CN109021185A - The synthetic method of pH stimuli responsive type star graphene dispersion agent - Google Patents
The synthetic method of pH stimuli responsive type star graphene dispersion agent Download PDFInfo
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- CN109021185A CN109021185A CN201810301637.2A CN201810301637A CN109021185A CN 109021185 A CN109021185 A CN 109021185A CN 201810301637 A CN201810301637 A CN 201810301637A CN 109021185 A CN109021185 A CN 109021185A
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- agent
- macromole evocating
- catalyst
- graphene dispersion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 239000006185 dispersion Substances 0.000 title claims abstract description 53
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 116
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical class CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 8
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 38
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- 239000003446 ligand Substances 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 20
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 12
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
- -1 N, N- dimethyl aminoethyl Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic methods of pH stimuli responsive type star graphene dispersion agent, the following steps are included: a, use ARGET-ATRP method using alpha-brominated ethyl isobutyrate as initiator cause styrene polymerization obtain the first macromole evocating agent, be labeled as PS-Br；B, it uses alpha-brominated ethyl isobutyrate to cause dimethylaminoethyl methacrylate for initiator to polymerize to obtain the second macromole evocating agent, is labeled as PDMAEMA-Br；C, it is synthesized using core, ARGET-ATRP method after first arm, using macromole evocating agent PS-Br and PDMAEMA-Br in step a and step b as arm, with divinylbenzene (DVB) for core, synthesizes star polymer, as graphene dispersion agent.Synthetic method through the invention can obtain that a kind of dispersion performance is good, graphene dispersion agent of stable storage.
Description
Technical field
The present invention relates to a kind of synthetic methods of graphene dispersion agent, more particularly to a kind of pH stimuli responsive type star stone
The synthetic method of black alkene dispersing agent.
Background technique
Graphene is a kind of two dimensional crystal material being made of sp2 hydbridized carbon atoms, it is considered to be most thin material in the world
Material.Due to tensile strength high, outstanding with specific surface area, thermally conductive, electric conductivity, caused widely in many sciemtifec and technical spheres
Concern, but these applications greatly receive its deliquescent limitation.In order to solve this problem, soluble dispersing agent
It is gradually developed and comes modified graphene surface, so that the dissolubility of graphene improves.Currently, it is logical for mainly improving graphene surface
The method for crossing covalent bond and non-covalent bond, the method for non-covalent bond are preferentially selected, because it avoids damage to the peculiar of graphene
Performance.In addition, there is also some potential applications, sensor, drug conveying etc. for graphene.Therefore, different types of response
Property dispersing agent be developed, including pH, temperature, light, redox response dispersing agent.Once the surface of graphene is divided
Powder is modified, these responses just can control the reunion and dispersion of graphene.But these dispersing agents or because self performance or because preparation
It is difficult to control or because the factors such as at high cost still have some deficits, needing those skilled in the art to develop, a kind of dispersion performance is good, stores
Stable graphene dispersion agent.
Summary of the invention
Of the existing technology in order to solve the problems, such as, the present invention provides a kind of pH stimuli responsive type star graphene dispersions
The synthetic method of agent, to improve the dissolubility of graphene in water.
To achieve the above object, the technical solution adopted by the present invention is that a kind of pH stimuli responsive type star graphene dispersion agent
Synthetic method, comprising the following steps:
A, using electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP) method, using alpha-brominated different
Ethyl butyrate is that initiator initiation styrene polymerization obtains the first macromole evocating agent, is labeled as PS-Br；
B, using electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP) method, using alpha-brominated different
Ethyl butyrate is that initiator initiation dimethylaminoethyl methacrylate polymerize to obtain the second macromole evocating agent, is labeled as
PDMAEMA-Br；
C, synthesized using core after first arm, ARGET-ATRP method, with macromole evocating agent PS-Br in step a and step b and
PDMAEMA-Br is arm, with divinylbenzene (DVB) for core, synthesizes star polymer, as graphene dispersion agent.
In one embodiment of the invention, the synthesis of the first macromole evocating agent are as follows: by styrene, the alpha-brominated isobutyl of initiator
Acetoacetic ester (EBIB), catalyst, ligand, reducing agent, solvent sequentially add in the three-necked flask equipped with thermometer, are bubbled deoxygenation
Gas, under the protection of argon gas or nitrogen, then 90-120 DEG C of reaction 5-24h of temperature post-processes to obtain the final product reaction product
To the first macromole evocating agent PS-Br, range of number-average molecular weight 8000-12000.
In one embodiment of the invention, the post-processing of first macromole evocating agent are as follows: the production for obtaining end of reaction
Object is diluted with solvent, crosses neutral alumina pillar, and vacuum distillation removes most of solvent and obtains product, and then vacuum drying oven is dry
It is dry, obtain flaxen solid.
In one embodiment of the invention, wherein the catalyst is transition metal halide CuCl2、CuBr2；The ligand
For pentamethyl-diethylenetriamine or three-(N, N- dimethyl aminoethyl) amine；The reducing agent is stannous octoate or ascorbic acid；
The solvent is any one of toluene, methyl phenyl ethers anisole, N,N-dimethylformamide, ethyl acetate or tetrahydrofuran.
In one embodiment of the invention, the catalyst: monomer=(0.01:100)~(0.05:100), the catalysis
Agent: ligand=(1:10)~(1:20), the catalyst: reducing agent=(1:10)~(1:20), is molar ratio above；Together
When, the solvent accounts for the 20%~100% of reaction system gross mass.
In one embodiment of the invention, the synthesis of the second macromole evocating agent are as follows: by dimethylaminoethyl methacrylate,
The alpha-brominated ethyl isobutyrate of initiator (EBIB) catalyst, ligand, reducing agent, solvent sequentially add three mouthfuls of burnings equipped with thermometer
It in bottle, is bubbled and removes oxygen, under argon gas or nitrogen protection, then 60-90 DEG C of reaction 8-24h of temperature carries out reaction product
Post-processing obtains the second largest initiator molecule PDMAEMA-Br, and number-average molecular weight is in 5000-7000.It polymerize as PDMAEMA
When object solution is presented acid, the tertiary amine groups height in polymer architecture protonates to form quaternary ammonium salt, is stabilized with ionic forms,
To improve the dissolubility of polymer in water.
In one embodiment of the invention, the post-processing of second macromole evocating agent are as follows: the production for obtaining end of reaction
Object is diluted with solvent, crosses neutral alumina pillar, and vacuum distillation removes most of solvent and obtains product, and then vacuum drying oven is dry
It is dry, it obtains connecing subdiaphanous solid.
In one embodiment of the invention, the catalyst is transition metal halide CuCl2、CuBr2；The ligand is five
Methyl diethylenetriamine or three-(N, N- dimethyl aminoethyl) amine；The reducing agent is stannous octoate or ascorbic acid；It is described
Solvent is one of toluene, methyl phenyl ethers anisole, N,N-dimethylformamide, ethyl acetate or tetrahydrofuran；
The catalyst: monomer=(0.03:100)~(0.06:100), the catalyst: ligand=(1:10)~(1:
20), the catalyst: reducing agent=(1:15)~(1:25), is molar ratio above；Meanwhile the solvent accounts for reaction system
The 30%~100% of gross mass.
In one embodiment of the invention, the synthetic method of the graphene dispersion agent are as follows: by the first macromole evocating agent,
Two macromole evocating agents and solvent are put into three-necked flask, to which the first macromole evocating agent and the second macromole evocating agent is complete
After dissolution, catalyst, ligand, reducing agent, cross-linker divinylbenzene is added, magnetic agitation is uniform, 20-50min is bubbled, in temperature
12-72h is reacted at 70-110 DEG C of degree, obtains product, as graphene dispersion agent.
In one embodiment of the invention, the catalyst is transition metal halide CuCl2, CuBr2；The ligand is five
Methyl diethylenetriamine or three-(N, N- dimethyl aminoethyl) amine；The reducing agent is stannous octoate or ascorbic acid；
The catalyst: ligand=(1:10)~(1:20), the catalyst: reducing agent=(1:15)~(1:25)；Institute
State the first macromole evocating agent: the second macromole evocating agent=(1:9)~(4:6), first macromole evocating agent and second
The sum of macromole evocating agent: crosslinking agent=(1:1)-(1:15), is molar ratio above；Meanwhile the solvent accounts for reaction system
The 75~100% of gross mass.The solvent is toluene and methyl phenyl ethers anisole.
The technical program has the advantages that
The present invention is using core after electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP), first arm
Synthetic method obtains a kind of different arm star polymer, as graphene dispersion agent.By with polystyrene (PS), polymethyl
Sour dimethylaminoethyl (PDMAEMA) is arm, with divinylbenzene (DVB) for core, so that the π of benzene ring structure is electric on PS strand
Son can interact with the pi-electron of graphene；The dispersing agent prepared simultaneously has pH stimuli responsive, and dispersing agent is in aqueous solution
Middle pH response is obvious, and the effect of dispersing agent dispersed graphite alkene is good, stable storage.
The present invention uses electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP), in system only
A small amount of (account for the several of monomer molar number and arrive several hundred ppm) high valence transition metal compound/ligand complex (M is addedt n+1X/L)
In the case of, a kind of reducing agent is introduced, by Mt n+1X/L is constantly reduced to low-valent transition metals halide/ligand complex (Mt nX/
L), guarantee can biggish [Mt nX/L]/[Mt n+1X/L] value, thus guarantee can system rate of polymerization.
Detailed description of the invention
Fig. 1 is the GPC curve of the first macromole evocating agent in embodiment 1；
Fig. 2 is the GPC curve of the second macromole evocating agent in embodiment 1；
Fig. 3 is the GPC curve of star graphene dispersion agent in embodiment 1；
Fig. 4 is the GPC curve of star graphene dispersion agent in embodiment 2；
Fig. 5 is the GPC curve of star graphene dispersion agent in embodiment 3；
Fig. 6 is the GPC curve of star graphene dispersion agent in embodiment 4；
Fig. 7 is the GPC curve of star graphene dispersion agent in embodiment 5；
Fig. 8 is star graphene dispersion agent synthetic route schematic diagram；
The CO of Fig. 9 star graphene dispersion agent2Stimuli responsive schematic diagram；
Figure 10 is star graphene dispersion agent dispersed graphite aqueous solution at different pH.
Specific embodiment
Below with reference to examples and drawings 1 to 10, the invention will be further described.
Embodiment 1
It is about 10000 macromole evocating agent PS-Br with ARGET-ATRP method synthesis number-average molecular weight
Styrene 32g, the alpha-brominated ethyl isobutyrate of initiator (EBIB) 0.693g, catalyst CuBr20.511g, ligand
PMDETA 0.1386g, reducing agent Sn (EH)20.2448g, solvent methyl phenyl ethers anisole 6.4g sequentially add three mouthfuls of burnings equipped with thermometer
In bottle, it is bubbled 30min and removes oxygen.It is reacted 5 hours for 90 DEG C under the protection of argon gas, monomer conversion is surveyed using gas-chromatography.Knot
Shu Hou, magnetic agitation dissolve it in tetrahydrofuran, cross neutral alumina pillar, and vacuum distillation removes most of solvent and obtains
Product, 40 DEG C of vacuum drying ovens are dry, obtain flaxen solid, as the first macromole evocating agent PS-Br.Pass through gel infiltration
Chromatography (GPC) carries out the measurement of molecular weight, as shown in Figure 1.
It is about 6000 macromole evocating agent PDMAEMA-Br using ARGET-ATRP method synthesis number-average molecular weight
Dimethylaminoethyl methacrylate 31.4g, the alpha-brominated ethyl isobutyrate of initiator (EBIB) 1.0207g, catalysis
Agent CuBr20.255g, ligand PMDETA 0.0693g, reducing agent Sn (EH)20.1224g, solvent toluene 50g, methyl phenyl ethers anisole
5.12g is sequentially added in the three-necked flask equipped with thermometer, is bubbled 30min and is removed oxygen.90 DEG C of reactions under the protection of argon gas
For 24 hours, monomer conversion is surveyed using gas-chromatography.After, it dissolves it in ethyl acetate, crosses neutral alumina pillar, subtract
Pressure is distilled off most of solvent and obtains product, and 40 DEG C of vacuum drying ovens are dry, obtains the solid of crocus, as the second macromolecular
Initiator PDMAEMA-Br.The measurement of molecular weight is carried out by gel permeation chromatography (GPC), as shown in Figure 2.
The synthesis of star graphene dispersion agent
First macromole evocating agent: the second macromole evocating agent=1:4, macromole evocating agent: crosslinking agent=1:1.
Taking molecular weight is 9600 macromole evocating agent PS-Br 2g, the macromole evocating agent PDMAEMA- that molecular weight is 6600
Br 5.5g, toluene 19g, methyl phenyl ethers anisole 3g is put into the three-necked flask equipped with temperature, and after it is completely dissolved, catalyst is added
CuBr20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)2, divinylbenzene 0.1354g, magnetic agitation is uniform,
It is bubbled 30min, 72h is reacted at 90 DEG C of temperature, neutral alumina column is crossed in tetrahydrofuran dissolution, and vacuum distillation removes most of
Solvent obtains yellow solid product, the as agent of star graphene dispersion after 40 DEG C of vacuum drying ovens are dry.The molecule of star dispersing agent
As shown in Figure 3, the synthetic route schematic diagram of star dispersing agent is as shown in Figure 8 for amount.
Embodiment 2
Difference from Example 1 is that the proportion that the synthesis of the star graphene dispersion agent of the present embodiment uses is: first
Macromole evocating agent: the second macromole evocating agent=1:4, macromole evocating agent: crosslinking agent=1:5.
Taking molecular weight is 9600 macromole evocating agent PS-Br 2g, the macromole evocating agent PDMAEMA- that molecular weight is 6600
Br 5.5g, toluene 19g, methyl phenyl ethers anisole 3g is put into the three-necked flask equipped with temperature, and after it is completely dissolved, catalyst is added
CuBr20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)2, divinylbenzene 0.6771g, magnetic agitation is uniform,
It is bubbled 30min, 72h is reacted at 90 DEG C of temperature, neutral alumina column is crossed in tetrahydrofuran dissolution, and vacuum distillation removes most of
Solvent obtains yellow solid product, the as agent of star graphene dispersion after 40 DEG C of vacuum drying ovens are dry.The molecule of star dispersing agent
As shown in Figure 4, the synthetic route schematic diagram of star dispersing agent is as shown in Figure 8 for amount.
Embodiment 3
Difference from Example 1 is that the proportion that the synthesis of the star graphene dispersion agent of the present embodiment uses is: first
Macromole evocating agent: the second macromole evocating agent=1:4, macromole evocating agent: crosslinking agent=1:15.
Taking molecular weight is 9600 macromole evocating agent PS-Br 2g, the macromole evocating agent PDMAEMA- that molecular weight is 6600
Br 5.5g, toluene 19g, methyl phenyl ethers anisole 3g is put into the three-necked flask equipped with temperature, and after it is completely dissolved, catalyst is added
CuBr20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)2, divinylbenzene 2.0312g, magnetic agitation is uniform,
It is bubbled 30min, 72h is reacted at 90 DEG C of temperature, neutral alumina column is crossed in tetrahydrofuran dissolution, and vacuum distillation removes most of
Solvent obtains yellow solid product, the as agent of star graphene dispersion after 40 DEG C of vacuum drying ovens are dry.The molecule of star dispersing agent
As shown in Figure 5, the synthetic route schematic diagram of star dispersing agent is as shown in Figure 8 for amount.
Embodiment 4
Difference from Example 1 is that the proportion that the synthesis of the star graphene dispersion agent of the present embodiment uses is: first
Macromole evocating agent: the second macromole evocating agent=1:9, macromole evocating agent: crosslinking agent=1:1.
Taking molecular weight is 9600 macromole evocating agent PS-Br 2g, the macromole evocating agent PDMAEMA- that molecular weight is 6600
Br 12.375g, toluene 49.6590g, methyl phenyl ethers anisole 7.8409g is put into the three-necked flask equipped with temperature, after it is completely dissolved,
Catalyst CuBr is added20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)2, divinylbenzene 0.2708g, magnetic
Power stirs evenly, and is bubbled 30min, and 72h is reacted at 90 DEG C of temperature, and neutral alumina column, vacuum distillation are crossed in tetrahydrofuran dissolution
Most of solvent is removed, obtains yellow solid product, the as agent of star graphene dispersion after 40 DEG C of vacuum drying ovens are dry.Star point
As shown in Figure 6, the synthetic route schematic diagram of star dispersing agent is as shown in Figure 8 for the molecular weight of powder.
Embodiment 5
Difference from Example 1 is that the proportion that the synthesis of the star graphene dispersion agent of the present embodiment uses is: first
Macromole evocating agent: the second macromole evocating agent=4:6, macromole evocating agent: crosslinking agent=1:1.
Taking molecular weight is 9600 macromole evocating agent PS-Br 2g, the macromole evocating agent PDMAEMA- that molecular weight is 6600
Br 2.0625g, toluene 19g, methyl phenyl ethers anisole 3g is put into the three-necked flask equipped with temperature, and after it is completely dissolved, catalyst is added
CuBr20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)2, divinylbenzene 0.2708g, magnetic agitation is uniform,
It is bubbled 30min, 72h is reacted at 90 DEG C of temperature, neutral alumina column is crossed in tetrahydrofuran dissolution, and vacuum distillation removes most of
Solvent obtains yellow solid product, the as agent of star graphene dispersion after 40 DEG C of vacuum drying ovens are dry.The molecule of star dispersing agent
As shown in Figure 7, the synthetic route schematic diagram of star dispersing agent is as shown in Figure 8 for amount.
Embodiment 6
The preparation that graphene dispersion agent carries out graphene dispersing solution is prepared to above-described embodiment 1
10mg star dispersing agent is dissolved in the distilled water of 5mL, is completely dissolved to it, 10mg graphene is weighed and is put into, ultrasound
30min makes it be uniformly dispersed.Solution containing graphene is centrifuged (revolving speed 4500rpm), takes supernatant, as graphene
Dispersion liquid.
The CO of star graphene dispersion agent2Stimuli responsive test
Graphene dispersing solution is passed through CO230min is passed through CO2Afterwards, it is practically insoluble in the star graphene dispersion of water originally
Agent has been dissolved in water well.This is because CO2Be passed through so that system becomes acid, PDMAEMA is converted by nonionic state
Ionic state, as shown in Figure 9.
The principle is as follows:
Star graphene dispersion agent dispersed graphite aqueous solution at different pH compares
3%NaOH solution and 3%HCl solution is respectively configured, by star graphene dispersion agent in embodiment 1 in difference
Dispersed graphite alkene under pH value.Prepare graphene dispersing solution, after 7 days, under acid condition the dispersion liquid of (3%HCl) according to
So it is uniformly dispersed, and under alkaline condition, dispersing agent and graphene sink to bottom, as shown in Figure 10.
Above-mentioned specific embodiment is used only to illustrate the present invention, rather than is to limit the invention, in the present invention
Objective and scope of protection of the claims in, to any replacement and change not made the creative labor for making of the present invention,
Fall within the scope of protection of the patent of the present invention.
Claims (10)
1. a kind of synthetic method of pH stimuli responsive type star graphene dispersion agent, which comprises the following steps:
A, using electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP) method, using alpha-brominated isobutyric acid
Ethyl ester is that initiator initiation styrene polymerization obtains the first macromole evocating agent, is labeled as PS-Br；
B, using electronics transfer regenerated catalyst atom transfer radical polymerization (ARGET-ATRP) method, using alpha-brominated isobutyric acid
Ethyl ester is that initiator initiation dimethylaminoethyl methacrylate polymerize to obtain the second macromole evocating agent, is labeled as PDMAEMA-
Br；
C, it is synthesized using arm first, using macromole evocating agent PS-Br and PDMAEMA-Br in step a and step b as arm, with
Divinylbenzene (DVB) is core, synthesizes star polymer, as graphene dispersion agent.
2. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 1, which is characterized in that the
The synthesis of one macromole evocating agent are as follows: by styrene, the alpha-brominated ethyl isobutyrate of initiator (EBIB), catalyst, ligand, reduction
Agent, solvent sequentially add in the three-necked flask equipped with thermometer, are bubbled and remove oxygen, under the protection of argon gas or nitrogen, temperature
90-120 DEG C of reaction 5-24h, then post-processes reaction product and obtains the first macromole evocating agent PS-Br.
3. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 2, which is characterized in that institute
State the post-processing of the first macromole evocating agent are as follows: the product for obtaining end of reaction is diluted with solvent, crosses neutral alumina pillar,
Vacuum distillation removes most of solvent and obtains product, and then vacuum drying oven is dry, obtains flaxen solid.
4. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 2 or 3, feature exist
In wherein the catalyst is transition metal halide CuCl2、CuBr2；The ligand is pentamethyl-diethylenetriamine or three-
(N, N- dimethyl aminoethyl) amine；The reducing agent is stannous octoate or ascorbic acid；The solvent be toluene, methyl phenyl ethers anisole,
Any one of N,N-dimethylformamide, ethyl acetate or tetrahydrofuran.
5. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 4, which is characterized in that institute
State catalyst: monomer=(0.01:100)~(0.05:100), the catalyst: ligand=(1:10)~(1:20), it is described to urge
Agent: reducing agent=(1:10)~(1:20), is molar ratio above；Meanwhile the solvent accounts for reaction system gross mass
20%~100%.
6. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 1, which is characterized in that the
The synthesis of two macromole evocating agents are as follows: by dimethylaminoethyl methacrylate, the alpha-brominated ethyl isobutyrate of initiator (EBIB)
Catalyst, ligand, reducing agent, solvent sequentially add in the three-necked flask equipped with thermometer, are bubbled and remove oxygen, in argon gas or nitrogen
Under gas shielded, then 60-90 DEG C of reaction 8-24h of temperature post-processes reaction product and obtains the second largest initiator molecule
PDMAEMA-Br。
7. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 6, which is characterized in that institute
State the post-processing of the second macromole evocating agent are as follows: the product for obtaining end of reaction is diluted with solvent, crosses neutral alumina pillar,
Vacuum distillation removes most of solvent and obtains product, and then vacuum drying oven is dry, obtains connecing subdiaphanous solid.
8. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 6 or 7, feature exist
In the catalyst is transition metal halide CuCl2、CuBr2；The ligand is pentamethyl-diethylenetriamine or three-(N, N-
Dimethyl aminoethyl) amine；The reducing agent is stannous octoate or ascorbic acid；The solvent is toluene, methyl phenyl ethers anisole, N, N- bis-
One of methylformamide, ethyl acetate or tetrahydrofuran；
The catalyst: monomer=(0.03:100)~(0.06:100), the catalyst: ligand=(1:10)~(1:20),
The catalyst: reducing agent=(1:15)~(1:25), is molar ratio above；Meanwhile the solvent accounts for the total matter of reaction system
The 30%~100% of amount.
9. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 1, which is characterized in that stone
The synthetic method of black alkene dispersing agent are as follows: the first macromole evocating agent, the second macromole evocating agent and solvent are put into three-necked flask
In, after being completely dissolved the first macromole evocating agent and the second macromole evocating agent, catalyst, ligand, reducing agent, friendship is added
Joining agent divinylbenzene, magnetic agitation is uniform, and it is bubbled 20-50min, 12-72h is reacted at 70-110 DEG C of temperature, obtains product,
As graphene dispersion agent.
10. the synthetic method of pH stimuli responsive type star graphene dispersion agent according to claim 9, which is characterized in that
The catalyst is transition metal halide CuCl2、CuBr2；The ligand is pentamethyl-diethylenetriamine or three-(N, N- diformazans
Base amino-ethyl) amine；The reducing agent is stannous octoate or ascorbic acid；
The catalyst: ligand=(1:10)~(1:20), the catalyst: reducing agent=(1:15)~(1:25)；Described
One macromole evocating agent: the second macromole evocating agent=(1:9)~(4:6), first macromole evocating agent and second largest point
The sum of sub- initiator: crosslinking agent=(1:1)-(1:15), is molar ratio above；Meanwhile the solvent accounts for the total matter of reaction system
The 75~100% of amount.
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