CN116875190A - Elastic organosilicon finish paint connecting coating and preparation method and application thereof - Google Patents
Elastic organosilicon finish paint connecting coating and preparation method and application thereof Download PDFInfo
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- CN116875190A CN116875190A CN202310840332.XA CN202310840332A CN116875190A CN 116875190 A CN116875190 A CN 116875190A CN 202310840332 A CN202310840332 A CN 202310840332A CN 116875190 A CN116875190 A CN 116875190A
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- 239000003973 paint Substances 0.000 title claims abstract description 74
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 49
- 239000004593 Epoxy Substances 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 23
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 50
- 229910052710 silicon Inorganic materials 0.000 claims description 47
- 239000010703 silicon Substances 0.000 claims description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011229 interlayer Substances 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 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 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 4
- 239000002131 composite material Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 29
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000006254 rheological additive Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241001396798 Aldama Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003364 biologic glue Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical group CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2504/00—Epoxy polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The application provides an elastic organosilicon finish paint connecting coating, a preparation method and application thereof. The raw materials of the coating comprise a first component, a second component and a third component, wherein the first component comprises thermoplastic resin, epoxy resin, auxiliary agent, pigment and filler and solvent; the second component comprises 65-75 parts of amine-siloxane prepolymer resin and a solvent; the third component comprises polydimethylsiloxane, pigment filler and solvent; the amine-siloxane prepolymer resin is a prepolymer reaction product comprising phenolic amine resin and mono-epoxy functional trialkoxysilane, epoxy resin and methyltrimethoxysilane. When the connecting coating is matched with the elastic organosilicon finish paint and the epoxy primer for use, the adsorption capacity between the elastic organosilicon finish paint and the epoxy primer can be obviously improved, and meanwhile, the connecting coating has good acid-base resistance and salt-water resistance, and the preparation method is simple and easy to popularize.
Description
Technical Field
The application belongs to the technical field of coating materials, and particularly relates to an elastic organosilicon finish paint connecting coating, and a preparation method and application thereof.
Background
In recent years, elastomeric silicone topcoats have found application in a variety of fields. For example, the elastic organosilicon marine antifouling paint can make marine organisms difficult to form firm adhesion on the surface of a paint film by utilizing the high elastic modulus of the paint. In the aspect of product matching, the elastic organic silicon finishing paint is often matched with the epoxy primer to form anti-corrosion protection on the steel base material, but the interlayer adhesive force between the elastic organic silicon finishing paint and the epoxy primer is usually poor, and if the elastic organic silicon finishing paint is directly coated on the epoxy primer, the phenomena of foaming, falling and the like are easy to occur. To solve this problem, it is common practice in the industry to apply a thermoplastic or low crosslink density intermediate paint between the two coats to form an anchor between the primer and elastomeric topcoat by swelling. Chinese patent No. 107177309B discloses an intermediate connecting paint matched with an epoxy coating and an organosilicon coating, and the chemical mechanism of firm adhesion of mussel biological glue under water is used for reference, and a wet adhesion promoter containing catechol groups is introduced, so that the interface destruction effect of water molecules can be prevented, and the long-term water-resistant connecting effect is maintained. However, the interlayer adhesion formed in this way is often poor in reliability, and in the environment of chloride ion soaking or acid-base corrosion, connection failure is easy to occur, so that the finish paint is dropped off, and therefore, development of a connection coating with high interlayer adsorption performance is needed to solve the problem.
Disclosure of Invention
The application discloses an elastic organic silicon finish paint connecting coating, a preparation method and application thereof, and aims to solve the problem of poor adhesive force between an epoxy primer and an elastic organic silicon finish paint.
In order to achieve the technical effects, the application adopts the following technical scheme:
the application provides an elastic organic silicon finishing paint connecting coating, which is formed by mixing a first component, a second component and a third component according to the mass ratio of 5.2-6.2:1:0.6-0.7;
the first component comprises the following components in parts by weight: 5-15 parts of thermoplastic resin, 5-15 parts of epoxy resin, 0.3-2 parts of auxiliary agent, 45-55 parts of pigment and filler and 20-30 parts of solvent;
the second component comprises the following components in parts by weight: 65-75 parts of amine-siloxane prepolymer resin and 25-35 parts of solvent;
the third component comprises the following components in parts by weight: 50-60 parts of polydimethylsiloxane, 1-5 parts of pigment and filler and 35-45 parts of solvent.
Further, in the second component, the amine-siloxane prepolymer resin is a prepolymer reaction product of a phenolic amine resin, a monoepoxy functional trialkoxysilane, an epoxy resin, and methyltrimethoxysilane.
Further, the mass ratio of the phenolic amine resin to the monoepoxy functional trialkoxysilane to the epoxy resin to the methyltrimethoxysilane is 100:30.4-32.2:5.0-7.6:14.0-14.9.
Further, the weight average molecular weight of the amine-siloxane prepolymer resin is 1200-3000, and the active hydrogen equivalent is 240-290.
Further, the amine value of the phenolic amine resin is 230-300, and the active hydrogen equivalent is 120-135.
Further, the thermoplastic resin in the first component includes thermoplastic acrylic resin, petroleum resin and thermoplastic chloroether resin.
Further, the molecular weight of the thermoplastic resin is 100-10000.
Further, the weight average molecular weight of the epoxy resin is 390-420, the epoxy equivalent is 195-210, and the epoxy resin has 1-2 epoxy functional groups.
Further, in the third component, the polydimethylsiloxane is a hydroxyl-terminated polydimethylsiloxane having a weight average molecular weight of 1000 to 50000.
Further, the interlayer shear strength of the elastic organosilicon finish paint connecting coating and the epoxy primer is 11.6-12.4Mpa.
Further, the interlayer adhesion strength between the elastic organic silicon finishing paint connecting coating and the elastic organic silicon finishing paint is 5.1-5.3MPa.
Further, the pigment and filler comprises any one or the combination of more than two of titanium dioxide, iron oxide black, iron oxide red, talcum powder and silicon micro powder.
Further, the auxiliary agent comprises any one or a combination of more than two of an antifoaming agent, a leveling agent and a rheological auxiliary agent.
Further, the solvent comprises any one or a combination of more than two of dimethylbenzene, no. 100 solvent oil and No. 150 solvent oil.
The application also provides a preparation method of the elastic organosilicon finish paint connecting coating, which comprises the following steps: uniformly mixing thermoplastic resin, epoxy resin, pigment and filler, auxiliary agent and solvent to form a mixture, and regulating the viscosity of the mixture to 115+/-3 KU by using the solvent to obtain a first component;
mixing a solvent and phenolic amine resin, adding an epoxy silane coupling agent and epoxy resin, cooling after reaction, adding methyltrimethoxysilane, stirring uniformly, standing to obtain amine-siloxane prepolymer resin, and regulating the viscosity of the amine-siloxane prepolymer resin to 100+/-3 KU by using the solvent to obtain a second component;
uniformly mixing polydimethylsiloxane, pigment and filler and a solvent to form a mixture, and regulating the viscosity of the mixture to 90+/-3 KU by using the solvent to obtain a third component;
and uniformly mixing the first component, the second component and the third component to obtain the elastic organosilicon finish paint connecting coating.
Further, the preparation of the second component specifically comprises the steps of mixing a solvent and phenolic amine resin, controlling the temperature to be 40-50 ℃, adding an epoxy silane coupling agent and the epoxy resin under stirring, cooling to room temperature after reacting for 2 hours, adding methyltrimethoxysilane, standing for 24 hours after uniformly stirring to obtain an amine-siloxane prepolymer resin, and regulating the viscosity of the amine-siloxane prepolymer resin to 100+/-3 KU by using the solvent to prepare the second component.
The elastic organosilicon finish paint connecting coating is applied to the aspect of increasing the adhesive force between the epoxy primer and the elastic organosilicon finish paint.
Compared with the prior art, the application has the beneficial effects that:
1) The elastic organic silicon finishing paint connecting coating provided by the application has good interlayer adsorption performance, and the adhesion capability between the elastic organic silicon finishing paint and the epoxy antirust primer is obviously improved, so that the failure of the finishing paint coating caused by interlayer stripping is not easy to occur.
2) The elastic organic silicon finishing paint connecting coating provided by the application is stable in storage, has good acid-base resistance and salt-water resistance, can still keep interlayer adhesive force smaller than level 1 after being subjected to acid-base resistance and salt-water resistance tests for 3000 hours with the matched coating of the epoxy primer and the elastic organic silicon finishing paint, and has no phenomena of foaming, falling and the like.
3) The preparation method provided by the application is simple, the reagents can be purchased, the reaction process is mild, and the popularization is easy.
4) The interlayer shear strength between the elastic organosilicon finish paint connecting coating and the epoxy primer is 11.6-12.4MPa, and the interlayer adhesion strength between the elastic organosilicon finish paint connecting coating and the elastic organosilicon finish paint is 5.1-5.3MPa, which is far higher than that of other connecting coatings sold in the market.
Detailed Description
The application will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present application are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the application, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application in virtually any appropriately detailed embodiment.
The application provides an elastic organic silicon finishing paint connecting coating, which is formed by mixing a first component, a second component and a third component according to the mass ratio of 5.2-6.2:1:0.6-0.7;
the first component comprises the following components in parts by weight: 5-15 parts of thermoplastic resin, 5-15 parts of epoxy resin, 0.3-2 parts of auxiliary agent, 45-55 parts of pigment and filler and 20-30 parts of solvent;
the second component comprises the following components in parts by weight: 65-75 parts of amine-siloxane prepolymer resin and 25-35 parts of solvent;
the third component comprises the following components in parts by weight: 50-60 parts of polydimethylsiloxane, 1-5 parts of pigment and filler and 35-45 parts of solvent.
The application also provides a preparation method of the elastic organosilicon finish paint connecting coating, which comprises the following steps:
uniformly mixing thermoplastic resin, epoxy resin, pigment and filler, auxiliary agent and solvent to form a mixture, and regulating the viscosity of the mixture to 115+/-3 KU by using the solvent to obtain a first component;
mixing a solvent and phenolic amine resin, adding an epoxy silane coupling agent and epoxy resin, cooling after reaction, adding methyltrimethoxysilane, stirring uniformly, standing to obtain amine-siloxane prepolymer resin, and regulating the viscosity of the amine-siloxane prepolymer resin to 100+/-3 KU by using the solvent to obtain a second component;
uniformly mixing polydimethylsiloxane, pigment and filler and a solvent to form a mixture, and regulating the viscosity of the mixture to 90+/-3 KU by using the solvent to obtain a third component;
and uniformly mixing the first component, the second component and the third component according to the mass ratio of 5.2-6.2:1:0.6-0.7 to prepare the elastic organosilicon finish paint connecting coating.
The application is further illustrated by means of the following examples, which are not intended to limit the scope of the application. The reagents and starting materials used in the following examples were all commercially available, and the test methods in which the specific conditions were not specified were generally conducted under conventional conditions or under the conditions recommended by the respective manufacturers. For example, the phenolic amine resin used in the examples below has an amine number of 230-300, an active hydrogen equivalent of 120-135 (Kadlin NC 541), a weight average molecular weight of the epoxy trialkoxysilane of 220-280 (Dow Corning Z-6040), an epoxy equivalent of 195-210 (Nanya NPEL-128) and having 1-2 epoxy functional groups, a molecular weight of 100-10000 (Changxing 7119-X-50) and a molecular weight of the polydimethylsiloxane of 1000-50000 (Jib. RTV-630). The defoamer used in the examples below may be Pick BYK-052N, the dispersant may be Ephragma EFKA-4010, and the rheology aid may be Aldama Crayvallac ULTRA. In the following examples, the low-speed stirring means a rotation speed of 500r/min or less, the high-speed stirring or dispersing means a rotation speed of 2000r/min or more, and 1500-2000r/min is medium-speed stirring.
Example 1
The preparation method of the elastic organic silicon finishing paint connecting coating provided by the embodiment comprises the following steps:
(1) 150g of dimethylbenzene and 50g of No. 100 solvent oil are added into a stirring kettle, 100g of thermoplastic resin and 150g of epoxy resin are added under the condition of low-speed stirring, after stirring for 5min to be uniform, 3g of rheological additive, 5g of dispersing agent and 2g of defoamer are added, stirring is carried out at medium speed for 5-10min, then 200g of titanium pigment, 100g of talcum powder and 200g of silicon micropowder are sequentially added, high-speed dispersion is carried out for 25-30min, and finally the viscosity is adjusted to 112KU by 40g of dimethylbenzene, so that the first component is obtained.
(2) 256g of xylene and 450g of phenolic amine resin are added into a container, a stirrer is started to stir at the speed of 300r/min and heated to 50 ℃, then 144g of epoxy siloxane resin and 34g of epoxy resin (Nanya NPEL-128) are slowly added under the stirring condition, the stirring is continued and the temperature is controlled to react for 2 hours at 55 ℃, then the mixture is cooled to the room temperature, 66g of methyltrimethoxysilane is added, the mixture is stirred uniformly and then is left stand for 24 hours, and the amine-siloxane prepolymer resin is prepared, and then the viscosity is adjusted to 103KU by 50g of xylene, so that a second component is obtained.
(3) 600g of polydimethylsiloxane and 50g of iron oxide red are added into 310g of dimethylbenzene under low-speed stirring at a rotating speed of 300-500r/min, stirred for 10min until the mixture is uniform, and finally the viscosity is adjusted to 93KU by 40g of dimethylbenzene, so that a third component is obtained.
(4) And uniformly mixing the first component, the second component and the third component according to the mass ratio of 5.2:1:0.6 to obtain the connecting coating material for the elastic organosilicon finish paint.
Example 2
The preparation method of the elastic organic silicon finishing paint connecting coating provided by the embodiment comprises the following steps:
(1) 200g of dimethylbenzene is added into a stirring kettle, 150g of thermoplastic resin and 100g of epoxy resin are added under low-speed stirring, after stirring for 5min to be uniform, 3g of rheological additive, 5g of dispersing agent and 2g of defoaming agent are added, stirring is carried out at medium speed for 5-10min, then 100g of titanium white, 150g of talcum powder and 250g of silicon micropowder are sequentially added, high-speed dispersion is carried out for 25-30min, and finally the viscosity is regulated to 115KU by 40g of dimethylbenzene, so that the first component is obtained.
(2) 202g of xylene and 500g of phenolic amine resin are added into a container, a stirrer is started to stir at the rotation speed of 300r/min and heated to 50 ℃, then 152g of epoxy siloxane resin and 26g of epoxy resin are slowly added under stirring, the stirring is continued and the temperature is controlled to be 53 ℃ for 2 hours, then the reaction is cooled to room temperature, 70g of methyltrimethoxysilane is added, the mixture is stirred uniformly and then is kept stand for 24 hours, and amine-siloxane prepolymer resin is prepared, and then the viscosity is adjusted to 97KU by 50g of xylene, so that a second component is obtained.
(3) Under the condition of low-speed stirring at the rotating speed of 300-500r/min, 500g of polydimethylsiloxane and 10g of iron oxide black are added into 400g of dimethylbenzene, stirring is carried out for 10min until the mixture is uniform, and finally the viscosity is adjusted to 87KU by 40g of dimethylbenzene, so that a third component is obtained.
(4) And uniformly mixing the first component, the second component and the third component according to the mass ratio of 6.2:1:0.7 to obtain the connecting coating material for the elastic organosilicon finish paint.
Example 3
The preparation method of the elastic organic silicon finishing paint connecting coating provided by the embodiment comprises the following steps:
(1) 160g of dimethylbenzene is added into a stirring kettle, 50g of thermoplastic resin and 50g of epoxy resin are added under the condition of low-speed stirring, after stirring for 5min to be uniform, 3g of rheological additive is added, stirring is carried out for 5-10min at medium speed, then 100g of titanium pigment, 150g of talcum powder and 200g of silicon micropowder are sequentially added, high-speed dispersion is carried out for 25-30min, and finally 40g of dimethylbenzene is used for regulating the viscosity to 118KU, so that the first component is obtained.
(2) 300g of dimethylbenzene and 420g of phenolic amine resin are added into a container, a stirrer is started to stir at the speed of 300r/min and heated to 50 ℃, 134g of epoxy siloxane resin and 30g of epoxy resin are slowly added under the stirring condition, the stirring is continued and the temperature is controlled to react for 2 hours at 50 ℃, then the mixture is cooled to room temperature, 66g of methyltrimethoxysilane is added, the mixture is stirred uniformly and then stands for 24 hours, and amine-siloxane prepolymer resin is prepared, and then the viscosity is adjusted to 100KU by 50g of dimethylbenzene, so that a second component is obtained.
(3) Under the condition of low-speed stirring at the rotating speed of 300-500r/min, 500g of polydimethylsiloxane and 10g of iron oxide black are added into 400g of dimethylbenzene, stirring is carried out for 10min until the mixture is uniform, and finally the viscosity is adjusted to 90KU by 40g of dimethylbenzene, so that a third component is obtained.
(4) And uniformly mixing the first component, the second component and the third component according to the mass ratio of 6.2:1:0.7 to obtain the connecting coating material for the elastic organosilicon finish paint.
Example 4
The preparation method of the elastic organic silicon finishing paint connecting coating provided by the embodiment comprises the following steps:
(1) 160g of dimethylbenzene is added into a stirring kettle, 100g of thermoplastic resin and 100g of epoxy resin are added under the condition of low-speed stirring, after stirring for 5min to be uniform, 20g of rheological additive is added, stirring is carried out for 5-10min at medium speed, then 100g of titanium pigment, 200g of talcum powder and 250g of silicon micropowder are sequentially added, high-speed dispersion is carried out for 25-30min, and finally the viscosity is regulated to 115KU by 40g of dimethylbenzene, so that the first component is obtained.
(2) 300g of dimethylbenzene and 420g of phenolic amine resin are added into a container, a stirrer is started to stir at the speed of 300r/min and heated to 50 ℃, 134g of epoxy siloxane resin and 30g of epoxy resin are slowly added under the stirring condition, the stirring is continued and the temperature is controlled to be 52 ℃ for 2 hours, the reaction is carried out, then the reaction is cooled to room temperature, 66g of methyltrimethoxysilane is added, the reaction product is stirred uniformly and then stands for 24 hours, and amine-siloxane prepolymer resin is prepared, and then the viscosity is adjusted to 103KU by 50g of dimethylbenzene, so that a second component is obtained.
(3) Under the condition of low-speed stirring at the rotating speed of 300-500r/min, 500g of polydimethylsiloxane and 10g of iron oxide black are added into 400g of dimethylbenzene, stirring is carried out for 10min until the mixture is uniform, and finally the viscosity is adjusted to 93KU by 40g of dimethylbenzene, so that a third component is obtained.
(4) And uniformly mixing the first component, the second component and the third component according to the mass ratio of 6.2:1:0.7 to obtain the connecting coating material for the elastic organosilicon finish paint.
Comparative example 1
The only difference between comparative example 1 and example 1 is that in the method for preparing the elastomeric silicone topcoat tie-coat provided in comparative example 1, step (2) comprises: 306g of xylene and 694g of phenolic amine resin were added to the vessel and mixed uniformly to obtain a second component. The remaining conditions were the same as in example 1.
Comparative example 2
The only difference between comparative example 2 and example 1 is that in the method for preparing the elastomeric silicone topcoat tie-coat provided in comparative example 2, step (3) comprises: and replacing the polydimethylsiloxane of the third component with a thermoplastic resin to obtain the third component. The remaining conditions were the same as in example 1.
Comparative example 3
The only difference between comparative example 3 and example 1 is that in the method for preparing the elastomeric silicone topcoat tie coating provided in comparative example 3, step (2) comprises: the epoxy silicone resin was replaced with an equivalent amount of amino silicone resin, with the remaining conditions being the same as in example 1.
Comparative example 4
Comparative example 4 the only difference from example 1 is that in the method for preparing the elastomeric silicone topcoat tie coat provided in comparative example 4, step (2) comprises: methyltrimethoxysilane was replaced with ethyltriethoxysilane, the remaining conditions were the same as in example 1.
Comparative example 5
Comparative example 5 differs from example 1 only in that the method for preparing the elastomeric silicone topcoat tie-coat provided in comparative example 5 comprises: the first component, the second component and the third component were mixed in a weight ratio of 5:1:0.5, and the other conditions were the same as in example 1.
Comparative example 6
Comparative example 6 the only difference from example 1 is that comparative example 6 provides a method for preparing an elastomeric silicone topcoat tie coating comprising: phenolic amine resin, epoxy siloxane resin, epoxy resin and methyltrimethoxysilane in the second component are added according to the mol ratio of 1:1.1:0.2:0.9 to react, and the other conditions are kept consistent with example 1.
Comparative example 7
Comparative example 7 differs from example 1 only in that in the preparation method of the elastic silicone topcoat tie-coat provided in comparative example 7, no heating was performed in step (2), and the remaining conditions were kept identical to those of example 1.
Comparative example 8
The only difference between comparative example 8 and example 1 is that in the preparation of the elastomeric silicone top-coat bond coat provided in comparative example 8, step (3) includes a reduction in the amount of polydimethylsiloxane from 600g to 400g, and an increase in the amount of xylene to 560g, with the remaining conditions consistent with example 1.
Characterization of Performance
The properties of the elastomeric silicone top-coat tie-coats prepared in examples 1-4 and comparative examples 1-8 above were further tested and compared to commercially available silicone tie-coats.
The corresponding test results are shown in table 1. Each test result in table 1 is an average value of the test results of the multiple batches of products.
Table 1 comparative tables for Performance test of elastomeric Silicone topcoat tie-coats prepared in examples 1-4 and comparative examples 1-8
After the elastic organosilicon finish paint connecting coating prepared in the examples 1-4 forms a matched coating with the epoxy primer and the elastic organosilicon intermediate paint, the elastic organosilicon finish paint connecting coating is soaked in 5% sulfuric acid, 5% NaOH and 3% saline solution for 3000 hours respectively, no phenomena such as foaming, falling and the like occur on the surface of a paint film, and the interlayer adhesive force is between 0 and 1 level. The interlayer shear strength of the connecting coating material and the epoxy primer is between 11.6 and 12.4MPa, and the interlayer adhesion strength of the connecting coating material and the elastic organosilicon finish paint is between 5.1 and 5.3MPa. The properties are far better than the tie-coats prepared in comparative examples 1-8 and the silicone tie-coats commercially available.
In comparative example 1, the amine-siloxane prepolymer resin prepared by the reaction is replaced by an unmodified phenolic amine resin in an equivalent manner, and the effect of forming a matched coating by the finally prepared elastic organosilicon finish paint connecting coating, the epoxy primer and the elastic organosilicon intermediate paint is far less than that of example 1, and the amine-siloxane prepolymer resin is a prepolymer reaction product of phenolic amine resin, mono-epoxy functional trialkoxysilane, epoxy resin and methyltrimethoxysilane in a molar ratio of 1:1.00-1.06:0.10-0.15:0.80-0.85. The trialkoxysilane structure is introduced into the phenolic amine structure through reaction, and the reactivity of the silicon-based alkoxy structure is further improved through secondary addition of methyltrimethoxysilane, and the crosslinking node of the silicon-based alkoxy structure and the organosilicon finish paint is increased, so that the chemical bonding speed and density of the silicon-based alkoxy structure and the organosilicon finish paint are ensured.
The phenolic amine resins in the second component of examples 1-4 have amine numbers ranging from 230 to 300 and active hydrogen equivalent weights ranging from 120 to 135, and the molecular weight phenolic amine has relatively gentle reactivity and low viscosity suitable for modified addition.
The monoepoxy functional trialkoxysilane in the second component of examples 1-4 has a weight average molecular weight ranging from 220 to 280 with one epoxy functional group in the molecular structure. The siloxane has smaller molecular weight and only has one epoxy functional group, can be grafted in a phenolic amine structure, can not form chain polymerization, causes structural irregularity, has three alkoxy groups in the molecular structure, can carry out secondary addition reaction with silicon hydroxyl or silicon-based alkoxy groups, and improves the activity, thereby improving the chemical bonding capability with the high-elasticity organosilicon finishing paint.
The epoxy resins of examples 1-4, which have an epoxy equivalent weight of 200-600 and a weight average molecular weight of 390-600 and have 1-2 epoxy functional groups, mainly serve to adjust the crosslink density and reaction rate of the first and second components. By blocking the primary amine and prepolymerizing the phenolic amine resin, the reaction speed of the second component and the first component can be slowed down, and the final reaction rate between epoxy-amine functional groups can be improved, so that the resistance and physical properties of the paint film can be improved.
The thermoplastic resin of the first component of examples 1-4 has a molecular weight of 100-10000 and includes thermoplastic acrylic resins, petroleum resins and thermoplastic chloroether resins. The thermoplastic resin with the molecular weight has the functions of forming physical anchoring between the coating layers through swelling, and increasing the contact area between the two coating layers through a swelling mode so as to improve the density of chemical bonding and improve interlayer adhesive force.
The polydimethylsiloxane of the application is a hydroxyl-terminated polydimethylsiloxane with a weight-average molecular weight of 1000-50000. The silicon hydroxyl group carried by the compound can be utilized to react and add with the silicon-based alkoxy group of the second component. Because the molecular chain is longer, and the elastic organic silicon finishing paint has good compatibility with an organic silicon structure, the interface compatibility between the elastic organic silicon finishing paint and the connecting paint can be greatly improved, and the initial interface wetting and adhesion capability is improved.
The second component of the application is to modify phenolic amine by adopting epoxy siloxane, epoxy resin and trimethoxysilane to form amine-siloxane prepolymer with higher silicon-based alkoxy density, and simultaneously, the structure still has high active hydrogen content by controlling the reaction equivalent. In the reaction process, the monofunctionally epoxysiloxane is adopted, so that the reaction product is not thickened due to chain polymerization, one end of the silicon-based alkoxy is ensured to be positioned at the outer edge of the prepolymer, and the silicon-based alkoxy in the structure can be positioned at the edge of the molecular structure through secondary addition with trimethoxysilane, so that the reaction activity is not reduced due to the influence of steric hindrance.
When the first component, the second component and the third component are mixed, the silicon hydroxyl on the hydroxyl-terminated polydimethylsiloxane in the third component can carry out addition reaction with the silicon-based alkoxy of the second component, so that the long-chain polydimethylsiloxane and the main structure of the coating film form chemical bonding. The long-chain polydimethylsiloxane has good compatibility with the organic silicon resin, can promote the interfacial compatibility of the elastic organic silicon finish paint and the connecting paint in the initial coating stage, and achieves good wetting and mutual adsorption effects, so that the residual silicon-based alkoxy can fully contact with silicon hydroxyl contained in the organic silicon finish paint in the subsequent coating drying stage for reaction addition, and firm chemical bonding is formed.
The reaction of the second component and the first component is mainly the reaction between active hydrogen and epoxy groups, so that the coating forms a three-dimensional network structure, has good resistance and forms good bonding performance with the epoxy primer. In addition, the thermoplastic resin has the function of enabling the connecting paint to form a micro-rough interface between the primer and the top paint through limited swelling of the coating film, and increasing the contact area between the coating layers, thereby further increasing the interlayer adhesion capability.
While the application has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the application. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the scope thereof. Therefore, it is intended that the application not be limited to the particular embodiment disclosed for carrying out this application, but that the application will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The elastic organosilicon finish paint connecting coating is characterized by comprising the following raw materials:
the first component comprises the following components in parts by weight: 5-15 parts of thermoplastic resin, 5-15 parts of epoxy resin, 0.3-2 parts of auxiliary agent, 45-55 parts of pigment and filler and 20-30 parts of solvent;
the second component comprises the following components in parts by weight: 65-75 parts of amine-siloxane prepolymer resin and 25-35 parts of solvent;
the third component comprises the following components in parts by weight: 50-60 parts of polydimethylsiloxane, 1-5 parts of pigment and filler and 35-45 parts of solvent;
wherein the amine-siloxane prepolymer resin is a prepolymer reaction product comprising a phenolic amine resin, a monoepoxy functional trialkoxysilane, an epoxy resin, and methyltrimethoxysilane;
the preparation method of the amine-siloxane prepolymer resin comprises the following steps: reacting a mixed system containing phenolic amine resin, single epoxy functional trialkoxysilane, epoxy resin, methyltrimethoxysilane and a solvent, cooling, adding methyltrimethoxysilane, and uniformly mixing and reacting to prepare amine-siloxane prepolymer resin;
wherein the mass ratio of the phenolic amine resin to the monoepoxy functional trialkoxysilane to the epoxy resin to the methyltrimethoxysilane is 100:30.4-32.2:5.0-7.6:14.0-14.9.
2. The elastomeric silicone topcoat tie-coat of claim 1, wherein: the elastic organosilicon finish paint connecting coating comprises the first component, the second component and the third component which are mixed according to the mass ratio of 5.2-6.2:1:0.6-0.7.
3. The elastomeric silicone topcoat tie-coat of claim 2, wherein: the weight average molecular weight of the amine-siloxane prepolymer resin is 1200-3000, and the active hydrogen equivalent is 240-290;
and/or the amine value of the phenolic amine resin is 230-300, and the active hydrogen equivalent is 120-135.
4. The elastomeric silicone topcoat tie-coat of claim 1, wherein: the thermoplastic resin in the first component comprises any one of thermoplastic acrylic resin, petroleum resin and thermoplastic chloroether resin;
and/or the molecular weight of the thermoplastic resin is 100-10000.
5. The elastomeric silicone topcoat tie-coat of claim 1, wherein: the weight average molecular weight of the epoxy resin is 390-420, the epoxy equivalent is 195-210, and the epoxy resin has 1-2 epoxy functional groups;
and/or, the polydimethylsiloxane is a hydroxyl-terminated polydimethylsiloxane having a weight average molecular weight of 1000-50000.
6. The elastomeric silicone topcoat tie-coat of claim 1, wherein: the interlayer shear strength of the elastic organosilicon finish paint connecting coating and the epoxy primer is 11.6-12.4MPa;
and/or the interlayer adhesion strength between the elastic organic silicon finishing paint connecting coating and the elastic organic silicon finishing paint is 5.1-5.3MPa.
7. The elastomeric silicone topcoat tie-coat of claim 1, wherein: the pigment and filler comprises any one or more than two of titanium dioxide, iron oxide black, iron oxide red, talcum powder and silicon micropowder;
and/or the auxiliary agent comprises any one or more than two of an antifoaming agent, a leveling agent and a rheological auxiliary agent;
and/or the solvent comprises any one or more than two of dimethylbenzene, no. 100 solvent oil and No. 150 solvent oil.
8. A method of preparing the elastomeric silicone topcoat tie-coat of any one of claims 1-7, comprising:
uniformly mixing thermoplastic resin, epoxy resin, pigment and filler, auxiliary agent and solvent to form a mixture, and regulating the viscosity of the mixture to 115+/-3 KU by using the solvent to obtain a first component;
mixing a solvent and phenolic amine resin, adding an epoxy silane coupling agent and epoxy resin, cooling after reaction, adding methyltrimethoxysilane, stirring uniformly, standing to obtain amine-siloxane prepolymer resin, and regulating the viscosity of the amine-siloxane prepolymer resin to 100+/-3 KU by using the solvent to obtain a second component;
uniformly mixing polydimethylsiloxane, pigment and filler and a solvent to form a mixture, and regulating the viscosity of the mixture to 90+/-3 KU by using the solvent to obtain a third component;
and uniformly mixing the first component, the second component and the third component to obtain the elastic organosilicon finish paint connecting coating.
9. The method for preparing the elastic organosilicon finish paint connection coating according to claim 8, wherein the method comprises the following steps: the preparation of the second component specifically comprises the steps of mixing a solvent and phenolic amine resin, controlling the temperature to be 40-50 ℃, adding an epoxy silane coupling agent and the epoxy resin under stirring, cooling to room temperature after reacting for 2 hours, adding methyltrimethoxysilane, standing for 24 hours after uniformly stirring to obtain amine-siloxane prepolymer resin, and regulating the viscosity of the amine-siloxane prepolymer resin to 100+/-3 KU by using the solvent to obtain the second component;
and/or the first component, the second component and the third component are uniformly mixed according to the mass ratio of 5.2-6.2:1:0.6-0.7, so as to prepare the elastic organosilicon finish paint connecting coating.
10. A composite coating structure comprising an epoxy primer layer and an elastomeric silicone topcoat layer; the method is characterized in that: the composite coating structure further comprises the elastic organic silicon finish paint connecting coating of claim 1, wherein the epoxy primer layer is connected with the elastic organic silicon finish paint layer through the elastic organic silicon finish paint connecting coating.
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| CN104231920A (en) * | 2014-10-15 | 2014-12-24 | 大连海事大学 | Organic silicon middle connecting coating and preparation method thereof |
| CN107177309A (en) * | 2017-07-06 | 2017-09-19 | 中国船舶重工集团公司第七二五研究所 | A kind of epoxy coating and organic silicon coating are painted with middle connection is applied mechanically |
| US20180355189A1 (en) * | 2015-12-30 | 2018-12-13 | Dow Global Technologies Llc | Anti-biofouling coating based on epoxy resin and amine-functional polysiloxane |
| CN111500143A (en) * | 2020-06-03 | 2020-08-07 | 海洋化工研究院有限公司 | Organic silicon modified epoxy coating with corrosion prevention and transitional connection functions and preparation method thereof |
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| CN104231920A (en) * | 2014-10-15 | 2014-12-24 | 大连海事大学 | Organic silicon middle connecting coating and preparation method thereof |
| US20180355189A1 (en) * | 2015-12-30 | 2018-12-13 | Dow Global Technologies Llc | Anti-biofouling coating based on epoxy resin and amine-functional polysiloxane |
| CN107177309A (en) * | 2017-07-06 | 2017-09-19 | 中国船舶重工集团公司第七二五研究所 | A kind of epoxy coating and organic silicon coating are painted with middle connection is applied mechanically |
| CN111500143A (en) * | 2020-06-03 | 2020-08-07 | 海洋化工研究院有限公司 | Organic silicon modified epoxy coating with corrosion prevention and transitional connection functions and preparation method thereof |
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