CN109021185B - Synthesis method of pH stimulus response type star graphene dispersing agent - Google Patents
Synthesis method of pH stimulus response type star graphene dispersing agent Download PDFInfo
- Publication number
- CN109021185B CN109021185B CN201810301637.2A CN201810301637A CN109021185B CN 109021185 B CN109021185 B CN 109021185B CN 201810301637 A CN201810301637 A CN 201810301637A CN 109021185 B CN109021185 B CN 109021185B
- Authority
- CN
- China
- Prior art keywords
- macroinitiator
- solvent
- catalyst
- graphene
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 230000004044 response Effects 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 8
- LUVDOTZGISEUMH-UHFFFAOYSA-N 1-bromoethyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)Br LUVDOTZGISEUMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 34
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 28
- 239000003446 ligand Substances 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 14
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 13
- 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
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 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
- 230000005587 bubbling Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical group 0.000 claims description 7
- -1 N, N-dimethylaminoethyl Chemical group 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 230000027756 respiratory electron transport chain Effects 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract 2
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000009467 reduction Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
Landscapes
- 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 synthesis method of a pH stimulus response type star graphene dispersing agent, which comprises the following steps: a. initiating styrene polymerization by using alpha-bromoethyl isobutyrate as an initiator by an ARGET-ATRP method to obtain a first macromolecular initiator marked as PS-Br; b. initiating polymerization of dimethylaminoethyl methacrylate by using alpha-bromoisobutyrate as an initiator to obtain a second macromolecular initiator which is marked as PDMAEMA-Br; c. and (b) synthesizing a star polymer, namely the graphene dispersing agent, by adopting an arm-first-core and ARGET-ATRP method, taking the macromolecular initiators PS-Br and PDMAEMA-Br in the step a and the step b as arms, and taking Divinylbenzene (DVB) as a core. The graphene dispersing agent with good dispersing performance and stable storage can be obtained by the synthesis method.
Description
Technical Field
The invention relates to a synthesis method of a graphene dispersant, in particular to a synthesis method of a pH stimulus response type star graphene dispersant.
Background
Graphene is a two-dimensional crystalline material composed of sp2 hybridized carbon atoms, which is considered to be the thinnest material in the world. Due to their high specific surface area, outstanding tensile strength, thermal conductivity, and electrical conductivity, they have attracted considerable attention in many scientific fields, but these applications are greatly limited by their solubility. To solve this problem, soluble dispersants have been gradually developed to modify the surface of graphene so that the solubility of graphene is improved. Currently, the main improvement of the graphene surface is by covalent and non-covalent methods, which is preferred because it avoids destroying the characteristic properties of graphene. In addition, graphene also has several potential applications, sensors, drug delivery, and the like. Therefore, different kinds of responsive dispersants have been developed, including pH, temperature, light, redox responsive dispersants. These responses control the agglomeration and dispersion of graphene once its surface is modified by a dispersant. However, these dispersants are still insufficient due to their own performance, difficulty in controlling their preparation, or high cost, and thus it is necessary for those skilled in the art to develop a graphene dispersant having good dispersibility and storage stability.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a synthesis method of a pH stimulus response type star graphene dispersant, so as to improve the solubility of graphene in water.
In order to achieve the purpose, the technical scheme adopted by the invention is a synthesis method of a pH stimulus response type star graphene dispersant, which comprises the following steps:
a. adopting an electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) method, adopting alpha-bromoisobutyrate ethyl ester as an initiator to initiate styrene polymerization to obtain a first macromolecular initiator, and marking the first macromolecular initiator as PS-Br;
b. adopting an electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) method, adopting alpha-bromoethyl isobutyrate as an initiator to initiate dimethylaminoethyl methacrylate to polymerize to obtain a second macromolecular initiator, and marking the second macromolecular initiator as PDMAEMA-Br;
c. and (b) synthesizing a star polymer, namely the graphene dispersing agent, by adopting an arm-first-core and ARGET-ATRP method, taking the macromolecular initiators PS-Br and PDMAEMA-Br in the step a and the step b as arms, and taking Divinylbenzene (DVB) as a core.
In one embodiment of the present invention, the synthesis of the first macroinitiator is as follows: styrene, an initiator alpha-bromoethyl isobutyrate (EBIB), a catalyst, a ligand, a reducing agent and a solvent are sequentially added into a three-neck flask with a thermometer, oxygen is removed by bubbling, the reaction is carried out for 5 to 24 hours at the temperature of between 90 and 120 ℃ under the protection of argon or nitrogen, and then the reaction product is subjected to post-treatment to obtain a first macromolecular initiator PS-Br with the number average molecular weight range of 8000-12000.
In an embodiment of the present invention, the post-treatment of the first macroinitiator is: diluting the product obtained after the reaction with a solvent, passing through a neutral alumina column, distilling under reduced pressure to remove most of the solvent to obtain the product, and drying in a vacuum oven to obtain a light yellow solid.
In one embodiment of the present invention, the catalyst is a transition metal halide CuCl2、CuBr2(ii) a The ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid; the solvent is any one of toluene, anisole, N-dimethylformamide, ethyl acetate or tetrahydrofuran.
In one embodiment of the present invention, the molar ratio of the catalyst to the monomer (0.01:100) to the molar ratio of the catalyst to the ligand (1:10) to the molar ratio of the catalyst to the reducing agent (1:10) to the molar ratio of the reducing agent to the reducing agent (1:20) are the same as each other; meanwhile, the solvent accounts for 20-100% of the total mass of the reaction system.
In one embodiment of the present invention, the synthesis of the second macroinitiator is: adding dimethylaminoethyl methacrylate, an initiator alpha-bromoethyl isobutyrate (EBIB) catalyst, a ligand, a reducing agent and a solvent into a three-neck flask with a thermometer in sequence, bubbling to remove oxygen, reacting at 60-90 ℃ for 8-24h under the protection of argon or nitrogen, and then carrying out post-treatment on a reaction product to obtain a second macromolecular initiator PDMAEMA-Br, wherein the number average molecular weight is 5000-7000. When the PDMAEMA polymer solution is acidic, the tertiary amine groups in the polymer structure are highly protonated to form quaternary ammonium salts, and the quaternary ammonium salts exist stably in an ionic form, so that the solubility of the polymer in water is improved.
In an embodiment of the present invention, the post-treatment of the second macroinitiator is: diluting the product obtained after the reaction with a solvent, passing through a neutral alumina column, distilling under reduced pressure to remove most of the solvent to obtain the product, and drying in a vacuum oven to obtain a nearly colorless solid.
In one embodiment of the present invention, the catalyst is a transition metal halide CuCl2、CuBr2(ii) a The ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid; the above-mentionedThe solvent is one of toluene, anisole, N-dimethylformamide, ethyl acetate or tetrahydrofuran;
the molar ratio of the catalyst to the monomer (0.03:100) to the catalyst to the ligand (1:10) to (1:20) to the reducing agent (1:15) to (1: 25); meanwhile, the solvent accounts for 30-100% of the total mass of the reaction system.
In an embodiment of the present invention, a synthesis method of the graphene dispersant includes: putting a first macroinitiator, a second macroinitiator and a solvent into a three-neck flask, adding a catalyst, a ligand, a reducing agent and a cross-linking agent divinylbenzene after the first macroinitiator and the second macroinitiator are completely dissolved, uniformly stirring by magnetic force, bubbling for 20-50min, and reacting for 12-72h at the temperature of 70-110 ℃ to obtain a product, namely the graphene dispersing agent.
In an embodiment of the present invention, the catalyst is transition metal halides CuCl2, CuBr 2; the ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid;
the catalyst includes a ligand (1:10) to (1:20), and a reducing agent (1:15) to (1: 25); the first macroinitiator: (ii) a second macroinitiator ═ 1:9 to 4:6, the sum of the first and second macroinitiators: the crosslinking agent is (1:1) - (1:15), and the above are molar ratios; meanwhile, the solvent accounts for 75-100% of the total mass of the reaction system. The solvent is toluene and anisole.
The technical scheme has the following beneficial effects:
the invention adopts an electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) and a synthetic method of first arm and second core to obtain a star polymer with different arms, namely the graphene dispersant. Polystyrene (PS) and poly (dimethylaminoethyl methacrylate) (PDMAEMA) are used as arms, and Divinylbenzene (DVB) is used as a core, so that pi electrons of a benzene ring structure on a PS molecular chain can interact with pi electrons of graphene; meanwhile, the prepared dispersing agent has pH stimulation response, the pH response of the dispersing agent in an aqueous solution is obvious, the effect of dispersing graphene by the dispersing agent is good, and the storage is stable.
The invention adopts electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP), only a small amount (several to several hundred ppm of monomer mole) of high-valence transition metal compound/ligand complex (M) is added into the systemt n+1X/L), introducing a reducing agent, and adding Mt n+1The reduction of X/L to the lower transition metal halide/ligand complex (M) continuest nX/L), ensure that can be larger [ Mt nX/L]/[Mt n+1X/L]The value, thereby ensuring the polymerization rate of the system.
Drawings
FIG. 1 is a GPC curve of the first macroinitiator of example 1;
FIG. 2 is a GPC curve of the second macroinitiator of example 1;
FIG. 3 is a GPC curve of the star-shaped graphene dispersant in example 1;
FIG. 4 is a GPC curve of the star-shaped graphene dispersant in example 2;
FIG. 5 is a GPC curve of the star-shaped graphene dispersant in example 3;
FIG. 6 is a GPC curve of the star-shaped graphene dispersant in example 4;
FIG. 7 is a GPC curve of the star-shaped graphene dispersant in example 5;
FIG. 8 is a schematic diagram of a synthetic route for a star graphene dispersant;
FIG. 9 CO of radial graphene dispersant2A stimulus response diagram;
fig. 10 is a dispersion of an aqueous graphene solution at different pH with a star graphene dispersant.
Detailed Description
The invention will now be further described with reference to the following examples and figures 1 to 10.
Example 1
Synthesis of macroinitiator PS-Br with number average molecular weight of about 10000 by ARGET-ATRP method
32g of styrene, initiator α -Ethyl bromoisobutyrate (EBIB)0693g, catalyst CuBr20.511g, ligand PMDETA 0.1386g, reducing agent Sn (EH)20.2448g of anisole, 6.4g of solvent, were sequentially added to a three-necked flask equipped with a thermometer, and bubbled for 30min to remove oxygen. The reaction was carried out at 90 ℃ for 5 hours under the protection of argon, and the monomer conversion was determined by gas chromatography. And after the reaction is finished, dissolving the product in tetrahydrofuran by magnetic stirring, passing through a neutral alumina column, removing most of solvent by reduced pressure distillation to obtain a product, and drying the product in a vacuum oven at 40 ℃ to obtain a light yellow solid, namely the first macromolecular initiator PS-Br. The molecular weight was measured by Gel Permeation Chromatography (GPC) as shown in fig. 1.
Synthesis of macroinitiator PDMAEMA-Br with number average molecular weight of about 6000 by ARGET-ATRP method
31.4g of dimethylaminoethyl methacrylate, 1.0207g of initiator α -ethyl bromoisobutyrate (EBIB), and catalyst CuBr20.255g, ligand PMDETA 0.0693g, reducing agent Sn (EH)20.1224g, toluene solvent 50g and anisole 5.12g were sequentially charged into a three-necked flask equipped with a thermometer, and bubbled for 30min to remove oxygen. The reaction is carried out for 24h at 90 ℃ under the protection of argon, and the monomer conversion rate is measured by gas chromatography. And after the reaction is finished, dissolving the product in ethyl acetate, passing through a neutral alumina column, distilling under reduced pressure to remove most of the solvent to obtain a product, and drying in a vacuum oven at 40 ℃ to obtain an orange solid, namely a second macromolecular initiator PDMAEMA-Br. The molecular weight was measured by Gel Permeation Chromatography (GPC) as shown in fig. 2.
Synthesis of star graphene dispersant
First macroinitiator: a second macroinitiator ═ 1:4, macroinitiator: crosslinker 1: 1.
Putting 9600 g of macroinitiator PS-Br 2g, 6600 g of macroinitiator PDMAEMA-Br 5.5g, toluene 19g and anisole 3g into a three-neck flask with temperature, adding catalyst CuBr after the materials are completely dissolved20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)20.1354g of divinylbenzene, stirring evenly by magnetic force, bubbling for 30min, reacting for 72h at the temperature of 90 ℃, dissolving tetrahydrofuran, passing through a neutral alumina column, and removing the large part by reduced pressure distillationAnd drying part of the solvent in a vacuum oven at 40 ℃ to obtain a yellow solid product, namely the star graphene dispersing agent. The molecular weight of the star dispersant is shown in FIG. 3, and the synthetic route of the star dispersant is schematically shown in FIG. 8.
Example 2
The difference from embodiment 1 is that the ratio of the star graphene dispersant used in the synthesis of the present embodiment is: first macroinitiator: a second macroinitiator ═ 1:4, macroinitiator: crosslinker 1: 5.
Putting 9600 g of macroinitiator PS-Br 2g, 6600 g of macroinitiator PDMAEMA-Br 5.5g, toluene 19g and anisole 3g into a three-neck flask with temperature, adding catalyst CuBr after the materials are completely dissolved20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)20.6771g of divinylbenzene, stirring uniformly by magnetic force, bubbling for 30min, reacting for 72h at the temperature of 90 ℃, dissolving tetrahydrofuran, passing through a neutral alumina column, distilling under reduced pressure to remove most of solvent, and drying in a vacuum oven at the temperature of 40 ℃ to obtain a yellow solid product, namely the star-shaped graphene dispersing agent. The molecular weight of the star dispersant is shown in FIG. 4, and the synthetic route of the star dispersant is schematically shown in FIG. 8.
Example 3
The difference from embodiment 1 is that the ratio of the star graphene dispersant used in the synthesis of the present embodiment is: first macroinitiator: a second macroinitiator ═ 1:4, macroinitiator: crosslinker 1: 15.
Putting 9600 g of macroinitiator PS-Br 2g, 6600 g of macroinitiator PDMAEMA-Br 5.5g, toluene 19g and anisole 3g into a three-neck flask with temperature, adding catalyst CuBr after the materials are completely dissolved20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)22.0312g of divinylbenzene, stirring uniformly by magnetic force, bubbling for 30min, reacting for 72h at the temperature of 90 ℃, dissolving tetrahydrofuran, passing through a neutral alumina column, distilling under reduced pressure to remove most of solvent, and drying in a vacuum oven at the temperature of 40 ℃ to obtain a yellow solid product, namely the star-shaped graphene dispersing agent. The molecular weight of the star dispersant is shown in FIG. 5The synthetic scheme of the star-shaped dispersant is shown in FIG. 8.
Example 4
The difference from embodiment 1 is that the ratio of the star graphene dispersant used in the synthesis of the present embodiment is: first macroinitiator: a second macroinitiator ═ 1:9, macroinitiator: crosslinker 1: 1.
Putting 9600 g of macroinitiator PS-Br 2g, 6600 g of macroinitiator PDMAEMA-Br 12.375g, toluene 49.6590g and anisole 7.8409g into a three-neck flask with temperature, adding catalyst CuBr after the macroinitiator PDMAEMA-Br is completely dissolved20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)20.2708g of divinylbenzene, stirring uniformly by magnetic force, bubbling for 30min, reacting for 72h at the temperature of 90 ℃, dissolving tetrahydrofuran, passing through a neutral alumina column, distilling under reduced pressure to remove most of solvent, and drying in a vacuum oven at the temperature of 40 ℃ to obtain a yellow solid product, namely the star-shaped graphene dispersing agent. The molecular weight of the star dispersant is shown in FIG. 6, and the synthetic route of the star dispersant is schematically shown in FIG. 8.
Example 5
The difference from embodiment 1 is that the ratio of the star graphene dispersant used in the synthesis of the present embodiment is: first macroinitiator: a second macroinitiator ═ 4:6, macroinitiator: crosslinker 1: 1.
Putting 9600 g of macroinitiator PS-Br 2g, 6600 g of macroinitiator PDMAEMA-Br 2.0625g, 19g of toluene and 3g of anisole into a three-neck flask with temperature, and adding catalyst CuBr after the macroinitiator PDMAEMA-Br, toluene and anisole are completely dissolved20.2326g, ligand PMDETA 1.8052g, reducing agent Sn (EH)20.2708g of divinylbenzene, stirring uniformly by magnetic force, bubbling for 30min, reacting for 72h at the temperature of 90 ℃, dissolving tetrahydrofuran, passing through a neutral alumina column, distilling under reduced pressure to remove most of solvent, and drying in a vacuum oven at the temperature of 40 ℃ to obtain a yellow solid product, namely the star-shaped graphene dispersing agent. The molecular weight of the star dispersant is shown in FIG. 7, and the schematic diagram of the synthetic route of the star dispersant is shown in FIG. 8.
Example 6
Preparation of graphene dispersion solution for the graphene dispersant prepared in example 1
Dissolving 10mg of star-shaped dispersing agent in 5mL of distilled water, weighing 10mg of graphene when the star-shaped dispersing agent is completely dissolved, and performing ultrasonic treatment for 30min to uniformly disperse the graphene. And (3) centrifuging the solution containing the graphene (rotating speed of 4500rpm), and taking supernatant, namely the graphene dispersion liquid.
CO of star graphene dispersant2Stimulus response test
Introducing CO into the graphene dispersion liquid2Introducing CO for 30min2And then, the star-shaped graphene dispersing agent which is almost insoluble in water is well dissolved in water. This is due to CO2The system becomes acidic, and the PDMAEMA is converted from a non-ionic state to an ionic state, as shown in FIG. 9.
The principle is as follows:
comparison of graphene aqueous solutions dispersed by star-shaped graphene dispersant under different pH values
Respectively preparing a 3% NaOH solution and a 3% HCl solution, and dispersing graphene by the star-shaped graphene dispersing agent in the embodiment 1 under different pH values. After 7 days, the dispersion liquid under acidic condition (3% HCl) was still uniformly dispersed, while under alkaline condition, both the dispersant and graphene settled at the bottom, as shown in fig. 10.
The above-described embodiments are intended to be illustrative, rather than restrictive, of the present invention, and any alterations and modifications that do not create an inventive feature are intended to be included within the spirit of the invention and the scope of the appended claims.
Claims (10)
1. A synthetic method of a pH stimulus response type star graphene dispersant is characterized by comprising the following steps:
a. adopting an electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) method, adopting alpha-bromoisobutyrate ethyl ester as an initiator to initiate styrene polymerization to obtain a first macromolecular initiator, and marking the first macromolecular initiator as PS-Br;
b. adopting an electron transfer regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) method, adopting alpha-bromoethyl isobutyrate as an initiator to initiate dimethylaminoethyl methacrylate to polymerize to obtain a second macromolecular initiator, and marking the second macromolecular initiator as PDMAEMA-Br;
c. and (b) synthesizing a star polymer, namely the graphene dispersing agent, by using the macromolecular initiators PS-Br and PDMAEMA-Br in the step a and the step b as arms and using Divinylbenzene (DVB) as a core.
2. The method for synthesizing the pH stimulus-responsive radial graphene dispersant according to claim 1, wherein the synthesis of the first macroinitiator is as follows: styrene, an initiator alpha-bromoethyl isobutyrate (EBIB), a catalyst, a ligand, a reducing agent and a solvent are sequentially added into a three-neck flask with a thermometer, bubbling is carried out to remove oxygen, the reaction is carried out for 5-24h at the temperature of 90-120 ℃ under the protection of argon or nitrogen, and then the reaction product is subjected to post-treatment to obtain the first macromolecular initiator PS-Br.
3. The method for synthesizing the pH stimulus-responsive radial graphene dispersant according to claim 1, wherein the post-treatment of the first macroinitiator is: diluting the product obtained after the reaction with a solvent, passing through a neutral alumina column, distilling under reduced pressure to remove most of the solvent to obtain the product, and drying in a vacuum oven to obtain a light yellow solid.
4. The method for synthesizing the pH stimulus-responsive radial graphene dispersant according to claim 2 or 3, wherein the catalyst is a transition metal halide (CuCl)2、CuBr2(ii) a The ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid; the solvent is toluene, anisole, N-dimethylformamide, ethyl acetate or tetrahydrofuranAny one of (1).
5. The method for synthesizing a pH stimuli-responsive star graphene dispersant according to claim 4, wherein the catalyst is a monomer (0.01:100) to 0.05:100, the catalyst is a ligand (1:10) to 1:20, and the catalyst is a reducing agent (1:10) to 1:20, all in a molar ratio; meanwhile, the solvent accounts for 20-100% of the total mass of the reaction system.
6. The method for synthesizing the pH stimulus-responsive star graphene dispersant according to claim 1, wherein the synthesis of the second macroinitiator is: adding dimethylaminoethyl methacrylate, an initiator alpha-bromoethyl isobutyrate (EBIB) catalyst, a ligand, a reducing agent and a solvent into a three-neck flask with a thermometer in sequence, bubbling to remove oxygen, reacting at 60-90 ℃ for 8-24h under the protection of argon or nitrogen, and then carrying out post-treatment on a reaction product to obtain a second macromolecular initiator PDMAEMA-Br.
7. The method for synthesizing the pH stimulus-responsive radial graphene dispersant according to claim 6, wherein the post-treatment of the second macroinitiator is: diluting the product obtained after the reaction with a solvent, passing through a neutral alumina column, distilling under reduced pressure to remove most of the solvent to obtain the product, and drying in a vacuum oven to obtain a colorless solid.
8. The method for synthesizing the pH stimulus-responsive star graphene dispersant according to claim 6 or 7, wherein the catalyst is a transition metal halide (CuCl)2、CuBr2(ii) a The ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid; the solvent is one of toluene, anisole, N-dimethylformamide, ethyl acetate or tetrahydrofuran; the catalyst includes a monomer (0.03:100) to (0.06:100), a ligand (1:10) to (1:20), and a reducing agent (1:15) to (1:25) the above are all molar ratios; meanwhile, the solvent accounts for 30-100% of the total mass of the reaction system.
9. The method for synthesizing the pH stimulus-responsive star graphene dispersant according to claim 1, wherein the method for synthesizing the graphene dispersant is as follows: putting a first macroinitiator, a second macroinitiator and a solvent into a three-neck flask, adding a catalyst, a ligand, a reducing agent and a cross-linking agent divinylbenzene after the first macroinitiator and the second macroinitiator are completely dissolved, uniformly stirring by magnetic force, bubbling for 20-50min, and reacting for 12-72h at the temperature of 70-110 ℃ to obtain a product, namely the graphene dispersing agent.
10. The method for synthesizing the pH stimulus-responsive radial graphene dispersant according to claim 9, wherein the catalyst is a transition metal halide (CuCl)2、CuBr2(ii) a The ligand is pentamethyldiethylenetriamine or tri- (N, N-dimethylaminoethyl) amine; the reducing agent is stannous octoate or ascorbic acid; the solvent is toluene and anisole;
the catalyst includes a ligand (1:10) to (1:20), and a reducing agent (1:15) to (1: 25); the first macroinitiator: (ii) a second macroinitiator ═ 1:9 to 4:6, the sum of the first and second macroinitiators: the crosslinking agent is (1:1) - (1:15), and the above are molar ratios; meanwhile, the solvent accounts for 75-100% of the total mass of the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810301637.2A CN109021185B (en) | 2018-04-04 | 2018-04-04 | Synthesis method of pH stimulus response type star graphene dispersing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810301637.2A CN109021185B (en) | 2018-04-04 | 2018-04-04 | Synthesis method of pH stimulus response type star graphene dispersing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109021185A CN109021185A (en) | 2018-12-18 |
| CN109021185B true CN109021185B (en) | 2020-09-15 |
Family
ID=64629490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810301637.2A Active CN109021185B (en) | 2018-04-04 | 2018-04-04 | Synthesis method of pH stimulus response type star graphene dispersing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109021185B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655596B (en) * | 2019-10-18 | 2021-10-01 | 常州碳孚新材料技术有限公司 | Star-shaped cationic graphene dispersant and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
| CN105670440A (en) * | 2016-02-03 | 2016-06-15 | 常州大学 | Star-shaped acrylate resin and graphene nanometre coating and preparation method thereof |
-
2018
- 2018-04-04 CN CN201810301637.2A patent/CN109021185B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
| CN105670440A (en) * | 2016-02-03 | 2016-06-15 | 常州大学 | Star-shaped acrylate resin and graphene nanometre coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Graphene/star polymer nanocoating";Qiang Ren, et al.;《Progress in Organic Coatings》;20161205;第103卷;15-22 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109021185A (en) | 2018-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Granel et al. | Controlled radical polymerization of methacrylic monomers in the presence of a bis (ortho-chelated) arylnickel (II) complex and different activated alkyl halides | |
| Haddleton et al. | 3-Aminopropyl silica supported living radical polymerization of methyl methacrylate: dichlorotris (triphenylphosphine) ruthenium (II) mediated atom transfer polymerization | |
| EP0816385B1 (en) | Process for preparing vinyl polymer | |
| Aoshima et al. | New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds | |
| Öztürk et al. | One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization | |
| Yan et al. | Highly efficient synthesis of cylindrical polymer brushes with various side chains via click grafting-onto approach | |
| Nagelsdiek et al. | Synthesis of polymers containing cross-linkable groups by atom transfer radical polymerization: poly (allyl methacrylate) and copolymers of allyl methacrylate and styrene | |
| Li et al. | One‐pot synthesis of surface‐functionalized molecularly imprinted polymer microspheres by iniferter‐induced “living” radical precipitation polymerization | |
| US20170029535A1 (en) | Regulation of a controlled radical polymerization of acrylates by light | |
| CN101792503B (en) | Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof | |
| CN109021185B (en) | Synthesis method of pH stimulus response type star graphene dispersing agent | |
| Jiao et al. | Efficient one-pot synthesis of uniform, surface-functionalized, and “living” polymer microspheres by reverse atom transfer radical precipitation polymerization | |
| WO2006070858A1 (en) | Method for removing metal and method for producing polymer | |
| Zeng et al. | Atom‐Transfer Radical Polymerization of 2‐(N, N‐Dimethylamino) ethyl Acrylate | |
| Chen et al. | Reverse ATRP of ethyl acrylate with ionic liquids as reaction medium | |
| Popescu et al. | Multibrominated hyperbranched polymers: Synthesis and further functionalizations by arget atrp or click chemistry | |
| JP5770625B2 (en) | Vinyl ether-based star polymer and method for producing the same | |
| CN109071697B (en) | Process for producing highly branched polymer and highly branched polymer | |
| Greesh et al. | Preparation of poly (styrene‐b‐2‐hydroxyethyl acrylate) block copolymer using reverse iodine transfer polymerization | |
| JP5101816B2 (en) | Hyperbranched polymer | |
| Vivek et al. | Grafting of methacrylates and styrene on to polystyrene backbone via a “grafting from” ATRP process at ambient temperature | |
| KR101195534B1 (en) | Process for Preparation of Polythiophene Star Polymer and Polythiophene Star Polymer Prepared By the Same | |
| Cheng et al. | Synthesis of a photoactive gemini surfactant and its use in AGET ATRP miniemulsion polymerisation and UV curing | |
| Wang et al. | Synthesis and characterization of star graft copolymers with asymmetric mixed “V‐shaped” side chains via “click” chemistry on a hyperbranched polyglycerol core | |
| Suresh et al. | Synthesis of novel crosslinkable polymers by atom transfer radical polymerization of cardanyl acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231225 Address after: 102400 Room 301, floor 3, unit 2, building 10, yard 18, Yanshan Yanxin South Road, Fangshan District, Beijing Patentee after: China Resources Super Oil (Beijing) New Material Co.,Ltd. Address before: 213100 workshop 2, No.8 Lanxiang Road, West Taihu science and Technology Industrial Park, Wujin District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU C-TANFORD NEW MATERIAL TECHNOLOGY Co.,Ltd. |