CN104927650A - Preparation method of functional coating - Google Patents
Preparation method of functional coating Download PDFInfo
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- CN104927650A CN104927650A CN201510331147.3A CN201510331147A CN104927650A CN 104927650 A CN104927650 A CN 104927650A CN 201510331147 A CN201510331147 A CN 201510331147A CN 104927650 A CN104927650 A CN 104927650A
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Abstract
The invention discloses a preparation method of a functional coating. The coating can form a functional coating layer on the surface of a base material like plastic or metal or ceramic. The coating is composed of a composition of a bis(trimethylsilyl) silane coupling agent and other mono(trimethylsilyl) silane coupling agents, wherein the molar ratio of the bis(trimethylsilyl) silane coupling agent to the mono(trimethylsilyl) silane coupling agents is 6:1-1:1; a solution with the mass concentration of 2%-10% is prepared in a solvent; after a hydrolysis reaction lasting for 2 h-6 h, the surface of the base material is coated with the solution to form a siloxane coating film, and after drying and crosslinking at the temperature of 60 DEG C-120 DEG C, the uniform and flat coating layer is formed. The coating can form the coating layer with the surface resistant to solvent corrosion resistance and achieve functionalization for the surface of a base material like metal or inorganic nonmetal or an organic polymer.
Description
Technical field
The present invention relates to a kind of preparation method of functional paint, specifically relating to one can at plastics, and the surface of the base materials such as metal and pottery forms the top coat of one deck functionalization.
Background technology
Material surface guard technology conventional at present mainly contains plating, vacuum plating and chemical coating method etc.Plating is mainly applicable to the surfacecti proteon of metal base, by the reduction of metal ion in electrolytic solution, generates the metal plating with defencive function at its surface deposition.But this protection method needs the technological process of specific appliance arrangement and complexity, production efficiency is low and cost is higher.The scope of application of Vacuum Coating method is wider than electrochemical plating, and the materials such as plastics, metal and pottery can by Vacuum Coating method at its surface deposition protective coating.But vacuum plating needs to deposit the comparatively firm coating of one deck at substrate surface at a higher temperature sometimes, and this is to the material of some non-refractories and goods, and the application as organic high molecular polymer and thermo-sensitivity device etc. brings restriction.Similarly, also there is low and high with the equipment investment shortcoming of production efficiency in vacuum plating.The advantage of chemical coating method is easy and simple to handle, with low cost, applied widely etc.
Traditional chemical coating method adopts protective system to protect all kinds of substrate surface, as FEVE fluorocarbon resin, and the heavy-duty coating such as epoxy zinc-rich, rich aluminium.This kind of protective system has high thickness, high surface energy, temperature resistant grade is low, coating process is complicated and other performance of sacrificial coatings exchanges the feature of antiseptic property for.But this technology is not suitable for product size to be required accurately, in high temperature, acidity or alkaline, and the use under the severe environment such as organic solvent.
At present, will have the polymkeric substance of hydrophobic property, as polyvinylidene difluoride (PVDF), tetrafluoroethylene etc. are coated to the surface of base material, although can play the effect preventing nip, also bring some limitation.Bonding force such as between hydrophobic polymer and base material is relatively weak, is difficult to prepare thinner coating.Simultaneously in actual applications, when there being certain force of sliding friction to exist, coating easily and substrate peel off.Polyphenylene ethyl is a kind of thermoplastics, and the surface that can be deposited on various base material forms the film of continuous uniform, but is not suitable for using under friction and heating environment.In Chinese patent CN101992184A, disclose a kind of preparation method of resistant to corrosion super-hydrophobic coat, utilize sol-gel process to form pottery, silicon compound, metal oxide or metal nitride coatings on the surface of the small-bore tubing such as sampling probe, probe shape goods.Compared with the tetrafluoroethylene often used in prior art and polyphenylene ethyl coating, improve mechanical property.
So, for the difference of applied environment, form one deck protective layer at substrate surface, to the use properties improving material, increase the service life and have great importance.
Summary of the invention
In order to widen the scope of application of current material surface protection technology, making material can form one deck supercoat on its surface simultaneously under comparatively gentle processing environment, the invention provides a kind of easy and simple to handle, functional paint technology with low cost.Use this functional paint, effectively can improve the weather resistance of material under hot environment and solvent environment.
For achieving the above object; technical scheme provided by the invention is: a kind of preparation method of functional paint; its principal character is that this functional paint is made up of by certain mass ratio two (tri-alkoxy) silane coupling agent, list (tri-alkoxy) silane coupling agent and solvent; through the hydrolysis reaction of 2 ~ 6 hours; alkoxyl group is hydrolyzed in a solvent and generates silanol key; be coated to substrate surface through 60 ~ 120 DEG C of oven dry, between silanol key, dehydrating condensation forms the supercoat of one deck solvent resistant corrosion of high crosslink density.
The general structure of described two (tri-alkoxy) silane coupling agent is as follows:
In formula, n=1 ~ 3, X is hydrolysable group, comprises methoxyl group, oxyethyl group, methoxy ethoxy, and Y is amino, phenyl, ester group etc.Preferably two (3-triethoxysilylpropyltetrasulfide) amine, two (3-trimethoxy-silylpropyl) amine, two (the silica-based ethane of trimethoxy), two (triethoxy is silica-based) ethane, two (trimethoxysilyl methyl) ethene, two (3-trimethoxy silicon propyl group) fumarate, two (triethoxy is silica-based) ethene, two [(trimethoxy is silica-based) ethyl] benzene, two [3-(trimethoxy is silica-based) propyl group] quadrol, two [(trimethoxy is silica-based) methyl] benzene, the mixture of two [3-(methylamino) propyl group] Trimethoxy silane one or any multiple arbitrary proportion wherein.
The general structure of described list (tri-alkoxy) silane coupling agent is as follows:
In formula, n=0 ~ 3, Z is hydrolysable group, and comprising methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group and Cl, R is organo-functional group, mainly contains amino, epoxy group(ing), phenyl, fluoro-alkyl etc.Preferred list (tri-alkoxy) silane coupling agent comprises gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy diethoxy silane, diethylin is for Union carbide A-162, Union carbide A-162, phenyl triethoxysilane, ten trifluoro octyl group Trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl Trimethoxy silanes, 17 fluorine decyl triethoxyl silanes, the mixture of n-octyl Trimethoxy silane one or any multiple arbitrary proportion wherein.
Mol ratio 6:1 ~ the 1:1 of described two (tri-alkoxy) silane coupling agent and single (tri-alkoxy) silane coupling agent.
The described concentration of polymer solution prepared in a solvent is 2% ~ 10%.
Described solvent is methyl alcohol, ethanol, Virahol, the mixture of the wherein one or any several arbitrary proportion in butanols.
It is plastics that described functional paint is applicable to base material, the surfacecti proteon of pottery and metal etc.
Described functional paint provides a kind of coating with required surface energy and solvent resistant corrosion.
The invention has the beneficial effects as follows provide a kind of simple to operate; coating technology scheme with low cost; for the surface of the base materials such as plastics, metal and pottery provides protective coating, the protective coating that a kind of solvent resistant corrodes is provided, the surface of material is played a protective role.
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment
Embodiment 1:
A two (3-triethoxysilylpropyltetrasulfide) amine of () general and N-β (aminoethyl)-γ-aminopropyltrimethoxysilane in molar ratio 6:1 join in Virahol, be mixed with the aqueous isopropanol that mass concentration is 2%, room temperature magnetic agitation is hydrolyzed 6 hours, obtains coating.
B metallic substrate surface cleans up by (), naturally volatilized by the paint of preparation to surface to solvent Virahol.
C metal base is transferred in the baking oven of 80 DEG C by (), dry crosslinked 12 hours, and obtain the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.3 μm, the surface water contact angle recorded is 89 °.
Embodiment 2:
A two (3-trimethoxy-silylpropyl) amine of () general and γ-glycidyl ether oxygen propyl trimethoxy silicane in molar ratio 4:1 join in ethanol, be mixed with the ethanolic soln that massfraction is 5%, room temperature magnetic agitation is hydrolyzed 4 hours, obtains coating.
B () is clean by plastic basis material surface cleaning, naturally volatilized by the paint of preparation to surface to etoh solvent.
C plastic basis material is transferred in the baking oven of 80 DEG C by (), dry crosslinked 12 hours, and obtain the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.5 μm, the surface water contact angle recorded is 85 °
Embodiment 3:
A two (trimethoxy the is silica-based) ethane of () general and gamma-amino propyl trimethoxy silicane in molar ratio 1:1 join in butanols, be mixed with the butanol solution that massfraction is 2%, room temperature magnetic agitation is hydrolyzed 2 hours, obtains coating.
B ceramic substrate surface cleans up by (), naturally volatilized by the paint of preparation to surface to solvent butanols.
C ceramic base material is transferred in the baking oven of 120 DEG C by (), dry crosslinked 12 hours, and obtain the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.3 μm, the surface water contact angle recorded is 86 °
Embodiment 4:
A two [(trimethoxy the is silica-based) ethyl] benzene of () general and 17 fluorine decyl Trimethoxy silanes in molar ratio 4:1 join in ethanol, be mixed with the ethanolic soln that massfraction is 10%, room temperature magnetic agitation is hydrolyzed 4 hours, obtains coating.
B () is clean by plastic basis material surface cleaning, naturally volatilized by the paint of preparation to surface to etoh solvent.
C ceramic base material is transferred in the baking oven of 80 DEG C by (), dry crosslinked 12 hours, and obtain the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.7 μm, the surface water contact angle recorded is 112 °
Embodiment 5:
A two (3-(methylamino) propyl group) Trimethoxy silane and phenyl triethoxysilane mol ratio 1:1 join in Virahol by (), be mixed with the aqueous isopropanol that massfraction is 10%, room temperature magnetic agitation is hydrolyzed 2 hours, obtains coating.
B () is clean by cleaning metal surface, naturally volatilized by the paint of preparation to surface to solvent Virahol.
C metal transfer in the baking oven of 80 DEG C, dry crosslinked 12 hours, is obtained the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.75 μm by ().The surface water contact angle recorded is 103 °.
Embodiment 6:
A two [3-(trimethoxy is silica-based) propyl group] quadrol and ten trifluoro octyl group Trimethoxy silane mol ratio 6:1 join in Virahol by (), be mixed with the aqueous isopropanol that mass concentration is 5%, room temperature magnetic agitation is hydrolyzed 6 hours, obtains coating liquid.
B () is clean by cleaning metal surface, naturally volatilized by the paint of preparation to surface to solvent Virahol.
C (), by metal transfer in the baking oven of 80 DEG C, dry crosslinked 12 hours, obtain the protective layer of the high crosslink density that surface uniform is smooth, solvent resistant corrodes, thickness about 0.5 μm, the surface water contact angle recorded was 110 °
The coating prepared by above-described embodiment 1 ~ 6 is respectively at butylacetate, and in the mixed solvent of pimelinketone and butylacetate and pimelinketone, soak at 80 DEG C, the solvent resistant corrosive nature of testing coating, result is as follows:
| Solvent resistant corrosion (T=80 DEG C) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Butylacetate (72h) | Intact | Intact | Intact | Intact | Intact | Intact |
| Pimelinketone (72h) | Slight erosion | Intact | Slight erosion | Intact | Intact | Intact |
| Butylacetate/pimelinketone (72h) | Intact | Intact | Intact | Intact | Intact | Intact |
Claims (9)
1. the preparation method of a functional paint, it is characterized in that: this functional paint by two (tri-alkoxy) silane coupling agent, list (tri-alkoxy) silane coupling agent and solvent composition, the mol ratio 6:1 ~ 1:1 of two (tri-alkoxy) silane coupling agent and single (tri-alkoxy) silane coupling agent; Through the hydrolysis reaction of 2 ~ 6 hours, be coated on substrate surface and form coating after 60 ~ 120 DEG C dry.
2., according to method according to claim 1, described two (tri-alkoxy) silane coupling agent is characterized in that having following general structure:
In formula, n=1 ~ 3, X comprises methoxyl group, oxyethyl group, methoxy ethoxy, and Y is amino, phenyl or ester group.
3. method according to claim 2, described two (tri-alkoxy) silane coupling agents are two (3-triethoxysilylpropyltetrasulfide) amine, two (3-trimethoxy-silylpropyl) amine, two (the silica-based ethane of trimethoxy), two (triethoxy is silica-based) ethane, two (trimethoxysilyl methyl) ethene, two (3-trimethoxy silicon propyl group) fumarate, two (triethoxy is silica-based) ethene, two [(trimethoxy is silica-based) ethyl] benzene, two [3-(trimethoxy is silica-based) propyl group] quadrol, two [(trimethoxy is silica-based) methyl] benzene, two [3-(methylamino) propyl group] Trimethoxy silane wherein one or several.
4. method according to claim 1, the general structure of described list (tri-alkoxy) silane coupling agent is as follows:
In formula, n=0 ~ 3, it is amino, epoxy group(ing), phenyl or fluoro-alkyl that Z comprises methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group or Cl, R.
5. method according to claim 4, described list (tri-alkoxy) silane coupling agent is gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy diethoxy silane, diethylin is for Union carbide A-162, Union carbide A-162, phenyl triethoxysilane, ten trifluoro octyl group Trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl Trimethoxy silanes, 17 fluorine decyl triethoxyl silanes, n-octyl Trimethoxy silane wherein one or several.
6. method according to claim 1, the concentration of polymer solution that two (tri-alkoxy) silane coupling agent and single (tri-alkoxy) silane coupling agent are mixed with in a solvent is 2% ~ 10%.
7. method according to claim 1, described solvent is methyl alcohol, ethanol, wherein one or several the mixture in Virahol and butanols.
8. application rights requires the coating prepared by method described in 1, and the base material being applicable to apply comprises plastics, metal or pottery.
9. the coating prepared of method according to claim 1, a kind of coating with hydrophilic or hydrophobic solvent resistant corrosion of this functional paint formula.
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| CN201510331147.3A CN104927650A (en) | 2015-06-15 | 2015-06-15 | Preparation method of functional coating |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606768A (en) * | 2015-12-28 | 2016-05-25 | 上海维凯光电新材料有限公司 | Test liquid and test pen for detecting solvent-resistant performance of aluminum plating transferring paint |
| CN106280611A (en) * | 2016-08-24 | 2017-01-04 | 何国美 | Fast coating admittedly |
| CN107793797A (en) * | 2017-10-17 | 2018-03-13 | 中昊北方涂料工业研究设计院有限公司 | A kind of one-component Trend of Chrome-free cold curing refractory inorganic paint and its preparation |
| CN110157333A (en) * | 2019-06-12 | 2019-08-23 | 湖南辰砾新材料有限公司 | A kind of water-based anticorrosive paint and preparation method thereof |
| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
| CN113583035A (en) * | 2021-07-16 | 2021-11-02 | 浙江开化合成材料有限公司 | Method for preparing bis (3-trimethoxysilylpropyl) ethylenediamine by microchannel reactor |
| CN114621655A (en) * | 2022-04-13 | 2022-06-14 | 河南科技大学 | Preparation method of anticorrosive coating, coating and application of crown ether complex as anticorrosive coating additive |
| CN114843431A (en) * | 2022-05-20 | 2022-08-02 | 天津大学 | Zinc metal negative electrode with aminosilane polymer protective layer and preparation method thereof |
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| CN1343237A (en) * | 1999-02-05 | 2002-04-03 | 舍米塔尔公开有限公司 | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture |
| CN101376710A (en) * | 2007-08-28 | 2009-03-04 | 赢创德固赛有限责任公司 | Aqueous silane systems based on bis(trialkoxysilylalkyl)amines |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1343237A (en) * | 1999-02-05 | 2002-04-03 | 舍米塔尔公开有限公司 | Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture |
| CN101376710A (en) * | 2007-08-28 | 2009-03-04 | 赢创德固赛有限责任公司 | Aqueous silane systems based on bis(trialkoxysilylalkyl)amines |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105606768A (en) * | 2015-12-28 | 2016-05-25 | 上海维凯光电新材料有限公司 | Test liquid and test pen for detecting solvent-resistant performance of aluminum plating transferring paint |
| CN106280611A (en) * | 2016-08-24 | 2017-01-04 | 何国美 | Fast coating admittedly |
| CN107793797A (en) * | 2017-10-17 | 2018-03-13 | 中昊北方涂料工业研究设计院有限公司 | A kind of one-component Trend of Chrome-free cold curing refractory inorganic paint and its preparation |
| CN111777874A (en) * | 2019-04-04 | 2020-10-16 | 深圳先进技术研究院 | Nano silicon dioxide and surface modification method thereof |
| CN110157333A (en) * | 2019-06-12 | 2019-08-23 | 湖南辰砾新材料有限公司 | A kind of water-based anticorrosive paint and preparation method thereof |
| CN113583035A (en) * | 2021-07-16 | 2021-11-02 | 浙江开化合成材料有限公司 | Method for preparing bis (3-trimethoxysilylpropyl) ethylenediamine by microchannel reactor |
| CN113583035B (en) * | 2021-07-16 | 2024-02-09 | 浙江开化合成材料有限公司 | Method for preparing bis (3-trimethoxysilylpropyl) ethylenediamine by using microchannel reactor |
| CN114621655A (en) * | 2022-04-13 | 2022-06-14 | 河南科技大学 | Preparation method of anticorrosive coating, coating and application of crown ether complex as anticorrosive coating additive |
| CN114621655B (en) * | 2022-04-13 | 2023-04-07 | 河南科技大学 | Preparation method of anticorrosive coating, coating and application of crown ether complex as anticorrosive coating additive |
| CN114843431A (en) * | 2022-05-20 | 2022-08-02 | 天津大学 | Zinc metal negative electrode with aminosilane polymer protective layer and preparation method thereof |
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Application publication date: 20150923 |