CN116217965B - Polyurethane modified epoxy resin oil-in-water emulsion, preparation method thereof and coating - Google Patents
Polyurethane modified epoxy resin oil-in-water emulsion, preparation method thereof and coating Download PDFInfo
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- CN116217965B CN116217965B CN202211091338.3A CN202211091338A CN116217965B CN 116217965 B CN116217965 B CN 116217965B CN 202211091338 A CN202211091338 A CN 202211091338A CN 116217965 B CN116217965 B CN 116217965B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 170
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 170
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 82
- 239000004814 polyurethane Substances 0.000 title claims abstract description 82
- 239000007764 o/w emulsion Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 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 abstract description 86
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 63
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 57
- 229920001223 polyethylene glycol Polymers 0.000 claims description 57
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 23
- 229920000570 polyether Polymers 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 4
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 38
- 239000000839 emulsion Substances 0.000 abstract description 25
- 239000003973 paint Substances 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000001105 regulatory effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000001804 emulsifying effect Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001213 Polysorbate 20 Polymers 0.000 description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- -1 E-51 Chemical compound 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The application provides a polyurethane modified epoxy resin oil-in-water emulsion, a preparation method thereof and a coating, wherein the polyurethane modified epoxy resin oil-in-water emulsion comprises the following oil phase: polyurethane modified epoxy resin: 50 parts by mass; emulsifying agent: 1 to 10 parts by mass; the polyurethane modified epoxy resin is prepared by reacting bisphenol A type solid epoxy resin, bisphenol A type liquid epoxy resin and isocyanate blocked polyurethane prepolymer under the condition of a carbamate reaction catalyst. The polyurethane modified epoxy resin oil-in-water emulsion provided by the application has good stability, and the preparation method is simple, and the waterborne epoxy anticorrosive paint obtained by matching the emulsion with conventional fillers, functional auxiliary agents and curing agents has good corrosion resistance and flexibility.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to polyurethane modified epoxy resin oil-in-water emulsion, a preparation method thereof and a coating.
Background
The epoxy resin has excellent mechanical property, thermal stability and corrosion resistance, and the epoxy resin coating is used for protecting the steel bars and the steel structure for a long time, so that the service life of the structure in a severe environment is prolonged, and the epoxy resin coating becomes one of the most important protection technical means at home and abroad. Most of the traditional epoxy resin paint is solvent-based, is easy to pollute the environment, and with technological progress and improvement of performance requirements of marine engineering anti-corrosion coatings, the development of nontoxic, harmless and pollution-free environment-friendly paint is a target of paint development in China. The water-based epoxy resin anticorrosive paint is green and environment-friendly, and has excellent medium corrosion resistance, thereby meeting the current industry requirements.
The existing water-based epoxy resin anticorrosive paint is formed by stirring and mixing water-based epoxy emulsion, filler, auxiliary agent and the like to form a component A, and then curing and crosslinking the component A and a component B water-based epoxy curing agent, wherein the water-based epoxy emulsion is an important point for influencing the overall performance of a coating film.
The conventional waterborne epoxy anticorrosive paint is formed by mixing, crosslinking and curing conventional waterborne epoxy emulsion, filler, auxiliary agent and the like with a curing agent, and the performance is adjusted by adjusting the formula ratio of the conventional waterborne epoxy emulsion, so that the conventional waterborne epoxy anticorrosive paint is poor in flexibility and easy to crack after the performance such as corrosion resistance is met, and the requirement for coping with metal deformation is not met.
Disclosure of Invention
The application provides an oil-in-water emulsion of polyurethane modified epoxy resin, a preparation method thereof and a coating.
In a first aspect, the present application provides an oil-in-water emulsion of a polyurethane modified epoxy resin, wherein the oil phase comprises:
polyurethane modified epoxy resin: 50 parts by mass;
emulsifying agent: 1 to 10 parts by mass;
the polyurethane modified epoxy resin is prepared by reacting bisphenol A type solid epoxy resin, bisphenol A type liquid epoxy resin and isocyanate blocked polyurethane prepolymer.
In the technical scheme of the application, isocyanate groups on the surface of the isocyanate-terminated polyurethane prepolymer can react with hydroxyl groups on the surface of epoxy resin to obtain polyurethane modified epoxy resin, and the polyurethane modified epoxy resin is emulsified to obtain the oil-in-water emulsion.
In some embodiments of the application, the polyurethane modified epoxy resin is obtained by reacting raw materials comprising:
bisphenol a type solid epoxy resin: 30 parts by mass;
bisphenol a type liquid epoxy resin: 5-30 parts by mass;
isocyanate-terminated polyurethane prepolymer: 1-10 parts.
In some embodiments of the application, the bisphenol A type solid epoxy resin is one or more of E-03, E-06, E-12, E-20;
the bisphenol A type liquid epoxy resin is one or more of E-51, E-44 and E-41.
In some embodiments of the application, the emulsifier is one or more of tween 20, tween 80, span 60, span 80, epoxy polyethylene glycol block emulsifier.
In some embodiments of the application, the epoxy polyethylene glycol block emulsifier is obtained by reacting raw materials including:
bisphenol a type solid epoxy resin: 10-20 parts;
bisphenol a type liquid epoxy resin: 20-40 parts;
polyethylene glycol: 100 parts.
In some embodiments of the application, the epoxy polyethylene glycol block emulsifier is a nonionic non-reactive emulsifier.
In some embodiments of the application, the polyethylene glycol is one or more of polyethylene glycol 400, polyethylene glycol 2000, polyethylene glycol 4000.
In some embodiments of the application, the isocyanate-terminated polyurethane prepolymer comprises the following raw materials in parts by mass:
polyether polyol: 40 parts;
a diisocyanate: 10-30 parts.
In a second aspect, the application provides a method for preparing an oil-in-water emulsion of polyurethane modified epoxy resin, comprising the following steps:
reacting bisphenol A type solid epoxy resin, bisphenol A type liquid epoxy resin, isocyanate-terminated polyurethane prepolymer and a urethanization reaction catalyst to obtain dispersion liquid;
and adding an emulsifying agent into the dispersion liquid, and uniformly dispersing to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
According to the technical scheme, the preparation method is simple, the polyurethane modified epoxy resin is obtained by reacting the isocyanate-terminated polyurethane prepolymer with the epoxy resin under the condition of a carbamate reaction catalyst, the polyurethane modified epoxy resin oil-in-water emulsion is obtained by emulsifying the polyurethane modified epoxy resin by an emulsifying agent, and the obtained coating obtained by crosslinking and curing the polyurethane modified epoxy resin oil-in-water emulsion has good corrosion resistance and flexibility.
In some embodiments of the present application, the method for preparing the polyurethane modified epoxy resin oil-in-water emulsion comprises the following steps:
dehydrating bisphenol A solid epoxy resin and bisphenol A liquid epoxy resin, and then adding an isocyanate-terminated polyurethane prepolymer and a urethanization catalyst for reaction to obtain dispersion;
adding an emulsifying agent into the dispersion liquid for emulsification, adding water for uniform dispersion, and then adjusting the pH value to 6-7.5 to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
In a third aspect, the present application also provides a coating comprising: the polyurethane modified epoxy resin oil-in-water emulsion of any embodiment or the polyurethane modified epoxy resin oil-in-water emulsion prepared by the preparation method of any embodiment, a filler, a functional auxiliary agent and a curing agent.
In the technical scheme of the application, the polyurethane modified epoxy resin oil-in-water emulsion prepared by using the polyurethane modified epoxy resin oil-in-water emulsion described in any embodiment or the preparation method described in any embodiment has good corrosion resistance and flexibility when being matched with conventional fillers, functional additives and curing agents.
Detailed Description
Each example or embodiment in this specification is described in a progressive manner, each example focusing on differences from other examples.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The applicant notes that the aqueous epoxy anticorrosive paint has good corrosion resistance due to a high-density crosslinked structure, but most of molecular chain segments in the epoxy resin cured product are non-rotatable rigid chain segments, so brittle fracture occurs when stress concentration or external stress exceeds the bearing limit of the paint. For this reason, the flexibility of the aqueous epoxy anticorrosive paint is improved by adding toughening agents in the prior art, but the toughening agents can reduce the crosslinking density of the epoxy resin cured product while increasing the flexibility, thereby affecting the corrosion resistance of the paint.
Therefore, the applicant wants to develop a water-based epoxy emulsion, so that the water-based epoxy emulsion can simultaneously meet the corrosion resistance and flexibility of the water-based epoxy anticorrosive paint by matching with conventional fillers, auxiliary agents and curing agents.
In a first aspect, the present application provides an oil-in-water emulsion of a polyurethane modified epoxy resin, wherein the oil phase comprises:
polyurethane modified epoxy resin: 50 parts by mass;
emulsifying agent: 1 to 10 parts by mass;
the polyurethane modified epoxy resin is prepared by reacting bisphenol A type solid epoxy resin, bisphenol A type liquid epoxy resin and isocyanate blocked polyurethane prepolymer.
In the technical scheme of the application, isocyanate groups on the surface of the isocyanate-terminated polyurethane prepolymer can react with hydroxyl groups on the surface of epoxy resin to obtain polyurethane modified epoxy resin, and polyurethane modified epoxy emulsion is obtained through emulsification.
In the technical scheme of the application, bisphenol A type solid epoxy resin and bisphenol A type liquid epoxy resin are simultaneously used, wherein the bisphenol A type solid epoxy resin refers to epoxy resin with an epoxy value of 0.06-0.2, the bisphenol A type liquid epoxy resin refers to epoxy resin with an epoxy value of 0.41-0.54, and the bisphenol A type solid epoxy resin is liquid at normal temperature. The applicant finds that the polyurethane modified epoxy resin obtained by reacting a single bisphenol A type epoxy resin with an isocyanate-terminated polyurethane prepolymer is unstable in oil-in-water emulsion of the polyurethane modified epoxy resin obtained by emulsifying the polyurethane modified epoxy resin by using an emulsifying agent, and is easy to generate layering phenomenon, so that the use is influenced. The subsequent applicant finds through experiments that, by using bisphenol A type solid epoxy resin and bisphenol A type liquid epoxy resin with a certain proportion as raw materials, the prepared polyurethane modified epoxy resin oil-in-water emulsion has good stability, and the possible reason is that bisphenol A type epoxy resins with different molecular weights are modified by isocyanate-terminated polyurethane prepolymer, and the emulsion formed by emulsification is less prone to agglomeration compared with single polyurethane modified epoxy resin, so that the obtained emulsion has better stability.
In some embodiments of the application, the polyurethane modified epoxy resin is obtained by reacting raw materials comprising:
bisphenol a type solid epoxy resin: 30 parts by mass;
bisphenol a type liquid epoxy resin: 5-30 parts by mass;
isocyanate-terminated polyurethane prepolymer: 1-10 parts.
In some of the above embodiments, the urethanization reaction catalyst is not further limited, and may be routinely selected by those skilled in the art as needed, for example, the urethanization reaction catalyst may be selected from one of tertiary amine-based catalysts, organotin catalysts.
In some embodiments of the application, the bisphenol A type solid epoxy resin is one or more of E-03, E-06, E-12, E-20;
the bisphenol A liquid epoxy resin is one or more of E-51, E-44 and E-41.
In some embodiments, E-03, E-06, E-12 and E-20 are common bisphenol A solid epoxy resins, E-51, E-44 and E-41 are common bisphenol A liquid epoxy resins, the epoxy values are different, the viscosities are different, and polyurethane modified epoxy resin oil-in-water emulsion with different viscosities and epoxy values can be obtained by compounding bisphenol A solid epoxy resins and bisphenol A liquid epoxy resins of different types and can be selected according to the use environment of the water-based epoxy anticorrosive paint.
In some embodiments of the application, the emulsifier is one or more of tween 20, tween 80, span 60, span 80, epoxy polyethylene glycol block emulsifiers.
In some embodiments, tween 20, tween 80, span 60 and span 80 are all commonly used emulsifiers for preparing aqueous epoxy emulsion, and epoxy resin polyethylene glycol block emulsifiers are emulsifiers obtained by polymerizing epoxy resin and polyethylene glycol, and have a hydrophobic structure of an epoxy resin chain segment and a hydrophilic structure of a polyethylene glycol chain segment.
In some embodiments of the present application, the epoxy polyethylene glycol block emulsifier is obtained by reacting raw materials comprising:
bisphenol a type solid epoxy resin: 10-20 parts;
bisphenol a type liquid epoxy resin: 20-40 parts;
polyethylene glycol: 100 parts.
In some embodiments, according to the raw materials of the polyurethane modified epoxy resin, corresponding bisphenol A solid epoxy resin and bisphenol A liquid epoxy resin are selected and react with polyethylene glycol under the condition of an initiator to obtain an epoxy resin polyethylene glycol block emulsifier which takes the epoxy resin as a hydrophobic chain segment and polyethylene glycol as a hydrophilic chain segment, and the epoxy resin polyethylene glycol block emulsifier has good emulsifying property for the polyurethane modified epoxy resin provided by the application and takes the polyethylene glycol block emulsifier as an emulsifier, so that the prepared polyurethane modified epoxy resin oil-in-water emulsion has good stability; and if only a single type of epoxy resin is used for preparing the emulsifier, the effect is poor, and the storage stability of the obtained polyurethane modified epoxy resin oil-in-water emulsion is poor.
In some of the above embodiments, the initiator may be selected from thermal initiators or photoinitiators, more specifically, such as potassium persulfate, ammonium persulfate.
In some embodiments of the application, the epoxy polyethylene glycol block emulsifier is a nonionic non-reactive emulsifier.
In some embodiments, a relatively excessive polyethylene glycol is added into the raw material of the epoxy resin polyethylene glycol block emulsifier to fully react epoxy groups on the surface of the epoxy resin to obtain a nonionic non-reactive emulsifier, and the emulsifier only plays a role in preparing the epoxy resin emulsion, so that the epoxy resin polyethylene glycol block emulsifier obtained by the full reaction has better emulsifying property on the epoxy resin, and the obtained emulsion is more stable; on the other hand, when the epoxy emulsion is prepared into the coating and reacts with the curing agent, the emulsifier does not participate in the curing and crosslinking reaction, and the epoxy group at one end of the insufficiently reacted epoxy resin is prevented from reacting with the curing agent, so that the crosslinking degree of the coating is reduced, and the performance of the coating is reduced.
In some embodiments of the application, the polyethylene glycol is one or more of polyethylene glycol 400, polyethylene glycol 2000, polyethylene glycol 4000.
In some embodiments, because the hydrophilic end of the epoxy resin polyethylene glycol block emulsifier is polyethylene glycol, the longer the polyethylene glycol chain segment is, the stronger the hydrophilicity is, so that one or more of polyethylene glycol 400, polyethylene glycol 2000 and polyethylene glycol 4000 can be selected as raw materials according to actual needs to prepare the epoxy resin polyethylene glycol block emulsifier with better emulsifying property.
In some embodiments of the present application, a method for preparing an epoxy polyethylene glycol block emulsifier comprises the steps of:
fully mixing bisphenol A solid epoxy resin, bisphenol A liquid epoxy resin, an initiator and polyethylene glycol in a reactor, and reacting in a nitrogen atmosphere to obtain the epoxy resin polyethylene glycol block emulsifier.
In some embodiments, the preparation method of the epoxy resin polyethylene glycol block emulsifier is simple, and the structure of the epoxy resin polyethylene glycol block emulsifier can be regulated and controlled by changing the types of raw materials, so that the epoxy resin polyethylene glycol block emulsifier has good emulsifying property and low preparation cost.
In some of the above embodiments, more specifically, the preparation method of the epoxy resin polyethylene glycol block emulsifier comprises the following steps:
fully mixing bisphenol A solid epoxy resin, bisphenol A liquid epoxy resin, an initiator and polyethylene glycol in a reactor, and reacting at 140-160 ℃ for 1-5 h under nitrogen atmosphere to obtain the epoxy resin polyethylene glycol block emulsifier.
In some of the above embodiments, the initiator is not further limited and may be selected from one of ammonium persulfate, potassium persulfate, or sodium persulfate.
In some embodiments of the present application, the isocyanate-terminated polyurethane prepolymer includes the following raw materials in parts by mass:
polyether polyol: 40 parts;
a diisocyanate: 10-30 parts.
In some of the embodiments described above, the isocyanate-terminated polyurethane prepolymer materials are selected to be polyether polyols and diisocyanates because polyether polyols have more flexible segments than polyesters, and thus the resulting coatings are more flexible.
In some of the above embodiments, the polyether polyol and the diisocyanate are not limited, and any polyether polyol and diisocyanate commonly used in the art may be used. The polyether polyol may be selected from one or more of polyether 210, polyether 220, polyether 330, PTMG-1000, PTMG-1400; the diisocyanate may be one selected from TDI (toluene-2, 4-diisocyanate), MDI (diphenylmethane-4, 4 '-diisocyanate), HMDI (4, 4' -dicyclohexylmethane diisocyanate), IPDI (isophorone diisocyanate).
In some embodiments of the present application, a method of preparing an isocyanate-terminated polyurethane prepolymer includes the steps of:
after the polyether polyol is dehydrated, diisocyanate is added for reaction to obtain the isocyanate-terminated polyurethane prepolymer.
In some of the above embodiments, the isocyanate-terminated polyurethane prepolymer is simple to prepare and can reduce the production cost.
In some of the above embodiments, more specifically, a method for preparing an isocyanate-terminated polyurethane prepolymer, comprises the steps of:
polyether polyol is added into a reactor, vacuum dehydration is carried out for 1-2 h at 105-110 ℃, the temperature is reduced to 70-90 ℃, diisocyanate is added for reaction for 2-5 h, and the isocyanate-terminated polyurethane prepolymer is obtained.
In a second aspect, the application provides a method for preparing an oil-in-water emulsion of polyurethane modified epoxy resin, comprising the following steps:
reacting bisphenol A type solid epoxy resin, bisphenol A type liquid epoxy resin, isocyanate-terminated polyurethane prepolymer and a urethanization reaction catalyst to obtain dispersion liquid;
and adding an emulsifying agent into the dispersion liquid, and uniformly dispersing to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
According to the technical scheme, the preparation method is simple, the polyurethane modified epoxy resin is obtained by reacting the isocyanate-terminated polyurethane prepolymer with the epoxy resin under the condition of a carbamate reaction catalyst, the polyurethane modified epoxy resin oil-in-water emulsion is obtained by emulsifying the polyurethane modified epoxy resin by an emulsifying agent, and the obtained coating obtained by crosslinking and curing the polyurethane modified epoxy resin oil-in-water emulsion has good corrosion resistance and flexibility.
In some embodiments of the present application, a method of preparing an oil-in-water emulsion of a polyurethane modified epoxy resin comprises the steps of:
dehydrating bisphenol A solid epoxy resin and bisphenol A liquid epoxy resin, and then adding an isocyanate-terminated polyurethane prepolymer and a urethanization catalyst for reaction to obtain dispersion;
adding an emulsifying agent into the dispersion liquid for emulsification, adding water for uniform dispersion, and then adjusting the pH value to 6-7.5 to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
In some of the above embodiments, the preparation method of the polyurethane modified epoxy resin oil-in-water emulsion is further optimized, so that the obtained polyurethane modified epoxy resin oil-in-water emulsion is more stable.
In a third aspect, the present application also provides a coating comprising: the polyurethane modified epoxy resin oil-in-water emulsion of any embodiment or the polyurethane modified epoxy resin oil-in-water emulsion prepared by the preparation method of any embodiment, a filler, a functional auxiliary agent and a curing agent.
In the technical scheme of the application, the polyurethane modified epoxy resin oil-in-water emulsion prepared by using the polyurethane modified epoxy resin oil-in-water emulsion described in any embodiment or the preparation method described in any embodiment has good corrosion resistance and flexibility when being matched with conventional fillers, functional additives and curing agents.
In the present technical solution, the filler, the functional auxiliary agent and the curing agent are not further limited, and may be selected as needed by those skilled in the art. For example: the filler can be one or more of heavy calcium, calcined kaolin, talcum powder and superfine barium sulfate; the functional auxiliary agent can be one or more selected from wetting dispersant, preservative, anti-freezing agent, defoamer and thickener; the curing agent may be an amine curing agent.
Hereinafter, the polyurethane-modified epoxy resin oil-in-water emulsion of the present application, the preparation method thereof and the paint will be described in more detail by way of examples, but the present application is not limited to these examples at all.
Example 1
Epoxy resin polyethylene glycol block emulsifier synthesis: adding 10g of epoxy resin E20, 20g of epoxy resin E51,2.5g of potassium persulfate and 80g of PEG-4000 into a reactor, filling nitrogen for protection, and reacting at 140 ℃ for 2 hours to obtain an epoxy resin polyethylene glycol block emulsifier;
isocyanate-terminated polyurethane prepolymer synthesis: adding 40g of PTMG-1000 into a reactor, dehydrating in vacuum at 105 ℃ for 1h, cooling to 80 ℃, adding 17.79g of IPDI, and reacting for 2h to obtain an isocyanate-terminated polyurethane prepolymer;
preparation of polyurethane modified epoxy resin oil-in-water emulsion: 60g of epoxy resin E20 and 40g of epoxy resin E51 are added into a reactor, the temperature is raised to 105 ℃ and then the vacuum dehydration is carried out for 1h, 6g of isocyanate-terminated polyurethane prepolymer is added after the temperature is lowered to 80 ℃, the stirring speed is regulated to 300r/min, 0.4g of organic tin catalyst is added after the reaction is cooled to 75 ℃ for 1h, then 9g of epoxy resin polyethylene glycol block emulsifier is added after the reaction is cooled to 60 ℃, the emulsification is carried out for 2h, the temperature is lowered to 50 ℃ and the stirring speed is regulated to 1200r/min, 70g of deionized water is dripped, the dripping speed is 2.5g/min, 2g of sodium hydroxide aqueous solution with the concentration of 0.1g/L is added after the dripping is finished, the pH of the system is regulated to 6.5, and the heat preservation is carried out for 10min, thus obtaining the polyurethane modified epoxy resin oil-in-water emulsion.
Example 2
The epoxy polyethylene glycol block emulsifier synthesis was the same as in example 1.
Isocyanate-terminated polyurethane prepolymer synthesis: 56g of PTMG-1400 is added into a reactor, vacuum dehydration is carried out for 1h at 105 ℃, the temperature is reduced to 80 ℃, 17.79g of IPDI is added for reaction for 2h, and isocyanate-terminated polyurethane prepolymer is obtained;
preparation of polyurethane modified epoxy resin oil-in-water emulsion: 50g of epoxy resin E20 and 50g of epoxy resin E51 are added into a reactor, the temperature is raised to 105 ℃ and then the vacuum dehydration is carried out for 1h, 8g of isocyanate-terminated polyurethane prepolymer is added after the temperature is lowered to 80 ℃, the stirring speed is regulated to 300r/min, 0.4g of organic tin catalyst is added after the reaction is cooled to 75 ℃ for 1h, then 11g of epoxy resin polyethylene glycol block emulsifier is added after the reaction is cooled to 60 ℃, the emulsification is carried out for 2h, the temperature is lowered to 50 ℃ and the stirring speed is regulated to 1200r/min, 60g of deionized water is dripped, the dripping speed is 2.5g/min, the pH of the system is regulated to 7 after the dripping is completed, 2g of sodium hydroxide aqueous solution with the concentration of 0.2g/L is added, and the heat preservation is carried out for 10min, thus obtaining the polyurethane modified epoxy resin oil-in-water emulsion.
Example 3
The epoxy polyethylene glycol block emulsifier synthesis was the same as in example 1.
Isocyanate-terminated polyurethane prepolymer synthesis: adding 40g of PTMG-1000 into a reactor, dehydrating in vacuum at 105 ℃ for 1h, cooling to 80 ℃, adding 16g of IPDI, and reacting for 2h to obtain an isocyanate-terminated polyurethane prepolymer;
preparation of polyurethane modified epoxy resin oil-in-water emulsion: adding 80g of epoxy resin E20 and 20g of epoxy resin E51 into a reactor, heating to 105 ℃, vacuum dehydrating for 1h, cooling to 80 ℃, adding 10g of isocyanate-terminated polyurethane prepolymer, regulating the stirring speed to 300r/min, cooling to 75 ℃ after 2h of reaction, adding 0.4g of organotin catalyst for reaction for 1h, cooling to 60 ℃, adding 13g of epoxy resin polyethylene glycol block emulsifier, emulsifying for 2h, cooling to 50 ℃ and regulating the stirring speed to 1200r/min, dropwise adding 50g of deionized water, regulating the system pH to 7.5 after dropwise adding, and preserving heat for 10min to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
Comparative example 1
The epoxy polyethylene glycol block emulsifier synthesis was the same as in example 1.
Isocyanate-terminated polyurethane prepolymer synthesis: adding 40g of PTMG-1000 into a reactor, dehydrating in vacuum at 105 ℃ for 1h, cooling to 80 ℃, adding 19.56g of IPDI, and reacting for 2h to obtain an isocyanate-terminated polyurethane prepolymer;
preparation of polyurethane modified epoxy resin oil-in-water emulsion: 100g of epoxy resin E20 is added into a reactor, the temperature is raised to 105 ℃ and then is dehydrated for 1h in vacuum, 10g of isocyanate-terminated polyurethane prepolymer is added after the temperature is lowered to 80 ℃, the stirring speed is regulated to 300r/min, the temperature is lowered to 75 ℃ after the reaction for 2h, 0.6g of organotin catalyst is added for reaction for 1h, then 9g of epoxy resin polyethylene glycol block emulsifier is added after the temperature is lowered to 60 ℃, the temperature is reduced to 50 ℃ and the stirring speed is regulated to 1200r/min, 50g of deionized water is dripped, the dripping speed is 2.5g/min, 2g of sodium hydroxide aqueous solution with the concentration of 0.1g/L is added after the dripping is finished, the pH of the system is regulated to 6.5, and the temperature is kept for 10min, so as to obtain the polyurethane modified epoxy resin oil-in-water emulsion.
Comparative example 2
The epoxy polyethylene glycol block emulsifier synthesis was the same as in example 1.
Preparation of aqueous epoxy emulsion: adding 60g of epoxy resin E20 and 40g of epoxy resin E51 into a reactor, heating and melting, regulating the stirring speed to 300r/min, then cooling to 60 ℃, adding 9g of epoxy resin polyethylene glycol block emulsifier, emulsifying for 2h, cooling to 50 ℃ and regulating the stirring speed to 1200r/min, dripping 70g of deionized water, regulating the system pH to 6.5 by adding 2g of sodium hydroxide aqueous solution with the concentration of 0.1g/L after dripping, and preserving heat for 10min to obtain the aqueous epoxy emulsion.
Test example 1
Emulsion performance test: the emulsions prepared in examples 1 to 3 and comparative examples 1 and 2 were tested for properties, wherein:
emulsion appearance, non-volatiles, viscosity, thermal storage stability: testing is performed with reference to GB/T11175-2002;
volatile organics: testing is performed with reference to GB/T23986-2009;
the test results are shown in Table 1.
TABLE 1
Test example 2
And (3) testing the performance of the paint: examples 1 to 3, comparative examples 1 and 2 were mixed with the same filler and auxiliary agent in the same ratio, and then coated with the same amine curing agent, wherein:
and (3) a component A: polyurethane modified epoxy resin oil-in-water emulsion prepared in each example: 38%; propylene glycol methyl ether: 1.4%; titanium white powder: 5%; superfine barium sulfate: 30%; zinc phosphate: 10%; aluminum tripolyphosphate: 5%; dispersant TEGO-755W:0.5%; defoamer TEGO-902W:0.5%; substrate wetting agent TEGO-4100:0.3%; flash rust inhibitor TEGO-755W:0.3%; adhesion promoter Coatosil MP200:0.25%; water: 8.75%;
and the component B comprises the following components: epoxy amine curing agents;
and (3) carrying out step A: b at 8.5:1, uniformly spraying the mixture onto the surface of a tinplate steel plate, and performing performance test on the obtained paint film, wherein:
hardness: reference is made to GB/T6739-2006;
wet heat resistance: reference GB/T1740-2007;
salt spray resistance: reference is made to GB/T1771-2007;
water resistance: see GB/T1733-1993;
acid resistance and alkali resistance: reference is made to GB/T9274-1988A method;
flexibility: see GB/T1731-1993;
adhesion force: see GB/T9286-1998;
the test results are shown in table 2.
TABLE 2
As can be seen from the results in tables 1 and 2, the emulsion prepared in each example and the corresponding paint have better performance, and the emulsion prepared in comparative example 1 using a single epoxy resin has poorer thermal storage stability, and has a delamination phenomenon after being stored for 15d at 50 ℃, which is probably because the polyurethane modified epoxy resin obtained after the single epoxy resin is modified by the isocyanate-terminated polyurethane prepolymer is easy to agglomerate, and the agglomeration phenomenon can be aggravated by the rise of temperature, thereby delamination occurs, and the moisture-heat resistance, water resistance, salt fog resistance, flexibility and adhesive force of the corresponding paint are reduced to a certain extent, which indicates that the aqueous epoxy emulsion is a main factor affecting the aqueous epoxy resin paint; the emulsion prepared in comparative example 2 is not modified by polyurethane, the emulsion performance is not greatly affected, the humidity resistance and flexibility of the corresponding coating are reduced to a certain extent compared with the examples, particularly the flexibility is significantly reduced, the reason is probably that the isocyanate-terminated polyurethane prepolymer contains a molecular chain segment which is relatively flexible by polyether glycol, when the polyurethane modified epoxy emulsion is crosslinked and solidified under the action of a curing agent, a polymer with a soft and hard chain segment interpenetrating network structure can be formed, the flexibility of the waterborne epoxy anticorrosive coating can be improved, the crosslinking density of the polymer is not reduced, the corrosion resistance of the coating is not affected, the comparative example 2 does not contain polyurethane, and most of the molecular chain segments in the epoxy resin condensate are non-rotatable rigid chain segments, the flexibility is poor, so the flexibility is larger than the difference of the examples.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (5)
1. An oil-in-water emulsion of a polyurethane modified epoxy resin, wherein the oil phase comprises:
polyurethane modified epoxy resin: 50 parts by mass;
emulsifying agent: 1-10 parts by mass;
the polyurethane modified epoxy resin is prepared by reacting the following raw materials in the presence of a catalytic amount of a urethanization reaction catalyst:
bisphenol a type solid epoxy resin: 30 parts by mass;
bisphenol a type liquid epoxy resin: 5-30 parts by mass;
isocyanate-terminated polyurethane prepolymer: 1-10 parts by mass of an isocyanate-terminated polyurethane prepolymer, which comprises the following raw materials in parts by mass:
polyether polyol: 40 parts by mass of a polyether polyol comprising one or more of polyether 210, polyether 220, polyether 330, PTMG-1000, PTMG-1400;
a diisocyanate: 10-30 parts by mass;
the emulsifier is an epoxy resin polyethylene glycol block emulsifier, and the epoxy resin polyethylene glycol block emulsifier is obtained by reacting the following raw materials in the presence of an initiator:
the bisphenol a type solid epoxy resin: 10-20 parts by mass of a lubricant;
the bisphenol a type liquid epoxy resin: 20-40 parts by mass of a lubricant;
polyethylene glycol: 100 parts by mass;
wherein the bisphenol A type solid epoxy resin is one or more of E-03, E-06, E-12 and E-20;
the bisphenol A type liquid epoxy resin is one or more of E-51, E-44 and E-41.
2. The polyurethane modified epoxy resin oil-in-water emulsion of claim 1, wherein the epoxy resin polyethylene glycol block emulsifier is a nonionic non-reactive emulsifier.
3. The polyurethane modified epoxy resin oil-in-water emulsion of claim 1, wherein the polyethylene glycol is one or more of polyethylene glycol 400, polyethylene glycol 2000, polyethylene glycol 4000.
4. The preparation method of the polyurethane modified epoxy resin oil-in-water emulsion is characterized by comprising the following steps of:
reacting 30 parts by mass of bisphenol A type solid epoxy resin, 5-30 parts by mass of bisphenol A type liquid epoxy resin, 1-10 parts by mass of isocyanate-terminated polyurethane prepolymer and a urethanization reaction catalyst to obtain polyurethane modified epoxy resin;
the preparation method of the isocyanate-terminated polyurethane prepolymer comprises the following steps:
dehydrating 40 parts by mass of polyether polyol, and adding 10-30 parts by mass of diisocyanate to react to obtain isocyanate-terminated polyurethane, wherein the polyether polyol comprises one or more of polyether 210, polyether 220, polyether 330, PTMG-1000 and PTMG-1400;
adding 1-10 parts by mass of an emulsifier into 50 parts by mass of polyurethane modified epoxy resin, and uniformly dispersing to obtain polyurethane modified epoxy resin oil-in-water emulsion, wherein the emulsifier is an epoxy resin polyethylene glycol block emulsifier, and the epoxy resin polyethylene glycol block emulsifier is obtained by reacting the following raw materials in the presence of an initiator:
the bisphenol a type solid epoxy resin: 10-20 parts by mass of a lubricant;
the bisphenol a type liquid epoxy resin: 20-40 parts by mass of a lubricant;
polyethylene glycol: 100 parts by mass;
wherein the bisphenol A type solid epoxy resin is one or more of E-03, E-06, E-12 and E-20;
the bisphenol A type liquid epoxy resin is one or more of E-51, E-44 and E-41.
5. A coating, comprising: the polyurethane modified epoxy resin oil-in-water emulsion according to any one of claims 1 to 3 or the polyurethane modified epoxy resin oil-in-water emulsion prepared by the preparation method according to claim 4, a filler, a functional auxiliary agent and a curing agent.
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