CN105754081B - The organic polymer of one kind containing P and O (N) and preparation method thereof - Google Patents
The organic polymer of one kind containing P and O (N) and preparation method thereof Download PDFInfo
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Abstract
One kind contains P and O (N) organic polymer, the organic polymer is from P and O (N) and the organic monomer of alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino is contained, using the organic polymer containing P and O (N) generated after the crosslinked dose of crosslinking polycondensation reaction of solvent thermal polymerization method.The organic polymer for containing P and O (N) can be applied to the preparation of heterogeneous reaction catalyst, there is the dual-use function of carrier and part simultaneously, in the metal load type catalyst prepared as carrier loaded active metal component, its metal component high dispersive is in the carrier；This polymer again can be as the part similar to active metallic ion in homogeneous complex catalysis simultaneously.Due to the effect of coordinate bond stronger between the P in metal component and polymer support skeleton and O (N), active metal component is with monatomic form high dispersive in such polymer support, the utilization ratio of the metal greatly improved, and active metal component is not allowed to be easy to run off.
Description
Technical field
The present invention relates to a kind of preparation method of the organic polymer containing P and O (N), belong to materials synthesis and application technology
Field.
Background technology
In recent years, porous organic material (Macromolecules, 2013,34,471) design and synthesis be increasingly becoming it is micro-
One of new focus of Porous materials research field, it is organic with traditional inorganic microporous material compared with organic-metallic coordination polymer
The skeleton of microporous polymer is made up of pure organic molecule, each other by covalent key connection, have open duct with it is excellent
Porous.It is organic molecule building block precursor and molecular network importantly, due to the diversity of organic chemical synthesis method
Structure provide abundant synthesis path and building mode, the organic molecule building block of the introducing functionalization of purpose can be passed through
Make final material that there is corresponding property, can be with the porous of controlled material by the structure for adjusting precursor.In addition, exist
In most cases, compared with the molecular network structure fragility connected into by non-covalent bond, organic microporous polymer is all logical
Covalent key connection is crossed, while material porous is maintained, molecular network structure is more firm.
At present, porous organic material can be largely classified into following four according to different thinkings of constructing:(1) by intensive
Crosslinking prevents the closelypacked super cross-linked polymer (Hyper-Crosslinked Polymers, HCPs) of macromolecular chain；(2)
Macromolecular chain is forced effectively to occupy the intrinsic microporous polymer of void volume by rigidity or the molecular structure reversed
(Polymers of Intrinsic Microporosity,PIMs)；(3) molecular network is kept by building π-conjugated systems
Structural rigidity conjugation microporous polymer (Conjugated Microporous Polymers, CMPs) and (4) using appropriate
Polyfunctional group organic building block covalent organic frame (the Covalent Organic of crystalline microporous material are formed by reversible be condensed
Frameworks,COFs)。
Qing-hua Fan in 1999 et al. (J.Am.Chem.Soc, 1999,121,7407) is by didentate phosphine ligand BINAP
Amino-functional dough, for chiral glycol as co-monomer, p-phenylenediamine is crosslinking agent, has been synthesized first molten in dichloroethanes
The good chiral polymer of solution property, achieves good catalysis on the Polymer Supported after Ru metals in asyininetric hydrogenation
Effect.The polymer is solvable in many organic solvents such as dichloromethane etc., and polymer is dissolved in solvent and is similar to during reaction
Homogeneous reaction, but the application which also limits this polymer in some occasions such as fixed bed reaction.
2000, Shanghai Institute of Organic Chemistry Li Zhang et al. (Journal of Fluorine Chemistry, 2000,102,
55) F atom is introduced on the phenyl ring of hydroquinones, follow-up terephthalic acid (TPA) or paraphthaloyl chloride paraphthaloyl chloride
Crosslinking can must contain the petchem of F atom.Possible application field and prospect author for this polymer are not studied.
2002, Christine Saluzzo et al. (Tetrahedron:Asymmetry, 2002,13,1141) by hand
Property didentate phosphine ligand BINAP carry out aminomethyl function dough, subsequently with paraphthaloyl chloride, to crosslinking agents such as the isocyanic acids of benzene two
Crosslinking can form the chiral polymer containing BINAP parts in skeleton.Ru metals are in methyl acetoacetate on the Polymer Supported
Chiral catalysis hydrogenation in terms of achieve preferable effect.
Porous organic polymer is because of controllable chemical physical property, easy functionalization synthesis strategy, big specific area and
The advantages that cheap cost of material and cause the extensive concern of researchers, due in organic polymer adjustable changeable monomer component
Organo-functional group, so as to require the miscellaneous polymer of purposive synthesis for different reactions.Have porous
Carrier of the machine polymer as heterogeneous reaction, also expose some needs and solve the problems, such as and overcome, such as most of research all offices
The modification in BINAP parts is limited with polymerizeing, it is many for being short of in the function dough and polymerization studies of triphenylphosphine ligand, close
Into polymeric material be only limitted to reaction in solution, material synthesis processes are cumbersome, material to air and water more sensitivity etc., it is difficult
Subject monomers etc. are compactly introduced with general.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide one kind, and there is P and O (N), better heat stability to have
Machine polymer and preparation method thereof.
The present invention will introduce alcohol hydroxyl on the Research foundation of multiple polymers preparation method on the aromatic ring of triphenylphosphine monomer
Base (phenolic hydroxyl group) or amino group are as polymerized monomer, in autoclave or flask, using solvent thermal polymerization method, with terephthaldehyde
The cross-linking agents such as acyl chlorides form the organic polymer of esters or amide-type, have in the organic polymer backbones containing orphan to electricity
Sub- P and O (N), coordinate bond can be formed with active transition metal ion unoccupied orbital, and then form new catalytic active site, prepared
We term it the catalyst of the self-supported active metal component of organic polymer for the catalyst gone out.Herein, organic polymer one
Part of the aspect as active metal component, the on the other hand load as high-dispersion load active metal component high-specific surface area
Body.Follow-up experimental study shows, such a large amount of sudden and violent as the heterogeneous catalyst P and O (N) that carrier is formed by organic polymer
It is exposed in duct and surface, catalyst activity is higher, and stability is preferable.
Specifically, the synthesis step for changing polymer is：In having containing organic monomer and co-monomer
In solvent, crosslinking agent and acid binding agent are sequentially added, obtained reactant mixture is gathered
Reaction is closed, separation product, that is, obtains the organic polymer containing P and O (N).
Organic polymer provided by the invention, which is selected, contains P and the organic monomer of alcoholic extract hydroxyl group (phenolic hydroxyl group) or amido, high
Press and organic polymer of the cross-linked polymeric formation containing P and O (N) occurs in kettle or flask under crosslinking agent, catalyst action.Polymer
Organic monomer is from P and the organic ligand of alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino is contained in building-up process, wherein particularly preferably containing
There is an organic phosphine monomer of phenolic hydroxyl group and amino, the triphenylphosphine monomer preferably containing methylol (phenolic hydroxyl group) or amino-functional dough,
Small molecule is sloughed with hydroxyl or amino and acyl chlorides or carboxyl to be condensed to form ester bond or amido link, generation is organic with P and O (N)
Polymer；Triphenylphosphine monomer of the described organic monomer preferably containing methanol hydroxylethyl and phenolic hydroxyl group function dough.Synthesized has
Machine polymer specific surface area is 1~2000m2/g.Pore volume is 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
Polymer contains P and O (N), can be used as organic ligand, and stronger coordination occurs with metal component.
Polymer contains P and O (N), can be as excellent catalyst carrier, and the catalyst activity metal component of preparation can be with
Monatomic form high dispersive is in such organic polymer carrier.
The preparation method of organic polymer provided by the invention, its step are：(1) protected in 273~473K and inert gas
Protect under atmosphere, in the organic solvent containing organic monomer and co-monomer, sequentially add crosslinking agent and promote polycondensation reaction ties up acid
Agent, the mol ratio of organic monomer/co-monomer is 10:1~1:10, the mol ratio of crosslinking agent/acid binding agent is 10:1~1:10, it is organic
Concentration controls in 0.01-1g/mL monomer in organic solvent.Gained reactant mixture stirs 0.1~100 hour.It is wherein single altogether
Body can use the one or more of ethylene glycol, hydroquinones, ethylenediamine, p-phenylenediamine etc.；Organic solvent can use 1,4- dioxies
One or more of mixtures in six rings, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, methanol or ethanol or dichloromethane；Crosslinking
Agent can use adjacent (or to) phthalyl chloride, neighbour (or to) phthalic acid, malonyl chloride, malonic acid, succinyl chloride, fourth two
One or more in the homologue and derivative of acid, mesitylene formyl chloride, Trimesic acid and this several acyl chlorides and carboxylic acid；
Acid binding agent can use triethylamine, pyridine, NaOH, Na2CO3、NaHCO3, one or more in sodium acetate.(2) in 273~473K
Under inert gas shielding atmosphere, by above-mentioned solution, 273~473K under conditions of solvent thermal polymerization is quiet in autoclave is synthesized
Put 1~100 hour and carry out polymerisation, or be heated to 273~473K stirring reaction 1-100 hours.(3) by after above-mentioned polymerization
Polymer pour into poor solvent, you can be precipitated out, then precipitation is washed with excessive bad solution, and poor solvent is optional
With the one or more of methanol, ethanol, propyl alcohol, water etc..
The organic monomer is containing P and the organic ligand of alcoholic extract hydroxyl group (phenolic hydroxyl group) or amino, wherein particularly preferably containing
There are the organic phosphine monomer of phenolic hydroxyl group and amino, the triphenylphosphine monomer preferably containing methylol (phenolic hydroxyl group) or amino-functional dough.
Above-mentioned inert gas is argon gas or nitrogen.
The method of the separation product is precipitated out, Ran Houchen for the product after polymerisation is poured into poor solvent
Form sediment and washed with excessive bad solution, poor solvent is methanol, ethanol, propyl alcohol, the one or two or more kinds of water.
Outstanding properties of the present invention include：
Organic polymer synthesized by the present invention, the system of multiphase load type metallic catalyst is can be applied to as carrier
It is standby, due to having the double action of part and carrier concurrently containing P and O (N) polymer；Active metal group in the catalyst of self-supported metal
Dividing can be dispersed in a manner of single ion in this organic polymer carrier containing P and O (N).By such having containing P and O (N)
In the hydroformylation of olefin of the Rh base catalyst of machine Polymer-supported, fixed bed can be used, slurry bed system, tank reactor and
Drip bed reaction technique, the hydroformylation reaction activity of its alkene is high, and aldehyde product is selectively good.Metal ion and organic polymer
P and O (N) in thing form chemical coordination key, exist with the dispersity of monometallic ion, thus the utilization ratio of metal is big
It is big to improve.
Brief description of the drawings
Fig. 1 is the schematic diagram of three (4- methylols benzene) base phosphine organic polymer polymerization technique routes.
Fig. 2 is the schematic diagram of three (4- phenol) base phosphine organic polymer polymerization technique routes.
Fig. 3 is that three (4- aniline) bases are seen the schematic diagram of organic polymer polymerization technique route.
Embodiment：
In order to better illustrate the preparation process for containing P and O (N) organic polymer, it is organic containing P and O (N) that some are enumerated below
The Application Example of polymer polymerizing process and reaction evaluating, but the invention is not restricted to cited example.
Embodiment 1
It is under 298K and inert gas shielding atmosphere, 4.0 gram of three (4- methylols benzene) base phosphine and 1.0g ethylene glycol is (single altogether
Body) it is dissolved in 100.0ml dichloromethane solvents, rear to add 4mL triethylamines (acid binding agent), 1.8g paraphthaloyl chlorides are dissolved in 10mL
Dichloromethane is slowly added into above-mentioned solution.Add and stir 10min at room temperature, the solution being stirred is moved into autoclave, in
Under 373K and inert gas shielding atmosphere polymerization 12h is carried out using solvent thermal polymerization method.Treat that autoclave is cooled to room temperature, by kettle
Solution is poured into 200mL methanol, and precipitation is washed with excessive methanol, and vacuum drying is obtained by three (4- methylols benzene) base phosphines and right
The organic polymer that phthalyl chloride polycondensation is formed, Fig. 1 is three (4- methylols benzene) base phosphine organic polymer polymerization technique routes
Schematic diagram.
Embodiment 2
Under 298K and inert gas shielding atmosphere, by 4.0 gram of three (4- phenol) base phosphine and 1.0g ethylene glycol (co-monomer)
It is dissolved in 100.0ml dichloromethane solvents, rear to add 4mL triethylamines (acid binding agent), 1.8g paraphthaloyl chlorides are dissolved in 10mL bis-
Chloromethanes is slowly added into above-mentioned solution.Add and stir 10min at room temperature, the solution being stirred is moved into autoclave, in 373K
With under inert gas shielding atmosphere polymerization 12h is carried out using solvent thermal polymerization method.Treat that autoclave is cooled to room temperature, by solution in kettle
Pour into 200mL methanol, precipitation is washed with excessive methanol, and vacuum drying is obtained by three (4- phenol) base phosphines and paraphenylene terephthalamide
The organic polymer that chlorine polycondensation is formed, Fig. 2 are the schematic diagram of three (4- phenol) base phosphine organic polymer polymerization technique routes.
Embodiment 3
Under 298K and inert gas shielding atmosphere, by 4.0 gram of three (4- aniline) base phosphine and 1.0g ethylene glycol (co-monomer)
It is dissolved in 100.0ml dichloromethane solvents, rear to add 4mL triethylamines (acid binding agent), 1.8g paraphthaloyl chlorides are dissolved in 10mL bis-
Chloromethanes is slowly added into above-mentioned solution.Add and stir 10min at room temperature, the solution being stirred is moved into autoclave, in 373K
With under inert gas shielding atmosphere polymerization 12h is carried out using solvent thermal polymerization method.Treat that autoclave is cooled to room temperature, by solution in kettle
Pour into 200mL methanol, precipitation is washed with excessive methanol, and vacuum drying is obtained by three (4- aniline) base phosphine paraphthaloyl chlorides
The organic polymer that polycondensation is formed, Fig. 3 are the schematic diagram of three (4- aniline) base phosphine organic polymer polymerization technique routes.
Embodiment 4
In example 4,1.8g crosslinking agent paraphthaloyl chlorides are substituted except weighing 1.0 grams of crosslinking agent paraphthaloyl chlorides
Outside, remaining organic polymer building-up process is same as Example 1.
Embodiment 5
In embodiment 5,1.8g crosslinking agent paraphthaloyl chlorides are substituted except weighing 3.0 grams of crosslinking agent mesitylene formyl chlorides
Outside, remaining organic polymer building-up process is same as Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 4mL acid binding agent triethylamines with 2g acid binding agents NaOH, remaining organic polymer
Building-up process is same as Example 1.
Embodiment 7
In embodiment 7, in addition to substituting 100.0ml dichloromethane solvents with 50.0ml dichloromethane solvents, remaining
Organic polymer building-up process is same as Example 1.
Embodiment 8
In embodiment 8, in addition to substituting 100.0ml dichloromethane solvents with 100.0ml tetrahydrofuran solvents, remaining
Organic polymer building-up process is same as Example 1.
Embodiment 9
In embodiment 9, in addition to substituting 373K polymerization temperatures with 393K polymerization temperatures, the synthesis of remaining organic polymer
Process is same as Example 1.
Embodiment 10
In embodiment 10, in addition to substituting 12h polymerization times with 18h polymerization times, the synthesis of remaining organic polymer
Process is same as Example 1.
Embodiment 11
In embodiment 11, in addition to adding 1.0 grams of ethylene glycol as co-monomer, remaining organic polymer synthesized
Journey is same as Example 1.
Embodiment 12
In embodiment 12, it is placed on except being put into magneton in autoclave in oil bath in addition to stirring polymerization, remaining organic polymer
Thing building-up process is same as Example 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
In tetrahydrofuran solvent, prepared by 1.0 grams of embodiments 1 of addition polymerize the organic polymer formed by three (4- methylols benzene) base phosphines
Thing, this mixture is stirred 24 hours under 298K and inert gas shielding atmosphere, then at ambient temperature vacuum take away it is molten
Agent, that is, obtain by the catalyst of the self-supported metal of organic polymer.Three (4- methylols benzene) base phosphines of above-mentioned preparation are organic poly-
The self-supported active metal component catalyst of compound is encased in fixed bed reactors, and both ends load quartz sand.It is passed through reaction mixing
Gas (H2:CO:C2H4=1:1:1), in 393K, 1.0MPa, reaction mixture gas air speed 1000h-1Under the conditions of carry out hydroformylation it is anti-
Should.Collecting tank of the reaction through a deionized water equipped with 60ml coolings, which absorbs, to be collected, and reaction product propionic aldehyde is all dissolved in collection
In the water of tank.The obtained aqueous solution uses the HP-7890N gas chromatographic analysis equipped with HP-5 capillary columns and fid detector, adopts
Make internal standard with ethanol.Reaction end gas uses the HP-7890N gas phases equipped with Porapak-QS posts and TCD detectors after water absorbs
Chromatogram carries out on-line analysis.The organic polymer specific surface area and the reaction evaluating number of corresponding catalyst synthesized in embodiment 1-12
Table 1 is listed according to reaction result.
The organic polymer specific surface area and response data synthesized in the embodiment 1-12 of table 1
* experiment condition is 120 DEG C, 1MPa, distribution (ethene:CO:H2=1:1:1) air speed 1000h-1, TOF calculate when think
All Rh are avtive spots.
Claims (5)
- A kind of 1. preparation method of the organic polymer containing P and O or N, it is characterised in that：In having containing organic monomer and co-monomer In solvent, crosslinking agent and acid binding agent are sequentially added, obtained reactant mixture carries out polymerisation, separation product, that is, obtains Organic polymer containing P and O or N, organism is from containing methylol or phenolic hydroxyl group or amido functional group in polymer synthesis process The triphenylphosphine monomer of change, acyl chlorides on hydroxyl or amino and crosslinking agent or carboxyl on organic monomer slough small molecule condensation shape Into ester bond or amido link, organic polymer of the generation with P and O or N；Polymer surface area is in 1~2000m2Between/g, pore volume For 0.1~5.0cm3/ g, pore-size distribution is in 0.1~50.0nm；Wherein co-monomer be ethylene glycol, hydroquinones, ethylenediamine, to benzene The one or two or more kinds of diamines；Crosslinking agent is adjacent (or to) phthalyl chloride, neighbour (or to) phthalic acid, malonyl Chlorine, malonic acid, succinyl chloride, succinic acid, in the homologue and derivative of the cyanic acid of benzene two and this several acyl chlorides and carboxylic acid It is one or two or more kinds of.
- 2. the preparation method of organic polymer according to claim 1, it is characterised in that：Polymer contains P and O or N, can As organic ligand, stronger coordination occurs with metal component.
- 3. the preparation method of organic polymer according to claim 1, it is characterised in that：Polymer contains P and O or N, makees For excellent catalyst carrier, the catalyst activity metal component of preparation can be carried with monatomic form high dispersive in organic polymer In body.
- 4. the preparation method of organic polymer according to claim 1, it is characterised in that：Organic solvent is 1,4- dioxies six One or two or more kinds in ring, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, methanol or ethanol or dichloromethane；Acid binding agent is Triethylamine, pyridine, NaOH, Na2CO3、NaHCO3, one or two or more kinds in sodium acetate；Organic monomer in reactant mixture/ The mol ratio of co-monomer is 10:1~1:10, the mol ratio of crosslinking agent/acid binding agent is 10:1~1:10；Organic monomer is organic molten Concentration control is in 0.01-1g/mL in agent.
- 5. the preparation method of organic polymer according to claim 1, it is characterised in that：Polymerisation is in synthesis autoclave Middle progress, 273~473K stands 1~100 hour and carries out polymerisation, or 273~473K under conditions of solvent thermal polymerization Stirring reaction 1-100 hours；Charging is carried out with reaction under inert gas shielding atmosphere, the inert gas for argon gas or Nitrogen；Gained reactant mixture needs stirring 0.1~100 hour before polymerisation is carried out；The method of the separation product is precipitated out, then sediment for the product after polymerisation is poured into poor solvent Washed with the poor solvent of excess, poor solvent is methanol, ethanol, propyl alcohol, the one or two or more kinds of water.
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| 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 |
| CN108246330B (en) * | 2018-01-12 | 2019-12-24 | 北京化工大学 | Method for constructing monatomic catalyst based on lignin/metal supramolecular assembly |
| 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 |
| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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