CN107537562A - The organic copolymer heterogeneous catalyst of ionic liquid containing phosphine and its preparation and application - Google Patents
The organic copolymer heterogeneous catalyst of ionic liquid containing phosphine and its preparation and application Download PDFInfo
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Abstract
The present invention provides a kind of Porous-Organic copolymer heterogeneous catalyst of ionic liquid containing phosphine and its preparation and application, the phosphine ionic liquid Porous-Organic copolymer is formed by the organophosphorus ligand of olefin functionalities and the ionic liquid copolymerization of olefin functionalities, add or be added without Lewis acid metal salts, when adding Lewis acid metal salts, metal ion in metal salt forms coordinate bond with phosphine exposed in Porous-Organic copolymer, finally gives heterogeneous catalyst.Such catalyst is suitable for the reactors such as fixed bed, slurry bed system, tank reactor and trickle bed.Catalyst provided by the invention is applied in the coupling reaction technique of epoxide and carbon dioxide, combine the respective advantage of ionic liquid (as open loop nucleopilic reagent) and phosphine metal complex (activation epoxide), pass through modulation comonomer ratio and content of metal, the catalyst of acquisition can be made both there is high activity, the double dominant with higher stability.
Description
Technical field
Field of the present invention belongs to heterogeneous catalysis field, and in particular to one kind is urged containing phosphine-ionic liquid organic copolymer multiphase
Agent and its preparation and application, specifically can apply in carbon dioxide and epoxide coupling reaction.
Background technology
The design synthesis of porous organic polymer material is increasingly becoming one of new focus of porous material research field.With biography
The inorganic microporous material of system is compared with metal-organic framework material (MOFs), and the skeleton of organic microporous polymer is by pure organic
Molecule is formed, and between each other by covalent key connection, has open duct and excellent pore structure.Importantly, due to
The diversity of organic chemical synthesis method, abundant synthesis path and building mode are provided for the structure of organic molecule network,
It can make material that there is corresponding property by the organic molecule of the introducing functionalization of purpose, by the knot for adjusting organic molecule
Structure can be with the porous of controlled material.In addition, in most cases, the molecular network with being connected into by non-covalent bond
Unstability compare, pass through organic microporous polymer of covalent key connection, while material pore structure is maintained, molecule
Network structure is more firm.
Cyclic carbonate mainly includes the product of five-membered ring and hexatomic ring.Wherein again with five-membered ring particularly propene carbonate
It is most widely used with ethylene carbonate.Ethylene carbonate is that a kind of excellent polar high-boiling solvent and surfactant are former
Material, it is widely used in the fields such as plastics, printing and dyeing, Polymer Synthesizing, gas separation and electrochemistry.In Europe and Japan, largely
Ethylene carbonate is used for substituted acrylamide, urea system and waterglass as non-harmful soil quality stabilizing in concrete works
Agent；Sour gas (carbon dioxide, sulfur dioxide and the hydrogen sulfide in removing natural gas are used directly in South Korea's ethylene carbonate
Deng).In recent years, foreign countries are developed using ethylene carbonate as works such as Material synthesis dimethyl carbonate, ethylene glycol, functional polymers
Skill, its extensive use in organic synthesis field is illustrated, be a kind of potential organic chemical industry's basic material.
Earliest preparation of industrialization ethylene carbonate or propene carbonate are to be closed using ethylene glycol or propane diols with phosgene
Into reaction, serious pollution is produced due to phosgene severe toxicity and to environment, this method has been prohibited from using at present.So catalysis dioxy
Changing the coupling addition reaction of carbon and epoxide turns into current main flow course of reaction.
At present, the catalyst on carbon dioxide and epoxide synthesizing annular carbonate of document report mainly includes
The homogeneous catalysts such as transient metal complex, ionic liquid, quaternary ammonium salt, quaternary alkylphosphonium salts and alkali metal salt and metal oxide, divide
The heterogeneous catalyst such as son sieve, feature organic polymer and metal-organic framework material (Chemical Review, 1996,96,
951；Chemical Communications,2009,1,26；Green Chemistry, 2010,12,1514) it is above-mentioned homogeneously to urge
Agent activity is higher, but separates with product difficulty, complex process, and trace metal impurity fatal lack can be caused to downstream product
Fall into.Above-mentioned heterogeneous catalyst then exist activity it is relatively low, it is necessary to add soluble auxiliary agent or organic solvent, active component is easy to run off,
The problems such as repeat performance is bad.
The porous organic polymer material of vinyl polymerization has the spies such as high-specific surface area, hierarchical porous structure and easy modification
Point.As catalysis material, due to its unique swelling behavior, the activated centre in its duct can largely be utilized.Xiao Fengshou etc.
The metalloporphyrin porous material for reporting vinyl polymerization is used to be catalyzed carbon dioxide and epoxide coupling addition ring-type
Carbonic ester (Journal of Catalysis, 2016,338,202-209).Deng Weiqiao etc. reports even by sonogashira
The porous organic polymer based on salen- metal units that connection is formed is used to be catalyzed carbon dioxide and epoxide coupling adds
Into cyclic carbonate processed (Nature Communications, 2013,4,1960).But above-mentioned catalyst system and catalyzing need to add quaternary ammonium
Salt co-catalyst, cause product separating-purifying difficult.To solve the above problems, we are by introducing coordination phosphine site simultaneously
(being coordinated for Lewis acid metal ions, open loop is induced with epoxide oxygen compound effects) and ionic liquid (open loop nucleophilic
Reagent), the bis-activated pattern of multi-functional property is formed, had both improved concerted catalysis activity, and effectively immobilized metal, prevent
The loss of metal.
The content of the invention
It is an object of the invention to provide one kind to contain phosphine-ionic liquid Porous-Organic copolymer heterogeneous catalyst and its preparation
And application, it is applied particularly in carbon dioxide and epoxide coupling addition reaction.
The technical scheme is that：
One kind contains phosphine-ionic liquid Porous-Organic copolymer heterogeneous catalyst, the phosphine-ionic liquid Porous-Organic copolymerization
Thing is formed by the organophosphorus ligand of olefin functionalities and the ionic liquid copolymerization of olefin functionalities, is added in obtained copolymer
Enter or be added without Lewis acid metal salts, when adding Lewis acid metal salts, the metal ion in metal salt is with containing phosphine-ion
Exposed phosphine forms coordinate bond in liquid Porous-Organic copolymer, and products therefrom is containing phosphine-ionic liquid Porous-Organic copolymer
Heterogeneous catalyst.
The Lewis acid metal salts are selected from Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, the halogenation of Mg and rare earth metal
It is more than one or both of thing, halide MXnRepresent, wherein M is metallic element, X=Cl, Br, I；N=1-3's is just whole
Number；Metallic element loading is 0.01~10wt% in catalyst.
The olefin functionalities of the organophosphorus ligand of the olefin functionalities and the ionic liquid of olefin functionalities turn to
The alkylene functional group of end, preferably vinyl.
Organophosphorus ligand containing terminal olefin base is preferably the bidentate phosphites organophosphorus ligand containing vinyl, contained
There is the triphenylphosphine ligand of vinyl；The described ionic liquid containing terminal olefin is preferably glyoxaline ion liquid.
The organophosphorus ligand of the olefin functionalities is selected from：
The ionic liquid is selected from：
It is described to be obtained containing phosphine-ionic liquid Porous-Organic copolymer using solvent thermal polymerization method；It is described to contain phosphine-ionic liquid
Body Porous-Organic copolymer has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously containing macropore, mesopore and micro-
Hole, pore volume are 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
The present invention also provides a kind of preparation method of above-mentioned heterogeneous catalyst, including:The heterogeneous catalyst is by alkene
After the organophosphorus ligand of function dough and the ionic liquid mixing of olefin functionalities, using solvent thermal polymerization method, through freedom
Base initiator triggers the alkylene in organophosphorus ligand and ionic liquid that polymerisation occurs, and generates and contains with hierarchical porous structure
Phosphine-ionic liquid Porous-Organic copolymer, Lewis acid metal salts is added or be added without in obtained copolymer, obtain multiphase
Catalyst；
The situation for adding Lewis acid metal salts is that Lewis acid metal salts are dissolved in solvent, adds phosphine-ionic liquid
Body Porous-Organic copolymer, stirring, the metal ion in Lewis acid metal salts is set to be copolymerized with phosphine-ionic liquid Porous-Organic
Exposed phosphine forms coordinate bond in thing, boils off volatile solvent afterwards and obtains heterogeneous catalyst.
Concrete operation step includes：
A) under 273~473K, inert gas atmosphere, in organic solvent, the organophosphite ligand of olefin functionalities is added
The ionic liquid of body and olefin functionalities, add or do not add crosslinking agent, add radical initiator, will be mixed after mixing
Compound stirs 0.1~100 hour, and preferable mixing time scope is 0.1~1 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere,
Using solvent thermal polymerization method, stand 1~100 hour and carry out polymerisation, obtain a kind of organic copolymer containing phosphine-ionic liquid
Thing；
C) organic copolymer for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain with multi-stage porous
The organic copolymer containing exposed phosphine and ionic liquid of structure, i.e. the Porous-Organic copolymer containing phosphine-ionic liquid；
D) under 273~473K, inert gas atmosphere, in the solvent containing Lewis acidic metal salt, step is added
C) the Porous-Organic copolymer obtained, stir 0.1~100 hour, preferable mixing time is 0.1~1 hour, and vacuum has extracted
Solvent, obtain heterogeneous catalyst；
According to step a)-c) or step a)-d) operation obtain the heterogeneous catalysis containing phosphine-ionic liquid Porous-Organic copolymer
Agent.
Organic solvent described in step a) is in benzene, toluene, methanol, ethanol, tetrahydrofuran, dichloromethane or chloroform
It is one or more kinds of；The crosslinking agent be styrene, ethene, propylene, divinylbenzene, dimethoxymethane, diiodomethane,
It is more than one or both of paraformaldehyde or the acetylenylbenzenes of 1,3,5- tri-；The radical initiator be cyclohexanone peroxide,
Dibenzoyl peroxide, TBHP, the one or more of azodiisobutyronitrile or ABVN；
The mol ratio of organophosphorus ligand and ionic liquid described in step a) is 0.01:1~100:1；It is crosslinked in addition
In the case of agent, the mol ratio of organophosphorus ligand and crosslinking agent is 0.01:1~10:1；Organophosphorus ligand and radical initiator
Mol ratio be 300:1~10:1；Before aggregating into Porous-Organic copolymer, the concentration of organophosphorus ligand in organic solvent is
0.01-1000g/L；
Solvent described in step d) is in water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform
One or more, the metallic elements of the Lewis acid metal salts are Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and
More than one or both of rare earth metal, wherein Zn salt is ZnX2, Al salt is AlX3, Ag salt is AgX, and Au salt is AuX, Ca salt
For CaX2, Rh salt is RhX3, Ir salt is IrX3, wherein X=Cl, Br, I.
According to the present invention it is also provided a kind of above-mentioned heterogeneous catalyst is in the coupling reaction of epoxide and carbon dioxide
Application.
The phosphine of Lewis acid metal salts and organic polymer of the present invention carries out coordination bonding, and rare earth metal owns
Element can be coordinated with it.Therefore rare earth metal of the present invention includes but is not limited to yttrium and scandium.
Lewis acid metal salts of the present invention are lewis acid.
The reaction principle of the present invention：
The present invention is by typical biphosphine ligand or monophosphorus ligand (such as Biphephos, PPh3) aromatic ring on introduce ethene
Base (vinyl), and ionic liquid is also introduced into vinyl, solvent thermal polymerization method is utilized in autoclave, polymerization is allowed to and forms height
The organic copolymer of specific surface area and multi-stage artery structure, due to having containing for largely exposure lonely in the organic copolymer skeleton
The phosphine of electronics pair, catalyst carrier can be used as to form coordinate bond with active transition metal ion, and then form catalytic active site, and
Play a part of stable metal center.And ionic liquid has catalysis epoxidation compound and the work of carbon dioxide coupling in itself
Property, so, this copolymer also can be directly as active catalyst.In the catalyst, organic phosphine is provided simultaneously with carrier and part
Dual-use function, ionic liquid are main active components, and Lewis acid metal salts play a part of co-catalyst.Active metal group
Divide with monatomic form high dispersive in organic phosphine copolymerization carrier, substantially increase the utilization ratio of metal.And active component
Not easily run off, catalyst life length.
Beneficial effects of the present invention are：
Containing the multiple tooth and organophosphorus ligand construction unit of monodentate in heterogeneous catalyst skeleton of the present invention, wherein having
Machine Phosphine ligands make higher exposed phosphine on copolymer surface be present, active metal atom or ion and phosphine shape exposed on copolymer
Into coordinate bond, active component not easily runs off.Copolymer has high specific surface area porous level structure, possesses the dual of carrier and part
Function, active metal component in organic phosphine copolymerization carrier, substantially increase the utilization of metal with monatomic form high dispersive
Another function ingredients ionic liquid forms concerted catalysis effect in efficiency, and polymer, drastically increases catalytic activity.
Such coordination of bonding heterogeneous catalyst is applied to fixed bed, slurry bed system, tank reactor and trickle bed etc. and reacts work
Skill, hierarchical porous structure provided by the present invention containing phosphine-ionic liquid organic copolymer heterogeneous catalyst be applied to carbon dioxide and
Among the coupling addition reaction synthesizing annular carbonate of oxirane, combine ionic liquid (as open loop nucleopilic reagent) and
The respective advantage of phosphine-metal complex (activation epoxide), by modulation comonomer ratio and content of metal,
The catalyst of acquisition can be made both there is high activity, the double dominant with higher stability, reduce cyclic carbonate ester
The cost of industrialized production, catalyst stability is good, and the separation of product and catalyst is simply efficient, is carried for the production of cyclic carbonate ester
New industrial catalyst is supplied.
Brief description of the drawings
Fig. 1 is the Phosphine ligands of typical alkylene functionalization；
Fig. 2 is the ionic liquid of typical alkylene functionalization；
Fig. 3 is a kind of polymerization technique route schematic diagram.
Fig. 4 is the crosslinking agent used in polymerization.
Fig. 5 is catalyst13C,31P is composed.
Fig. 6 is in N2Catalyst thermogravimetric curve under atmosphere.
Embodiment
Following embodiments better illustrate to the present invention, but do not limit invention which is intended to be protected.
Embodiment 1
Under 298K and inert gas shielding atmosphere, by 10.0 grams of Vinyl-PPh3Monomer (accompanying drawing 1, L1) is dissolved in
In 100.0mL tetrahydrofuran solvents, while 2.0g divinyl imidazoles (accompanying drawing 2, M1) is added, 1.0 are added into above-mentioned solution
Gram radical initiator azodiisobutyronitrile, stir 2 hours.The solution being stirred is moved in autoclave, in 373K and inertia
Solvent thermal polymerization method polymerization 24h is utilized under gas shield atmosphere.Solution after above-mentioned polymerization is cooled to room temperature, and room temperature condition is true
Sky takes solvent away, that is, obtains by Vinyl-PPh3With the organic porous polymer of divinyl imidazoles organic monomer copolymerization.Fig. 3 is
Polymerization technique route schematic diagram.Weigh 1 gram of ZnCl2It is dissolved in 10.0mL toluene solvants, 10.0 grams of addition is obtained above organic
Copolymer, this mixture is stirred into 24h under 298K and inert gas shielding atmosphere, then again under room temperature condition vacuum take away it is molten
Agent, that is, obtain the multi-functional heterogeneous catalyst among the coupling addition reaction applied to carbon dioxide and epoxide.
Embodiment 2
In example 2, except weighing 10.0 grams of comonomer Vinyl-Biphephos monomers (accompanying drawing 1, L2), substitute
Vinyl PPh3Monomer, remaining catalyst synthesis processes are same as Example 1.
Embodiment 3
In embodiment 3, except weighing 2.0 grams of divinyl benzo imidazoles monomers (accompanying drawing 2, M4), divinyl is substituted
Imidazoles monomer, remaining catalyst synthesis processes are same as Example 1.
Embodiment 4
In example 4, in addition to substituting 100.0mL tetrahydrofuran solvents with 50.0mL tetrahydrofuran solvents, remaining
Catalyst preparation process is same as Example 1.
Embodiment 5
In embodiment 5, in addition to substituting 100.0mL tetrahydrofuran solvents with 100.0mL dichloromethane solvents, remaining
Catalyst preparation process is same as Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 373K polymerization temperatures with 393K polymerization temperatures, remaining catalyst preparation process
It is same as Example 1.
Embodiment 7
In embodiment 7, except with 12h polymerization times substitute 24h polymerization times in addition to, remaining catalyst preparation process with
Embodiment 1 is identical.
Embodiment 8
In embodiment 8, except adding 10.0 grams of divinylbenzenes (accompanying drawing 4, N1), remaining catalyst preparation process
It is same as Example 1.
Embodiment 9
In embodiment 9, except weighing 1 gram of AlCl3It is dissolved in 10.0mL toluene solvants, remaining catalyst preparation process
It is same as Example 1.
Claims (10)
1. one kind contains phosphine-ionic liquid Porous-Organic copolymer heterogeneous catalyst, it is characterised in that：Phosphine-the ionic liquid has
Machine porous copolymers are formed by the organophosphorus ligand of olefin functionalities and the ionic liquid copolymerization of olefin functionalities, are obtained
Lewis acid metal salts are added or are added without in copolymer, when adding Lewis acid metal salts, the metal ion in metal salt
With forming coordinate bond containing phosphine exposed in phosphine-ionic liquid Porous-Organic copolymer, products therefrom is organic containing phosphine-ionic liquid
The heterogeneous catalyst of porous copolymers.
2. according to the heterogeneous catalyst described in claim 1, it is characterised in that：The Lewis acid metal salts are selected from Zn, Al,
It is more than one or both of halide of Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth metal, halide MXnRepresent,
Wherein M is metallic element, X=Cl, Br, I；N=1-3 positive integer；In catalyst metallic element loading be 0.01~
10wt%.
3. according to the heterogeneous catalyst described in claim 1, it is characterised in that：The organophosphorus ligand of the olefin functionalities and
The olefin functionalities of the ionic liquid of olefin functionalities turn to the alkylene functional group of end, preferably vinyl.
4. according to the heterogeneous catalyst described in claim 3, it is characterised in that：Organophosphorus ligand containing terminal olefin base is preferred
For the bidentate phosphites organophosphorus ligand containing vinyl, the triphenylphosphine ligand containing vinyl；Described contains end
The ionic liquid of alkene is preferably glyoxaline ion liquid.
5. according to the heterogeneous catalyst described in claim 1, it is characterised in that：The organophosphorus ligand choosing of the olefin functionalities
From：
The ionic liquid is selected from：
6. according to the heterogeneous catalyst described in claim 1, it is characterised in that：It is described to be copolymerized containing phosphine-ionic liquid Porous-Organic
Thing is obtained using solvent thermal polymerization method；It is described that there is hierarchical porous structure containing phosphine-ionic liquid Porous-Organic copolymer, compare surface
Product is 100~3000m2/ g, simultaneously containing macropore, mesopore and micropore, pore volume is 0.1~5.0cm3/ g, pore-size distribution 0.2~
50.0nm。
A kind of 7. preparation method of any heterogeneous catalysts of claim 1-6, it is characterised in that:The heterogeneous catalyst is
After the organophosphorus ligand of olefin functionalities and the ionic liquid of olefin functionalities are mixed, using solvent thermal polymerization method,
Trigger the alkylene in organophosphorus ligand and ionic liquid that polymerisation occurs through radical initiator, generation has multi-stage porous knot
Structure contains phosphine-ionic liquid Porous-Organic copolymer, adds or is added without Lewis acid metal salts in obtained copolymer, obtain
Heterogeneous catalyst；
The situation for adding Lewis acid metal salts is that Lewis acid metal salts are dissolved in solvent, and adding phosphine-ionic liquid has
Machine porous copolymers, stirring, make in the metal ion and phosphine-ionic liquid Porous-Organic copolymer in Lewis acid metal salts
Exposed phosphine forms coordinate bond, boils off volatile solvent afterwards and obtains heterogeneous catalyst.
A kind of 8. preparation method described in claim 7, it is characterised in that：
Concrete operation step includes：
A) under 273~473K, inert gas atmosphere, in organic solvent, add olefin functionalities organophosphorus ligand and
The ionic liquid of olefin functionalities, add or do not add crosslinking agent, radical initiator is added, after mixing, by mixture
Stirring 0.1~100 hour, preferable mixing time scope are 0.1~1 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, used
Solvent thermal polymerization method, stand 1~100 hour and carry out polymerisation, obtain a kind of organic copolymer containing phosphine-ionic liquid；
C) organic copolymer for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain with hierarchical porous structure
The organic copolymer containing exposed phosphine and ionic liquid, i.e. the Porous-Organic copolymer containing phosphine-ionic liquid；
D) under 273~473K, inert gas atmosphere, in the solvent containing Lewis acidic metal salt, add step c) and obtain
The Porous-Organic copolymer arrived, stir 0.1~100 hour, preferable mixing time is 0.1~1 hour, and vacuum extracts organic molten
Agent, obtain heterogeneous catalyst；
According to step a)-c) or step a)-d) operation obtain the heterogeneous catalyst containing phosphine-ionic liquid Porous-Organic copolymer.
9. according to the heterogeneous catalyst described in claim 8, it is characterised in that：Organic solvent described in step a) be benzene, toluene,
It is one or more kinds of in methanol, ethanol, tetrahydrofuran, dichloromethane or chloroform；The crosslinking agent is styrene, second
Alkene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or one kind in the acetylenylbenzenes of 1,3,5- tri- or
It is two or more；The radical initiator is cyclohexanone peroxide, dibenzoyl peroxide, TBHP, azo two
The one or more of isobutyronitrile or ABVN；
The mol ratio of organophosphorus ligand and ionic liquid described in step a) is 0.01:1~100:1；In addition crosslinking agent
In the case of, the mol ratio of organophosphorus ligand and crosslinking agent is 0.01:1~10:1；Organophosphorus ligand and radical initiator rub
You are than being 300:1~10:1；Before aggregating into Porous-Organic copolymer, the concentration of organophosphorus ligand in organic solvent is 0.01-
1000g/L；
Solvent described in step d) is a kind of in water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform
Or it is two or more, the metallic element of the Lewis acid metal salts is Zn, Al, Ag, Au, Cu, Ca, Rh, Ir, Co, Mg and rare earth
More than one or both of metal, wherein Zn salt is ZnX2, Al salt is AlX3, Ag salt is AgX, and Au salt is AuX, and Ca salt is
CaX2, Rh salt is RhX3, Ir salt is IrX3, wherein X=Cl, Br, I.
10. a kind of any heterogeneous catalysts of claim 1-6 are in the coupling reaction of epoxide and carbon dioxide
Using.
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| CN110743621A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Trivalent copper catalyst, preparation method thereof and application thereof in acetylene hydrochlorination |
| CN117229432A (en) * | 2023-11-14 | 2023-12-15 | 传化智联股份有限公司 | Organic rare earth phosphate catalyst and preparation method and application thereof |
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| CN117229432A (en) * | 2023-11-14 | 2023-12-15 | 传化智联股份有限公司 | Organic rare earth phosphate catalyst and preparation method and application thereof |
| CN117229432B (en) * | 2023-11-14 | 2024-02-13 | 传化智联股份有限公司 | Organic rare earth phosphate catalyst and preparation method and application thereof |
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