CN115612066A - Micromolecular corrosion inhibitor modified waterborne epoxy curing agent and preparation method thereof - Google Patents
Micromolecular corrosion inhibitor modified waterborne epoxy curing agent and preparation method thereof Download PDFInfo
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- CN115612066A CN115612066A CN202211372925.XA CN202211372925A CN115612066A CN 115612066 A CN115612066 A CN 115612066A CN 202211372925 A CN202211372925 A CN 202211372925A CN 115612066 A CN115612066 A CN 115612066A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 66
- 238000005260 corrosion Methods 0.000 title claims abstract description 66
- 239000004593 Epoxy Substances 0.000 title claims abstract description 54
- 239000003112 inhibitor Substances 0.000 title claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 alicyclic amine Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 22
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QTKDDPSHNLZGRO-UHFFFAOYSA-N 4-methylcyclohexane-1,3-diamine Chemical compound CC1CCC(N)CC1N QTKDDPSHNLZGRO-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 2
- IDLHTECVNDEOIY-UHFFFAOYSA-N 2-pyridin-4-ylethanamine Chemical compound NCCC1=CC=NC=C1 IDLHTECVNDEOIY-UHFFFAOYSA-N 0.000 claims description 2
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 claims description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 229920006334 epoxy coating Polymers 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 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 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 244000226021 Anacardium occidentale Species 0.000 description 4
- 235000020226 cashew nut Nutrition 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UFZOLVFGAOAEHD-UHFFFAOYSA-N benzaldehyde;phenol Chemical compound OC1=CC=CC=C1.O=CC1=CC=CC=C1 UFZOLVFGAOAEHD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- UZRCGISJYYLJMA-UHFFFAOYSA-N phenol;styrene Chemical compound OC1=CC=CC=C1.C=CC1=CC=CC=C1 UZRCGISJYYLJMA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a micromolecular corrosion inhibitor modified waterborne epoxy curing agent and a preparation method thereof, and the preparation method comprises the following steps: heating alicyclic amine to 65-75 ℃; uniformly mixing polyether alcohol diglycidyl ether and epoxy resin, slowly dripping the mixture into alicyclic amine, and reacting for 4-5 hours to obtain an epoxy-polyamine addition product; adding a micromolecular corrosion inhibitor, and reacting for 3-4 h at 70-80 ℃ to obtain the corrosion inhibitor modified waterborne epoxy curing agent. The preparation method is simple in process flow, and the prepared waterborne epoxy curing agent can endow a waterborne epoxy coating with excellent water resistance, corrosion resistance and high mechanical property.
Description
Technical Field
The invention belongs to the technical field of waterborne epoxy resin curing agents, and particularly relates to a waterborne epoxy curing agent modified by a micromolecular corrosion inhibitor and a preparation method thereof.
Background
The epoxy resin is one of three general thermosetting resins, has no use value when independently forming a film, and can form a three-dimensional network cross-linked structure only when an epoxy curing agent is added, so that the epoxy resin shows excellent performance. The two-component epoxy resin coating has the advantages of excellent mechanical property, chemical resistance, corrosion resistance, high adhesive force and the like, and is widely applied to the field of metal corrosion prevention. However, the traditional epoxy resin anticorrosive paint is a typical solvent-based system, contains a certain proportion of volatile compounds, can release a large amount of organic solvents in the processes of construction, curing and film forming, and causes great harm to the environment and human health. In recent years, with the development of coating technology, the market share of waterborne epoxy resin coatings has increased from health and environmental concerns. However, the water resistance and corrosion resistance of the current two-component water-based epoxy resin coating are still different from those of the traditional solvent-based epoxy system, especially in the field of heavy corrosion resistance.
Currently, the epoxy-polyamine adduct is prepared from aliphatic polyamine as a general rule in the case of aqueous epoxy curing agents. For example, CN109161001A discloses a waterborne epoxy resin curing agent of epoxy-polyamine adduct prepared from aliphatic polyamine, and by using benzaldehyde phenol polyoxyethylene ether (obtained by oxidizing styrene phenol polyoxyethylene ether) for blocking, better corrosion resistance is endowed to a coating; CN10604632A discloses an epoxy-polyamine adduct water-borne epoxy resin curing agent prepared from triethylene tetramine, and the problem of poor hardness of a water-borne epoxy coating is solved by introducing a silane coupling agent. Although aliphatic polyamines can impart better hydrophilicity and toughness to the curing agent, the coating film produced by such curing agent has low hardness, poor water resistance, and poor corrosion resistance, and cannot protect metals for a long period of time.
The organic corrosion inhibitors are various in types, and one type of the organic corrosion inhibitors is heterocyclic compounds containing nitrogen, sulfur, oxygen, phosphorus and other heteroatoms. Owing to the electronegative elements such as N, S, O and P, the corrosion inhibitor has the capability of being rapidly adsorbed on the metal surface, and can generate a coordination reaction with transition metal containing empty orbitals to generate a passivation layer, thereby delaying the progress of metal corrosion. The addition of trace or small amount of chemical matter can lower the corrosion rate of metal material in medium obviously while maintaining the original physical and mechanical performance of metal material unchanged.
The corrosion inhibitor is a feasible means for improving the corrosion resistance of the coating, but the corrosion inhibitor cannot play a role in long-acting protection by directly adding the corrosion inhibitor, and the common solution is to use nano microspheres to encapsulate the corrosion inhibitor. For example, CN111253831A discloses a scheme for encapsulating a corrosion inhibitor by using lignin microspheres, wherein the corrosion inhibitor encapsulated by the lignin microspheres is released under the change of pH caused by corrosion, so that the self-repairing capability of an epoxy coating is successfully endowed; CN110105843A discloses a method for encapsulating a corrosion inhibitor by a CuO microcapsule, and successfully constructs an anticorrosive coating material with double effects of pH response and self-repair. However, this method is complicated and has high requirements for the process, and the introduction of the nanospheres into the coating may cause the adhesion of the coating to be reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a micromolecule corrosion inhibitor modified waterborne epoxy curing agent with simple process and good stability for corrosion prevention, which is used for solving the problems of poor water resistance, insufficient long-term corrosion resistance and the like of a coating obtained by curing waterborne epoxy resin by using the existing curing agent.
The technical scheme adopted by the invention is as follows:
a preparation method of a micromolecular corrosion inhibitor modified waterborne epoxy curing agent is characterized by comprising the following steps:
(1) Mixing polyether alcohol diglycidyl ether with epoxy resin to obtain an epoxy prepolymer; adding the epoxy prepolymer into alicyclic polyamine for reaction to obtain an epoxy addition product;
(2) Adding a micromolecular corrosion inhibitor to continue the reaction;
(3) Adding a solvent to adjust the solid content to obtain a micromolecular corrosion inhibitor modified waterborne epoxy curing agent;
the micromolecular corrosion inhibitor has two molecular structural characteristics at the same time: (a) a heterocyclic ring containing nitrogen and/or sulfur in the molecular structure; and (b) the molecular structure has primary amine or epoxy group.
Preferably, in the step (1), the epoxy resin is one or more of bisphenol a epoxy resin and bio-based epoxy resin.
Preferably, the bisphenol A type epoxy resin is E-20, E-44, E-51; the bio-based epoxy resin is NC-514s.
Preferably, in the step (1), the epoxy prepolymer is slowly dripped into alicyclic polyamine, and stirred and reacted for 4-5 h at the temperature of 65-75 ℃; in the step (2), the reaction temperature is increased to 75-85 ℃, the micromolecular corrosion inhibitor is slowly added, and the mixture is stirred and reacts for 3-4 hours; in the step (3), slowly dripping the solvent, and stirring for reaction for 1 +/-0.5 h.
Preferably, in the step (1), the polyether alcohol diglycidyl ether is one or more of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and polyhexamethylene glycol diglycidyl ether; the epoxy value of the polyether alcohol diglycidyl ether is 0.2-0.4; the molar ratio of the epoxy resin to the polyether alcohol diglycidyl ether is 4 to 8.
Preferably, in the step (1), the alicyclic polyamine is one of 1, 2-cyclohexanediamine, 1-methyl-2, 4-cyclohexanediamine, isophoronediamine and 1, 8-diamino-p-menthane; the molar ratio of the alicyclic polyamine to the epoxy prepolymer is 2-2.2.
Preferably, in the step (2), the small molecule corrosion inhibitor is one of 2-aminothiazole, 2-aminobenzothiazole, 4- (2-aminoethyl) pyridine, benzotriazole, 5-methyl-1H-benzotriazole and 4-epoxypropane oxy carbazole; the adding mass of the micromolecular corrosion inhibitor accounts for 3-30% of the mass of the epoxy addition compound.
Preferably, in the step (3), the solvent is one or more of water, propylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether and ethylene glycol propyl ether; the solid content of the waterborne epoxy curing agent modified by the micromolecular corrosion inhibitor is 55-75%.
Preferably, the molar ratio of the epoxy resin to the polyether alcohol diglycidyl ether is 6; the molar ratio of the alicyclic polyamine to the epoxy prepolymer is 2.1.
A micromolecular corrosion inhibitor modified waterborne epoxy curing agent prepared by the preparation method.
The principle of the invention is that epoxy resin and poly (alcohol ether-diglycidyl ether) with different proportions are introduced into polyamine to adjust the hydrophily and lipophilicity of the epoxy resin, so that the curing agent and the waterborne epoxy resin have better compatibility. Meanwhile, the selected alicyclic polyamine can endow the cured coating film with better mechanical property and water resistance. In addition, the invention also introduces the micromolecule corrosion inhibitor in a covalent bond mode, compared with the corrosion inhibitor existing in a free state, the grafted corrosion inhibitor micromolecule does not generate adverse effect on the compatibility of the curing agent and the epoxy resin, can consume primary amine of the curing agent, prevents incomplete curing caused by over-high reaction rate, and is beneficial to improving the strength and the water resistance of the coating; the introduced corrosion inhibitor micromolecules are enriched on the surface side of the metal base material in the curing stage, and form a passivation layer with metal after corrosion is generated, so that the continuous occurrence of corrosion is delayed. The whole process flow is simple, and the prepared micromolecule corrosion inhibitor modified waterborne epoxy curing agent endows waterborne epoxy with excellent water resistance and long-term corrosion resistance.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) Based on an epoxy-polyamine addition method, the synthesis process is simple, the stability is good, and the adaptability with the waterborne epoxy resin is high.
(2) The alicyclic polyamine is selected, and the cured coating has high hardness and good toughness.
(3) The micromolecule corrosion inhibitor is introduced in a covalent bond mode, so that the coating has better water resistance and long-term corrosion resistance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
10.7g of isophorone diamine was added to a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 9.54g of bisphenol A type epoxy resin E-44 and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirred further, and reacted for 5 hours. Heating to 75 ℃, slowly adding 0.81g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4 hours. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor aqueous epoxy curing agent with the solid content of 60%.
Example 2
10.7g of isophorone diamine was added to a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃ and then a mixture of 9.54g of bisphenol A type epoxy resin E-44 and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and the reaction was continued for 5 hours with stirring. Heating to 75 ℃, slowly adding 2.25g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4h. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor water-based epoxy curing agent with the solid content of 65%.
Example 3
10.7g of isophorone diamine was added into a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 15.54g of cashew nut shell oil-based epoxy resin NC-514s and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirring was continued to react for 5 hours. Heating to 75 ℃, slowly adding 2.77g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4h. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor water-based epoxy curing agent with the solid content of 65%.
Example 4
8.16g of 1-methyl-2, 4-cyclohexanediamine was added to a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 15.54g of cashew nut shell oil-based epoxy resin NC-514s and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirring was continued for a reaction time of 5 hours. Heating to 75 ℃, slowly adding 2.55g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4 hours. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor water-based epoxy curing agent with the solid content of 65%.
Example 5
8.16g of 1-methyl-2, 4-cyclohexanediamine was charged into a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 15.54g of cashew nut shell oil-based epoxy resin NC-514s and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirring was continued for a reaction time of 5 hours. Heating to 75 ℃, slowly adding 4.77g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4h. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor water-based epoxy curing agent with the solid content of 70%.
Example 6
8.16g of 1-methyl-2, 4-cyclohexanediamine was charged into a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 8.28g of bisphenol A type epoxy resin E-44 and 7.5g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirring was continued and the reaction was carried out for 5 hours. Heating to 75 ℃, slowly adding 5.98g of 4-epoxypropane oxy carbazole, continuously stirring, and reacting for 4h. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the micromolecule corrosion inhibitor water-based epoxy curing agent with the solid content of 75%.
Comparative example 1
12.26g of triethylene tetramine was charged into a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 9.54g of bisphenol A type epoxy resin E-44 and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirred continuously, and reacted for 5 hours. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the water-based epoxy curing agent with the solid content of 60%.
Comparative example 2
10.7g of isophorone diamine was added to a 250mL three-necked flask equipped with a stirrer and a condenser, heated to 65 ℃, and then a mixture of 15.54g of cashew nut shell oil-based epoxy resin NC-514s and 5.63g of polyethylene glycol diglycidyl ether (epoxy value = 0.32) was slowly added, and stirring was continued to react for 5 hours. The temperature is increased to 75 ℃ and the reaction is carried out for 4h. Slowly adding deionized water, stirring for 1h at 65 ℃, and adjusting to obtain the water-based epoxy curing agent with the solid content of 60%.
The aqueous epoxy curing agents obtained in examples 1 to 6 and comparative examples 1 to 2 were mixed with a commercially available aqueous epoxy resin (3 EE104W, high-mingmbh resin ltd. Of foster city) in a stoichiometric ratio of 0.9. Then, a film is coated on the steel plate, the steel plate is placed at room temperature for 1d and then is cured at 150 ℃ for 3h, and the test results of the film performance corresponding to different curing agents are shown in table 1.
Table 1: results of Performance test of each example
The test results referred to the following test methods or standards:
measuring the surface dry time GB/T1728-1779;
the adhesion is measured by a cross-cut method, GB/T9286-1998;
measuring pencil hardness of a paint film, GB/T6739-1996;
measuring the flexibility of a paint film, GB/T1731-1993;
the water absorption test method comprises the following steps: and weighing the cured film, completely immersing the cured film in deionized water, taking out the cured film after 24 hours at room temperature, carefully drying the surface by using filter paper, weighing the weight of the cured film, and obtaining the water absorption ratio by the weight difference before and after immersion and the weight ratio before immersion.
Determination of Water resistance, GB/1733-1993;
the test method for the salt water resistance comprises the following steps: soaking the coated steel plate in 3.5wt% sodium chloride solution for 30d, observing whether the surface of the coating has blistering and blushing, and whether the surface of the iron base material has corrosion and the corrosion severity;
the comparison result shows that the hardness, the water resistance and the corrosion resistance of the waterborne epoxy coating prepared by the waterborne epoxy curing agent modified by the micromolecule corrosion inhibitor are obviously improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a micromolecule corrosion inhibitor modified waterborne epoxy curing agent is characterized by comprising the following steps:
(1) Mixing polyether alcohol diglycidyl ether with epoxy resin to obtain an epoxy prepolymer; adding the epoxy prepolymer into alicyclic polyamine for reaction to obtain an epoxy adduct;
(2) Adding a micromolecular corrosion inhibitor to continue the reaction;
(3) Adding a solvent to adjust the solid content to obtain a micromolecular corrosion inhibitor modified waterborne epoxy curing agent;
the micromolecular corrosion inhibitor has two molecular structural characteristics at the same time: (a) a heterocyclic ring containing nitrogen and/or sulfur in the molecular structure; and (b) the molecular structure has primary amine or epoxy group.
2. The method according to claim 1, wherein in the step (1), the epoxy resin is one or more of bisphenol a epoxy resin and bio-based epoxy resin.
3. The method according to claim 2, wherein the bisphenol a type epoxy resin is E-20, E-44, E-51; the bio-based epoxy resin is NC-514s.
4. The preparation method according to any one of claims 1 to 3, wherein in the step (1), the epoxy prepolymer is slowly dropped into the alicyclic polyamine, and the mixture is stirred and reacted for 4 to 5 hours at a temperature of between 65 and 75 ℃; in the step (2), the reaction temperature is increased to 75-85 ℃, the micromolecular corrosion inhibitor is slowly added, and the mixture is stirred and reacts for 3-4 hours; in the step (3), slowly dripping the solvent, and stirring for reaction for 1 +/-0.5 h.
5. The method according to claim 4, wherein in the step (1), the polyether alcohol diglycidyl ether is one or more of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polyhexamethylene glycol diglycidyl ether; the epoxy value of the polyether alcohol diglycidyl ether is 0.2-0.4; the molar ratio of the epoxy resin to the polyether alcohol diglycidyl ether is 4 to 8.
6. The method according to claim 5, wherein in the step (1), the alicyclic polyamine is one of 1, 2-cyclohexanediamine, 1-methyl-2, 4-cyclohexanediamine, isophoronediamine, and 1, 8-diamino-p-menthane; the molar ratio of the alicyclic polyamine to the epoxy prepolymer is (2).
7. The preparation method according to claim 5 or 6, characterized in that in the step (2), the micromolecule corrosion inhibitor is one of 2-aminothiazole, 2-aminobenzothiazole, 4- (2-aminoethyl) pyridine, benzotriazole, 5-methyl-1H-benzotriazole and 4-epoxypropane oxy carbazole; the adding mass of the micromolecular corrosion inhibitor accounts for 3-30% of the mass of the epoxy addition compound.
8. The method according to claim 7, wherein in the step (3), the solvent is one or more selected from water, propylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, and ethylene glycol propyl ether; the solid content of the waterborne epoxy curing agent modified by the micromolecular corrosion inhibitor is 55-75%.
9. The preparation method according to claim 8, wherein the molar ratio of the epoxy resin to the polyether alcohol diglycidyl ether is from 6 to 7; the molar ratio of the alicyclic polyamine to the epoxy prepolymer is 2.1.
10. A micromolecular corrosion inhibitor modified waterborne epoxy curing agent prepared by the preparation method of any one of claims 1-9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770657A (en) * | 1994-07-25 | 1998-06-23 | Henkel Corporation | Curing agents for aqueous epoxy resins |
| CN106047068A (en) * | 2016-07-06 | 2016-10-26 | 陕西科技大学 | VOC-free (volatile organic compounds free) epoxy resin and HNT (halloysite nanotube) composite self-repair coating and preparation method thereof |
| CN110511356A (en) * | 2019-08-30 | 2019-11-29 | 华南理工大学 | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770657A (en) * | 1994-07-25 | 1998-06-23 | Henkel Corporation | Curing agents for aqueous epoxy resins |
| CN106047068A (en) * | 2016-07-06 | 2016-10-26 | 陕西科技大学 | VOC-free (volatile organic compounds free) epoxy resin and HNT (halloysite nanotube) composite self-repair coating and preparation method thereof |
| CN110511356A (en) * | 2019-08-30 | 2019-11-29 | 华南理工大学 | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof |
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