CN112625194A - Preparation method of special dispersion polymer for graphene - Google Patents
Preparation method of special dispersion polymer for graphene Download PDFInfo
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- CN112625194A CN112625194A CN202011279848.4A CN202011279848A CN112625194A CN 112625194 A CN112625194 A CN 112625194A CN 202011279848 A CN202011279848 A CN 202011279848A CN 112625194 A CN112625194 A CN 112625194A
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- dispersion polymer
- graphene dispersion
- graphene
- preparation
- epoxy resin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 239000004815 dispersion polymer Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- -1 perfluoroalkyl ethyl acrylate Chemical compound 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- OZZOVSQSDIWNIP-UHFFFAOYSA-N acetic acid;azane Chemical compound [NH4+].[NH4+].CC([O-])=O.CC([O-])=O OZZOVSQSDIWNIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 claims description 3
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000002966 varnish Substances 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of a special graphene dispersion polymer, and aims to solve the problems that a graphene material cannot be applied to a water-based paint due to the limitation of an application auxiliary agent in the field of paints, so that the performance improvement of an environment-friendly paint and the research of new products and other related works are severely restricted. The high molecular polymer prepared by the invention not only contains benzene rings in epoxy resin, but also contains carboxyl with an anchoring effect on graphene and the characteristics of high coating and low surface energy which are unique to a functional long-chain monomer, and can enable graphene slurry to have high solid content, low viscosity, good fluidity and excellent storage stability when being prepared with graphene, thereby providing a huge formula adjustment space for preparing high-performance barrier coating and having extremely high market space and application value.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a preparation method of a special graphene dispersion polymer.
Background
The graphene is sp2The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
Graphene is produced in large scale in China, but due to the fact that strong van der waals acting force exists among graphene, graphene cannot exist in a single-layer form stably, once the graphene is agglomerated and stacked, various performances of the graphene are reduced sharply, and once layer stacking occurs, the graphene layers are difficult to open and need to be peeled off again.
When the graphene is applied to the field of coatings, the dispersibility of graphene is often improved through a dispersant, but the graphene is different from common inorganic powder, the conventional dispersant and dispersing means are difficult to achieve the dispersing effect, the application of the graphene is limited by application auxiliaries in the field of coatings, and the high-performance material cannot be applied to water-based coatings, so that the performance improvement of environment-friendly coatings, the research of new products and other related works are severely restricted.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a special graphene dispersion polymer, which can enable graphene slurry to have high solid content, low viscosity, good fluidity and excellent storage stability through carboxyl with an anchoring effect on graphene and the characteristics of high coating and low surface energy which are unique to a functional long-chain monomer, and achieves the purposes of providing a huge formula adjustment space for preparing a high-performance barrier coating and having extremely high market space and application value.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of a special graphene dispersion polymer comprises the following specific preparation steps: the method comprises the following steps: 245.0g-355.0g of epoxy resin and 8-12g of itaconic acid are added into a reaction vessel provided with a stirring temperature rise and protection device, the reaction is carried out at the temperature of 80-120 ℃, esterification of the epoxy resin is carried out to generate a large amount of double bonds, carboxyl is introduced in the reaction process, and the reaction is stopped when the acid value is measured to reach 60mg/g-150 mg/g.
Step two: adding 500g of long-chain alkyl acrylate 420-one and 2-8g of free radical initiator, and reacting at 80-150 ℃ for 4-6h to obtain the copolymer.
Step three: and adding a neutralizing agent into the copolymer, and neutralizing by using the neutralizing agent until the pH value is 7.0 +/-0.5 to obtain the high-molecular surfactant.
The invention is further configured to: the long-chain alkyl acrylate is one or more of the following: perfluoroalkyl ethyl acrylate, tridecyl methacrylate, tetradecyl methacrylate, hexadecyl perfluoroalkyl acrylate, octadecyl perfluoroalkyl acrylate, and docodecyl perfluoroalkyl acrylate.
The invention is further configured to: the epoxy resin is one or a mixture of E type, F type and S type epoxy resin.
The invention is further configured to: the neutralizing agent is one or more of triethylamine, ammonium diacetate and dimethylethanolamine.
The invention is further configured to: the free radical initiator is one or a mixture of several of methyl ethyl ketone peroxide, benzoyl peroxide, ammonium persulfate and potassium persulfate.
The invention is further configured to: the epoxy value of the epoxy resin was 0.51.
In conclusion, the invention has the following beneficial effects:
the invention and graphene preparation can enable the graphene slurry to have high solid content, low viscosity, good fluidity and excellent storage stability, provide a huge formula adjustment space for preparing high-performance barrier coating, and have extremely high market space and application value.
Detailed Description
The present invention will be described in detail with reference to examples.
The first embodiment is as follows:
the method comprises the following steps: 245.0g of E51 type epoxy resin and 8g of itaconic acid are added into a reaction vessel provided with a stirring temperature rise and protection device, the epoxy value of the epoxy resin is 0.51, the reaction is carried out at the temperature of 80 ℃, the esterification of the epoxy resin is carried out to generate a large amount of double bonds, carboxyl is introduced in the reaction process, and the reaction is stopped when the acid value is measured to reach 60 mg/g.
Step two: adding 420g of perfluoroalkyl ethyl acrylate and 2g of methyl ethyl ketone peroxide initiator, and reacting at the temperature of 80 ℃ for 4h to obtain the copolymer.
Step three: triethylamine is added into the copolymer, and the copolymer is neutralized by the triethylamine until the PH value is 7.0 +/-0.5 to obtain the high molecular polymer.
Example two:
the method comprises the following steps: 355.0g of F51 type epoxy resin and 12g of itaconic acid are added into a reaction vessel provided with a stirring temperature-rising and protecting device, the epoxy value of the epoxy resin is 0.51, the reaction is carried out at the temperature of 120 ℃, the esterification of the epoxy resin is carried out to generate a large amount of double bonds, carboxyl is introduced in the reaction process, and the reaction is stopped when the acid value is measured to reach 150 mg/g.
Step two: 500g of a mixture of tridecyl methacrylate and tetradecyl methacrylate and 8g of benzoyl peroxide initiator were added and reacted at 150 ℃ for 6 hours to obtain a copolymer.
Step three: ammonium diacetate was added to the copolymer and neutralized to pH 7.0. + -. 0.5 by ammonium diacetate to give a high molecular weight polymer.
Example three:
the method comprises the following steps: 3000g of S-type epoxy resin and 10g of itaconic acid are added into a reaction vessel provided with a stirring temperature rise and protection device, the epoxy value of the epoxy resin is 0.51, the reaction is carried out at the temperature of 100 ℃, the esterification of the epoxy resin is carried out to generate a large amount of double bonds, carboxyl is introduced in the reaction process, and the reaction is stopped when the acid value is measured to reach 100 mg/g.
Step two: 460g of a mixture of cetylperfluoroalkylacrylate, octadecylperfluoroalkylacrylate and docodecylperfluoroalkylacrylate and 5g of a mixture of ammonium persulfate and potassium persulfate were added and reacted at a temperature of 120 ℃ for 5 hours to obtain a copolymer.
Step three: dimethylethanolamine was added to the copolymer and neutralized to pH 7.0. + -. 0.5 by dimethylethanolamine to give a high-molecular polymer.
The reaction vessel may be a tank polymerization reactor, a loop polymerization reactor, a tower polymerization reactor, or a fluidized bed polymerization reactor.
The high molecular polymer is colorless or light yellow to dark brown transparent viscous liquid after being prepared, can be dissolved in water and environment-friendly solvents such as acid ether and acid ester solvents such as DPM and DPNB, and can be used for dispersing graphene to prepare low-viscosity high-content graphene slurry with the content of 7.5-20%.
The high molecular polymer prepared by the invention not only contains benzene rings in epoxy resin, but also contains carboxyl with an anchoring effect on graphene and the characteristics of high coating and low surface energy which are unique to a functional long-chain monomer, and can enable graphene slurry to have high solid content, low viscosity, good fluidity and excellent storage stability when being prepared with graphene, thereby providing a huge formula adjustment space for preparing high-performance barrier coating and having extremely high market space and application value.
Experimental methods
The instrument comprises the following steps: x-ray diffractometer, energy spectrometer
Sample preparation: sample 1, a black plastic bottom plate, on which a white paint is coated, and a coating section is to be analyzed; sample 2, a tinplate, was coated with a varnish and analyzed for the distribution of graphene therein.
1. Analysis by Electron microscopy
Fast scanning: at a certain point, the parameters of the electron microscope and the focal length are adjusted, then the observation point is moved to another region which is not observed, the image is rapidly scanned and collected to obtain an SEM image, and the fluctuation of the height of the paint film can be clearly seen.
Low vacuum backscattering: in the low vacuum mode, the ionization action of residual gas molecules in an electron microscope is utilized, the gas ionization consumes the electric charges enriched on the surface of the sample, the accelerating voltage is set to be 10kV, the vacuum degree is 10Pa, the diameter of an electron beam spot is 20nm, and after the focal length is adjusted, an SEM component image is collected, so that the layering condition of the coating can be clearly seen.
2. Energy spectrometer map elemental analysis
And carrying out element analysis on the element composition of each layer of the paint film to obtain an EDS (electronic discharge spectroscopy) spectrum.
TABLE I, Performance test comparison
The results in table 1 show that the comprehensive performance of each example is better, and the high molecular polymer prepared by the invention can better disperse graphene in the coating, and has excellent dispersion performance.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (6)
1. A preparation method of a special graphene dispersion polymer comprises the following specific preparation steps: the method comprises the following steps: 245.0g-355.0g of epoxy resin and 8-12g of itaconic acid are added into a reaction vessel provided with a stirring temperature rise and protection device, the reaction is carried out at the temperature of 80-120 ℃, esterification of the epoxy resin is carried out to generate a large amount of double bonds, carboxyl is introduced in the reaction process, and the reaction is stopped when the acid value is measured to reach 60mg/g-150 mg/g.
Step two: adding 500g of long-chain alkyl acrylate 420-one and 2-8g of free radical initiator, and reacting at 80-150 ℃ for 4-6h to obtain the copolymer.
Step three: and adding a neutralizing agent into the copolymer, and neutralizing by using the neutralizing agent until the pH value is 7.0 +/-0.5 to obtain the high-molecular surfactant.
2. The preparation method of the special graphene dispersion polymer according to claim 1, wherein the special graphene dispersion polymer comprises: the long-chain alkyl acrylate is one or more of the following: perfluoroalkyl ethyl acrylate, tridecyl methacrylate, tetradecyl methacrylate, hexadecyl perfluoroalkyl acrylate, octadecyl perfluoroalkyl acrylate, and docodecyl perfluoroalkyl acrylate.
3. The preparation method of the special graphene dispersion polymer according to claim 2, wherein the special graphene dispersion polymer comprises: the epoxy resin is one or a mixture of E type, F type and S type epoxy resin.
4. The preparation method of the special graphene dispersion polymer according to claim 1, wherein the special graphene dispersion polymer comprises: the neutralizing agent is one or more of triethylamine, ammonium diacetate and dimethylethanolamine.
5. The preparation method of the special graphene dispersion polymer according to claim 1, wherein the special graphene dispersion polymer comprises: the free radical initiator is one or a mixture of several of methyl ethyl ketone peroxide, benzoyl peroxide, ammonium persulfate and potassium persulfate.
6. The preparation method of the special graphene dispersion polymer according to claim 1, wherein the special graphene dispersion polymer comprises: the epoxy value of the epoxy resin was 0.51.
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CN202011279848.4A CN112625194A (en) | 2020-11-16 | 2020-11-16 | Preparation method of special dispersion polymer for graphene |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040116599A1 (en) * | 2001-03-10 | 2004-06-17 | Fuchang Liu | Epoxy polyester, its emulsion and its preparation as well as water-base coatings containing the emusion |
CN1970618A (en) * | 2006-11-28 | 2007-05-30 | 中国化工建设总公司常州涂料化工研究院 | Acrylic acid series non-aqueous dispersoid |
CN101029111A (en) * | 2007-04-06 | 2007-09-05 | 东南大学 | Production of fluoride acrylic-resin multipolymer anti-adhesive agent |
CN101096584A (en) * | 2007-06-22 | 2008-01-02 | 中国科学院广州化学研究所 | High-strength water-based itaconic acid epoxide resin grouting material and preparation method thereof |
CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
-
2020
- 2020-11-16 CN CN202011279848.4A patent/CN112625194A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040116599A1 (en) * | 2001-03-10 | 2004-06-17 | Fuchang Liu | Epoxy polyester, its emulsion and its preparation as well as water-base coatings containing the emusion |
CN1970618A (en) * | 2006-11-28 | 2007-05-30 | 中国化工建设总公司常州涂料化工研究院 | Acrylic acid series non-aqueous dispersoid |
CN101029111A (en) * | 2007-04-06 | 2007-09-05 | 东南大学 | Production of fluoride acrylic-resin multipolymer anti-adhesive agent |
CN101096584A (en) * | 2007-06-22 | 2008-01-02 | 中国科学院广州化学研究所 | High-strength water-based itaconic acid epoxide resin grouting material and preparation method thereof |
CN102718945A (en) * | 2012-06-12 | 2012-10-10 | 中国科学院宁波材料技术与工程研究所 | Itaconic acid-based epoxy resin composition and method for preparing cured substance |
CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
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