CN107602744A - A kind of superhigh cross-linking microporous polymer and preparation method thereof - Google Patents
A kind of superhigh cross-linking microporous polymer and preparation method thereof Download PDFInfo
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- CN107602744A CN107602744A CN201710827250.6A CN201710827250A CN107602744A CN 107602744 A CN107602744 A CN 107602744A CN 201710827250 A CN201710827250 A CN 201710827250A CN 107602744 A CN107602744 A CN 107602744A
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Abstract
The present invention relates to a kind of preparation method of the superhigh cross-linking microporous polymer with high-specific surface area.This method uses from the step of addition polymerization one and superhigh cross-linking microporous polymer is made.With divinylbenzene (DVB) for monomer, lewis acid is catalyst, during monomer, catalyst are added sequentially in the polytetrafluoroethyllining lining of the stainless steel cauldron containing solvent, is mixed, sealing；Heated up polymerization in water-bath, and at 25 DEG C~85 DEG C, 4~48 hours reaction time, products therefrom is washed through solvent, soaked, filtering, washing, drying, and obtains superhigh cross-linking microporous polymer for reaction temperature control.The preparation process of the present invention is simple, and time-consuming short, no small molecule by-product produces, and atom utilization is high, and catalyst amount is few.For the superhigh cross-linking microporous polymer pore-size distribution of gained between 10 below nm and 20 ~ 150 nm, specific surface area is up to 890.7 m2/ g, available for gas molecule with the absorption of organic pollution with separating.
Description
Technical field
The present invention relates to a kind of preparation method of the superhigh cross-linking microporous polymer with high-specific surface area, belong to macromolecule
Field of material technology.
Background technology
Micropore organic polymer with high-specific surface area（microporous organic polymers, MOPs）
The various fields such as the enrichment of gas is with separating, catalyst carrier, chromatography separation media, SPE material have extensive use
On the way.
At present, MOPs can be divided mainly into from tool microporous polymer（polymer of intrinsic microprosity,
PIMs）, covalent organic framework（covalent organic frameworks, COFs）, conjugation microporous polymer
(conjugated microporous polymers, CMPs) and superhigh cross-linking polymer（hypercrosslinked
polymers, HCPs）.Wherein, because HCPs preparation process does not need noble metal catalyst, required monomer source is wider
It is general, thus its industrial prospect is the most good.HCPs preparation method can simply be divided into two major classes according to polymerization methodses：（1）
Polymer precursor post-crosslinking method；（2）Small molecule condensation methods.In polymer precursor post-crosslinking method, it is complete that preparation reaction is divided into two steps
Into.Linear or low cross-linking polymer is prepared first, then utilizes additional crosslink agent（Referring to Yuwan Yang et al.,
Journal of Materials Chemistry A 2016, 4(39), 15072-15080）Or the function that polymer carries
Base（Such as suspended double bond, referring to Anne Kari Nyhus et al., Journal of Polymer Science Part A-
Polymer Chemistry 2000, 38(8), 1366-1378）, under Louis acid catalysis, post-crosslinking reaction is carried out, is obtained
To the polymer of superhigh cross-linking.In small molecule condensation methods, preparing one step of reaction can complete.Selected small molecule can be containing
The molecule of multiple function bases（Referring to Colin D. Wood et al., Chemistry of Materials 2007,19,
2034-2048）Or comprise only the phenmethylol molecule of One function base（Referring to Yali Luo et al., Polymer
Chemistry 2013, 4, 1126-1131）, under Louis acid catalysis, an one-step polycondensation obtains superhigh cross-linking polymer.
However, because polymer precursor post-crosslinking method needs previously prepared suitable polymer precursor so that polymerization process
Complexity, take；And in small molecule condensation methods, polycondensation reaction has small molecule by-product generation, so the atom profit of raw material
It is low with rate, and small molecule by-product is mostly toxic compounds（Hydrogen chloride or methanol）, it is unfavorable for environmental protection.
The content of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of divinylbenzene that is based on from addition polymerization
React the method that a step prepares the superhigh cross-linking microporous polymer with high-specific surface area.
The technical scheme is that：
A kind of preparation method of the superhigh cross-linking microporous polymer with high-specific surface area, using from addition polymerization, with divinyl
Benzene (DVB) is monomer, and in Louis acid catalysis, polymerization obtains in next step, and step is as follows：
During divinylbenzene, catalyst are added sequentially in the polytetrafluoroethyllining lining of the stainless steel cauldron containing solvent, mix
It is even, sealing；Heat up polymerization in water-bath, and at 25 DEG C~85 DEG C, 4~48 hours reaction time, gained produces for reaction temperature control
Thing is washed through solvent, soaked, filtering, washing, drying, and obtains superhigh cross-linking microporous polymer；
Described monomer and the volume ratio of solvent are 2 ~ 66.7:100；
Described catalyst and the mass ratio of monomer are 5 ~ 200:100；
Described catalyst is anhydrous ferric trichloride or anhydrous stannic chloride；
Described solvent is acetonitrile, tetrahydrofuran, dichloroethanes or acetone.
It is 10 ~ 50 according to the volume ratio of currently preferred, described monomer and solvent:100.
It is 10 ~ 40 according to the mass ratio of currently preferred, described catalyst and monomer:100.
It is anhydrous ferric trichloride according to currently preferred, described catalyst.
It is dichloroethanes according to currently preferred, described solvent.
According to 80 DEG C currently preferred, described of reaction temperature.
It it is 24 hours according to currently preferred, the described reaction time.
According to the present invention most preferably, a kind of preparation method of the superhigh cross-linking microporous polymer with high-specific surface area,
Step is as follows：
1.5 ml divinylbenzenes monomers are added sequentially to containing the stainless of 15 ml dichloroethanes with 0.2757 g anhydrous ferric trichlorides
In the polytetrafluoroethyllining lining of steel reactor, mix, sealing；It is subsequently placed in water-bath, bath temperature is set as 80 DEG C, reaction
24 hours；Stop heating, be cooled to room temperature, washed with methanol, then with 1M HCl soaked overnights, filter, wash, dry, obtain
Poly- divinylbenzene superhigh cross-linking microporous polymer, yield 91.3%, gained superhigh cross-linking microporous polymer specific surface area are
890.7 m2/g。
The present invention prepares the superhigh cross-linking microporous polymer with high-specific surface area, and a step obtains from addition polymerization, prepares
Process is simple, and time-consuming short, no small molecule by-product produces, and atom utilization is high, and catalyst amount is few.
The superhigh cross-linking microporous polymer of gained of the invention, pore-size distribution is between 10 below nm and 20 ~ 150 nm, institute
The specific surface area for obtaining superhigh cross-linking microporous polymer is up to 890.7 m2/ g, available for adsorbing separation micromolecular compound（Such as：
H2, CO2, polycyclic aromatic hydrocarbon etc.）.
Brief description of the drawings
Fig. 1：The pore-size distribution of superhigh cross-linking microporous polymer obtained by the embodiment of the present invention 1.
Fig. 2：The carbon-13 nmr spectra of superhigh cross-linking microporous polymer obtained by the embodiment of the present invention 2.
Embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described.The divinylbenzene monomer used in embodiment is
Divinylbenzene 80（Trade name, the content for representing divinylbenzene are 80%, vinyl ethylbenzene 20%）, Aladdin reagent（China）It is limited
Products.
Embodiment 1
1.5 ml divinylbenzenes monomers are added sequentially to containing the stainless of 15 ml dichloroethanes with 0.2757 g anhydrous ferric trichlorides
In the polytetrafluoroethyllining lining of steel reactor, mix, sealing；It is subsequently placed in water-bath, bath temperature is set as 80 DEG C, reaction
24 hours；Stop heating, be cooled to room temperature, washed with methanol, then with 1M HCl soaked overnights, filter, wash, dry, obtain
Poly- divinylbenzene superhigh cross-linking microporous polymer, yield 91.3%, gained superhigh cross-linking microporous polymer specific surface area are
890.7 m2/g。
Embodiment 2
4.35 ml divinylbenzenes monomers are added sequentially to containing the stainless of 6.525 ml acetonitriles with 0.8033 g anhydrous ferric trichlorides
In the polytetrafluoroethyllining lining of steel reactor, mix, sealing；It is subsequently placed in water-bath, bath temperature is set as 80 DEG C, reaction
24 hours；Stop heating, be cooled to room temperature, washed with methanol, then with 1M HCl soaked overnights, filter, wash, dry, obtain
Poly- divinylbenzene superhigh cross-linking microporous polymer, yield 88.7%, gained superhigh cross-linking microporous polymer specific surface area are
61.32 m2/g。
Embodiment 3
4.35 ml divinylbenzenes monomers and 0.7905 g anhydrous ferric trichlorides are added sequentially to containing 6.525 ml tetrahydrofurans
In the polytetrafluoroethyllining lining of stainless steel cauldron, mix, sealing；It is subsequently placed in water-bath, bath temperature is set as 80 DEG C,
Reaction 24 hours；Stop heating, be cooled to room temperature, washed with methanol, then with 1M HCl soaked overnights, filter, wash, dry,
Poly- divinylbenzene superhigh cross-linking microporous polymer, yield 101% are obtained, gained superhigh cross-linking microporous polymer specific surface area is
6.49 m2/g。
Claims (9)
1. a kind of preparation method of the superhigh cross-linking microporous polymer with high-specific surface area, it is characterised in that use and gather from addition
Legal that poly- divinylbenzene superhigh cross-linking microporous polymer is made, step is as follows：
During divinylbenzene, catalyst are added sequentially in the polytetrafluoroethyllining lining of the stainless steel cauldron containing solvent, mix
It is even, sealing；The volume ratio that the monomer accounts for solvent is 2 ~ 66.7:100；Described catalyst and the mass ratio of monomer are 5 ~ 200:
100；Described monomer is divinylbenzene 80；Described catalyst is anhydrous ferric trichloride or anhydrous stannic chloride；Described is molten
Agent is acetonitrile, tetrahydrofuran, dichloroethanes or acetone；
Heat up polymerization in water-bath, and at 25 DEG C~85 DEG C, 4~48 hours reaction time, products therefrom passes through for reaction temperature control
Solvent washing, immersion, filter, wash, drying, obtaining poly- divinylbenzene superhigh cross-linking microporous polymer.
2. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Monomer and solvent volume ratio be 2 ~ 66.7:100.
3. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Catalyst and monomer mass ratio be 5 ~ 200:100.
4. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Monomer be divinylbenzene 80.
5. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Catalyst be anhydrous ferric trichloride or anhydrous stannic chloride.
6. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Solvent be acetonitrile, tetrahydrofuran, dichloroethanes or acetone.
7. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
Reaction temperature be 25 DEG C~85 DEG C.
8. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that described
4~48 hours reaction time.
9. the method for poly- divinylbenzene superhigh cross-linking microporous polymer is prepared as claimed in claim 1, it is characterised in that step
It is as follows：
1.5 ml divinylbenzenes monomers are added sequentially to containing the stainless of 15 ml dichloroethanes with 0.2757 g anhydrous ferric trichlorides
In the polytetrafluoroethyllining lining of steel reactor, mix, sealing；It is subsequently placed in water-bath, bath temperature is set as 80 DEG C, reaction
24 hours；Stop heating, be cooled to room temperature, washed with methanol, then with 1M HCl soaked overnights, filter, wash, dry, obtain
Poly- divinylbenzene superhigh cross-linking microporous polymer, yield 91.3%, gained superhigh cross-linking microporous polymer specific surface area are
890.7 m2/g。
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Cited By (5)
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| CN108793155A (en) * | 2018-07-03 | 2018-11-13 | 济南大学 | A kind of preparation method of high-specific surface area lotus root shape porous carbon materials |
| CN108976334A (en) * | 2018-06-22 | 2018-12-11 | 济南大学 | Three-dimensional cross-linked soluble polydivinylbenezene microgel of one kind and preparation method thereof |
| CN110423335A (en) * | 2019-07-30 | 2019-11-08 | 华中科技大学 | A kind of micropore ladder polymer and its synthetic method and application |
| CN110437489A (en) * | 2019-08-30 | 2019-11-12 | 济南大学 | A kind of method that waste and old expanded polystyrene (EPS) recycling prepares super cross-linked porous material |
| CN112646132A (en) * | 2020-12-09 | 2021-04-13 | 济南大学 | Hypercrosslinked microporous polymer with high hydrogen storage performance and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976334A (en) * | 2018-06-22 | 2018-12-11 | 济南大学 | Three-dimensional cross-linked soluble polydivinylbenezene microgel of one kind and preparation method thereof |
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| CN110423335A (en) * | 2019-07-30 | 2019-11-08 | 华中科技大学 | A kind of micropore ladder polymer and its synthetic method and application |
| CN110437489A (en) * | 2019-08-30 | 2019-11-12 | 济南大学 | A kind of method that waste and old expanded polystyrene (EPS) recycling prepares super cross-linked porous material |
| CN112646132A (en) * | 2020-12-09 | 2021-04-13 | 济南大学 | Hypercrosslinked microporous polymer with high hydrogen storage performance and preparation method thereof |
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