CN106140302A - A kind of containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and methods and applications thereof - Google Patents
A kind of containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and methods and applications thereof Download PDFInfo
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- CN106140302A CN106140302A CN201510157747.2A CN201510157747A CN106140302A CN 106140302 A CN106140302 A CN 106140302A CN 201510157747 A CN201510157747 A CN 201510157747A CN 106140302 A CN106140302 A CN 106140302A
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract
nullThe invention discloses a kind of hierarchical porous structure containing organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation method thereof and the application in hydroformylation of olefin，Heterogeneous catalyst is with metal Rh、Co or Ir is as active component，Using hierarchical porous structure organic mixed polymers Han phosphine as carrier，Form by multiple tooth organophosphorus ligand and monodentate organophosphorus ligand copolymerization containing the organic mixed polymers of phosphine，Preparation method is under noble gas，In organic solvent，Organophosphorus ligand、Add or without cross-linking agent、Radical initiator，It is mixed，Stirring，In autoclave，Use solvent thermal polymerization method，Carry out polyreaction，Obtain a kind of organic mixed polymers Han phosphine，In the solvent containing active component presoma，Add the carrier obtained，Stirring，Vacuum extracts organic solvent，Obtain heterogeneous catalyst，This type of coordination of bonding heterogeneous catalyst mixes monodentate P part and the ratio of multiple tooth P part in copolymer carrier by modulation，The catalyst that can make acquisition had both had higher stability.
Description
Technical field
The invention belongs to heterogeneous catalysis field, be specifically related to a kind of organic mixed polymers-metal heterogeneous catalyst Han phosphine
And its preparation method and application.
Background technology
The design of porous organic material and synthesis are increasingly becoming one of new focus of poromerics research field, with
Traditional inorganic microporous material is compared with organic-metallic coordination polymer, and the skeleton of organic microporous polymer is by pure
Pure organic molecule is constituted, and connects each other by covalent bond, has open duct and excellent porous.
The more important thing is, due to the multiformity of organic chemical synthesis method, the structure for organic molecule network provides
Abundant synthesis path and framework mode, can make finally by purpose introducing the organic molecule of functionalization
Material there is corresponding character, by regulation organic molecule structure can be with the porous of controlled material.Remove
Beyond this, in most of the cases, compared with the molecular network structure fragility connected into by non-covalent bond,
Organic microporous polymer is all to be connected by covalent bond, while material hole character is maintained, and molecular network
Network structure is more firm.
Hydroformylation of olefin (Hydroformylation, also known as OXO-Synthesis) refers to transition metal
Alkene under carbonyl-complexes catalysis and synthesis gas (CO/H2) generate the reaction of the aldehyde of a high carbon than raw material olefin,
It is to realize industrial even phase complex catalysis process the earliest.The product aldehyde of hydroformylation of olefin is to have very much
Chemical intermediate, it can be used to synthesis of carboxylic acid and corresponding ester, and fatty amine etc., most important
Purposes is that it can be hydroconverted into alcohol, and alcohol itself can be wide as organic solvent, plasticizer and surfactant etc.
General it is applied to field of fine chemical.
Table 1 describes the manufacturing condition of five generation catalyst of commercial Application and catalytic performance compares,
The most industrialized five generation catalyst are homogeneous catalyst, the most do not solve part and gold in course of reaction
The losing issue belonged to.
Patent CN1319580A describes the multiple bidentate phosphite ester ligand with larger space steric hindrance, these
Part is coordinated the homogeneous catalyst formed, the hydroformylation reaction of its higher olefins with Rh and Co etc., has relatively
The selectivity of the most different ratio of high aldehyde.But homogeneous catalyst is not easily recycled and part synthesis more difficulty.
Patent CN1210514A reports the Rh complex compound catalyst of hydroformylation of olefin, and Rh complex is
Multiple tooth organonitrogen compound is used to make part, containing at least one uncle being protonated in weak acid in part
Nitrilo, but catalyst faces the problem being not easily recycled equally.
In patent CN102911021A, utilize Rh coordination compound and biphenyl backbone or dinaphthalene skeleton biphosphine ligand, with
And the composite catalyst system of triphenylphosphine or phosphite ester triphenylmethyl methacrylate monophosphorus ligand composition is catalyst, at straight chain
In hydroformylation of olefin, n-alkanal has higher selectivity, which decreases expensive pair of phosphine and joins
The consumption of body, but catalyst system and catalyzing or homogeneous, catalyst cannot reuse.
Coordinating with Rh also with bis-phosphite and triphenylphosphine in patent CN1986055A, composition is compound urges
Change system, in the hydroformylation reaction of propylene, hutanal and isobutylaldehyde mol ratio, more than 20, significantly extend
Service life of bisphosphite ligands, hence it is evident that reduce the consumption of triaryl phosphine, but substantially or all
Phase reaction, faces the problem that catalyst recycles difficulty equally.
Manufacturing condition and the catalytic performance of five generation catalyst of table 1 commercial Application compare
Hydroformylation of olefin is presently believed to be industrial largest homogeneous reaction process, leads to every year
Cross aldehyde that hydroformylation of olefin produces and alcohol be about 9,000,000 tons, industrial currently used be homogeneous catalysis
Agent, catalyst recycles difficulty, and production cost is the highest.Hydroformylation of olefin homogeneous catalyst is many
Change the inexorable trend being to develop mutually.But traditional homogeneous catalysis heterogenize method exposes a series of needs to be solved
The problem determined and overcome, especially heterogenize rear catalyst poor stability, loss of active component is serious.
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 organic mixed polymers-metal Han phosphine heterogeneous
Catalyst and its preparation method and application.
The technical scheme is that
A kind of organic mixed polymers-metal heterogeneous catalyst Han phosphine, with the one in metal Rh, Co or Ir, two kinds,
Three kinds as active component, with organic mixed polymers containing phosphine as carrier, in catalyst, metal loading is
0.01～10wt%, containing the organic mixed polymers of phosphine by the multiple tooth organophosphorus ligand containing alkylene with containing alkylene
Monodentate organophosphorus ligand copolymerization forms.The p-shaped that active metal component is exposed with mixed copolymer carrier becomes multiple and joins
Position key, it is the most different more excellent than showing in aldehyde technique that the catalyst of formation produces height at olefin hydroformylation.
Described alkylene is preferably vinyl, and the described multiple tooth organophosphorus ligand containing alkylene is containing second
The bidentate phosphites organophosphor ligand of thiazolinyl, the described monodentate organophosphorus ligand containing alkylene is containing second
The triphenylphosphine ligand of thiazolinyl.
Described organic mixed copolymer carrier has hierarchical porous structure, and specific surface area is 100～3000m2/ g, contains simultaneously
Having macropore, mesopore and micropore, pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
Described heterogeneous catalyst is by after multiple tooth organophosphorus ligand and the mixing of monodentate organophosphorus ligand, uses molten
Agent thermal polymerization, the alkylene generation polyreaction in radical initiator causes organophosphorus ligand, generate
Having hierarchical porous structure containing the organic mixed polymers of phosphine as carrier, the presoma of active component and carrier are organic molten
Stirring in agent, active component becomes multiple coordinate bond with containing p-shaped exposed in the organic mixed copolymer carrier of phosphine, boils off and wave
After the property sent out solvent, obtain being coordinated the heterogeneous catalyst of of bonding.
The preparation method of heterogeneous catalyst is:
A) 273～473K, under inert gas atmosphere, in organic solvent, add monodentate organophosphorus ligand and
Multiple tooth organophosphorus ligand, interpolation or without cross-linking agent, add radical initiator, after mixing, will be mixed
Compound stirs 0.1～100 hour, and preferred mixing time scope is 0.1～50 hour；
B) it is transferred to mixed solution prepared for step a) synthesize in autoclave, 273～473K, indifferent gas bromhidrosis
Under atmosphere, use solvent thermal polymerization method, stand and carry out polyreaction in 1～100 hour, obtain a kind of organic mixed containing phosphine
Polymers；
C) the mixed polymers obtained by step b), vacuum extracts solvent at ambient temperature, i.e. obtains having multistage
The organic mixed polymers containing exposed P of pore structure, the carrier of the most described heterogeneous catalyst；
D) 273～473K, under inert gas atmosphere, in the solvent containing active component presoma, add
The organic mixed copolymer carrier that step c) obtains, stirs 0.1～100 hour, and preferably mixing time scope 0.1～50 is little
Time, afterwards, vacuum extracts organic solvent, obtains heterogeneous catalyst.
Organic solvent described in step a) is benzene, toluene, oxolane, methanol, ethanol, dichloromethane
Or in chloroform one or more；Described cross-linking agent is styrene, ethylene, propylene, divinyl
One or two in base benzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-tri-acetylenylbenzene
More than Zhong；Described radical initiator is cyclohexanone peroxide, dibenzoyl peroxide, t-butyl peroxy
Change hydrogen, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile) one or more.
The mol ratio of the monodentate organophosphorus ligand described in step a) and multiple tooth organophosphorus ligand is
0.01:1～100:1, in the case of cross-linking agent adds, monodentate organophosphorus ligand with the mol ratio of cross-linking agent is
0.01:1～10:1, monodentate organophosphorus ligand is 300:1～10:1 with the mol ratio of radical initiator, aggregates into
Before organic mixed polymers, monodentate organophosphorus ligand concentration range in organic solvent is 0.01-1000g/L.
Solvent described in step d) is water, benzene, toluene, oxolane, methanol, ethanol, dichloromethane
Or in chloroform one or more, described active component be the one in Rh, Co, Ir, two kinds
Or three kinds, wherein the presoma of Rh is Rh (CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；
The presoma of Co is Co (CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2；The presoma of Ir is
Ir(CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4.In catalyst, metal loading scope is
0.01～10wt%.
Time prepared by the present invention, can be by the parameters of regulating catalyst and then control the catalyst prepared
Performance, to be applicable to different alkene, the hydroformylation reaction of different process.This type of containing the organic mixed polymers of phosphine-
Metal heterogeneous catalyst is used for hydroformylation of olefin, and catalysis activity is high, and product stereo selectivity is good, can
In fixed bed, trickle bed, slurry bed system and bubbling bed reaction process.
The reaction principle of the present invention:
The present invention will introduce vinyl (Vinyl) base on the aromatic ring of typical biphosphine ligand such as Biphephos
Group, a kind of multiple tooth organophosphorus ligand (Vinyl Biphephos) conduct polymerization monomer containing vinyl,
Solvent thermal polymerization method is utilized, with monodentate organophosphorus ligand such as three (4-vinyl benzene) base phosphine altogether in autoclave
Combinate form becomes to have the organic mixed polymers of high surface and multi-stage artery structure, due in this organic mixed polymer backbone
There is a large amount of P exposing and containing lone pair electrons, can be as catalyst carrier and active transition metal ion unoccupied orbital
Form multiple coordinate bond, and then form catalytic active site.In this catalyst, organic phosphine mixes polymers to be had simultaneously
Standby carrier and the dual-use function of part, active metal component high dispersive in this carrier, p-shaped exposed with high concentration
Become multiple coordinate bond.Active metal component with monatomic form high dispersive in organic phosphine mixes copolymer carrier, greatly
Improve greatly the utilization ratio of metal.And active component not easily runs off, catalyst life is long, many in skeleton
Tooth Phosphine ligands has significant stereoeffect, and the catalyst prepared is remarkably improved the three-dimensional selection of product
Property.
Containing P in the organic mixed copolymer carrier skeleton of catalyst provided by the present invention, organic mixed polymers has part concurrently
Dual-use function with carrier；Active metal component can be dispersed in this big table in the way of monatomic or ion
In the organic mixed copolymer carrier of area hierarchical porous structure, substantially increase metal utilization ratio.Carrier organic phosphine mixes
Monophosphorus ligand construction unit in polymer backbone makes mixed polymers have higher P concentration, easy and active metal group
Dividing and form double or multi-metal-P coordinate bond, this coordinate bond has stronger chemical bonding ability so that live
Property component not easily runs off.
The invention have the benefit that
Containing multiple tooth and monodentate organophosphorus ligand construction unit in heterogeneous catalyst skeleton of the present invention, its
Middle monodentate organophosphorus ligand makes to there is higher exposed P on the surface of mixed polymers, and multiple tooth Phosphine ligands then has significantly
Stereoeffect, active metal atom or ion become multiple coordinate bond with the exposed p-shaped on mixed polymers, activity
Component not easily runs off, and the active component of catalyst is Rh, Co or Ir, and this type of catalyst has higher solid
Selectivity, mixed polymers has high-specific surface area hierarchical porous structure, possesses the dual-use function of carrier and part, lives
Property metal component, improves in organic phosphine mixes copolymer carrier duct or on surface with monatomic form high dispersive
The utilization ratio of metal component.
This type of coordination of bonding heterogeneous catalyst is applicable to fixed bed, slurry bed system, and bubbling bed and trickle bed etc. react
Technique, hierarchical porous structure provided by the present invention is applied to alkene containing phosphine organic polymer-metal heterogeneous catalyst
Hydroformylation reaction, it is possible to significantly improve the conversion ratio of alkene and the selectivity of n-alkanal, alkene can be solved
Long-standing stability and poor selectivity during hydroformylation reaction heterogenize, and metal component loss
The problem such as serious.The product simultaneously using the hydroformylation of olefin of this catalyst has the most different higher ratio,
Reducing the industrial cost of olefin hydroformylation, catalyst stability is good, reactant and product and catalysis
The separation of agent is simple and efficient, produces for olefin hydroformylation and provides new industrialization technology.
Accompanying drawing explanation
In Fig. 1, A figure is the biphosphine ligand of typical alkylene functionalization, and B figure is Vinyl Biphephos
Structural representation.
Fig. 2 is Vinyl Biphephos polymerization technique route schematic diagram.
Fig. 3 is the typical monodentate organophosphorus ligand and multiple tooth organophosphorus ligand and cross-linking agent used in polymerization
Schematic diagram, wherein, L1-L16 is monodentate organophosphorus ligand, and L17-L19 is monodentate organophosphorus ligand, L20 and
L21 is cross-linking agent.
Fig. 4 is Vinyl Biphephos part1H composes.
Fig. 5 is Vinyl Biphephos part13C composes.
Fig. 6 is Vinyl Biphephos part31P composes.
Fig. 7 is the high resolution mass spectrum of Vinyl Biphephos part.
Fig. 8 is N2The catalyst thermogravimetric curve of embodiment 1 synthesis under atmosphere.
Detailed description of the invention
The present invention is better illustrated by following embodiment, but is not intended to invention which is intended to be protected.
Embodiment 1
Under 298K and inert gas shielding atmosphere, by 10.0 grams of Vinyl Biphephos monomers (accompanying drawing 1)
It is dissolved in 100.0ml tetrahydrofuran solvent, is simultaneously introduced 2.5g co-monomer three (4-vinyl benzene) base phosphine (L1),
In above-mentioned solution, add 1.0 grams of radical initiator azodiisobutyronitriles, stir 2 hours.To be stirred
Solution move in autoclave, utilize under 373K and inert gas shielding atmosphere solvent thermal polymerization method polymerization 24
h.Solution after above-mentioned polymerization is cooled to room temperature, and room temperature condition vacuum takes solvent away, i.e. obtains by Vinyl
The organic phosphine of Biphephos and three (4-vinyl benzene) base phosphine organic monomer copolymerization mixes polymers.Fig. 2 is Vinyl
The schematic diagram of the organic mixed copolymer carrier polymerization technique route of Biphephos.Weigh 3.13 milligrams of acetylacetone,2,4-pentanediones three
Rhodium carbonyl is dissolved in 10.0ml tetrahydrofuran solvent, adds 1.0 grams of above-mentioned prepared organic mixed polymers, by this
Mixture stirs 24 hours under 298K and inert gas shielding atmosphere, and vacuum is taken out the most at ambient temperature
Walk solvent, i.e. obtain the coordination of bonding heterogeneous catalyst being applied to hydroformylation of olefin.
Embodiment 2
In example 2, except weighing 10.0 grams of co-monomers three (4-vinyl benzene) base phosphine (L1), substitute
2.5 grams of co-monomer three (4-vinyl benzene) base phosphines, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 3
In embodiment 3, except weighing 0.1 gram of radical initiator azodiisobutyronitrile replacement 1.0 grams certainly
Outside by base initiator azodiisobutyronitrile, remaining catalyst preparation process is same as in Example 1.
Embodiment 4
In example 4, in addition to substituting 100.0ml tetrahydrofuran solvent with 50.0ml tetrahydrofuran solvent,
Remaining catalyst preparation process is same as in Example 1.
Embodiment 5
In embodiment 5, except substituting 100.0ml tetrahydrofuran solvent with 100.0ml dichloromethane solvent
Outward, remaining catalyst preparation process is same as in Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 373K polymerization temperature with 393K polymerization temperature, remaining catalysis
Agent preparation process is same as in Example 1.
Embodiment 7
In embodiment 7, in addition to substituting 24h polymerization time with 12h polymerization time, remaining catalyst
Preparation process is same as in Example 1.
Embodiment 8
In embodiment 8, except add 10.0 grams of L20 as cross-linking agent in addition to, its remaining catalyst system
Standby process is same as in Example 1.
Embodiment 9
In embodiment 9, except add 1.0 grams of styrene as cross-linking agent in addition to, remaining catalyst system
Standby process is same as in Example 1.
Embodiment 10
In embodiment 10, weigh 14.05 milligrams of acetylacetone,2,4-pentanedione dicarbapentaborane cobalts and substitute acetylacetone,2,4-pentanedione three rhodium carbonyl
Being dissolved in outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 11
In embodiment 11, weigh 2.05 milligrams of acetylacetone,2,4-pentanedione three carbonyl iridium and substitute acetylacetone,2,4-pentanedione three rhodium carbonyl
Being dissolved in outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as in Example 1.
Embodiment 12
By in the catalyst 0.5g fixed bed reactors of above-mentioned preparation, two ends load quartz sand.Trace feed pump
Pumping into 1-octene, its flow is 0.1ml/min, and mass flowmenter controls synthesis gas (H2: CO=1:1) air speed
1000h-1, under the conditions of 373K, 1MPa, carry out hydroformylation reaction.React the collecting tank through ice bath cooling to receive
Collection.Obtained fluid product uses the HP-7890N gas phase color being furnished with HP-5 capillary column and fid detector
Analysis of spectrum, uses normal propyl alcohol to make internal standard.Collecting tank tail gas out uses is furnished with Porapak-QS post and TCD
The HP-7890N gas chromatogram of detector carries out on-line analysis.Reaction result is listed in table 1.
The specific surface area of catalyst synthesized in table 1 embodiment 1-11 and 1-octene response data
* experiment condition is 100 DEG C, and 1MPa, 1-octene flow is 0.1ml/min, synthesis gas (CO:H2=1:1) air speed 1000h-1, TOF thinks institute when calculating
Some metals are all avtive spots.* represents that reaction temperature is 230 DEG C, and the active component of embodiment 10 is Co, and the active component of embodiment 11 is Ir.
Claims (10)
1. organic mixed polymers-metal heterogeneous catalyst Han phosphine, it is characterised in that: in described heterogeneous catalyst
Using the one in metal Rh, Co or Ir, two kinds, three kinds as active component, with containing the organic mixed polymers of phosphine
For carrier, containing the organic mixed polymers of phosphine by the multiple tooth organophosphorus ligand containing alkylene and the monodentate containing alkylene
Organophosphorus ligand copolymerization forms, and in catalyst, metal loading scope is 0.01～10wt%.
2. according to the heterogeneous catalyst described in claim 1, it is characterised in that: described alkylene is ethylene
Base functional group.
3. according to the heterogeneous catalyst described in claim 1, it is characterised in that: described containing alkylene
Multiple tooth organophosphorus ligand is the bidentate phosphites organophosphor ligand containing vinyl, described containing alkylene
Monodentate organophosphorus ligand be the triphenylphosphine ligand containing vinyl.
4. according to the heterogeneous catalyst described in claim 1, it is characterised in that: described organic mixed polymers carries
Body has hierarchical porous structure, and specific surface area is 100～3000m2/ g, contains macropore, mesopore and micropore simultaneously,
Pore volume is 0.1～5.0cm3/ g, pore-size distribution is 0.2～50.0nm.
5. according to the heterogeneous catalyst described in claim 1, it is characterised in that: described heterogeneous catalyst is
After multiple tooth organophosphorus ligand and monodentate organophosphorus ligand are mixed, use solvent thermal polymerization method, draw through free radical
Sending out agent and cause the alkylene generation polyreaction in organophosphorus ligand, it is organic containing phosphine that generation has hierarchical porous structure
Mixed polymers stirs with carrier in organic solvent as carrier, the presoma of active component, active component with contain
In the organic mixed copolymer carrier of phosphine, exposed p-shaped becomes multiple coordinate bond, after boiling off volatile solvent, is coordinated
The heterogeneous catalyst of of bonding.
6. the preparation method of the arbitrary described heterogeneous catalyst of claim 1-5, it is characterised in that:
A) 273～473K, under inert gas atmosphere, in organic solvent, add monodentate organophosphorus ligand and
Multiple tooth organophosphorus ligand, interpolation or without cross-linking agent, add radical initiator, after mixing, will be mixed
Compound stirs 0.1～100 hour, and preferred mixing time scope is 0.1～50 hour；
B) it is transferred to mixed solution prepared for step a) synthesize in autoclave, 273～473K, indifferent gas bromhidrosis
Under atmosphere, use solvent thermal polymerization method, stand and carry out polyreaction in 1～100 hour, obtain a kind of organic containing phosphine
Mixed polymers；
C) the mixed polymers obtained by step b), vacuum extracts solvent at ambient temperature, i.e. obtains having multistage
The organic mixed polymers containing exposed P of pore structure, the carrier of the most described heterogeneous catalyst；
D) 273～473K, under inert gas atmosphere, in the solvent containing active component presoma, add
The organic mixed copolymer carrier that step c) obtains, stirs 0.1～100 hour, preferably mixing time scope 0.1～50
Hour, afterwards, vacuum extracts organic solvent, obtains heterogeneous catalyst.
7. according to the preparation method described in claim 6, it is characterised in that: organic molten described in step a)
Agent be in benzene, toluene, oxolane, methanol, ethanol, dichloromethane or chloroform one or both with
On；Described cross-linking agent is styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodo-
One or more in methane, paraformaldehyde or 1,3,5-tri-acetylenylbenzene；Described free radical causes
Agent is cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or azo
One or more of two different heptonitriles.
8. according to the preparation method described in claim 6, it is characterised in that: the monodentate described in step a) has
The mol ratio of machine Phosphine ligands and multiple tooth organophosphorus ligand is 0.01:1～100:1, in the case of cross-linking agent adds,
Monodentate organophosphorus ligand is 0.01:1～10:1 with the mol ratio of cross-linking agent, and monodentate organophosphorus ligand draws with free radical
The mol ratio sending out agent is 300:1～10:1, and before aggregating into organic mixed polymers, monodentate organophosphorus ligand is organic molten
Concentration range in agent is 0.01-1000g/L.
9. according to the preparation method described in claim 6, it is characterised in that: the solvent described in step d) is
In water, benzene, toluene, oxolane, methanol, ethanol, dichloromethane or chloroform one or both with
On, described active component is one or more in Rh, Co, Ir, and wherein the presoma of Rh is
Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3；The presoma of Co is Co (CH3COO)2、
Co(CO)2(acac)、Co(acac)2、CoCl2；The presoma of Ir is Ir (CO)3(acac)、Ir(CH3COO)3、
Ir(acac)3、IrCl4, in catalyst, metal loading scope is 0.01～10wt%.
10. according to the application in hydroformylation of olefin of the claim 1-5 arbitrary described heterogeneous catalyst,
It is characterized in that: the catalyst that parameters when being prepared by regulating catalyst and then control is prepared
Performance, to be applicable to different alkene, the hydroformylation reaction of different process.
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| CN201510157747.2A CN106140302B (en) | 2015-04-03 | 2015-04-03 | One kind containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its methods and applications |
| PCT/CN2015/095604 WO2016155339A1 (en) | 2015-04-03 | 2015-11-26 | Phosphine-containing organic mixed polymer-metal heterogeneous catalyst, and preparation method therefor and application thereof |
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| CN114591159A (en) * | 2022-03-10 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for internal olefin hydroformylation reaction by using phosphine oxide polymer supported catalyst |
| CN115873221A (en) * | 2021-12-17 | 2023-03-31 | 浙江新和成股份有限公司 | Phosphorus-containing polymer and preparation method and application thereof |
| CN116178623A (en) * | 2021-11-26 | 2023-05-30 | 中国科学院大连化学物理研究所 | Phosphine ligand organic polymer and application thereof |
| WO2023125073A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Methods for preparing organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst |
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| JP3892932B2 (en) * | 1997-03-11 | 2007-03-14 | 高砂香料工業株式会社 | Optically active phosphine derivatives having a vinyl group, polymers using the same, and transition metal complexes thereof |
| JP3892931B2 (en) * | 1997-03-11 | 2007-03-14 | 高砂香料工業株式会社 | Optically active phosphine derivative having two vinyl groups, polymer using the same, and transition metal complexes thereof |
| US6660876B2 (en) * | 2001-11-26 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions |
| 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 |
| CN101642719B (en) * | 2008-08-07 | 2012-08-22 | 中国科学院大连化学物理研究所 | Anchor ligand modified metal supported catalyst and preparation method and application thereof |
| AU2009313838B2 (en) * | 2008-11-14 | 2015-02-05 | University Of Kansas | Polymer-supported transition metal catalyst complexes and methods of use |
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| WO2016155339A1 (en) | 2016-10-06 |
| CN106140302B (en) | 2018-11-27 |
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