CN105777988A - P-containing organic polymer, preparation method and applications thereof - Google Patents
P-containing organic polymer, preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a P-containing organic polymer. The organic polymer is a polydentate organic phosphine monomer, which comprises P and an alkenyl group. A solvothermal polymerization method is adopted, and an initiator is added to trigger polymerization reactions to obtain the organic phosphine polymer with a large specific surface area and multilevel pore structure. The organic phosphine polymer is used to prepare a heterogeneous reaction catalyst, and can be used as a carrier and a ligand at the same time. When the organic phosphine polymer is used as a carrier, active components are loaded on the carrier to prepare a metal supported catalyst, and the metal components are highly dispersed in the carrier. The organic phosphine polymer can also be used as a ligand of active metal ions in homogeneous complex catalysis. Active metal components are highly dispersed in the organic polymer in a form of single atoms, the utilization rate of metal is greatly improved; and due to the stereo effect of immobilized diphosphine ligand, the catalyst prepared from the polymer taken as the carrier can prominently improve the stereo selectivity of products in some reactions such as hydroformylation reactions of higher olefin.
Description
Technical field
The present invention relates to a kind of containing P organic polymer 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 are increasingly becoming one of new focus of poromerics research field, and with traditional inorganic microporous material compared with organic-metallic coordination polymer, the skeleton of organic microporous polymer is made up of pure organic molecule, connect each other by covalent bond, there is open duct and excellent porous.The more important thing is, multiformity with chemical machine synthetic method, structure for organic molecule building block precursor Yu molecular network provides abundant synthesis path and building mode, final material can be made to have corresponding character by the organic molecule building block of the introducing functionalization of purposiveness, can the porous of controlled material by regulating the structure of precursor.In addition, in most of the cases, compared with the molecular network structure fragility connected into by non-covalent bond, organic microporous polymer is all connected by covalent bond, and while material hole character is maintained, molecular network structure is more firm.
At present, porous organic material can be largely classified into the following four (1) the closelypacked super cross linked polymer (Hyper-CrosslinkedPolymers, HCPs) by intensive crosslinking prevention macromolecular chain according to different thinkings of constructing；(2) macromolecular chain is forced can not effectively to occupy the intrinsic microporous polymer (PolymersofIntrinsicMicroporosity, PIMs) of void volume by the molecular structure of rigidity or torsion；(3) by building the conjugation microporous polymer (ConjugatedMicroporousPolymers that π-conjugated systems keeps the structural rigidity of molecular network, CMPs) and (4) utilize the organic building block of suitable polyfunctional group by reversible condensation formed crystalline microporous material covalency organic frame (CovalentOrganicFrameworks, COFs).
Patent CN1319580A describes several homogeneous bidentate phosphite ligands with larger space steric hindrance, and the homogeneous catalyst obtained after these coordinations such as part and Rh, Co achieves good stereo selectivity (product is just different relatively good) in the hydroformylation reaction of higher olefins.But homogeneous reaction catalyst is not easily recycled, and production cost is significantly high.
In patent CN1210514A; hydroformylation of olefin carries out under rhodium complex catalyzed; rhodium complex has one and multiple tooth, not phosphorous can generate the organonitrogen compound of complex with the 8th race's metal and make ligand; rhodium complex is also containing at least one tertiary nitrogen group being protonated in weak acid, but catalyst faces the problem being not easily recycled equally.
In patent CN102911021A; utilize rhodium complex and biphenyl backbone or dinaphthalene skeleton biphosphine ligand; and the composite catalyst system of triphenylphosphine or phosphite ester triphenylmethyl methacrylate monophosphorus ligand composition is catalyst; in linear alkene hydroformylation reaction, n-alkanal has higher selectivity; which decrease the consumption of expensive biphosphine ligand; but catalyst system and catalyzing or homogeneous, catalyst reuses again without way.Patent CN1986055A coordinates with Rh also with bis-phosphite and triphenylphosphine; composition meets catalyst system and catalyzing; in the hydroformylation reaction of propylene; hutanal and isobutylaldehyde mol ratio are more than 20; significantly extend the service life of bisphosphite ligands; significantly reduce the consumption of triaryl phosphine, but substantially or homogeneous reaction, face the problem that difficulty recycled by catalyst equally.
2014; Xiao Fengshou; Ding Yunjie et al. (Chem.Commun.; 2014; 50; 11844) three (4-vinyl benzene) base phosphine is aggregating by the method utilizing solvent thermal polymerization; called after POLs; catalyst prepared by this organic polymer achieves good activity in hydroformylation of olefin; and active component not easily runs off; but owing to being the polymerization of monophosphorus ligand, in using hydroformylation of higher olefins reacts, do not obtain good stereo selectivity with the catalyst that this polymer prepares for carrier.
Porous organic polymer is because of controlled chemical physical property, easy functionalization synthesis strategy, the advantages such as big specific area and cheap cost of material and cause the extensive concern of researcheres, because of the organo-functional group in its adjustable changeable monomer component, such that it is able to for the synthesis that different requirements is purposive organic polymer miscellaneous, increasing research simultaneously shows that porous organic polymer shows wide application prospect in homogeneous catalysis heterogenize field.But, using the porous Organic substance carrier as heterogeneous reaction, also some problems needing to solve and overcome are exposed, the material such as loaded down with trivial details in polymer material poor heat stability, material synthesis processes is comparatively sensitive to air and water, organic polymer is not high enough as carrier reaction selectivity, it is difficult to the general subject monomers of introducing compactly etc..
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide a kind of containing P organic polymer and its preparation method and application.
The present invention is on the Research foundation of multiple organic polymer preparation method, typical biphosphine ligand such as Biphephos (see photo) aromatic ring will introduce vinyl groups as polymerization single polymerization monomer, autoclave utilizes solvent thermal polymerization method, it is polymerized to form the organic polymer with high surface and multi-stage artery structure, owing to this organic polymer backbones having a large amount of P exposing and containing lone pair electrons, this organic polymer can form coordinate bond as catalyst carrier with active transition metal ion unoccupied orbital, and then form new catalytic active site, the catalyst prepared is we term it organic polymer is from the catalyst of load active metal component.Organic polymer is on the one hand as the part of active metal component, on the other hand as the carrier of high-dispersion load active metal component high-specific surface area.
Of the present invention containing P organic polymer using the multiple tooth organic phosphine monomer containing P and alkylene as substrate, adopt solvent thermal polymerization method, cause the alkylene generation polyreaction in multiple tooth organic phosphine monomer through radical initiator, generate the organic polymer containing P.
Organic polymer monomer is preferably the multiple tooth organophosphorus ligand of olefin-containing base functionalization.
Multiple tooth organic phosphine monomer the best is the multidentate phosphite organophosphor monomer containing vinyl, wherein preferred two tooth organophosphorus ligand VinylBiphephos.
Radical initiator is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The specific surface area of organic polymer is 10～3000m2/g.Organic polymer has hierarchical porous structure, contains macropore, mesopore and micropore simultaneously, and its pore volume is 0.1～5.0cm3/ g, pore-size distribution is at 0.2～50.0nm.
Specifically, organic polymer provided by the invention selects the multiple tooth organic phosphine monomer containing P and alkylene, adopts solvent thermal polymerization method to generate the organic polymer containing P after the polyreaction that initiator causes its alkylene to occur.Described organic monomer preferably bidentate phosphites organophosphorus ligand containing P and vinyl-arene.It addition, synthesized organic polymer specific surface area is 10～3000m2/ g, pore volume is 0.5～5.0cm3/ g, pore-size distribution is at 0.5～50.0nm.
The preparation method step of the present invention is: (1) is under 273～473K and inert gas shielding atmosphere; in the organic solvent containing organic monomer; being sequentially added into (being total to) monomer, cross-linking agent and radical initiator, the weight ratio wherein (being total to) monomer/cross-linking agent is 0.01:1～10:1；The weight ratio of cross-linking agent/radical initiator is 300:1～10:1.Gained reactant mixture stirs 0.1～100 hour.Wherein organic solvent can adopt one or more mixture in benzene, toluene, oxolane, methanol or ethanol or chloroform；(being total to) monomer can adopt one or more in three (4-styrene) base phosphine, triphenylbenzene, biphenyl, toluene, benzene, phenol or chlorobenzene；Cross-linking agent can adopt one or more in dimethoxymethane, styrene, ethylene, propylene, divinylbenzene, diiodomethane, paraformaldehyde or 1,3,5-tri-acetylenylbenzene；Radical initiator can adopt one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).(2) under 273～473K and inert gas shielding atmosphere, above-mentioned solution is stood when solvent thermal polymerization in synthesizing autoclave and within 1～100 hour, carries out polyreaction.(3) the polymer vacuum at ambient temperature after above-mentioned polymerization is extracted solvent, namely obtained the organic polymer of the high surface area containing P and hierarchical porous structure.
The outstanding properties of the present invention includes:
Synthesized by the present invention containing P organic polymer, it can be used as carrier to can be applicable to the preparation of multiphase load type metallic catalyst, due in skeleton containing P, organic polymer has the dual function of part and carrier concurrently；In the catalyst of carried metal, active metal component can be dispersed in the way of isolated son in this high surface area hierarchical porous structure organic polymer.By in hydroformylation of olefin catalyst based for Rh carrier loaded for this type of high surface area hierarchical porous structure organic polymer; fixing bed can be adopted; slurry bed system; tank reactor and trickle bed reaction process; the hydroformylation reaction activity of its alkene is high; aldehyde product selectivity is good, is particularly due to the steric effect of biphosphine ligand, and in the hydroformylation reaction of higher olefins, the selectivity of n-alkanal is greatly improved；Metal ion has become stronger coordinate bond with the p-shaped in organic polymer, exists with the dispersity of monometallic ion.
The invention have the benefit that
Synthesized by the present invention containing P organic polymer, can be applicable to the heterogeneous reactions such as multiple gas-particle two-phase or gas-liquid-solid three-phase as carrier loaded metallic catalyst, there is significant advantage, it is expected to solve reactivity and the poor selectivity of the homogeneous reaction medium-term and long-term existence of heterogenize process, and metal component runs off the problem such as serious.
Accompanying drawing explanation
Fig. 1 is multiple tooth Phosphine ligands (left side) and VinylBiphephos (right side) structural representation of typical alkylene functionalization.
Fig. 2 is vinyl functionalization didentate phosphine ligand VinylBiphephos polymerization technique route schematic diagram.
Fig. 3 is the schematic diagram of typical co-monomer and the cross-linking agent used in polymerization, and wherein, co-monomer is L1-L18, and cross-linking agent is L19 and L20.
Detailed description of the invention
In order to better illustrate the preparation process containing P organic polymer, enumerate some Application Examples containing P organic polymer polymerization process and reaction evaluating below, 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 100.0ml tetrahydrofuran solvent; it is simultaneously introduced divinylbenzene (L19) 5.0g; in above-mentioned solution, add 1.0 grams of radical initiator azodiisobutyronitriles, stir 2 hours.The solution being stirred is moved in autoclave, utilizes solvent thermal polymerization method to carry out polymerization 24h under 373K and inert gas shielding atmosphere.Solution after above-mentioned polymerization is cooled to room temperature, and room temperature condition vacuum takes solvent away, namely obtains the organic phosphine polymer being aggregating by VinylBiphephos organic monomer.Fig. 1 is the schematic diagram of VinylBiphephos organic polymer polymerization technique route.
Embodiment 2
Under 298K and inert gas shielding atmosphere; 10.0 grams of VinylBiphephos monomers (accompanying drawing 1) and 10.0g tri-(4-vinyl benzene) base phosphine are dissolved in 100.0ml tetrahydrofuran solvent; it is simultaneously introduced divinylbenzene (L19) 5.0g; in above-mentioned solution, add 1.0 grams of radical initiator azodiisobutyronitriles, stir 2 hours.The solution being stirred is moved in autoclave, utilizes solvent-thermal method to carry out polymerization 24h under 373K and inert gas shielding atmosphere.Solution after above-mentioned polymerization is cooled to room temperature, and room temperature condition vacuum takes solvent away, namely obtains the organic polymer formed by VinylBiphephos and three (4-vinyl benzene) base phosphine copolymerization.
Embodiment 3
In embodiment 3, except weighing 0.1 gram of radical initiator azodiisobutyronitrile and substituting 1.0 grams of radical initiator azodiisobutyronitriles, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 4
In example 4, except substituting 100.0ml tetrahydrofuran solvent with 50.0ml tetrahydrofuran solvent, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 5
In embodiment 5, except substituting 100.0ml tetrahydrofuran solvent with 100.0ml dichloromethane solvent, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 6
In embodiment 6, except substituting 373K polymerization temperature with 393K polymerization temperature, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 7
In embodiment 7, except substituting 24h polymerization time with 12h polymerization time, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 8
In embodiment 8, except add 10.0 grams of L20 as cross-linking agent except, remaining organic polymer building-up process and embodiment 1 are identical.
Embodiment 9
In embodiment 9, except add 1.0 grams of styrene as cross-linking agent except, remaining organic polymer building-up process and embodiment 1 are identical.
Embodiment 10
Under 298K and inert gas shielding atmosphere; weigh 50.10 milligrams of rhodium dicarbonyl acetylacetonates (I) and be dissolved in 10.0ml tetrahydrofuran solvent; add the VinylBiphephos of the 1.0 grams of embodiment 1 preparations organic polymer formed; this mixture is stirred 24 hours under 298K and inert gas shielding atmosphere; then vacuum takes solvent away at ambient temperature, namely obtains by organic polymer from the catalyst of carried metal.Being encased in fixed bed reactors by the catalyst of above-mentioned preparation, two ends load quartz sand.Pass into reaction mixture gas (H2:CO:C3H6=1:1:1), at 393K, 1.0MPa, reaction mixture gas air speed 2000h-1Hydroformylation reaction is carried out under condition.Reacting to absorb through a collecting tank equipped with the deionized water of 60ml cooling and collect, product is all dissolved in the water of collecting tank.Obtained aqueous solution adopts the HP-7890N gas chromatographic analysis being furnished with HP-5 capillary column and fid detector, mark in adopting ethanol to make.After water absorbs, reaction end gas adopts the HP-7890N gas chromatogram being furnished with Porapak-QS post and TCD detector to carry out on-line analysis.Reaction result is listed in table 1.
The organic polymer specific surface area synthesized in table 1 embodiment 1-9 and response data
* experiment condition is 120 DEG C, 1MPa, distribution (propylene: CO:H2=1:1:1) air speed 2000h-1, TOF thinks that all of Rh is all avtive spot when calculating.
Claims (10)
1. one kind containing P organic polymer, it is characterized in that: the multiple tooth organic phosphine monomer containing P and alkylene is as substrate, adopt solvent thermal polymerization method, cause the alkylene generation polyreaction in multiple tooth organic phosphine monomer through radical initiator, generate the organic polymer containing P.
2. the organic polymer described in claim 1, it is characterised in that: organic polymer monomer is preferably the multiple tooth organophosphorus ligand of olefin-containing base functionalization.
3. the organic polymer described in claim 1 or 2, it is characterised in that: multiple tooth organic phosphine monomer the best is the multidentate phosphite organophosphor monomer containing vinyl functionalization.
4. the organic polymer described in claim 1, it is characterised in that: radical initiator is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
5. the organic polymer described in claim 1, it is characterised in that: the specific surface area of organic polymer is 10～3000m2/g；Organic polymer has hierarchical porous structure, contains macropore, mesopore and micropore simultaneously, and its pore volume is 0.1～5.0cm3/ g, pore-size distribution is at 0.2～50.0nm.
6. preparation method containing P organic polymer described in a claim 1, it is characterised in that:
Concrete preparation process is:
A) under 273～473K, inert gas atmosphere, in the organic solvent containing organic polymer monomer, add (being total to) monomer, cross-linking agent and radical initiator, after mixing, stir the mixture for 0.1～100 hour；
B) by the solution in step a) in synthesis autoclave, 273～473K, under inert gas atmosphere, solvent thermal polymerization method, stand and carry out polyreaction in 1～100 hour；
C) by the step b) polymer obtained, vacuum extracts solvent at ambient temperature, namely obtains the organic polymer containing P.
7. in accordance with the method for claim 6, it is characterised in that: the organic solvent described in step a) be in benzene, toluene, oxolane, methanol, ethanol or chloroform one or more.
8. in accordance with the method for claim 6, it is characterised in that: the weight ratio of (being total to) monomer described in step a) and cross-linking agent is 0.01:1～10:1；The weight ratio of cross-linking agent and radical initiator is 300:1～10:1.
9. in accordance with the method for claim 6, it is characterised in that: (being total to) monomer described in step a) is one or more in triphenylbenzene, biphenyl, toluene, benzene, phenol or chlorobenzene；
Radical initiator is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).
10. application containing P organic polymer described in a claim 1, it is characterised in that by catalyst based in the hydroformylation reaction of alkene for Rh carrier loaded for this type of organic polymer containing P.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107793304A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院大连化学物理研究所 | A kind of method that alkene high selectivity prepares aldehyde |
| CN107790188A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院大连化学物理研究所 | A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application |
| CN108067307A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation and application of multiphase asymmetric hydroformylation catalyst |
| CN109806911A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application |
| CN111533837A (en) * | 2020-04-20 | 2020-08-14 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
| CN112844474A (en) * | 2020-12-24 | 2021-05-28 | 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 |
| CN112892603A (en) * | 2019-12-03 | 2021-06-04 | 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 |
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| CN107793304A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院大连化学物理研究所 | A kind of method that alkene high selectivity prepares aldehyde |
| CN107790188A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院大连化学物理研究所 | A kind of metal organic copolymer containing phosphine catalyst and its preparation method and application |
| 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 |
| CN108067307A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation and application of multiphase asymmetric hydroformylation catalyst |
| 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 |
| CN109806911A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of highly selective catalyst for preparing linear chain aldehyde and its preparation and application |
| 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 |
| CN112892603A (en) * | 2019-12-03 | 2021-06-04 | 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 |
| 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 |
| CN111533837A (en) * | 2020-04-20 | 2020-08-14 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
| CN112844474A (en) * | 2020-12-24 | 2021-05-28 | 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 |
| 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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