CN112680076A - Preparation method of functional graphene reinforced waterborne polyurethane anticorrosive coating - Google Patents
Preparation method of functional graphene reinforced waterborne polyurethane anticorrosive coating Download PDFInfo
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- CN112680076A CN112680076A CN201910987015.4A CN201910987015A CN112680076A CN 112680076 A CN112680076 A CN 112680076A CN 201910987015 A CN201910987015 A CN 201910987015A CN 112680076 A CN112680076 A CN 112680076A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 22
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract 4
- 230000000694 effects Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 239000012972 dimethylethanolamine Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 4
- 239000010410 layer Substances 0.000 claims 2
- 239000007921 spray Substances 0.000 claims 2
- 230000002776 aggregation Effects 0.000 claims 1
- 238000004220 aggregation Methods 0.000 claims 1
- 238000007611 bar coating method Methods 0.000 claims 1
- 239000011229 interlayer Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 14
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 230000001680 brushing effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000011527 polyurethane coating Substances 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CPIKPEAXEXFEGT-UHFFFAOYSA-N CN(CCO)C.[N].[N] Chemical compound CN(CCO)C.[N].[N] CPIKPEAXEXFEGT-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
本发明公开了一种功能化石墨烯增强水性聚氨酯防腐涂层的制备方法。主要步骤在于对氧化石墨(GO)的制备及其功能化改性，然后将功能化的氧化石墨烯掺杂到水性聚氨酯涂料内，最后利用棒涂或喷涂的方法将复合涂层涂覆在金属表面。其特征在于：(1)以功能化的氧化石墨烯为增强体，以水性聚氨酯为基体，制备出高防腐效率的石墨烯防腐涂料：(2)改性后的氧化石墨烯在水性聚氨酯中具有良好的分散性与相容性；(3)改性后的防腐涂层的防腐效果较纯水性聚氨酯有大幅度的提升；(4)该功能化石墨烯可以作为水性涂料的掺杂粒子，通过刷涂或者喷涂的方式涂覆到被保护的金属表面。
The invention discloses a preparation method of a functionalized graphene reinforced water-based polyurethane anti-corrosion coating. The main steps are the preparation of graphite oxide (GO) and its functional modification, then doping the functionalized graphene oxide into the waterborne polyurethane coating, and finally coating the composite coating on the metal by rod coating or spraying. surface. It is characterized in that: (1) using functionalized graphene oxide as a reinforcement, and using water-based polyurethane as a matrix, a graphene anti-corrosion coating with high anti-corrosion efficiency is prepared: (2) the modified graphene oxide has Good dispersibility and compatibility; (3) The anti-corrosion effect of the modified anti-corrosion coating is greatly improved compared with pure water-based polyurethane; (4) The functionalized graphene can be used as doping particles for water-based coatings, Apply to the protected metal surface by brushing or spraying.
Description
Technical Field
The invention belongs to the technical field of preparation of graphene anticorrosive coatings, and particularly relates to a modification of a functionalized graphene material and a preparation process of a waterborne polyurethane anticorrosive coating.
Background
Corrosion of metal surfaces, particularly automobiles, ships, high-speed railways and other metal equipment, has been one of the most urgent problems in metal protection, causing enormous economic losses to countries each year. Metal corrosion often occurs at the metal/electrolyte solution interface, and the most effective methods of protection include coating techniques and surface treatments. The invention mainly researches the anticorrosion performance of the functional graphene reinforced waterborne polyurethane. Graphene as a two-dimensional graphite carbon material has high specific surface area, high mechanical properties and excellent barrier properties. However, graphene sheets are not well dispersed in organic coatings due to strong van der waals forces between the graphene sheets. And the compatibility between the inorganic nano graphene and the high molecular polymer is poor, and the interface bonding force is weak, so in order to improve the dispersion compatibility and the interface bonding force of the graphene and the polymer, diisocyanate and hydroxyl and carboxyl on the surface of the diisocyanate form a urethane bond to be grafted to the surface of graphene oxide, and then the graphene oxide functionalized by polyisocyanate is bonded into an aqueous polyurethane matrix, so that the barrier property of the graphene is better exerted, and the corrosion resistance and the mechanical property of the composite coating are improved.
Disclosure of Invention
The invention aims to provide a preparation method of a functional graphene reinforced waterborne polyurethane anticorrosive coating, and the modified graphene oxide reinforced waterborne polyurethane remarkably improves the anticorrosive performance of the coating.
The technical scheme of the invention is as follows: firstly, preparing graphene oxide by adopting an improved Hummers method, then carrying out functional modification on the graphene oxide by using isophorone diisocyanate through a thermal reflux method, and then further modifying the graphene oxide by using nitrogen-nitrogen dimethylethanolamine. And finally, dissolving the obtained functionalized graphene in an aqueous solution, and adding a certain amount of SDBS into the aqueous polyurethane. Stirring for a certain time, standing for a certain time, and then carrying out vacuum defoaming. The coating is uniformly coated on a metal substrate by adopting a brush coating method, and is dried for 1-1.5 hours at the temperature of 115 ℃ and 125 ℃ after being cured for 1-1.5 hours at normal temperature, so that the coating with excellent corrosion resistance can be obtained.
The main innovation points of the invention are as follows: the IPDI and DMEA covalently modified graphene oxide reduces the self-agglomeration of the graphene oxide in the polymer, improves the dispersibility and compatibility of the graphene oxide in the polymer and enables the graphene oxide to play the greatest shielding role.
The method for preparing the functionalized graphene comprises the following steps: the method is characterized in that crystalline flake graphite is used as a raw material, and an improved Hummers method is adopted to prepare graphene oxide. Preparing graphene oxide powder into a graphene oxide allyl ketone solution with a certain concentration, performing ultrasonic dispersion for 0.5-1.5 hours, adding a certain amount of isophorone diisocyanate, refluxing for 11-13 hours at a certain temperature, then adding 20-30g of N-dimethyl ethanolamine, continuing heating for a certain time, and finally performing suction filtration, washing and freeze drying to obtain functionalized graphene powder (GO-IP).
The preparation process of the functionalized graphene anticorrosive paint in the method is as follows: dissolving the obtained functionalized graphene in an aqueous solution, adding a certain amount of SDBS (sodium dodecyl benzene sulfonate) for water bath and ultrasonic treatment for a certain time, adding waterborne polyurethane for mechanical stirring for a certain time, and adding a film-forming assistant to obtain the anticorrosive coating.
The preparation process of the functionalized graphene oxide anticorrosive coating in the method is as follows: the coating is brushed on the treated metal substrate by a brushing method, and is cured for 1-1.5 hours at room temperature, and is dried for 0.5-1.5 hours at the temperature of 115 ℃ and 125 ℃ to obtain the coating with excellent corrosion resistance.
According to the invention, a scanning electron microscope is adopted to represent good dispersion compatibility of the functionalized graphene in the waterborne polyurethane, and an electrochemical workstation is used to represent excellent anticorrosion performance of the anticorrosion coating.
Drawings
FIG. 1 is a diagram of the corrosion prevention mechanism for preparing a coating.
Fig. 2 is a cross-sectional SEM image of the corrosion protection coating.
Fig. 3 is a plot of the frequency of breakpoints of the corrosion protection coating.
Fig. 4 is a water absorption diagram of the anticorrosive coating.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
an improved Hummers method is adopted, and crystalline flake graphite is used as a raw material to prepare the graphene oxide dispersion liquid. Preparing functionalized graphene, namely freeze-drying the prepared graphene oxide into powder. 0.7g of GO powder was weighed into a beaker, followed by 200ml of acetone solution, sonicated (200w) in a sonicator for 1h, and then transferred to a 500ml three-necked flask. 0.1ml of dibutyltin dilaurate and 80g of IPDI were added with magnetic stirring and the mixture was heated to 85 ℃ under nitrogen protection for 10 h. Then, the temperature was lowered to 65 ℃ and 25g of DMEA was added and the reaction was continued for 2 h. And washing the residual reactant with acetone, and freeze-drying to obtain GO-IP powder. IP-GO (0.03g) and SDBS (0.03g) were dispersed in 8.5mL of ethanol solution (5%), sonicated for 1h, then 10g of WPU was added and vigorously stirred on a magnetic stirrer for 1 hour. Then, a WPU paint having a solid content of 20% was obtained. And (3) defoaming in vacuum for 30 minutes, brushing the coating on the treated metal substrate, curing at room temperature for 1 hour, and drying at 120 ℃ for 1 hour to obtain a coating with excellent corrosion resistance on the metal surface.
Example 2:
an improved Hummers method is adopted, and crystalline flake graphite is used as a raw material to prepare the graphene oxide dispersion liquid. Preparing functionalized graphene oxide, and freeze-drying the prepared graphene oxide into powder. 0.7g of GO powder was weighed into a beaker, followed by 200ml of acetone solution, sonicated (250w) in a sonicator for 1h, and then transferred to a 500ml three-necked flask. 0.1ml of dibutyltin dilaurate and 80g of IPDI were added with magnetic stirring, and the temperature was raised to 85 ℃ under the protection of nitrogen for reaction for 15 h. Then, the temperature was lowered to 65 ℃ and 25g of DMEA was added and the reaction was continued for 3 h. And washing the residual reactant with acetone, and freeze-drying to obtain GO-IP powder. IP-GO (0.05g) and SDBS (0.05g) were dispersed in 8.5mL ethanol solution (3%), sonicated for 1h, then 10g WPU was added and vigorously stirred on a magnetic stirrer for 1 hour. Then, a WPU paint having a solid content of 20% was obtained. And (3) defoaming in vacuum for 30min, brushing the coating on the treated metal substrate, curing at room temperature for 1h, and drying at 120 ℃ for 1.5 h to obtain a coating with excellent corrosion resistance on the metal surface. And finally, respectively using pure water polyurethane, graphite oxide and reduced graphene oxide reinforced waterborne polyurethane (namely WPU, GO/WPU and RGO/WPU) to perform anticorrosion test comparison with functionalized graphene reinforced waterborne polyurethane (GO-IP/WPU).
Claims (10)
1. A preparation method of a functionalized graphene reinforced waterborne polyurethane anticorrosive coating mainly comprises the steps of dispersing oxidized graphene in acetone in an ultrasonic mode, adding a certain amount of isophorone diisocyanate (IPDI) at a certain temperature, mechanically stirring for 10-24 hours, adding a certain amount of N-dimethyl ethanolamine (DMEA), thermally refluxing for a certain time, washing and drying to obtain functionalized graphene powder. Dispersing the obtained functional graphene oxide powder and SDBS in an ethanol solution with a certain concentration according to a certain mass ratio, adding a certain amount of waterborne polyurethane, simply and mechanically stirring, and then coating the functional graphene oxide powder and the SDBS on the surface of a protected metal by a brush coating or spraying method. And placing the coated coating for 1-5h at normal temperature, and then placing the coating into a drying oven to be dried at a certain temperature. The problem of interlayer aggregation of graphene sheets is solved by a covalent grafting method, and the problem of compatibility between inorganic nanoparticles and high molecular polymers is also solved. The problem of dispersibility of the functionalized graphene in the water-based paint is further solved by a non-covalent grafting method. The electrochemical workstation test, the salt spray test and the results show that the anticorrosion effect of the modified anticorrosion coating is greatly improved compared with that of pure water polyurethane.
2. The method according to claim 1, wherein the number of graphene layers prepared by the modified hummer method is less than 2, and the sheet diameter is 1-10 μm. The number of the functionalized graphene layers is less than 3, and the sheet diameter is 1-5 mu m.
3. The method of claim 1, wherein the graphene oxide is non-covalently modified with SDBS by covalent modification with IPDI and DMEA by thermal refluxing.
4. The process of claim 1, wherein GO is reacted with IPDI at 80-90 ℃ for 10-24h and 3-6h with DMEA at 60-70 ℃.
5. The method of claim 1, conditions for ultrasonically dispersing graphene oxide and functionalized graphene: the power is 200-; the mass ratio of the SDBS to the functionalized graphene is 0.9-1: 1.
6. The method of claim 1, wherein the functionalized graphene is dispersed with an ethanol concentration of 3-7%.
7. The method of claim 1, wherein the functionalized graphene is uniformly dispersed in water, and then the aqueous polyurethane with the solid content of 37% is diluted into the aqueous polyurethane with the solid content of 18-22% by using the dispersion liquid.
8. The method of claim 1, wherein the functionalized graphene aqueous polyurethane mixed solution is coated on the surface of the protected metal after being stirred for 1.5-2.5 hours.
9. The heating temperature of the coating in the oven was 115-125 ℃.
10. A method according to claim 1, characterized in that a spray or bar coating method is used.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958151A (en) * | 2022-07-04 | 2022-08-30 | 北京理工大学珠海学院 | Composite anticorrosive material containing modified graphene oxide and preparation method thereof |
| CN115594995A (en) * | 2022-08-11 | 2023-01-13 | 赵子龙（Cn） | A kind of preparation method of filler for coating |
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| CN104629603A (en) * | 2015-02-11 | 2015-05-20 | 上海理工大学 | Graphene-containing metal surface treatment agent and preparation method of anti-corrosion coating |
| CN105153905A (en) * | 2015-07-03 | 2015-12-16 | 泰山玻璃纤维有限公司 | Preparation method and application of graphene modified polyurethane film-forming agent |
| CN110183939A (en) * | 2019-06-26 | 2019-08-30 | 陕西科技大学 | A kind of preparation method of graphene/anti-corrosive paint of epoxy resin |
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2019
- 2019-10-18 CN CN201910987015.4A patent/CN112680076A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013112590A (en) * | 2011-11-30 | 2013-06-10 | Sekisui Chem Co Ltd | Isocyanate group-modified carbon material and method for producing the same |
| CN104130669A (en) * | 2014-08-13 | 2014-11-05 | 陕西科技大学 | Highly hydrophobic antistatic composite coating and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958151A (en) * | 2022-07-04 | 2022-08-30 | 北京理工大学珠海学院 | Composite anticorrosive material containing modified graphene oxide and preparation method thereof |
| CN115594995A (en) * | 2022-08-11 | 2023-01-13 | 赵子龙（Cn） | A kind of preparation method of filler for coating |
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