CN106140302B - One kind containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its methods and applications - Google Patents
One kind containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its methods and applications Download PDFInfo
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- CN106140302B CN106140302B CN201510157747.2A CN201510157747A CN106140302B CN 106140302 B CN106140302 B CN 106140302B CN 201510157747 A CN201510157747 A CN 201510157747A CN 106140302 B CN106140302 B CN 106140302B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- 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
The invention discloses a kind of application of hierarchical porous structure containing organic mixed polymers-metal heterogeneous catalyst of phosphine and preparation method thereof and in hydroformylation of olefin,Heterogeneous catalyst is with metal Rh,Co or Ir are as active component,Contain the organic mixed polymers of phosphine as carrier using hierarchical porous structure,Organic mixed polymers containing phosphine is copolymerized by multiple tooth organophosphorus ligand and monodentate organophosphorus ligand,Preparation method is under inert gas,In organic solvent,Organophosphorus ligand,Crosslinking agent or not in addition,Radical initiator,It is mixed,Stirring,In autoclave,Using solvent thermal polymerization method,Carry out polymerization reaction,Obtain a kind of organic mixed polymers containing phosphine,In the solvent containing active component presoma,Obtained carrier is added,Stirring,Vacuum extracts organic solvent,Obtain heterogeneous catalyst,Such coordination bond type heterogeneous catalyst mixes the ratio of monodentate P ligand and multiple tooth P ligand in copolymer carrier by modulation,It can make the catalyst obtained both stability with higher.
Description
Technical field
The invention belongs to heterogeneous catalysis fields, and in particular to one kind containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its
Preparation method and application.
Background technique
The design and synthesis of porous organic material are increasingly becoming new one of the hot spot of poromerics research field, and traditional
Inorganic microporous material is compared with organic-metallic coordination polymer, and the skeleton of organic microporous polymer is by pure organic molecule structure
At each other by covalent key connection, with open duct and excellent porous.Importantly, since organic chemistry closes
At the diversity of method, synthesis path and framework mode abundant is provided for the building of organic molecule network, it can be by having
The organic molecule that destination introduces functionalization makes final material have corresponding property, and the structure by adjusting organic molecule can
With the porous of controlled material.In addition to this, in most cases, with the molecular network structure that is connected by non-covalent bond
Fragility is compared, organic microporous polymer be all by being covalently keyed, while material porous is maintained, molecular network
Structure is more firm.
Hydroformylation of olefin (Hydroformylation, also known as OXO-Synthesis) refers to transition-metal-carbonyl
Alkene and synthesis gas (CO/H under complex-catalyzed2) generate higher than a raw material olefin carbon aldehyde reaction, be to realize earliest
Industrial even phase complex catalysis process.The product aldehyde of hydroformylation of olefin is very useful chemical intermediate, it can
To 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
It is widely used in field of fine chemical as organic solvent, plasticizer and surfactant etc..
Table 1 describes the manufacturing condition of five generation catalyst of industrial application and catalytic performance compares, work
Five generation catalyst of industry are homogeneous catalyst, always without solving the losing issue of ligand and metal in reaction process.
Patent CN1319580A describes a variety of bidentate phosphite ester ligands with larger space steric hindrance, these ligands with
The homogeneous catalyst that the coordinations such as Rh and Co are formed, the hydroformylation reaction of higher olefins, the selection with the just different ratio of higher aldehyde
Property.But homogeneous catalyst is not easily recycled and ligand synthesis is more difficult.
Patent CN1210514A reports the Rh complex compound catalyst of hydroformylation of olefin, and Rh complex compound is using more
The organonitrogen compound of tooth makees ligand, containing the tertiary nitrogen group that at least one can be protonated in weak acid in ligand, but catalyst
Equally face the problem of being not easily recycled.
In patent CN102911021A, Rh 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 selectivity with higher, reduces the dosage of expensive biphosphine ligand, but catalyst system is still in this way
Homogeneous, catalyst can not reuse.
Cooperate in patent CN1986055A also with bis-phosphite and triphenylphosphine and Rh, forms composite catalyzing body
System, in the hydroformylation reaction of propylene, n-butanal and isobutylaldehyde molar ratio are greater than 20, significantly extend bisphosphite ligands
Service life, hence it is evident that reduce the dosage of triaryl phosphine, but substantially or homogeneous reaction, equally face catalyst recycling benefit
With difficult problem.
The manufacturing condition of five generation catalyst of industrial application and catalytic performance compare table 1
Hydroformylation of olefin is presently believed to be industrial largest homogeneous reaction process, passes through alkene every year
The aldehyde and alcohol of hydroformylation reaction production is about 9,000,000 tons, and industrially used at present is homogeneous catalyst, catalyst recycling benefit
With difficulty, the production cost is very high.The heterogeneouss of hydroformylation of olefin homogeneous catalyst are the inexorable trends of development.But it passes
The homogeneous catalysis heterogeneouss method of system exposes a series of needs and solves the problems, such as and overcome that especially heterogeneouss rear catalyst is steady
Qualitative difference, loss of active component are serious etc..
Summary of the invention
To solve the above-mentioned problems, the purpose of the present invention is to provide a kind of organic mixed polymers-metal heterogeneous catalysis containing phosphine
Agent and its preparation method and application.
The technical scheme is that：
A kind of organic mixed polymers-metal heterogeneous catalyst containing phosphine, with one of metal Rh, Co or Ir, two kinds, three kinds of works
For active component, using organic mixed polymers containing phosphine as carrier, metal loading is 0.01~10wt% in catalyst, organic mixed containing phosphine
Polymers is copolymerized by the multiple tooth organophosphorus ligand containing alkylene and the monodentate organophosphorus ligand containing alkylene.Active metal
Exposed p-shaped produces Gao Zhengyi in olefin hydroformylation at multiple coordinate bond, the catalyst of formation in component and mixed copolymer carrier
It is more excellent than being showed in aldehyde technique.
The alkylene is preferably vinyl, and the multiple tooth organophosphorus ligand containing alkylene is containing vinyl
Bidentate phosphites organophosphor ligand, the monodentate organophosphorus ligand containing alkylene are that the triphenylphosphine containing vinyl is matched
Body.
Organic mixed copolymer carrier has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously containing big
Hole, mesoporous and micropore, 0.1~5.0cm of Kong Rongwei3/ g, pore-size distribution is in 0.2~50.0nm.
The heterogeneous catalyst is after mixing multiple tooth organophosphorus ligand and monodentate organophosphorus ligand, using solvent hot polymerization
It is legal, cause the alkylene in organophosphorus ligand through radical initiator and polymerization reaction occurs, generation contains with hierarchical porous structure
The organic mixed polymers of phosphine is stirred as carrier, the presoma of active component with carrier in organic solvent, and active component has with containing phosphine
Machine mixes p-shaped exposed in copolymer carrier into multiple coordinate bond, after boiling off volatile solvent, obtains the heterogeneous catalysis of coordination bond type
Agent.
The preparation method of heterogeneous catalyst is：
A) at 273~473K, inert gas atmosphere, in organic solvent, monodentate organophosphorus ligand is added and multiple tooth has
Whether machine Phosphine ligands, addition crosslinking agent or not, add radical initiator, and after mixing, it is small to stir the mixture for 0.1~100
When, preferred mixing time range is 0.1~50 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere,
Using solvent thermal polymerization method, 1~100 hour progress polymerization reaction is stood, obtains a kind of organic mixed polymers containing phosphine；
C) the mixed polymers for obtaining step b), vacuum abstraction solvent is at room temperature to get to hierarchical porous structure
Organic mixed polymers containing exposed P, i.e., the carrier of the described heterogeneous catalyst；
D) at 273~473K, inert gas atmosphere, in the solvent containing active component presoma, step c) is added
Obtained organic mixed copolymer carrier stirs 0.1~100 hour, preferably mixing time range 0.1~50 hour, and later, vacuum is taken out
Except organic solvent, heterogeneous catalyst is obtained.
Organic solvent described in step a) is benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, dichloromethane or chloroform
Middle one or more；The crosslinking agent is styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodo-
One or more of tri- acetylenylbenzene of methane, paraformaldehyde or 1,3,5-；The radical initiator is peroxidating
Cyclohexanone, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or azobisisoheptonitrile it is one or two kinds of with
On.
The molar ratio of monodentate organophosphorus ligand and multiple tooth organophosphorus ligand described in step a) is 0.01:1~100:1,
In the case where crosslinking agent addition, the molar ratio of monodentate organophosphorus ligand and crosslinking agent is 0.01:1~10:1, monodentate organic phosphine
The molar ratio of ligand and radical initiator is 300:1~10:1, before aggregating into organic mixed polymers, monodentate organophosphorus ligand is having
Concentration range in solvent is 0.01-1000g/L.
Solvent described in step d) is water, benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, dichloromethane or chloroform
Middle one or more, the active component are one of Rh, Co, Ir, two or three, 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.It urges
Metal loading range is 0.01~10wt% in agent.
When prepared by the present invention, the property for the catalyst prepared can be controlled by the parameters of regulating catalyst
Can, to be suitable for different alkene, the hydroformylation reaction of different process.Such organic mixed polymers-metal heterogeneous catalyst containing phosphine
For hydroformylation of olefin, catalytic activity is high, and product stereoselectivity is good, can be used for fixed bed, trickle bed, slurry bed system and
It is bubbled in bed reaction technique.
Reaction principle of the invention：
The present invention will on the aromatic ring of typical biphosphine ligand such as Biphephos introduce vinyl (Vinyl) group, i.e., one
Multiple tooth organophosphorus ligand (Vinyl Biphephos) of the kind containing vinyl is used as polymerized monomer, and solvent is utilized in autoclave
Thermal polymerization is copolymerized to be formed with high surface area and multistage pore canal with monodentate organophosphorus ligand such as three (4- vinyl benzene) base phosphine
Organic mixed polymers of structure can be used as catalysis due to having a large amount of Ps of the exposure containing lone pair electrons in organic mixed polymer backbone
Agent carrier and active transition metal ion unoccupied orbital form multiple coordinate bond, and then form catalytic active site.In the catalyst,
Organic phosphine mixes polymers and is provided simultaneously with the dual function of carrier and ligand, and active metal component high dispersive is and highly concentrated in the carrier
Exposed p-shaped is spent into multiple coordinate bond.Active metal component is mixed in copolymer carrier with monatomic form high dispersive in organic phosphine, significantly
Improve the utilization efficiency of metal.And active component not easily runs off, catalyst life is long, and the multiple tooth Phosphine ligands in skeleton have aobvious
The stereoeffect of work, the catalyst prepared are remarkably improved the stereoselectivity of product.
Contain P in the organic mixed copolymer carrier skeleton of catalyst provided by the present invention, organic mixed polymers has both ligand and load
The dual function of body；Active metal component can be dispersed in this high surface area hierarchical porous structure in a manner of monatomic or ion
In organic mixed copolymer carrier, metal utilization efficiency is substantially increased.Carrier organic phosphine mixes the monophosphorus ligand structure in polymer backbone
Unit makes mixed polymers have higher P concentration, is easy to form double or multi-metal-P coordinate bond, the coordination with active metal component
Key has stronger chemical bonding ability, so that active component not easily runs off.
Beneficial effects of the present invention are：
Contain multiple tooth and monodentate organophosphorus ligand structural unit in heterogeneous catalyst skeleton of the present invention, wherein monodentate
Organophosphorus ligand makes on the surface of mixed polymers in the presence of higher exposed P, and multiple tooth Phosphine ligands then have significant stereoeffect, activity
Exposed p-shaped on metallic atom or ion and mixed polymers is at multiple coordinate bond, and active component not easily runs off, the active group of catalyst
It is divided into Rh, Co or Ir, such catalyst stereoselectivity with higher, mixing polymers has high-specific surface area hierarchical porous structure,
Has the dual function of carrier and ligand, active metal component mixes copolymer carrier duct in organic phosphine with monatomic form high dispersive
In or surface on, improve the utilization efficiency of metal component.
Such coordination bond type heterogeneous catalyst is suitable for fixed bed, slurry bed system, the reaction process such as bubbling bed and trickle bed, sheet
Hierarchical porous structure organic polymer containing phosphine-metal heterogeneous catalyst provided by inventing is applied to hydroformylation of olefin, energy
The conversion ratio of alkene and the selectivity of n-alkanal are enough significantly improved, can solve length during hydroformylation of olefin heterogeneouss
Stability and poor selectivity existing for phase and metal component are lost the problems such as serious.The alkene hydrogen of the catalyst is used simultaneously
The product of formylation reaction just different ratio with higher, reduces the industrial cost of olefin hydroformylation, catalyst stabilization
Property it is good, separating for reactant and product and catalyst is simple and efficiently, produces for olefin hydroformylation and provides new industry
Change technology.
Detailed description of the invention
In Fig. 1, A figure is the biphosphine ligand of typical alkylene functionalization, and B figure is Vinyl Biphephos structural representation
Figure.
Fig. 2 is Vinyl Biphephos polymerization technique route schematic diagram.
Fig. 3 is the signal of typical the monodentate organophosphorus ligand and multiple tooth organophosphorus ligand and crosslinking agent used in polymerization
Figure, wherein L1-L16 is monodentate organophosphorus ligand, and L17-L19 is multiple tooth organophosphorus ligand, and L20 and L21 are crosslinking agent.
Fig. 4 is Vinyl Biphephos ligand1H spectrum.
Fig. 5 is Vinyl Biphephos ligand13C spectrum.
Fig. 6 is Vinyl Biphephos ligand31P spectrum.
Fig. 7 is the high resolution mass spectrum of Vinyl Biphephos ligand.
Fig. 8 is N2The catalyst thermogravimetric curve that embodiment 1 synthesizes under atmosphere.
Specific embodiment
Following embodiments better illustrate the present invention, but do not limit invention which is intended to be protected.
Embodiment 1
At 298K and inert gas shielding atmosphere, 10.0 grams of Vinyl Biphephos monomers (attached drawing 1) are dissolved in
In 100.0ml tetrahydrofuran solvent, while 2.5g co-monomer three (4- vinyl benzene) base phosphine (L1) is added, adds into above-mentioned solution
Enter 1.0 grams of radical initiator azodiisobutyronitriles, stirs 2 hours.The solution being stirred is moved in autoclave, in 373K and
Under inert gas shielding atmosphere for 24 hours using the polymerization of solvent thermal polymerization method.Solution after above-mentioned polymerization is cooled to room temperature, room temperature item
Part vacuum takes solvent away to get organic to being copolymerized by Vinyl Biphephos and three (4- vinyl benzene) base phosphine organic monomers
Phosphine mixes polymers.Fig. 2 is the schematic diagram of the organic mixed copolymer carrier polymerization technique route of Vinyl Biphephos.Weigh 3.13 milligrams
Three rhodium carbonyl of acetylacetone,2,4-pentanedione is dissolved in 10.0ml tetrahydrofuran solvent, and 1.0 grams of organic mixed polymers obtained above are added, this is mixed
It closes object to stir 24 hours at 298K and inert gas shielding atmosphere, then vacuum takes solvent away at room temperature, that is, obtains
Coordination bond type heterogeneous catalyst applied to hydroformylation of olefin.
Embodiment 2
In example 2, in addition to weighing 10.0 grams of co-monomers three (4- vinyl benzene) base phosphine (L1), 2.5 grams of lists altogether are substituted
Body three (4- vinyl benzene) base phosphine, remaining catalyst synthesis processes are same as Example 1.
Embodiment 3
In embodiment 3,1.0 grams of free radicals initiations are substituted in addition to weighing 0.1 gram of radical initiator azodiisobutyronitrile
Outside agent azodiisobutyronitrile, remaining catalyst preparation process is same as Example 1.
Embodiment 4
In example 4, other than substituting 100.0ml tetrahydrofuran solvent with 50.0ml tetrahydrofuran solvent, remaining
Catalyst preparation process is same as Example 1.
Embodiment 5
In embodiment 5, other than substituting 100.0ml tetrahydrofuran solvent with 100.0ml dichloromethane solvent, remaining
Catalyst preparation process is same as Example 1.
Embodiment 6
In embodiment 6, other than substituting 373K polymerization temperature with 393K polymerization temperature, remaining catalyst preparation process
It is same as Example 1.
Embodiment 7
In embodiment 7, in addition to 12h polymerization time substitution for 24 hours other than polymerization time, remaining catalyst preparation process with
Embodiment 1 is identical.
Embodiment 8
In embodiment 8, other than adding 10.0 grams of L20 as crosslinking agent, remaining catalyst preparation process with
Embodiment 1 is identical.
Embodiment 9
In embodiment 9, other than adding 1.0 grams of styrene as crosslinking agent, remaining catalyst preparation process with
Embodiment 1 is identical.
Embodiment 10
In embodiment 10, weighs 14.05 milligrams of acetylacetone,2,4-pentanedione dicarbapentaborane cobalt substitution three rhodium carbonyls of acetylacetone,2,4-pentanedione and be dissolved in
Outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as Example 1.
Embodiment 11
In embodiment 11, weighs 2.05 milligrams of acetylacetone,2,4-pentanediones, three carbonyl iridium substitution three rhodium carbonyl of acetylacetone,2,4-pentanedione and be dissolved in
Outside 10.0ml tetrahydrofuran solvent, remaining catalyst synthesis processes is same as Example 1.
Embodiment 12
By in the catalyst 0.5g fixed bed reactors of above-mentioned preparation, both ends are packed into quartz sand.Micro feed pump is pumped into 1-
Octene, flow 0.1ml/min, mass flowmenter control synthesis gas (H2:CO=1:1) air speed 1000h-1, in 373K, 1MPa
Under the conditions of carry out hydroformylation reaction.Reaction is collected through the cooling collecting tank of ice bath.Obtained liquid product, which uses, is furnished with HP-5
The HP-7890N gas chromatographic analysis of capillary column and fid detector, makees internal standard using normal propyl alcohol.The tail gas that collecting tank comes out is adopted
On-line analysis is carried out with the HP-7890N gas-chromatography equipped with Porapak-QS column and TCD detector.Reaction result is listed in table 1.
The specific surface area of catalyst and 1- octene response data synthesized in 1 embodiment 1-11 of table
* it is 0.1ml/min, synthesis gas (CO that experiment condition, which is 100 DEG C, 1MPa, 1- octene flows,:H2=1:1) air speed
1000h-1, TOF calculate when think that all metals are active sites.* indicates that reaction temperature is 230 DEG C, the work of embodiment 10
Property group be divided into Co, the active component of embodiment 11 is Ir.
Claims (8)
1. a kind of containing the organic mixed polymers of phosphine-application of the metal heterogeneous catalyst in hydroformylation of olefin, it is characterised in that：
Parameters when being prepared by regulating catalyst control the performance of the catalyst prepared, to be suitable for different alkene
Hydrocarbon, the hydroformylation reaction of different process；
Organic mixed polymers-metal heterogeneous catalyst containing phosphine, using one of metal Rh, Co or Ir, two kinds, three kinds as live
Property component, using organic mixed polymers containing phosphine as carrier, organic mixed polymers containing phosphine is by the multiple tooth organophosphorus ligand containing alkylene and contains
There is the monodentate organophosphorus ligand of alkylene to be copolymerized, metal loading range is 0.01~10wt% in catalyst；Described
Multiple tooth organophosphorus ligand containing alkylene is：
The monodentate organophosphorus ligand containing alkylene is：
One of.
2. application of the heterogeneous catalyst described in accordance with the claim 1 in hydroformylation of olefin, it is characterised in that：It is described
Organic mixed copolymer carrier have hierarchical porous structure, specific surface area be 100~3000m2/ g, simultaneously containing macropore, mesoporous and micro-
Hole, 0.1~5.0cm of Kong Rongwei3/ g, pore-size distribution is in 0.2~50.0nm.
3. application of the heterogeneous catalyst described in accordance with the claim 1 in hydroformylation of olefin, it is characterised in that：It is described
Heterogeneous catalyst be after mixing multiple tooth organophosphorus ligand and monodentate organophosphorus ligand, using solvent thermal polymerization method, through freedom
Base initiator causes the alkylene in organophosphorus ligand and polymerization reaction occurs, and generating has hierarchical porous structure organic mixed polymers containing phosphine
As carrier, the presoma of active component stirs in organic solvent with carrier, active component and organic mixed copolymer carrier containing phosphine
In exposed p-shaped at multiple coordinate bond, after boiling off volatile solvent, obtain the heterogeneous catalyst of coordination bond type.
4. according to application of any heterogeneous catalyst of claim 1-3 in hydroformylation of olefin, which is characterized in that
The preparation method of organic mixed polymers-metal heterogeneous catalyst containing phosphine is：
A) at 273~473K, inert gas atmosphere, in organic solvent, monodentate organophosphorus ligand and multiple tooth organic phosphine is added
Whether ligand, addition crosslinking agent or not, add radical initiator, after mixing, stir the mixture for 0.1~100 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, is used
Solvent thermal polymerization method stands 1~100 hour progress polymerization reaction, obtains a kind of organic mixed polymers containing phosphine；
C) the mixed polymers for obtaining step b), vacuum abstraction solvent is at room temperature to get to having hierarchical porous structure containing
There are organic mixed polymers of exposed P, i.e., the carrier of the described heterogeneous catalyst；
D) at 273~473K, inert gas atmosphere, in the solvent containing active component presoma, step c) is added and obtains
Organic mixed copolymer carrier, stir 0.1~100 hour, later, vacuum extract organic solvent, obtain heterogeneous catalyst.
5. application of the heterogeneous catalyst in hydroformylation of olefin according to claim 4, it is characterised in that：Step
A) organic solvent described in is benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, one or two kinds of in dichloromethane or chloroform
More than；The crosslinking agent is styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde
Or one or more of tri- acetylenylbenzene of 1,3,5-；The radical initiator is cyclohexanone peroxide, peroxidating
Dibenzoyl, tert-butyl hydroperoxide, the one or more of azodiisobutyronitrile or azobisisoheptonitrile.
6. application of the heterogeneous catalyst in hydroformylation of olefin according to claim 4, it is characterised in that：Step
A) molar ratio of monodentate organophosphorus ligand and multiple tooth organophosphorus ligand described in is 0.01:1~100:1, it is added in crosslinking agent
In the case where, the molar ratio of monodentate organophosphorus ligand and crosslinking agent is 0.01:1~10:1, monodentate organophosphorus ligand and free radical
The molar ratio of initiator is 300:1~10:1, before aggregating into organic mixed polymers, monodentate organophosphorus ligand in organic solvent dense
Degree range is 0.01-1000g/L.
7. application of the heterogeneous catalyst in hydroformylation of olefin according to claim 4, it is characterised in that：Step
D) solvent described in is water, benzene, toluene, tetrahydrofuran, methanol, ethyl alcohol, one or two kinds of in dichloromethane or chloroform
More than, the active component is one or more of 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, gold in catalyst
Category loading range is 0.01~10wt%.
8. application of the heterogeneous catalyst in hydroformylation of olefin according to claim 4, it is characterised in that：Step
A) the mixing time range in and d) is 0.1~50 hour.
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| 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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| 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 |
| CN110982105B (en) * | 2019-11-06 | 2022-07-29 | 华侨大学 | Ruthenium nanoparticle-loaded catalyst |
| CN112892604B (en) * | 2019-12-03 | 2022-09-20 | 中国科学院大连化学物理研究所 | Organic amine and CO 2 Heterogeneous catalysis method for preparing formamide |
| CN112898138B (en) * | 2019-12-03 | 2022-09-27 | 中国科学院大连化学物理研究所 | High-value utilization method of Fischer-Tropsch product |
| CN113877635B (en) * | 2021-10-27 | 2024-02-06 | 南京延长反应技术研究院有限公司 | Iridium-based catalyst, preparation method thereof and hydroformylation method |
| 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 |
| CN116410390B (en) * | 2021-12-31 | 2024-05-10 | 中国石油天然气股份有限公司 | Preparation method of organic phosphine ligand polymer and bidentate phosphine ligand copolymer catalyst |
| CN114591159B (en) * | 2022-03-10 | 2023-04-07 | 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 |
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| US6143834A (en) * | 1997-03-11 | 2000-11-07 | Takasago International Corporation | Optically active phosphine derivative having at least two vinyl groups, polymer produced using the same as monomer, and transition metal complexes of these |
| CN101642719A (en) * | 2008-08-07 | 2010-02-10 | 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 |
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| CN102281948A (en) * | 2008-11-14 | 2011-12-14 | 堪萨斯大学 | Polymer-supported transition metal catalyst complexes and methods of use |
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| 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 |
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| CN106140302A (en) | 2016-11-23 |
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