AU2021402785B2 - Polyurethane modified graphene microsheet and preparation method therefor - Google Patents
Polyurethane modified graphene microsheet and preparation method therefor Download PDFInfo
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- AU2021402785B2 AU2021402785B2 AU2021402785A AU2021402785A AU2021402785B2 AU 2021402785 B2 AU2021402785 B2 AU 2021402785B2 AU 2021402785 A AU2021402785 A AU 2021402785A AU 2021402785 A AU2021402785 A AU 2021402785A AU 2021402785 B2 AU2021402785 B2 AU 2021402785B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title abstract description 8
- 229920002635 polyurethane Polymers 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 230000018044 dehydration Effects 0.000 claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 238000004806 packaging method and process Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 239000002064 nanoplatelet Substances 0.000 claims description 50
- 239000004593 Epoxy Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 238000005452 bending Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 45
- 239000011159 matrix material Substances 0.000 description 26
- 238000000227 grinding Methods 0.000 description 18
- 238000001723 curing Methods 0.000 description 16
- 238000010422 painting Methods 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 239000013530 defoamer Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 229920006334 epoxy coating Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QPLNUHHRGZVCLQ-UHFFFAOYSA-K aluminum;[oxido(phosphonooxy)phosphoryl] phosphate Chemical compound [Al+3].OP([O-])(=O)OP([O-])(=O)OP(O)([O-])=O QPLNUHHRGZVCLQ-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Provided in the present disclosure are a polyurethane modified graphene microsheet and a preparation method therefor, the preparation method specifically comprising: adding graphene oxide and polyol into a three-neck flask according to a ratio, stirring and mixing same, and carrying out high-temperature vacuum dehydration at the same time; continuously mixing and stirring same after the high-temperature vacuum dehydration is finished, stopping heating, controlling the reaction temperature, cooling to room temperature, gradually adding isocyanate, monitoring the reaction temperature, adjusting the adding rate according to the reaction temperature, and controlling the reaction temperature to be maintained below T°C; and finally, after isocyanate is added and reacted for 10-30 min, controlling the reaction temperature within a range of 75-85°C by using oil bath heating, stirring and reacting for 1.5-3 h, and filtering and packaging by using a filter screen to complete the preparation of a polyurethane modified graphene microsheet. The polyurethane modified graphene microsheet prepared in the present disclosure is used in an epoxy resin coating material, and graphene may be uniformly oriented and distributed in a coating, thus greatly improving the corrosion resistance of the coating.
Description
Description
Polyurethane-Modified Graphene Nanoplatelet and Preparation Method Therefor
Technical Field
The present invention belongs to the field of paint, and relates to an epoxy paint modification
technology, in particular to a polyurethane-modified graphene nanoplatelet and a preparation
method therefor.
Background
As the environment protection policy becomes stricter in China, the need for application of
environment-friendly long-life protective paint in marine engineering equipment, ships, petrochemical industry, bridges and major equipment is increasingly urgent. The common solvent
anti-corrosive paint will be gradually eliminated from the market, and the solvent-free paint will be
used more and more widely, among which the solvent-free epoxy paint is one of the most widely
used varieties. The solvent-free epoxy paint has the advantages of strong adhesion, good corrosion
resistance and long service life. However, the paint has the disadvantages of large viscosity, short
mixed application period, low low-temperature curing speed, high brittleness of coating, poor ply
adhesion and not significant "labyrinth" shielding effect, and is far from meeting the use demand of
long-term corrosion protection of steel structure in a harsh environment. Graphene (Gr) has a
two-dimensional sheet structure composed of carbon atoms, with the characteristics of high strength,
strong physical barrier property and good thermal stability, and can improve the anti-settling
performance of paint in idea conditions when added to solvent-free epoxy paint, and significantly
improve the flexibility, corrosion resistance, and high and low temperature tolerance of the coating,
but greatly reduces the practical application effect of graphene nanoplatelets in coatings due to
defects of high surface polarity and easy aggregation and stacking, and further accelerates the
electrochemical corrosion of metal substrates because of formation of an electric channel by
bonding in sealing coatings due to conductivity, so the key to the popularization and application of
graphene-modified paint is to solve the long-term dispersion stability of graphene and the
compatibility with organic resin.
A patent for invention with a publication number of CN110128943A relates to a graphene
high-efficiency anti-corrosive paint, a preparation method therefor and products thereof. The
Description
graphene high-efficiency anti-corrosive paint prepared from solvent-based epoxy resin, anti-rust
pigment, organic solvent, curing agent, etc. enhances the long residual action of corrosion
protection to a certain extent by using the characteristics of graphene, but more solvents and
catalysts are used for dispersion reaction in the preparation method, so the environmental protection
is poor.
Summary
The purpose of the present invention is to provide a polyurethane-modified graphene
nanoplatelet and a preparation method therefor. The polyurethane-modified graphene nanoplatelet is
prepared from polyol, isocyanate and graphene oxide through processes of dehydration, addition
polymerization and purification. The polyurethane-modified graphene nanoplatelet prepared by the
present invention is used to modify epoxy resin, the graphene block polymer is formed by addition
polymerization of the polyurethane prepolymer-modified graphene oxide nanoplatelet and hydroxyl
groups on the epoxy molecular chain, which realizes chemical bonding between the graphene
nanoplatelet and the resin matrix so that the graphene nanoplatelet can be in completely directional
arrangement in the resin matrix to form a labyrinth effect so as to give full play to the shielding
property of the graphene nanoplatelet, thus greatly improving the corrosion protection of the
coating.
The purpose of the present invention is realized by the following technical solution:
The present invention also provides a preparation method for a polyurethane-modified
graphene nanoplatelet, comprising the following steps:
Step (1): adding graphene oxide and polyol to a three-necked flask in a proportion, stirring and
mixing, and conducting high-temperature vacuum dehydration;
Step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the reaction temperature to cool to room temperature, gradually adding
isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the
reaction temperature, and keeping the reaction temperature below TC;
Step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
Description
for 1.5-3 h, filtering and packaging with a filter screen, and cooling to room temperature after
packaging to complete the preparation of a polyurethane-modified graphene nanoplatelet.
Preferably, the polyol, the isocyanate and the graphene oxide are as follows by mass:
Polyol 60-100 Isocyanate 80-150
Graphene oxide 1-10.
Preferably, in step (1), the specific method for high-temperature vacuum dehydration
comprises: controlling the temperature within the range of 105-120°C by heating with an oil bath,
and conducting vacuum dehydration with a vacuum pump for 1.5-3 h.
Preferably, in step (3), the mesh number of the filter screen is 150-250.
Preferably, the polyol is any one or more of PTMG1000, PTMG650, PCDL1000,
diethanolamine and triethanolamine.
Preferably, the isocyanate is any one or more of HDI (1,6-hexamethylene diisocyanate), MDI
(methylene diphenyl diisocyanate), IPDI (isophorone diisocyanate), HMDI
(dicyclohexylmethane-4,4'-diisocyanate), TDI (toluene diisocynate), and LDI (L-lysine
diisocyanate).
Preferably, in step (2), the range of T is 70-80°C.
The present invention also provides a polyurethane-modified graphene nanoplatelet, which is
prepared by any one of the above preparation methods.
The present invention also provides an application of a polyurethane-modified graphene
nanoplatelet, which is used for modification of solvent-free epoxy paint. The polyurethane-modified
graphene nanoplatelet prepared by the present invention is used to modify solvent-free epoxy paint
by the following specific method:
Step (1): adding the polyurethane-modified graphene nanoplatelet to solvent-free epoxy resin
in the proportion of the formula, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of
the paint;
Step (2): adding wetting dispersant, anti-rust pigment and thickening agent to the matrix resin
in a proportion in one time, and grinding with a sand mill at room temperature for 2-5 h at a speed
controlled to 1000-2500 r/min;
Description
Step (3): in the grinding process, adding defoamer in batches with the usage amount controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less than 50
ptm, and filtering and packaging with a filter screen to prepare a paint matrix; Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified solvent-free epoxy paint which can be used for painting. Preferably, the components in the proportion of the formula are as follows by mass: Solvent-free epoxy resin 20-70 Polyurethane-modified graphene nanoplatelet 1-20 Wetting dispersant 0-5 Anti-rust pigment 1-40 Thickening agent 1-5 Defoamer 1-5 Curing agent 10-35. Preferably, the polyurethane-modified graphene nanoplatelet is mainly prepared from polyol, isocyanate and graphene oxide through processes of dehydration, addition polymerization and purification. Preferably, the solvent-free epoxy resin is any one or a combination of more of low molecular weight modified bisphenol A epoxy resin, low molecular weight modified bisphenol F epoxy resin, low molecular weight cycloaliphatic epoxy resin and low molecular weight phenolic modified epoxy resin. Preferably, the wetting dispersant is solvent-free associated polyurethane and/or solvent-free acrylic dispersant. Preferably, the anti-rust pigment is any one or a combination of more of zinc phosphate, aluminum triphosphate, glass flake, iron oxide red and zinc powder. Preferably, the defoamer is organic silicon defoamer containing hydrophobic ions. Preferably, the thickening agent is any one of organic soil, fumed silica and polyamide thickening agent. Preferably, the curing agent is any one or more of DETA (diethylenetriamine), TETA (triethylene tetramine), DEPA (diethylaminopropylamine), TEPA (tetraethylenepentamine), MDA
Description
(menthane diamine), IPDA (isophorone diamine), DDS (diaminodiphenyl sulfone) and DDM
(diaminodiphenyl-methane).
Preferably, the filter screen used in step (3) has 150-250 meshes, optimally 200 meshes.
The present invention also provides long-term anti-corrosive graphene-modified solvent-free
epoxy paint, which is prepared by any one of the above preparation methods.
The present invention has the following beneficial effects:
In the present invention, graphene is chemically grafted onto an epoxy molecular chain, and
the graphene nanoplatelet is subjected to limited dispersion by chemical bonding, which solves the
problem that graphene nanoplatelets are easy to aggregate and stack and realize the long-term stable
dispersion of graphene nanoplatelets in the paint. Moreover, in the present invention, the graphene
oxide nanoplatelet is chemically grafted onto an epoxy molecular chain using polyurethane
structure, then subjected to ring opening polymerization by an epoxy group and an amino group in
the curing agent to form a compact three-dimensional network structure and completely spread out
by chemical bonding, which can realize directional arrangement of the graphene nanoplatelet in the
coating so as to fully reflect the characteristics of ultra-high specific surface area, superhydrophobicity and high shielding property of the graphene, thus proving favorable guarantee
for the long-term corrosion protection of the coating, and can further improve the corrosion
resistance of the coating in combination with traditional anti-rust pigment.
Description of Drawings
Fig. 1 shows a low-magnification fracture morphology of pure epoxy resin in embodiments of
the present invention.
Fig. 2 shows a high-magnification fracture morphology of pure epoxy resin in embodiments of
the present invention.
Fig. 3 shows a low-magnification fracture morphology of graphene-modified epoxy resin in
embodiments of the present invention.
Fig. 4 shows a high-magnification fracture morphology of graphene-modified epoxy resin in
embodiments of the present invention.
Fig. 5 shows mechanical properties of modified and unmodified epoxy resin.
Fig. 6 shows a macro morphology of a salt spray test of a graphene-modified solvent-free
Description
epoxy coating, wherein Fig. 6(a) shows an original morphology of a coating before a salt spray test,
and Fig. 6(b) shows a corrosion morphology of a coating after a salt spray test.
Fig. 7 shows a macro morphology of a salt spray test of a solvent-free epoxy coating of a
reference example, wherein Fig. 7(a) shows an original morphology of a coating before a salt spray
test, and Fig. 7(b) shows a corrosion morphology of a coating after a salt spray test.
Detailed Description
The implementation modes of the present invention are further described below in detail in
combination with drawings and the embodiments. The following embodiments are only used for
illustrating the present invention, not used for limiting the scope of the present invention.
A preparation method for a polyurethane-modified graphene nanoplatelet is as follows:
Embodiment 1:
Step (1): adding 1 g of graphene oxide and 60 g of polyol to a three-necked flask, stirring and
mixing, controlling the temperature within the range of 105-120°C by heating with an oil bath, and
conducting vacuum dehydration with a vacuum pump for 1.5-3 h;
Step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the reaction temperature to cool to room temperature, gradually adding 80 g of
isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the
reaction temperature, and keeping the reaction temperature below TC;
Step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
for 1.5-3 h, and filtering and packaging with a 200-mesh filter screen to complete the preparation of
a polyurethane-modified graphene nanoplatelet.
Embodiment 2:
Step (1): adding 5 g of graphene oxide and 70 g of polyol to a three-necked flask, stirring and
mixing, controlling the temperature within the range of 105-120°C by heating with an oil bath, and
conducting vacuum dehydration with a vacuum pump for 1.5-3 h;
Step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the reaction temperature to cool to room temperature, gradually adding 100 g of
Description
isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the
reaction temperature, and keeping the reaction temperature below TC;
Step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
for 1.5-3 h, and filtering and packaging with a 200-mesh filter screen to complete the preparation of
a polyurethane-modified graphene nanoplatelet.
Embodiment 3:
Step (1): adding 8 g of graphene oxide and 80 g of polyol to a three-necked flask, stirring and
mixing, controlling the temperature within the range of 105-120°C by heating with an oil bath, and
conducting vacuum dehydration with a vacuum pump for 1.5-3 h;
Step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the reaction temperature to cool to room temperature, gradually adding 130 g of
isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the
reaction temperature, and keeping the reaction temperature below TC;
Step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
for 1.5-3 h, and filtering and packaging with a 200-mesh filter screen to complete the preparation of
a polyurethane-modified graphene nanoplatelet.
Embodiment 4:
Step (1): adding 10 g of graphene oxide and 100 g of polyol to a three-necked flask, stirring
and mixing, controlling the temperature within the range of 105-120°C by heating with an oil bath,
and conducting vacuum dehydration with a vacuum pump for 1.5-3 h;
Step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the reaction temperature to cool to room temperature, gradually adding 140 g of
isocyanate, monitoring the reaction temperature, adjusting the addition rate according to the
reaction temperature, and keeping the reaction temperature below TC;
Step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
for 1.5-3 h, and filtering and packaging with a 200-mesh filter screen to complete the preparation of
a polyurethane-modified graphene nanoplatelet.
Description
Embodiments in which the polyurethane-modified graphene nanoplatelet prepared above is
used to modify solvent-free epoxy paint are as follows:
Embodiment 5: adding 1 g of polyurethane-modified graphene nanoplatelet to 20 g of
solvent-free epoxy resin, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of the
paint;
Step (2): adding 1 g of wetting dispersant, 1 g of anti-rust pigment and 1 g of thickening agent
to the matrix resin in one time, and grinding with a sand mill at room temperature for 2-5 h at a
speed controlled to 1000-2500 r/min;
Step (3): in the grinding process, adding 1 g of defoamer in batches with the usage amount
controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less
than 50 pm, and filtering and packaging with a 200-mesh filter screen to prepare a paint matrix;
Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with 10
g of curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified
solvent-free epoxy paint which can be used for painting.
Embodiment 6: adding 2 g of polyurethane-modified graphene nanoplatelet to 25 g of
solvent-free epoxy resin, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of the
paint;
Step (2): adding 2 g of wetting dispersant, 1 g of anti-rust pigment and 2 g of thickening agent
to the matrix resin in one time, and grinding with a sand mill at room temperature for 2-5 h at a
speed controlled to 1000-2500 r/min;
Step (3): in the grinding process, adding 1 g of defoamer in batches with the usage amount
controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less
than 50 pm, and filtering and packaging with a 200-mesh filter screen to prepare a paint matrix;
Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with 10
g of curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified
solvent-free epoxy paint which can be used for painting.
Embodiment 7: adding 10 g of polyurethane-modified graphene nanoplatelet to 25 g of
solvent-free epoxy resin, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of the
paint;
Description
Step (2): adding 3 g of anti-rust pigment and 2 g of thickening agent to the matrix resin in one
time, and grinding with a sand mill at room temperature for 2-5 h at a speed controlled to
1000-2500 r/min;
Step (3): in the grinding process, adding 2 g of defoamer in batches with the usage amount
controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less
than 50 pm, and filtering and packaging with a 200-mesh filter screen to prepare a paint matrix;
Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with 10
g of curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified
solvent-free epoxy paint which can be used for painting.
Embodiment 8: adding 15 g of polyurethane-modified graphene nanoplatelet to 50 g of
solvent-free epoxy resin, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of the
paint;
Step (2): adding 3 g of anti-rust pigment and 3 g of thickening agent to the matrix resin in one
time, and grinding with a sand mill at room temperature for 2-5 h at a speed controlled to
1000-2500 r/min;
Step (3): in the grinding process, adding 4 g of defoamer in batches with the usage amount
controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less
than 50 m, and filtering and packaging with a 200-mesh filter screen to prepare a paint matrix;
Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with 10
g of curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified
solvent-free epoxy paint which can be used for painting.
Embodiment 9: adding 20 g of polyurethane-modified graphene nanoplatelet to 70 g of
solvent-free epoxy resin, and stirring at 60°C-80°C for 20-60 min to prepare matrix resin of the
paint;
Step (2): adding 4 g of anti-rust pigment and 5 g of thickening agent to the matrix resin in one
time, and grinding with a sand mill at room temperature for 2-5 h at a speed controlled to
1000-2500 r/min;
Step (3): in the grinding process, adding 4 g of defoamer in batches with the usage amount
controlled to not more than 5% of the total amount of the formula, grinding until the fineness is less
than 50 m, and filtering and packaging with a 200-mesh filter screen to prepare a paint matrix;
Description
Step (4): stirring and curing the paint matrix for 30-40 min before painting, and mixing with 10
g of curing agent in the above proportion to obtain long-term anti-corrosive graphene-modified
solvent-free epoxy paint which can be used for painting.
Structures obtained by electron microscope scanning of the solvent-free epoxy paint modified
by the polyurethane-modified graphene nanoplatelet prepared in embodiment 5 of the present
invention and the pure solvent-free epoxy paint are shown in Fig. 1 to Fig. 4. It can be seen from
Fig. 1 to Fig. 4 that the fracture morphology of the pure epoxy resin is smooth and flat without
ductile failure characteristics such as diffusion cracks and steps, which belongs to obvious brittle
fracture, the fracture morphology of cured resin shows structural features such as a large number of
vortexes, ditches and steps after the graphene oxide nanoplatelet is chemically grafted onto an
epoxy molecular chain using polyurethane structure, indicating that the material is subjected to
resistance in different directions when subjected to mechanical failure and diffused irregularly in the
stress failure direction, showing obvious ductile fracture characteristics. This is due to the large
specific surface area and excellent mechanical properties of the directionally arranged graphene
nanoplatelet structure, which plays an obvious strengthening role in epoxy resin, thus enhancing the
toughness of epoxy resin and improving the defect of brittleness of epoxy resin.
Tensile and bending properties of the pure epoxy resin material and the graphene-modified
epoxy resin material prepared in embodiment 5 are tested with reference to Standard GBT
228.1-2010 "Metallic materials - Tensile testing - Part 1: Method of test at room temperature" and
Standard GB/T 232-2010 "Metallic materials - Bend test", and the results are shown in Fig. 5.
Compared with the pure epoxy resin, the epoxy resin with the polyurethane-modified graphene
nanoplatelet has higher tensile strength and bending strength and better comprehensive mechanical
properties.
Different coating templates prepared by applying the graphene-modified solvent-free epoxy
paint prepared in embodiment 5 and the epoxy paint without the polyurethane-modified graphene
nanoplatelet to Q235 steel plates are subjected to the comparative test of salt spray resistance with
reference to Standard GB/T 10125-2012 "Corrosion tests in artificial atmospheres - Salt spray tests",
and the macro morphologies before and after standing for 5000 h in the atmosphere of neutral salt
spray are shown in the figures. It can be seen that the corrosion diffusion of the crossed part of the
solvent-free epoxy coating with the polyurethane-modified graphene nanoplatelet is significantly
Description
better than that of the solvent-free epoxy coating without modified graphene nanoplatelet, the
corrosion width is smaller, and the diffusion corrosion is slighter at the intersection of two scratches,
so it can be determined that the uniformly distributed graphene nanoplatelets have good shielding
property, which can significantly improve the corrosion resistance of the coating.
The above embodiments are only used for describing the present invention rather than limiting
the same. Although the present invention is described in detail with reference to the embodiments,
those ordinary skilled in the art shall understand that the technical solution of the present invention
can be combined, amended or equivalently replaced without departing from the spirit and the scope
of the technical solution of the present invention. The combination, amendment or equivalent
replacement shall be covered within the scope of the claims of the present invention.
Claims (7)
1. A preparation method for a polyurethane-modified graphene nanoplatelet, comprising the
following steps:
step (1): adding graphene oxide and polyol to a three-necked flask in a proportion, stirring and
mixing, and conducting high-temperature vacuum dehydration;
step (2): continuing mixing and stirring after high-temperature vacuum dehydration, stopping
heating, controlling the temperature to cool to room temperature, gradually adding isocyanate,
monitoring the reaction temperature, adjusting the addition rate according to the reaction
temperature, and keeping the reaction temperature below TC and wherein the range of T is
-80'C;
step (3): after adding isocyanate for reaction for 10-30 min, controlling the reaction
temperature within the range of 75-85C by heating with an oil bath, keeping the stirring reaction
for 1.5-3 h, and filtering and packaging with a filter screen to complete the preparation of a
polyurethane-modified graphene nanoplatelet.
2. The preparation method for a polyurethane-modified graphene nanoplatelet according to
claim 1, wherein the polyol, the isocyanate and the graphene oxide are as follows by mass:
polyol 60-100 isocyanate 80-150
graphene oxide 1-10.
3. The preparation method for a polyurethane-modified graphene nanoplatelet according to
claim 1, wherein in step (1), the specific method for high-temperature vacuum dehydration
comprises: controlling the temperature within the range of 105-120°C by heating with an oil bath,
and conducting vacuum dehydration with a vacuum pump for 1.5-3 h.
4. The preparation method for a polyurethane-modified graphene nanoplatelet according to
claim 1, wherein in step (3), the mesh number of the filter screen is 150-250.
5. The preparation method for a polyurethane-modified graphene nanoplatelet according to
claim 1, wherein the polyol is any one or more of PTMG100, PTMG650, PCDL1000,
diethanolamine and triethanolamine.
6. The preparation method for a polyurethane-modified graphene nanoplatelet according to
claim 1, wherein the isocyanate is any one or more of HDI, MDI, IPDI, HMDI, TDI and LDI.
Claims
7. A polyurethane-modified graphene nanoplatelet, being prepared by the preparation method
of any one of claims 1-6.
DrawingsofofDescription Drawings Description
I
SU8010 3.0kV 12. 9mm x500 SE(L) 100um Fig. 1 Fig. 1
SU8010 3.0kV 12.9mm x1.00k SE(L) 50. Oum
Fig. 2 Fig. 2
DrawingsofofDescription Drawings Description
SU8010 3.0kV 13.3mm x500 SE(L) 100um
Fig. 3 Fig. 3
I SU8010 3.0kV 13. 3mm x1.00k SE(L) 50. Oum
Fig. 4 Fig. 4
DrawingsofofDescription Drawings Description
100 100 Tensile Tensile 拉伸强 度 strength strength 90 90 弯曲强 度 Bending Bending strength strength 80 80
70 70
60 60 /MPa
50 50
40 40
30 30
20 20
10 10
0 0 纯 环epoxy Pure Pure 氧树 epoxy 脂 resin resin 石墨 烯改性环氧 Graphene-modified 树脂 epoxy resin Graphene-modified epoxy resin
Fig. 5 Fig. 5
a a b b
Fig. 6 Fig. 6
3
DrawingsofofDescription Drawings Description
a a b b
Fig. 7 Fig. 7
4
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| CN202011476438.9A CN112608436A (en) | 2020-12-14 | 2020-12-14 | Polyurethane modified graphene microchip and preparation method thereof |
| CN202011476438.9 | 2020-12-14 | ||
| PCT/CN2021/137546 WO2022127745A1 (en) | 2020-12-14 | 2021-12-13 | Polyurethane modified graphene microsheet and preparation method therefor |
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| CN115449248A (en) * | 2022-10-14 | 2022-12-09 | 山东京博装备制造安装有限公司 | Graphene heavy-duty anticorrosive paint for outer wall of earthing storage tank |
| CN116284655B (en) * | 2023-01-10 | 2024-01-09 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
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| CN103408718B (en) * | 2013-08-05 | 2015-10-28 | 江苏大学 | A kind of preparation method of graphene oxide-polyurethane foam material and application thereof |
| CN104693989A (en) * | 2015-03-26 | 2015-06-10 | 东南大学 | Preparation method for graphene modified polyurethane-epoxy resin waterborne damping coating |
| EP3208300A1 (en) * | 2016-02-17 | 2017-08-23 | Repsol, S.A. | Polymer compositions of polyol ether and graphene oxide for polyurethane applications |
| CN106220826B (en) * | 2016-08-04 | 2019-10-11 | 中海油常州涂料化工研究院有限公司 | A kind of preparation method for the water-soluble isocyanate curing agent that graphene is modified |
| WO2018089638A1 (en) * | 2016-11-09 | 2018-05-17 | Basf Se | Polyurethane comprising graphene nano structure |
| CN106832183B (en) * | 2016-12-14 | 2019-12-24 | 武汉科利尔新材料有限公司 | Graphene modified cathode polyurethane electrophoretic resin and electrophoretic paint composition thereof |
| CN106832189A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene compound polyurethane material |
| GB2565048B (en) * | 2017-07-26 | 2023-04-19 | Talga Tech Limited | Functionalised graphene composition |
| CN107778449A (en) * | 2017-09-20 | 2018-03-09 | 青岛瑞利特新材料科技有限公司 | A kind of graphene modified aqueous polyurethane resin and preparation method thereof |
| CN109749582A (en) * | 2019-01-22 | 2019-05-14 | 雷洪军 | A kind of graphene heat radiation coating and preparation method thereof |
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| CN112538304A (en) * | 2019-09-20 | 2021-03-23 | 南京博科新材料产业研究院有限公司 | Modified graphene epoxy composite anticorrosive paint and preparation method thereof |
| CN111410905A (en) * | 2020-04-26 | 2020-07-14 | 朱建程 | Functional graphene modified polyurethane conductive anticorrosive coating and preparation method thereof |
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