CN116004113B - Anticorrosive paint for highway bridge crash barrier and preparation method thereof - Google Patents
Anticorrosive paint for highway bridge crash barrier and preparation method thereof Download PDFInfo
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- CN116004113B CN116004113B CN202310019647.8A CN202310019647A CN116004113B CN 116004113 B CN116004113 B CN 116004113B CN 202310019647 A CN202310019647 A CN 202310019647A CN 116004113 B CN116004113 B CN 116004113B
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- 239000003973 paint Substances 0.000 title claims abstract description 66
- 230000004888 barrier function Effects 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 32
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 28
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229950008618 perfluamine Drugs 0.000 claims abstract description 17
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 claims abstract description 17
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 235000010980 cellulose Nutrition 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical group [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 108010059892 Cellulase Proteins 0.000 claims description 6
- 229940106157 cellulase Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkyl ketene dimer Chemical compound 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 4
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- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- 230000035515 penetration Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000003628 erosive effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 238000002161 passivation Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Paints Or Removers (AREA)
Abstract
The application relates to the field of anti-corrosion paint, and particularly discloses an anti-corrosion paint for a highway bridge anti-collision guardrail and a preparation method thereof. The anticorrosive paint for the highway bridge anti-collision guardrail comprises 2-4 parts of graphene, 1-3 parts of nano silicon, 7-8 parts of polydopamine, 1.5-3 parts of modified cellulose, 2-4 parts of resin material, 0.5-0.8 part of perfluoro tripropylamine, 1 part of dispersing agent, 2-6 parts of ionic liquid solvent, 1-3 parts of dioctyl phthalate and the balance of deionized water, wherein the modified cellulose is modified hydrophobic nano cellulose; the preparation method comprises the following steps: after the graphene and the nano silicon have better dispersibility through ball milling, adding the graphene and the nano silicon into a solution cooled to room temperature and dissolved with the modified nano cellulose, adding a dispersing agent and perfluoro tripropylamine for ultrasonic dispersion, and sequentially adding polydopamine, a resin material and dioctyl phthalate to obtain the anti-corrosion coating. The composition provided by the application can be used for corrosion prevention of highway bridge guardrails, and has the advantages of good interface binding force and corrosion resistance.
Description
Technical Field
The application relates to the field of anti-corrosion paint, in particular to anti-corrosion paint for a highway bridge anti-collision guardrail and a preparation method thereof.
Background
The highway bridge anti-collision guardrail is common equipment in urban construction, is used as an important component in highway and bridge construction, has the effects of inducing road alignment and improving road area environment, and plays an important role in guiding people and vehicles to pass and protecting the safety of the pedestrians and vehicles. The anticollision barrier is generally all installed in outdoor environment, and the weather is drenched in the weather, and the difference in temperature that the change of season day night caused all can produce different degree damage and oxidation to the guardrail surface, causes anticollision barrier's corrosion, influences the road appearance, reduces the warning effect to driving and pedestrian, very easily causes accident potential.
At present, the domestic anticorrosion work on the anti-collision guardrail is mainly performed by utilizing a metal coating or an organic material composite coating, so that a large amount of energy is consumed, and when the guardrail is used for a long time, under the effects of sunlight insolation, wind and rain erosion, thermal expansion and contraction, automobile exhaust and acid rain salt mist, the coating is lost, the interfacial binding force is reduced, and the coating falls off to prevent the guardrail from losing the anticorrosion capability.
Disclosure of Invention
The application provides an anticorrosive paint for a highway bridge anti-collision guardrail and a preparation method thereof, which aim to improve the acid and alkali corrosion resistance of the anticorrosive paint for the highway bridge anti-collision guardrail and strengthen the interfacial binding force.
In a first aspect, the application provides an anticorrosive paint for a highway bridge crash barrier, which adopts the following technical scheme: the anticorrosive paint for the public road bridge roof beam crash barrier comprises 2-4 parts of graphene, 1-3 parts of nano silicon, 7-8 parts of polydopamine, 1.5-3 parts of modified cellulose, 2-4 parts of resin material, 0.5-0.8 part of perfluoro tripropylamine, 1 part of dispersing agent, 2-6 parts of ionic liquid solvent, 1-3 parts of dioctyl phthalate and the balance deionized water, wherein the modified cellulose is modified hydrophobic nano cellulose.
By adopting the technical scheme, a large number of intramolecular and intermolecular hydrogen bonds can be formed in the modified nanocellulose, the modified nanocellulose is combined with a resin material in the coating to form a composite net structure, and other materials are used as framework materials and are combined on the framework materials in a mode of being wrapped by the composite or being grafted by covalent bonds. The polydopamine is added as a reinforcing material, a large number of active functional groups exist on the surface of the polydopamine, and the polydopamine and the modified nanocellulose are grafted together to form extremely strong adhesive force with a metal substrate, the polydopamine can be adhered to the surface of skeleton raw materials such as modified cellulose, so that the binding force between an anti-corrosion coating and the metal substrate is improved, and meanwhile, the long polydopamine molecular long chain and the resin material molecular long chain are wound into a network structure to enhance the toughness and the shock resistance of the coating, so that the interfacial binding force between the coating and the metal is enhanced, and the corrosion resistance of the coating is also enhanced. The rest of the reinforcing materials of graphene and nano-silicon can fill microcracks and pore channels generated in the curing process of the resin, and the reinforcing materials of graphene and nano-silicon act together with polydopamine adhered to the surface of modified cellulose, so that the excellent permeation resistance of graphene and nano-silicon is utilized to block permeation of corrosion small molecules into the coating, and corrosion resistance is improved; the nano silicon and the perfluoro tripropylamine provide a large amount of silicon and fluorine elements, and the nano silicon and the perfluoro tripropylamine are attached to a framework material, so that the surface energy of the coating is reduced, corrosion molecules are difficult to spread and permeate on the surface of the coating, and the hydrophobic and oleophobic capacity of the coating is improved; while improving the dispersibility of graphene and nano silicon, dioctyl phthalate enhances the flexibility of the resin material and modified nano cellulose, and improves the impact strength of the wear-resistant coating.
Optionally, the modified nanocellulose is prepared by the steps of:
(1) Removing impurities on the surface of the material by grinding, cleaning and heating microcrystalline cellulose;
(2) Placing the treated cellulose into a mixed solution of acetic acid and cellulase for enzymolysis for 30-40min at 50-60 ℃;
(3) Diluting with water to terminate the reaction, continuously centrifuging and washing, concentrating and drying to obtain nanocellulose;
(4) At 80-105 ℃, sodium carbonate is used as a catalyst, alkyl ketene dimer is added and continuously stirred for 20-24 hours, and then concentrated and dried to prepare the modified nanocellulose.
By adopting the technical scheme, the cellulose has good crystallinity and dispersibility by adding acetic acid and cellulase for pretreatment, the agglomeration phenomenon among particles caused by a large amount of hydrophilic free hydroxyl groups in the cellulose is improved, the combination of other raw materials in the coating and nano cellulose is facilitated, the cellulose treated by the cellulase also has better flexibility, alkyl ketene dimer is added subsequently, particles of the cellulose can be adsorbed with rich carboxyl groups on the cellulose, and finally the hydrophobically modified nano cellulose is obtained.
Optionally, the resin material comprises an epoxy resin.
By adopting the technical scheme, the epoxy resin has better bonding strength and chemical resistance, is suitable for acting together with other raw materials as a matrix, and enhances the interface bonding force between the corrosion-resistant coating and metal.
Optionally, the resin material further comprises one or two of polyamide resin and phenolic resin.
By adopting the technical scheme, the polyamide resin has the excellent performances of strong adhesive force, water resistance and folding resistance, the phenolic resin has better high temperature resistance and bonding capability, and the two resins and the epoxy resin are added to act together, so that the corrosion-resistant coating has better chemical stability, and the interface bonding capability of the wear-resistant coating and metal is enhanced.
Optionally, the ionic liquid solvent is 1-butyl-3 methylimidazole chloride.
By adopting the technical scheme, the 1-butyl-3-methylimidazole chloride has higher cellulose dissolving capacity, the subsequent steps can be conveniently and smoothly carried out, and meanwhile, the 1-butyl-3-methylimidazole chloride can form intermolecular acting force with a resin material, so that the coating has higher thermal stability and toughness.
Optionally, the anticorrosive paint further comprises silicon carbide, zinc oxide and aluminum tripolyphosphate.
By adopting the technical scheme, the color of the anticorrosive paint is increased, the anticorrosive paint has strong chelating ability with metal ions, and can form a passivation layer on the surface of metal by coaction with a resin material, so that the anticorrosive ability of the paint is enhanced.
Optionally, the dispersing agent is one or two of a silane coupling agent and a titanium coupling agent.
By adopting the technical scheme, the silane coupling agent and the titanium coupling agent are added to increase the dispersibility of graphene and nano-silicon in the coating, enhance the bonding force between the framework material and the graphene and between the framework material and the nano-silicon, enhance the bonding capability of cellulose and resin, form a chemical bond with higher strength between interfaces, and improve the interface bonding capability with metal.
In a second aspect, the application provides a preparation process of an anticorrosive paint for a highway bridge anti-collision guardrail, which adopts the following technical scheme:
a preparation process of an anticorrosive paint for a highway bridge anti-collision guardrail comprises the following steps:
(1) Ball milling graphene and deionized water for 10-12 hours in a ratio of 1:20-40, adding nano silicon, and continuing ball milling for 2-3 hours;
(2) Heating an ionic liquid solvent to 100-110 ℃, then putting the ionic liquid solvent into modified nanocellulose for dissolution, cooling to room temperature, and then adding the graphene, the nano silicon powder, the perfluoro tripropylamine and the dispersing agent which are ball-milled in the step (1), and performing ultrasonic dispersion to obtain a mixed dispersion liquid;
(3) And sequentially adding polydopamine, a resin material and dioctyl phthalate into the mixed dispersion liquid, and stirring and grinding to obtain the anticorrosive paint for the highway bridge crash barrier.
By adopting the technical scheme, the modified nanocellulose, the graphene and the nano silicon powder can be well dispersed in the paint, so that the anticorrosive paint which is tightly connected with the metal layer and has high toughness and high impact strength for the highway bridge anti-collision guardrail is obtained.
In summary, the application has the following beneficial effects:
1. because the nano silicon and the perfluoro tripropylamine are adopted in the application, the wear-resistant coating has the characteristics of oleophobic and hydrophobic properties, so that the surface of the wear-resistant coating is not easy to adhere, and the corrosion resistance and pollution resistance of the wear-resistant coating are enhanced; the nano silicon and the graphene are adhered to the modified nano cellulose in a covalent bond mode and uniformly distributed, and are combined with the resin material and the polydopamine to form a compact structure through overlapping and winding, so that the anticorrosive paint for the highway bridge anti-collision guardrail, which has good toughness, is not easy to crack and is tightly combined with a metal interface, is obtained.
2. In the application, the epoxy resin is preferably adopted, and the epoxy resin is taken as a matrix to better act together with the nanocellulose to improve the interface bonding capability because the epoxy resin has good bonding capability.
3. According to the method disclosed by the application, the graphene has higher stripping degree through ball milling, so that the dispersibility of the graphene in the modified nanocellulose and the resin material is improved, the anti-corrosion coating has good impact strength and toughness, and the stability of the anti-corrosion coating is enhanced.
Detailed Description
The present application will be described in further detail with reference to examples.
In the present application, each raw material is commercially available.
Preparation example of modified nanocellulose
Preparation example 1
The modified nanocellulose is prepared by the following steps:
(1) Taking 5kg of microcrystalline cellulose, grinding for 2.5 hours, washing and filtering with deionized water, and heating to 120 ℃ to remove impurities on the surface of the material;
(2) Placing the treated cellulose into a mixed solution of 2kg of acetic acid, 0.5kg of cellulase and 5kg of deionized water for enzymolysis for 30min at 50 ℃;
(3) Diluting with water to terminate the reaction, centrifuging with deionized water at 1500r/min, and concentrating and drying at 50deg.C to obtain nanocellulose;
(4) Taking 1kg of sodium carbonate as a catalyst at 80 ℃, adding 10kg of alkyl ketene dimer, continuously stirring for 20 hours, concentrating and drying to obtain the modified nanocellulose.
Preparation example 2
The modified nanocellulose is prepared by the following steps:
(1) Taking 5kg of microcrystalline cellulose, grinding for 2.5 hours, washing and filtering with deionized water, and heating to 120 ℃ to remove impurities on the surface of the material;
(2) Placing the treated cellulose into a mixed solution of 2kg of acetic acid, 0.5kg of cellulase and 5kg of deionized water for enzymolysis for 40min at 60 ℃;
(3) Diluting with water to terminate the reaction, continuously centrifuging with deionized water at 1500r/min, and concentrating and drying at 50deg.C to obtain nanocellulose;
(4) Taking 1kg of sodium carbonate as a catalyst at 105 ℃, adding 10kg of alkyl ketene dimer, continuously stirring for 24 hours, concentrating and drying to obtain the modified nanocellulose.
Examples
Example 1
(1) Ball milling graphene and deionized water for 10 hours in a ratio of 1:20, adding nano silicon, and continuing ball milling for 2 hours;
(2) Heating 1-butyl-3 methylimidazole chloride to 100 ℃, then putting the mixture into modified nanocellulose for dissolution, cooling to room temperature, then adding the graphene and the nano silicon powder which are ball-milled in the step (1), perfluoro tripropylamine and isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate, and performing ultrasonic dispersion to obtain a mixed dispersion;
(3) And sequentially adding polydopamine, epoxy resin and dioctyl phthalate into the mixed dispersion liquid, and stirring at 80 ℃ for 1h to obtain the anticorrosive paint for the highway bridge anti-collision guardrail.
The modified nanocellulose prepared in preparation example 1 was used in this example.
Example 2
(1) Ball-milling graphene and deionized water for 11 hours in a ratio of 1:30, adding nano silicon, and continuing ball milling for 2.5 hours;
(2) Heating 1-butyl-3 methylimidazole chloride to 105 ℃, then putting the mixture into modified nanocellulose for dissolution, cooling to room temperature, then adding the graphene and the nano silicon powder which are ball-milled in the step (1), perfluoro tripropylamine and isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate, and performing ultrasonic dispersion to obtain a mixed dispersion;
(3) And sequentially adding polydopamine, epoxy resin and dioctyl phthalate into the mixed dispersion liquid, and stirring at 80 ℃ for 1h to obtain the anticorrosive paint for the highway bridge anti-collision guardrail.
The modified nanocellulose prepared in preparation example 1 was used in this example.
Example 3
(1) Ball-milling graphene and deionized water for 12 hours in a ratio of 1:40, adding nano silicon, and continuing ball milling for 3 hours;
(2) Heating 1-butyl-3 methylimidazole chloride to 110 ℃, then putting the mixture into modified nanocellulose for dissolution, cooling to room temperature, adding the graphene and the nano silicon powder which are ball-milled in the step (1), perfluoro tripropylamine and isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate, and performing ultrasonic dispersion to obtain a mixed dispersion;
(3) And sequentially adding polydopamine, epoxy resin and dioctyl phthalate into the mixed dispersion liquid, and stirring at 80 ℃ for 1h to obtain the anticorrosive paint for the highway bridge anti-collision guardrail.
The modified nanocellulose prepared in preparation example 2 was used in this example.
TABLE 1 raw materials and weights (kg) of the raw materials in examples 1 to 3
| Raw materials | Example 1 | Example 2 | Example 3 |
| Graphene | 2 | 3 | 4 |
| Nano silicon | 3 | 2 | 1 |
| Polydopamine | 7 | 7 | 8 |
| Modified nanocellulose | 3 | 2 | 1.5 |
| Resin material | 3 | 2 | 4 |
| Perfluoro tripropylamine | 0.5 | 0.7 | 0.8 |
| Dispersing agent | 1.5 | 1 | 2 |
| 1-butyl-3-methylimidazole chloride | 2 | 6 | 4 |
| Dioctyl phthalate | 1 | 2 | 3 |
Example 4
An anticorrosive paint for a highway bridge crash barrier is different from example 1 in that 1.5kg of epoxy resin and 1.5kg of polyurethane resin are used as raw materials.
Example 5
An anticorrosive paint for a highway bridge crash barrier is different from example 1 in that 1.5kg of epoxy resin and 1.5kg of phenolic resin are adopted as raw materials.
Example 6
An anticorrosive paint for a highway bridge crash barrier is different from the anticorrosive paint in embodiment 1 in that 1kg of epoxy resin, 1kg of polyurethane resin and 1kg of phenolic resin are adopted as raw materials.
Example 7
An anticorrosive paint for a highway bridge crash barrier is different from example 6 in that a 3-aminopropyl triethoxysilane coupling agent is used as a dispersing agent in a raw material.
Example 8
An anticorrosive paint for a highway bridge crash barrier, which is different from example 6 in that the dispersant in the raw material is 1kg of 3-aminopropyl triethoxysilane coupling agent and 0.5kg of isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate.
Example 9
The anticorrosive paint for the public road bridge roof beam crash barrier is different from the embodiment 8 in that silicon carbide, zinc oxide and aluminum tripolyphosphate are added, and the preparation steps are as follows:
(1) Ball milling graphene and deionized water for 10 hours in a ratio of 1:20, adding nano silicon, and continuing ball milling for 2 hours;
(2) Heating 1-butyl-3 methylimidazole chloride to 100 ℃, then putting the mixture into modified nanocellulose for dissolution, cooling to room temperature, and then adding the graphene, the nano silicon powder, the perfluoro tripropylamine and the dispersing agent which are ball-milled in the step (1), and performing ultrasonic dispersion to obtain a mixed dispersion;
(3) And sequentially adding polydopamine, a resin material, dioctyl phthalate, 0.5kg of silicon carbide, 0.5kg of zinc oxide and 0.5kg of aluminum tripolyphosphate into the mixed dispersion liquid, and stirring at 80 ℃ for 1h to obtain the anticorrosive paint for the highway bridge crash barrier.
Comparative example
Comparative example 1
An anticorrosive paint for a highway bridge crash barrier is different from example 1 in that graphene and nano silicon are not added.
Comparative example 2
An anticorrosive paint for a highway bridge crash barrier, which is different from example 1 in that polydopamine is not added.
Comparative example 3
An anticorrosive paint for a highway bridge crash barrier, which is different from example 1 in that modified hydrophobic nanocellulose is not added.
Comparative example 4
An anticorrosive paint for a highway bridge crash barrier is different from example 1 in that the added cellulose is nano cellulose which is not hydrophobically modified.
Comparative example 5
An anticorrosive paint for a highway bridge crash barrier, which is different from example 1 in that perfluoro tripropylamine and dioctyl phthalate are not added.
Performance test
Detection method/test method
Impact strength test: an impact resistance tester is adopted, and the method is referred to GB/T1732-1993 'paint film impact resistance testing method';
adhesion test: the test method refers to GB/T5210-2006, adhesion test of paint and varnish pulling-off method;
corrosion resistance: acid and alkali resistance were tested, using the immersion method, see GB/T9274-1988 determination of liquid Medium resistance of paints and varnishes.
TABLE 2 Performance test results
As can be seen by combining examples 1-3 and comparative example 2 and combining table 2, the impact resistance, adhesion and corrosion resistance of examples 1-3 are far higher than those of comparative example 2, which indicates that adding polydopamine into the anticorrosive paint can form covalent bonds with modified nanocellulose in the paint and resin materials, long chains are wound to form a network structure, the impact strength of the anticorrosive paint is enhanced, and polydopamine is grafted on the modified nanocellulose to form extremely strong adhesion with metal materials, so that the binding force between the materials and the anticorrosive paint layer is improved.
As can be seen by combining examples 1-3 and comparative examples 3-4 and combining Table 2, the impact resistance, adhesive force and corrosion resistance of examples 1-3 are far higher than those of comparative examples 3-4, and it is demonstrated that the modified cellulose with better properties can be obtained by modifying nanocellulose in the application, and the modified cellulose is added into the anticorrosive paint to make the anticorrosive paint have good toughening and hydrophobic effects, so that the hydrophobicity of the anticorrosive paint can be improved, the adhesive capacity of the anticorrosive paint and a matrix can be enhanced by introducing functional groups, thus the corrosion resistance of the anticorrosive paint is improved, and the binding force of the anticorrosive paint and a metal base layer is enhanced.
As can be seen by combining examples 1-3 and comparative example 5 and combining Table 2, the impact resistance, adhesion and corrosion resistance of examples 1-3 are significantly higher than those of comparative example 5, and the coatings are in punctiform corrosion without dioctyl phthalate and perfluorotripropylamine, and the impact resistance is reduced compared with that of examples 1-3, which means that dioctyl phthalate can be added to interact with hydrophobically modified cellulose to improve the adhesion and impact resistance of the anticorrosive paint, and perfluorotripropylamine provides a large amount of fluorine elements to adhere to the framework material to prevent penetration of corrosive molecules so as to further enhance the anticorrosive ability of the anticorrosive paint.
As can be seen from the combination of examples 1-3 and comparative example 1 and table 2, the corrosion resistance and adhesion of examples 1-3 are higher than those of comparative example 1, which indicates that the addition of graphene and nano-silicon can fill the pores in the network structure of polydopamine, nano-cellulose and resin material to form a compact structure to prevent penetration of corrosive molecules, and effectively improve the corrosion resistance of the corrosion-resistant coating.
As can be seen from the combination of examples 1 to 6 and Table 2, when the resin materials in the raw materials are selected from a plurality of combinations of the resin materials, the impact strength, particularly the adhesion of the paint is greatly improved, which means that the proper combination of the resin materials is adopted to improve the performance of the anticorrosive paint.
As can be seen from the combination of examples 6 and 7-8 and the combination of table 2, the dispersing agent can make graphene and nano silicon have good dispersibility when using the silane coupling agent and the titanate coupling agent, and enhance the combination ability of modified cellulose and resin material, thereby improving the interfacial adhesion between the anticorrosive paint and metal and the impact resistance of the anticorrosive paint.
It can be seen from the combination of examples 8 and 9 and the combination of table 2 that the addition of pigment does not affect the corrosion resistance, impact resistance, adhesion and other properties of the paint when adding pigment, but rather the good metal chelating ability of the pigment cooperates with the resin material to not only add different colors to the paint, but also enhance the corrosion resistance of the paint.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
1. The anti-corrosion coating for the highway bridge anti-collision guardrail is characterized by comprising the following raw materials in parts by weight:
2-4 parts of graphene, 1-3 parts of nano silicon, 7-8 parts of polydopamine, 1.5-3 parts of modified cellulose, 2-4 parts of resin material, 0.5-0.8 part of perfluorotripropylamine, 1 part of dispersing agent, 2-6 parts of ionic liquid solvent, 1-3 parts of dioctyl phthalate and the balance of deionized water, wherein the modified cellulose is modified nano cellulose, and the modified nano cellulose is prepared by the following steps:
(1) Removing impurities on the surface of the material by grinding, cleaning and heating microcrystalline cellulose;
(2) Placing the treated cellulose into a mixed solution of acetic acid and cellulase for enzymolysis for 30-40min at 50-60 ℃;
(3) Diluting with water to terminate the reaction, continuously centrifuging and washing, concentrating and drying to obtain nanocellulose;
(4) At 80-105 ℃, sodium carbonate is used as a catalyst, alkyl ketene dimer is added and continuously stirred for 20-24 hours, and then concentrated and dried to prepare the modified nanocellulose; the resin material includes an epoxy resin.
2. The anticorrosive paint for highway bridge crash barrier according to claim 1, wherein: the resin material also comprises one or two of polyamide resin and phenolic resin.
3. The anticorrosive paint for highway bridge crash barrier according to claim 1, wherein: the ionic liquid solvent is 1-butyl-3-methylimidazole chloride.
4. The anticorrosive paint for highway bridge crash barrier according to claim 1, wherein: the anticorrosive paint also comprises silicon carbide, zinc oxide and aluminum tripolyphosphate.
5. The anticorrosive paint for highway bridge crash barrier according to claim 1, wherein: the dispersing agent is one or two of a silane coupling agent and a titanium coupling agent.
6. A process for preparing the anticorrosive paint for the public road bridge roof beam crash barrier according to any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
(1) Mixing graphene and deionized water in a mass ratio of 1:20-40, ball milling for 10-12 hours, adding nano silicon, and continuing ball milling for 2-3 hours;
(2) Heating an ionic liquid solvent to 100-110 ℃, then putting the ionic liquid solvent into modified nanocellulose for dissolution, cooling to room temperature, and then adding the graphene, the nano silicon, the perfluoro tripropylamine and the dispersing agent which are subjected to ball milling in the step (1), and performing ultrasonic dispersion to obtain a mixed dispersion;
(3) And sequentially adding polydopamine, a resin material and dioctyl phthalate into the mixed dispersion liquid, and stirring and grinding to obtain the anticorrosive paint for the highway bridge crash barrier.
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