CN106397652B - A method of preparing super big hole high-specific surface polymer - Google Patents
A method of preparing super big hole high-specific surface polymer Download PDFInfo
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- 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
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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
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Abstract
The present invention relates to a kind of methods for preparing super big hole high-specific surface polymer.This method passes through cryogenic freezing first and polymerize to obtain super large pore polymer, is then utilized respectively radical reaction or Friedel-Crafts reaction carries out post-crosslinking to it, obtain super big hole high-specific surface polymer.Using divinylbenzene as monomer, using dimethyl sulfoxide as solvent, crystal is pore-foaming agent, selects redox initiation system, polymerization obtains super large pore polymer, then using this polymer as presoma, using dichloroethanes as solvent, post-crosslinking is carried out to it by the way that radical initiator or ferric trichloride is added, the isothermal reaction 18 hours in 85 DEG C of oil baths, it is washed, it is dry, obtain super big hole high-specific surface polymer.Preparation method of the invention is simple and reliable, and post-processing is simple, and resulting polymer had not only had super large pore structure, but also had high specific surface area, and pore diameter range is mainly distributed between 5 ~ 100 nm and 20 ~ 200 μm, and specific surface area reaches as high as 1214.19 m2/g。
Description
Technical field
The present invention relates to a kind of methods for preparing super big hole high-specific surface polymer, belong to high polymer material technology neck
Domain.
Background technique
Porous material is since the characteristic with high-specific surface area is in numerous necks such as absorption, catalysis, surface reaction, gas storages
Domain tool has been widely used.
Currently, post-crosslinking reaction is one of the main method for preparing high-specific surface polymer porous material.Post-crosslinking is anti-
It should refer to and construct new tie point in initial polymer network structure, to be generated in the skeleton structure of polymer more
Crosslink sites, and be fixed up, the chemical reaction process for keeping the polymer molecule segment mutually wound more stable.It can be divided into
Friedel-Crafts reaction post-crosslinking（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
Post-crosslinking（Urska Sevsek, Jirí Brus, Karel Jerabek, Peter Krajnc, Polymer, 2014,
55, 410-415）.Wherein, Friedel-Crafts reaction post-crosslinking is sufficiently to be swollen polymer precursor in a solvent, keeps strand abundant
Diastole occurs Friedel-Crafts reaction using original functional group under the action of catalyst, new bound site is generated on polymer backbone
Point, and this solvent swelling state of polymer is fixed up, after solvent removes, since strand is fixed without sending out
Raw retraction or collapsing phenomenon, thus the hole of structural integrity is retained, and new hole knot is generated on the basis of original copolymer
Structure obtains high-specific surface area material.CN103910823A discloses a kind of polar group modification poly- diethyl of suspended double bond post-crosslinking
First using divinylbenzene as monomer, using toluene and normal heptane as pore-foaming agent, polar monomer is added in the preparation method of alkene benzene resin,
Poly- divinylbenzene resins presoma is obtained by suspension polymerization, then using dichloroethanes as solvent, after Friedel-Crafts reaction
The method of crosslinking 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 for preparing absorption resin, with divinylbenzene and phenylmethane bismaleimide
Polymerizate is obtained using suspension polymerisation using toluene and normal heptane as pore-foaming agent for monomer, organic solvent, which is added, makes polymerizate
Swelling obtains absorption resin by the method for Friedel-Crafts reaction post-crosslinking, and obtained resin specific surface area is 710 ~ 1060 m2/g。
Radical reaction post-crosslinking is sufficiently to be swollen polymer precursor, is caused by addition initiator such as di-tert-butyl peroxide
Polymerization carries out Raolical polymerizable, new hole is generated on the basis of original pore structure, obtains the high polymerization of specific surface area
Object, resulting polymers aperture are 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 for preparing high specific surface area porous material.Itself and common solvent pore side
Method is compared, since reaction temperature is on the boiling point of solvent, and in an enclosed system, so that solvent may be at gas
State-liquid subcritical state increases the compatibility of solvent and polymer, thus available more nano-pore structures.
Xiao Fengshou et al. is prepared for porous poly- divinylbenzene material and is used for water-oil separating using the method for solvent thermal polymerization
（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, the obtained resin of above two method although specific surface area with higher, but because its pore-size distribution is to receive
Meter level range, so leading to it, when carrying out sample absorption, resistance to mass tranfer is larger, and time of equilibrium adsorption is longer, is unfavorable for it extensively
Application.
Super large pore polymer is a kind of polymer for running through pore structure with micron order, and this unique pore structure makes it
With high throughput, the characteristics 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 big partial size polymer microballoon of macropore, with methyl methacrylate
Ester etc. is monomer, and ethylene glycol dimethacrylate etc. is crosslinking agent, using the mixture of methylene chloride, toluene and chlorobenzene as pore
Agent obtains polymer microballoon by suspension polymerisation, and the aperture of thus obtained microsphere is between 150 ~ 500 nm.CN100562530C is disclosed
A kind of preparation method of super large pore polymer microsphere, with styrene etc. for monomer, divinylbenzene etc. is crosslinking agent, with cyclohexanol
Deng for pore-foaming agent, super big hole microballoon 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 usually smaller.
Summary of the invention
For above-mentioned limitation, the present invention proposes to prepare super large pore polymer by the method that cryogenic freezing polymerize first
Then presoma carries out post-crosslinking to it using the method that solvent thermal polymerization and post-crosslinking reaction combine, prepares the high ratio of 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, steps are as follows：
It first by suitable divinylbenzene and initiator, is added in solvent, mixes, after being passed through nitrogen deoxygenation, go to note
In emitter, sealing is reacted 96 hours at -18 DEG C, is taken out, is placed under room temperature environment, sufficiently washs after crystal dissolves, and is done
It is dry, obtain super large pore polymer presoma；It takes polymer precursor, initiator or catalyst, solvent to be added in reaction kettle, leads to
After entering nitrogen deoxygenation, sealing, swelling is placed in 85 DEG C of oil baths isothermal reaction 18 hours, is washed, and it is dry, obtain the high ratio of super big hole
Surface polymer；
The volume ratio of the divinylbenzene monomer and solvent is 20:80；
The mass ratio of the initiator and divinylbenzene monomer is 0.01：1；
The initiator is redox initiation system；
The solvent is dimethyl sulfoxide, and crystal is pore-foaming agent；
Initiator is benzoyl peroxide when the described post-crosslinking, and catalyst is anhydrous ferric trichloride；
Solvent is dichloroethanes when the described post-crosslinking.
Preferred according to the present invention, the monomer is divinylbenzene 80.
Preferred according to the present invention, the reaction kettle is polytetrafluoroethyllining lining.
Preferred according to the present invention, the post-crosslinking mode is Friedel-Crafts reaction post-crosslinking.
Freezing polymerization reaction temperature of the present invention is lower than the fusing point of dimethyl sulfoxide, and reaction temperature is higher than when post-crosslinking
The boiling point of dichloroethanes.
Polymer produced by the present invention had not only had super large pore structure, but also had high specific surface area, and 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。
Most preferred according to the present invention, a kind of super big hole high-specific surface area congeals the preparation method of glue, and steps are as follows：
4.0 ml divinylbenzene monomers are dissolved in 16 ml dimethyl sulfoxides, and 36.8 mg benzoyl peroxides, 19 μ l are added
N,N-Dimethylaniline mixes, and logical 5 min of nitrogen removes oxygen and room temperature is placed in, to two after reacting 96 hours at -18 DEG C
Methyl sulfoxide crystal melts, and sufficiently washs, dry, obtains super large pore polymer presoma；Take 20 ml dichloroethanes and 40 mg
Anhydrous FeCl3In reaction kettle, 100 mg polymer precursors are added in ultrasonic disperse, are passed through 10 min of nitrogen, remove oxygen
Afterwards, it seals, is swollen 1 hour, is subsequently placed in 85 DEG C of oil baths and reacts 18 hours, sufficiently washed after cooling, it is dry, obtain super large
Hole high-specific surface polymer.Resulting polymers specific surface area is up to 1214.19 m2/g。
It the advantages of polymerization of present invention combination cryogenic freezing and post-crosslinking reaction, is obtained first by the method that cryogenic freezing polymerize
To the polymer precursor with super large pore structure, the specific surface area of polymer is then improved by post-crosslinking reaction, and will
Post-crosslinking reaction is placed in a solvent hot system and carries out, and is promoted the progress of post-crosslinking reaction by means of solvent thermal reaction.
The present invention uses the pore of solvent crystal, and preparation method is simple and reliable, and post-processing is simple, and resulting polymer both had
Super large pore structure, and there is high specific surface area, 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。
Detailed description of the invention
Attached drawing is the infrared spectrum of polymer before and after post-crosslinking：Precursor is polybenzazole precursor prepared by embodiment 1
Body；Friedel-Crafts reaction is Friedel-Crafts reaction post-crosslinking polymer prepared by embodiment 2；Radical
Initiated reaction is radical reaction post-crosslinking polymer prepared by embodiment 3.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further described.Divinylbenzene monomer used in embodiment is
Divinylbenzene 80（Trade name indicates that the content of divinylbenzene is 80%, vinyl ethylbenzene 20%）, Aladdin reagent（China）It is limited
Products.
Embodiment 1
4.0 ml divinylbenzene monomers are dissolved in 16 ml dimethyl sulfoxides, and 36.8 mg benzoyl peroxides, 19 μ l are added
N,N-Dimethylaniline mixes, and logical 5 min of nitrogen removes oxygen and room temperature is placed in, to two after reacting 96 hours at -18 DEG C
Methyl sulfoxide crystal melts, and is sufficiently washed, then removing methanol is washed with deionized with methanol, is put into 50 DEG C of baking ovens and is dried to
Constant weight obtains super large pore polymer.Obtained polymer specific surface area is 140.35 m2/g。
Embodiment 2
Take 20 ml dichloroethanes and the anhydrous FeCl of 40 mg3In reaction kettle, 100 mg embodiments 1 are added in ultrasonic disperse
Middle resulting polymers presoma is passed through 10 min of nitrogen, and after removing oxygen, sealing is swollen 1 hour, is subsequently placed in 85 DEG C of oil baths
Middle reaction 18 hours, is sufficiently washed after cooling with methanol, with the salt acid elution of 0.1 mol/L, is impregnated, then rushed with deionized water
It washes, is put into 50 DEG C of baking ovens and dries to constant weight, obtain super big hole high-specific surface polymer.Resulting polymers specific surface area is
1214.19 m2/g。
Embodiment 3
It takes 20 ml dichloroethanes and 10 mg benzoyl peroxides in reaction kettle, dissolves, be added in 100 mg embodiments 1
Resulting polymers presoma is passed through 10 min of nitrogen, and after removing oxygen, sealing is swollen 1 hour, is subsequently placed in 85 DEG C of oil baths
Reaction 18 hours is sufficiently washed with methanol after cooling, then is washed with deionized, and is put into 50 DEG C of baking ovens and is dried to constant weight, obtains
Super big hole high-specific surface polymer.Resulting polymers specific surface area is 84.77 m2/g。
Claims (6)
1. a kind of preparation method of super big hole high-specific surface polymer, which is characterized in that polymerize first by cryogenic freezing
Method prepares super large pore polymer presoma, after then being carried out using the method that solvent thermal polymerization and post-crosslinking reaction combine to it
Crosslinking, is prepared super big hole high-specific surface polymer, specific step is as follows：
It is added to suitable divinylbenzene and initiator in solvent, mixes, after being passed through nitrogen deoxygenation, go in syringe, it is close
Envelope, reacts 96 hours at -18 DEG C, takes out, is placed under room temperature environment, sufficiently washs after crystal thawing, dry, obtains super large
Pore polymer presoma；Polymer precursor, catalyst, solvent is taken to be added in reaction kettle, after being passed through nitrogen deoxygenation, sealing,
Swelling, is placed in 85 DEG C of oil baths isothermal reaction 18 hours, washs, dry, obtains super big hole high-specific surface polymer；
The solvent is dimethyl sulfoxide, and crystal is pore-foaming agent；
The catalyst is anhydrous ferric trichloride；
The solvent being added when post-crosslinking is dichloroethanes.
2. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that the divinylbenzene with it is molten
The volume ratio of agent is 20:80.
3. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that the initiator and two
The mass ratio of Ethenylbenzene is 0.01:1.
4. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that the initiator is oxygen
Change reduction initiating system.
5. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that the reaction kettle is poly-
Tetrafluoroethene liner.
6. the preparation method of super large pore polymer material as described in claim 1, which is characterized in that steps are as follows：
4.0mL divinylbenzene monomer is dissolved in 16mL dimethyl sulfoxide, and 36.8mg benzoyl peroxide, 19 μ L N, N- bis- are added
Methylaniline mixes, and logical nitrogen 5min removes oxygen and room temperature is placed in, to dimethyl sulfoxide after reacting 96 hours at -18 DEG C
Crystal melts, and sufficiently washs, dry, obtains super large pore polymer presoma；Take 20mL dichloroethanes and the anhydrous FeCl of 40mg3In
In reaction kettle, 100mg polymer precursor is added in ultrasonic disperse, is passed through nitrogen 10min, and after removing oxygen, sealing is swollen 1h,
It is subsequently placed in 85 DEG C of oil baths and reacts 18 hours, sufficiently washed after cooling, it is dry, obtain super big hole high-specific surface polymer.
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| CN107602744B (en) * | 2017-03-08 | 2019-09-27 | 济南大学 | A kind of superhigh cross-linking microporous polymer and preparation method thereof |
| 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 |
| CN109517211B (en) * | 2018-09-28 | 2021-10-15 | 浙江工业大学 | Amino porous polymer and preparation method and application thereof |
| CN109400780B (en) * | 2018-11-02 | 2021-04-16 | 湖南大学 | Method for free radical polymerization of electron-deficient olefin |
| CN112063405B (en) * | 2020-09-14 | 2022-04-01 | 浙江大学台州研究院 | Pyrolysis-based waste tire treatment method |
| 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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| CN103910823A (en) * | 2014-03-21 | 2014-07-09 | 中南大学 | Preparation method and application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin |
| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
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| CN1903890A (en) * | 2005-07-27 | 2007-01-31 | 中国科学院过程工程研究所 | Preparation method of super large pore polymer microsphere and its product |
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| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
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