CN105504332B - A kind of preparation method of porous organic polymer integral material - Google Patents
A kind of preparation method of porous organic polymer integral material Download PDFInfo
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Abstract
The present invention relates to a kind of preparations of the porous organic polymer integral material based on sulfydryl-epoxy click chemistry reaction, specifically by multi-epoxy monomer 2, 2', 2 ", 2 " ' [1, 2 ethanetetrayls four (4, 1 phenylene methylene oxygen)] tetraoxane (tetraphenylolethane glycidyl ether, TPEGE), organic more thiol crosslinkers, pore-foaming agent and catalyst mixing and ultrasonic dissolution, then occur at a certain temperature after sulfydryl-epoxy click chemistry (thiol epoxy click reaction) can a step prepare porous organic polymer integral material.The preparation method has many advantages, such as easy to operate quick, versatile, and a series of different organic polymer integral materials can be prepared according to no application demand.
Description
Technical field
The present invention relates to a kind of systems of the porous organic polymer integral material based on sulfydryl-epoxy click chemistry reaction
It is standby, multi-epoxy organic monomer, organic dimercapto or more thiol crosslinkers, pore-foaming agent and catalyst are specifically mixed into ultrasound
After uniformly, prepared using sulfydryl-epoxy click chemistry reaction (thiol-epoxy click reaction) step with specific
The organic polymer integral material of porous structure.
Background technology
Porous integral material has the characteristics that preparation is easy, modifiability is strong and permeability is good, is just being subject to more and more
Concern, has been widely used in chromatographic isolation analysis field at present.By the difference of chemical property, porous integral material can be divided into
Three classes, i.e. organic whole material, inorganic integral material and organic-inorganic hybrid integral material.Wherein inorganic and organic and inorganic
Hybrid integral material have good mechanical property, it is strong to Organic Solvent Tolerant the features such as, but there is also pH stability it is poor the shortcomings of, and
And their preparation process is all comparatively laborious, it is necessary to consume more times and manpower, thus also influence their preparation and repeat
Property.In contrast, organic polymer integral material occurs earliest, and application is also more extensive at present.It is good with pH stability,
The advantages that preparation is simple, and internal gutter property adjustments facilitate.But there is also mechanical performance is poor, easily swelling in organic solvent
The shortcomings of.And since its internal gutter is inhomogenous, it is caused to be imitated in liquid chromatogram application center pillar, especially to small molecule chemical combination
The splitter of object is imitated well below packed column and other two kinds of integral posts.Therefore there is an urgent need to develop a kind of new method to be used to prepare
Stability is more preferable, the more homogeneous organic polymer integral material of internal gutter.
At present, free radical polymerization (free radical polymerization) is prepared by organic polymer integral material
In be commonly used polymerization methods.Although this polymerization methods reaction speed is very fast, due to its phase separation ratio faster
And it is unordered, it frequently can lead to that the microstructure of prepared integral material is irregular, it can there are more microns in internal gutter
Grade spheric granules, it is poor so as to cause the permeability of integral material, there are significant eddy diffusivity phenomenon in chromatographic isolation, from
And its separating effect is seriously affected.By numerous researcher years of researches, such as epoxy has been had been developed that at present
Ring-opening polymerisation (ring-opening polymerization), Controlled Living Radical Polymerization (controllable living
Radical polymerization) etc. a variety of different methods traditional free radical polymerization to be replaced to prepare organic polymer
Object integral material.Although these methods can overcome the shortcomings of that conventional free radical polymerize to a certain extent, due to its own
Mostly there is also reaction speed compared with the problems such as slow, experiment condition is harsh, operating process is cumbersome, therefore can not obtain always extensively
Using.
Click chemistry reacts, and the click chemistry reaction of sulfydryl is based especially on, because it is with good reaction selectivity, condition temperature
With yield it is high the features such as, be widely used in noval chemical compound synthesis, the preparation of polymer and hydrogel and material at present
Surface modification etc..Sulfydryl-epoxy click chemistry reaction is reacted as a kind of typically click chemistry based on sulfydryl, because
Its reaction efficiency is high, it is easy to operate the advantages that, had obtained relatively broad application at present in industry and biomedicine field.
However it is surprising that application of the reaction in terms of macromolecule polyalcohol synthesis is also fewer, and it is whole in porous polymer
Application in terms of the preparation of body material is even more there is not yet relevant patent or document report at present.
In order to further improve the stability of porous organic polymer integral material, and effectively improve its interior microscopic knot
The phenomenon that structure is inhomogenous, the present invention have developed a kind of based on sulfydryl-epoxy click chemistry reaction (thiol-epoxy click
Reaction) new method of porous organic polymer integral material is prepared.Organic polymer entirety material prepared by this method
Material not only has the three dimensional skeletal structure of high-sequential, but also high mechanical strength, permeability are good.In addition, this method also have with
Lower feature：1st, preparation process is easier；2nd, it is versatile, a variety of organic more thiol crosslinkers are can be applied to, for different
Organic crosslinking agent reaction condition is relatively；3rd, preparation process takes short, and preparation can be completed within general 6h；4th, reaction condition
Mildly, it is easily controllable, favorable reproducibility；5th, prepared porous integral material is easy to carry out sequent surface modification, more to meet
Different practical application requests.
The content of the invention
The purpose of the invention is to it is easier, quickly prepare it is a series of porous with high-sequential pore passage structure
Organic polymer integral material, while make prepared organic polymer integral material that there is the stability of height and can modify
Property, in order to carry out further follow-up modification to meet different practical application requests.
To achieve the above object, the technical solution adopted by the present invention is：
With 2,2', 2 ", 2 " '-[1,2- ethanetetrayls four (4,1- phenylene methylenes oxygen)] tetraoxane
(tetraphenylolethane glycidyl ether, TPEGE) is multi-epoxy monomer, by selecting different organic more mercaptos
Based cross-linker (such as 1,6- ethanthiols (1,6-hexanedithiol, HDT) or trimethylolpropane tris (3-thiopropionate)
(trimethylolpropane tris (3-mercaptopropionate), TPTM) or four -3-thiopropionate of pentaerythrite
(pentaerythritol tetrakis (3-mercaptopropionate), PTM)) and pore system is adjusted to prepare one
Series has different physics and the porous organic polymer integral material of chemical property.It is and prepared more by this method
Hole organic polymer integral material have very strong modifiability, can by the methods of physical absorption or chemical bonding to its table
Face carries out modification, to meet different practical application requests.
The preparation of organic polymer porous integral material based on sulfydryl-epoxy click chemistry reaction：Multi-epoxy is organic
Ultrasound is uniform after monomer, organic dimercapto or more thiol crosslinkers, pore-foaming agent and catalyst mixing and removes dissolving therein
After oxygen, prepared using sulfydryl-epoxy click chemistry reaction (thiol-epoxy click reaction) come a step with height
Spend the porous organic polymer integral material of orderly pore passage structure.
Its detailed process is as follows：
1) 40mg multi-epoxy organic monomers are added in into reaction vessel；
2) organic dimercapto or more sulfydryl cross-linking reagents are added in into reaction vessel, there is organic cross-linking reagent and multi-epoxy
Mole (mol) of machine monomer is than being 4:1-1:4；
3) dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO) of 80-320 μ L, 0-80 μ are added in into reaction vessel
The polyethylene glycol (PEG 200) (preferably 10-80 μ L) of L and the water (H of 0-50 μ L2O) (preferably 5-50 μ L)；
4) the pore-foaming agent polyethylene glycol 10,000 (PEG10,000) of 0-25mg is added in into reaction vessel；
5) catalyst of 2-15 μ L is added in into reaction vessel；
6) by above-mentioned mixed system, ultrasound 20-30min is completely dissolved it to form homogeneous transparent solution at normal temperatures, and removes
Remove dissolved oxygen therein；
7) obtained mixed solution in step 6) is introduced into container and sealed；
8) the obtained container for filling mixed solution in step 7) is placed at 40-120 DEG C and reacted, until being formed solid
Body；
9) rinse above-mentioned integral material with methanol, with remove pore-foaming agent and unreacted or it is unbonded on substance, obtain band
There is the porous hybrid integral material of organo-functional group.
Process is prepared in situ in porous organic polymer integral material the present invention is based on sulfydryl-epoxy click chemistry reaction
Schematically as follows：
, 3), 4), 5) and 6) step 1), 2) reaction vessel used is centrifuge tube in；Employed in the step 1)
Multi-epoxy organic monomer for 2,2', 2 ", 2 " '-[1,2- ethanetetrayls four (4,1- phenylene methylenes oxygen)] tetraoxane
(tetraphenylolethane glycidyl ether,TPEGE)；Organic dimercapto or more employed in the step 2)
Thiol crosslinkers are 1,6- ethanthiols (1,6-hexanedithiol, HDT) or trimethylolpropane tris (3- mercaptopropionic acids
Ester) (trimethylolpropane tris (3-mercaptopropionate), TPTM) or four -3- sulfydryls third of pentaerythrite
Acid esters (pentaerythritol tetrakis (3-mercaptopropionate), PTM)；Employed in the step 5)
Catalyst is the KOH aqueous solutions that concentration is 0.25mol/L；Container used is capillary or conventional liquid phase in the step 7)
Chromatographic column or centrifuge tube；When reaction time in the step 8) is 2-6 small.
This method reacts (thiol-epoxy click reaction) using sulfydryl-epoxy click chemistry, although
Presence to dissolved oxygen in system is simultaneously insensitive, but in order to avoid it generates shadow to the pattern of prepared porous integral material
It rings, reaction preferably carries out deoxygenation before starting.The formation of this integral material only needs to react at one temperature, and can be with
The porous integral material of different-shape is prepared by regulating and controlling reaction temperature.
This method is to react (thiol-epoxy click reaction) based on sulfydryl-epoxy click chemistry to prepare
Porous integral material.Therefore with very high reaction efficiency, the preparation of porous integral material can be completed in a short time.We
Method feed stock conversion is very high so that prepared porous organic polymer integral material have the higher degree of cross linking, therefore with
Stability higher is compared using the organic whole material prepared by free radical polymerization before.In addition, prepared porous integral material
Three dimensional skeletal structure with high-sequential, and its aperture and pore structure can add in multi-epoxy monomer/more mercaptos by changing
The content or reaction temperature of the ratio of based cross-linker either composition either pore-foaming agent and the catalyst of porogenic solvents carry out
Regulation and control.
Hybrid integral material prepared by the present invention has the three dimensional skeletal structure of high-sequential, is highly suitable for chromatography point
From analysis.Liquid chromatogram investigate the result shows that, the characteristic that shows is handed over epoxy monomer used and organic more sulfydryls
The chromatography retention properties for joining agent are consistent.Different organic more thiol crosslinkers are selected in this experiment, using the equal energy of the preparation method
Porous organic polymer integral material is successfully prepared, and shows the chromatography consistent with the organic functions monomer added in and protects
Stay characteristic.The hydrophobicity showed such as prepared obtained porous integral post is with the hydrophobic increasing of more thiol crosslinkers
Enhance by force.
Description of the drawings
Fig. 1 is chromatographic isolation result of the benzene homologues on TPEGE-PTM Organic Polymer Monolithic Columns.
Fig. 2 is the graph of pore diameter distribution of TPEGE-PTM organic polymer integral materials.
Specific embodiment
Embodiment 1
1st, the TPEGE of 40mg is added in into centrifuge tube.
2nd, the PTM of 26mg is added in into above-mentioned centrifuge tube.
3rd, the DMSO of 160 μ L, the H of the 200 and 20 μ L of PEG of 40 μ L are added in into above-mentioned centrifuge tube2O。
4th, the pore-foaming agent PEG 10,000 of 10mg is added in into above-mentioned centrifuge tube.
5th, the catalyst (KOH aqueous solutions, concentration 0.25mol/L) of 5 μ L is added in into reaction vessel.
6th, by above-mentioned centrifuge tube, ultrasound 20min is uniformly mixed each component therein at normal temperatures, and removes and be dissolved in
Dissolved oxygen therein.
The 7th, the pre-polymerization liquid obtained in step 6 is introduced into 75 μm (internal diameters) for first passing through sulfhydrylation processing in advance with syringe
Capillary in, sealed with silica gel with postcapillary both ends, then seal the effective sealed membrane of centrifugation equipped with remaining pre-polymerization liquid.
8th, the capillary in step 7 and centrifuge tube are placed in 50 DEG C of water-bath, react 4h, it is pre- in centrifuge tube at this time
Poly- liquid has formed the solid of yellow.
9th, capillary is rinsed with methanol and water, pore-foaming agent therein and some substances for having neither part nor lot in reaction is gone out and obtained
Capillary organic whole column.To in centrifuge tube then with first alcohol and water repeatedly washing by soaking i.e. obtain organic whole material.
Fig. 1 is capillary liquid chromatography separating resulting of the benzene homologues on TPEGE-PTM Organic Polymer Monolithic Columns.Chromatography
Condition be acetonitrile/water (60/40, v/v), flow velocity 240nL/min.Peak in chromatogram is followed successively by 1：Benzene, 2：Toluene, 3：Second
Benzene, 4：Propyl benzene, 5：Butylbenzene, peak sequence grow from weak to strong appearance by hydrophobicity, are typical reverse-phase chromatography retention mechanism.It retains
On the one hand effect is to be determined by the hydrophobic property of TPEGE, on the other hand determined again by used organic more thiol crosslinkers PTM
It is fixed.By being found after calculating its column effect, the pillar to the columns of above-mentioned 5 compounds effect in 100, more than 000N/m,
Reach as high as 132,000N/m (benzene).All Organic Polymer Monolithic Columns using free radical polymerization of report before significantly larger than
Column effect in addition column effect also than most inorganic integral posts and organic-inorganic hybridization monolithic column it is high.This illustrates this hair
Bright introduced method can be used for the quick capillary Organic Polymer Monolithic Columns for preparing and having high separability energy.
Fig. 2 is the graph of pore diameter distribution of TPEGE-PTM organic polymer integral materials.Integral material as can be seen from Figure 2
Pore-size distribution is very narrow, illustrates the pore structure high-sequential inside the organic polymer integral material, aperture ratio is more uniform, also turns out
Sulfydryl-epoxy click chemistry reaction (thiol-epoxy click reaction), which can be used for preparing, has high-sequential
Three dimensional skeletal structure porous organic polymer integral material.
Embodiment 2
1st, the TPEGE of 40mg is added in into centrifuge tube.
2nd, the TPTM of 27mg is added in into above-mentioned centrifuge tube.
3rd, the DMSO of 160 μ L, the H of the 200 and 20 μ L of PEG of 40 μ L are added in into above-mentioned centrifuge tube2O。
4th, the pore-foaming agent PEG 10,000 of 15mg is added in into above-mentioned centrifuge tube.
5th, the catalyst (KOH aqueous solutions, concentration 0.25mol/L) of 5 μ L is added in into reaction vessel.
6th, by above-mentioned centrifuge tube, ultrasound 20min is uniformly mixed each component therein at normal temperatures, and removes and be dissolved in
Dissolved oxygen therein.
The 7th, the pre-polymerization liquid obtained in step 6 is introduced into 75 μm (internal diameters) for first passing through sulfhydrylation processing in advance with syringe
Capillary in, sealed with silica gel with postcapillary both ends, then seal the effective sealed membrane of centrifugation equipped with remaining pre-polymerization liquid.
8th, the capillary in step 7 and centrifuge tube are placed in 60 DEG C of water-bath, react 4h, it is pre- in centrifuge tube at this time
Poly- liquid has formed the solid of yellow.
9th, capillary is rinsed with methanol and water, pore-foaming agent therein and some substances for having neither part nor lot in reaction is gone out and obtained
Capillary hydridization integral post.To in centrifuge tube then with first alcohol and water repeatedly washing by soaking i.e. obtain hybrid integral material.
By carrying out chromatographic evaluation to TPEGE-TPTM Organic Polymer Monolithic Columns, it is found that it divides micromolecular compound
Also very good from effect, column effect reaches as high as 128,000N/m (propyl benzene), this further proves that the method that the present invention is introduced exists
Prepare the high efficiency and stability in terms of the capillary Organic Polymer Monolithic Columns with high separability energy.In addition, comparison is implemented
The concrete operations flow of example 1 and embodiment 2, it can be found that different organic more thiol crosslinkers are employed, but the two is either
Without apparent difference in pre-polymerization liquid proportioning or concrete operations, unique difference is exactly that embodiment 2 is more than in embodiment 1
Add the pore-foaming agent PEG10000 of 5mg and improve reaction temperature.It is very high general that this illustrates that the method introduced of the present invention has
Property, can easily replace reagent and adjustment proportioning should to meet different reality with the integral material without characteristic to prepare
Use demand.
Claims (7)
1. a kind of preparation method of porous organic polymer integral material, it is characterised in that：Its process is as follows,
1）40 mg multi-epoxy organic monomers are added in into reaction vessel；
2）Organic dimercapto or more sulfydryl cross-linking reagents are added in into reaction vessel, makes organic cross-linking reagent and the organic list of multi-epoxy
Mole of body（mol）Than for 4:1-1:4；
3）The dimethyl sulfoxide (DMSO) of 80-320 μ L is added in into reaction vessel（dimethyl sulfoxide, DMSO）, 0-80 μ L
Polyethylene glycol and 0-50 μ L water（H2O）；
4）The pore-foaming agent polyethylene glycol 10,000 of 0-25 mg is added in into reaction vessel（PEG 10,000）；
5）The catalyst of 2-15 μ L is added in into reaction vessel；
6）By above-mentioned mixed system, ultrasound 20-30 min are completely dissolved it to form the solution of homogeneous transparent at normal temperatures, and remove
Remove dissolved oxygen therein；
7）By step 6）In obtained mixed solution be introduced into container and seal；
8）By step 7）In the obtained container for filling mixed solution be placed in 40-120oIt is reacted under C, until forming solid；
9）Rinse above-mentioned integral material with methanol, with remove pore-foaming agent and unreacted or it is unbonded on substance, obtain
The porous organic polymer integral material of machine functional group.
2. according to the method described in claim 1, it is characterized in that：The step 1）、2）、3）、4）、5）With 6）In it is used anti-
It is centrifuge tube to answer container.
3. according to the method described in claim 1, it is characterized in that：The step 1）The middle multi-epoxy organic monomer used for 2,
2', 2'', 2'''- [1,2- ethanetetrayls four (4,1- phenylene methylenes oxygen)] tetraoxane
（tetraphenylolethane glycidyl ether, TPEGE）.
4. according to the method described in claim 1, it is characterized in that：The step 2）The organic dimercapto or more sulfydryls of middle use
Crosslinking agent is 1,6- ethanthiols（1,6-hexanedithiol, HDT）Or trimethylolpropane tris (3-thiopropionate)
（trimethylolpropane tris(3-mercaptopropionate), TPTM）Or four -3- mercaptopropionic acids of pentaerythrite
Ester（pentaerythritol tetrakis(3-mercaptopropionate), PTM）.
5. according to the method described in claim 1, it is characterized in that：The step 5）Employed in catalyst be that concentration is
The KOH aqueous solutions of 0.25 mol/L.
6. according to the method described in claim 1, it is characterized in that：The step 7）In used container for capillary or often
Advise liquid-phase chromatographic column or centrifuge tube.
7. according to the method described in claim 1, it is characterized in that：The step 8）In reaction time for 2-6 it is small when.
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Non-Patent Citations (3)
| Title |
|---|
| "Efficient synthesis of multifunctional polymers via thiol–epoxy "click" chemistry";Swati De et al.;《Chemistry Communication》;20121231;第48卷;第3130–3132页 * |
| "Evaluation and control of thioleene/thioleepoxy hybrid networks";Jacquelyn A. Carioscia et al.;《Polymer》;20071231;第48卷;第1526-1532页 * |
| "Photolatent amines producing a strong base as photocatalyst for the in-situ preparation of organiceinorganic hybrid coatings";Marco Sangermano et al.;《Polymer》;20140222;第55卷;第1628-1635页 * |
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