionic liquid-containing organic porous copolymer heterogeneous catalyst and preparation and application thereof, wherein the phosphine-ionic liquid organic porous copolymer is prepared by copolymerizing olefin functionalized organic phosphine ligands and olefin functionalized ionic liquid, Lewis acidic metal salt is added or not added, and when the Lewis acidic metal salt is added, metal ions in the metal salt and naked phosphine in the organic porous copolymer form coordinate bonds, so that the heterogeneous catalyst is finally obtained. The catalyst is suitable for reactors such as fixed bed, slurry bed, kettle type reactor and trickle bed. The catalyst provided by the invention is applied to a coupling reaction process of an epoxy compound and carbon dioxide, integrates respective advantages of an ionic liquid (used as a ring-opening nucleophilic reagent) and a phosphine-metal coordination compound (activated epoxy compound), and can be used for preparing the catalyst which has both extremely high activity and high stability by modulating the proportion of a comonomer and the metal load.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysis, and particularly relates to a phosphine-ionic liquid-containing organic copolymer heterogeneous catalyst, and preparation and application thereof, and particularly can be applied to coupling reaction of carbon dioxide and an epoxy compound.
Background
The design and synthesis of porous organic polymer materials are becoming one of the new hotspots in the research field of porous materials. Compared with the traditional inorganic microporous materials and metal organic framework Materials (MOFs), the framework of the organic microporous polymer is composed of pure organic molecules, and the organic microporous polymer is connected with each other through covalent bonds and has open pore channels and excellent pore structures. More importantly, due to the diversity of organic chemical synthesis methods, abundant synthesis paths and construction modes are provided for the construction of an organic molecule network, the material can have corresponding properties by purposefully introducing functionalized organic molecules, and the pore properties of the material can be regulated and controlled by adjusting the structure of the organic molecules. In addition, in most cases, covalently linked organic microporous polymers have a more robust molecular network structure while the material pore structure is maintained, as compared to the instability of non-covalently linked molecular networks.
The cyclic carbonates mainly include products of five-membered rings and six-membered rings. Among them, five-membered rings, particularly propylene carbonate and ethylene carbonate, are most widely used. Ethylene carbonate is an excellent polar high-boiling point solvent and surfactant raw material, and is widely applied to the fields of plastics, printing and dyeing, polymer synthesis, gas separation, electrochemistry and the like. In Europe and Japan, a great deal of ethylene carbonate is used to replace acrylamide, urea system and water glass as a pollution-free soil stabilizer in concrete engineering; ethylene carbonate is directly used in korea to remove acid gases (carbon dioxide, sulfur dioxide, hydrogen sulfide, etc.) from natural gas. In recent years, processes for synthesizing dimethyl carbonate, ethylene glycol, functional polymers and the like by taking vinyl carbonate as a raw material are developed abroad, show wide application of the processes in the field of organic synthesis, and are potential organic chemical basic raw materials.
The earliest industrial preparation of ethylene carbonate or propylene carbonate was a synthetic reaction of ethylene glycol or propylene glycol with phosgene, which is prohibited at present due to the extreme toxicity of phosgene and severe environmental pollution. Therefore, the catalytic coupling addition reaction of carbon dioxide and epoxy compound becomes the mainstream reaction process at present.
At present, the catalysts reported in literature for synthesizing cyclic carbonates from carbon dioxide and epoxy compounds mainly include homogeneous catalysts such as transition metal complexes, ionic liquids, quaternary ammonium salts, quaternary phosphonium salts and alkali metal salts, and heterogeneous catalysts such as metal oxides, molecular sieves, functional organic polymers and metal organic framework materials (Chemical reviews, 1996,96, 951; Chemical Communications,2009,1, 26; Green Chemistry,2010,12,1514), which have high activity, but are difficult to separate from products, complicated in process, and trace metal impurities cause fatal defects to downstream products. The heterogeneous catalyst has the problems of low activity, addition of a soluble auxiliary agent or an organic solvent, easy loss of active components, poor reusability and the like.
The vinyl polymerized porous organic polymer material has the characteristics of high specific surface area, multi-level pore structure, easy modification and the like. As a catalytic material, the active center in the pore channel can be utilized in a large amount due to the unique swelling property. Shownet al reported that vinyl-polymerized metalloporphyrin porous materials were used to catalyze the coupling addition of carbon dioxide and epoxy compounds to produce cyclic carbonates (Journal of Catalysis,2016,338, 202-209). Deng Weiqiao et al reported that porous organic polymers based on salen-metal units formed by sonogashira coupling are useful for catalyzing the coupling addition of carbon dioxide and epoxy compounds to cyclic carbonates (Nature Communications,2013,4, 1960). However, the above catalytic system needs to add quaternary ammonium salt cocatalyst, which results in difficult separation and purification of the product. In order to solve the problems, a multifunctional double-activation mode is formed by simultaneously introducing a coordination phosphine site (used for coordination of Lewis acidic metal ions and induction of ring opening by action of the Lewis acidic metal ions and epoxy oxide compounds) and an ionic liquid (ring opening nucleophile), so that the synergistic catalytic activity is improved, the metal is effectively immobilized, and the loss of the metal is prevented.
Disclosure of Invention
The invention aims to provide a phosphine-ionic liquid-containing organic porous copolymer heterogeneous catalyst, and preparation and application thereof, and the catalyst is particularly applied to coupling addition reaction of carbon dioxide and an epoxy compound.
The technical scheme of the invention is as follows:
a phosphine-ionic liquid-containing organic porous copolymer heterogeneous catalyst is prepared by copolymerizing olefin functionalized organic phosphine ligand and olefin functionalized ionic liquid, adding or not adding Lewis acidic metal salt into the obtained copolymer, and forming coordinate bonds between metal ions in the metal salt and exposed phosphine in the phosphine-ionic liquid-containing organic porous copolymer when adding the Lewis acidic metal salt to obtain the product of the phosphine-ionic liquid-containing organic porous copolymer heterogeneous catalyst.
The Lewis acid metal salt is one or more than two of halides of Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth metal, and MX is used as the halidenWherein M is a metal element, X ═ Cl, Br, I; n is a positive integer from 1 to 3; the loading amount of the metal elements in the catalyst is 0.01-10 wt%.
The olefin of the olefin-functionalized organophosphine ligand and the olefin-functionalized ionic liquid is functionalized to be a terminal olefin-based functional group, preferably a vinyl group.
The organic phosphine ligand containing terminal olefin group is preferably bidentate phosphite organic phosphine ligand containing vinyl group, triphenylphosphine ligand containing vinyl group; the ionic liquid containing terminal olefin is preferably imidazole ionic liquid.
The alkene-functionalized organophosphine ligand is selected from the group consisting of:
the ionic liquid is selected from:
the phosphine-ionic liquid-containing organic porous copolymer is obtained by a solvent thermal polymerization method; the phosphine-ionic liquid-containing organic porous copolymer has a hierarchical pore structure and a specific surface area of 100-3000 m2The volume of the pores is 0.1-5.0 cm3(ii)/g, the pore size distribution is 0.2 to 50.0 nm.
The invention also provides a preparation method of the heterogeneous catalyst, which comprises the following steps of mixing the olefin functionalized organic phosphine ligand and the olefin functionalized ionic liquid, initiating the polymerization reaction of the organic phosphine ligand and the olefin group in the ionic liquid by a free radical initiator by adopting a solvent thermal polymerization method to generate the phosphine-ionic liquid-containing organic porous copolymer with a hierarchical pore structure, and adding or not adding Lewis acidic metal salt into the obtained copolymer to obtain the heterogeneous catalyst;
adding Lewis acidic metal salt is that dissolving Lewis acidic metal salt in solvent, adding phosphine-ionic liquid organic porous copolymer, stirring to make metal ions in Lewis acidic metal salt and exposed phosphine in phosphine-ionic liquid organic porous copolymer form coordinate bond, and evaporating volatile solvent to obtain heterogeneous catalyst.
The method comprises the following specific operation steps:
a) adding an olefin functionalized organic phosphine ligand and an olefin functionalized ionic liquid into an organic solvent at 273-473K under an inert gas atmosphere, adding or not adding a cross-linking agent, adding a free radical initiator, mixing, and stirring the mixture for 0.1-100 hours, wherein the preferable stirring time range is 0.1-1 hour;
b) transferring the mixed solution prepared in the step a) into a synthesis autoclave, standing for 1-100 hours at 273-473K in an inert gas atmosphere by adopting a solvent thermal polymerization method to perform a polymerization reaction, thereby obtaining an organic copolymer containing phosphine-ionic liquid;
c) vacuum-pumping the solvent from the organic copolymer obtained in the step b) at room temperature to obtain an organic copolymer containing naked phosphine and ionic liquid with a hierarchical pore structure, namely an organic porous copolymer containing phosphine-ionic liquid;
d) adding the organic porous copolymer obtained in the step c) into a solvent containing Lewis acidic metal salt at 273-473K under an inert gas atmosphere, stirring for 0.1-100 hours, preferably for 0.1-1 hour, and removing the organic solvent in vacuum to obtain a heterogeneous catalyst;
the heterogeneous catalyst containing the phosphine-ionic liquid organic porous copolymer is obtained according to the operations of the steps a) to c) or the steps a) to d).
The organic solvent in the step a) is one or more than two of benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane or trichloromethane; the cross-linking agent is one or more than two of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3, 5-triethylalkynyl benzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile;
the molar ratio of the organic phosphine ligand to the ionic liquid in the step a) is 0.01: 1-100: 1; when the cross-linking agent is added, the molar ratio of the organic phosphine ligand to the cross-linking agent is 0.01: 1-10: 1; the molar ratio of the organic phosphine ligand to the free radical initiator is 300: 1-10: 1; before the organic porous copolymer is polymerized, the concentration of the organic phosphine ligand in the organic solvent is 0.01-1000 g/L;
in the step d), the solvent is one or more than two of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane, the metal elements of the Lewis acidic metal salt are one or more than two of Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth metals, wherein the Zn salt is ZnX2The Al salt is AlX3Ag salt is AgX, Au salt is AuX, Ca salt is CaX2The Rh salt is RhX3The Ir salt is IrX3Wherein X ═ Cl, Br, I.
According to the present invention there is also provided the use of a heterogeneous catalyst as described above in a coupling reaction between an epoxy compound and carbon dioxide.
The Lewis acidic metal salt is coordinated and bonded with phosphine of an organic polymer, and all elements of rare earth metal can be coordinated with the Lewis acidic metal salt. Thus, the rare earth metals described herein include, but are not limited to, yttrium and scandium.
The Lewis acid metal salt is Lewis acid.
The reaction principle of the invention is as follows:
the invention will typically employ a bisphosphine ligand or a monophosphine ligand (e.g., Biphephos, PPh)3) The organic copolymer is polymerized to form an organic copolymer with high specific surface area and a hierarchical pore structure by a solvent thermal polymerization method in an autoclave, and the organic copolymer has a large amount of exposed phosphine containing lone electron pairs in a framework, so that the organic copolymer can be used as a catalyst carrier to form coordinate bonds with active transition metal ions to form catalytic active sites and has the function of stabilizing metal centers. And ionic liquid bookThe copolymer has activity of catalyzing the coupling of the epoxy compound and the carbon dioxide, so the copolymer can also be directly used as an active catalyst. In the catalyst, the organic phosphine has double functions of a carrier and a ligand, the ionic liquid is a main active component, and the Lewis acidic metal salt plays a role of a cocatalyst. The active metal component is highly dispersed in the organic phosphine copolymer carrier in a single atom form, so that the utilization efficiency of the metal is greatly improved. And the active components are not easy to lose, and the service life of the catalyst is long.
The invention has the beneficial effects that:
the heterogeneous catalyst framework contains multidentate and monodentate organic phosphine ligand structural units, wherein the organic phosphine ligand enables higher exposed phosphine to exist on the surface of the copolymer, active metal atoms or ions form coordination bonds with the exposed phosphine on the copolymer, and active components are not easy to lose. The copolymer has a porous structure with high specific surface area, has dual functions of a carrier and a ligand, the active metal component is highly dispersed in the organic phosphine copolymer carrier in a single atom form, the utilization efficiency of metal is greatly improved, and the active metal component and another functional component in the polymer form a synergistic catalytic action with ionic liquid, so that the catalytic activity is greatly improved.
The multi-stage hole structure phosphine-ionic liquid organic copolymer heterogeneous catalyst provided by the invention is applied to the synthesis of cyclic carbonate through the coupling addition reaction of carbon dioxide and ethylene oxide, integrates the advantages of ionic liquid (used as a ring-opening nucleophilic reagent) and phosphine-metal coordination compound (activated epoxy compound), can enable the obtained catalyst to have both extremely high activity and higher stability by adjusting the proportion of comonomer and the metal load, reduces the cost of the industrial production of cyclic carbonate, has good stability, is simple and efficient in separation of products and catalysts, and provides a new industrial catalyst for the production of the cyclic carbonate.
Drawings
FIG. 1 is a diagram of a typical alkylene-functionalized phosphine ligand;
FIG. 2 is a typical olefin-based functionalized ionic liquid;
FIG. 3 is a schematic diagram of a polymerization technique route.
FIG. 4 is a cross-linking agent used in the polymerization.
FIG. 5 shows a catalyst13C，31P spectrum.
FIG. 6 is a graph at N2Thermogravimetric curve of catalyst under atmosphere.
Detailed Description
The following examples illustrate the invention better without limiting its scope.
Example 1
Under the protection of 298K and inert gas, 10.0 g of Vinyl-PPh3The monomer (FIG. 1, L1) was dissolved in 100.0mL of tetrahydrofuran solvent, 2.0g of divinylimidazole (FIG. 2, M1) was added, and 1.0 g of azobisisobutyronitrile, a radical initiator, was added to the above solution and stirred for 2 hours. The stirred solution was transferred to an autoclave and polymerized for 24h by thermal solvent polymerization under 373K and inert gas atmosphere. Cooling the polymerized solution to room temperature, and removing the solvent in vacuum at room temperature to obtain Vinyl-PPh3And a divinylimidazole organic monomer. FIG. 3 is a schematic diagram of a polymerization technique route. Weighing 1 g of ZnCl2Dissolving in 10.0mL of toluene solvent, adding 10.0 g of the organic copolymer prepared above, stirring the mixture for 24h under the protection of 298K and inert gas, and then vacuumizing the solvent at room temperature to obtain the multifunctional heterogeneous catalyst applied to the coupling addition reaction of carbon dioxide and epoxy compounds.
Example 2
In example 2, except that 10.0 g of the comonomer Vinyl-Biphephos monomer (FIG. 1, L2) was weighed out in place of the Vinyl PPh3The monomer and the rest of the catalyst synthesis process are the same as in example 1.
Example 3
In example 3, the catalyst synthesis procedure was the same as in example 1 except that 2.0g of divinylbenzimidazole monomer (FIG. 2, M4) was weighed instead of divinylimidazole monomer.
Example 4
In example 4, the catalyst preparation process was the same as in example 1 except that 50.0mL of tetrahydrofuran solvent was used instead of 100.0mL of tetrahydrofuran solvent.
Example 5
In example 5, the catalyst preparation process was the same as in example 1 except that 100.0mL of a tetrahydrofuran solvent was replaced with 100.0mL of a dichloromethane solvent.
Example 6
In example 6, the catalyst preparation was the same as in example 1 except that 393K instead of 373K polymerization temperature was used.
Example 7
In example 7, the catalyst preparation was the same as in example 1 except that the 24h polymerization time was replaced by 12h polymerization time.
Example 8
In example 8, the catalyst preparation was the same as in example 1 except that 10.0 g of divinylbenzene (FIG. 4, N1) was additionally added.
Example 9
In example 9, except that 1 gram of AlCl was weighed3Dissolved in 10.0mL of toluene solvent and the rest of the catalyst preparation was the same as in example 1.
Claims (9)
1. A heterogeneous catalyst containing phosphine-ionic liquid organic porous copolymer, which is characterized in that: the phosphine-ionic liquid-containing organic porous copolymer is prepared by copolymerizing olefin functionalized organic phosphine ligands and olefin functionalized ionic liquid, Lewis acidic metal salt is added into the obtained copolymer, when the Lewis acidic metal salt is added, metal ions in the metal salt and phosphine exposed in the phosphine-ionic liquid-containing organic porous copolymer form coordinate bonds, and the obtained product is a heterogeneous catalyst containing the phosphine-ionic liquid-containing organic porous copolymer;
the alkene-functionalized organophosphine ligand is selected from the group consisting of:
the ionic liquid is selected from:
2. the heterogeneous catalyst of claim 1 wherein: the Lewis acid metal salt is one or more than two of halides of Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth metal, and MX is used as the halidenWherein M is a metal element, X = Cl, Br, I; n = a positive integer from 1-3; the loading amount of the metal elements in the catalyst is 0.01-10 wt%.
3. The heterogeneous catalyst of claim 1 wherein:
when the olefin-functionalized organophosphine ligand is selected as L2, the ionic liquid may also be selected from:
4. the heterogeneous catalyst of claim 1 wherein: the phosphine-ionic liquid-containing organic porous copolymer is obtained by a solvent thermal polymerization method; the phosphine-ionic liquid-containing organic porous copolymer has a hierarchical pore structure and a specific surface area of 100-3000 m2The volume of the pores is 0.1-5.0 cm3(ii)/g, the pore size distribution is 0.2 to 50.0 nm.
5. A preparation method of the heterogeneous catalyst of any one of claims 1 to 4, wherein the heterogeneous catalyst is prepared by mixing an olefin functionalized organic phosphine ligand and an olefin functionalized ionic liquid, initiating a polymerization reaction between the organic phosphine ligand and an olefin group in the ionic liquid by a free radical initiator by adopting a solvent thermal polymerization method to generate a phosphine-ionic liquid-containing organic porous copolymer with a hierarchical pore structure, and adding Lewis acidic metal salt into the obtained copolymer to obtain the heterogeneous catalyst;
adding Lewis acidic metal salt is that dissolving Lewis acidic metal salt in solvent, adding phosphine-ionic liquid organic porous copolymer, stirring to make metal ions in Lewis acidic metal salt and exposed phosphine in phosphine-ionic liquid organic porous copolymer form coordinate bond, and evaporating volatile solvent to obtain heterogeneous catalyst.
6. A method of manufacturing as claimed in claim 5, wherein:
the method comprises the following specific operation steps:
a) adding an olefin functionalized organic phosphine ligand and an olefin functionalized ionic liquid into an organic solvent at 273-473K under an inert gas atmosphere, adding or not adding a cross-linking agent, adding a free radical initiator, mixing, and stirring the mixture for 0.1-100 hours;
b) transferring the mixed solution prepared in the step a) into a synthesis autoclave, standing for 1-100 hours at 273-473K in an inert gas atmosphere by adopting a solvent thermal polymerization method to perform a polymerization reaction, thereby obtaining an organic copolymer containing phosphine-ionic liquid;
c) vacuum-pumping the solvent from the organic copolymer obtained in the step b) at room temperature to obtain an organic copolymer containing naked phosphine and ionic liquid with a hierarchical pore structure, namely an organic porous copolymer containing phosphine-ionic liquid;
d) adding the organic porous copolymer obtained in the step c) into a solvent containing Lewis acidic metal salt at 273-473K under an inert gas atmosphere, stirring for 0.1-100 hours, and removing the organic solvent in vacuum to obtain a heterogeneous catalyst;
the heterogeneous catalyst containing the phosphine-ionic liquid organic porous copolymer is obtained according to the operations of the steps a) to d).
7. The method of claim 6, wherein: the organic solvent in the step a) is one or more than two of benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane or trichloromethane; the cross-linking agent is one or more than two of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3, 5-triethylalkynyl benzene; the free radical initiator is one or more than two of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile;
the molar ratio of the organic phosphine ligand to the ionic liquid in the step a) is 0.01: 1-100: 1; when the cross-linking agent is added, the molar ratio of the organic phosphine ligand to the cross-linking agent is 0.01: 1-10: 1; the molar ratio of the organic phosphine ligand to the free radical initiator is 300: 1-10: 1; before the organic porous copolymer is polymerized, the concentration of the organic phosphine ligand in the organic solvent is 0.01-1000 g/L;
in the step d), the solvent is one or more than two of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane, the metal elements of the Lewis acidic metal salt are one or more than two of Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth metals, wherein the Zn salt is ZnX2The Al salt is AlX3Ag salt is AgX, Au salt is AuX, Ca salt is CaX2The Rh salt is RhX3The Ir salt is IrX3Wherein X = Cl, Br, I.
8. The method of claim 6, wherein: the stirring time in the step a) is 0.1-1 hour; the stirring time in the step d) is 0.1-1 hour.
9. Use of a heterogeneous catalyst according to any of claims 1 to 4 in a coupling reaction between an epoxy compound and carbon dioxide.
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| CN103657450A (en) * | 2013-11-08 | 2014-03-26 | 江南大学 | Polyvinyl acetate/polyion liquid semi-interpenetrating polymer network film and thermosetting preparation method thereof |
| CN105367541A (en) * | 2014-08-11 | 2016-03-02 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate through polyionic liquid nanometer catalysis cycloaddition reaction |
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| CN103657450A (en) * | 2013-11-08 | 2014-03-26 | 江南大学 | Polyvinyl acetate/polyion liquid semi-interpenetrating polymer network film and thermosetting preparation method thereof |
| CN105367541A (en) * | 2014-08-11 | 2016-03-02 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate through polyionic liquid nanometer catalysis cycloaddition reaction |
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