CN118421190B - Bio-based anticorrosive paint and preparation method thereof - Google Patents
Bio-based anticorrosive paint and preparation method thereof Download PDFInfo
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- CN118421190B CN118421190B CN202410875181.6A CN202410875181A CN118421190B CN 118421190 B CN118421190 B CN 118421190B CN 202410875181 A CN202410875181 A CN 202410875181A CN 118421190 B CN118421190 B CN 118421190B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
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- 235000019438 castor oil Nutrition 0.000 claims abstract description 58
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- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 26
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- 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 abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
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- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 4
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- ZXFNSBMXKNDSMV-UHFFFAOYSA-N 3-ethoxysilylpropane-1-thiol Chemical compound CCO[SiH2]CCCS ZXFNSBMXKNDSMV-UHFFFAOYSA-N 0.000 claims 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 claims description 3
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- 229920000881 Modified starch Polymers 0.000 abstract 1
- 239000004368 Modified starch Substances 0.000 abstract 1
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- 239000004033 plastic Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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Landscapes
- Paints Or Removers (AREA)
Abstract
The application discloses a bio-based anticorrosive paint and a preparation method thereof, belonging to the technical field of bio-based anticorrosive paint; the novel plastic is characterized by comprising the following components in parts by weight: 18-32 parts of castor oil, 4-9 parts of self-made castor oil-based silane coupling agent, 3.5-5.5 parts of self-made modified graphene oxide, 16-28 parts of isophorone diisocyanate and 6-15 parts of solvent. The bio-based anticorrosive paint provided by the application has the advantages that the natural materials with equivalent components are relatively environment-friendly, and the environmental impact is small; the natural source of the modified starch has better biodegradability and meets the requirement of sustainable development; in the preparation process of the coating, the self-made castor oil-based silane coupling agent is provided with polyhydroxy groups, and when reacting with isocyanate, internal crosslinking points are provided; the internal crosslinking provided by the polyhydroxy and the self-made modified graphene oxide prepared by two-step modification are crosslinked for two times, so that the mechanical property and the surface corrosion resistance of the coating are greatly enhanced.
Description
Technical Field
The invention belongs to the technical field of bio-based anti-corrosion paint, and particularly relates to a bio-based anti-corrosion paint and a preparation method thereof.
Background
Under the background of double carbon, the substitution of the traditional petrochemical-based products by the biological-based products has important significance for realizing sustainable development; the development level of anticorrosive paint is a standard for measuring the advanced degree of paint industry and plays an important role in transformation.
The traditional anticorrosive paint generally contains a large amount of organic solvents and heavy metals, and the substances cause serious environmental pollution in the using and discarding processes, and the bio-based anticorrosive paint mainly adopts natural or renewable resources as raw materials, so that the bio-based anticorrosive paint is more environment-friendly. And the bio-based materials are typically derived from plants or other renewable sources, which have relatively low carbon emissions during production, helping to reduce greenhouse gas emissions.
The prior art includes, for example, the Chinese invention patent with publication number CN 115322648A: the modified graphene doped bio-based epoxy-phenol system resin anticorrosive paint is prepared by introducing modified graphene into a bio-based epoxy-phenol formula system. However, the disadvantage is that the epoxy-phenol system coating used in the method requires that the coating be maintained under vacuum and cured at high temperature for the specific application; the process complexity of specific application is high, and strict temperature control needs to be executed in the use process so as to ensure uniform solidification; and the length of the curing time can greatly influence the coating performance.
The prior art includes, for example, the Chinese invention patent with publication number CN 108285665A: the marine organism-based anticorrosive paint and the preparation method thereof have the advantages of environmental friendliness, simple preparation process, good controllability and easy operation; but the adopted coating component comprises marine algae cystis extract; as a natural material, the production cost of the extract of the ascophyllum is high, and the algae material in the coating is easy to subside and aggregate, so that the uneven quality problem of the coating is more easily caused; and the addition of algae extract may provide a nutrient source for microorganisms, resulting in microbial growth on the paint surface, thereby affecting the durability of the paint.
The prior art has the characteristics of the bio-based anticorrosive paint, but when the bio-based anticorrosive paint is applied to the marine field with stricter environmental requirements and worse application environment, the bio-based anticorrosive performance prepared by the prior art still has a larger gap with the traditional anticorrosive paint, and the drying rate and the adhesive force of the bio-based paint also have larger lifting space.
Therefore, there is an urgent need to introduce new process technologies to solve the above problems and to seek a more viable solution.
Disclosure of Invention
In order to solve the defect problems in the technical scheme, the invention aims to provide a bio-based anticorrosive paint and a preparation method thereof; the aim of the invention can be achieved by the following technical scheme: the bio-based anticorrosive paint comprises the following components in parts by weight: 18-32 parts of castor oil, 4-9 parts of self-made castor oil-based silane coupling agent, 3.5-5.5 parts of self-made modified graphene oxide, 16-28 parts of isophorone diisocyanate and 6-15 parts of solvent;
The solvent is one of butanone or 2-butanone.
Further, the bio-based anticorrosive paint comprises the following components in parts by weight: 28 parts of castor oil, 8 parts of self-made castor oil-based silane coupling agent, 5 parts of self-made modified graphene oxide, 24 parts of isophorone diisocyanate and 12 parts of solvent.
The preparation and synthesis method of the self-made castor oil-based silane coupling agent comprises the following steps: adding castor oil and mercaptopropyl ethoxysilane into a reaction vessel, and then adding a photoinitiator; after stirring and mixing uniformly, placing the mixture under a 365nm ultraviolet lamp, and carrying out irradiation reaction for 12 hours; the self-made castor oil-based silane coupling agent is prepared.
Further, the photoinitiator is any one of benzoin dimethyl ether or 1173 photoinitiator with the mass fraction of 3 percent.
In the preparation and synthesis process, the reaction vessel needs to exhaust air and is filled with inert gas;
Further, in the reaction vessel, argon is filled as the inert gas.
Further, the irradiation power of the ultraviolet lamp is 20mW/cm 2;
Further, the photoinitiators were all purchased from guangdong Weng Jiang chemical company, inc.
The preparation and synthesis method of the self-made modified graphene oxide comprises the following steps: hydrolyzing gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane with acetic acid, and reacting for 1h while stirring; then, adding graphene oxide aqueous solution into the hydrolyzed mixed solution; then, placing the mixed solution in a microwave reactor, heating to 110 ℃, stirring while heating, centrifuging the solution after 30min, collecting a product, and repeatedly washing with deionized water to obtain an intermediate product; preparing an intermediate product into a solution, and adding a polyoxypropylene diamine aqueous solution; mixing the two materials, placing the materials in a microwave reactor, heating to 80 ℃, stirring while heating to 80 ℃, and continuing stirring for 10min; finally, collecting through a centrifugal speed of 25000 r/min, and washing with ethanol/deionized water for a plurality of times to remove the polypropylene oxide diamine which does not participate in the reaction, thus obtaining the self-made modified graphene oxide.
Further, the concentration of the acetic acid is 4.6mol/L;
Further, the mass fraction of the polyoxypropylene diamine in the polyoxypropylene diamine aqueous solution is 10%;
further, the structural formula of the polyoxypropylene diamine is shown as follows
。
The preparation method of the bio-based anticorrosive paint comprises the following steps: adding castor oil, a solvent and a self-made castor oil-based silane coupling agent into a reaction container, heating the reaction container to 70 ℃, then dripping 1-2 drops of dibutyltin dilaurate, dripping isophorone diisocyanate, and continuously stirring for 2-3 hours; maintaining the temperature of the reaction vessel at 70 ℃; in the reaction process, 2-butanone is dripped to adjust the viscosity of the reaction system, prevent the reaction system from solidifying, and after 2-3 hours of reaction, the pre-polymerization stage is finished; then adding self-made modified graphene oxide, performing chain extension reaction, continuously stirring and reacting for 4 hours, and determining the content of the residual isocyanate groups in a reaction system based on titration by a di-n-butylamine method in the reaction process; after the isocyanate groups in the reaction system are completely reacted; and (3) placing the prepared product in a vacuum drying oven, and drying at 80 ℃ to constant weight to obtain the bio-based anticorrosive paint.
The invention has the beneficial effects that:
1. the bio-based anticorrosive paint comprises castor oil and a self-made castor oil-based silane coupling agent; the paint contains natural materials with equivalent components, and has little influence on the environment; and because of its natural source, it also meets the requirement of sustainable development;
2. According to the self-made modified graphene oxide prepared by introducing the two-step modification, the molecular length of the surface of the prepared modified graphene oxide is increased, so that the steric hindrance between adjacent graphene is stronger, and the dispersion stability of the graphene oxide is greatly enhanced; and silane bridging introduced between graphene oxide and polyoxypropylene diamine is avoided by the modified graphene, so that the connection of a plurality of graphene sheets is avoided; the polyoxypropylene diamine leaves molecular tails on the surface of graphene, and terminal amino groups are introduced at molecular terminals, so that the interface bonding performance between the graphene and a matrix is improved, the adhesion performance of the coating is enhanced, and meanwhile, the coating is endowed with stronger corrosion resistance;
3. The self-made castor oil-based silane coupling agent in the components has a natural long-chain fatty acid structure, so that a hydrophobic interface is generated, the water resistance of the coating can be greatly improved, and the corrosion is greatly delayed; the self-made castor oil-based silane coupling agent has polyhydroxy, and provides internal crosslinking points when reacting with isocyanate; and wherein the silane groups are capable of hydrolyzing to form silicon hydroxyl groups, providing external crosslinking points; the two are self-condensed in the curing process to form a crosslinked network, so that the self-condensation type polyurethane resin has better mechanical properties; the internal crosslinking provided by the polyhydroxy and the self-made modified graphene oxide prepared by two-step modification are crosslinked for two times, so that the mechanical property and the surface property of the coating are greatly enhanced;
4. in the drying process of the coating, the internal crosslinking and the external crosslinking form a complex three-dimensional crosslinking network, so that the crosslinking network not only improves the mechanical property and the surface property of the coating, but also promotes the stability and the curing speed of the coating in the drying process. And because the double crosslinking provides more reaction sites, the curing reaction can be performed more quickly, and the time required for drying the coating is reduced; meanwhile, due to the high crosslinking density, the coating can reach final mechanical properties more quickly, so that the time for completely drying is greatly reduced.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" indicated in the examples below are parts by weight.
Example 1
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 18 parts of castor oil, 3.5 parts of self-made modified graphene oxide, 4 parts of self-made castor oil-based silane coupling agent, 16 parts of isophorone diisocyanate and 6 parts of solvent;
Wherein the solvent is 2-butanone;
Wherein the castor oil is purchased from Ala Ding Shiji, inc., and has a hydroxyl value of 164mgKOH/g;
self-made castor oil based silane coupling the preparation and synthesis method of the agent comprises the following steps: the whole reaction process is carried out in an atmosphere filled with inert gas argon, 6g of castor oil and 3g of mercaptopropyl ethoxysilane are added into a reaction vessel, and then 0.1g of photoinitiator is added; after stirring and mixing uniformly, placing the mixture under a 365nm ultraviolet lamp, and carrying out irradiation reaction for 12 hours; the self-made castor oil-based silane coupling agent is prepared;
Wherein the photoinitiator is benzoin dimethyl ether with the mass fraction of 3%;
wherein the photoinitiator benzoin dimethyl ether was purchased from guangdong Weng Jiang chemical reagent limited;
wherein the irradiation power of the ultraviolet lamp is 20mW/cm 2.
The preparation and synthesis method of the self-made modified graphene oxide comprises the following steps: 28ml of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane was hydrolyzed with 7.6ml of acetic acid, and reacted for 1 hour while stirring; subsequently, 40mL of an aqueous graphene oxide solution (2 mg/mL) was added to the hydrolyzed mixed solution; then, placing the mixed solution into a microwave reactor, pressurizing and heating to 110 ℃, stirring at the same time, and treating for 30min; centrifuging the solution at a speed of 25000 rpm to collect a product, and repeatedly washing with deionized water to obtain an intermediate product; the intermediate product was prepared as a 60mL solution (concentration: 1 mg/mL) and 30mL of an aqueous polyoxypropylene diamine solution was added; mixing the two materials, placing the materials in a microwave reactor, heating to 80 ℃, stirring while heating to 80 ℃, and continuing stirring for 10min; finally, collecting the final product through a centrifugal speed of 25000 r/min, and washing with ethanol/deionized water for multiple times to remove the polyoxypropylene diamine which possibly does not participate in the reaction, thus obtaining the final product, namely the self-made modified graphene oxide.
Wherein the concentration of the acetic acid is 4.6mol/L;
Wherein the mass fraction of the polyoxypropylene diamine in the polyoxypropylene diamine aqueous solution is 10%;
wherein the structural formula of the polyoxypropylene diamine is shown as follows
；
Wherein the polyoxypropylene diamine is purchased from Hubei Jiufeng chemical industry Limited company;
Wherein, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane is purchased from Kang Jin new materials science and technology Co., ltd, GAS number is: 2530-83-8.
A preparation method of a bio-based anticorrosive paint comprises the following steps: adding castor oil, a solvent and a self-made castor oil-based silane coupling agent into a reaction container, heating the reaction container to 70 ℃, then dripping 1-2 drops of dibutyltin dilaurate, dripping isophorone diisocyanate, and continuously stirring for 2-3 hours; maintaining the temperature of the reaction vessel at 70 ℃; in the reaction process, 2-butanone is dripped to adjust the viscosity of the reaction system, prevent the reaction system from solidifying, and after 2-3 hours of reaction, the pre-polymerization stage is finished; then adding self-made modified graphene oxide, performing chain extension reaction, continuously stirring and reacting for 4 hours, and determining the content of the residual isocyanate groups in a reaction system based on titration by a di-n-butylamine method in the reaction process; after the isocyanate groups in the reaction system are completely reacted; and (3) placing the prepared product in a vacuum drying oven, and drying at 80 ℃ to constant weight to obtain the bio-based anticorrosive paint.
Example 2
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 21 parts of castor oil, 4 parts of self-made modified graphene oxide, 6 parts of self-made castor oil-based silane coupling agent, 18 parts of isophorone diisocyanate and 8 parts of solvent;
wherein the solvent is butanone;
wherein, in the preparation and synthesis process of the self-made castor oil-based silane coupling agent, the photoinitiator adopted is 1173 photoinitiator purchased from Guangdong Weng Jiang chemical reagent Co., ltd, and the GAS number is: 7473-98-5;
in example 2, the preparation method of the self-made modified graphene oxide and the preparation method of the bio-based anticorrosive paint are the same as those in example 1.
Example 3
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 25 parts of castor oil, 4.5 parts of self-made modified graphene oxide, 8 parts of self-made castor oil-based silane coupling agent, 22 parts of isophorone diisocyanate and 10 parts of solvent;
Wherein the solvent is 2-butanone;
In example 3, the preparation method of the self-made castor oil-based silane coupling agent, the preparation method of the self-made modified graphene oxide and the preparation method of the bio-based anticorrosive paint are the same as those in example 1.
Example 4
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 28 parts of castor oil, 5 parts of self-made modified graphene oxide, 8 parts of self-made castor oil-based silane coupling agent, 24 parts of isophorone diisocyanate and 12 parts of solvent;
Wherein the solvent is 2-butanone;
In example 4, the preparation method of the self-made castor oil-based silane coupling agent, the preparation method of the self-made modified graphene oxide and the preparation method of the bio-based anticorrosive paint are the same as those in example 1.
Example 5
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 32 parts of castor oil, 5.5 parts of self-made modified graphene oxide, 9 parts of self-made castor oil-based silane coupling agent, 28 parts of isophorone diisocyanate and 15 parts of solvent;
Wherein the solvent is 2-butanone;
In example 5, the preparation method of the self-made castor oil-based silane coupling agent, the preparation method of the self-made modified graphene oxide and the preparation method of the bio-based anticorrosive paint are the same as those in example 1.
Comparative example 1
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 28 parts of castor oil, 5 parts of graphene oxide, 8 parts of self-made castor oil-based silane coupling agent, 24 parts of isophorone diisocyanate and 12 parts of solvent;
Wherein the solvent is 2-butanone;
This comparative example 1 is based on example 4, except that graphene oxide, which has not been modified at all, is used in the comparative example 1, except for the above-described components; the preparation and synthesis methods of the bio-based anticorrosive paint are the same as those of example 4.
Comparative example 2
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 28 parts of castor oil, 5 parts of self-made modified graphene oxide, 8 parts of silane coupling agent, 24 parts of isophorone diisocyanate and 12 parts of solvent;
Wherein the solvent is 2-butanone;
Wherein the silane coupling agent is purchased from commercial models: a Mickey A-Link597;
this comparative example 2 is based on example 4, except that a commercially available silane coupling agent was used in the comparative example 2, except for the above-mentioned components; the preparation and synthesis methods of the bio-based anticorrosive paint are the same as those of example 4.
Comparative example 3
A bio-based anticorrosive paint and a preparation method thereof comprise the following components in parts by weight: 28 parts of castor oil, 5 parts of graphene oxide, 8 parts of a silane coupling agent, 24 parts of isophorone diisocyanate and 12 parts of a solvent;
Wherein the solvent is 2-butanone;
Wherein the silane coupling agent is purchased from commercial models: a Mickey A-Link597;
This comparative example 3 is based on example 4, except that graphene oxide, which has not been modified at all, is used in the comparative example 3 with a commercially available silane coupling agent, except that the above two components are different; the preparation and synthesis methods of the bio-based anticorrosive paint are the same as those of example 4.
Test examples
Coating the coating prepared in the examples 1-5 and the comparative examples 1-3 on a metal substrate in a brushing mode, wherein after the coating is finished, the coating drying time is tested by referring to a standard reference standard GB/T1728-2020 'paint film and putty film drying time measuring method'; the test results are shown in table 1;
TABLE 1
After the coatings prepared in examples 1 to 5 and comparative examples 1 to 3 were completely dried, the coatings were placed in a ventilated place and dried in the shade for 7 days, and then the following coating performance tests were performed;
Adhesion test: testing by referring to a related testing method in GB/T5210-2006 adhesive force test of a colored paint and a varnish pulling method;
Acid resistance test, salt water resistance test: testing is carried out by referring to the relevant testing method in GB/T9274-1988 determination of liquid medium resistance of paint and varnish; wherein the acid resistance test uses 5wt.% H 2SO4 solution and the salt resistance test uses 3wt.% NaCl solution;
Salt spray resistance test: testing by referring to a related testing method in GB/T31588.1-2015 'determination of circulating corrosion resistant environment of paint and varnish'; the method for testing the salt spray resistance comprises the following steps: placing a sample to be tested in a salt spray box, wherein the coating of the sample faces upwards; setting the temperature of a salt fog box at 35 ℃, the salt fog pressure at 1kg/cm 2 and the air source at 5kg/cm 2, periodically and continuously spraying with atomized 5wt.% NaCl aqueous solution, observing the change of a sample substrate to be tested during spraying, and recording the time when a corrosion phenomenon starts to appear;
The paint performance test results are shown in table 2;
TABLE 2
Comprehensive performance analysis: as can be seen from the analysis of the test data in Table 1, after the metal substrate is coated with the coating with the thickness of 150 micrometers, the surface drying time of the coating in examples 1-5 is within 1 h; whereas comparative examples 1-3 all required approximately 2 hours; and the complete drying times of examples 1-5 were all within 14 hours; the complete drying times of comparative examples 1-3 were all substantially about 20 hours; with examples 1-5 of the coating formulations of the present application, the complete drying time was greatly reduced.
From the analysis of the test data in Table 2, the bio-based coatings prepared in examples 1-5 were applied to metal substrates according to the relevant coating performance test criteria, and the test data showed that: the acid resistance can reach about 1000 hours basically, and the salt water resistance is over 1200 hours; especially, the salt fog resistance is more than 1200h; the coatings prepared in examples 1-5 have excellent corrosion resistance; the adhesive force is more than 7.0MPa, and the paint has excellent paint adhesive capacity; even the adhesion of example 4 can exceed 10MPa.
Comparative example 1 differs from example 4 only in that graphene oxide, which has not been modified at all, was used in comparative example 1, and each coating property has a large difference from examples 1 to 5, probably because:
The self-made modified graphene oxide used in examples 1-5 is prepared by two-step modification, so that the molecular length of the surface of the prepared modified graphene oxide is increased, the steric hindrance between adjacent graphene is stronger, and the dispersion stability of the graphene oxide is greatly enhanced; and silane bridging introduced between graphene oxide and polyoxypropylene diamine is avoided by the modified graphene, so that the connection of a plurality of graphene sheets is avoided; the polyoxypropylene diamine leaves molecular tails on the surface of graphene, and terminal amino groups are introduced at the molecular terminals, so that the interface bonding performance between the graphene and a matrix is improved, and the coating has stronger corrosion resistance;
Comparative example 2 differs from example 4 in that a commercially available silane coupling agent was used in comparative example 2; the self-made castor oil-based silane coupling agent adopted by the application; so that examples 1-5 have more natural derived components with less environmental impact than comparative example 2; and because of its natural source, it also meets the requirement of sustainable development.
Comparative example 3, which uses graphene oxide without any modification and a commercially available silane coupling agent, has the worst corrosion resistance and adhesion properties among comparative examples 1 to 3;
Examples 1-5 the replacement of any of the formulation components resulted in a significant deterioration in the corrosion protection performance and drying rate of the biobased coating, probably due to: the self-made castor oil-based silane coupling agent in the components of the examples 1-5 has a natural long-chain fatty acid structure, so that a hydrophobic interface is generated, the water resistance of the coating can be greatly improved, and the corrosion is greatly delayed; and wherein the silane groups are capable of hydrolyzing to form silicon hydroxyl groups, providing external crosslinking points; the two are self-condensed in the curing process to form a crosslinked network, so that the self-condensation type polyurethane resin has better mechanical properties; in the preparation process of the coating, the self-made castor oil-based silane coupling agent is provided with polyhydroxy groups, and provides internal crosslinking points when reacting with isocyanate; the internal crosslinking provided by the polyhydroxy and the self-made modified graphene oxide prepared by two-step modification are crosslinked for two times, so that the mechanical property and the surface property of the coating are greatly enhanced.
And in combination with the data in tables 1 and 2, it can be found that the drying speed of the paint has a positive correlation with the adhesion and the corrosion resistance; the faster the drying speed, the greater the adhesion and the greater the corrosion resistance.
The possible reason is that in the drying process of the coating, the internal crosslinking and the external crosslinking form a complex three-dimensional crosslinking network, so that the crosslinking network not only improves the mechanical property and the surface property of the coating, but also promotes the stability and the curing speed of the coating in the drying process; the self-made modified graphene oxide and the self-made castor oil-based silane coupling agent in the paint formula have synergistic effect, and as more reaction sites are provided by double crosslinking, the curing reaction can be performed more quickly, and the time required for drying the paint is reduced; meanwhile, due to the high crosslinking density, the coating can reach final mechanical properties more quickly, so that the time for completely drying is greatly reduced.
The bio-based anticorrosive paint comprises castor oil and a self-made castor oil-based silane coupling agent; the paint contains natural materials with equivalent components, has little influence on the environment and is more environment-friendly; and because of its natural source, it also meets the requirement of sustainable development.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The bio-based anticorrosive paint is characterized by comprising the following components in parts by weight: 18-32 parts of castor oil, 4-9 parts of self-made castor oil-based silane coupling agent, 3.5-5.5 parts of self-made modified graphene oxide, 16-28 parts of isophorone diisocyanate and 6-15 parts of solvent;
The preparation method of the self-made castor oil-based silane coupling agent comprises the following steps: adding castor oil and mercaptopropyl ethoxysilane into a reaction vessel, and then adding a photoinitiator; after stirring and mixing uniformly, placing the mixture under an ultraviolet lamp, and carrying out irradiation reaction for 12 hours; the self-made castor oil-based silane coupling agent is prepared;
The preparation and synthesis method of the self-made modified graphene oxide comprises the following steps: hydrolyzing gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane with acetic acid, and reacting for 1h while stirring; then, adding graphene oxide aqueous solution into the hydrolyzed mixed solution; then, placing the mixed solution in a microwave reactor, heating to 110 ℃, stirring while heating, centrifuging the solution after 30min, collecting a product, and repeatedly washing with deionized water to obtain an intermediate product; preparing an intermediate product into a solution, and adding a polyoxypropylene diamine aqueous solution; mixing the two materials, placing the materials in a microwave reactor, heating to 80 ℃, stirring while heating to 80 ℃, and continuing stirring for 10min; finally centrifugally collecting, and washing with ethanol/deionized water for multiple times to remove the polyoxypropylene diamine which does not participate in the reaction, thus obtaining the self-made modified graphene oxide;
The solvent is one of butanone or 2-butanone.
2. The bio-based anticorrosive paint according to claim 1, wherein the composition comprises, in parts by weight: 28 parts of castor oil, 8 parts of self-made castor oil-based silane coupling agent, 5 parts of self-made modified graphene oxide, 24 parts of isophorone diisocyanate and 12 parts of solvent.
3. The bio-based anticorrosive paint according to claim 1, wherein the photoinitiator is any one of benzoin dimethyl ether or 1173 photoinitiator with a mass fraction of 3% in the preparation and synthesis process of the self-made castor oil-based silane coupling agent.
4. The bio-based anticorrosive paint according to claim 1, wherein the reaction vessel is required to be exhausted with inert gas during the preparation and synthesis of the self-made castor oil-based silane coupling agent.
5. The bio-based anticorrosive paint according to claim 1, wherein the irradiation power of the ultraviolet lamp is 20mW/cm 2 in the preparation and synthesis process of the self-made castor oil-based silane coupling agent; the wavelength of the ultraviolet lamp is 365nm.
6. The bio-based anticorrosive paint according to claim 1, wherein the concentration of acetic acid in the preparation and synthesis process of the self-made modified graphene oxide is 4.6mol/L.
7. The bio-based anticorrosive paint according to claim 1, wherein the mass fraction of the polyoxypropylene diamine in the polyoxypropylene diamine aqueous solution in the preparation and synthesis process of the self-made modified graphene oxide is 10%.
8. The bio-based anticorrosive paint according to claim 1, wherein the concentration of the graphene oxide aqueous solution in the preparation and synthesis process of the self-made modified graphene oxide is 2 mg/mL.
9. A method of preparing a biobased anticorrosive paint according to any one of claims 1 to 8, wherein the method of preparing the biobased anticorrosive paint comprises: adding castor oil, a solvent and a self-made castor oil-based silane coupling agent into a reaction container, heating the reaction container to 70 ℃, then dripping 1-2 drops of dibutyltin dilaurate, dripping isophorone diisocyanate, and continuously stirring for 2-3 hours; maintaining the temperature of the reaction vessel at 70 ℃; in the reaction process, 2-butanone is dripped to adjust the viscosity of the reaction system, prevent the reaction system from solidifying, and after 2-3 hours of reaction, the pre-polymerization stage is finished; then adding self-made modified graphene oxide, performing chain extension reaction, continuously stirring and reacting for 4 hours, and determining the content of the residual isocyanate groups in a reaction system based on titration by a di-n-butylamine method in the reaction process; after the isocyanate groups in the reaction system are completely reacted; and (3) placing the prepared product in a vacuum drying oven, and drying at 80 ℃ to constant weight to obtain the bio-based anticorrosive paint.
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| CN109943202A (en) * | 2018-05-10 | 2019-06-28 | 成都拜迪新材料有限公司 | A kind of aqueous epoxy nano fiber anticorrosive paint and preparation method thereof |
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| CN109943202A (en) * | 2018-05-10 | 2019-06-28 | 成都拜迪新材料有限公司 | A kind of aqueous epoxy nano fiber anticorrosive paint and preparation method thereof |
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