CN105777988B - A kind of organic polymer containing P and its preparation method and application - Google Patents
A kind of organic polymer containing P and its preparation method and application Download PDFInfo
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Abstract
A kind of organic polymer containing P, the organic polymer is the multiple tooth organic phosphine monomer containing P and alkylene, using solvent thermal polymerization method, the organic phosphine polymer of generation bigger serface hierarchical porous structure after initiator initiated polymerization.The organic phosphine polymer is applied to the preparation of heterogeneous reaction catalyst, there is the dual-use function of carrier and part simultaneously, in the metal load type catalyst prepared as carrier loaded active metal component, its metal component high dispersive, again can be as the part similar to active metallic ion in homogeneous complex catalysis in the carrier.Active metal component in such organic polymer, substantially increases the utilization ratio of metal with monatomic form high dispersive；Due to by the stereoeffect of the immobilized biphosphine ligand to get off, in the hydroformylation reaction of some reactions such as higher olefins, the stereoselectivity of product is remarkably improved using the polymer as catalyst made from carrier.
Description
Technical field
The present invention relates to a kind of organic polymer containing P and preparation method thereof, belong to materials synthesis and applied technical field.
Background technology
In recent years, porous organic material (Macromolecules, 2013,34,471) design and synthesis be increasingly becoming it is micro-
One of new focus of Porous materials research field, it is organic with traditional inorganic microporous material compared with organic-metallic coordination polymer
The skeleton of microporous polymer is made up of pure organic molecule, each other by covalent key connection, have open duct with it is excellent
Porous.It is organic molecule building block precursor and molecular network importantly, due to the diversity of organic chemical synthesis method
Structure provide abundant synthesis path and building mode, the organic molecule building block of the introducing functionalization of purpose can be passed through
Make final material that there is corresponding property, can be with the porous of controlled material by the structure for adjusting precursor.In addition, exist
In most cases, compared with the molecular network structure fragility connected into by non-covalent bond, organic microporous polymer is all logical
Covalent key connection is crossed, while material porous is maintained, molecular network structure is more firm.
At present, porous organic material can be largely classified into following four (1) by intensive according to different thinkings of constructing
Crosslinking prevents the closelypacked super cross-linked polymer (Hyper-Crosslinked Polymers, HCPs) of macromolecular chain；(2)
Macromolecular chain is forced effectively to occupy the intrinsic microporous polymer of void volume by rigidity or the molecular structure reversed
(Polymers of Intrinsic Microporosity,PIMs)；(3) molecular network is kept by building π-conjugated systems
Structural rigidity conjugation microporous polymer (Conjugated Microporous Polymers, CMPs) and (4) using appropriate
Polyfunctional group organic building block covalent organic frame (the Covalent Organic of crystalline microporous material are formed by reversible be condensed
Frameworks,COFs)。
Patent CN1319580A describes several homogeneous bidentate phosphite ligands with larger space steric hindrance, and these are matched somebody with somebody
The homogeneous catalyst obtained after the coordination such as body and Rh, Co achieves three-dimensional choosing well in the hydroformylation reaction of higher olefins
Selecting property (product is just different relatively good).But homogeneous reaction catalyst is not easily recycled, production cost is very high.
In patent CN1210514A, hydroformylation of olefin has one in rhodium complex catalyzed lower progress, rhodium complex
Individual multiple tooth, the not phosphorous organonitrogen compound that complex compound can be generated with the 8th race's metal make ligand, and rhodium complex also contains
At least one tertiary nitrogen group that can be protonated in weak acid, but catalyst equally faces the problem of being not easily recycled.
In patent CN102911021A, rhodium complex and biphenyl backbone or dinaphthalene skeleton biphosphine ligand, and triphen are utilized
The composite catalyst system of base phosphine or phosphite ester triphenylmethyl methacrylate monophosphorus ligand composition is catalyst, in linear alkene hydroformylation reaction
Middle n-alkanal has higher selectivity, so reduces the dosage of expensive biphosphine ligand, but catalyst system and catalyzing is still
Homogeneous, catalyst reuses again without method.Also with bis-phosphite and triphenyl in patent CN1986055A
Phosphine coordinates with Rh, and composition meets catalyst system and catalyzing, and in the hydroformylation reaction of propylene, n-butanal and isobutylaldehyde mol ratio are more than
20, significantly extend the service life of bisphosphite ligands, hence it is evident that the dosage of triaryl phosphine is reduced, but substantially or
Phase reaction, equally face catalyst and recycle the problem of difficult.
2014, Xiao Fengshou, Ding Yunjie et al. (Chem.Commun., 2014,50,11844) utilized solvent thermal polymerization
Three (4- vinyl benzenes) base phosphines are aggregating by method, are named as POLs, and catalyst prepared by the organic polymer is in alkene hydrogen
Good activity is achieved in formylation reaction, and active component not easily runs off, but due to being the polymerization of monophosphorus ligand, with this
Polymer is that catalyst made from carrier does not obtain good stereoselectivity in hydroformylation of higher olefins reaction.
Porous organic polymer is because of controllable chemical physical property, easy functionalization synthesis strategy, big specific area and
The advantages that cheap cost of material and cause the extensive concern of researchers, because of the organic functional in its adjustable changeable monomer component
Group, so as to for the miscellaneous organic polymer of the purposive synthesis of different requirements, while more and more grind
Study carefully and show that porous organic polymer shows wide application prospect in homogeneous catalysis heterogeneouss field.However, have porous
Carrier of the machine thing as heterogeneous reaction, also expose some needs and solve the problems, such as and overcome, such as polymer material heat endurance
Difference, material synthesis processes are cumbersome etc., and material is more sensitive to air and water, and organic polymer is inadequate as carrier reaction selectivity
It is high, it is difficult to general compactly to introduce subject monomers etc..
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of organic polymer containing P and preparation method thereof with
Using.
The present invention is on the Research foundation of a variety of organic polymer preparation methods, by typical biphosphine ligand such as
Vinyl groups is introduced on Biphephos (see photo) aromatic rings as polymerized monomer, solvent thermal polymerization method is utilized in autoclave,
The organic polymer with high surface area and multi-stage artery structure is polymerized to form, it is big due to having in the organic polymer backbones
Amount P of the exposure containing lone pair electrons, the organic polymer can be used as catalyst carrier and active transition metal ion unoccupied orbital shape
Into coordinate bond, and then new catalytic active site is formed, we term it the self-supported activity of organic polymer for the catalyst prepared
The catalyst of metal component.Part of the organic polymer one side as active metal component, on the other hand bears as high dispersive
Carry the carrier of active metal component high-specific surface area.
Multiple tooth organic phosphine monomer of the organic polymer containing P of the present invention to contain P and alkylene uses as substrate
Solvent thermal polymerization method, trigger the alkylene in multiple tooth organic phosphine monomer that polymerisation occurs through radical initiator, generate containing P's
Organic polymer.
Organic polymer monomer is preferably the multiple tooth organophosphorus ligand of olefin-containing base functionalization.
Multidentate phosphite organophosphor monomer of the multiple tooth organic phosphine monomer most preferably containing vinyl, wherein it is preferred that two teeth are organic
Phosphine ligands VinylBiphephos.
Radical initiator is cyclohexanone peroxide, dibenzoyl peroxide, TBHP, azodiisobutyronitrile
Or the one or more of ABVN.
The specific surface area of organic polymer is 10~3000m2/g.Organic polymer has hierarchical porous structure, contains simultaneously
Macropore, mesopore and micropore, its pore volume are 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
Specifically, organic polymer provided by the invention selects the multiple tooth organic phosphine monomer containing P and alkylene, adopts
The organic polymer containing P is generated after the polymerisation for triggering its alkylene to occur through initiator with solvent thermal polymerization method.It is described
Bidentate phosphites organophosphorus ligand of the organic monomer preferably containing P and vinyl-arene.In addition, synthesized organic polymer
Specific surface area is 10~3000m2/ g, pore volume are 0.5~5.0cm3/ g, pore-size distribution is in 0.5~50.0nm.
The present invention preparation method step be：(1) under 273~473K and inert gas shielding atmosphere, containing organic list
In the organic solvent of body, (common) monomer, crosslinking agent and radical initiator are sequentially added, wherein the weight of (common) monomer/crosslinking agent
Amount is than being 0.01:1~10:1；The weight ratio of crosslinking agent/radical initiator is 300:1~10:1.Gained reactant mixture stirs
Mix 0.1~100 hour.Wherein organic solvent can be using one in benzene, toluene, tetrahydrofuran, methanol or ethanol or chloroform
Kind or several mixtures；(common) monomer can use three (4- styrene) base phosphine, triphenylbenzene, biphenyl, toluene, benzene, phenol or chlorine
One or more in benzene；Crosslinking agent can use dimethoxymethane, styrene, ethene, propylene, divinylbenzene, diiodo- first
One or more in alkane, paraformaldehyde or the acetylenylbenzenes of 1,3,5- tri-；Radical initiator can use cyclohexanone peroxide, mistake
Aoxidize the one or more of dibenzoyl, TBHP, azodiisobutyronitrile or ABVN.(2) 273~
Under 473K and inert gas shielding atmosphere, above-mentioned solution is stood 1~100 under conditions of solvent thermal polymerization in synthesizing autoclave
Hour carries out polymerisation.(3) by the polymer after above-mentioned polymerization, vacuum extracts solvent at ambient temperature, that is, obtains producing
The organic polymer of high surface area and hierarchical porous structure containing P.
The outstanding properties of the present invention include：
Organic polymer containing P synthesized by the present invention, multiphase load type metallic catalyst is can be applied to as carrier
Preparation, due to containing P in skeleton, organic polymer has the double action of part and carrier concurrently；The catalyst of self-supported metal
Middle active metal component can be dispersed in a manner of single ion in this high surface area hierarchical porous structure organic polymer.By this
In the hydroformylation of olefin of the carrier loaded Rh base catalyst of class high surface area hierarchical porous structure organic polymer, it can use
Fixed bed, slurry bed system, tank reactor and drip bed reaction technique, the hydroformylation reaction activity of its alkene is high, aldehyde product
Selectivity is good, is particularly due to the steric effect of biphosphine ligand, the selectivity of n-alkanal in the hydroformylation reaction of higher olefins
It is greatly improved；P-shaped in metal ion and organic polymer is into stronger coordinate bond, with the scattered of monometallic ion
State is present.
Beneficial effects of the present invention are：
Organic polymer containing P synthesized by the present invention, a variety of gas-solids are can be applied to as carrier loaded metallic catalyst
The heterogeneous reaction such as two-phase or gas-liquid-solid three-phase, there is significant advantage, be expected to solve to grow during homogeneous reaction heterogeneouss
Reactivity existing for phase and poor selectivity, and metal component are lost in the problems such as serious.
Brief description of the drawings
Fig. 1 is multiple tooth Phosphine ligands (left side) and VinylBiphephos (right side) structural representation of typical alkylene functionalization
Figure.
Fig. 2 is vinyl functionalization didentate phosphine ligand VinylBiphephos polymerization technique route schematic diagrames.
Fig. 3 is the schematic diagram for the typical co-monomer and crosslinking agent used in polymerization, wherein, co-monomer L1-L19, hand over
Connection agent is L20 and L21.
Embodiment
In order to better illustrate the preparation process of the organic polymer containing P, some organic polymers containing P are enumerated below and were polymerize
The Application Example of journey and reaction evaluating, but the invention is not restricted to cited example.
Embodiment 1
Under 298K and inert gas shielding atmosphere, 10.0 grams of VinylBiphephos parts (accompanying drawing 1) are dissolved in
In 100.0ml tetrahydrofuran solvents, while divinylbenzene (L20) 5.0g is added, 1.0 grams of free radicals are added into above-mentioned solution
Initiator azodiisobutyronitrile, stir 2 hours.The solution being stirred is moved in autoclave, in 373K and inert gas shielding
Under atmosphere polymerization 24h is carried out using solvent thermal polymerization method.Solution after above-mentioned polymerization is cooled to room temperature, and room temperature condition vacuum is taken out
Solvent is walked, that is, obtains the organic phosphine polymer being aggregating by VinylBiphephos organic monomers.Fig. 1 is
The schematic diagram of VinylBiphephos organic polymer polymerization technique routes.
Embodiment 2
Under 298K and inert gas shielding atmosphere, by 10.0 grams of VinylBiphephos monomers (accompanying drawing 1) and 10.0g tri-
(4- vinyl benzenes) base phosphine is dissolved in 100.0ml tetrahydrofuran solvents, while adds divinylbenzene (L20) 5.0g, to above-mentioned
1.0 grams of radical initiator azodiisobutyronitriles are added in solution, are stirred 2 hours.The solution being stirred is moved in autoclave,
Under 373K and inert gas shielding atmosphere polymerization 24h is carried out using solvent-thermal method.Solution after above-mentioned polymerization is cooled to room
Temperature, room temperature condition vacuum take solvent away, that is, obtain being copolymerized what is formed by VinylBiphephos and three (4- vinyl benzenes) base phosphines
Organic polymer.
Embodiment 3
In embodiment 3,1.0 grams of free radicals initiations are substituted except weighing 0.1 gram of radical initiator azodiisobutyronitrile
Outside agent azodiisobutyronitrile, remaining organic polymer building-up process is same as Example 1.
Embodiment 4
In example 4, in addition to substituting 100.0ml tetrahydrofuran solvents with 50.0ml tetrahydrofuran solvents, remaining
Organic polymer building-up 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
Organic polymer building-up process is same as Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 373K polymerization temperatures with 393K polymerization temperatures, the synthesis of remaining organic polymer
Process is same as Example 1.
Embodiment 7
In embodiment 7, in addition to substituting 24h polymerization times with 12h polymerization times, remaining organic polymer synthesized
Journey is same as Example 1.
Embodiment 8
In embodiment 8, in addition to adding 10.0 grams of L20 as crosslinking agent, remaining organic polymer building-up process
It is same as Example 1.
Embodiment 9
In embodiment 9, in addition to adding 1.0 grams of styrene as crosslinking agent, remaining organic polymer synthesized
Journey is same as Example 1.
Embodiment 10
Under 298K and inert gas shielding atmosphere, weigh 50.10 milligrams of rhodium dicarbonyl acetylacetonates (I) and be dissolved in 10.0ml
In tetrahydrofuran solvent, the organic polymer that VinylBiphephos prepared by 1.0 grams of embodiments 1 is formed is added, this is mixed
Thing stirs 24 hours under 298K and inert gas shielding atmosphere, and then vacuum takes solvent away at ambient temperature, that is, obtain by
The catalyst of the self-supported metal of organic polymer.The catalyst of above-mentioned preparation is encased in fixed bed reactors, both ends load
Quartz sand.It is passed through reaction mixture gas (H2:CO:C3H6=1:1:1), in 393K, 1.0MPa, reaction mixture gas air speed 2000h-1Bar
Hydroformylation reaction is carried out under part.Collecting tank of the reaction through a deionized water equipped with 60ml coolings, which absorbs, to be collected, reaction production
Thing is all dissolved in the water of collecting tank.The obtained aqueous solution uses the HP-7890N equipped with HP-5 capillary columns and fid detector
Gas chromatographic analysis, internal standard is made using ethanol.Reaction end gas, which uses, after water absorbs is furnished with Porapak-QS posts and TCD detectors
HP-7890N gas-chromatographies carry out on-line analysis.Reaction result is listed in table 1.
The organic polymer specific surface area and response data synthesized in the embodiment 1-9 of table 1
* experiment condition is 120 DEG C, 1MPa, distribution (propylene:CO:H2=1:1:1) air speed 2000h-1, TOF calculate when think
All Rh are avtive spots.
Claims (8)
- A kind of 1. organic polymer containing P, it is characterised in that：Specifically preparation process is：A) under 273~473K, inert gas atmosphere, in the organic solvent of the monomer of organic polymer containing P, addition co-monomer, Crosslinking agent and radical initiator, after mixing, stir the mixture for 0.1~100 hour；B) by the solution in step a) in autoclave is synthesized, 273~473K, under inert gas atmosphere, solvent thermal polymerization method is quiet Put 1~100 hour and carry out polymerisation；C) polymer for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain organic polymer containing P；The monomer of organic polymer containing P is：The co-monomer is selected from as follows：The crosslinking agent is selected from as follows：
- 2. according to the organic polymer containing P described in claim 1, it is characterised in that：Radical initiator be cyclohexanone peroxide, Dibenzoyl peroxide, TBHP, the one or more of azodiisobutyronitrile or ABVN.
- 3. according to the organic polymer containing P described in claim 1, it is characterised in that：The specific surface area of the organic polymer containing P is 10 ~3000m2/g；Organic polymer containing P has hierarchical porous structure, and simultaneously containing macropore, mesopore and micropore, its pore volume is 0.1~ 5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
- A kind of 4. preparation method of any organic polymers containing P of claim 1-3, it is characterised in that：Specifically preparation process is：A) under 273~473K, inert gas atmosphere, in the organic solvent containing organic polymer monomer, add co-monomer, hand over Join agent and radical initiator, after mixing, stir the mixture for 0.1~100 hour；B) by the solution in step a) in autoclave is synthesized, 273~473K, under inert gas atmosphere, solvent thermal polymerization method is quiet Put 1~100 hour and carry out polymerisation；C) polymer for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain organic polymer containing P.
- 5. in accordance with the method for claim 4, it is characterised in that：Organic solvent described in step a) is benzene, toluene, tetrahydrochysene It is one or more kinds of in furans, methanol, ethanol or chloroform.
- 6. in accordance with the method for claim 4, it is characterised in that：The weight ratio of co-monomer and crosslinking agent described in step a) For 0.01:1~10:1.
- 7. in accordance with the method for claim 4, it is characterised in that：Crosslinking agent and radical initiator described in step a) Weight ratio is 300:1~10:1.
- 8. the application of any organic polymers containing P of a kind of claim 1-3, it is characterised in that by such organic polymer containing P The carrier loaded Rh bases catalyst of thing is used in the hydroformylation reaction of alkene.
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| CN107790188B (en) * | 2016-09-07 | 2020-09-04 | 中国科学院大连化学物理研究所 | Metal-phosphine-containing organic copolymer catalyst and preparation method and application thereof |
| CN107793304B (en) * | 2016-09-07 | 2021-03-16 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde by olefin with high selectivity |
| CN108067307B (en) * | 2016-11-15 | 2020-09-01 | 中国科学院大连化学物理研究所 | Preparation and application of heterogeneous asymmetric hydroformylation catalyst |
| CN109806911B (en) * | 2017-11-21 | 2022-01-21 | 中国科学院大连化学物理研究所 | Catalyst for preparing straight-chain aldehyde with high selectivity and preparation and application thereof |
| CN112892603B (en) * | 2019-12-03 | 2022-04-12 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for nitrogen formylation reaction and preparation and application thereof |
| CN111533837B (en) * | 2020-04-20 | 2022-02-11 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
| CN112844474B (en) * | 2020-12-24 | 2023-04-14 | 广东新华粤石化集团股份公司 | Organic polymer catalyst for hydroformylation of high-carbon olefin and application thereof |
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| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
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