CN117866520A - Modified phenoxy resin cold zinc spraying coating and preparation method and application thereof - Google Patents
Modified phenoxy resin cold zinc spraying coating and preparation method and application thereof Download PDFInfo
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- CN117866520A CN117866520A CN202311716331.0A CN202311716331A CN117866520A CN 117866520 A CN117866520 A CN 117866520A CN 202311716331 A CN202311716331 A CN 202311716331A CN 117866520 A CN117866520 A CN 117866520A
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- zinc
- phenoxy resin
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- zinc powder
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 238000000576 coating method Methods 0.000 title claims abstract description 133
- 239000011248 coating agent Substances 0.000 title claims abstract description 128
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 103
- 239000011701 zinc Substances 0.000 title claims abstract description 103
- 229920006287 phenoxy resin Polymers 0.000 title claims abstract description 89
- 239000013034 phenoxy resin Substances 0.000 title claims abstract description 89
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 title claims abstract description 54
- 238000005507 spraying Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 28
- 239000007921 spray Substances 0.000 claims abstract description 26
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 238000010276 construction Methods 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000005484 gravity Effects 0.000 abstract description 6
- 239000000725 suspension Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000010288 cold spraying Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- DZNGZUACARPUOS-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Fe+2].[Zn+2] Chemical compound [Si]([O-])([O-])([O-])[O-].[Fe+2].[Zn+2] DZNGZUACARPUOS-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of coatings, and discloses a modified phenoxy resin cold zinc spraying coating, a preparation method and application thereof. The modified phenoxy resin cold spray zinc coating comprises the following components: phenoxy resin, styrene-acrylonitrile copolymer, polymethyl silicate hydrolytic polycondensate, zinc powder and solvent; the mass portion ratio of the zinc powder to the phenoxy resin is (80-88): (1.6-2.5). The styrene-acrylonitrile copolymer in the modified phenoxy resin cold zinc spraying coating can modify phenoxy resin, effectively improves the dispersion of zinc powder in the coating, ensures that the stable suspension of the zinc powder with high specific gravity in the coating can not be precipitated, and ensures that the zinc powder is uniformly arranged in the film forming process, thereby forming a cathode protection network with excellent stability and no blind spots on the surface of the coating, and the coating has excellent salt spray resistance; the polymethyl silicate hydrolytic polycondensate and zinc powder undergo complex reaction, so that the coating has excellent rainmark and bloom resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a modified phenoxy resin cold zinc spraying coating, and a preparation method and application thereof.
Background
The existing protective coating primer for heavy corrosion protection of steel structure industry widely adopts epoxy zinc-rich coating and inorganic zinc-rich coating, and theoretically, the higher the zinc content in the coating, the better the cathodic protection effect and the better the corrosion resistance.
The epoxy zinc-rich paint is a bi-component paint, bisphenol A epoxy resin is selected as a zinc powder binder, an amine curing agent is generally adopted, and active hydrogen on nitrogen atoms in primary amine and secondary amine is utilized to open epoxy groups so as to crosslink and cure the epoxy groups, and the film forming mechanism is reaction crosslinking film forming. Therefore, the problem of the pot life of the paint exists, the pot life of the epoxy zinc-rich paint is generally 4 hours, and the viscosity of the epoxy zinc-rich paint system exceeding the pot life is increased sharply, and the performance is reduced sharply until the epoxy zinc-rich paint cannot be used; the zinc content of the national standard epoxy zinc-rich paint coating is 70%, the rest 30% is relative insulating materials such as film-forming resin, curing agent, auxiliary agent and the like, zinc powder contacted with the steel substrate can form a conductive path with the substrate to exert a cathode protection effect, and zinc powder particles which are dispersed in the coating and are not directly contacted with the substrate are wrapped by the insulating material and cannot undergo primary cell reaction, so that the corrosion resistance of the coating can be reduced.
The inorganic zinc-rich paint is a double-component paint, takes an ethyl silicate hydrolysis prepolymer as a film forming substance, forms zinc-silicate-zinc, zinc-silicate-iron and other compounds by the action of bonding zinc powder and a substrate, tightly covers the surface of steel, and plays a good role in protecting the steel together with the electrochemical action of the zinc powder. The dry film zinc content of the national standard inorganic zinc-rich paint coating is generally 80 percent. The film forming material of the hydrolyzed prepolymer of the ethyl silicate is a pure inorganic substance, and the flexibility, the adhesive force and the compactness of the product are poor. The flexibility and the adhesive force of the product are improved by adding polyvinyl butyral PVB, and the polyvinyl butyral PVB has high viscosity, so that the polyvinyl butyral PVB can discharge extremely large VOC in the production and construction processes, thereby causing air environmental pollution. The construction of the inorganic zinc-rich paint also has strict requirements on humidity, film thickness and cleanliness of a base material, and paint film defects are easily caused by improper process control. Practice proves that the inorganic zinc-rich paint has extremely wide range of application and the reworking rate is as high as more than 90% once the defects of cracking, peeling, foaming, pinholes, softening and the like are generated, and has great influence on the coating cost and the product delivery period.
In recent years, with the development of technology, new materials and new technologies in the field of industrial heavy corrosion prevention are continuously emerging, and the high performance and easy construction of zinc-rich paint become an important direction and research hot spot for the development of industrial corrosion-resistant paint. Cold zinc spraying paint has been widely used in industrial corrosion prevention field in recent years due to its technical advantages, but it also has revealed more problems, such as that the storage time of conventional cold zinc spraying paint in the market cannot be too long, and zinc powder with high specific gravity is deposited on the bottom of the barrel for more than 90 days, so that hard sedimentation is formed, i.e. the storage stability is poor. After the conventional cold zinc spraying coating is sprayed with rain, zinc powder and rainwater undergo oxidation reaction to generate a large amount of zinc hydroxide, and the zinc hydroxide can absorb surrounding rainwater to form a sticky white paste, and the zinc hydroxide reacts with carbon dioxide in the air drying process to generate zinc carbonate which changes color into solid white zinc salt to cause the coating to turn white and bloom; the conventional cold zinc spraying adopts thermoplastic acrylic resin as a main film forming material, so that the coating is easily separated from the substrate due to the fact that the pigment-base ratio exceeds a critical value.
Therefore, there is a need to provide a new zinc coating which has good storage stability and also has good corrosion resistance and film forming properties.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a modified phenoxy resin cold zinc spraying coating and a preparation method and application thereof. The styrene-acrylonitrile copolymer in the modified phenoxy resin cold zinc spraying coating can modify phenoxy resin, effectively improves the dispersion of zinc powder in the coating, ensures that the stable suspension of the zinc powder with high specific gravity in the coating can not be precipitated, and ensures that the zinc powder is uniformly arranged in the film forming process, thereby forming a cathode protection network with excellent stability and no blind spots on the surface of the coating, and the coating has excellent salt fog resistance; the polymethyl silicate hydrolytic polycondensate and zinc powder undergo complex reaction to inhibit the rapid oxidation of the zinc powder, and the zinc powder coating does not generate white spots after rain, so that the anti-rain mark anti-bloom performance of the coating is excellent.
The modified phenoxy resin cold zinc spraying coating provided by the invention solves some defects existing in the prior art, such as relatively low zinc content of an epoxy zinc-rich coating, and failure to form a complete conductive path ensures that all zinc powder plays a role of sacrificial anode protection and cathode protection; the alcohol-soluble inorganic zinc-rich primer has higher VOC (volatile organic compound) content, lower volume solid content, higher requirements on site coating environment and coating process during construction, improper process control and easy occurrence of paint film defects; the conventional cold spray zinc has the defects of easy precipitation, easy blushing and blobbing of the coating after rain, poor adhesive force of the coating, and the like.
The first aspect of the invention provides a modified phenoxy resin cold spray zinc coating.
Specifically, the modified phenoxy resin cold zinc spraying coating comprises the following components: phenoxy resin, styrene-acrylonitrile copolymer, polymethyl silicate hydrolytic polycondensate, zinc powder and solvent;
the mass portion ratio of the zinc powder to the phenoxy resin is (80-88): (1.6-2.5).
Preferably, the modified phenoxy resin cold zinc spraying coating comprises the following components in parts by mass: 1.6 to 2.0 parts of phenoxy resin, 0.6 to 1.8 parts of styrene-acrylonitrile copolymer, 0.1 to 0.8 part of polymethyl silicate hydrolytic polycondensate, 80 to 88 parts of zinc powder and 10 to 20 parts of solvent. The proper selection of the components can prepare the coating with better performance.
Further preferably, the modified phenoxy resin cold zinc spraying coating comprises the following components in parts by weight: 1.6 to 2.0 parts of phenoxy resin, 0.8 to 1.2 parts of styrene-acrylonitrile copolymer, 0.2 to 0.3 part of polymethyl silicate hydrolytic polycondensate, 80 to 83 parts of zinc powder and 12 to 15 parts of solvent.
Preferably, the phenoxy resin is thermoplastic epoxy resin obtained by reacting bisphenol A with epichlorohydrin. The phenoxy resin has large hydroxyl group content, and the formed paint film (or coating) has high adhesive force to a metal substrate, can bear zinc powder and can provide excellent paint film flexibility.
Preferably, the weight average molecular weight of the phenoxy resin is 25000 to 70000, more preferably 25000 to 60000.
Preferably, the phenoxy resin contains a polyhydroxy ether structure of ethylene glycol in an alpha form.
Preferably, the zinc powder contains more than 99.5% of zinc element by mass and more than 97% of metal zinc by mass.
Preferably, the zinc powder has at least one of 500-600 mesh, 700-800 mesh and 900-1000 mesh.
Preferably, the solvent is an organic solvent, for example, cyclohexanone is further preferred. Cyclohexanone is a strong solvent with excellent dissolving capacity for phenoxy resin, improves the adhesive force of a paint film and can reduce the viscosity of the paint. The volatilization rate is slow, so that the paint film is smooth and beautiful.
Preferably, the styrene-acrylonitrile copolymer is a solid resin, the structure of the styrene-acrylonitrile copolymer is provided with amino functional groups, a large number of hydrogen bonds can be generated, and the association of the hydrogen bonds can form thixotropic effect.
The adopted styrene-acrylonitrile copolymer has extremely high molecular weight and extremely high thixotropic property, effectively improves the dispersion of zinc powder in the paint, can effectively fix the zinc powder in the storage process, ensures that the zinc powder with high specific gravity can not be precipitated in stable suspension in the paint, prevents the zinc powder paint from sagging in the construction spraying process and ensures that the zinc powder is uniformly arranged in the film forming process.
Preferably, the polymethyl silicate hydrolytic polycondensate has the formula C 10 H 30 O 13 Si 4 The molecular weight was 470.68.
The adopted polymethyl silicate hydrolytic polycondensate endows the coating with low surface tension and excellent hydrophobic property, and alkoxy groups in the polymethyl silicate hydrolytic polycondensate absorb water in the air and generate hydrolysis reaction in the drying film forming process, so that methyl silicate oligomer containing a certain hydroxyl group can be generated to generate complexation reaction with zinc powder, and the rapid oxidation of the zinc powder is inhibited, so that the common disadvantages of black spots, uneven color and the like can not occur in outdoor rain of the zinc-rich coating.
Further preferably, siO in the polymethyl silicate hydrolysis polycondensate 2 The mass fraction content is 51%.
Preferably, the preparation process of the polymethyl silicate hydrolytic polycondensate is as follows:
(1) 180-185 parts by mass of methyl silicate is put into a container (such as a three-necked bottle);
(2) Adding 90-100 parts by mass of isopropanol under stirring, heating to 32-35 ℃, and preserving heat;
(3) Preparing a mixture, wherein the composition of the mixture is 0.8-1.1 parts by mass of hydrochloric acid, 1.5-1.6 parts by mass of zinc chloride and 25-27 parts by mass of deionized water, dripping the mixture into the container in the step (1), and controlling the temperature of materials in the container to be less than or equal to 55 ℃;
(4) After the dripping is finished, preserving the heat and stirring for 1-2h at 45-55 ℃;
(5) And after the heat preservation is finished, testing the product after the rest for 3 to 4 hours, and obtaining the poly (methyl silicate) polycondensate after the gel time of the product is between 10 and 15 minutes.
Preferably, the modified phenoxy resin cold zinc spraying coating comprises the following components in parts by mass: 1.6 to 2.0 parts of phenoxy resin, 0.8 to 1.2 parts of styrene-acrylonitrile copolymer, 0.2 to 0.3 part of polymethyl silicate hydrolytic polycondensate, 80 to 83 parts of zinc powder and 12 to 15 parts of cyclohexanone.
The zinc powder adopted is more active than iron and is easy to lose electrons, in the early stage of corrosion, the zinc powder and the steel base material form a primary battery, the electrode potential of the zinc is negative to that of the iron, the zinc is an anode (commonly called a sacrificial anode), the iron is a cathode, current flows from the zinc to the iron, and the steel base material is protected by the cathode. In the later corrosion stage, zinc powder is continuously corroded in the service process of the coating, corrosion products, namely basic zinc carbonate, commonly called white rust, are deposited on the gaps of the zinc powder and the surfaces of steel, the zinc powder is compact in structure and non-conductive, is a indissolvable stable compound, can block and shield corrosion of a corrosion medium, and has an anti-corrosion effect.
The second aspect of the invention provides a preparation method of the modified phenoxy resin cold zinc spraying coating.
Specifically, the preparation method of the modified phenoxy resin cold spray zinc coating comprises the following steps:
and mixing the components to prepare the modified phenoxy resin cold zinc spraying coating.
Preferably, the preparation method comprises the following steps:
adding a solvent into a container, adding phenoxy resin under uniform stirring, dispersing at high speed to dissolve the solid phenoxy resin until the solution is transparent and has no particles, keeping uniform stirring, adding the styrene-acrylonitrile copolymer, dispersing at high speed for 20-30min until the solid styrene-acrylonitrile copolymer is completely dissolved, and making the resin liquid into paste; stirring at constant speed, adding zinc powder, and dispersing at high speed for 20-30min until fineness is less than or equal to 30 μm; and (3) charging nitrogen into the container, stirring the poly methyl silicate hydrolytic polycondensate at a constant speed, stirring for 5-10min, filtering, and discharging to obtain the modified phenoxy resin cold zinc spraying coating.
The application method of the modified phenoxy resin cold spray zinc coating comprises the following steps:
and during construction operation, the modified phenoxy resin cold zinc spraying coating is coated on a metal substrate, and the modified phenoxy resin cold zinc spraying coating is obtained after drying.
Preferably, the coating mode comprises any one of roller coating, spraying and brushing.
The third aspect of the invention provides application of the modified phenoxy resin cold zinc spraying coating.
Specifically, the modified phenoxy resin cold zinc spraying coating is applied to the field of corrosion prevention.
Preferably, the application is in the field of corrosion protection of metal equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) The styrene-acrylonitrile copolymer in the modified phenoxy resin cold zinc spraying coating can modify phenoxy resin, effectively improves the dispersion of zinc powder in the coating, ensures that the stable suspension of the zinc powder with high specific gravity in the coating can not be precipitated, and ensures that the zinc powder is uniformly arranged in the film forming process, thereby forming a cathode protection network with excellent stability and no blind spots on the surface of the coating, and the coating has excellent salt fog resistance; the polymethyl silicate hydrolytic polycondensate and zinc powder undergo complex reaction to inhibit the rapid oxidation of the zinc powder, and the zinc powder coating does not generate white spots after rain, so that the anti-rain mark anti-bloom performance of the coating is excellent.
(2) The modified phenoxy resin cold zinc spraying coating is free from the limitation of environment, equipment and places, and is more convenient to construct; the zinc powder coating is mainly prepared from zinc powder with purity higher than 99.9%, volatile solvent and organic film-forming resin, and compared with other double-component zinc-rich coatings, the zinc powder coating is a single-component coating and has no limitation of pot life; the zinc content in the modified phenoxy resin cold zinc spraying coating is higher, the dry film contains more than 95% of metal zinc, and the coating resistance is extremely low to 10 3 Omega cm, thus having excellent cathodic protection effect. The main film forming matters are the phenoxy resin with ultra-high molecular weight and the styrene-acrylonitrile copolymer, the phenoxy resin endows the coating with excellent adhesive force, durability and solvent resistance, amino groups in the molecular chemical structure of the styrene-acrylonitrile copolymer generate hydrogen bond combination to form a three-dimensional network structure, the structure can be destroyed when being sheared, the system is a mobile phase, the three-dimensional structure of the hydrogen bond can be automatically recovered after the shearing force is eliminated, the viscosity of the system is increased, the dispersion of zinc powder in the coating is effectively improved, the stable suspension of the zinc powder with high specific gravity in the coating can not be precipitated, and the zinc powder is uniformly arranged in the film forming process, so that a cathode protection network with excellent stability and no blind spots is formed on the surface of the coating, and the salt mist resistance of the coating is excellent; the introduction of the poly (methyl silicate) polycondensate makes the coating excellent in anti-rainmark and anti-bloom properties. The coating property of the alloy can also meet the requirements of JT/T1266-2019 bridge steel structure cold zinc spraying corrosion prevention technical condition on cold zinc spraying coating property.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The model numbers of some of the components used in the following examples or comparative examples are shown in Table 1 below.
TABLE 1
The preparation process of the polymethyl silicate hydrolytic polycondensate is as follows:
(1) 185 parts by mass of methyl silicate is put into a container (for example, a three-necked bottle);
(2) Adding 100 parts by mass of isopropanol into the container in the step (1) under stirring, heating to 35 ℃, and preserving heat;
(3) Preparing a mixture, wherein the composition of the mixture is 1.1 parts by mass of hydrochloric acid, 1.6 parts by mass of zinc chloride and 27 parts by mass of deionized water, dripping the mixture into the container in the step (1), and controlling the temperature of materials in the container to be less than or equal to 55 ℃;
(4) After the dripping is finished, preserving heat and stirring for 2 hours at 55 ℃;
(5) And after the heat preservation is finished and the reaction time is kept for 4 hours, testing the product, wherein the gel time of the product is 10-15 minutes, and the poly (methyl silicate) polycondensate is obtained.
Example 1
The modified phenoxy resin cold zinc spraying coating comprises the following components in parts by mass: phenoxy resin YP-50S1.6, styrene-acrylonitrile copolymer 0.9, polymethyl silicate hydrolytic polycondensate 0.2, 600 mesh zinc powder 81 and cyclohexanone 12.
A preparation method of a modified phenoxy resin cold spray zinc coating comprises the following steps:
adding cyclohexanone according to the formula amount into a kettle, adding phenoxy resin YP-50S under constant stirring, dispersing at high speed (dispersion speed is 500 r/min) to enable the solid phenoxy resin to be dissolved until the solution is transparent and particle-free, adding styrene-acrylonitrile copolymer under constant stirring, dispersing at high speed for 30min until the solid styrene-acrylonitrile copolymer is completely dissolved, and making the resin liquid into paste; adding 600-mesh zinc powder while stirring at constant speed, and dispersing at high speed for 30min until fineness is less than or equal to 30 μm; and (3) charging nitrogen into the kettle, adding the polymethyl silicate hydrolytic polycondensate under the protection of the nitrogen and keeping constant stirring, stirring at medium speed (100 rpm) for 10 minutes, and filtering and discharging to obtain the modified phenoxy resin cold spraying zinc coating.
Example 2
The modified phenoxy resin cold zinc spraying coating comprises the following components in parts by mass: JER-1256.6 parts of phenoxy resin, 1.2 parts of styrene-acrylonitrile copolymer, 0.2 part of polymethyl silicate hydrolytic polycondensate, 82 parts of zinc powder (42 parts of 600-mesh zinc powder and 40 parts of 1000-mesh zinc powder) and 15 parts of cyclohexanone.
A preparation method of a modified phenoxy resin cold spray zinc coating comprises the following steps:
adding cyclohexanone according to the formula amount into a kettle, adding phenoxy resin JER-1256 under constant stirring, dispersing at high speed (dispersion speed 500 r/min) to enable the solid phenoxy resin to be dissolved until the solution is transparent and particle-free, adding styrene-acrylonitrile copolymer under constant stirring, dispersing at high speed for 30min until the solid styrene-acrylonitrile copolymer is completely dissolved, and making the resin liquid into paste; stirring at constant speed, adding zinc powder, and dispersing at high speed for 30min until fineness is less than or equal to 30 μm; and (3) charging nitrogen into the kettle, adding the polymethyl silicate hydrolytic polycondensate under the protection of the nitrogen and keeping constant stirring, stirring at medium speed (100 rpm) for 10 minutes, and filtering and discharging to obtain the modified phenoxy resin cold spraying zinc coating.
Example 3
The modified phenoxy resin cold zinc spraying coating comprises the following components in parts by mass: 2 parts of phenoxy resin PKHA, 1.2 parts of styrene-acrylonitrile copolymer, 0.3 part of polymethyl silicate hydrolytic polycondensate, 82 parts of zinc powder (42 parts of 800-mesh zinc powder and 40 parts of 1000-mesh zinc powder) and 15 parts of cyclohexanone.
A preparation method of a modified phenoxy resin cold spray zinc coating comprises the following steps:
adding cyclohexanone according to the formula amount into a kettle, adding phenoxy resin PKHA under constant stirring, dispersing at high speed (dispersion speed is 500 r/min) to enable the solid phenoxy resin to be dissolved until the solution is transparent and has no particles, adding styrene-acrylonitrile copolymer under constant stirring, dispersing at high speed for 30min until the solid styrene-acrylonitrile copolymer is completely dissolved, and making the resin liquid into paste; adding 600-mesh zinc powder while stirring at constant speed, and dispersing at high speed for 30min until fineness is less than or equal to 30 μm; and (3) charging nitrogen into the kettle, adding the polymethyl silicate hydrolytic polycondensate under the protection of the nitrogen and keeping constant stirring, stirring at medium speed (100 rpm) for 10 minutes, and filtering and discharging to obtain the modified phenoxy resin cold spraying zinc coating.
Comparative example 1
A preparation method of a conventional cold zinc spraying coating comprises the following steps:
adding 20 parts by weight of W770 cold zinc spraying resin of the modern Wohan company into a kettle according to the formula amount, adding 80 parts by weight of 800-mesh zinc powder under uniform stirring, dispersing at high speed for 30min until the fineness is less than or equal to 30 mu m, and filtering and discharging to obtain the conventional cold zinc spraying coating.
Comparative example 2
The epoxy zinc-rich paint comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 10:1.
the preparation method of the epoxy zinc-rich paint comprises the following steps:
preparation of a main agent: adding 17 parts by weight of 601-75 epoxy resin of Jiangsu Sanmu chemical company into a kettle according to the formula amount, adding 3 parts by weight of polyamide wax slurry under uniform stirring, dispersing at high speed for 10min until no obvious particles exist in the resin liquid, adding 70 parts by weight of 600-mesh zinc powder under uniform stirring, dispersing at high speed for 30min until the fineness is less than or equal to 30 mu m, filtering and discharging to obtain the main agent of the epoxy zinc-rich paint.
Preparation of a curing agent: adding 80 parts by weight of polyamide curing agent and 20 parts by weight of dimethylbenzene into a kettle according to the formula amount, dispersing at medium speed for 10 minutes until the solution is uniformly mixed and transparent, and filtering and discharging to obtain the curing agent.
During construction operation, the main agent and the curing agent are mixed according to the mass ratio of 10: and 1, uniformly mixing and stirring to obtain the epoxy zinc-rich paint.
Comparative example 3
The inorganic zinc-rich paint comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 5:1.
the preparation method of the inorganic zinc-rich paint comprises the following steps:
preparation of a main agent: adding 25 parts by weight of PVB (polyvinyl butyral Ding Quanzhi) resin solution with 17% solid content into a kettle according to the formula amount, adding 3 parts by weight of polyamide wax slurry under uniform stirring, dispersing at high speed for 10min until no obvious particles exist in the resin solution, adding 80 parts by weight of 600-mesh zinc powder under uniform stirring, dispersing at high speed for 30min until the fineness is less than or equal to 30 mu m, filtering and discharging to obtain the inorganic zinc-rich paint main agent.
The curing agent is commercially available ethyl silicate hydrolysate with the solid content of 22%, and the mass ratio of the main agent to the curing agent is 5:1, mixing and stirring uniformly to obtain the inorganic zinc-rich paint.
Comparative example 4
The phenoxy resin in the example 1 of the invention is replaced by epoxy resin in equal quantity, and the rest components and the preparation process are the same.
Because the TG point (glass transition temperature) of the epoxy resin is low, it usually exists in a liquid form, and needs to react and crosslink with a curing agent to cure into a film, so that a one-component coating cannot be achieved; the zinc powder coating prepared without the curing agent has poor salt spray resistance, and foaming occurs after 200 hours; the weight average molecular weight of the bisphenol A epoxy resin is between 350 and 1500, which is far lower than 25000 to 60000 of phenoxy resin, and the small addition amount of the bisphenol A epoxy resin can not bond zinc powder coating, so that the coating has poor pulling-off adhesion.
Comparative example 5
The styrene-acrylonitrile copolymer in example 1 of the present invention was replaced with an acrylonitrile-butadiene-styrene copolymer, and the remaining components and the preparation process were the same.
Because the amino group in the molecular structure of the acrylonitrile-butadiene-styrene copolymer is crosslinked and shielded, hydrogen bond complexation cannot be generated in the liquid phase after the dissolution, and the thixotropic effect is avoided, the prepared zinc powder coating is extremely easy to sink to form hard precipitation; the acrylonitrile-butadiene-styrene copolymer is elastic plastic, and the prepared zinc powder coating has poor adhesion effect on a metal substrate.
Comparative example 6
The polymethyl silicate hydrolytic polycondensate in example 1 of the present invention was replaced with a polyethyl silicate hydrolytic polycondensate, and the remaining components and the preparation process were the same.
Because the methoxy groups in methyl silicate are much more active than the ethoxy groups in ethyl silicate, the poly-methyl silicate polycondensate is cured to form a film quickly during the hydrolysis polycondensation curing reaction, the drying time of the coating is obviously different, the coating prepared in the example 1 can be dried and hard at 25 ℃ and 60% air humidity for 50 minutes, and the coating in the comparative example 6 cannot be dried and hard at 130 minutes, cannot be subjected to a complexing reaction with zinc powder in the air quickly, and the flexibility and the anti-rain-flower property of a paint film are affected.
Product effect test
The paints prepared in the above examples and comparative examples were tested for neutral salt spray resistance, pull-apart adhesion, flexibility, pot life, and resistance to rain and bloom, and the results are shown in table 2.
The coating test performance is prepared by the examples and the comparative examples, wherein the base material of the neutral salt spray resistance and pull-open adhesion test project is selected to be 150 x 70 x 5mm sand-blast steel plate, the sand-blast cleanliness is Sa2.5, and the film thickness is regulated to be 80-100 mu m; the flexible test project substrate was selected to be 150 x 70 x 5 x 0.2mm tinplate, and was thoroughly polished with 400 mesh sandpaper to a film thickness of 21-25 μm; the substrate of the test item for resistance to rain and bloom was a 400mm x 1mm carbon steel plate, which was thoroughly polished with 400 mesh sandpaper and the film thickness was specified to be 90 μm.
The neutral salt spray resistance of the coating is tested according to the GB/T1771 method;
the pull-off adhesion performance of the coating was tested according to the GB/T5210 method;
the flexibility of the paint coating was tested according to the GB/T1731 method;
the pot life performance of the coating is tested according to the GB/T31416 method;
the storage stability of the coating was tested according to the method of GB 6753.3;
the anti-rain and anti-bloom test of the coating is to put the test board into a rain test box, take out the test board after 168 hours and observe the appearance change condition of the coating, and the white zinc salt spots ooze out or not, and the paint film has obvious bloom or not.
TABLE 2
As can be seen from Table 2, the neutral salt fog resistance and the pull-off adhesion of the coating prepared by the embodiment of the invention are obviously better than those of the coatings of the comparative examples.
It can be seen from Table 2 that (1) the coating formed by the modified phenoxy resin cold zinc spraying coating has excellent salt spray resistance, and the salt spray resistance can reach more than 8000 hours;
(2) The coating formed by the modified phenoxy resin cold zinc spraying coating has excellent adhesive force, and the pulling adhesive force can reach more than 8 MPa;
(3) The coating formed by the modified phenoxy resin cold zinc spraying coating has excellent flexibility, and the flexibility is 1 mm;
(4) Compared with the traditional two-component zinc-rich paint, the modified phenoxy resin cold zinc-spraying paint provided by the invention is a single-component paint without limitation of pot life;
(5) Compared with the traditional two-component zinc-rich paint and the conventional cold zinc-spraying paint, the modified phenoxy resin cold zinc-spraying paint has excellent heat storage stability and sedimentation degree of 10 grades;
(6) The coating formed by the modified phenoxy resin cold spray zinc coating has excellent rain and flower resistance compared with the conventional cold spray zinc coating.
The foregoing examples are merely illustrative of the technical solution of the present invention and are not intended to limit the specific embodiments of the present invention. Other variations or modifications of the above description will be apparent to those of skill in the art. It is not necessary or highly desirable to list all embodiments herein. All technical schemes obtained by adopting equivalent substitution or equivalent transformation fall within the protection scope of the invention.
Claims (10)
1. The modified phenoxy resin cold spray zinc coating is characterized by comprising the following components: phenoxy resin, styrene-acrylonitrile copolymer, polymethyl silicate hydrolytic polycondensate, zinc powder and solvent;
the mass portion ratio of the zinc powder to the phenoxy resin is (80-88): (1.6-2.5).
2. The modified phenoxy resin cold spray zinc coating according to claim 1, comprising the following components in parts by weight: 1.6 to 2.0 parts of phenoxy resin, 0.6 to 1.8 parts of styrene-acrylonitrile copolymer, 0.1 to 0.8 part of polymethyl silicate hydrolytic polycondensate, 80 to 88 parts of zinc powder and 10 to 20 parts of solvent.
3. The modified phenoxy resin cold spray zinc coating according to claim 1, wherein the phenoxy resin has a weight average molecular weight of 25000 to 70000.
4. The modified phenoxy resin cold zinc spraying coating according to claim 1, wherein the zinc powder contains more than 99.5% of zinc element by mass and more than 97% of metal zinc by mass.
5. The modified phenoxy resin cold spray zinc coating according to any one of claims 1 to 4, wherein the zinc powder has at least one of a mesh size of 500 to 600 mesh, 700 to 800 mesh, and 900 to 1000 mesh.
6. The modified phenoxy resin cold spray zinc coating according to claim 1, wherein the solvent is cyclohexanone.
7. The modified phenoxy resin cold spray zinc coating according to claim 6, comprising the following components in parts by mass: 1.6 to 2.0 parts of phenoxy resin, 0.8 to 1.2 parts of styrene-acrylonitrile copolymer, 0.2 to 0.3 part of polymethyl silicate hydrolytic polycondensate, 80 to 83 parts of zinc powder and 12 to 15 parts of cyclohexanone.
8. The method for preparing the modified phenoxy resin cold spray zinc coating according to any one of claims 1 to 7, comprising the following steps:
and mixing the components to prepare the modified phenoxy resin cold zinc spraying coating.
9. The use method of the modified phenoxy resin cold spray zinc coating according to any one of claims 1 to 7, comprising the following steps:
and during construction operation, the modified phenoxy resin cold zinc spraying coating is coated on a metal substrate, and the modified phenoxy resin cold zinc spraying coating is obtained after drying.
10. Use of the modified phenoxy resin cold spray zinc coating according to any one of claims 1 to 7 in the field of corrosion protection.
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