CN112961574A - Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof - Google Patents
Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof Download PDFInfo
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- CN112961574A CN112961574A CN202110290125.2A CN202110290125A CN112961574A CN 112961574 A CN112961574 A CN 112961574A CN 202110290125 A CN202110290125 A CN 202110290125A CN 112961574 A CN112961574 A CN 112961574A
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- epoxy
- phosphorus
- epoxy resin
- emulsion
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 162
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 150
- 239000011574 phosphorus Substances 0.000 title claims abstract description 150
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000000839 emulsion Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims description 22
- 238000004945 emulsification Methods 0.000 title description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 117
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000178 monomer Substances 0.000 claims abstract description 62
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 39
- 239000006184 cosolvent Substances 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 12
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002421 anti-septic effect Effects 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 claims description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000008118 PEG 6000 Substances 0.000 claims description 2
- -1 PEG-2000 Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 2
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 20
- 239000003973 paint Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 229920006334 epoxy coating Polymers 0.000 abstract description 4
- 239000008235 industrial water Substances 0.000 abstract description 4
- 239000003595 mist Substances 0.000 abstract description 4
- 239000006260 foam Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 17
- 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 17
- 229910000165 zinc phosphate Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 10
- 229920000578 graft copolymer Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The application relates to the technical field of water-based paint, and provides a water-based nonionic phosphorus-containing epoxy anticorrosive emulsion which comprises the following components in parts by weight: 200-300 parts of epoxy resin; 20-100 parts of phosphorus-containing acrylic monomer modified epoxy resin; 5-20 parts of an epoxy diluent; 8-25 parts of an emulsifier; 15-30 parts of a cosolvent; 0.1-1 part of a catalyst; 120-350 parts of water. The solid content of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion can reach 65%, so that the wet adhesion, water resistance, acid and alkali resistance, salt water resistance, salt mist resistance and anticorrosive performance of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are greatly improved, the performances of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are not inferior to those of an oily epoxy coating, and the development of industrial water-based is greatly promoted.
Description
Technical Field
The application belongs to the technical field of water-based paint, and particularly relates to a water-based nonionic phosphorus-containing epoxy anticorrosive emulsion and a preparation method thereof.
Background
Industrial anticorrosive paint is an important part of the paint industry, and environmental protection and water-based development are inevitable trends of the paint industry. The water-based anticorrosive paint takes water as a dispersion medium, has low price, no odor and no combustion, greatly improves the safety in the processes of storage, transportation and use, does not contain organic solvents or volatile organic compounds, does not cause air pollution, and meets the requirement of current environmental protection.
The aqueous epoxy resin is a stable dispersion system in which an epoxy resin is dispersed in the form of fine particles or droplets in a dispersion medium having water as a continuous phase. Because the epoxy resin is thermosetting resin with a linear structure, a water-based epoxy curing agent must be added before construction, a chemical crosslinking reaction occurs in a room temperature environment, and the original soluble and meltable property of the epoxy resin is changed into an insoluble and infusible space network structure after the epoxy resin is cured, so that excellent performance is shown.
Most of epoxy emulsion in the current market has low solid content, poor wet adhesion and poor salt spray performance in a high-humidity environment, and particularly when the temperature in summer is high, the activation period of the water-based epoxy emulsion and the water-based curing agent is short, so that the performance is seriously reduced, and the anticorrosion effect is greatly influenced.
Disclosure of Invention
The application aims to provide a water-based nonionic phosphorus-containing epoxy anticorrosive emulsion and a preparation method thereof, and aims to solve the problems of low solid content, poor wet adhesion, poor salt spray performance in a high-humidity environment and poor anticorrosive effect of most epoxy emulsions in the prior art.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides an aqueous nonionic phosphorus-containing epoxy antiseptic emulsion, which comprises the following components in parts by weight:
in a second aspect, the present application provides a method for preparing an aqueous nonionic phosphorous epoxy antiseptic emulsion, comprising the steps of:
providing components according to the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion;
carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst to obtain a first mixture;
carrying out second mixing treatment on the first mixture and an emulsifier to obtain a second mixture;
carrying out third mixing treatment on the second mixture, epoxy resin and an epoxy diluent to obtain a third mixture;
and dripping water into the third mixture within 1-3 hours, and then filtering to obtain the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion.
According to the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion provided by the first aspect of the application, epoxy resin and phosphorus-containing acrylic acid monomer modified epoxy resin are used as main components and are cooperated with an epoxy diluent, an emulsifier, a cosolvent and a catalyst to carry out compounding, wherein the phosphorus-containing acrylic acid monomer modified epoxy resin is introduced to improve the wet adhesion of the epoxy resin and is combined with the epoxy resin to form an epoxy-phosphorus-containing acrylic acid multi-graft copolymer, epoxy groups are reserved at two ends of macromolecules of the epoxy-phosphorus-containing acrylic acid multi-graft copolymer, so that a more compact film can be formed through a crosslinking reaction with a subsequent water-based curing agent, and the; meanwhile, the provided emulsifier contains an epoxy group, can improve the compatibility of the emulsifier and epoxy resin, also contains a lipophilic group, can form a stable structure with the epoxy resin and a grafted monomer group, and has good emulsifying capacity; the solid content of the obtained water-based nonionic phosphorus-containing epoxy anticorrosive emulsion can reach 65%, the wet adhesion, the water resistance, the acid and alkali resistance, the salt water resistance, the salt mist resistance and the anticorrosive performance of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are greatly improved, the performances of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are not inferior to those of an oily epoxy coating, and the development of industrial water-based is greatly promoted.
The preparation method of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion provided by the second aspect of the application is simple and convenient, can better improve the stability of the emulsion, overcomes the defect of poor water resistance of emulsion coating, and can realize large-scale industrial production.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides an aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion, which comprises the following components in parts by weight:
according to the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion provided by the first aspect of the application, epoxy resin and phosphorus-containing acrylic acid monomer modified epoxy resin are used as main components and are cooperated with an epoxy diluent, an emulsifier, a cosolvent and a catalyst to carry out compounding, wherein the phosphorus-containing acrylic acid monomer modified epoxy resin is introduced to improve the wet adhesion of the epoxy resin and is combined with the epoxy resin to form an epoxy-phosphorus-containing acrylic acid multi-graft copolymer, epoxy groups are reserved at two ends of macromolecules of the epoxy-phosphorus-containing acrylic acid multi-graft copolymer, so that a more compact film can be formed through a crosslinking reaction with a subsequent water-based curing agent, and the; meanwhile, the provided emulsifier contains an epoxy group, can improve the compatibility of the emulsifier and epoxy resin, also contains a lipophilic group, can form a stable structure with the epoxy resin and a grafted monomer group, and has good emulsifying capacity; the solid content of the obtained water-based nonionic phosphorus-containing epoxy anticorrosive emulsion can reach 65%, the wet adhesion, the water resistance, the acid and alkali resistance, the salt water resistance, the salt mist resistance and the anticorrosive performance of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are greatly improved, the performances of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion are not inferior to those of an oily epoxy coating, and the development of industrial water-based is greatly promoted.
Specifically, the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 200-300 parts of epoxy resin, the epoxy resin has secondary hydroxyl and epoxy groups and has good bonding strength and chemical resistance, and the epoxy resin is used as a main component of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion, so that on one hand, the obtained emulsion can be ensured to form a cross-linked network structure well, the adhesive force is improved, on the other hand, the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion can be favorably subjected to cross-linking reaction with other components for modification treatment on the basis of the epoxy resin, and the obtained aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion has excellent performance.
In some embodiments, the epoxy resin is at least one of E-51, E-44, E-20, and E-12.
In a specific embodiment, the addition parts of the epoxy resin in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts and 300 parts.
Specifically, the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 20-100 parts of phosphorus-containing acrylic monomer modified epoxy resin; the introduction of the phosphorus-containing acrylic monomer modified epoxy resin can improve the wet adhesion of the epoxy resin, the epoxy resin is combined with the epoxy resin to form an epoxy-phosphorus-containing acrylic acid multi-graft copolymer, and epoxy groups are reserved at two ends of macromolecules of the epoxy-phosphorus-containing acrylic acid multi-graft copolymer, so that the epoxy-phosphorus-containing acrylic acid multi-graft copolymer can form a more compact film through a crosslinking reaction with a subsequent aqueous curing agent, and the adhesion is.
In some embodiments, the phosphorus-containing acrylic monomer modified epoxy resin is obtained by polymerizing epoxy resin, catalyst, phosphorus-containing acrylic monomer, styrene, butyl acrylate, lauryl acrylate and isobornyl acrylate, the phosphorus-containing acrylic monomer modified epoxy resin is obtained by polymerization reaction of all monomers, the phosphorus-containing acrylic monomer modified epoxy resin is modified by taking the epoxy resin as a basic component, active free radicals are generated on secondary carbon and tertiary carbon of the epoxy resin, acrylic monomers are introduced by a graft copolymerization method, mainly phosphorus-containing acrylic monomers are introduced to improve the wet adhesion of the epoxy resin, and finally the epoxy-phosphorus-containing acrylic multi-graft copolymer is synthesized, epoxy groups are reserved at two ends of macromolecules of the epoxy resin so as to be convenient for forming a denser film through a crosslinking reaction with a subsequent water-based curing agent.
Further, in the polymerization reaction process of the phosphorus-containing acrylic monomer modified epoxy resin, the mass ratio of the epoxy resin, the catalyst, the phosphorus-containing acrylic monomer, the styrene, the butyl acrylate, the lauryl acrylate and the isobornyl acrylate is as follows: (4-4.5), (0.1-0.5), (0.5-1.0), (2-2.5), (1-1.5) and (1.4-2), the mass ratio of the monomers is controlled, so that the phosphorus-containing acrylic acid monomer modified epoxy resin obtained by the reaction has better performance, and is favorable for interacting with epoxy resin to synthesize the epoxy-phosphorus-containing acrylic acid multi-graft copolymer.
In the specific embodiment of the invention, in the polymerization reaction process of the phosphorus-containing acrylic monomer modified epoxy resin, the mass ratio of the epoxy resin, the catalyst, the phosphorus-containing acrylic monomer, the styrene, the butyl acrylate, the lauryl acrylate and the isobornyl acrylate is as follows: 4:0.1:0.5:2:1:1:1.4, and the mass ratio of the monomers is controlled, so that the obtained phosphorus-containing acrylic monomer modified epoxy resin has excellent performance.
In some embodiments, the phosphorus-containing acrylic monomer is selected from at least one of SolvaPAM-100, SolvaPAM-200, 2-hydroxyethyl methacrylate phosphate, ethylene glycol methacrylate phosphate, 10- (2-methacryloyloxy) monodecanyl phosphate. At least one of the phosphorus-containing acrylic acid monomers is selected for reaction, so that the epoxy resin can be well modified, and the wet adhesion of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion can be improved.
Wherein, the types of the epoxy resin and the catalyst of the phosphorus-containing acrylic acid monomer modified epoxy resin are consistent with the types of the epoxy resin and the catalyst in the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion.
In a specific embodiment, the adding parts of the phosphorus-containing acrylic monomer modified epoxy resin in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts and 100 parts.
In some embodiments, the method of preparing the phosphorus-containing acrylic monomer modified epoxy resin comprises the steps of:
s01, pre-emulsification: stirring and uniformly stirring a catalyst, a phosphorus-containing acrylic acid monomer, styrene, butyl acrylate, lauryl acrylate, isobornyl acrylate and other monomers at normal temperature and normal pressure to obtain a pre-emulsion;
s02, polymerization: adding epoxy resin and a cosolvent into the bottom of a reaction kettle, heating to 75-85 ℃, and stirring for dissolving for 20-40 minutes; then heating to 120-160 ℃;
s03, placing the pre-emulsion with the mass percentage of 5% -10% into the bottom of a reaction kettle, reacting and preserving the temperature for 10-30 minutes, wherein the dropping time is 240 minutes plus 120-;
s04, post elimination: and (3) keeping the temperature of the polymerization modifier at 130-170 ℃, adding a catalyst, keeping the temperature for 60-120 minutes, cooling to 70-80 ℃ after the heat preservation is finished, and filtering to obtain the phosphorus-containing acrylic monomer modified epoxy resin.
The water-based nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 8-25 parts of an emulsifier, wherein the emulsifier contains an epoxy group and a lipophilic group, the epoxy group can improve the compatibility of the emulsifier and epoxy resin, and the lipophilic group can form a stable structure with the epoxy resin and a grafted monomer group, so that the emulsion has good emulsifying capacity.
In some embodiments, the emulsifier is obtained by mixing polyethylene glycol, polypropylene glycol, polyether amine, epoxy resin and a catalyst, and the emulsifier obtained by mixing a plurality of substances has an epoxy group and an oleophilic group, so that the emulsifier can be favorably acted with other components to form the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion with stable performance.
Furthermore, in the emulsifier, the mass ratio of the polyethylene glycol, the polypropylene glycol, the polyether amine, the epoxy resin and the catalyst is (2-2.5) to (0.9-1.5): (5-5.5) (0.1-0.5), the mass ratio of each monomer is controlled, so that the obtained emulsifier has excellent performance. In the specific embodiment of the invention, the mass ratio of the polyethylene glycol, the polypropylene glycol, the polyether amine, the epoxy resin and the catalyst is 2:2:0.9:5: 0.1.
In some embodiments, the emulsifier is at least one polyethylene glycol selected from the group consisting of PEG-400, PEG-1000, PEG-2000, PEG-4000, and PEG-6000.
In some embodiments, the emulsifier is at least one polypropylene glycol selected from PPG-600, PPG-1000, PPG-2000, PPG-3000.
In some embodiments, the emulsifier is at least one polyetheramine selected from polyetheramine MA-240, polyetheramine MA-223, and polyetheramine M-1000.
Wherein the type of the catalyst of the emulsifier is consistent with that of the catalyst in the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion.
In a specific embodiment, the adding parts of the emulsifier in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts and 25 parts.
In some embodiments, the method of preparing the emulsifier comprises the steps of:
under the protection of dry nitrogen, adding polyethylene glycol, polypropylene glycol, polyether amine and epoxy resin into a reaction kettle with a reflux condensing device, stirring and dissolving at 50-80 ℃, heating to 100-180 ℃ after complete dissolution, slowly adding a catalyst, keeping the temperature for 3-6 hours, and cooling to obtain the emulsifier.
Specifically, the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 5-20 parts of epoxy diluent, wherein the epoxy diluent can directly participate in the curing reaction of epoxy resin to form a part of a cross-linked network structure of a cured epoxy resin, so that the performance of a cured product is hardly influenced, and the toughness of a curing system can be increased.
In some embodiments, the epoxy diluent employs at least one of ethylene glycol diglycidyl ether, 1,4 cyclohexanedimethanol diglycidyl ether, benzyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, and diglycidyl hexahydrophthalate.
In a specific embodiment, the addition parts of the epoxy diluent in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts and 20 parts.
Specifically, the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 15-30 parts of cosolvent; the cosolvent is added to improve the solubility of the epoxy resin and the phosphorus-containing acrylic acid monomer modified epoxy resin and ensure a good dissolving effect.
In some embodiments, the co-solvent employs at least one of propylene glycol methyl ether, sec-butyl alcohol, n-butyl alcohol, ethylene glycol butyl ether, ethylene glycol tertiary butyl ether.
In a specific embodiment, the adding parts of the cosolvent in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts and 30 parts.
Specifically, the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion comprises 0.1-1 part of catalyst; the catalyst is added to facilitate the interaction of all the components to form the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion.
In some embodiments, the catalyst is selected from at least one of boron trifluoride, triphenylphosphine, sodium hydroxide, benzylamine, di-t-amyl peroxide, di-t-butyl peroxide.
In a specific embodiment, the addition parts of the catalyst in the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are selected from 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and 1.0 part.
The second aspect of the embodiments of the present application provides a method for preparing an aqueous nonionic phosphorous epoxy anticorrosive emulsion, comprising the following steps:
G01. providing components according to the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion;
G02. carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst to obtain a first mixture;
G03. carrying out second mixing treatment on the first mixture and the emulsifier to obtain a second mixture;
G04. performing third mixing treatment on the second mixture, epoxy resin and an epoxy diluent to obtain a third mixture;
G05. and dripping water into the third mixture within 1-3 hours, and then filtering to obtain the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion.
The preparation method of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion provided by the second aspect of the application is simple and convenient, can better improve the stability of the emulsion, overcomes the defect of poor water resistance of emulsion coating, and can realize large-scale industrial production.
In step G01, the components are provided according to the aqueous nonionic phosphorous epoxy antiseptic emulsion, and the types and addition amounts of the components are as discussed above, and will not be described herein again for the sake of brevity.
In step G02, carrying out first mixing treatment on the phosphorus-containing acrylic monomer modified epoxy resin, the cosolvent and the catalyst to obtain a first mixture; the temperature of the first mixing treatment is 80-90 ℃, the temperature of the first mixing treatment is controlled to be high, and the phosphorus-containing acrylic monomer modified epoxy resin can be completely dissolved.
In step G03, performing a second mixing treatment on the first mixture and the emulsifier to obtain a second mixture; in the second mixing treatment process, the temperature of the mixing treatment is controlled to be 80-90 ℃, and the time of the mixing treatment is 0.5-1 hour.
Step G04, performing third mixing treatment on the second mixture, epoxy resin and epoxy diluent to obtain a third mixture; in the third mixing treatment process, the temperature of the mixing treatment is 80-90 ℃, and the time of the mixing treatment is 0.5-1 hour.
And G05, dripping water into the third mixture within 1-3 hours, and then filtering to obtain the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion, wherein the dripping water speed is ensured to be slow at a constant speed, the stirring speed is ensured to be enough to fully and uniformly disperse the epoxy resin in the water adding process, the stirring speed can be properly reduced after the emulsion is completely phase-converted, and the dripping time is about 1-3 hours.
In some embodiments, the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion has a solid content of 55-65%, a pH value of 7-8, an epoxy value of 0.1-0.25 mol/100g, and a viscosity of 1000-6000 mpa.s.
The following description will be given with reference to specific examples.
Example 1
Water-based nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof
Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
The aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion comprises the following components in parts by weight:
wherein the epoxy resin is a mixture of 100 parts of epoxy resin E-51 and 160 parts of epoxy resin E-20;
the epoxy diluent is hexahydrophthalic acid diglycidyl ester;
the cosolvent is propylene glycol methyl ether;
the catalyst is a mixture of 0.2 part of benzylamine and 0.2 part of catalyst di-tert-amyl peroxide;
the emulsifier is prepared from polyethylene glycol PEG-1000, polypropylene glycol PPG-600, polyether amine MA-240, epoxy resin E-51, epoxy resin E20 and catalyst benzylamine according to the weight ratio of 3: 5: 8: 10:16: 0.2, preparing;
the phosphorus-containing acrylic monomer modified epoxy resin is prepared from epoxy resin E51, a catalyst dipentyl peroxide, a phosphorus-containing acrylic monomer PAM-100, styrene, butyl acrylate, lauryl acrylate and isobornyl acrylate according to the weight ratio of 100:0.2:50:20:30:10: 2.
Preparation method of aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
(1) Providing components according to the aqueous nonionic phosphorous epoxy corrosion inhibiting emulsion provided in example 1;
(2) preparation of the emulsifier: under the protection of dry nitrogen, adding polyethylene glycol, polypropylene glycol, polyether amine and epoxy resin in a formula amount into a reaction kettle with a reflux condensing device, stirring and dissolving at 60 ℃, heating to 120 ℃ after complete dissolution, slowly adding a catalyst, keeping the temperature for 3 hours, and cooling to obtain an emulsifier for later use;
(3) preparation of phosphorus-containing acrylic monomer modified epoxy resin:
a) pre-emulsification: at normal temperature and normal pressure, stirring and uniformly stirring the catalyst, the phosphorus-containing acrylic acid monomer, styrene, butyl acrylate, lauryl acrylate, isobornyl acrylate and other monomers according to the formula ratio for later use;
b) polymerization: adding epoxy resin and cosolvent in a formula amount into the bottom of a reaction kettle, heating to 85 ℃, stirring for dissolving for 20 minutes, and then heating to 140 ℃; taking 5% of the pre-emulsion obtained in the step a) as seeds, putting the seeds into the bottom of a reaction kettle at one time, reacting and preserving the temperature for 30 minutes, wherein the dripping time is 200 minutes, and the reaction temperature is 140 ℃;
c) post-elimination: keeping the temperature of the polymer modifier obtained in the step b) to 140 ℃, adding the catalyst with the formula amount at one time, keeping the temperature for 60 minutes, cooling to 80 ℃ after the heat preservation is finished, filtering and discharging for later use;
(4) emulsification of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion: carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst at 90 ℃ to obtain a first mixture;
carrying out second mixing treatment on the first mixture and the emulsifier at 90 ℃ for 0.5 hour to obtain a second mixture;
performing third mixing treatment on the second mixture, epoxy resin and epoxy diluent at 90 ℃ to obtain a third mixture;
and dripping water into the third mixture within 3 hours, cooling to 45 ℃, and then filtering to obtain the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion.
The solid content of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 57 percent; the pH value of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 7; the epoxy value of the prepared aqueous nonionic phosphorus-containing epoxy antiseptic emulsion is 0.15mol/100 g.
Example 2
Water-based nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof
Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
The aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion comprises the following components in parts by weight:
wherein the epoxy resin is a mixture of 70 parts of epoxy resin E-51 and 180 parts of epoxy resin E-20;
the epoxy diluent is 1,4 cyclohexanedimethanol diglycidyl ether;
the cosolvent is ethylene glycol butyl ether;
the catalyst was a mixture of 0.2 parts sodium hydroxide and 0.2 parts catalyst ditert-amyl peroxide;
the emulsifier is prepared from polyethylene glycol PEG-600, polypropylene glycol PPG-2000, polyether amine MA-2200, epoxy resin E-51, epoxy resin E20 and catalyst benzylamine according to the weight ratio of 6: 10: 2: 7:7: 0.2, preparing;
the phosphorus-containing acrylic monomer modified epoxy resin is prepared from epoxy resin E51, a catalyst dipentyl peroxide, a phosphorus-containing acrylic monomer PAM-100, styrene, butyl acrylate, lauryl acrylate and isobornyl acrylate according to the weight ratio of 100:0.2:30:50:20:18: 7.
Preparation method of aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
(1) Providing components according to the aqueous nonionic phosphorous epoxy corrosion inhibiting emulsion provided in example 2;
(2) preparation of the emulsifier: under the protection of dry nitrogen, adding polyethylene glycol, polypropylene glycol, polyether amine and epoxy resin in a formula amount into a reaction kettle with a reflux condensing device, stirring and dissolving at 65 ℃, heating to 130 ℃ after complete dissolution, slowly adding a catalyst, keeping the temperature for 3 hours, and cooling to obtain an emulsifier for later use;
(3) preparation of phosphorus-containing acrylic monomer modified epoxy resin:
a) pre-emulsification: at normal temperature and normal pressure, stirring and uniformly stirring the catalyst, the phosphorus-containing acrylic acid monomer, styrene, butyl acrylate, lauryl acrylate, isobornyl acrylate and other monomers according to the formula ratio for later use;
b) polymerization: adding epoxy resin and cosolvent in a formula amount into the bottom of a reaction kettle, heating to 85 ℃, stirring for dissolving for 20 minutes, and then heating to 140 ℃; taking 8% of the pre-emulsion obtained in the step a) as seeds, putting the seeds into the bottom of a reaction kettle at one time, reacting and preserving the temperature for 30 minutes, wherein the dripping time is 180 minutes, and the reaction temperature is 140 ℃;
c) post-elimination: keeping the temperature of the polymer modifier obtained in the step b) to 140 ℃, adding the catalyst with the formula amount at one time, keeping the temperature for 60 minutes, cooling to 80 ℃ after the heat preservation is finished, filtering and discharging for later use;
(4) emulsification of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion: carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst at 90 ℃ to obtain a first mixture;
carrying out second mixing treatment on the first mixture and the emulsifier at 90 ℃ for 0.5 hour to obtain a second mixture;
performing third mixing treatment on the second mixture, epoxy resin and epoxy diluent at 90 ℃ to obtain a third mixture;
and (3) dropwise adding water into the third mixture within 2 hours, cooling to 40 ℃, and then filtering to obtain the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion.
The solid content of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 65 percent; the pH value of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 7; the epoxy value of the prepared aqueous nonionic phosphorus-containing epoxy antiseptic emulsion is 0.22mol/100 g.
Example 3
Water-based nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof
Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
The aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion comprises the following components in parts by weight:
wherein the epoxy resin is a mixture of 50 parts of epoxy resin E-51 and 200 parts of epoxy resin E-20;
the epoxy diluent is ethylene glycol diglycidyl ether;
the cosolvent is propylene glycol methyl ether;
the catalyst is a mixture of 0.2 part of triphenylphosphine and 0.2 part of catalyst di-tert-butyl peroxide;
the emulsifier is prepared from polyethylene glycol PEG-2000, polypropylene glycol PPG-100, polyetheramine MA-223, epoxy resin E-51, epoxy resin E20 and catalyst triphenylphosphine according to the weight ratio of 6: 2: 10: 5:20: 0.2, preparing;
the phosphorus-containing acrylic monomer modified epoxy resin is prepared from epoxy resin E51, a catalyst dipentyl peroxide, a phosphorus-containing acrylic monomer PAM-100, styrene, butyl acrylate, lauryl acrylate and isobornyl acrylate according to the weight ratio of 100:0.2:20:40:25:18: 15.
Preparation method of aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion
(1) Providing components according to the aqueous nonionic phosphorous epoxy corrosion inhibiting emulsion provided in example 3;
(2) preparation of the emulsifier: under the protection of dry nitrogen, adding polyethylene glycol, polypropylene glycol, polyether amine and epoxy resin in a formula amount into a reaction kettle with a reflux condensing device, stirring and dissolving at 60 ℃, heating to 150 ℃ after complete dissolution, slowly adding a catalyst, keeping the temperature for 4 hours, and cooling to obtain an emulsifier for later use;
(3) preparation of phosphorus-containing acrylic monomer modified epoxy resin:
a) pre-emulsification: at normal temperature and normal pressure, stirring and uniformly stirring the catalyst, the phosphorus-containing acrylic acid monomer, styrene, butyl acrylate, lauryl acrylate, isobornyl acrylate and other monomers according to the formula ratio for later use;
b) polymerization: adding epoxy resin and cosolvent in a formula amount into the bottom of a reaction kettle, heating to 85 ℃, stirring for dissolving for 20 minutes, and then heating to 140 ℃; taking 10% of the pre-emulsion obtained in the step a) as seeds, putting the seeds into the bottom of a reaction kettle at one time, reacting and preserving the temperature for 30 minutes, wherein the dripping time is 240 minutes, and the reaction temperature is 140 ℃;
c) post-elimination: keeping the temperature of the polymer modifier obtained in the step b) to 140 ℃, adding the catalyst with the formula amount at one time, keeping the temperature for 120 minutes, cooling to 70 ℃ after the heat preservation is finished, filtering and discharging for later use;
(4) emulsification of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion: carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst at 90 ℃ to obtain a first mixture;
carrying out second mixing treatment on the first mixture and the emulsifier at 90 ℃ for 0.5 hour to obtain a second mixture;
performing third mixing treatment on the second mixture, epoxy resin and epoxy diluent at 90 ℃ to obtain a third mixture;
and (3) dropwise adding water into the third mixture within 2 hours, cooling to 45 ℃, and then filtering to obtain the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion.
The solid content of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 60 percent; the pH value of the prepared aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion is 7; the epoxy value of the prepared aqueous nonionic phosphorus-containing epoxy antiseptic emulsion is 0.18mol/100 g.
And (3) performance testing:
the performance of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion prepared in the above examples 1 to 3 was tested, the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion prepared in the above examples 1 to 3 was prepared into epoxy zinc phosphate primer and epoxy zinc rich primer, and the following performances of the epoxy zinc phosphate primer and the epoxy zinc rich primer were measured respectively:
testing for salt water resistance: tested according to the test method of GB/T9274-.
Testing the salt spray resistance: test with reference to GB/T1771-2007 test method.
Water resistance test: tested according to the GB/T1733-1993 test method.
Moisture and heat resistance test: test with reference to GB/T1740-2007 test method.
The formula of the epoxy zinc phosphate primer is shown in the following table 1, and the preparation method comprises the following steps of; adding the raw materials with the serial numbers of 1-7 into a stirring cylinder according to the serial numbers, stirring for 10 minutes at 1200r/min, then grinding to the fineness of below 30um, sequentially adding the raw materials with the serial numbers of 8-13, stirring for 45 minutes at 2000r/min, taking a small amount of the raw materials, scraping a membrane on a glass plate without shrinkage cavity, and filtering and discharging the product by using 250-mesh filter cloth. After standing and defoaming, adding the mixture with the sequence number 14, stirring uniformly, and performing spray plate test.
TABLE 1
The formulation of the epoxy zinc rich primer is shown in the following table 2, and the preparation method comprises the following steps: adding the raw materials with the serial numbers of 1-6 into a stirring cylinder in sequence according to the serial numbers, stirring for 10 minutes at 800r/min, then stirring for 45 minutes after rising to 2000r/min, taking a small amount of the raw materials, scraping a membrane on a glass plate without shrinkage cavity, filtering by using a 250-mesh filter cloth, and discharging. After standing and defoaming, adding the mixture with the serial number of 7-8, stirring uniformly, and testing by a spray plate.
TABLE 2
And (4) analyzing results:
the performance analysis of the epoxy zinc phosphate primers prepared in examples 1 to 3 is shown in Table 3, wherein in the water resistance, the epoxy zinc phosphate primer obtained in example 1 does not foam for 600 hours, the epoxy zinc phosphate primer obtained in example 2 does not foam for 720 hours, the epoxy zinc phosphate primer obtained in example 3 does not foam for 800 hours, and in the salt water resistance, the epoxy zinc phosphate primer obtained in example 1 does not foam for 650 hours, the epoxy zinc phosphate primer obtained in example 2 does not foam for 700 hours, the epoxy zinc phosphate primer obtained in example 3 does not foam for 650 hours, and in the salt water resistance, the epoxy zinc phosphate primer obtained in example 1 does not foam for 500 hours, the epoxy zinc phosphate primer obtained in example 2 does not foam for 550 hours, the epoxy zinc phosphate primer obtained in example 3 does not foam for 530 hours, and in the moisture and heat resistance, the epoxy zinc phosphate primer obtained in example 1 does not foam for 700 hours, the epoxy zinc phosphate primer obtained in example 2 did not foam for 640 hours, and the epoxy zinc phosphate primer obtained in example 3 did not foam for 600 hours.
The performance analysis of the epoxy zinc rich primers prepared in examples 1 to 3 is shown in table 3, wherein in the water resistance, the epoxy zinc rich primer obtained in example 1 does not foam in 780 hours, the epoxy zinc rich primer obtained in example 2 does not foam in 820 hours, the epoxy zinc rich primer obtained in example 3 does not foam in 840 hours, in the salt water resistance, the epoxy zinc rich primer obtained in example 1 does not foam in 650 hours, the epoxy zinc rich primer obtained in example 2 does not foam in 680 hours, the epoxy zinc rich primer obtained in example 3 does not foam in 600 hours, in the salt spray resistance, the epoxy zinc rich primer obtained in example 1 does not foam in 900 hours, the epoxy zinc rich primer obtained in example 2 does not foam in 1200 hours, the epoxy zinc rich primer obtained in example 3 does not foam in 1250 hours, in the moisture and heat resistance, and in the epoxy zinc rich primer obtained in example 1 does not foam in 600 hours, the epoxy zinc rich primer obtained in example 2 did not foam for 720 hours, and the epoxy zinc rich primer obtained in example 3 did not foam for 650 hours.
Even if the humidity environment reaches 80%, the zinc-rich primer prepared by matching the aqueous nonionic phosphorus-containing epoxy anti-corrosion emulsion with the epoxy curing agent has good hardness and wet adhesion performance, the moisture and heat resistance at 40 ℃ can reach 500 hours without bubbling or falling off, the salt spray resistance of 70um can reach 1200 hours without bubbling, and the salt spray resistance of the aqueous nonionic phosphorus-containing epoxy anti-corrosion emulsion with the double-component polyurethane finish can reach 2000 hours without bubbling. The epoxy emulsion is matched with primer made of zinc phosphate antirust pigment, and an epoxy curing agent is added, and the epoxy emulsion is dried for 7 days at normal temperature, does not foam after being resistant to humidity and heat for 400 hours, does not foam and fall off after being resistant to water for 720 hours, does not foam after being resistant to salt water for 720 hours, and does not foam and fall off after being resistant to salt mist for 500 hours.
In conclusion, the solid content of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion obtained in the embodiment of the application can reach 65%, the wet adhesion, the water resistance, the acid and alkali resistance, the salt water resistance, the salt spray resistance and the anticorrosive performance of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are greatly improved, the performances of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion are not inferior to those of an oily epoxy coating, and the development of industrial water-based is greatly promoted.
TABLE 3
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The water-based nonionic phosphorus-containing epoxy anticorrosive emulsion is characterized by comprising the following components in parts by weight:
2. the aqueous nonionic phosphorus-containing epoxy antiseptic emulsion according to claim 1, wherein the phosphorus-containing acrylic monomer modified epoxy resin is obtained by polymerization of epoxy resin, catalyst, phosphorus-containing acrylic monomer, styrene, butyl acrylate, lauryl acrylate, and isobornyl acrylate; and the mass ratio of the epoxy resin, the catalyst, the phosphorus-containing acrylic monomer, the styrene, the butyl acrylate, the lauryl acrylate and the isobornyl acrylate is as follows: (4 to 4.5) (0.1 to 0.5) (0.5 to 1.0) (2 to 2.5) (1 to 1.5) (1 to 1.4 to 2)
3. The aqueous nonionic phosphorous epoxy preservative emulsion according to claim 2, wherein the phosphorous acrylic monomer is selected from at least one of solvelet PAM-100, solvelet PAM-200, 2-hydroxyethyl methacrylate phosphate, ethylene glycol methacrylate phosphate, 10- (2-methacryloyloxy) monodecanyl phosphate.
4. The aqueous nonionic phosphorus-containing epoxy antiseptic emulsion according to claim 1, wherein the emulsifier is obtained by mixing polyethylene glycol, polypropylene glycol, polyether amine, epoxy resin and a catalyst; and the mass ratio of the polyethylene glycol, the polypropylene glycol, the polyether amine, the epoxy resin and the catalyst is (2-2.5): (0.9-1.5): (5 to 5.5) and (0.1 to 0.5).
5. The aqueous nonionic phosphorus-containing epoxy antiseptic emulsion according to claim 4, wherein the polyethylene glycol is at least one selected from the group consisting of PEG-400, PEG-1000, PEG-2000, PEG-4000, PEG-6000; and/or the presence of a gas in the gas,
the polypropylene glycol is at least one selected from PPG-600, PPG-1000, PPG-2000 and PPG-3000; and/or the presence of a gas in the gas,
the polyether amine is at least one selected from the group consisting of polyether amine MA-240, polyether amine MA-223 and polyether amine M-1000.
6. The aqueous nonionic phosphorus-containing epoxy corrosion-inhibiting emulsion of claim 1 or 2, wherein the epoxy resin is at least one of E-51, E-44, E-20, and E-12.
7. The aqueous nonionic phosphorus-containing epoxy corrosion inhibiting emulsion of claim 1,2, or 4 wherein the catalyst is selected from at least one of boron trifluoride, triphenylphosphine, sodium hydroxide, benzylamine, di-t-amyl peroxide, di-t-butyl peroxide.
8. The aqueous nonionic phosphorus-containing epoxy corrosion-inhibiting emulsion of claim 1, wherein the epoxy diluent is at least one of ethylene glycol diglycidyl ether, 1,4 cyclohexane dimethanol diglycidyl ether, benzyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, and diglycidyl hexahydrophthalate; and/or the presence of a gas in the gas,
the cosolvent is at least one of propylene glycol methyl ether, sec-butyl alcohol, n-butyl alcohol, ethylene glycol butyl ether and ethylene glycol tertiary butyl ether.
9. The preparation method of the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion is characterized by comprising the following steps:
the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion according to any one of claims 1 to 8, comprising components;
carrying out first mixing treatment on phosphorus-containing acrylic monomer modified epoxy resin, a cosolvent and a catalyst to obtain a first mixture;
carrying out second mixing treatment on the first mixture and an emulsifier to obtain a second mixture;
carrying out third mixing treatment on the second mixture, epoxy resin and an epoxy diluent to obtain a third mixture;
and dripping water into the third mixture within 1-3 hours, and then filtering to obtain the water-based nonionic phosphorus-containing epoxy anticorrosive emulsion.
10. The preparation method of the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion according to claim 9, wherein the aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion has a solid content of 55-65%, a pH value of 7-8, an epoxy value of 0.1-0.25 mol/100g, and a viscosity of 1000-6000 mpa.s.
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Application publication date: 20210615 |