CN117050628A - Preparation method of transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material - Google Patents
Preparation method of transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material Download PDFInfo
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- CN117050628A CN117050628A CN202310818672.2A CN202310818672A CN117050628A CN 117050628 A CN117050628 A CN 117050628A CN 202310818672 A CN202310818672 A CN 202310818672A CN 117050628 A CN117050628 A CN 117050628A
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- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 polysiloxane Polymers 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000002519 antifouling agent Substances 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 239000004721 Polyphenylene oxide Chemical class 0.000 claims abstract description 12
- 229920000570 polyether Chemical class 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- LIQZZAPDGRFJIP-UHFFFAOYSA-L [dodecanoyloxy-bis(2-methylpropyl)stannyl] dodecanoate Chemical group CC(C)C[Sn+2]CC(C)C.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O LIQZZAPDGRFJIP-UHFFFAOYSA-L 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000001637 borneol derivatives Chemical class 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012456 homogeneous solution Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229940116229 borneol Drugs 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002552 poly(isobornyl acrylate) polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002966 varnish 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an antifouling coating technology, and aims to provide a preparation method of a transparent hydrophobic organic silicon polyurethane antifouling anticorrosive coating material. Comprising the following steps: weighing polysiloxane compounds, polyether compounds and isocyanate compounds, adding the polysiloxane compounds, the polyether compounds and the isocyanate compounds into a reactor filled with a solvent, and cooling and refluxing the mixture to react to generate an organosilicon polyurethane prepolymer solution; and continuously adding an antifouling agent, a catalyst and a chain extender, and cooling and refluxing to react to obtain an organosilicon polyurethane solution, namely the coating material. The coating product has the comprehensive properties of high stain resistance, high light transmittance, environmental protection, stain resistance and hydrophobicity; the grafted anti-fouling agent does not need to be released to the environment, so that not only is the limited pollution of the anti-fouling agent to the environment ensured, but also the long-term high-efficiency long-acting anti-fouling capability of the anti-fouling agent in a coating is ensured; the homogeneous solution is obtained by grafting the antifouling agent, so that the antifouling coating material with high light transmittance can be prepared.
Description
Technical Field
The invention belongs to an antifouling coating technology, and particularly relates to a preparation method of a transparent hydrophobic organic silicon polyurethane antifouling anticorrosive coating material.
Background
The glass surface anti-fouling technology is widely applied to various fields such as buildings, automobiles, home furnishings and the like, not only is the cleaning time reduced, but also the risk of high-altitude cleaning of cleaning staff can be reduced, and a large amount of manpower and material resource consumption is reduced. However, during actual use, the anti-fouling surface is easily contaminated with various contaminants and subjected to pressure from various locations. Such as self-cleaning windows, dirt-proof and oil-proof dining tables, windshields of automobiles, rearview mirrors, glass windows or glass curtain walls of skyscrapers, and the like, not only are highly transparent surfaces, but also have strong repellency to water and oil, and pollution prevention and corrosion resistance are also required.
The existing methods for constructing the glass anti-fouling surface mainly comprise three methods: (1) Constructing a micro-nano structure on the original anti-fouling coating through a series of processing, and carrying out hydrophobic surface modification on the surface of the micro-nano structure; (2) Constructing a porous layer structure, and infusing a low-surface-energy lubricating liquid into the porous layer structure to form a liquid-infused porous lubricating surface; (3) The low surface energy substance is used for covalent grafting on the surface of the coating to form a molecular brush structure, so that the sliding angle of the liquid on the surface of the molecular brush structure is reduced, and the liquid can freely roll off on the surface.
Although the above methods can enhance the anti-fouling effect of the glass surface, the operation is too complex and the practicability is not high. The reasons are as follows: (1) The super-hydrophobic surface achieved by constructing the micro-nano surface structure has a low application range in life, and the surface is easily damaged; (2) The durability in the porous lubrication surface of the infused low surface energy liquid is not strong, and leakage of the lubrication liquid can lead to a deepening of the contamination level; (3) Molecular brush structures are built on the surface, the hydrophobic angle is not high, and the structure is extremely easy to wear, and the transparency of the coating is sacrificed to a certain extent.
In view of the above-mentioned drawbacks of the prior art, the application and popularization of the antifouling coating are greatly limited, and thus, it is necessary to propose a new preparation technology of antifouling and anticorrosive coating materials.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a transparent hydrophobic type organic silicon polyurethane antifouling and anticorrosive coating material.
In order to solve the technical problems, the invention adopts the following solutions:
the preparation method of the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material comprises the following steps:
(1) Weighing polysiloxane compounds, polyether compounds and isocyanate compounds according to a mass ratio of 50:50:1, and adding the polysiloxane compounds, the polyether compounds and the isocyanate compounds into a reactor filled with a solvent; cooling and refluxing for 2-3 hours under the condition of stirring and 60-80 ℃ to react to generate an organosilicon polyurethane prepolymer solution;
(2) Continuously adding an antifouling agent, a catalyst and a chain extender into the reaction vessel in the step (1), wherein the mass of the antifouling agent is 0.004 times that of the polysiloxane compound, and the mass ratio of the antifouling agent to the catalyst to the chain extender is 2:1:3; continuously cooling and refluxing for 3 hours under the condition of stirring and 60-80 ℃ to obtain the organic silicon polyurethane solution, namely the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material.
As a preferable scheme of the invention, the polysiloxane compound is symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane compound, and the molecular weight of the polysiloxane compound is 3000-5000.
As a preferred embodiment of the present invention, the polyether compound is polytetrahydrofuran diol or polycarbonate diol, and has a molecular weight of 1000 to 2000.
As a preferable embodiment of the present invention, the isocyanate compound is one of hexamethylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
As a preferred embodiment of the present invention, the solvent is tetrahydrofuran or xylene.
As a preferable scheme of the invention, the mass ratio of the solvent to the polysiloxane compound is 6:1.
As a preferred embodiment of the present invention, the antifouling agent is a fluorine-containing compound or a modified borneol compound.
As a preferred embodiment of the present invention, the catalyst is diisobutyltin dilaurate.
As a preferred embodiment of the present invention, the chain extender is 1, 4-butanediol.
The invention further provides a use method of the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material, which comprises the following steps:
(1) Uniformly diluting the organic silicon polyurethane solution by using tetrahydrofuran solution to make the mass fraction of the organic silicon polyurethane be 10%;
(2) Uniformly coating a proper amount of diluent on the surface of clean glass, and drying for 3 hours at 28-32 ℃; and then heating to 60 ℃ and curing for 3-5 hours, thus forming the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating on the surface of the glass.
Compared with the prior art, the invention has the beneficial effects that:
1. silicone polyurethanes, generally referred to as a class of modified resins made from silicone oligomers together with polyurethane resins, are commonly used to prepare two-component polyurethane paints. When the prior art is used for the anti-fouling coating, the problems of opacity, easy blushing and poor anti-fouling effect exist. After the reasonably modified organic silicon polyurethane is applied to the surface of the glass, the invention can realize high anti-fouling, high light transmission, environmental protection and anti-fouling.
2. The coating product obtained by the invention has the comprehensive properties of high anti-fouling property, high light transmittance, environmental protection, antifouling property and hydrophobicity.
3. The invention enhances the antifouling property of the coating by grafting the antifouling agent on the organosilicon polyurethane. Conventional coatings are often difficult to provide long-lasting anti-fouling because conventional coatings achieve an anti-fouling effect by release of an anti-fouling agent; compared with the method, the grafted anti-fouling agent does not need to be released to the environment, so that not only is the limited pollution of the anti-fouling agent to the environment ensured, but also the long-term high-efficiency long-acting anti-fouling capability of the anti-fouling agent in a coating is ensured.
4. In addition, since conventional coating materials are easily physically blended with an antifouling agent to lose transparency, heterogeneous coatings occur, and it is difficult to have high light transmittance. The invention obtains homogeneous solution by grafting the antifouling agent, thereby being capable of preparing the antifouling coating material with high light transmittance.
Detailed Description
The following describes in detail the specific implementation of the present invention by way of specific examples.
The reagents used in each example can be purchased directly from commercial sources or made self-contained according to the teachings of the prior publications. In each of the examples and comparative examples, the parts of each reagent were parts by mass.
The preparation method of the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material comprises the following steps:
(1) Weighing polysiloxane compounds, polyether compounds and isocyanate compounds according to a mass ratio of 50:50:1, and adding the polysiloxane compounds, the polyether compounds and the isocyanate compounds into a reactor filled with a solvent; cooling and refluxing for 2-3 hours under the condition of stirring and 60-80 ℃ to react to generate an organosilicon polyurethane prepolymer solution;
wherein, the polysiloxane compound is symmetrical alcohol hydroxyl double-end-capped polydimethylsiloxane compound, preferably double-end hydroxypropyl silicone oil, and the molecular weight of the polysiloxane compound is 3000-5000; the polyether compound can be polytetrahydrofuran glycol or polycarbonate glycol, and the molecular weight of the polyether compound is 1000-2000; the isocyanate compound is selected from one of hexamethylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate; the solvent is tetrahydrofuran or xylene, and the mass ratio of solvent to polysiloxane is 6:1.
(2) Continuously adding an antifouling agent, a catalyst and a chain extender into the reaction vessel in the step (1), wherein the mass of the antifouling agent is 0.004 times that of the polysiloxane compound, and the mass ratio of the antifouling agent to the catalyst to the chain extender is 2:1:3; continuously cooling and refluxing for 3 hours under the conditions of stirring and 60-80 ℃ to obtain an organosilicon polyurethane solution, namely the transparent hydrophobic organosilicon polyurethane antifouling and anticorrosive coating material;
wherein the antifouling agent is fluorine-containing compound or modified borneol compound. As a preferred alternative to this, the fluorine-containing compound is specifically 2,3,5, 6-tetrafluoro-terephthalyl alcohol, 2, 3-tetrafluoro-1, 4-butanediol 1, 6-dihydroxy-2, 3,4, 5-octafluorohexane or optionally one of 2,3, 4, 5-octafluoro-1, 6-hexane diol. The modified borneol compound is specifically a product obtained by modifying borneol acrylate or borneol methacrylate, and the modification method can refer to the record in the publication of 'preparation of water-resistant and durable antibacterial adhesion polyurethane coating containing weak amphiphilic poly (isobornyl acrylate) side chains'. The catalyst can be diisobutyltin dilaurate; the chain extender may be 1, 4-butanediol.
The application method of the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material comprises the following steps:
(1) Uniformly diluting the organic silicon polyurethane solution by using tetrahydrofuran solution to make the mass fraction of the organic silicon polyurethane be 10%; (2) Uniformly coating a proper amount of diluent on the surface of clean glass, and drying for 3 hours at 28-32 ℃; and then heating to 60 ℃ and curing for 3-5 hours, thus forming the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating on the surface of the glass. The thickness of the finally formed coating can be between 150 and 200um by controlling the coating amount of the diluent.
Based on the content of the preparation method, the invention provides 4 specific examples; the preparation process of each example is the same, and the specific formulation and parameters are shown in table 1:
TABLE 1
Comparative example 1
Preparation of prepolymer polyurethane: taking 500 parts of double-end hydroxypropyl silicone oil with a molecular weight of 3000, 500 parts of polytetrahydrofuran glycol with a molecular weight of 1000 and 10 parts of hexamethylene diisocyanate, and dissolving the components in 1000 parts of tetrahydrofuran solvent; then, the mixture is condensed, refluxed and stirred for 2 hours at a high temperature of 60 ℃ with a stirring speed of 250r/min.
Curing of the silicone polyurethane coating: and uniformly diluting the polyurethane prepolymer solution by using the tetrahydrofuran solution to ensure that the mass fraction of the polyurethane prepolymer solution is 10 percent, uniformly coating 0.4ml of the polyurethane prepolymer solution on a glass slide, curing for 3 hours at 30 ℃, and curing for 5 hours at 60 ℃ to obtain the transparent hydrophobic polyurethane antifouling coating.
Antifouling coating performance test method and results:
1. contact angle of water
The water contact angle of the coating surface was measured using an XG-CAMC3 type full-automatic contact angle measuring instrument manufactured by Shanghai Xuan standard instruments Co. The photo measurement was performed using a 3 μl deionized water drop test, with 5 seconds to 10 seconds of dropping the coating surface, and 6 points were selected for each coating surface for measurement. The contact angle of deionized water on the surface of the coating was measured by an angle measurement method, and the average value was obtained. Meanwhile, a rolling contact angle measuring module of the instrument is used, 6 points are selected for measurement, and the rolling water contact angle of the surface of the coating is measured by adopting an inclined plate method and is averaged.
2. Antibacterial property
The experimental steps are as follows: the coverslip (1 8 ×1 mm 2) coated with the coated sample was immersed in a sterile phosphate buffer solution for 24 hours to sufficiently leach out small molecules that may be present, and then sterilized at high temperature and high pressure. The sample was placed in a six-well plate, and l mL of E.coli suspension having a concentration of about 108CFU/mL was added, and 4mL of phosphate buffer solution was added, and incubated in an incubator at 37℃for 5 hours. Taking out the cover glass, removing the liquid on the surface of the sample by using a sterile cotton swab, placing the cover glass in 10mL of sterile phosphoric acid buffer solution for 5min, vibrating and eluting surface bacteria. The resulting eluate was diluted stepwise according to 10 3 、10 4 100ul of each of the multiple diluted bacterial solutions was poured onto LB solid medium, and cultured in an incubator at 37℃for 5 hours, and colony counts were performed on plates with colony counts of 10.300. And uncoated coverslip (asBlank control), the average percent reduction in bacterial colonies was obtained from three plates as parallel controls. Antibacterial ratio (E) b ) Calculated by the following formula:
wherein N is b And N c The numbers of colonies corresponding to the comparative example and the numbers of colonies corresponding to the experimental group of the experimental example sample are respectively referred to.
With reference to the above, a performance test against staphylococcus aureus was performed.
3. Acid resistance
Comparative example 1, examples 1-4 were immersed in 30% sulfuric acid solution at 80 c for 15 days, the damage of the immersed coating was observed, the damage grade was classified into one to four grades, wherein four grades represent the worst acid resistance of the coating, and the test results are shown in table 3.
4. Alkali resistance
The coatings of comparative example 1 and examples 1 to 4 were immersed in a sodium hydroxide solution having a mass concentration of 5% at a temperature of 80℃for 15 days, the damage of the coatings after immersion was observed, and the damage grades were classified into one to four grades, wherein four grades represent the worst alkali resistance of the coatings, and the test results are shown in Table 3.
5. Coating adhesion Property
The coatings of comparative example 1 and examples 1 to 4 were tested according to the standard GB/T9286-1998, cross-cut test for paint and varnish films, and the failure rating was divided into 0-5, wherein 5 indicates the worst adhesion of the coating, and the test results are shown in Table 3.
6. Salt water resistance
The coatings of comparative example 1 and examples 1 to 4 were immersed in a 3% sodium chloride solution for 30 days at a temperature of 80 c or less, the damage of the immersed coating was observed, and the damage was classified into one to four stages, wherein four stages means that the coating had the worst salt water resistance, and the test results are shown in table 2.
7. Transparency test
The ultraviolet spectrophotometer instrument can measure the transmittance of a measurement substance in the visible light range. The coating comparative examples, examples 1-4, were kept at the same thickness and the sample coatings of the same thickness were measured using an ultraviolet spectrophotometer. The higher the transmittance, the better the light transmission properties of the coating. Wherein the transmittance was 100%, indicating that the coating was completely light transmitting.
TABLE 2
As can be seen from the results in Table 2, the anticorrosive paint provided by the invention has excellent acid resistance, alkali resistance and salt water resistance, and the prepared coating has excellent coating adhesive force, so that the coating is not easy to fall off.
The invention leads the coating material to have high anti-fouling performance through the introduction of the environment-friendly anti-fouling agent. In addition, the coating material has excellent antibacterial property, does not release any bactericide, is more environment-friendly, and has good light transmission performance after being coated on the surface of glass.
Claims (10)
1. The preparation method of the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material is characterized by comprising the following steps of:
(1) Weighing polysiloxane compounds, polyether compounds and isocyanate compounds according to a mass ratio of 50:50:1, and adding the polysiloxane compounds, the polyether compounds and the isocyanate compounds into a reactor filled with a solvent; cooling and refluxing for 2-3 hours under the condition of stirring and 60-80 ℃ to react to generate an organosilicon polyurethane prepolymer solution;
(2) Continuously adding an antifouling agent, a catalyst and a chain extender into the reaction vessel in the step (1), wherein the mass of the antifouling agent is 0.004 times that of the polysiloxane compound, and the mass ratio of the antifouling agent to the catalyst to the chain extender is 2:1:3; continuously cooling and refluxing for 3 hours under the condition of stirring and 60-80 ℃ to obtain the organic silicon polyurethane solution, namely the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating material.
2. The method of claim 1, wherein the polysiloxane is a symmetrical alcohol hydroxyl double end blocked polydimethylsiloxane having a molecular weight of 3000-5000.
3. The method according to claim 1, wherein the polyether compound is polytetrahydrofuran diol or polycarbonate diol, and has a molecular weight of 1000 to 2000.
4. The method according to claim 1, wherein the isocyanate-based compound is one of hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
5. The method of claim 1, wherein the solvent is tetrahydrofuran or xylene.
6. The method of claim 1, wherein the mass ratio of solvent to polysiloxane is 6:1.
7. The method of claim 1, wherein the anti-fouling agent is a fluorochemical or modified borneol based compound.
8. The method of claim 1, wherein the catalyst is diisobutyltin dilaurate.
9. The method of claim 1, wherein the chain extender is 1, 4-butanediol.
10. The method for using the transparent hydrophobic type organic silicon polyurethane antifouling and anticorrosive coating material according to claim 1, which is characterized by comprising the following steps:
(1) Uniformly diluting the organic silicon polyurethane solution by using tetrahydrofuran solution to make the mass fraction of the organic silicon polyurethane be 10%;
(2) Uniformly coating a proper amount of diluent on the surface of clean glass, and drying for 3 hours at 28-32 ℃; and then heating to 60 ℃ and curing for 3-5 hours, thus forming the transparent hydrophobic organic silicon polyurethane antifouling and anticorrosive coating on the surface of the glass.
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