CN114316713A - High-nitric-acid-resistance water-based acrylic resin coating - Google Patents
High-nitric-acid-resistance water-based acrylic resin coating Download PDFInfo
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 79
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 45
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims abstract description 14
- 239000000049 pigment Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 239000012736 aqueous medium Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- JCUYNPHEESTECG-UHFFFAOYSA-N 3-amino-6-(4-aminophenyl)benzene-1,2-disulfonic acid Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O JCUYNPHEESTECG-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000012966 redox initiator Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000021323 fish oil Nutrition 0.000 claims description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003223 protective agent Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- -1 zirconium aluminate Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 239000012085 test solution Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 6
- 229920003180 amino resin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to a high-nitric-acid-resistance water-based acrylic resin coating which comprises 40-50 parts of nitric-acid-resistance water-based acrylic resin, 3-6 parts of pigment, 2-5 parts of epoxy resin, 10-20 parts of sulfonated polybenzoxazine resin and 5-8 parts of titanium acetylacetonate. The modified and modified water-based acrylic resin improves the nitric acid resistance of the modified and modified water-based acrylic resin from the aspects of increasing the sealing property, increasing the mechanical strength and the like.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-nitric-acid-resistance water-based acrylic resin coating.
Background
The water-soluble acrylic resin coating has the advantages of no fire hazard, no benzene poisoning, reduction of atmospheric pollution and the like, has the characteristics of light color, excellent light and color retention, good baking resistance, good stability and the like, and is a variety with great development prospect.
At present, most of water-based acrylic resin coatings on the market are water-based acrylic amino resin coatings, and acrylic-amino baking paints have the advantages of low curing temperature and no need of additionally adding a curing agent, but have poor corrosion resistance, and the corrosion resistance of the acrylic-amino baking paints cannot be improved even if the proportion of the water-based acrylic resin and the water-based amino resin is adjusted.
For example, the high weather-resistant steel structure water-based acrylic resin disclosed in CN 112794940 a has improved water resistance, corrosion resistance and weather resistance, and the technical proposal is to improve the corrosion resistance by improving the hardness of the surface, and the curing temperature is higher; CN 108467648B discloses a coating prepared from acrylic resin and amino resin, which has the advantages of good stability and good pollution resistance, and the technical scheme also reduces the curing temperature, but the corrosion resistance is poor.
Disclosure of Invention
The invention aims to provide a high-nitric acid resistance water-based acrylic resin coating which has the advantages of good sealing property, excellent mechanical strength and difficult corrosion.
The technical scheme adopted by the invention for solving the problems is as follows:
the paint comprises 40-50 parts of nitric acid-resistant water-based acrylic resin, 3-6 parts of pigment, 2-5 parts of epoxy resin, 10-20 parts of sulfonated polybenzoxazine resin and 5-8 parts of titanium acetylacetonate.
Further, the preparation method of the coating comprises the following steps:
the method comprises the following steps: preparation of nitric acid-resistant water-based acrylic resin
S1: weighing 25-50 parts of acrylic acid monomer, 45-75 parts of methacrylic acid monomer, 5-10 parts of acrylamide, 5-10 parts of vinyl acetate and 10-15 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: adding 5-10 parts of unsaturated sulfated fish oil into an aqueous medium in which 2-3 parts of a surfactant are dissolved;
s3: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dripping 9 parts by mass into the aqueous medium in the step (2) for 2-3 h, and stirring and reacting at 100-110 ℃;
s4: mixing 1-3 parts of carbon nano copper and 0.1-0.5 part of coupling agent into the remaining 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s5: adding the mixed monomer with the surface modified by S4 into the solution obtained by S3, dropwise adding 1-3 parts of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin;
step two: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10-20 parts of sulfonated polybenzoxazine and 2-5 parts of epoxy resin;
step three: uniformly mixing 40-50 parts of nitric acid-resistant water-based acrylic resin, 3-6 parts of pigment, 2-5 parts of epoxy resin and 10-20 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring。
The above parts are all parts by mass.
Further, the preparation method of the carbon nano-copper comprises the following steps:
s1, heating and ultrasonically treating the carbon microspheres by using a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 5: 1-2 at the temperature of 60-70 ℃, reacting for 4-6 h, and then acidifying the carbon microspheres;
s2, washing and drying the acidified carbon microspheres, then putting the acidified carbon microspheres into a diluent, stirring and uniformly mixing the acidified carbon microspheres, then adding triethylsilane and a reduction protective agent in batches, and stirring and reacting for 2-3 hours at room temperature to obtain hydroxyl-containing carbon microspheres;
and S3, mixing the nano-copper into the solution, performing ultrasonic dispersion reaction for 1-2 hours, performing centrifugal separation, washing and drying to obtain the carbon nano-copper.
Further, the surfactant is cetyl trimethyl ammonium bromide or stearyl trimethyl ammonium chloride.
Further, the coupling agent is a zirconium-based coupling agent containing zirconium aluminate.
Compared with the prior art, the invention has the advantages that:
(1) the paint added with the unsaturated sulfated fish oil modified acrylic resin has better surface closure and is not easy to corrode to generate cracks;
(2) the carbon nano copper can be crosslinked with acrylic resin, so that the mechanical strength is increased, the corrosion resistance of the acrylic resin is improved, and the ductility of the coating can be increased;
(3) the modified and modified water-based acrylic resin and titanium acetylacetonate form a chelate crosslinked network, and compared with other curing agents for curing acrylic resin, the corrosion resistance of the modified and modified water-based acrylic resin is obviously improved;
(4) the epoxy resin has good corrosion resistance, the chemical stability of the mixture of the polybenzoxazine resin and the epoxy resin is high, and the sulfonated polybenzoxazine resin can introduce a functional group with strong electroabsorbability, can be polymerized by self-opening ring at a specific temperature, reduces the curing temperature, and does not reduce the glass transition temperature of the resin, so that a self-opening ring-crosslinked network framework can be formed by the resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The technical effects of the acrylic resin with high nitric acid resistance and the preparation method thereof according to the present invention will be further described with reference to the following specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention, and all modifications and substitutions based on the above principles should be within the protection scope of the present invention.
Example 1
The method comprises the following steps: preparation of carbon nano-copper
S1, immersing 25 parts of carbon microspheres in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 5: 1-2, heating at 60-70 ℃ for ultrasonic treatment, reacting for 4-6 hours, and then acidifying the carbon microspheres;
s2, washing and drying the acidified carbon microspheres, putting the acidified carbon microspheres into a diluent, stirring and uniformly mixing, adding 3g of triethylsilane and 1g of reduction protective agent in batches, and stirring and reacting for 2-3 h at room temperature to obtain hydroxyl-containing carbon microspheres;
and S3, mixing 6 parts of nano-copper into the solution, performing ultrasonic dispersion reaction for 1-2 hours, performing centrifugal separation, washing and drying to obtain the carbon nano-copper.
Step two: preparation of nitric acid-resistant water-based acrylic resin
S1: weighing 25 parts of acrylic acid monomer, 45 parts of methacrylic acid monomer, 5 parts of acrylamide, 5 parts of vinyl acetate and 10 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: adding 5 parts of unsaturated sulfated fish oil into an aqueous medium dissolved with 2 parts of surfactant;
s3: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dropwise adding 9 parts by mass into the aqueous medium of S2 for 2-3 h, and stirring and reacting at 100-110 ℃;
s4: mixing 1 part of carbon nano copper and 0.1 part of coupling agent into the rest 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s5: and adding the mixed monomer with the surface modified by S4 into the solution obtained by S3, dropwise adding 1 part of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin.
Step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10 parts of sulfonated polybenzoxazine and 2 parts of epoxy resin;
step four: uniformly mixing 40 parts of nitric acid-resistant water-based acrylic resin, 3 parts of pigment, 2 parts of epoxy resin and 10 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water, and uniformly stirring。
According to the requirements in GB/T8013.2-2018 standard, the nitric acid resistance performance is measured:
before the test, the surface of the acrylic resin with high resistance to nitric acid water is lightly wiped off with alcohol, and the glass or synthetic resin ring with an inner diameter of 32mm and a height of 30mm is fixed on the effective surface with vaseline or paraffin, and the periphery of the glass or synthetic resin ring is sealed. A test solution of nitric acid at a concentration of 50g/L was prepared from analytically pure nitric acid (. beta. =1.40 g/mL) and tertiary water in accordance with GB/T6682.
The sample remained horizontal. At a test temperature of 20 ℃. + -. 2 ℃, the nitric acid test solution is injected at 1/2, which is the ring height, and is covered with a glass plate or a synthetic resin plate. After standing for 25min, the glass ring was removed and the sample was gently washed with tap water and dried. The surface of the high nitric acid resistant water-based acrylic resin is still intact through visual inspection.
Example 2
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of nitric acid-resistant water-based acrylic resin
S1: weighing 35 parts of acrylic monomer, 50 parts of methacrylic monomer, 5 parts of acrylamide, 5 parts of vinyl acetate and 15 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: adding 8 parts of unsaturated sulfated fish oil into an aqueous medium dissolved with 2.5 parts of surfactant;
s3: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dropwise adding 9 parts by mass into the aqueous medium of S2 for 2-3 h, and stirring and reacting at 100-110 ℃;
s4: mixing 2 parts of carbon nano copper and 0.3 part of coupling agent into the rest 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s5: adding the mixed monomer with the surface modified by S4 into the solution obtained by S3, dropwise adding 2 parts of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin;
step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 15 parts of sulfonated polybenzoxazine and 3 parts of epoxy resin;
step four: uniformly mixing 45 parts of nitric acid-resistant water-based acrylic resin, 4 parts of pigment, 3 parts of epoxy resin and 15 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water, and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking that the surface of the high-nitric-acid-resistance water-based acrylic resin is still intact after the nitric acid test solution is treated for 25 min.
Example 3
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of nitric acid-resistant water-based acrylic resin
S1: weighing 50 parts of acrylic monomer, 70 parts of methacrylic monomer, 10 parts of acrylamide, 10 parts of vinyl acetate and 10 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: adding 10 parts of unsaturated sulfated fish oil into an aqueous medium dissolved with 3 parts of surfactant;
s3: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dropwise adding 9 parts by mass into the aqueous medium of S2 for 2-3 h, and stirring and reacting at 100-110 ℃;
s4: mixing 3 parts of carbon nano copper and 0.5 part of coupling agent into the rest 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s5: adding the mixed monomer with the surface modified by S4 into the solution obtained by S3, dropwise adding 3 parts of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin;
step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 20 parts of sulfonated polybenzoxazine and 5 parts of epoxy resin;
step four: uniformly mixing 45 parts of nitric acid-resistant water-based acrylic resin, 4 parts of pigment, 5 parts of epoxy resin and 15 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water, and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking that the surface of the high-nitric-acid-resistance water-based acrylic resin is still intact after the nitric acid test solution is treated for 25 min.
Comparative example 1
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of aqueous acrylic resin
S1: weighing 25 parts of acrylic acid monomer, 45 parts of methacrylic acid monomer, 5 parts of acrylamide, 5 parts of vinyl acetate and 10 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dripping 9 parts by mass into an aqueous medium dissolved with 2 parts of surfactant for 2-3 h, and stirring and reacting at 100-110 ℃;
s3: mixing 1 part of carbon nano copper and 0.1 part of coupling agent into the rest 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s4: and adding the mixed monomer with the surface modified by S3 into the solution obtained by S2, dropwise adding 1 part of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin.
Step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10 parts of sulfonated polybenzoxazine and 2 parts of epoxy resin;
step four: uniformly mixing 40 parts of the water-based acrylic resin obtained in the step two, 3 parts of pigment, 2 parts of epoxy resin and 10 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking that a plurality of cracks appear on the surface of the water-based acrylic resin and the cracks are corroded by nitric acid after the water-based acrylic resin is treated by a nitric acid test solution for 16 min.
Comparative example 2
The method comprises the following steps: preparation of aqueous acrylic resin
S1: weighing 25 parts of acrylic acid monomer, 45 parts of methacrylic acid monomer, 5 parts of acrylamide, 5 parts of vinyl acetate and 10 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: dropwise adding the mixed monomer solution of S1 into an aqueous medium dissolved with 2 parts of surfactant for 2.5-3.5 h, and stirring and reacting at 100-110 ℃;
s3: dropping 1 part of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, adjusting the pH value to 4.0-5.0, and preparing the high-nitric-acid-resistance water-based acrylic resin.
Step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10 parts of sulfonated polybenzoxazine and 2 parts of epoxy resin;
step four: uniformly mixing 40 parts of the water-based acrylic resin obtained in the step two, 3 parts of pigment, 2 parts of epoxy resin and 10 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking the surface of the acrylic resin to generate mottled depressions after treating the acrylic resin for 15min by using a nitric acid test solution.
Comparative example 3
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of aqueous acrylic resin
S1: weighing 25 parts of acrylic acid monomer, 45 parts of methacrylic acid monomer, 5 parts of acrylamide, 5 parts of vinyl acetate and 10 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dripping 9 parts by mass into an aqueous medium dissolved with 2 parts of surfactant for 2-3 h, and stirring and reacting at 100-110 ℃;
s3: mixing 1 part of nano copper and 0.3 part of coupling agent into the rest 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s4: and adding the mixed monomer with the surface modified by S3 into the solution obtained by S2, dropwise adding 1 part of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin.
Step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10 parts of sulfonated polybenzoxazine and 2 parts of epoxy resin;
step (ii) ofFourthly, the method comprises the following steps: uniformly mixing 40 parts of the water-based acrylic resin obtained in the step two, 3 parts of pigment, 2 parts of epoxy resin and 10 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring。
The prepared acrylic resin is oxidized after being placed in the air for a period of time, the nitric acid resistance performance is measured according to the requirements in the GB/T8013.2-2018 standard, the surface of the acrylic resin is still intact through visual inspection after the acrylic resin is treated by a nitric acid test solution for 20min, but the surface of the acrylic resin is corroded and mottled and incomplete after 25 min.
Comparative example 4
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of nitric acid resistant Water-based acrylic resin As in example 1
Step three: uniformly mixing 45 parts of nitric acid-resistant water-based acrylic resin, 4 parts of pigment and a neutralizing agent, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking that the surface of the high-nitric-acid-resistance water-based acrylic resin is still intact after the nitric acid test solution is treated for 25 min.
Comparative example 5
The method comprises the following steps: preparation of carbon nano-copper is the same as example 1
Step two: preparation of nitric acid resistant Water-based acrylic resin As in example 1
Step three: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10 parts of sulfonated polybenzoxazine and 2 parts of epoxy resin;
step four: uniformly mixing 40 parts of the water-based acrylic resin obtained in the step two, 3 parts of pigment, 2 parts of epoxy resin and 10 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 15-20 parts of amino resin, adding deionized water, and uniformly stirring。
And (3) according to the requirements in the GB/T8013.2-2018 standard, carrying out nitric acid resistance performance measurement, and visually checking whether the surface of the acrylic resin is corroded and mottled after the acrylic resin is treated by a nitric acid test solution for 18 min.
TABLE 1
As can be seen from the tables and the above examples, the corrosion resistance effect of comparative example 1, comparative example 2, comparative example 3, and comparative example 5, in which the carbon nanocopper is not modified with the unsaturated sulfated oil, the carbon nanocopper is replaced with the nanocopper, and the titanium acetylacetonate curing agent is replaced with the amino resin, is inferior to that of examples 1 to 3, and in comparative example 3, although the acrylic resin is directly modified with the nanocopper, the corrosion resistance and the ductility are improved, but the nanocopper is very easy to oxidize, and the coating cannot be normally used. Comparative example 4 no sulfonated polybenzoxazine resin was added and the coating prepared was low in chemical stability and high in curing temperature.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (5)
1. The high-nitric-acid-resistance water-based acrylic resin coating is characterized by comprising the following components in parts by weight: the paint comprises 40-50 parts of nitric acid-resistant water-based acrylic resin, 3-6 parts of pigment, 2-5 parts of epoxy resin, 10-20 parts of sulfonated polybenzoxazine resin and 5-8 parts of titanium acetylacetonate.
2. The high nitric acid resistance water-based acrylic resin paint as claimed in claim 1, wherein the manufacturing method of the paint comprises the following steps:
the method comprises the following steps: preparation of nitric acid-resistant water-based acrylic resin
S1: weighing 25-50 parts of acrylic acid monomer, 45-75 parts of methacrylic acid monomer, 5-10 parts of acrylamide, 5-10 parts of vinyl acetate and 10-15 parts of acrylonitrile according to a proportion, and uniformly mixing;
s2: adding 5-10 parts of unsaturated sulfated fish oil into an aqueous medium in which 2-3 parts of a surfactant are dissolved;
s3: dividing the mixed monomer solution of S1 into 9:1 parts by mass, dropwise adding 9 parts by mass into the aqueous medium of S2 for 2-3 h, and stirring and reacting at 100-110 ℃;
s4: mixing 1-3 parts of carbon nano copper and 0.1-0.5 part of coupling agent into the remaining 1 part of mixed monomer by mass, and performing mixed ultrasonic treatment for 2-3 hours to perform surface modification;
s5: adding the mixed monomer with the surface modified by S4 into the solution obtained by S3, dropwise adding 1-3 parts of redox initiator, reacting at room temperature for 1-1.5 h to form polyacrylic resin, and adjusting the pH value to 4.0-5.0 to prepare the high-nitric-acid-resistance water-based acrylic resin;
step two: preparation of sulfonated polybenzoxazine resin
Dissolving 1mol of benzidine disulfonic acid and 2mol of 3-pentadecylphenol in excessive formaldehyde to generate sulfonated polybenzoxazine, and uniformly mixing 10-20 parts of sulfonated polybenzoxazine and 2-5 parts of epoxy resin;
step three: uniformly mixing 40-50 parts of nitric acid-resistant water-based acrylic resin, 3-6 parts of pigment, 2-5 parts of epoxy resin and 10-20 parts of sulfonated polybenzoxazine resin, adjusting the pH value to 4.0-5.0, adding 5-8 parts of titanium acetylacetonate, adding deionized water and uniformly stirring；
The above parts are all parts by mass.
3. The high nitric acid resistant water-based acrylic resin coating as claimed in claim 2, wherein the preparation method of the carbon nano-copper comprises the following steps:
s1, immersing 20-30 parts of carbon microspheres in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 5: 1-2, heating at 60-70 ℃ for ultrasonic treatment, reacting for 4-6 hours, and then acidifying the carbon microspheres;
s2, washing and drying the acidified carbon microspheres, then putting the acidified carbon microspheres into a diluent, stirring and uniformly mixing the acidified carbon microspheres, then adding triethylsilane and a reduction protective agent in batches, and stirring and reacting for 2-3 hours at room temperature to obtain hydroxyl-containing carbon microspheres;
s3, mixing 5-8 parts of nano-copper into the solution, performing ultrasonic dispersion reaction for 1-2 hours, performing centrifugal separation, washing and drying to obtain the carbon nano-copper.
4. The high nitric acid resistant aqueous acrylic resin coating according to claim 2, wherein the surfactant is cetyl trimethyl ammonium bromide or stearyl trimethyl ammonium chloride.
5. The high nitric acid resistant aqueous acrylic resin coating according to claim 2, wherein said coupling agent is a zirconium based coupling agent containing zirconium aluminate.
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