CN106397652A - Method for preparing super-macroporous high-specific-area polymer - Google Patents
Method for preparing super-macroporous high-specific-area polymer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
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Abstract
The invention relates to a method for preparing a super-macroporous high-specific-area polymer. The method includes obtaining a super-macroporous polymer through low-temperature freezing polymerization, and subjecting the super-macroporous polymer to post-crosslinking through free radical reaction or Friedel-Crafts alkylation reaction so as to obtain the super-macroporous high-specific-area polymer. The method further includes taking a divinyl benzene as a monomer, dimethyl sulfoxide as a solvent and a crystal as a pore-foaming agent, selecting a redox initiation system and polymerizing to obtain the super-macroporous polymer; taking the super-macroporous polymer as a precursor and dichloroethane as a solvent, adding a free radical initiator or ferric trichloride to perform post-crosslinking, carrying out thermostatic reaction in oil bath at 85 DEG C for 18 hours, washing and drying so as to obtain the super-macroporous high-specific-area polymer. The method is simple and reliable and simple in post-treatment. The super-macroporous high-specific-area polymer has a super-macroporous structure and a high specific area, the pore size range is mainly between 5-100 nm and 20-200 micrometers, and the maximum specific area can be up to 1214.19 m<2>/g.
Description
Technical field
The present invention relates to a kind of method preparing super big hole high-specific surface polymer, belong to high polymer material technology neck
Domain.
Background technology
Porous material is due to having the characteristic of high-specific surface area in numerous necks such as absorption, catalysis, surface reaction, gas storages
Domain tool has been widely used.
At present, post-crosslinking reaction is to prepare one of main method of high-specific surface polymer porous material.Crosslinked anti-afterwards
Should refer to construct new junction point in initial polymer network structure, thus producing more in the framing structure of polymer
Crosslink sites, and being fixed up, make the chemical reaction process that the polymer molecule segment that is mutually wound around is more stable.It can be divided into
Crosslinked after Friedel-Crafts reaction（Jou-Hyeon Ahn, Jin-Eon Jang, Chang-Gun Oh, Son-Ki Ihm, Jamie
Cortez, David C. Sherrington, Macromolecules, 2006, 39, 627-632）And radical reaction
Crosslinked afterwards（Urska Sevsek, Jirí Brus, Karel Jerabek, Peter Krajnc, Polymer, 2014,
55, 410-415）.Wherein, after Friedel-Crafts reaction, crosslinking is that polymer precursor is fully swelling in a solvent, makes strand abundant
Diastole, utilizes original functional group that Friedel-Crafts reaction occurs under catalyst action, produces new bound site on polymer backbone
Point, and this solvent swelling state of polymer is fixed up, after solvent removes, because strand is fixed without sending out
Raw retraction or phenomenon of caving in, thus the hole of structural integrity is retained, and produces new hole knot on the basis of original copolymer
Structure, obtains high-specific surface area material.CN103910823A discloses a kind of polar group and modifies crosslinked poly- diethyl after suspended double bond
The preparation method of alkene benzene resin, first with divinylbenzene as monomer, with toluene and normal heptane as porogen, adds polar monomer,
Poly- divinylbenzene resins presoma is obtained by suspension polymerization, then with dichloroethanes as solvent, after Friedel-Crafts reaction
Crosslinked method obtains poly- divinylbenzene resins, and the average pore size of gained resin is 6 ~ 13 nm, and specific surface area is 700 ~ 1200
m2/g.CN105218730A discloses a kind of method preparing adsorbent resin, with divinylbenzene and phenylmethane BMI
For monomer, with toluene and normal heptane as porogen, polymerizate is obtained using suspension polymerisation, add organic solvent to make polymerizate
Swelling, after Friedel-Crafts reaction, crosslinked method obtains adsorbent resin, and the resin specific surface area obtaining is 710 ~ 1060 m2/g.
After radical reaction, crosslinking is that polymer precursor is fully swelling, is caused by adding initiator such as di-tert-butyl peroxide
Polymerization, carries out Raolical polymerizable, produces new hole on the basis of original pore structure, obtain the high polymerization of specific surface area
Thing, resulting polymers aperture is 2 ~ 100 nm, and specific surface area is 408.2 ~ 778.6 m2/g（Krasimira Soukupová,
Alessandro Sassi, Karel Jerˇábek, Reactive & Functional Polymers, 2009, 69,
353–357）.
Solvent thermal reaction is also a kind of method preparing high specific surface area porous material.Itself and conventional solvent pore side
Method is compared, and because reaction temperature is on the boiling point of solvent, and is in an enclosed system so that solvent may be at gas
The subcritical state of state-liquid, increased the compatibility of solvent and polymer, thus can obtain more nano-pore structures.
Xiao Fengshou et al. is prepared for porous poly- divinylbenzene material using the method for solvent thermal polymerization and uses it for oil-water separation
（Yonglai Zhang, Shu Wei, Fujian Liu, Yunchen Du, Sen Liu, Yanyan Ji,
Toshiyuki Yokoi, Takashi Tatsumi, Fengshou Xiao, Nano Today, 2009, 4, 135-
142）.Resulting materials specific surface area reaches as high as 702 m2/g.
However, although the resin that above two method obtains has higher specific surface area, because its pore-size distribution is to receive
Meter level scope, so leading to it, when carrying out sample adsorption, resistance to mass tranfer is larger, and time of equilibrium adsorption is longer, is unfavorable for that it is extensive
Application.
Super large pore polymer be a kind of there is the polymer that micron order runs through pore structure, this unique pore structure makes it
There is high flux, the feature of low mass transfer resistance, therefore, it is widely used in Solid-Phase Extraction, medicine controlled releasing and adsorbing separation etc.
Various fields.CN105037626A discloses a kind of preparation method of macropore big particle diameter polymer microballoon, with methyl methacrylate
Ester etc. is monomer, and ethylene glycol dimethacrylate etc. is cross-linking agent, with the mixture of dichloromethane, toluene and chlorobenzene as pore
Agent, obtains polymer microballoon by suspension polymerisation, the aperture of thus obtained microsphere is between 150 ~ 500 nm.CN100562530C is open
A kind of preparation method of super large pore polymer microsphere, with styrene etc. as monomer, divinylbenzene etc. is cross-linking agent, with Hexalin
Deng for porogen, super big hole microsphere is prepared by suspension polymerisation, the pore-size distribution of thus obtained microsphere is at 10 ~ 200 nm and 1 ~ 60 μm
Between, specific surface area only up to reach 203.8 m2/ g, thus the adsorption capacity of such material is generally less.
Content of the invention
For above-mentioned limitation, the method that the present invention proposes to first pass through freezing polymerization prepares super large pore polymer
Presoma, crosslinking after then it being carried out using the method that solvent thermal polymerization and post-crosslinking reaction combine, the high ratio of preparation super big hole
The new method of surface polymer.
The technical scheme is that:
A kind of preparation method of super big hole high-specific surface polymer, step is as follows：
First by appropriate divinylbenzene and initiator, it is added in solvent, mix, after being passed through nitrogen deoxygenation, go to syringe
In, sealing, react 96 hours at -18 DEG C, take out, be placed under room temperature environment, fully wash after crystal dissolves, be dried, obtain
To super large pore polymer presoma；Take polymer precursor, initiator or catalyst, solvent to be added in reactor, be passed through nitrogen
After gas deoxygenation, sealing, swelling, it is placed in isothermal reaction 18 hours in 85 DEG C of oil baths, washing, it is dried, obtain super big hole high-ratio surface
Accumulation compound；
Described divinylbenzene monomer is 20 with the volume ratio of solvent:80；
Described initiator is 0.01 with the mass ratio of divinylbenzene monomer：1；
Described initiator is redox initiation system；
Described solvent is dimethyl sulfoxide, and its crystal is porogen；
When described rear crosslinked, initiator is benzoyl peroxide, and catalyst is anhydrous ferric trichloride；
When described rear crosslinked, solvent is dichloroethanes.
It is divinylbenzene 80 according to currently preferred, described monomer.
It is polytetrafluoroethyllining lining according to currently preferred, described reactor.
It is crosslinked after Friedel-Crafts reaction according to currently preferred, described rear crosslinking method.
Freezing polymerization reaction temperature of the present invention is less than the fusing point of dimethyl sulfoxide, and during crosslinking, reaction temperature is higher than afterwards
The boiling point of dichloroethanes.
The polymer that the present invention is obtained both had had super large pore structure, had high specific surface area again, and its pore diameter range is main
It is distributed between 5 ~ 100 nm and 20 ~ 200 μm, specific surface area reaches as high as 1214.19 m2/g.
According to the present invention most preferably, a kind of super big hole high-specific surface area congeals the preparation method of glue, and step is as follows：
4.0 ml divinylbenzene monomers are dissolved in 16 ml dimethyl sulfoxide, addition 36.8 mg benzoyl peroxides, 19 μ l N,
Accelerine, mixes, and logical nitrogen 5 min removes oxygen, after reacting 96 hours, is placed in room temperature, treats diformazan at -18 DEG C
Base sulfoxide crystal melts, and fully washs, and is dried, obtains super large pore polymer presoma；Take 20 ml dichloroethanes and 40 mg no
Water FeCl3In reactor, ultrasonic disperse, add 100 mg polymer precursors, be passed through nitrogen 10 min, after removing oxygen,
Sealing, swelling 1 hour, is subsequently placed in 85 DEG C of oil baths and reacts 18 hours, fully wash after cooling, be dried, obtain super big hole high
Specific surface area polymer.Resulting polymers specific surface area reaches 1214.19 m2/g.
The present invention combines freezing polymerization and the advantage of post-crosslinking reaction, and the method first passing through freezing polymerization obtains
To the polymer precursor with super large pore structure, then improve the specific surface area of polymer by post-crosslinking reaction, and will
Post-crosslinking reaction is placed in a solvent hot system and carries out, and promotes the carrying out of post-crosslinking reaction by means of solvent thermal reaction.
The present invention adopts solvent crystal pore, and preparation method is simple and reliable, and post processing is simple, and the polymer of gained both had
Super large pore structure, has high specific surface area again, and its pore diameter range is mainly distributed between 5 ~ 100 nm and 20 ~ 200 μm, than
Surface area reaches as high as 1214.19 m2/g.
Brief description
The infrared spectrum of polymer before and after accompanying drawing is crosslinked after being：Precursor is the polybenzazole precursor of embodiment 1 preparation
Body；Friedel-Crafts reaction is cross linked polymer after Friedel-Crafts reaction prepared by embodiment 2；Radical
Initiated reaction is cross linked polymer after radical reaction prepared by embodiment 3.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described.Used in embodiment, divinylbenzene monomer is
Divinylbenzene 80（Trade name, represents that the content of divinylbenzene is 80%, vinyl ethylbenzene 20%）, Aladdin reagent（China）Limited
Products.
Embodiment 1
4.0 ml divinylbenzene monomers are dissolved in 16 ml dimethyl sulfoxide, addition 36.8 mg benzoyl peroxides, 19 μ l N,
Accelerine, mixes, and logical nitrogen 5 min removes oxygen, after reacting 96 hours, is placed in room temperature, treats diformazan at -18 DEG C
Base sulfoxide crystal melts, and is fully washed with methanol, then is washed with deionized removing methanol, puts in 50 DEG C of baking ovens and be dried to perseverance
Weight, obtains super large pore polymer.The polymer specific surface area obtaining is 140.35 m2/g.
Embodiment 2
Take 20 ml dichloroethanes and the anhydrous FeCl of 40 mg3In reactor, ultrasonic disperse, add institute in 100 mg embodiments 1
Obtain polymer precursor, be passed through nitrogen 10 min, after removing oxygen, sealing, swelling 1 hour, it is subsequently placed in 85 DEG C of oil baths anti-
Answer 18 hours, fully washed with methanol after cooling, with the salt acid elution of 0.1 mol/L, immersion, then deionized water is rinsed, and puts
Enter in 50 DEG C of baking ovens and dry to constant weight, obtain super big hole high-specific surface polymer.Resulting polymers specific surface area is 1214.19
m2/g.
Embodiment 3
Take 20 ml dichloroethanes and 10 mg benzoyl peroxides in reactor, dissolving, add gained in 100 mg embodiments 1
Polymer precursor, is passed through nitrogen 10 min, after removing oxygen, sealing, and swelling 1 hour, it is subsequently placed in reaction in 85 DEG C of oil baths
18 hours, fully washed with methanol after cooling, then be washed with deionized, put in 50 DEG C of baking ovens and dry to constant weight, obtain super large
Hole high-specific surface polymer.Resulting polymers specific surface area is 84.77 m2/g.
Claims (9)
1. a kind of method preparing super big hole high-specific surface polymer.
2. by 20 parts of divinylbenzene 80 and 0.01 part of initiator, it is added in 80 parts of solvent, mix, be passed through nitrogen deoxygenation
Afterwards, go in syringe, sealing, react 96 hours at -18 DEG C, take out, be placed under room temperature environment, use after crystal dissolves
Cleaning mixture fully washs, and obtains super large pore polymer presoma after being dried；Take 1 part of presoma, 0.1 part of initiator or catalysis
Agent, dichloroethanes are added in reactor, after being passed through nitrogen deoxygenation, sealing, and swelling 1 hour, it is placed in constant temperature in 85 DEG C of oil baths anti-
Answer 18 hours, washing, be dried, obtain super big hole high-specific surface polymer.
3. preparation method as claimed in claim 1 is it is characterised in that described monomer is divinylbenzene 80.
4. preparation method as claimed in claim 1 is it is characterised in that described initiator is redox initiation system.
5. it is characterised in that described solvent is dimethyl sulfoxide, its crystal is to cause to preparation method as claimed in claim 1
Hole agent.
6. preparation method as claimed in claim 1 is it is characterised in that described freezing polymerization reaction temperature is less than dimethyl Asia
The fusing point of sulfone.
7. preparation method as claimed in claim 1 is it is characterised in that described reactor has polytetrafluoroethyllining lining.
8. preparation method as claimed in claim 1 is it is characterised in that described initiator is benzoyl peroxide, catalyst
For anhydrous ferric trichloride.
9. preparation method as claimed in claim 1 is it is characterised in that described post-crosslinking reaction temperature is 85 DEG C, higher than two
The boiling point of ethyl chloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602744A (en) * | 2017-03-08 | 2018-01-19 | 济南大学 | A kind of superhigh cross-linking microporous polymer and preparation method thereof |
| CN109400780A (en) * | 2018-11-02 | 2019-03-01 | 湖南大学 | A kind of method of short of electricity subclass alkene free radical polymerization |
| CN109517211A (en) * | 2018-09-28 | 2019-03-26 | 浙江工业大学 | A kind of amino porous polymer and the preparation method and application thereof |
| CN110467707A (en) * | 2018-05-10 | 2019-11-19 | 北京工业大学 | A kind of method of modifying effectively improving MOFs water stability and ammonia gas absorption performance |
| CN112063405A (en) * | 2020-09-14 | 2020-12-11 | 浙江大学台州研究院 | Pyrolysis-based waste tire treatment method |
| CN114014966A (en) * | 2021-09-28 | 2022-02-08 | 广东工业大学 | Amide group modified ultrahigh cross-linked adsorption resin and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602744A (en) * | 2017-03-08 | 2018-01-19 | 济南大学 | A kind of superhigh cross-linking microporous polymer and preparation method thereof |
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| CN110467707A (en) * | 2018-05-10 | 2019-11-19 | 北京工业大学 | A kind of method of modifying effectively improving MOFs water stability and ammonia gas absorption performance |
| CN110467707B (en) * | 2018-05-10 | 2022-01-28 | 北京工业大学 | Modification method for effectively improving stability of MOFs water and ammonia adsorption performance |
| CN109517211A (en) * | 2018-09-28 | 2019-03-26 | 浙江工业大学 | A kind of amino porous polymer and the preparation method and application thereof |
| CN109517211B (en) * | 2018-09-28 | 2021-10-15 | 浙江工业大学 | Amino porous polymer and preparation method and application thereof |
| CN109400780A (en) * | 2018-11-02 | 2019-03-01 | 湖南大学 | A kind of method of short of electricity subclass alkene free radical polymerization |
| CN109400780B (en) * | 2018-11-02 | 2021-04-16 | 湖南大学 | Method for free radical polymerization of electron-deficient olefin |
| CN112063405A (en) * | 2020-09-14 | 2020-12-11 | 浙江大学台州研究院 | Pyrolysis-based waste tire treatment method |
| CN112063405B (en) * | 2020-09-14 | 2022-04-01 | 浙江大学台州研究院 | Pyrolysis-based waste tire treatment method |
| CN114014966A (en) * | 2021-09-28 | 2022-02-08 | 广东工业大学 | Amide group modified ultrahigh cross-linked adsorption resin and preparation method and application thereof |
| CN114014966B (en) * | 2021-09-28 | 2023-11-07 | 广东工业大学 | Amide group modified ultrahigh crosslinked adsorption resin and preparation method and application thereof |
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