CN106317742B - A kind of function nano network structure polymer material and the preparation method and application thereof - Google Patents
A kind of function nano network structure polymer material and the preparation method and application thereof Download PDFInfo
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- CN106317742B CN106317742B CN201610629519.5A CN201610629519A CN106317742B CN 106317742 B CN106317742 B CN 106317742B CN 201610629519 A CN201610629519 A CN 201610629519A CN 106317742 B CN106317742 B CN 106317742B
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- 239000002861 polymer material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004793 Polystyrene Substances 0.000 claims abstract description 66
- 229920002223 polystyrene Polymers 0.000 claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 108
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000012046 mixed solvent Substances 0.000 claims description 46
- 238000010992 reflux Methods 0.000 claims description 37
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 12
- 239000002077 nanosphere Substances 0.000 abstract description 8
- 238000013517 stratification Methods 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 229920001400 block copolymer Polymers 0.000 description 34
- 230000006837 decompression Effects 0.000 description 32
- 238000003756 stirring Methods 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 17
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 17
- 238000003760 magnetic stirring Methods 0.000 description 16
- 239000003643 water by type Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical group CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
The present invention provides a kind of function nano network structure polymer materials and the preparation method and application thereof.Wherein, the function nano network structure polymer material be the copolymer containing polystyrene block existing for crosslinking agent under the conditions of primary reconstruction be made.The function nano network structure polymer material is the tridimensional network being made of the spherical network element of nanometer, the specific surface area of the porous skeleton structure of pore passage structure, stabilization with stratification, the core-shell nanospheres network element accurately customized and customized function lining block, the function nano network structure polymer material is 180 660m2/ g, micropore specific area are 5 140m2Typical micropore mesoporous macropore stratification pore size distribution$ is presented in/g；It prepares in organic steam adsorbing domain and as presoma in novel nano network structure polymer material there is extensive potential application.
Description
Technical field
The present invention relates to field of nanometer material technology more particularly to a kind of function nano network structure polymer material and its preparations
Method and application.
Background technology
Specific surface area polymer is a kind of with unique, the three-dimensional stratification nanometer network pore passage structure being connected
Porous polymer material.There is Specific surface area polymer stratification, porous, each level nano pore mutually to cooperate with
Advantage, absorption with detach, be catalyzed, the fields such as biomedicine are with potential application advantage.
The critical issue that design prepares Specific surface area polymer material is constructing for network element, at present
The Specific surface area polymer with accurate customized network unit prepared is required to cumbersome network element presoma and prepares
Process, also, the porous polymer prepared at present by self-assembly method lacks stable porous skeleton structure mostly, and this is also influenced
Poromeric stratification and structural rigidity.Therefore, prepare have stablize porous skeleton structure, can accurate customized network list
The Specific surface area polymer of member is still a prodigious challenge.
Invention content
The purpose of the present invention is overcoming shortcoming in the prior art, a kind of function nano network structure polymerization is provided
Object material and the preparation method and application thereof, the Specific surface area Polymer preparation technology is simple, and with the micro- of stabilization
Hole on framework structure.
To achieve the above object, the application provides the following technical solutions：
In a first aspect, the present invention provides a kind of function nano network structure polymer material, the function nano network
Architectural polymeric materials be the copolymer containing polystyrene block existing for crosslinking agent under the conditions of primary reconstruction be made.
Preferably, the function nano network structure polymer material is the three dimensional network being made of the spherical network element of nanometer
The grain size of shape structure, the spherical network element of nanometer is 10-30nm (further preferably 22.9-28.7nm), the nanometer
Spherical network element is nucleocapsid.
Further preferably, the spherical network element of the nanometer is nucleocapsid, and shell thickness is 5-9nm (further
Preferably 5.8-8.4nm).
Preferably, micropore-mesoporous-macropore stratification pore structure is presented in the function nano network structure polymer material
Distribution, specific surface area 180-660m2/ g (further preferably 188-656m2/ g), micropore specific area is 5-140m2/ g (into
One step is preferably 6-132m2/ g), Kong Rongwei 0.1-1.3cm3/ g (further preferably 0.41-1.27cm3/g)。
Preferably, the copolymer containing polystyrene block includes polyethylene oxide-b- polystyrene (PEO-b-
PS), polymethyl methacrylate-b- polystyrene (PMMA-b-PS) and the polystyrene-b- polyacrylic acid tert-butyl esters (PS-b-
One or more of PtBA).
Preferably, the crosslinking agent includes but not limited to carbon tetrachloride (CCl4), one in dimethoxymethane (FDA)
Kind is several.
Preferably, the ratio of the volume of the quality and crosslinking agent of the copolymer containing polystyrene block is 0.005-
0.2:1(g/ml)。
It is further preferred that the crosslinking agent is carbon tetrachloride (CCl4), then the copolymer containing polystyrene block
Quality and the carbon tetrachloride (CCl4) volume ratio be 0.005-0.02:1(g/ml).
It is further preferred that the crosslinking agent is dimethoxymethane (FDA), then the copolymerization containing polystyrene block
The ratio of the quality of object and the volume of the dimethoxymethane (FDA) is 0.1-0.2:1 (g/ml) (still more preferably for
0.15:1(g/ml))。
Second aspect, the present invention provides a kind of preparation methods of function nano network structure polymer material, including with
Lower step：
(1) copolymer containing polystyrene block is mixed to get the copolymerization containing polystyrene block with solvent, crosslinking agent
Object solution；
(2) after mixing the copolymer solution containing polystyrene block obtained in step (1) with catalyst, in 45-75
It is stirred at reflux 1-24h at DEG C, adds acetone/hydrochloric acid/water mixed solvent and terminates reaction, after filtration, washing and drying, obtain
Function nano network structure polymer material.
It is understood that the present invention to described in step (1) by containing polystyrene block copolymer and solvent, hand over
The step of connection agent mixing, is not particularly limited, and may be used well known to those skilled in the art for that will contain polystyrene block
The method that is mixed with solvent, crosslinking agent of copolymer.
Preferably, the step of copolymer containing polystyrene block being mixed with solvent, crosslinking agent in step (1), specifically
Including：Solvent, crosslinking agent are added in the copolymer containing polystyrene block, stirring to the copolymerization containing polystyrene block
Object is completely dissolved, and obtains the copolymer solution containing polystyrene block.
Preferably, the copolymer containing polystyrene block described in step (1) includes but not limited to polyethylene oxide-b-
Polystyrene (PEO-b-PS), polymethyl methacrylate-b- polystyrene (PMMA-b-PS) and polystyrene-b- polypropylene
One or more of tert-butyl acrylate (PS-b-PtBA).
Preferably, the ratio of the volume of the quality and crosslinking agent of the copolymer containing polystyrene block is 0.005-
0.2:1(g/ml)。
Preferably, the solvent described in step (1) include but not limited to carbon tetrachloride, one kind in 1,2- dichloroethanes or
It is several.
Preferably, the crosslinking agent described in step (1) includes but not limited in carbon tetrachloride, dimethoxymethane (FDA)
One or more.
Preferably, the solvent described in step (1) and the crosslinking agent are carbon tetrachloride (CCl4), then it is described containing poly-
The quality of the copolymer of styrene block and the carbon tetrachloride (CCl4) volume ratio be 0.005-0.02:1(g/ml).
Preferably, solvent is 1,2- dichloroethanes in step (1), and crosslinking agent is dimethoxymethane, then described to contain polyphenyl
The ratio of the quality of the copolymer of ethylene block and the volume of the dimethoxymethane (FDA) is 0.1-0.2:1 (g/ml) (more into
One step is preferably 0.15:1(g/ml))；The volume ratio of the 1,2- dichloroethanes and dimethoxymethane is 10-20:1(ml/
Ml (it is still more preferably) 15:1(ml/ml)).
Preferably, the catalyst described in step (2) includes but not limited to aluminum trichloride (anhydrous) (AlCl3), anhydrous trichlorine
Change iron (FeCl3One or more of).
Preferably, the catalyst described in step (2) and the copolymer containing polystyrene block described in step (1)
Mass ratio is 0.6-4:1(g/g).
It is further preferred that the catalyst described in step (2) is copolymerized with described in step (1) containing polystyrene block
The mass ratio of object is 2.4：1(g/g).
Preferably, reflux temperature described in step (2) is 60-75 DEG C (further preferably 75 DEG C).
Preferably, return time described in step (2) is 10-24h (further preferably for 24 hours).
Preferably, the reflux that being stirred at reflux described in step (2) uses in step includes carrying anhydrous calcium chloride
Drying tube.
Preferably, contain polystyrene block described in acetone/hydrochloric acid/water mixed solvent described in step (2) and step (1)
The volume ratio of copolymer solution is 1-3:1(ml/ml).
Preferably, contain polystyrene block described in acetone/hydrochloric acid/water mixed solvent described in step (2) and step (1)
The volume ratio of copolymer solution is 1:1(ml/ml).
Preferably, the mass ratio of hydrochloric acid and water is 3-4 in acetone/hydrochloric acid/water mixed solvent described in step (2):100
(mg/mg), the ratio of the volume of the total volume and acetone of hydrochloric acid and water is 1：2-4(ml/ml).
It is further preferred that the mass ratio of hydrochloric acid and water is in acetone/hydrochloric acid/water mixed solvent described in step (2)
3.7:100 (mg/mg), acetone are 3 with the volume ratio of hydrochloric acid and water summation:1(ml/ml).
It is understood that in the step (2), do not have to the preparation method of the acetone/hydrochloric acid/water mixed solvent
The preparation method well known to those skilled in the art for acetone/hydrochloric acid/water mixed solvent may be used i.e. in special limitation
It can.Optionally, the preparation method of the acetone/hydrochloric acid/water mixed solvent, includes the following steps：Hydrochloric acid and water are first pressed into quality
Compare 3-4：100 are configured to aqueous hydrochloric acid solution, then it is 2-4 to press acetone with aqueous hydrochloric acid solution volume ratio:1 prepare obtain acetone/hydrochloric acid/
Water mixed solvent.
It is understood that in the step (2), the method for the washing is not particularly limited, ability may be used
The method washed known to field technique personnel.Optionally, the method for the washing described in step (2), includes the following steps：
It is washed 1-5 times (preferably 3 times) using acetone/hydrochloric acid/water mixed solvent, each 3-7h (preferably 6h), then is washed with ethyl alcohol
1-3 times (preferably 1 time).
It is understood that in the step (2), the method for the drying is not particularly limited, ability may be used
Dry method known to field technique personnel.Optionally, the method for the drying described in step (2), includes the following steps：
The dry 10-14h (preferably 12h) under 60-100 DEG C (preferably 80 DEG C).
Preferably, function nano network structure polymer material described in step (2) is by the spherical network element structure of nanometer
At tridimensional network, the grain size of the spherical network element of nanometer is 10-30nm (further preferably 22.9-
28.7nm), the spherical network element of the nanometer is nucleocapsid.
It is further preferred that the spherical network element of nanometer is nucleocapsid, shell thickness is 5-9nm (further
Preferably 5.8-8.4nm).
Preferably, typical micropore-mesoporous-is presented in the function nano network structure polymer material described in step (2)
Macropore stratification pore size distribution$, specific surface area 180-660m2/ g (further preferably 188-656m2/ g), micropore specific surface
Product is 5-140m2/ g (further preferably 6-132m2/ g), Kong Rongwei 0.1-1.3cm3/ g (further preferably 0.41-
1.27cm3/g)。
Preferably, function nano network structure polymer material as described in relation to the first aspect is using as described in second aspect
Function nano network structure polymer material preparation method be made.
The principle of the present invention：Self-assembly method is induced to prepare function nano network structure polymer material using super crosslinking.
First, the di-block copolymer containing polystyrene block is dissolved completely in solvent and crosslinking agent that form uniform macromolecule molten
Liquid.It is adjacent due to the crosslinked action between polystyrene block after Fu Ke (Friedel-Crafts) super cross-linking reaction starts
Linear polymeric linked together clustering by covalent bond, but the effect that is separated makes the crosslinking polyphenyl inside these clusters again
Ethylene and another block component are phase separations；With continuing for cross-linking reaction, the Brownian movement collision of high score submanifold and
The super cross-linking reaction of polystyrene promotes further to connect the cluster for becoming bigger between cluster and cluster, and final connection forms spherical knot
Structure.Since crosslinked polystyrene and another block component are phase separation always, and crosslinked polystyrene and solvent compatibility are more
It is good, therefore crosslinked polystyrene is in the outer layer of super crosslinking induction self assembly aggregation, another block is in inside, forms nucleocapsid
Nanospheres.Super cross-linking reaction between core-shell nanospheres shell is again so that they, which are further connected, forms three dimensional network
Network.The linear kernel component of network element serves as functional lining block, thus reaction ultimately forms function nano network structure and gathers
Close object material.
The third aspect, the present invention provides a kind of function nano network structure polymer material answering in gas absorption
With.
Fourth aspect, the present invention provides a kind of function nano network structure polymer materials to prepare nanometer polymer material
Application in terms of material.
Preferably, the nanometer polymer material is Specific surface area polymer material.
Beneficial effects of the present invention are as follows：
(1) preparation process of function nano network structure polymer material provided by the invention is simple, does not need cumbersome net
Network unit forerunner production procedure can directly prepare the Specific surface area with accurate core-shell nanospheres network element
Polymer material；
(2) function nano network structure polymer material provided by the invention has the pore passage structure of stratification, stabilization
The advantages that porous skeleton structure, the network element accurately customized and customized function lining block.
Description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of application for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the stereoscan photograph of function nano network structure polymer material provided in an embodiment of the present invention, wherein
Scheme (A), the stereoscan photograph that (B) is function nano network structure polymer material under different amplification；
Fig. 2 is the transmission electron microscope photo of function nano network structure polymer material provided in an embodiment of the present invention, wherein
Scheme (A), the transmission electron microscope photo that (B) is function nano network structure polymer material under different amplification；
Fig. 3 is handled for function nano network structure polymer material provided in an embodiment of the present invention progress embedded section and is used in combination
The transmission electron microscope photo of sample after ruthenium tetroxide steam-colour；
Fig. 4 is nitrogen adsorption-desorption isothermal of function nano network structure polymer material provided in an embodiment of the present invention
Line chart (A) and graph of pore diameter distribution (B).
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
It is understood that in embodiment provided by the invention, Am-b-Bn indicates that the molecular weight of A blocks is m, B block
Molecular weight is n.By taking embodiment 1 as an example, PEO116-b-PS362Indicate that the molecular weight of PEO blocks is that the molecular weight of 116, PS blocks is
362。
It should be understood that in embodiment provided by the invention, the preparation method that acetone/hydrochloric acid/water mixed solvent is, including
Following steps：The mass ratio for first pressing hydrochloric acid and water is 3.7:100 ratio is configured to aqueous hydrochloric acid solution, then by acetone and the salt
The volume ratio of aqueous acid is 3:1 ratio is prepared to obtain acetone/hydrochloric acid/water mixed solvent.
Embodiment 1
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS362It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material one.
Electronic Speculum characterization is scanned to function nano network structure polymer material one, as shown in Figure 1, the results showed that function
Specific surface area polymer material one is formed by a large amount of uniform spherical network element stacks.
Transmission electron microscope characterization further is carried out to it, as shown in Figure 2, the results showed that function nano network structure polymeric material
The network element of material one is uniform core-shell nanospheres；Mean outside diameter, internal diameter, the shell thickness point of core-shell nanospheres
It Wei not 22.9,11.3 and 5.8nm.
Fig. 3 is to carry out embedded section processing to function nano network structure polymer material one and contaminated with ruthenium tetroxide steam
The transmission electron microscope photo of sample after color.By Fig. 3 it can be seen that the solid stain that a large amount of average grain diameters are 11.7nm, corresponds to quilt
The PEO components of dyeing.Thus prove that the shell of the network element of function nano network structure polymer material one is crosslinking polyphenyl
Ethylene, core are polyethylene oxide lining block.
Fig. 4 is nitrogen adsorption-desorption isothermal curve figure (A) and the holes DFT of function nano network structure polymer material one
Diameter scatter chart (B), the results showed that：BET surface area is 502m2/ g, wherein micropore specific area and external pore specific surface area
Respectively 50 and 452m2/ g, Kong Rongwei 1.27cm3/g.The most probable size of micropore is it can be seen from DFT pore size distribution curves
1.5nm；Middle macropore is distributed in the size range of 2.3-137nm.
Embodiment 2
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PMMA are weighed136-b-PS666It is added in 100ml three-neck flasks, adds 30mlCCl4, in room temperature
Lower stirring and dissolving, forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material two.
The shell of the network element for the function nano network configuration polymer material two being prepared is crosslinked polystyrene,
Core is polymethyl methacrylate lining block.
Embodiment 3
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PS are weighed397-b-PtBA69It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material three.
Polyacrylic acid tert-butyl ester group in the function nano network structure polymer material three that IR Characterization result is shown
Divide and be hydrolyzed to polyacrylic acid, therefore the shell of its network element is crosslinked polystyrene, core is polyacrylic acid lining block.
Effect example 1
Advantageous effect in order to further illustrate the present invention, the function nano network structure that embodiment 1-3 is prepared
Polymer has carried out nitrogen adsorption-desorption isotherm test, and the results are shown in Table 1.
The specific surface area and Kong Rong of 1 different function Specific surface area polymer of table
The result shows that：The function nano network structure polymer that embodiment 1-3 is prepared has higher specific surface area,
And the porous skeleton structure stablized, and function lining block is customizable.
Embodiment 4
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material four.
Embodiment 5
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS718It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material five.
Effect example 2
Advantageous effect in order to further illustrate the present invention, the function nano network knot that embodiment 1,4 and 5 is prepared
Structure polymer has carried out nitrogen adsorption-desorption isotherm test, and outer diameter, the internal diameter of network element are characterized by transmission electron microscope
And shell thickness, as a result as shown in table 2 and table 3.
The specific surface area and Kong Rong of 2 different function Specific surface area polymer of table
The size of 3 different function Specific surface area polymer network unit of table
| Outer diameter (nm) | Internal diameter (nm) | Shell thickness (nm) | |
| Embodiment 1 | 22.9 | 11.3 | 5.8 |
| Embodiment 4 | 27.3 | 12.1 | 7.6 |
| Embodiment 5 | 28.7 | 11.9 | 8.4 |
The result shows that：The molecular weight of polystyrene block is bigger, and the shell of network element is thicker, can be by adjusting polyphenyl second
The molecular size range of alkene block, the size of accurate customized network unit.
Embodiment 6
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS362It is added in 100ml three-neck flasks, adds 60mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 60ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material six.
Embodiment 7
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS362It is added in 100ml three-neck flasks, adds 15mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 15ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material seven.
Effect example 3
Advantageous effect in order to further illustrate the present invention, the function nano network knot that embodiment 1,6 and 7 is prepared
Structure polymer has carried out nitrogen adsorption-desorption isotherm test, and the results are shown in Table 4.
The specific surface area and Kong Rong of 4 different function Specific surface area polymer of table
Embodiment 8
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.18g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material eight.
Embodiment 9
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.42g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material nine.
Embodiment 10
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 1.2g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material ten.
Effect example 4
Advantageous effect in order to further illustrate the present invention, the function nano net that embodiment 4,8,9 and 10 is prepared
Network structural polymer has carried out nitrogen adsorption-desorption isotherm test, and the results are shown in Table 5.
The specific surface area and Kong Rong of 5 different function Specific surface area polymer of table
Embodiment 11
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 45 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material 11.
Embodiment 12
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 60 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction for 24 hours；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material 12.
Effect example 5
Advantageous effect in order to further illustrate the present invention, the function nano network that embodiment 4,11 and 12 is prepared
Structural polymer has carried out nitrogen adsorption-desorption isotherm test, and the results are shown in Table 6.
The specific surface area and Kong Rong of 6 different function Specific surface area polymer of table
Embodiment 13
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction 1h；30ml acetone/hydrochloric acid/water mixed solvent is added to terminate
Reaction, decompression filters at room temperature, then is washed 3 times, each 6h with acetone/hydrochloric acid/water mixed solvent, is then washed 1 time with ethyl alcohol,
It is all filtered each time after washing with decompression and obtains sample, obtained sample constant pressure and dry 12h at 80 DEG C will be filtered for the last time, obtained
To function nano network configuration polymer material 13.
Embodiment 14
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction 3h；30ml acetone/hydrochloric acid/water mixed solvent is added to terminate
Reaction, decompression filters at room temperature, then is washed 3 times, each 6h with acetone/hydrochloric acid/water mixed solvent, is then washed 1 time with ethyl alcohol,
It is all filtered each time after washing with decompression and obtains sample, obtained sample constant pressure and dry 12h at 80 DEG C will be filtered for the last time, obtained
To function nano network configuration polymer material 14.
Embodiment 15
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS635It is added in 100ml three-neck flasks, adds 30mlCCl4, at room temperature
Stirring and dissolving forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous AlCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction 10h；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material 15.
Effect example 6
Advantageous effect in order to further illustrate the present invention, the function nano that embodiment 4,13,14 and 15 is prepared
Network structure polymer has carried out nitrogen adsorption-desorption isotherm test, and the results are shown in Table 7.
The specific surface area and Kong Rong of 7 different function Specific surface area polymer of table
Embodiment 16
The present invention provides a kind of preparation methods of function nano network structure polymer material, include the following steps：
(1) 0.3g PEO are weighed116-b-PS362It is added in 100ml three-neck flasks, adds 30mL 1,2- dichloroethanes
With the mixed solvent of 2mL FDA, dissolving is stirred at room temperature, forms uniform block copolymer solution；
(2) block copolymer solution obtained by step (1) is placed in 75 DEG C of waters bath with thermostatic control, starts to stir after being passed through condensed water
Load onto the drying tube for being loaded with anhydrous calcium chloride simultaneously；The anhydrous FeCl of 0.72g are added after reflux 30min3, continue under magnetic stirring
It is heated to reflux and carries out Fu Ke (Friedel-Crafts) super cross-linking reaction 10h；It is whole that 30ml acetone/hydrochloric acid/water mixed solvent is added
It only reacts, decompression filters at room temperature, then is washed 3 times with acetone/hydrochloric acid/water mixed solvent, and each 6h then washs 1 with ethyl alcohol
It is secondary, it is all filtered with decompression obtain sample each time after washing, obtained sample constant pressure and dry at 80 DEG C will be filtered for the last time
12h obtains function nano network configuration polymer material 15.
The BET surface area of prepared function nano network structure polymer material 15 is 656m2/g, wherein micropore ratio
Surface area and external pore specific surface area are respectively 68m2/ g and 588m2/ g, Kong Rongwei 0.61cm3/g。
Application Example 1
Advantageous effect in order to further illustrate the present invention, the function nano network structure that will be prepared in embodiment 1
Polymer material one is used as organic steam sorbing material.It is 298K in temperature, when vapour pressure P/P0=0.9, the function nano
Network structure polymer material a pair of methanol, propyl alcohol, hexamethylene and toluene organic steam adsorbance be respectively 12.6,24.9,
5.2 and 3.6mmol/g.The result shows that function nano network structure polymer material a pair of polarity organic steam is shown
Good absorption property.
Application Example 2
Advantageous effect in order to further illustrate the present invention, the function nano network structure that will be prepared in embodiment 2
Polymer material two is used as presoma, under the nitrogen atmosphere of 400mL/min flow velocitys, with the heating rate of 5 DEG C/min, through 1000
DEG C charing 3h, obtain the Specific surface area Carbon Materials with hollow carbon nanospheres network element.
The BET surface area of the prepared Specific surface area Carbon Materials with hollow carbon nanospheres network element is
1304m2/ g, wherein micropore specific area and external pore specific surface area are respectively 598m2/ g and 706m2/ g, Kong Rongwei 1.70cm3/
g。
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate the application example, and simultaneously
The non-restriction to embodiment.For those of ordinary skill in the art, it can also do on the basis of the above description
Go out other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.And thus drawn
Among the obvious changes or variations that Shen goes out are still in the protection domain of the application.
Claims (8)
1. a kind of function nano network structure polymer material, which is characterized in that the function nano network structure polymeric material
Material be the copolymer containing polystyrene block existing for crosslinking agent, solvent under the conditions of primary reconstruction and cross-linking reaction system occurs
；
The copolymer containing polystyrene block includes polyethylene oxide-b- polystyrene, polymethyl methacrylate-b-
One or more of polystyrene and the polystyrene-b- polyacrylic acid tert-butyl esters；The crosslinking agent includes carbon tetrachloride, two
One or more of methoxyl group methane；The solvent includes one or more of carbon tetrachloride, 1,2- dichloroethanes.
2. function nano network structure polymer material as described in claim 1, which is characterized in that the function nano network
Architectural polymeric materials are the tridimensional network being made of the spherical network element of nanometer, the grain of the spherical network element of nanometer
Diameter is 10-30nm, and the spherical network element of nanometer is nucleocapsid.
3. function nano network structure polymer material as described in claim 1, which is characterized in that described embedding containing polystyrene
The copolymer of section is 0.005-0.2 with the mass volume ratio of the crosslinking agent:1(g/ml).
4. a kind of preparation method of function nano network structure polymer material, which is characterized in that include the following steps：
(1) that the copolymer containing polystyrene block is mixed to get the copolymer containing polystyrene block with solvent, crosslinking agent is molten
Liquid；
(2) after mixing the copolymer solution containing polystyrene block obtained in step (1) with catalyst, at 45-75 DEG C
It is stirred at reflux 1-24h, acetone/hydrochloric acid/water mixed solvent is added and terminates reaction, after filtration, washing and drying, obtain function
Specific surface area polymer material；
The copolymer containing polystyrene block described in step (1) includes polyethylene oxide-b- polystyrene, polymethyl
One or more of sour methyl esters-b- polystyrene and the polystyrene-b- polyacrylic acid tert-butyl esters；Friendship described in step (1)
It includes one or more of carbon tetrachloride, dimethoxymethane to join agent；Solvent described in step (1) includes carbon tetrachloride, 1,
One or more of 2- dichloroethanes；Catalyst described in step (2) includes in aluminum trichloride (anhydrous), anhydrous ferric trichloride
One or more.
5. the preparation method of function nano network structure polymer material as claimed in claim 4, which is characterized in that step
(1) mass volume ratio of copolymer and the crosslinking agent described in containing polystyrene block is 0.005-0.2:1(g/ml)；Step
Suddenly the mass ratio of the catalyst described in (2) and the copolymer containing polystyrene block described in step (1) is 0.6-4:1
(g/g)。
6. function nano made from a kind of preparation method of function nano network structure polymer material as claimed in claim 4
Network structure polymer material.
7. a kind of application of function nano network structure polymer material as described in claim 1 in gas absorption.
8. a kind of function nano network structure polymer material as described in claim 1 or function as claimed in claim 4
Application of the preparation method of Specific surface area polymer material in preparing nanometer polymer material.
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| CN101698477A (en) * | 2009-11-10 | 2010-04-28 | 中山大学 | Polystyrene group hierarchical mesoporous carbon material, preparation method and application thereof |
| CN103450582A (en) * | 2013-08-30 | 2013-12-18 | 中山大学 | Powdery polystyrene aerogel, as well as preparation method and application thereof |
| CN103980594A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Ultra violet radiation cross-linking polymeric material for 3D printing and preparation method and product thereof |
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| JPS57111333A (en) * | 1980-12-29 | 1982-07-10 | Dainippon Printing Co Ltd | Porous material and preparation of same |
| CN101698477A (en) * | 2009-11-10 | 2010-04-28 | 中山大学 | Polystyrene group hierarchical mesoporous carbon material, preparation method and application thereof |
| CN103450582A (en) * | 2013-08-30 | 2013-12-18 | 中山大学 | Powdery polystyrene aerogel, as well as preparation method and application thereof |
| CN103980594A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Ultra violet radiation cross-linking polymeric material for 3D printing and preparation method and product thereof |
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