CN105754081A - P and O (N) containing organic polymer and preparation method thereof - Google Patents
P and O (N) containing organic polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a P and O (N) containing organic polymer.Organic monomers containing P, O (N) and alcoholic hydroxyl groups (phenolic hydroxyl groups) or amino groups are selected for generation of the P and O (N) containing organic polymer according to a solvent thermal polymerization method by condensation polymerization with a cross-linking agent for cross linking.The P and O (N) containing organic polymer is applicable to preparation of heterogeneous reaction catalysts and has dual functions of a carrier and a ligand, and when the polymer serve as the carrier to load active metal components to prepare supported metal catalysts, the metal components are highly dispersed in the carrier; the P and O (N) containing organic polymer can also serve as a ligand similar to reactive metal ions in homogeneous complex catalysis.Due to a strong coordinate bond function between P and O (N) in a polymer carrier skeleton and the metal components, the active metal components in a monatomic form are highly dispersed in the polymer carrier, and accordingly metal utilization efficiency is greatly improved, and the active metal components are less prone to losing.
Description
Technical field
The preparation method that the present invention relates to a kind of organic polymer containing P and O (N), belongs 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 following four according to different thinkings of constructing: (1) stops the closelypacked super cross linked polymer (Hyper-CrosslinkedPolymers, HCPs) of macromolecular chain by intensive crosslinking；(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).
Qing-huaFan in 1999 et al. (J.Am.Chem.Soc, 1999,121,7407) by didentate phosphine ligand BINAP amino-functional dough, the glycol of chirality is as co-monomer, p-phenylenediamine is cross-linking agent, has synthesized the good chiral polymer of dissolubility in dichloroethanes first, and this Polymer Supported achieves after Ru metal good catalytic effect in asyininetric hydrogenation.This polymer is solvable at many organic solvents in dichloromethane etc., and during reaction, polymer is dissolved in solvent based and is similar to homogeneous reaction, but which also limits the application in some occasion such as fixed bed reaction of this polymer.
2000, the organic institute in Shanghai LiZhang et al. (JournalofFluorineChemistry, 2000,102,55) introducing on the phenyl ring of hydroquinone by F atom, follow-up crosslinking with p-phthalic acid or paraphthaloyl chloride paraphthaloyl chloride can petchem containing F atom.Possible application field and prospect author not research for this polymer.
2002, ChristineSaluzzo et al. (Tetrahedron:Asymmetry, 2002,13,1141) the didentate phosphine ligand BINAP of chirality is carried out aminomethyl functionalization, follow-up paraphthaloyl chloride, can form the chiral polymer containing BINAP part in skeleton to cross-linking agents such as benzene two Carbimide .s.On this Polymer Supported, Ru metal achieves good effect in the chiral catalysis hydrogenation of methyl acetoacetate.
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, due to the organo-functional group in organic polymer adjustable changeable monomer component, such that it is able to require purposive synthesis polymer miscellaneous for different reactions.Using the porous organic polymer carrier as heterogeneous reaction, also some problems needing to solve and overcome are exposed, as major part research is all confined to the modification of BINAP part and is polymerized, a lot of for shortcoming on the functionalization of triphenylphosphine ligand and polymerization studies, the polymeric material of synthesis is only limitted to that the reaction in solution, material synthesis processes be loaded down with trivial details, material is comparatively sensitive etc. to air and water, it is difficult to general introduce subject monomers etc. compactly.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide one and there is P and O (N), organic polymer of better heat stability and preparation method thereof.
The present invention is on the Research foundation of multiple polymers preparation method, the aromatic ring of triphenylphosphine monomer will introduce alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino group as polymerization single polymerization monomer, in autoclave or flask, utilize solvent thermal polymerization method, the organic polymer of esters or amide-type is formed with cross-linking agents such as paraphthaloyl chlorides, this organic polymer backbones have containing lone pair electrons P and O (N), coordinate bond can be formed with active transition metal ion unoccupied orbital, and then define new catalytic active site, the catalyst prepared is we term it organic polymer is from the catalyst of load active metal component.Here, 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.Follow-up experimentation shows, this type of heterogeneous catalyst P and O (N) formed as carrier by organic polymer is exposed in duct and surface in a large number, and catalyst activity is higher, and stability is better.
Specifically, the synthesis step changing polymer is: in the organic solvent containing organic monomer and co-monomer, being sequentially added into cross-linking agent and acid binding agent, the reactant mixture obtained carries out polyreaction, separate product, namely obtain the organic polymer containing P and O (N).
Organic polymer provided by the invention selects the organic monomer containing P and alcoholic extract hydroxyl group (phenolic hydroxyl group) or amido, autoclave or occur cross-linked polymeric to form the organic polymer containing P and O (N) in flask under cross-linking agent, catalyst action.In polymer synthesis process, organic monomer selects the organic ligand containing P and alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino, wherein particularly preferably contain the organic phosphine monomer of phenolic hydroxyl group and amino, preferably containing the triphenylphosphine monomer of methylol (phenolic hydroxyl group) or amino-functional dough, slough little molecule condensation with hydroxyl or amino and acyl chlorides or carboxyl and form ester bond or amido link, generate the organic polymer with P and O (N)；Described organic monomer preferably triphenylphosphine monomer containing methanol hydroxylethyl and phenolic hydroxyl group functionalization.Synthesized organic polymer specific surface area is 1～2000m2/g.Pore volume is 0.1～5.0cm3/ g, pore-size distribution is at 0.2～50.0nm.
Polymer contains P and O (N), as organic ligand, with metal component, stronger coordination can occur.
Polymer contains P and O (N), can as excellent catalyst carrier, and the catalyst activity metal component of preparation can with monatomic form high dispersive in such organic polymer carrier.
The preparation method of organic polymer provided by the invention; the steps include: that (1) is under 273～473K and inert gas shielding atmosphere; in the organic solvent containing organic monomer and co-monomer; it is sequentially added into cross-linking agent and promotes the acid binding agent of polycondensation reaction; the mol ratio of organic monomer/co-monomer is 10:1～1:10; the mol ratio of cross-linking agent/acid binding agent is 10:1～1:10, and organic monomer concentration in organic solvent controls at 0.01-1g/mL.Gained reactant mixture stirs 0.1～100 hour.Wherein co-monomer can adopt one or more of ethylene glycol, hydroquinone, ethylenediamine, p-phenylenediamine etc.；Organic solvent can adopt one or more mixture in 1,4-dioxane, dimethyl sulfoxide, oxolane, benzene, toluene, methanol or ethanol or dichloromethane；Cross-linking agent can adopt and face (or to) phthalyl chloride, face one or more in the homologue of (or to) phthalic acid, malonyl chloride, malonic acid, succinyl chloride, succinic acid, mesitylene formyl chloride, Trimesic acid and this several acyl chlorides and carboxylic acid and derivant；Acid binding agent can adopt triethylamine, pyridine, NaOH, Na2CO3、NaHCO3, one or more in sodium acetate.(2) under 273～473K and inert gas shielding atmosphere, by above-mentioned solution in synthesis autoclave when solvent thermal polymerization 273～473K stand and within 1～100 hour, carry out polyreaction, or be heated to 273～473K stirring reaction 1-100 hour.(3) pouring in poor solvent by the polymer after above-mentioned polymerization, can be precipitated out, then precipitation is with excessive bad solution washing, and poor solvent can be selected for methanol, ethanol, propanol, one or more of water etc..
In accordance with the method for claim 4, it is characterized in that: described organic monomer is the organic ligand containing P and alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino, wherein particularly preferably contain the organic phosphine monomer of phenolic hydroxyl group and amino, it is preferable that containing the triphenylphosphine monomer of methylol (phenolic hydroxyl group) or amino-functional dough.Above-mentioned noble gas is argon or nitrogen.
The method of described separation product is pour in poor solvent by the product after polyreaction, is precipitated out, and then precipitation is with excessive bad solution washing, and poor solvent is first
Outstanding properties of the present invention includes:
Organic polymer synthesized by the present invention, it can be used as carrier to can be applicable to the preparation of multiphase load type metallic catalyst, owing to having the dual function of part and carrier concurrently containing P and O (N) polymer；In the catalyst of carried metal, active metal component can be dispersed in the way of isolated son in this organic polymer carrier containing P and O (N).By in this type of hydroformylation of olefin catalyst based for Rh containing the organic polymer load of P and O (N); fixing bed, slurry bed system, tank reactor and trickle bed reaction process can be adopted; the hydroformylation reaction activity of its alkene is high, and aldehyde product selectivity is good.Metal ion defines chemical coordination key with P and O (N) in organic polymer, exists with the dispersity of monometallic ion, thus the utilization ratio of metal is greatly improved.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of three (4-methylol benzene) base phosphine organic polymer polymerization technique route.
Fig. 2 is the schematic diagram of three (4-phenol) base phosphine organic polymer polymerization technique route.
Fig. 3 is that three (4-aniline) base is seen the schematic diagram of organic polymer polymerization technique route.
Detailed description of the invention:
In order to better illustrate the preparation process containing P and O (N) organic polymer, enumerate some Application Examples containing P and O (N) 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; 4.0 gram of three (4-methylol benzene) base phosphine and 1.0g ethylene glycol (co-monomer) are dissolved in 100.0ml dichloromethane solvent; rear addition 4mL triethylamine (acid binding agent), 1.8g paraphthaloyl chloride is dissolved in 10mL dichloromethane and is slowly added in above-mentioned solution.Add stirring 10min under room temperature, the solution being stirred is moved to autoclave, utilize solvent thermal polymerization method to carry out polymerization 12h under 373K and inert gas shielding atmosphere.Treat that autoclave is cooled to room temperature, solution in still is poured in 200mL methanol, precipitation excessive methanol washs, namely vacuum drying obtains the organic polymer formed by three (4-methylol benzene) base phosphines and paraphthaloyl chloride polycondensation, and Fig. 1 is the schematic diagram of three (4-methylol benzene) base phosphine organic polymer polymerization technique route.
Embodiment 2
Under 298K and inert gas shielding atmosphere; 4.0 gram of three (4-phenol) base phosphine and 1.0g ethylene glycol (co-monomer) are dissolved in 100.0ml dichloromethane solvent; rear addition 4mL triethylamine (acid binding agent), 1.8g paraphthaloyl chloride is dissolved in 10mL dichloromethane and is slowly added in above-mentioned solution.Add stirring 10min under room temperature, the solution being stirred is moved to autoclave, utilize solvent thermal polymerization method to carry out polymerization 12h under 373K and inert gas shielding atmosphere.Treat that autoclave is cooled to room temperature, solution in still is poured in 200mL methanol, precipitation excessive methanol washs, namely vacuum drying obtains the organic polymer formed by three (4-phenol) base phosphines and paraphthaloyl chloride polycondensation, and Fig. 2 is the schematic diagram of three (4-phenol) base phosphine organic polymer polymerization technique route.
Embodiment 3
Under 298K and inert gas shielding atmosphere; 4.0 gram of three (4-aniline) base phosphine and 1.0g ethylene glycol (co-monomer) are dissolved in 100.0ml dichloromethane solvent; rear addition 4mL triethylamine (acid binding agent), 1.8g paraphthaloyl chloride is dissolved in 10mL dichloromethane and is slowly added in above-mentioned solution.Add stirring 10min under room temperature, the solution being stirred is moved to autoclave, utilize solvent thermal polymerization method to carry out polymerization 12h under 373K and inert gas shielding atmosphere.Treat that autoclave is cooled to room temperature, solution in still is poured in 200mL methanol, precipitation excessive methanol washs, namely vacuum drying obtains the organic polymer formed by three (4-aniline) base phosphine paraphthaloyl chloride polycondensation, and Fig. 3 is the schematic diagram of three (4-aniline) base phosphine organic polymer polymerization technique route.
Embodiment 4
In example 4, except weighing 1.0 grams of cross-linking agent paraphthaloyl chlorides and substituting 1.8g cross-linking agent paraphthaloyl chloride, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 5
In embodiment 5, except weighing 3.0 grams of cross-linking agent mesitylene formyl chlorides and substituting 1.8g cross-linking agent paraphthaloyl chloride, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 6
In embodiment 6, except substituting 4mL acid binding agent triethylamine with 2g acid binding agent NaOH, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 7
In embodiment 7, except substituting 100.0ml dichloromethane solvent with 50.0ml dichloromethane solvent, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 8
In embodiment 8, except substituting 100.0ml dichloromethane solvent with 100.0ml tetrahydrofuran solvent, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 9
In embodiment 9, except substituting 373K polymerization temperature with 393K polymerization temperature, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 10
In embodiment 10, except substituting 12h polymerization time with 18h polymerization time, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 11
In embodiment 11, except add 1.0 grams of ethylene glycol as co-monomer except, remaining organic polymer building-up process and embodiment 1 are identical.
Embodiment 12
In embodiment 12, being placed in oil bath except stirring polymerization except putting into magneton in autoclave, remaining organic polymer building-up process is identical with embodiment 1.
Embodiment 13
Under 298K and inert gas shielding atmosphere; weigh 50.10 milligrams of rhodium dicarbonyl acetylacetonates (I) and be dissolved in 10.0ml tetrahydrofuran solvent; what add 1.0 grams of embodiment 1 preparations is polymerized, by three (4-methylol benzene) base phosphine, the 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 three (4-methylol benzene) base phosphine organic polymer of above-mentioned preparation from load active metal component catalyst, two ends load quartz sand.Pass into reaction mixture gas (H2:CO:C2H4=1:1:1), at 393K, 1.0MPa, reaction mixture gas air speed 1000h-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 propionic aldehyde 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.In embodiment 1-12, the organic polymer specific surface area of synthesis and the reaction evaluating data reaction result of corresponding catalyst are listed in table 1.
The organic polymer specific surface area synthesized in table 1 embodiment 1-12 and response data
* experiment condition is 120 DEG C, 1MPa, distribution (ethylene: CO:H2=1:1:1) air speed 1000h-1, TOF thinks that all of Rh is all avtive spot when calculating.
Claims (7)
1. the preparation method containing the organic polymer of P and O (N), it is characterized in that: in polymer synthesis process, organic monomer selects the organic ligand containing P and alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino, wherein particularly preferably contain the organic phosphine monomer of phenolic hydroxyl group and amino, preferably containing the triphenylphosphine monomer of methylol (phenolic hydroxyl group) or amino-functional dough, slough little molecule condensation with hydroxyl or amino and acyl chlorides or carboxyl and form ester bond or amido link, generate the organic polymer with P and O (N)；Polymer surface area is at 1～2000m2Between/g, pore volume is 0.1～5.0cm3/ g, pore-size distribution is at 0.1～50.0nm.
2. the organic polymer described in claim 1, it is characterised in that: polymer contains P and O (N), as organic ligand, with metal component, stronger coordination can occur.
3. the organic polymer described in claim 1, it is characterized in that: polymer contains P and O (N), can as excellent catalyst carrier, the catalyst activity metal component of preparation can with monatomic form high dispersive in such organic polymer carrier.
4. the preparation method of the organic polymer described in a claim 1, it is characterized in that: in the organic solvent containing organic monomer and co-monomer, it is sequentially added into cross-linking agent and acid binding agent, the reactant mixture obtained carries out polyreaction, separate product, namely obtain the organic polymer containing P and O (N).
5. the preparation method of the organic polymer described in claim 4, it is characterised in that: wherein co-monomer be ethylene glycol, hydroquinone, ethylenediamine, p-phenylenediamine one or two or more kinds；Organic solvent is one or two or more kinds in 1,4-dioxane, dimethyl sulfoxide, oxolane, benzene, toluene, methanol or ethanol or dichloromethane；Cross-linking agent for facing (or to) phthalyl chloride, face (or to) phthalic acid, malonyl chloride, malonic acid, succinyl chloride, succinic acid, mesitylene formyl chloride, Trimesic acid, to one or two or more kinds in the homologue of benzene two cyanic acid and this several acyl chlorides and carboxylic acid and derivant；Acid binding agent is triethylamine, pyridine, NaOH, Na2CO3、NaHCO3, one or two or more kinds in sodium acetate；In reactant mixture, the mol ratio of organic monomer/co-monomer is 10:1～1:10, and the mol ratio of cross-linking agent/acid binding agent is 10:1～1:10；Organic monomer concentration in organic solvent controls at 0.01-1g/mL.
6. in accordance with the method for claim 4, it is characterized in that: described organic monomer is the organic ligand containing P and alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino, wherein particularly preferably contain the organic phosphine monomer of phenolic hydroxyl group and amino, it is preferable that containing the triphenylphosphine monomer of methylol (phenolic hydroxyl group) or amino-functional dough.
7. in accordance with the method for claim 4, it is characterised in that: polyreaction carries out in synthesis autoclave, and when solvent thermal polymerization, 273～473K stands and within 1～100 hour, carries out polyreaction, or is heated to 273～473K stirring reaction 1-100 hour；Reinforced and reaction all carries out under inert gas shielding atmosphere, and described noble gas is argon or nitrogen；Gained reactant mixture needs stirring 0.1～100 hour before carrying out polyreaction；
The method of described separation product is pour in poor solvent by the product after polyreaction, is precipitated out, and then precipitation is with excessive bad solution washing, and poor solvent is methanol, ethanol, propanol, one or two or more kinds of water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417913A (en) * | 2017-08-22 | 2017-12-01 | 广东工业大学 | A kind of method of heavy metal in organic microporous polymer of nanometer and absorption drinking water |
| CN108246330A (en) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling |
| CN113522366A (en) * | 2021-07-27 | 2021-10-22 | 中国科学院兰州化学物理研究所 | Monophosphine-containing porous organic polymer in-situ packaging rhodium catalytic material, and preparation method and application thereof |
| CN114522730A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for morpholine nitrogen formylation reaction and preparation and application thereof |
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| US4680370A (en) * | 1985-09-30 | 1987-07-14 | The Dow Chemical Company | Branched polycarbonate composition from tris(hydroxyaryl)phosphorus compound |
| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
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| US4680370A (en) * | 1985-09-30 | 1987-07-14 | The Dow Chemical Company | Branched polycarbonate composition from tris(hydroxyaryl)phosphorus compound |
| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417913A (en) * | 2017-08-22 | 2017-12-01 | 广东工业大学 | A kind of method of heavy metal in organic microporous polymer of nanometer and absorption drinking water |
| CN107417913B (en) * | 2017-08-22 | 2020-04-14 | 广东工业大学 | Nano organic microporous polymer and method for adsorbing heavy metals in drinking water |
| CN108246330A (en) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling |
| CN114522730A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for morpholine nitrogen formylation reaction and preparation and application thereof |
| CN114522730B (en) * | 2020-11-23 | 2024-02-27 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for morpholine nitrogen formylation reaction, and preparation and application thereof |
| CN113522366A (en) * | 2021-07-27 | 2021-10-22 | 中国科学院兰州化学物理研究所 | Monophosphine-containing porous organic polymer in-situ packaging rhodium catalytic material, and preparation method and application thereof |
| CN113522366B (en) * | 2021-07-27 | 2022-08-02 | 中国科学院兰州化学物理研究所 | Monophosphine-containing porous organic polymer in-situ packaging rhodium catalytic material, and preparation method and application thereof |
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