CN110982075A - Preparation method of hard hydrophobic coating without solvent addition - Google Patents
Preparation method of hard hydrophobic coating without solvent addition Download PDFInfo
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- CN110982075A CN110982075A CN201911171060.9A CN201911171060A CN110982075A CN 110982075 A CN110982075 A CN 110982075A CN 201911171060 A CN201911171060 A CN 201911171060A CN 110982075 A CN110982075 A CN 110982075A
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- siloxane
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- aliphatic
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- 238000000576 coating method Methods 0.000 title claims abstract description 87
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002904 solvent Substances 0.000 title claims abstract description 9
- -1 siloxane chain Chemical group 0.000 claims abstract description 102
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004140 cleaning Methods 0.000 claims abstract description 26
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000010276 construction Methods 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 229910000077 silane Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 15
- 238000004528 spin coating Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 230000007774 longterm Effects 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910008051 Si-OH Inorganic materials 0.000 claims description 2
- 229910006358 Si—OH Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001241 acetals Chemical class 0.000 claims description 2
- 150000008431 aliphatic amides Chemical class 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 150000008430 aromatic amides Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- CEQGXFSRENZDFH-UHFFFAOYSA-N triethoxy(sulfanyl)silane Chemical compound CCO[Si](S)(OCC)OCC CEQGXFSRENZDFH-UHFFFAOYSA-N 0.000 claims description 2
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- ZFNFNJYRZOQPJF-UHFFFAOYSA-N trimethoxy(sulfanyl)silane Chemical compound CO[Si](S)(OC)OC ZFNFNJYRZOQPJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 description 5
- 235000019000 fluorine Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- 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
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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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
- 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
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a hard hydrophobic coating without solvent addition. The preparation method has the advantages that dibutyltin dilaurate is selected as a cohydrolysis raw material, the hydrolysis condensation process of a siloxane system is promoted in a catalytic mode, the binding force between the coating and the substrate is enhanced by the selection of epoxy silane, the whole siloxane chain system forms a net structure due to the addition of the curing agent primary amino siloxane, the hardness of the coating is greatly improved, meanwhile, the surface energy of the coating is reduced due to the addition of the fluorine-based siloxane, and the hydrophobic capacity of the coating is improved. The room temperature cured hard self-cleaning coating is finally prepared, and has the advantages of simple process, low energy consumption, low pollution, high efficiency and the like, and has excellent properties of hardness, self-cleaning, good adhesive force and the like. The coating has the advantages that: the material can be cured at room temperature for 24 hours to reach the highest hardness, has long storage period and simple construction, and can be applied to the protection and the hydrophobic property of the surface of the material.
Description
Technical Field
The invention relates to a preparation method of a hard transparent hydrophobic film suitable for the surface of a high-speed rail and an automobile windshield. The functional coating which is rapidly cured at room temperature is prepared through siloxane reaction among different components, and the prepared transparent hard coating has good protection and functionality.
Background
Coatings have a wide variety of effects in our daily lives. The use of coatings from domestic household to military aviation meets a wide range of requirements and has a profound impact on the protection of material surfaces. Recent predictions predict that world coating demand will increase by 3.7% annually in recent years to 5470 million tons for a total value of 1930 million dollars. The functional coating has excellent characteristics of water resistance, fog resistance, snow resistance, pollution resistance, oxidation resistance, corrosion resistance and the like, and is widely applied to the aspects of building industry, automobile industry, metal industry, pipeline transportation and the like. After decades of research, the organosilicone attracts the wide attention of scientists due to its unique properties, and is considered as one of the first choice materials for preparing hard transparent high-performance coatings. Compared with the traditional organic coating, the organic siloxane has a unique Si-O-Si skeleton structure and organic groups (-OCH) combined with silicon atoms3) Provides possibility for modifying siloxane network, and the characteristics endow the coating with excellent flexibility, weather resistance, water resistance, optical transmittance and the like. However, the polysiloxane obtained by co-hydrolysis/condensation has poor mechanical properties and adhesion, lacks self-cleaning, anti-icing, anti-freezing and other functionalities, and has long curing time, which greatly limits the wide application of the coating. Meanwhile, with the increase of awareness of environmental protection and awareness of human health and safety, it is required that the content of harmful solvent volatile in the prepared coating should be controlled to a certain level. The current requirement for VOC levels is<250g/L, despite the reports of low VOC coatings, these volatile materials still cause some harm to the environment and human body.
Patent application No. 03814008.X discloses a composition based on epoxy modified polysiloxane resins. This patent prepares epoxy modified polysiloxane coatings by selecting polysiloxanes having molecular weights in the range of 400-1000, epoxy resin having an epoxy equivalent weight of 100-5000 and mixing with an amino hardener, and forming a polymer network by amino groups and silanol groups of hydrolyzed polysiloxanes. However, the prepared coating has longer curing time (two weeks), and the addition of the solvent is not beneficial to the wide application of the coating.
In the long-term operation process of the high-speed railway, the high-speed railway is likely to be scratched by external materials to generate dust. To solve these problems, we most often use a method of cleaning and repairing the damaged film, which causes waste of water and human resources. Therefore, the development of a coating which is simple, environment-friendly and low in cost and has the advantages of flexibility, light transmission, scratch resistance, self-cleaning property and the like has very important practical significance.
Disclosure of Invention
The invention aims to provide a preparation method of a room temperature curing self-cleaning coating, which can be cured for 24 hours at room temperature to reach the highest hardness, has long storage period and simple construction, and is applied to the protection and hydrophobic property of the surface of a material.
According to the invention, epoxy siloxane, other siloxane monomers and dibutyl tin dilaurate are subjected to cohydrolysis condensation to obtain long-chain molecules, and then primary amino siloxane is added for curing to obtain a reticular molecular structure. The fluorinated siloxane gradually migrates to the surface in the condensation process of the system, which is beneficial to reducing the surface energy of the coating and improving the hydrophobicity of the coating.
The technical scheme of the invention is as follows: the room-temperature cured self-cleaning coating comprises the following components in mol percent:
epoxy siloxane: 3.8 to 24 percent
Other siloxanes: 72 to 96 percent
Primary amino siloxane: 1.6 to 12 percent
Fluorinated siloxanes: 0.03 to 2 percent
Dibutyl tin dilaurate: 0.1 to 0.4 percent
Wherein, X and Y can represent any one of C, O, NH, S and Se, and the numerical range of m, n and z is 0 to 12; r1、R2A monovalent organic group having 1 to 3 carbon atoms, for example, methyl, ethyl, propyl, etc.; r3A monovalent organic group selected from the group consisting of 1 to 20 any atoms, including but not limited to aliphatic hydrocarbons, halogenated hydrocarbons, aliphatic alcohols, aliphatic ethers, acetals, epoxides, aliphatic thiols, aliphatic amines, aliphatic nitro groups, aliphatic ketones, aliphatic aldehydes, aliphatic carboxylic acids, aliphatic carboxylates, aliphatic amino acids, aliphatic esters, aliphatic anhydrides, aliphatic acid halides, aliphatic amides, aliphatic nitriles, aliphatic oxysulfides, aliphatic phosphines, aromatic hydrocarbons, aromatic halogenated hydrocarbons, aromatic ethers, aromatic enolphenols, aromatic thiols, aromatic amines, aromatic nitro compounds, aromatic ketones, aromatic aldehydes, aromatic carboxylic acids, aromatic greases, aromatic amino acids and their salts, aromatic anhydrides, aromatic acid halides, aromatic amides, aromatic nitriles, aromatic oxysulfides, aromatic phosphorus compounds, aromatic heterocycles, alkynes, fluorines, and the like; r4Selected from halogen, hydroxy and alkoxy having up to 3 carbon atoms, e.g. Cl, H, -OCH3Etc.; r5，R6Is selected from R3And hydrogen, and the like.
The invention further solves the technical problem that when the addition amount of the epoxy siloxane is 12 percent and the content of the primary amino siloxane is 6 percent, the prepared coating has the best adhesion and surface hardness.
The invention further solves the technical problem that when the addition amount of the fluorinated siloxane is 0.09 percent, the prepared coating has the best hydrophobic angle and better self-cleaning performance.
The invention further solves the technical problem that when the addition amount of the dibutyl tin dilaurate is 0.2%, the prepared coating has a more complete network structure, and the hardness of the coating is further improved.
The invention discloses a method for preparing a room temperature curing hard self-cleaning coating in one step, which comprises the following steps:
step (a): epoxy siloxane, other siloxane, fluorinated siloxane and dibutyl tin dilaurate are mixed at certain temperature and stirred for certain time for standby.
Step (b): adding primary amino siloxane into the solution prepared in the step (a), stirring for a period of time, and sealing for later use.
Step (c): coating the substrate with the solution prepared in the step (b) in a certain manner, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Preferably, the optimum molar ratio of epoxysiloxane to other siloxane to fluorinated siloxane to dibutyl tin dilaurate in step (a) is 4:25:0.09:0.056 at room temperature of 25 deg.C and stirring time of 10-30 min.
Preferably, the other siloxane monomers in step (a) include, but are not limited to, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, mercaptotrimethoxysilane, mercaptotriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, polydimethylsiloxane (hydroxyl terminated), and the like.
Preferably, the optimal mole ratio of the primary amino siloxane to the epoxy siloxane in step (b) is 1:2, and the stirring time is 5-10 min.
Preferably, the substrate in step (c) includes, but is not limited to, a glass substrate, a silicon substrate, a metal substrate, a fabric, paper, PVC, PC, wood, concrete, and the like. Coating methods include, but are not limited to, spray coating, spin coating, dipping, drop coating, roll coating.
Preferably, the curing temperature in step (c) is between 25 ℃ and 30 ℃ to facilitate rapid curing of the coating.
In particular, the moisture of the curing process is derived from air. Dibutyl tin dilaurate is preferentially hydrolyzed to form Si-OH to react and condense with the rest siloxane, and the whole precursor system can be cured in a short time by adding water in advance, so that the effect of long-term storage cannot be achieved.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a room-temperature cured hard self-cleaning coating. The preparation method has the advantages that dibutyltin dilaurate is selected as a cohydrolysis raw material, the hydrolysis condensation process of a siloxane system is promoted in a catalytic mode, the binding force between the coating and the substrate is enhanced by the selection of epoxy silane, the whole siloxane chain system forms a net structure due to the addition of the curing agent primary amino siloxane, the hardness of the coating is greatly improved, meanwhile, the surface energy of the coating is reduced due to the addition of the fluorine-based siloxane, and the hydrophobic capacity of the coating is improved. The prepared coating has the advantages of simple method, simple process, low energy consumption, low pollution, high efficiency and the like, and has excellent performances of hardness, self-cleaning, good adhesive force and the like, so that the coating has wide market application prospect.
Drawings
The first graph is a corresponding transmittance graph of raw materials in different molar ratios;
FIG. two is an SEM photograph of example 7;
fig. three is a schematic diagram of self-cleaning in example 7.
The specific implementation mode is as follows:
example 1:
step (a): epoxy siloxane, other siloxane, dibutyl tin dilaurate in a molar ratio of 4:25:0.06, were blended at room temperature at 25 deg.C, and stirred for 10 min.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 2:
step (a): epoxy siloxane, other siloxane, dibutyl tin dilaurate in a molar ratio of 4:25:0.09 at room temperature at 25 deg.C, and stirring for 10 min.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 3:
step (a): epoxy siloxane, other siloxanes, dibutyl tin dilaurate in a molar ratio of 4:25:0.12, were blended at room temperature 25 ℃ and stirred for 10 min.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 4:
step (a): epoxysiloxanes other siloxanes dibutyl tin dilaurate: the fluoro siloxane was blended at room temperature and 25 ℃ in a molar ratio of 4:25:0.09: 0.014, and stirred for 10 min.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 5:
step (a): epoxysiloxanes other siloxanes dibutyl tin dilaurate: the fluorine-based siloxane is blended at room temperature of 25 ℃ according to the molar ratio of 4:25:0.09: 0.028, and is stirred for 10min for later use.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 6:
step (a): epoxysiloxanes other siloxanes dibutyl tin dilaurate: the fluoro siloxane is blended at room temperature of 25 ℃ according to the molar ratio of 4:25:0.09: 0.048, and is stirred for 10min for standby.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 7:
step (a): epoxysiloxanes other siloxanes dibutyl tin dilaurate: the fluoro siloxane is blended at room temperature of 25 ℃ according to the molar ratio of 4:25:0.09:0.056, and is stirred for 10min for standby.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Example 8:
step (a): epoxysiloxanes other siloxanes dibutyl tin dilaurate: the fluoro siloxane is blended at room temperature of 25 ℃ according to the molar ratio of 4:25:0.09: 0.07, and is stirred for 10min for standby.
Step (b): according to the primary amino siloxane: and (b) adding primary amino siloxane into the solution prepared in the step (a) at the molar ratio of 1:2, stirring for 5min, and sealing for later use.
Step (c): and (c) coating the solution prepared in the step (b) on a glass substrate in a spin coating mode, and standing at room temperature for 24 hours to obtain the hard self-cleaning coating.
Formulation and test data for each example
As can be seen from cases 1 to 3, an appropriate increase in the amount of dibutyltin dilaurate contributes to an increase in hardness. According to cases 3 to 8, the hydrophobic angle of the coating surface gradually increased and eventually stabilized with increasing addition of the fluorosilicone, reaching a maximum of 107 °. As can be seen from cases 1 to 8, the addition of the epoxysiloxane greatly enhances the bonding force between the substrate and the coating, and the Adhesion (ASTM) reaches 5B. The precursor solution prepared in the step (b) is not obviously changed after being placed for 3 months and is in a low-viscosity liquid state. Since the primary amino siloxane can form bisazo chromophore during storage, the solution can be changed from colorless to yellow, but the color of the film is not influenced after spin coating.
In conclusion, the transparent coating with excellent hardness and self-cleaning capability is prepared by a simple process method, and the transparent coating is beneficial to practical application.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (12)
1. The invention aims to provide a preparation method of a hard hydrophobic coating without solvent addition, which is characterized in that dibutyl tin dilaurate is selected as a cohydrolysis raw material to catalyze and promote the hydrolysis condensation process of a siloxane system, the selection of epoxy silane enhances the binding force between the coating and a substrate, the addition of curing agent primary amino siloxane enables the whole siloxane chain system to form a net structure, the hardness of the coating is greatly improved, meanwhile, the addition of fluoro siloxane reduces the surface energy of the coating, improves the hydrophobic capacity of the coating, and obtains a room-temperature curing self-cleaning coating, wherein the coating has the advantages that: the material can be cured at room temperature for 24 hours to reach the highest hardness, has long storage period and simple construction, and can be applied to the protection and the hydrophobic property of the surface of the material.
2. The technical scheme of the invention is as follows: the selected raw materials comprise the following components in percentage by mole:
epoxy siloxane: 3.8 to 24 percent
Other siloxanes: 72 to 96 percent
Primary amino siloxane: 1.6 to 12 percent
Fluorinated siloxanes: 0.03 to 2 percent
Dibutyl tin dilaurate: 0.1 to 0.4 percent
Wherein, X and Y can represent any one of C, O, NH, S and Se, and the numerical range of m, n and z is 0 to 12; r1、R2A monovalent organic group having 1 to 3 carbon atoms, for example, methyl, ethyl, propyl, etc.; r3Selected from monovalent organic group combinations of any of 1 to 20 atoms, including but not limited to fatsHydrocarbons, halogenated hydrocarbons, aliphatic alcohols, aliphatic ethers, acetals, epoxides, aliphatic thiols, aliphatic amines, aliphatic nitro groups, aliphatic ketones, aliphatic aldehydes, aliphatic carboxylic acids, aliphatic carboxylates, aliphatic amino acids, aliphatic esters, aliphatic anhydrides, aliphatic acid halides, aliphatic amides, aliphatic nitriles, aliphatic sulfur oxides, aliphatic phosphorous, aromatic hydrocarbons, aromatic halohydrocarbons, aromatic ethers, aromatic alcohol phenols, aromatic thiols, aromatic amines, aromatic nitro compounds, aromatic ketones, aromatic aldehydes, aromatic carboxylic acids, aromatic esters, aromatic amino acids and their acid salts, aromatic acid anhydrides, aromatic acid halides, aromatic amides, aromatic nitriles, aromatic sulfur oxides, aromatic phosphorus compounds, aromatic heterocycles, alkynes, fluorine, and the like; r4Selected from halogen, hydroxy and alkoxy having up to 3 carbon atoms, e.g. Cl, H, -OCH3Etc.; r5，R6Is selected from R3And hydrogen, and the like.
3. The method for preparing a hard hydrophobic coating without solvent addition according to claim 1, characterized in that: when the addition amount of the epoxy siloxane is 16 wt% and the content of the primary amino siloxane is 8 wt%, the prepared coating has the best adhesion and surface hardness.
4. The room temperature curable self-cleaning coating of claim 1, characterized in that: when the addition amount of the fluorinated siloxane is 0.7 percent, the prepared coating has the best hydrophobic angle and better self-cleaning performance.
5. The method for preparing a hard hydrophobic coating without solvent addition according to claim 1, characterized in that: when the addition amount of the dibutyl tin dilaurate is 1.2%, the prepared coating has a more complete network structure, and the hardness of the coating is further improved.
6. The method for preparing a hard hydrophobic coating without solvent addition according to claim 1, characterized in that: the steps are as follows
Step (a): epoxy siloxane, other siloxane, fluorinated siloxane and dibutyl tin dilaurate are blended at a certain temperature and stirred for a certain time for standby;
step (b): adding primary amino siloxane into the solution prepared in the step (a), stirring for a period of time, and sealing for later use;
step (c): coating the substrate with the solution prepared in the step (b) in a certain mode, and standing at room temperature for 24 hours to obtain the hard hydrophobic coating.
7. The method for preparing the room temperature curing hard self-cleaning coating according to claim 6, which is characterized in that: the optimum molar ratio of epoxysiloxane to other siloxanes fluorinated siloxane to dibutyl tin dilaurate in step (a) is 4:25:0.09:0.056 at 25 deg.C and stirring for 10-30 min.
8. The method according to claim 6, characterized in that: other siloxane monomers in step (a) include, but are not limited to, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, mercaptotrimethoxysilane, mercaptotriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, polydimethylsiloxane (hydroxyl terminated), and the like.
9. The method according to claim 6, characterized in that: the optimal mole ratio of the adding amount of the primary amino siloxane to the adding amount of the epoxy siloxane in the step (b) is 1:2, and the stirring time is 5-10 min.
10. The method according to claim 6, characterized in that: the substrate in step (c) includes, but is not limited to, a glass substrate, a silicon substrate, a metal substrate, a fabric, paper, PVC, PC, wood, concrete, etc.; coating methods include, but are not limited to, spray coating, spin coating, dipping, drop coating, roll coating.
11. The method according to claim 6, characterized in that: the curing temperature in the step (c) is 25-30 ℃, which is beneficial to the rapid curing of the coating.
12. In particular, the moisture in the curing process is derived from air, dibutyl tin dilaurate is preferentially hydrolyzed to form Si-OH, and reacts with the rest siloxane for condensation, and the whole precursor system can be cured in a short time by adding water in advance, so that the effect of long-term storage cannot be achieved.
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| CN112175520A (en) * | 2020-08-24 | 2021-01-05 | 青岛科技大学 | Preparation method and application of super-hydrophobic, transparent and durable coating |
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