AU2021103862A4 - Impact-resistant Anti-corrosive Interpenetrating Polymer Network Coating - Google Patents
Impact-resistant Anti-corrosive Interpenetrating Polymer Network Coating Download PDFInfo
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- AU2021103862A4 AU2021103862A4 AU2021103862A AU2021103862A AU2021103862A4 AU 2021103862 A4 AU2021103862 A4 AU 2021103862A4 AU 2021103862 A AU2021103862 A AU 2021103862A AU 2021103862 A AU2021103862 A AU 2021103862A AU 2021103862 A4 AU2021103862 A4 AU 2021103862A4
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- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims abstract description 4
- 229920002647 polyamide Polymers 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 38
- 239000006255 coating slurry Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 25
- 150000005130 benzoxazines Chemical class 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000003712 anti-aging effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 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 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 5
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 4
- HBMFCGVCUHLQPN-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol;zinc Chemical compound [Zn].C1=CC=C2NC(CS)=NC2=C1 HBMFCGVCUHLQPN-UHFFFAOYSA-N 0.000 claims description 4
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 4
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 4
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 4
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 4
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 claims description 4
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940081974 saccharin Drugs 0.000 claims description 3
- 235000019204 saccharin Nutrition 0.000 claims description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000035515 penetration Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 230000005856 abnormality Effects 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- JIJAYWGYIDJVJI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 JIJAYWGYIDJVJI-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
IMPACT-RESISTANTANTI-CORROSIVE INTERPENETRATING POLYMER
NETWORK COATING
ABSTRACT
The present disclosure provides an impact-resistant anti-corrosive interpenetrating polymer
network coating, and belongs to the technical field of anti-corrosive coatings. In the present
disclosure, the impact-resistant anti-corrosive interpenetrating polymer network coating is prepared
by blending hydroxymethyl polyamide (HMPA) and a benzoxazine resin, dispersing in a liquid PA,
and treating with a curing agent. The impact-resistant anti-corrosive interpenetrating polymer
network coating features improved adhesion, toughness, compactness, strong penetration resistance,
resistance to a variety of chemicals, improved resistance to water and salt water, high modulus, high
strength, desirable heat resistance, low water absorption and flame retardancy. The curing process
of the coating prevents the release of small molecules, so the coating has low shrinkage, low water
absorption and low dielectric constant, achieving improved processing and use performance.
Description
[01] The present disclosure belongs to the technical field of chemical industry, and specifically provides an impact-resistant anti-corrosive interpenetrating polymer network coating.
[02] Interpenetrating polymer network anti-corrosive coating is a new type of anti-corrosive series coating. It is an interpenetrating polymer network (IPN) formed by interpenetrating a rubber network and a plastic network that can produce the same effect. It is also called "polymeralloy", featuring improved comprehensive performance and stable production technology. The product has improved physical and mechanical properties and improved corrosion resistance to sulfuric acid, hydrochloric acid, phosphoric acid, salt water, caustic alkali, gasoline, etc. at room temperature, and is easy for construction and operation. It can be widely used in anti-corrosion engineering, including the anti-corrosion of enterprise equipment, pipelines, tanks, sewage tanks, buildings, metals and cement surfaces. At present, most of the interpenetrating polymer network coatings on the market use polyurethane and epoxy resin to form the interpenetrating polymer network. In these similar coatings, polyurethane has poor gloss and color retention and is easy to yellow, making it hard to repair the coating film in case of damage. The isocyanate and diformaldehyde in the coating are irritating to the human body. The isocyanate is reactive and sensitive to water, damp and alcohols, and a high water content of the coating will seriously affect the performance of the coating, making the coating film prone to defects such as blisters, pinholes or discoloration. In addition, the epoxy component has poor weather resistance, such that the coating is easy to chalk to deteriorate the fullness in outdoor applications. To meet the existing use requirements and market requirements, it is urgently necessary for those skilled in the art to develop a method for preparing an impact resistant anti-corrosive interpenetrating polymer network coating.
[03] In order to address the above problems or provide a useful alternative, an objective of the present disclosure is to provide an impact-resistant anti-corrosive interpenetrating polymer network coating.
[04] The present disclosure is implemented through the following technical solution.
[05] An impact-resistant anti-corrosive interpenetrating polymer network coating includes an independently packaged coating slurry and an independently packaged curing agent slurry, and the coating is produced by mixing the coating slurry and the curing agent slurry before use, where the mixing of the independently packaged coating slurry and the independently packaged curing agent slurry includes: mixing the coating slurry and the curing agent slurry in a weight ratio of 10:(0.8-0.9) before use; or applying the coating slurry alone, and evenly spraying the curing agent slurry on a surface of the coating slurry according to the weight ratio of the coating slurry to the curing agent slurry, that is, 10:(0.8-0.9).
[06] The coating slurry may be prepared as follows:
[07] a: preparation of modified benzoxazine: adding 10.4-12.7 parts of cardanol, 25-33 parts of a 22-24% aqueous formaldehyde solution, 12.5-13.4 parts of 2,6-diisopropylaniline, 0.4-0.5 parts of lignin and 33-37 parts of toluene into a reactor provided with a condenser and a thermometer; electromagnetically stirring at room temperature for 10-15 min to make the components fully mixed; stirring at 75-80°C for 2-4 h; dispersing a resultant product in dioxane; washing with a 4-6% ammonia solution, and then washing with water until neutral; adding anhydrous calcium sulfate to remove the water, filtering, and removing the solvent by rotary evaporation with a rotary evaporator; drying to a constant weight at 50-65°C to obtain the modified benzoxazine;
[08] b: preparation of a benzoxazine resin mixed powder: mixing 23-25 parts of the modified benzoxazine resin, 35-41 parts of a bisphenol A benzoxazine resin, 34-45 parts of hydroxymethyl polyamide (HMPA) and 17-22 parts of an inorganic filler to obtain a mixture; melt-blending and extruding the obtained mixture, cooling, and then pulverizing to obtain the benzoxazine resin mixed powder, where the melt-blending is carried out at 178-185°C for 1-2 min; the inorganic filler includes the following components in parts by weight: 2-6 parts of polyaniline and 4-8 parts of diabase powder; c: mixing: mixing liquid PA with the benzoxazine resin mixed powder, carbon black, polyethyleneimine, an accelerator and an anti-aging agent evenly to obtain a liquid mixture, where the liquid mixture includes the following components in parts by weight: 20-23 parts of the liquid PA, 41-45 parts of the benzoxazine resin mixed powder, 4-5 parts of the carbon black, 1-2 parts of the polyethyleneimine, 0.5-1 part of the accelerator and 0.5-1 part of the anti-aging agent; and d: grinding and stirring: transferring the obtained liquid mixture to a three-roll grinder, heating to 75-85°C, grinding for 5-10 min, and dispersing the liquid mixture to obtain the coating slurry.
[09] Further, the curing agent slurry may be prepared as follows: evenly mixing the following components in parts by weight at 25-30°C: 12-15 parts of isophthaloyl dichloride, 0.5-1 part of 18 crown-6, 0.2-0.4 parts of benzyltriethylammonium chloride, 0.5-1 part of sodium n-butyl naphthalene sulfonate and 2-4 parts of dichloromethane, and sealing.
[10] Further, the anti-aging agent in step c may be a mixture of styrenated phenol and zinc 2 mercaptomethylbenzimidazole in a weight ratio of 2:1.
[11] Further, the accelerator in step c may be one of saccharin and N-butyl maleimide.
[12] The HMPA in step b may be one of HMPA 1010 and HMPA 1313 with 4-6% by mass of hydroxymethyl.
[13] One of the key technologies of the preparation method of the impact-resistant anti-corrosive interpenetrating polymer network coating provided by the present disclosure is to use plastics with different properties such as PA, chlorinated polyether and benzoxazine to mutually match and promote each other. Due to the hydrogen chloride released by the cross-linking reaction of the HMPA and the PA, the benzoxazine does not need a curing agent during the cross-linking curing process. Because of the presence of the active hydrogen, the cross-linking density is rapidly increased, and the hydrogen chloride is absorbed, thus presenting a highly reactive cationic structure, thereby reducing the curing temperature. In this way, the benzoxazine interpenetrates with the PA molecular chain to form a unified cross-linked network structure, such that the coating has better comprehensive performance such as higher impact strength and better anti-corrosion performance.
[14] The reaction process of forming the interpenetrating polymer network is simply as follows:
WI Oi0 N
[15] The present disclosure has the following effects:
[16] The present disclosure does not use the conventional rubber and plastic interpenetrating polymer network formation mode, but uses two plastic phases, namely, the PA and the benzoxazine resin to form the interpenetrating polymer network. The present disclosure improves the impact toughness and adhesion of the benzoxazine resin and even the coating as a whole, and improves the fluidity of the coating, while still maintaining the advantages of the benzoxazine resin. The PA used in the present disclosure is HMPA. The present disclosure utilizes the hydroxymethyl or active hydrogen to react to form chemical bonds during the formation or curing of the benzoxazine resin interpenetrating polymer network to achieve the purpose of synchronous modification. Through the formation of the PA interpenetrating polymer network, the present disclosure improves the adhesion of the coating to the substrate, improves the brittleness of the benzoxazine resin, increases the mechanical strength of the composite material, and increases the curing rate so as to help reduce the molding difficulty of the coating. Due to the introduction of the PA, the concentration of the benzoxazine resin in the resin mixture is correspondingly reduced, and the curing rate of the resin is slowed down, such that it can be applied to the anti-corrosive coating. The PA-modified benzoxazine resin improves the impact toughness and adhesion of the benzoxazine resin, and improves the fluidity of the benzoxazine resin, while still maintaining the advantages of the benzoxazine resin. The present disclosure utilizes the hydroxymethyl or active hydrogen to react to form chemical bonds during the resin synthesis or curing process to achieve the purpose of modification. The PA has high toughness, high compatibility with the benzoxazine resin and high heat resistance and modulus. The addition of the PA to the benzoxazine resin can improve the toughness of the matrix resin without reducing other properties. The mechanisms of the PA here are mainly fracture anchoring and toughening by forming a semi-interpenetrating polymer network polymer with a thermoplastic. In the fracture anchoring mechanism, a tough thermoplastic resin is used as the second phase, which has a rigidity close to that of the matrix and has a certain degree of toughness and a high elongation at break. When the volume fraction of the second phase is appropriate, the fracture anchoring mechanism occur. In the toughening mechanism realized by a semi-interpenetrating polymer network structure, when the amount of the thermoplastic resin used in the system is large, the PA continuously penetrates the thermosetting resin network, playing the role of "forced tolerance" and "synergistic effect". Due to the presence of the thermoplastic resin and the thermosetting resin network in the semi-interpenetrating polymer network structure, the cross-linked network maintains high toughness, low water absorption, high chemical stability and high dimensional stability. The cross-linking reaction of the polyethyleneimine with the curing agent slurry to form the cross-linked PA, and the 18-crown-6, the benzyltriethylammonium chloride and the sodium n-butyl naphthalene sulfonate promote the cross-linking reaction. Further, the cross linking and interpenetration of the benzoxazine with the PA is realized, which further improves the impact strength and corrosion resistance of the coating film. In addition, the formed interpenetrating polymer network has damping properties to play a certain role.
[17] Compared with the prior art, the present disclosure has the following preferred features.
[18] In the present disclosure, the coating slurry and the curing agent are separately packaged, such that the interpenetrating polymer network anti-corrosive coating is more convenient and reasonable to use, which is different from the preparation of the interpenetrating polymer network anti-corrosive coating in the past. In the present disclosure, the impact-resistant anti-corrosive interpenetrating polymer network coating is prepared by blending the HMPA and the benzoxazine resin, dispersing in the liquid PA, and treating with the curing agent. The impact-resistant anti corrosive interpenetrating polymer network coating features improved adhesion, toughness, compactness, strong penetration resistance, resistance to a variety of chemicals, improved resistance to water and salt water, high modulus, high strength, desirable heat resistance, low water absorption and flame retardancy. The curing process of the coating prevents the release of small molecules, so the coating has low shrinkage, low water absorption and low dielectric constant, achieving improved processing and use performance.
[19] The present disclosure is described below with reference to the specific examples, but the present disclosure is not limited thereto.
[20] Example 1
[21] A coating includes an independently packaged coating slurry and an independently packaged curing agent slurry, and the coating is produced by mixing the coating slurry and the curing agent slurry before use, where the mixing of the independently packaged coating slurry and the independently packaged curing agent slurry includes: mix the coating slurry and the curing agent slurry in a weight ratio of 10:0.9 before use. The coating slurry is prepared as follows. (1) Preparation of modified benzoxazine: add 12.7 parts of cardanol, 33 parts of a 24% aqueous formaldehyde solution, 13.4 parts of 2,6-diisopropylaniline, 0.5 parts of lignin and 37 parts of toluene into a reactor provided with a condenser and a thermometer; electromagnetically stir at room temperature for 15 min to make the components fully mixed; stir at 80°C for 4 h; disperse a resultant product in dioxane; wash with a 4-6% ammonia solution, and then wash with water until neutral; add anhydrous calcium sulfate to remove the water, filter, and remove the solvent by rotary evaporation with a rotary evaporator; dry to a constant weight at 50-65°C to obtain the modified benzoxazine. (2) Preparation of a benzoxazine resin mixed powder: mix 25 parts of the modified benzoxazine resin, 41 parts of a bisphenol A benzoxazine resin, 45 parts of hydroxymethyl polyamide (HMPA) and 22 parts of an inorganic filler to obtain a mixture; melt-blend and extrude the obtained mixture, cool, and then pulverize to obtain the benzoxazine resin mixed powder, where the melt-blending is carried out at 185°C for 2 min. The inorganic filler includes the following components in parts by weight: 6 parts of polyaniline and 8 parts of diabase powder. (3) Mixing: mix liquid PA with the benzoxazine resin mixed powder, carbon black, polyethyleneimine, an accelerator and an anti-aging agent evenly to obtain a liquid mixture, where the liquid mixture includes the following components in parts by weight: 20-23 parts of the liquid PA, 45 parts of the benzoxazine resin mixed powder, 5 parts of the carbon black, 2 parts of the polyethyleneimine, 1 part of the accelerator N-butyl maleimide and 1 part of the anti-aging agent. (4) Grinding and stirring: transfer the obtained liquid mixture to a three-roll grinder, heat to 85°C, grind for 10 min, and disperse the liquid mixture to obtain the coating slurry. The curing agent slurry is prepared as follows: evenly mix the following components in parts by weight at 30°C: 15 parts of isophthaloyl dichloride, 1 part of 18-crown-6, 0.4 parts of benzyltriethylammonium chloride, 1 part of sodium n butyl naphthalene sulfonate and 4 parts of dichloromethane, and seal. The anti-aging agent in step
(3) is a mixture of styrenated phenol and zinc 2-mercaptomethylbenzimidazole in a weight ratio of 2:1. The HMPA in step (2) is HMPA 1010 with 6% by mass of hydroxymethyl.
[22] Example 2
[23] A coating includes an independently packaged coating slurry and an independently packaged curing agent slurry, and the coating is produced by mixing the coating slurry and the curing agent slurry before use, where the coating slurry is applied alone, and the curing agent slurry evenly sprayed on a surface of the coating slurry according to a weight ratio of the coating slurry to the curing agent slurry, that is, 10:0.8.
[24] The coating slurry is prepared as follows. (1) Preparation of modified benzoxazine: add 10.4 parts of cardanol, 25-33 parts of a 22% aqueous formaldehyde solution, 12.5 parts of 2,6 diisopropylaniline, 0.4 parts of lignin and 33 parts of toluene into a reactor provided with a condenser and a thermometer; electromagnetically stir at room temperature for 10 min to make the components fully mixed; stir at 75°C for 2-4 h; disperse a resultant product in dioxane; wash with a 4% ammonia solution, and then wash with water until neutral; add anhydrous calcium sulfate to remove the water, filter, and remove the solvent by rotary evaporation with a rotary evaporator; dry to a constant weight at 50°C to obtain the modified benzoxazine. (2) Preparation of a benzoxazine resin mixed powder: mix 23 parts of the modified benzoxazine resin, 35 parts of a bisphenol A benzoxazine resin, 34 parts of HMPA and 17 parts of an inorganic filler to obtain a mixture; melt blend and extrude the obtained mixture, cool, and then pulverize to obtain the benzoxazine resin mixed powder, where the melt-blending is carried out at 178°C for 1 min; the inorganic filler includes the following components in parts by weight: 6 parts of polyaniline and 8 parts of diabase powder. (3) Mixing: mix liquid PA with the benzoxazine resin mixed powder, carbon black, polyethyleneimine, an accelerator and an anti-aging agent evenly to obtain a liquid mixture, where the liquid mixture includes the following components in parts by weight: 20-23 parts of the liquid PA, 41 parts of the benzoxazine resin mixed powder, 5 parts of the carbon black, 1-2 parts of the polyethyleneimine, 0.5 parts of the accelerator saccharin and 0.5 parts of the anti-aging agent. (4) Grinding and stirring: transfer the obtained liquid mixture to a three-roll grinder, heat to 75°C, grinding for 5 min, and disperse the liquid mixture to obtain the coating slurry.
[25] Further, the curing agent slurry is prepared as follows: evenly mix the following components in parts by weight at 25-30°C: 12 parts of isophthaloyl dichloride, 0.5 parts of 18 crown-6, 0.2 parts of benzyltriethylammonium chloride, 0.5 parts of sodium n-butyl naphthalene sulfonate and 2 parts of dichloromethane, and seal. The anti-aging agent in step (3) is a mixture of styrenated phenol and zinc 2-mercaptomethylbenzimidazole in a weight ratio of 2:1. The HMPA in step (2) is HMPA 1313 with 4% by mass of hydroxymethyl.
[26] Comparative Example 1
[27] Compared with Example 2, in this comparative example, except that the modified benzoxazine resin is omitted in step (2), the other steps are the same.
[28] Comparative Example 2
[29] Compared with Example 2, in this comparative example, except that the HMPA is omitted in step (2), the other steps are the same.
[30] Comparative Example 3
[31] Compared with Example 2, in this comparative example, except that the polyethyleneimine is omitted in step (3), the other steps are the same.
[32] Comparative Example 4
[33] Compared with Example 2, in this comparative example, except that the polyaniline is omitted in step (2), the other steps are the same.
[34] Comparative Example 5
[35] Compared with Example 2, in this comparative example, except that the diabase powder is omitted in step (2), the other steps are the same.
[36] The impact-resistant anti-corrosive interpenetrating polymer network coating of Examples 1 to 2 and Comparative Examples 1 to 5 were subjected to performance tests, and the test results are shown in Table 1.
[37] Table 1 Performance test results of impact-resistant anti-corrosive interpenetrating polymer network coating of Examples 1 to 2 and Comparative Examples 1 to 5 Example 2 Comparative Comparative Comparative Comparativ Comparativ Items Example 1 Example 1 Example 2 Example 3 e Example 4 e Example 5 Pencil hardness 5H 5H 5H 5H 5H 5H 5H Impact 55.3 57.2 51.5 52.7 51.8 52.3 53.2 resistance /cm Bending test 1.3 1.2 1.1 1.2 1.3 1.1 1.2 /mm Cross-cut test /level Acid resistance 360h 360h 168h 168h 168h 168h 168h (5% sulfuric 36h36h16h16h16h18h18h without without without without without without acid solution, 48 without h) abnormality abnormality abnormality abnormality abnormality abnormality abnormality
Alkali 360 h 360 h 168 h 168 h 168 h 168 h 168 h resistance (2% without without without without without without without NaOH, 48 h) abnormality abnormality abnormality abnormality abnormality abnormality abnormality Alkali resistance 240 h 240 h 168 h 168 h 168 h 168 h 168 h
[saturated without without without without without without without Ca(OH)2 abnormality abnormality abnormality abnormality abnormality abnormality abnormality solution] 240h 240h 168h 168h 168h 168h 168h Water resistance without without without without without without without abnormality abnormality abnormality abnormality abnormality abnormality abnormality
Salt water 360 h 360 h 168 h 168 h 168 h 168 h 168 h resistance (3% without without without without without without without NaCl, 48 h) abnormality abnormality abnormality abnormality abnormality abnormality abnormality
240h 240h 144h 144h 144h 144h 144h without without without without without Salt spray without without blistering, blistering, blistering, blistering, blistering, blistering, blistering, resistance rusting or rusting or rusting or rusting or rusting or rusting or rusting or peeling peeling peeling peeling peeling peeling peeling
[38] Note: The above tests referred to the following standards: GB/T 1720-1979 Method of Test for Adhesion of Coating films; GB/T 1723-1993 Determination of Viscosity of Coatings; GB/T 1727-1992 General Preparationof Coatingfilm; GB/T 1728-1979 Methods of Testfor Drying Time of Coatings of Coatings and Putties; GB/T 1730-2007 Coatings and Varnishes - Pendulum Damping Test; GB/T 1731-1993 Determination of Flexibility of Films; GB/T 1732-1993 Determination of Impact Resistance of Film; GB/T 3186-2006 Coatings Varnishes and Raw Materials for Coatings and Varnishes - Sampling; GB 9274-1988 Coatings and Varnishes Determination of Resistance to Liquids; GB/T 9278-2008 Temperatures and Humidity for Conditioning and Testing of Coating Specimens; GB/T 9754-2007 Coatings and Varnishes Determination of Specular Gloss of Non-metallic Coating films at 20, 60 °and 85°; and GB/T 9761-2008 Coatings and Varnishes - Visual Comparison of the Color of Coatings.
Claims (5)
1. An impact-resistant anti-corrosive interpenetrating polymer network coating, wherein the coating comprises an independently packaged coating slurry and an independently packaged curing agent slurry, and the coating is produced by mixing the coating slurry and the curing agent slurry before use; the mixing of the independently packaged coating slurry and the independently packaged curing agent slurry comprises: mixing the coating slurry and the curing agent slurry in a weight ratio of 10:(0.8-0.9) before use; or applying the coating slurry alone, and evenly spraying the curing agent slurry on a surface of the coating slurry according to the weight ratio of the coating slurry to the curing agent slurry, that is, 10:(0.8-0.9).
2. The impact-resistant anti-corrosive interpenetrating polymer network coating according to claim 1, wherein the coating slurry is prepared as follows: a: preparation of modified benzoxazine: adding 10.4-12.7 parts of cardanol, 25-33 parts of a 22 24% aqueous formaldehyde solution, 12.5-13.4 parts of 2,6-diisopropylaniline, 0.4-0.5 parts of lignin and 33-37 parts of toluene into a reactor provided with a condenser and a thermometer; electromagnetically stirring at room temperature for 10-15 min to make the components fully mixed; stirring at 75-80°C for 2-4 h; dispersing a resultant product in dioxane; washing with a 4-6% ammonia solution, and then washing with water until neutral; adding anhydrous calcium sulfate to remove the water, filtering, and removing the solvent by rotary evaporation with a rotary evaporator; drying to a constant weight at 50-65°C to obtain the modified benzoxazine; b: preparation of a benzoxazine resin mixed powder: mixing 23-25 parts of the modified benzoxazine resin, 35-41 parts of a bisphenol A benzoxazine resin, 34-45 parts of hydroxymethyl polyamide (HMPA) and 17-22 parts of an inorganic filler to obtain a mixture; melt-blending and extruding the obtained mixture, cooling, and then pulverizing to obtain the benzoxazine resin mixed powder, wherein the melt-blending is carried out at 178-185°C for 1-2 min; the inorganic filler comprises the following components in parts by weight: 2-6 parts of polyaniline and 4-8 parts of diabase powder; c: mixing: mixing liquid PA with the benzoxazine resin mixed powder, carbon black, polyethyleneimine, an accelerator and an anti-aging agent evenly to obtain a liquid mixture, wherein the liquid mixture comprises the following components in parts by weight: 20-23 parts of the liquid PA, 41-45 parts of the benzoxazine resin mixed powder, 4-5 parts of the carbon black, 1 2 parts of the polyethyleneimine, 0.5-1 part of the accelerator and 0.5-1 part of the anti-aging agent; and d: grinding and stirring: transferring the obtained liquid mixture to a three-roll grinder, heating to 75-85°C, grinding for 5-10 min, and dispersing the liquid mixture to obtain the coating slurry.
3. The impact-resistant anti-corrosive interpenetrating polymer network coating according to claim 1, wherein the curing agent slurry is prepared as follows: evenly mixing the following components in parts by weight at 25-30°C: 12-15 parts of isophthaloyl dichloride, 0.5-1 part of 18 crown-6, 0.2-0.4 parts of benzyltriethylammonium chloride, 0.5-1 part of sodium n-butyl naphthalene sulfonate and 2-4 parts of dichloromethane, and sealing.
4. The impact-resistant anti-corrosive interpenetrating polymer network coating according to claim 1, wherein the anti-aging agent in step c is a mixture of styrenated phenol and zinc 2 mercaptomethylbenzimidazole in a weight ratio of 2:1; wherein the accelerator in step c is one of saccharin and N-butyl maleimide.
5. The impact-resistant anti-corrosive interpenetrating polymer network coating according to claim 1, wherein the HMPA in step b is one of HMPA 1010 and HMPA 1313 with 4-6% by mass of hydroxymethyl.
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