WO2020082677A1 - Silicon-containing copolymer nano coating and preparation method therefor - Google Patents

Silicon-containing copolymer nano coating and preparation method therefor Download PDF

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Publication number
WO2020082677A1
WO2020082677A1 PCT/CN2019/079112 CN2019079112W WO2020082677A1 WO 2020082677 A1 WO2020082677 A1 WO 2020082677A1 CN 2019079112 W CN2019079112 W CN 2019079112W WO 2020082677 A1 WO2020082677 A1 WO 2020082677A1
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silicon
containing copolymer
comonomer
discharge
copolymer nano
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PCT/CN2019/079112
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French (fr)
Chinese (zh)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Publication of WO2020082677A1 publication Critical patent/WO2020082677A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D149/00—Coating compositions based on homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/517—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515

Definitions

  • the invention relates to the technical field of plasma chemical vapor deposition, in particular to a silicon-containing copolymer nano-coating and a preparation method thereof.
  • Patent CN101316882A "Durable transparent coating for aircraft cabin windows” uses silicone as a soft coating to improve the durability of acrylic substrates used in aircraft window applications.
  • CN107587119A Screening method of a composite structure high-insulation hard nano-protective coating screens out low-dipole moment and highly chemically inert silicone monomers, and the free volume and density of the coating are regulated by multifunctional monomers.
  • the coating has abrasion resistance and insulation.
  • the low dipole moment and unsaturated hydrocarbons and hydrocarbon derivatives are introduced first, and the silicone monomer is introduced after the deposition step is completed. Proceed to deposition.
  • Low dipole moments (such as fluorocarbon resin monomers) generally have a symmetrical molecular structure, the entire molecule is non-polar, has a very low surface energy, and has good hydrophobic properties. But at the same time, the friction coefficient of this kind of material is very low, which makes the composite layer easily slide and deform under the action of external force, and has poor wear resistance, rigidity and hardness.
  • the present invention is to overcome the above shortcomings and provide a method for preparing a nano-coating by copolymerizing a monomer having a low surface energy resin and a silicone monomer.
  • a silicon-containing copolymer nano-coating characterized in that the substrate is exposed to a comonomer vapor atmosphere, and a chemical vapor deposition reaction is initiated on the surface of the substrate by plasma discharge to form a protective coating;
  • the comonomer vapor is vaporized one or more substances in the following comonomer 1, and one or more of the following comonomer 2, or a mixture of comonomer 2;
  • the comonomer 1 has the structure represented by the following formula (I), (II) or (III):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are groups connected to an unsaturated carbon bond, and can be independently selected from hydrogen, alkyl, aryl, halogen, or haloalkyl.
  • X is hydrogen, or a substituent of the hydrophobic alkyl chain, which may be halogen.
  • the comonomer 2 has the structure represented by the following formula (IV):
  • comonomer 2 is siloxane and / or its derivatives.
  • R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are groups connected to unsaturated carbon-carbon double bonds and Si atoms, and can be independently selected from hydrogen, alkyl, aryl, halogen and halogenated alkyl , Halogenated aryl, alkoxy or vinyl.
  • m and n are integers from 0-20, and k is an integer from 0-8.
  • Each structural formula in comonomer 1 contains an unsaturated bond, which is a carbon-carbon double bond or a carbon-carbon triple bond, which can be used either for self-polymerization or with unsaturated bonds in comonomer 2 Formation of alternating copolymers, block copolymers, graft copolymers, etc. Under the action of plasma, the Si-O bond of siloxane can be opened to chemically bond with the unsaturated bond of comonomer 1 to form a C-Si bond or a C-O bond.
  • the group connected to the unsaturated bond is preferably a series of hydrophobic groups such as alkyl, aryl, haloalkyl, alkenyl, etc. More preferably, the group connected to the unsaturated bond is selected Fluoroalkyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from hydrogen, alkyl, or halogen.
  • R 11 , R 12 and R 13 are independently selected from hydrogen, alkyl, halogen or alkoxy.
  • halogen is preferably fluorine or chlorine.
  • the ring structure of siloxane has a low ring tension, but it is an entropy increasing reaction during the ring opening process, and the reaction becomes extremely easy under the action of plasma.
  • the molecular structure of the siloxane is cyclic or cross-linked.
  • the cyclic siloxane is specifically hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane.
  • the comonomer 1 is one selected from structural formula (I), formula (II), and formula (III), or a mixture of any two types, or a mixture of three types.
  • n and n are integers of 2-10.
  • the base material may be solid materials such as metal, optical instruments, clothing fabrics, electronic devices, and medical devices.
  • the invention also discloses a method for preparing a silicon-containing copolymer nano-coating, which is characterized by comprising the following steps:
  • the plasma source gas in step (2) may be one or a mixture of helium, argon, nitrogen, and hydrogen.
  • step (2) the molar ratio of the comonomer 1 to the comonomer 2 is 1: 1000-1000: 1.
  • the volume of the plasma chamber is 1L-5000L
  • the flow rate of the plasma source gas is 5-1000 sccm
  • the flow rate of the monomer vapor is 1-2000 ⁇ L / min.
  • a plasma discharge step for pretreatment of the substrate is further included.
  • the pretreatment is started to perform pretreatment on the substrate with plasma discharge.
  • the power of the plasma discharge for pretreatment is 1-900W, and the continuous discharge time is 1-5400s.
  • the coating deposition stage is entered (that is, the plasma discharge for pretreatment is converted to the plasma discharge for deposition).
  • the plasma discharge mode and parameters of the two stages may be the same or different.
  • the power of the plasma discharge for deposition is 2-500 W, and the continuous discharge time is 600-20000s.
  • the plasma discharge (plasma discharge for pretreatment and / or plasma discharge for deposition) is radio frequency discharge, microwave discharge, intermediate frequency discharge, Penning discharge or electric spark discharge.
  • the plasma discharge (pretreatment plasma discharge and / or deposition plasma discharge) method is microwave discharge. More preferably, the frequency of the microwave discharge is 500MHz-200KMHz.
  • the coating of the present application is used to perform chemical corrosion-resistant hydrophobic protection treatment on the surface of the substrate.
  • the present invention has the following beneficial effects: Compared with the prior art, the present invention utilizes plasma chemical vapor deposition technology to copolymerize unsaturated dipole moment monomers containing low bond and organosilicon monomers, based on A high- and low-temperature resistant silicon-containing copolymer nano-coating was formed on the surface of the material. The introduction of silicone groups in the coating improves its high and low temperature resistance.
  • the main chain of the silicone resin is inorganic Si-O bonds, its bond energy is higher than that of CC bonds, and it has high temperature stability; Si-O-Si bond angle Large, Si-O bond length is long, its glass transition temperature is very low, has good low temperature resistance, so that the coating can be used for a long time at -60 °C -350 °C, even at high and low temperature rapid transition In the environment, it can still maintain excellent performance.
  • the present invention provides a coating formed by copolymerization, which solves the shortcomings of the peeling between the coating in the two-layer composite structure of the low dipole moment coating and the silicone coating, and improves the resistance of the coating during use External friction.
  • the invention uses the plasma technology to initiate monomer copolymerization, saving the research and development costs of different monomer copolymerization catalyst development and screening.
  • a method for preparing a silicon-containing copolymer nano-coating through the following steps:
  • the comonomer 1a and the comonomer 2a are vaporized and simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the two monomers was 80 ⁇ L / min
  • the lead-in time was 2000 s
  • the plasma discharge for pretreatment was adjusted to the plasma discharge for deposition.
  • the plasma discharge was intermittent microwave discharge, and the discharge was turned off every 200 ⁇ s for 3ms.
  • the device for generating plasma discharge for pretreatment and the device for generating plasma discharge for coating deposition may be one set or two separate devices.
  • the plasma discharge device (for example, electrode) for pretreatment is preferably arranged in the reaction chamber and around the substrate, so as to facilitate the quick connection with the coating process after pretreatment; and the plasma discharge device for the deposition stage of the coating can be arranged in It is arranged outside the reaction chamber and away from the reaction chamber, so as to selectively or as far as possible avoid the negative influence of the plasma discharge on the substrate during the coating process.
  • a method for preparing a silicon-containing copolymer nano-coating through the following steps:
  • a method for preparing a silicon-containing copolymer nano-coating through the following steps:
  • the comonomer 1c and the comonomer 2c are vaporized and simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the two monomers was 150 ⁇ L / min
  • the lead-in time was 3000 s
  • the plasma discharge for pretreatment was adjusted to the plasma discharge for deposition.
  • the discharge in the deposition stage is intermittent microwave discharge, and the discharge is turned off every 100 ⁇ s for 5ms.
  • Example 2 Compared with Example 1, the comonomer 1a was changed to 1d, and the comonomer 2a was changed to monomer 2d.
  • Example 1 Compared with Example 1, the monomer 1a is changed to a mixture of 1a and 1b, and the molar ratio of the two is 1: 1, and other conditions remain unchanged.
  • Example 1 Compared with Example 1, the discharge power in the pretreatment stage in step (2) was changed to 600 W, and other conditions were not changed.
  • Example 2 Compared with Example 2, the monomer 2b was replaced with a mixture of monomers 2b and 2c, and the molar ratio of the two was 1: 2, and other conditions were not changed.
  • the microwave discharge frequency in the pretreatment stage of step (2) is set to 50 KMHz, and other conditions are not changed.
  • the discharge time in the deposition stage of step (3) was set to 4000s, and other conditions were not changed.
  • Example 1 Compared with Example 1, the comonomer 1a was changed to 2b, and other conditions were not changed.
  • Example 3 Compared with Example 3, the comonomer 1c was changed to 1a and 1c mixture (molar ratio is 1: 1), and the comonomer 2c was changed to 2a and 2c mixture (molar ratio is 1: 1)
  • step (3) does not add comonomer 2a, and other conditions are not changed.
  • step (3) does not add monomer copolymerization 1a, and other conditions are not changed.
  • the substrates plated in the above examples were tested for coating thickness, water contact angle, pencil hardness level, and abrasion resistance.
  • the thickness of the nano-coating is tested using the US Filmetrics F20-UV-film thickness measuring instrument.
  • Nano-coating water contact angle is tested according to GB / T 30447-2013 standard.
  • the pencil hardness test method is based on ASTM D3363 pencil hardness.
  • test method For high and low temperature resistance test, refer to GB / T 2424.1-2005.
  • the test method is to place it at -60 °C for 24h, and after returning to room temperature, evenly heat up to 350 °C within 2h. After placing at 350 °C for 24h, observe the appearance of the sample surface and determine whether the surface water drop angle drops ( ⁇ 2 ° fluctuation is the error range).
  • the abrasion resistance test was conducted in an alcohol abrasion tester.
  • the eraser test fixture was selected for the test.
  • the test conditions were a load of 100g, a rotation speed of 60cycle / min, and the number of cycles was measured. The coating was not worn.
  • the coating prepared by copolymerizing the monomer of the low surface energy resin and the silicon-containing organic monomer by the method of the present application can reach the pencil hardness level of 1H and has excellent abrasion resistance; at -60 °C- Used in the temperature range of 350 °C, the appearance of the coating is still not affected, and the contact angle of the coating is almost unchanged.
  • the monomer of the low surface energy resin is mixed and copolymerized with the silicon-containing organic monomer, compared with the single type of monomer, it shows the increase of the deposition speed of the nano coating (the film thickness increases at the same time) and the pencil hardness level. Other effects.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

Disclosed is a preparation method for a silicon-containing copolymer nano coating. The silicon-containing copolymer nano coating is formed by exposing a base material to the atmosphere of two comonomer vapors and initiating copolymerization on the surface of the base material by utilizing plasma discharge such that a chemical vapor deposition reaction occurs, wherein one comonomer has an unsaturated bond which is a carbon-carbon double bond or a carbon-carbon triple bond, and the other comonomer is organic silicon. Also disclosed is a silicon-containing copolymer nano coating.

Description

一种含硅共聚物纳米涂层及其制备方法Nano-coating of silicon-containing copolymer and preparation method thereof 技术领域Technical field
本发明涉及等离子体化学气相沉积技术领域，具体涉及到一种含硅共聚物纳米涂层及其制备方法。The invention relates to the technical field of plasma chemical vapor deposition, in particular to a silicon-containing copolymer nano-coating and a preparation method thereof.
背景技术Background technique
众所周知，有机硅树脂由于主链为无机Si-O键，它的键能比C-C键高，具有高温稳定性；Si-O-Si键角大，Si-O键长较长，其玻璃化转变温度很低，具有很好的耐低温性能。但其机械性能较差和耐油性能较差使有机硅树脂在实际应用中受到限制。专利CN101316882A《用于航空器客舱窗户的耐用透明涂层》利用硅氧烷作为软涂层改善用于航空器窗户应用的丙烯酸类基材的耐用性。CN107587119A《一种复合结构高绝缘硬质纳米防护涂层的制备方法》筛选出低偶极矩和高化学惰性的有机硅单体，通过多官能度单体调控涂层的自由体积和致密性，使得涂层具有耐磨性和绝缘性，其复合结构高绝缘涂层制备方法中先通入将低偶极矩和不饱和烃及烃类衍生物，完成沉积步骤后再通入有机硅单体进行沉积。低偶极矩(如氟碳树脂单体)一般分子结构排列对称，整个分子呈非极性特点，具有非常低的表面能，有很好的疏水性能。但同时这类材料的摩擦系数很低，使得复合层与层之间在外力作用下易于滑动和变形，耐磨性、刚性和硬度较差。As we all know, because the main chain of the silicone resin is inorganic Si-O bond, its bond energy is higher than the CC bond, and it has high temperature stability; the Si-O-Si bond angle is large, the Si-O bond length is long, and its glass transition The temperature is very low and it has good low temperature resistance. However, its poor mechanical properties and poor oil resistance limit the silicone resin in practical applications. Patent CN101316882A "Durable transparent coating for aircraft cabin windows" uses silicone as a soft coating to improve the durability of acrylic substrates used in aircraft window applications. CN107587119A "Preparation method of a composite structure high-insulation hard nano-protective coating" screens out low-dipole moment and highly chemically inert silicone monomers, and the free volume and density of the coating are regulated by multifunctional monomers. The coating has abrasion resistance and insulation. In the preparation method of the composite structure high insulation coating, the low dipole moment and unsaturated hydrocarbons and hydrocarbon derivatives are introduced first, and the silicone monomer is introduced after the deposition step is completed. Proceed to deposition. Low dipole moments (such as fluorocarbon resin monomers) generally have a symmetrical molecular structure, the entire molecule is non-polar, has a very low surface energy, and has good hydrophobic properties. But at the same time, the friction coefficient of this kind of material is very low, which makes the composite layer easily slide and deform under the action of external force, and has poor wear resistance, rigidity and hardness.
如何将有机硅树脂和低表面能树脂优点结合，形成既有较高机械性能、耐油性能，又有较好耐低温性能、耐磨性和绝缘性的纳米涂层，是目前纳米涂层领域研究的热点方向之一。How to combine the advantages of silicone resin and low surface energy resin to form a nano-coating with high mechanical properties, oil resistance, and low temperature resistance, wear resistance and insulation is the current research in the field of nano-coatings One of the hot spots.
发明内容Summary of the invention
本发明是为了克服以上缺点，提供一种将具有低表面能树脂的单体和有机硅单体共聚制备纳米涂层的方法。The present invention is to overcome the above shortcomings and provide a method for preparing a nano-coating by copolymerizing a monomer having a low surface energy resin and a silicone monomer.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种含硅共聚物纳米涂层，其特征在于，将基材暴露于共聚单体蒸汽氛围中，通过等离子体放电在基材表面引发共聚发生化学气相沉积反应而形成保护涂层；A silicon-containing copolymer nano-coating, characterized in that the substrate is exposed to a comonomer vapor atmosphere, and a chemical vapor deposition reaction is initiated on the surface of the substrate by plasma discharge to form a protective coating;
所述共聚单体蒸汽为汽化的下述共聚单体1中的一种或多种物质，和下述共聚单体2中的一种或多种，或者共聚单体2的混合物；The comonomer vapor is vaporized one or more substances in the following comonomer 1, and one or more of the following comonomer 2, or a mixture of comonomer 2;
所述共聚单体1具有如下式(I)、(II)或(III)所示结构：The comonomer 1 has the structure represented by the following formula (I), (II) or (III):
Figure PCTCN2019079112-appb-000001
Figure PCTCN2019079112-appb-000001
R 1、R 2、R 3、R 4、R 5、R 6、R 7是与不饱和碳键连接的基团，可 独立地选自氢、烷基、芳基、卤素或卤代烷基。X是氢，或者是疏水烷基链的取代基，可为卤素。 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are groups connected to an unsaturated carbon bond, and can be independently selected from hydrogen, alkyl, aryl, halogen, or haloalkyl. X is hydrogen, or a substituent of the hydrophobic alkyl chain, which may be halogen.
所述共聚单体2具有如下的式(IV)所示结构：The comonomer 2 has the structure represented by the following formula (IV):
Figure PCTCN2019079112-appb-000002
Figure PCTCN2019079112-appb-000002
或者，共聚单体2为硅氧烷和/或其衍生物。Alternatively, comonomer 2 is siloxane and / or its derivatives.
R 8、R 9、R 10、R 11、R 12、R 13是与不饱和碳碳双键、Si原子相连的基团，可独立地选自氢、烷基、芳基、卤素、卤代烷基、卤代芳基、烷氧基或乙烯基。m、n为0-20的整数，k为0-8的整数。 R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are groups connected to unsaturated carbon-carbon double bonds and Si atoms, and can be independently selected from hydrogen, alkyl, aryl, halogen and halogenated alkyl , Halogenated aryl, alkoxy or vinyl. m and n are integers from 0-20, and k is an integer from 0-8.
共聚单体1中各结构式均含有不饱和键，所述不饱和键为碳碳双键或碳碳三键，其既可用于自身聚合反应，也可与共聚单体2中的不饱和键反应形成交替共聚物、嵌段共聚物、接枝共聚物等。在等离子体作用下，硅氧烷的Si-O键可以被打开与共聚单体1的不饱和键进行化学键合，形成C-Si键或者C-O键。Each structural formula in comonomer 1 contains an unsaturated bond, which is a carbon-carbon double bond or a carbon-carbon triple bond, which can be used either for self-polymerization or with unsaturated bonds in comonomer 2 Formation of alternating copolymers, block copolymers, graft copolymers, etc. Under the action of plasma, the Si-O bond of siloxane can be opened to chemically bond with the unsaturated bond of comonomer 1 to form a C-Si bond or a C-O bond.
为了提高涂层的疏水性能，与不饱和键相连的基团优选为烷基、芳基、卤代烷基、烯基等一系列疏水基团，更为优选地，与不饱和键相连的基团选择氟代烷基。In order to improve the hydrophobic performance of the coating, the group connected to the unsaturated bond is preferably a series of hydrophobic groups such as alkyl, aryl, haloalkyl, alkenyl, etc. More preferably, the group connected to the unsaturated bond is selected Fluoroalkyl.
进一步地，R 1、R 2、R 3、R 4、R 5、R 6、R 7独立地选自氢、烷基或卤素。 Further, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from hydrogen, alkyl, or halogen.
进一步地，R 11、R 12、R 13独立地选自氢、烷基、卤素或烷氧基。 Further, R 11 , R 12 and R 13 are independently selected from hydrogen, alkyl, halogen or alkoxy.
更进一步地，卤素优选为氟或氯。Further, the halogen is preferably fluorine or chlorine.
环状结构的硅氧烷，环张力不大，但开环过程时是熵增反应，在等离子体作用下反应变得异常容易。优选地，硅氧烷的分子结构 为环状或交联结构。The ring structure of siloxane has a low ring tension, but it is an entropy increasing reaction during the ring opening process, and the reaction becomes extremely easy under the action of plasma. Preferably, the molecular structure of the siloxane is cyclic or cross-linked.
更优选地，环状硅氧烷具体为六甲基环三硅氧烷、八甲基环四硅氧烷和/或十甲基环五硅氧烷。More preferably, the cyclic siloxane is specifically hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane.
进一步地，共聚单体1为选自具有结构式(I)、式(II)、式(III)中的一种，或者为任意两种的混合物，或者为三种的混合物。Further, the comonomer 1 is one selected from structural formula (I), formula (II), and formula (III), or a mixture of any two types, or a mixture of three types.
优选地，m、n为2-10的整数。Preferably, m and n are integers of 2-10.
进一步地，所述基材可以是金属、光学仪器、衣服织物、电子器件、医疗器械等固体材料。Further, the base material may be solid materials such as metal, optical instruments, clothing fabrics, electronic devices, and medical devices.
本发明还公开了一种含硅共聚物纳米涂层的制备方法，其特征在于，包括以下步骤：The invention also discloses a method for preparing a silicon-containing copolymer nano-coating, which is characterized by comprising the following steps:
(1)将基材置于等离子体室的反应腔体内，将反应腔体内的真空度抽到0.1-1000毫托；(1) Place the substrate in the reaction chamber of the plasma chamber, and evacuate the vacuum in the reaction chamber to 0.1-1000 mTorr;
(2)通入等离子体源气体，开启沉积用等离子体放电，将共聚单体1、共聚单体2经汽化后同时导入反应腔体进行化学气相沉积反应；(2) Into the plasma source gas, start the plasma discharge for deposition, the comonomer 1, comonomer 2 after vaporization into the reaction chamber at the same time for chemical vapor deposition reaction;
(3)关闭沉积用等离子体放电，通入洁净的压缩空气或者惰性气体恢复至常压，打开腔体，取出基材。(3) Turn off the plasma discharge for deposition, pass clean compressed air or inert gas to return to normal pressure, open the cavity, and take out the substrate.
其中，步骤(2)中所述等离子体源气体可以是氦气、氩气、氮气、氢气中的一种或者多种的混合物。Wherein, the plasma source gas in step (2) may be one or a mixture of helium, argon, nitrogen, and hydrogen.
进一步地，步骤(2)中共聚单体1与共聚单体2通入摩尔量的比例为1：1000-1000：1。Further, in step (2), the molar ratio of the comonomer 1 to the comonomer 2 is 1: 1000-1000: 1.
进一步地，等离子体室的容积为1L-5000L，等离子体源气体流量为5-1000sccm，通入单体蒸汽的流量为1-2000μL/min。Further, the volume of the plasma chamber is 1L-5000L, the flow rate of the plasma source gas is 5-1000 sccm, and the flow rate of the monomer vapor is 1-2000 μL / min.
进一步地，所述步骤(2)中，在通入所述等离子体源气体后以及在所述沉积用等离子体放电之前，还包括对基材进行预处理用等离子体放电工序。Further, in the step (2), after passing the plasma source gas and before the plasma discharge for deposition, a plasma discharge step for pretreatment of the substrate is further included.
步骤(2)中通入等离子体源气体后，开启预处理用等离子体放电对基材进行预处理。预处理用等离子体放电的功率为1-900W，持续放电时间为1-5400s。After the plasma source gas is introduced in step (2), the pretreatment is started to perform pretreatment on the substrate with plasma discharge. The power of the plasma discharge for pretreatment is 1-900W, and the continuous discharge time is 1-5400s.
预处理阶段结束后进入涂层沉积阶段(即预处理用等离子体放电转换为沉积用等离子体放电)，两个阶段的等离子体放电方式以及参数可以相同也可以不同。After the pretreatment stage is completed, the coating deposition stage is entered (that is, the plasma discharge for pretreatment is converted to the plasma discharge for deposition). The plasma discharge mode and parameters of the two stages may be the same or different.
进一步地，所述步骤(2)中，沉积用等离子体放电的功率为2-500W，持续放电时间为600-20000s。Further, in the step (2), the power of the plasma discharge for deposition is 2-500 W, and the continuous discharge time is 600-20000s.
进一步地，所述等离子体放电(预处理用等离子体放电和/或沉积用等离子体放电)方式为射频放电、微波放电、中频放电、潘宁放电或电火花放电。Further, the plasma discharge (plasma discharge for pretreatment and / or plasma discharge for deposition) is radio frequency discharge, microwave discharge, intermediate frequency discharge, Penning discharge or electric spark discharge.
优选地，所述等离子体放电(预处理用等离子体放电和/或沉积用等离子体放电)方式为微波放电。更为优选地，所述微波放电的频率为500MHz-200KMHz。Preferably, the plasma discharge (pretreatment plasma discharge and / or deposition plasma discharge) method is microwave discharge. More preferably, the frequency of the microwave discharge is 500MHz-200KMHz.
进一步地，采用本申请的涂层对基材的表面进行耐化学腐蚀疏水防护处理。Further, the coating of the present application is used to perform chemical corrosion-resistant hydrophobic protection treatment on the surface of the substrate.
采用上述技术方案，本发明具有如下有益效果：与现有技术相比，本发明利用等离子体化学气相沉积技术，将含不饱和键的低偶极矩单体和有机硅单体共聚，在基材表面形成了一种耐高低温的含硅共聚物纳米涂层。涂层中引入有机硅基团提高了其耐高低温性能，有机硅树脂由于主链为无机Si-O键，它的键能比C-C键高，具有 高温稳定性；Si-O-Si键角大，Si-O键长较长，其玻璃化转变温度很低，具有很好的耐低温性能，使涂层可以在-60℃-350℃下均可以长时间使用，即使在高低温急遽转变的环境中，仍能保持性能优良。Using the above technical solution, the present invention has the following beneficial effects: Compared with the prior art, the present invention utilizes plasma chemical vapor deposition technology to copolymerize unsaturated dipole moment monomers containing low bond and organosilicon monomers, based on A high- and low-temperature resistant silicon-containing copolymer nano-coating was formed on the surface of the material. The introduction of silicone groups in the coating improves its high and low temperature resistance. Since the main chain of the silicone resin is inorganic Si-O bonds, its bond energy is higher than that of CC bonds, and it has high temperature stability; Si-O-Si bond angle Large, Si-O bond length is long, its glass transition temperature is very low, has good low temperature resistance, so that the coating can be used for a long time at -60 ℃ -350 ℃, even at high and low temperature rapid transition In the environment, it can still maintain excellent performance.
另外，本发明提供了一种共聚而成的涂层，解决了之前低偶极矩涂层与有机硅涂层两层复合结构中涂层之间剥离的缺点，提高了涂层使用过程中耐外力摩擦性。本发明利用等离子体技术引发单体共聚，节省了不同单体共聚催化剂开发、筛选的研发费用。In addition, the present invention provides a coating formed by copolymerization, which solves the shortcomings of the peeling between the coating in the two-layer composite structure of the low dipole moment coating and the silicone coating, and improves the resistance of the coating during use External friction. The invention uses the plasma technology to initiate monomer copolymerization, saving the research and development costs of different monomer copolymerization catalyst development and screening.
具体实施方式detailed description
实施例1Example 1
一种含硅共聚物纳米涂层制备方法，经过如下步骤：A method for preparing a silicon-containing copolymer nano-coating, through the following steps:
(1)将金属铜片放置于200L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到14毫托。(1) Place the metal copper sheet in the 200L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum of 14 mTorr.
(2)通入氩气，流量为20sccm，开启微波式等离子体放电对金属铜片进行预处理(即开启微波式的预处理用等离子体放电)，预处理阶段放电功率为500W，微波放电频率为500MHz，持续放电100s。(2) Introduce argon gas with a flow rate of 20 sccm. Turn on the microwave plasma discharge to pretreat the metal copper sheet (that is, turn on the microwave pretreatment plasma discharge). The discharge power in the pretreatment stage is 500 W, and the microwave discharge frequency 500MHz, continuous discharge for 100s.
(3)将共聚单体1a、共聚单体2a汽化后同时导入反应腔体，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中两种单体流量均为80μL/min，通入时间2000s，预处理用等离子体放电调整为沉积用等离子体放电。沉积阶段等离子体放电为间歇式微波放电，放电时每隔200μs关闭3ms。(3) The comonomer 1a and the comonomer 2a are vaporized and simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating. During the preparation of the coating, the flow rate of the two monomers was 80 μL / min, the lead-in time was 2000 s, and the plasma discharge for pretreatment was adjusted to the plasma discharge for deposition. During the deposition phase, the plasma discharge was intermittent microwave discharge, and the discharge was turned off every 200μs for 3ms.
(4)涂层制备结束后，通入氮气，使反应腔体恢复至常压，打开腔体，取出金属铜片。(4) After the preparation of the coating is completed, nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the metal copper sheet is taken out.
Figure PCTCN2019079112-appb-000003
Figure PCTCN2019079112-appb-000003
其中，生成预处理用等离子体放电的装置和生成涂层的沉积用等离子体放电的装置可以是一套，也可以为两套独立装置。预处理用等离子体放电装置(例如电极)优选地设置在反应腔体内，且围绕基材设置，从而便于预处理后快速与涂层工艺衔接；而涂层用沉积阶段等离子体放电装置可以布设在反应腔体之外且远离反应腔体设置，从而可选择地或尽可能地避免涂层过程中等离子体放电对基材的消极影响。Among them, the device for generating plasma discharge for pretreatment and the device for generating plasma discharge for coating deposition may be one set or two separate devices. The plasma discharge device (for example, electrode) for pretreatment is preferably arranged in the reaction chamber and around the substrate, so as to facilitate the quick connection with the coating process after pretreatment; and the plasma discharge device for the deposition stage of the coating can be arranged in It is arranged outside the reaction chamber and away from the reaction chamber, so as to selectively or as far as possible avoid the negative influence of the plasma discharge on the substrate during the coating process.
实施例2Example 2
一种含硅共聚物纳米涂层制备方法，经过如下步骤：A method for preparing a silicon-containing copolymer nano-coating, through the following steps:
(1)将聚乙烯板材放置于500L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到30毫托。(1) Place the polyethylene sheet in the 500L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum of 30 mTorr.
(2)通入氩气，流量为40sccm，开启微波等离子体放电对聚乙烯板材进行预处理(即开启微波方式的预处理用等离子体放电)，预处理阶段放电功率为300W，微波放电频率为1KMHz，持续放电50s。(2) Introduce argon gas with a flow rate of 40 sccm. Turn on the microwave plasma discharge to pretreat the polyethylene sheet (that is, turn on the microwave pretreatment plasma discharge). The discharge power in the pretreatment stage is 300W, and the microwave discharge frequency is 1KMHz, continuous discharge for 50s.
(3)将共聚单体1b、共聚单体2b汽化后同时导入反应腔体，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中两种单体流量均为200μL/min，通入时间2000s，预处理用等离子体放电调整为沉积用等离子体放电。沉积阶段放电为间歇式微波放电， 放电时每隔100μs关闭2ms。(3) After vaporizing comonomer 1b and comonomer 2b, they are simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating. During the preparation of the coating, the flow rate of the two monomers was 200 μL / min, and the passing time was 2000 s. The plasma discharge for pretreatment was adjusted to the plasma discharge for deposition. The discharge in the deposition stage was an intermittent microwave discharge, and the discharge was turned off every 100 μs for 2 ms.
(4)涂层制备结束后，通入氮气，使反应腔体恢复至常压，打开腔体，取出聚乙烯板材。(4) After the coating preparation is completed, nitrogen gas is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the polyethylene sheet is taken out.
Figure PCTCN2019079112-appb-000004
Figure PCTCN2019079112-appb-000004
实施例3Example 3
一种含硅共聚物纳米涂层制备方法，经过如下步骤：A method for preparing a silicon-containing copolymer nano-coating, through the following steps:
(1)将手机壳体放置于1000L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到50毫托。(1) Place the mobile phone case in a 1000L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum of 50 mTorr.
(2)通入氩气，流量为80sccm，开启微波等离子体放电对手机壳体进行预处理(即开启微波方式的预处理用等离子体放电)，预处理阶段放电功率为500W，微波放电频率为10KMHz，持续放电50s。(2) Introduce argon gas with a flow rate of 80sccm. Turn on the microwave plasma discharge to pretreat the mobile phone case (that is, turn on the microwave pretreatment plasma discharge). The discharge power in the pretreatment stage is 500W and the microwave discharge frequency is 10KMHz, continuous discharge for 50s.
(3)将共聚单体1c、共聚单体2c汽化后同时导入反应腔体，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中两种单体流量均为150μL/min，通入时间3000s，预处理用等离子体放电调整为沉积用等离子体放电。沉积阶段放电为间歇式微波放电，放电时每隔100μs关闭5ms。(3) The comonomer 1c and the comonomer 2c are vaporized and simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating. During the preparation of the coating, the flow rate of the two monomers was 150 μL / min, the lead-in time was 3000 s, and the plasma discharge for pretreatment was adjusted to the plasma discharge for deposition. The discharge in the deposition stage is intermittent microwave discharge, and the discharge is turned off every 100μs for 5ms.
(4)涂层制备结束后，通入压缩空气，使反应腔体恢复至常压，打开腔体，取出手机壳体。(4) After the preparation of the coating is completed, compressed air is introduced to restore the reaction chamber to normal pressure, the chamber is opened, and the mobile phone case is taken out.
Figure PCTCN2019079112-appb-000005
Figure PCTCN2019079112-appb-000005
实施例4Example 4
与实施例1相比，将共聚单体1a改为1d，共聚单体2a改为单体2d。Compared with Example 1, the comonomer 1a was changed to 1d, and the comonomer 2a was changed to monomer 2d.
Figure PCTCN2019079112-appb-000006
Figure PCTCN2019079112-appb-000006
实施例5Example 5
与实施例2相比，将单体1a改为单体1e，单体2a改为单体2e。Compared with Example 2, monomer 1a was changed to monomer 1e, and monomer 2a was changed to monomer 2e.
Figure PCTCN2019079112-appb-000007
Figure PCTCN2019079112-appb-000007
实施例6Example 6
与实施例1相比，将单体1a改为1a、1b的混合物，且两者的摩尔比为1:1，其他条件不变。Compared with Example 1, the monomer 1a is changed to a mixture of 1a and 1b, and the molar ratio of the two is 1: 1, and other conditions remain unchanged.
实施例7Example 7
与实施例1相比，将步骤(2)中的预处理阶段放电功率更换为600w，其他条件不改变。Compared with Example 1, the discharge power in the pretreatment stage in step (2) was changed to 600 W, and other conditions were not changed.
实施例8Example 8
与实施例2相比，将单体2b更换为单体2b、2c的混合物，且两者的摩尔比为1:2，其他条件不改变。Compared with Example 2, the monomer 2b was replaced with a mixture of monomers 2b and 2c, and the molar ratio of the two was 1: 2, and other conditions were not changed.
实施例9Example 9
与实施例1相比，将步骤(2)预处理阶段微波放电频率设置为50KMHz，其他条件不改变。Compared with Example 1, the microwave discharge frequency in the pretreatment stage of step (2) is set to 50 KMHz, and other conditions are not changed.
实施例10Example 10
与实施例1相比，将步骤(3)沉积阶段放电时间设置为4000s，其他条件不改变。Compared with Example 1, the discharge time in the deposition stage of step (3) was set to 4000s, and other conditions were not changed.
实施例11Example 11
与实施例1相比，共聚单体1a改为2b，其他条件不改变。Compared with Example 1, the comonomer 1a was changed to 2b, and other conditions were not changed.
实施例12Example 12
与实施例3相比，共聚单体1c改为1a、1c混合物(摩尔比为1：1)，共聚单体2c改为2a、2c混合物(摩尔比为1：1)Compared with Example 3, the comonomer 1c was changed to 1a and 1c mixture (molar ratio is 1: 1), and the comonomer 2c was changed to 2a and 2c mixture (molar ratio is 1: 1)
对比实施例1Comparative Example 1
与实施例1相比，步骤(3)不加入共聚单体2a，其他条件不改变。Compared with Example 1, step (3) does not add comonomer 2a, and other conditions are not changed.
对比实施例2Comparative Example 2
与实施例1相比，步骤(3)不加入单体共聚1a，其他条件不改变。Compared with Example 1, step (3) does not add monomer copolymerization 1a, and other conditions are not changed.
将上述各实施例施镀后的基材，进行涂层厚度、水接触角、铅笔硬度等级、耐磨性的测试。The substrates plated in the above examples were tested for coating thickness, water contact angle, pencil hardness level, and abrasion resistance.
纳米涂层厚度，使用美国FilmetricsF20-UV-薄膜厚度测量仪进行检测。The thickness of the nano-coating is tested using the US Filmetrics F20-UV-film thickness measuring instrument.
纳米涂层水接触角，根据GB/T 30447-2013标准进行测试。Nano-coating water contact angle is tested according to GB / T 30447-2013 standard.
铅笔硬度等级测试方法，根据ASTM D3363铅笔硬度进行测试。The pencil hardness test method is based on ASTM D3363 pencil hardness.
耐高低温测试，参考GB/T 2424.1-2005。测试方法为在-60℃下放置24h，恢复到室温后，2h内均匀升温至350℃，350℃下放置24h后，观察样品表面外观，并测定表面水滴角是否下降(±2°波动为误差范围)。For high and low temperature resistance test, refer to GB / T 2424.1-2005. The test method is to place it at -60 ℃ for 24h, and after returning to room temperature, evenly heat up to 350 ℃ within 2h. After placing at 350 ℃ for 24h, observe the appearance of the sample surface and determine whether the surface water drop angle drops (± 2 ° fluctuation is the error range).
耐磨性测试，在酒精耐磨试验机进行，选择橡皮擦测试夹具进行测试，测试条件为载荷100g，转速60cycle/min，测定循环次数涂层未磨损。The abrasion resistance test was conducted in an alcohol abrasion tester. The eraser test fixture was selected for the test. The test conditions were a load of 100g, a rotation speed of 60cycle / min, and the number of cycles was measured. The coating was not worn.
表1Table 1
Figure PCTCN2019079112-appb-000008
Figure PCTCN2019079112-appb-000008
从上述表格中的数据来看，采用本申请方法将低表面能树脂的单体与含硅有机单体共聚制备出的涂层均能达到1H铅笔硬度等级，耐摩性优异；在-60℃-350℃温度范围内使用，涂层的外观仍无影响，涂层的接触角几乎没有变化。此外，当低表面能树脂的单体与含硅有机单体混合共聚之后，相比于单类单体，体现出了纳米涂层的沉积速度提高(同样时间膜厚增加)、铅笔硬度等级提升等效果。From the data in the above table, the coating prepared by copolymerizing the monomer of the low surface energy resin and the silicon-containing organic monomer by the method of the present application can reach the pencil hardness level of 1H and has excellent abrasion resistance; at -60 ℃- Used in the temperature range of 350 ℃, the appearance of the coating is still not affected, and the contact angle of the coating is almost unchanged. In addition, when the monomer of the low surface energy resin is mixed and copolymerized with the silicon-containing organic monomer, compared with the single type of monomer, it shows the increase of the deposition speed of the nano coating (the film thickness increases at the same time) and the pencil hardness level. Other effects.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than limiting it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or replacements do not deviate from the essence of the corresponding technical solutions of the technical solutions of the embodiments of the invention range.

Claims (20)

  1. 一种含硅共聚物纳米涂层，其特征在于，将基材暴露于共聚单体蒸汽氛围中，通过等离子体放电在基材表面引发共聚发生化学气相沉积反应而形成保护涂层；A silicon-containing copolymer nano-coating, characterized in that the substrate is exposed to a comonomer vapor atmosphere, and a chemical vapor deposition reaction is initiated on the surface of the substrate by plasma discharge to form a protective coating;
    所述共聚单体蒸汽为汽化的下述共聚单体1中的一种或多种物质和下述共聚单体2中的一种或多种，或者共聚单体2的混合物；The comonomer vapor is vaporized one or more substances in the following comonomer 1 and one or more in the following comonomer 2, or a mixture of comonomer 2;
    所述共聚单体1具有如下式(I)、(II)或(III)所示结构：The comonomer 1 has the structure represented by the following formula (I), (II) or (III):
    共聚单体1：Comonomer 1:
    Figure PCTCN2019079112-appb-100001
    Figure PCTCN2019079112-appb-100001
    R 1、R 2、R 3、R 4、R 5、R 6、R 7为独立地选自氢、烷基、芳基、卤素或卤代烷基，X为氢或卤素； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, alkyl, aryl, halogen or haloalkyl, and X is hydrogen or halogen;
    共聚单体2具有如下式(IV)，或者共聚单体2为硅氧烷和/或其衍生物；Comonomer 2 has the following formula (IV), or comonomer 2 is siloxane and / or its derivatives;
    Figure PCTCN2019079112-appb-100002
    Figure PCTCN2019079112-appb-100002
    R 8、R 9、R 10、R 11、R 12、R 13独立地选自氢、烷基、芳基、卤代芳基、卤素、卤代烷基、烷氧基或乙烯基，m、n为0-20的整数，k为0-8的整数。 R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen, alkyl, aryl, halogenated aryl, halogen, halogenated alkyl, alkoxy or vinyl, m, n are An integer of 0-20, k is an integer of 0-8.
  2. 根据权利要求1所述的含硅共聚物纳米涂层，其特征在于，R 1、R 2、 R 3、R 4、R 5、R 6、R 7独立地选自氢、烷基或卤素。 The silicon-containing copolymer nanocoating according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from hydrogen, alkyl, or halogen.
  3. 根据权利要求1所述的含硅共聚物纳米涂层，其特征在于，R 11、R 12、R 13独立地选自氢、烷基、卤素或烷氧基。 Silicon-containing copolymer according to claim 1 of the nano-coating, wherein, R 11, R 12, R 13 are independently selected from hydrogen, alkyl, halogen or alkoxy.
  4. 根据权利要求2所述的含硅共聚物纳米涂层，其特征在于，卤素为氟。The silicon-containing copolymer nano-coating according to claim 2, wherein the halogen is fluorine.
  5. 根据权利要求3所述的含硅共聚物纳米涂层，其特征在于，卤素为氯。The silicon-containing copolymer nano-coating according to claim 3, wherein the halogen is chlorine.
  6. 根据权利要求1所述的含硅共聚物纳米涂层，其特征在于，硅氧烷分子结构为环状或交联结构。The silicon-containing copolymer nano-coating according to claim 1, wherein the molecular structure of the siloxane is cyclic or cross-linked.
  7. 根据权利要求6所述的含硅共聚物纳米涂层，其特征在于，环状硅氧烷为六甲基环三硅氧烷、八甲基环四硅氧烷和/或十甲基环五硅氧烷。The silicon-containing copolymer nano-coating according to claim 6, wherein the cyclic siloxane is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopenta Siloxane.
  8. 根据权利要求1所述的含硅共聚物纳米涂层，其特征在于，共聚单体1为选自具有结构式(I)、式(II)、式(III)中的一种或者为任意两种的混合物或者为三种的混合物。The silicon-containing copolymer nano-coating according to claim 1, wherein the comonomer 1 is one selected from the group consisting of structural formula (I), formula (II), and formula (III) or any two Or a mixture of three.
  9. 根据权利要求1所述的含硅共聚物纳米涂层，其特征在于，m、n为2-10的整数。The silicon-containing copolymer nano-coating according to claim 1, wherein m and n are integers of 2-10.
  10. 根据权利要求1所述的一种含硅共聚物纳米涂层，其特征在于，基材为金属、光学仪器、衣服织物、电子器件或医疗器械。The silicon-containing copolymer nano-coating according to claim 1, wherein the substrate is metal, optical instrument, clothing fabric, electronic device or medical device.
  11. 一种权利要求1-10任一项所述含硅共聚物纳米涂层的制备方法，其特征在于，包括以下步骤：A method for preparing a silicon-containing copolymer nano-coating according to any one of claims 1-10, comprising the following steps:
    (1)将基材置于等离子体室的反应腔体内，将反应腔体内的真空度抽到0.01-1000毫托；(1) Place the substrate in the reaction chamber of the plasma chamber, and pump the vacuum in the reaction chamber to 0.01-1000 mtorr;
    (2)通入等离子体源气体，开启沉积用等离子体放电，将共聚单体1、共聚单体2经汽化后同时导入反应腔体进行化学气相沉积反应；(2) Into the plasma source gas, start the plasma discharge for deposition, the comonomer 1, comonomer 2 after vaporization into the reaction chamber at the same time for chemical vapor deposition reaction;
    (3)关闭沉积用等离子体放电，通入洁净的压缩空气或者惰性气体恢复至常压，打开腔体，取出基材。(3) Turn off the plasma discharge for deposition, pass clean compressed air or inert gas to return to normal pressure, open the cavity, and take out the substrate.
  12. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，共聚单体1与共聚单体2通入摩尔量的比例为1：1000-1000：1。The method for preparing a silicon-containing copolymer nanocoating according to claim 11, wherein the ratio of the molar amount of comonomer 1 to comonomer 2 is 1: 1000-1000: 1.
  13. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，步骤(2)所述的等离子体源气体可以是氦气、氩气、氮气、氢气中的一种或者若干种的混合物。The method for preparing a silicon-containing copolymer nano-coating according to claim 11, wherein the plasma source gas in step (2) may be one or more of helium, argon, nitrogen, and hydrogen mixture.
  14. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，等离子体室的容积为1L-5000L，等离子体源气体流量为5-1000sccm，通入单体蒸汽的流量为1-2000μL/min。The method for preparing a silicon-containing copolymer nano-coating according to claim 11, wherein the volume of the plasma chamber is 1L-5000L, the flow rate of the plasma source gas is 5-1000sccm, and the flow rate of the monomer vapor is 1 -2000μL / min.
  15. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，所述步骤(2)中，在通入所述等离子体源气体后以及在所述沉积用等离子体放电之前，还包括对基材进行预处理用等离子体放电工序。The method for preparing a silicon-containing copolymer nano-coating according to claim 11, wherein in the step (2), after passing the plasma source gas and before the plasma discharge for deposition, It also includes a plasma discharge process for pretreatment of the substrate.
  16. 根据权利要求15所述含硅共聚物纳米涂层的制备方法，其特征在于，所述预处理用等离子体放电的功率为1-900W，持续放电时间为1-5400s。The method for preparing a silicon-containing copolymer nano-coating according to claim 15, wherein the power of the plasma discharge for pretreatment is 1-900W, and the continuous discharge time is 1-5400s.
  17. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，所述步骤(2)中，所述沉积用等离子体放电的功率为2-500W，持续放电时间为600-20000s。The method for preparing a silicon-containing copolymer nano-coating according to claim 11, wherein in the step (2), the power of the plasma discharge for deposition is 2-500W, and the continuous discharge time is 600-20000s .
  18. 根据权利要求11或15所述含硅共聚物纳米涂层的制备方法，其特征在于，所述等离子体放电方式为射频放电、微波放电、中频放电、潘宁放电或电火花放电。The method for preparing a silicon-containing copolymer nano-coating according to claim 11 or 15, wherein the plasma discharge method is radio frequency discharge, microwave discharge, intermediate frequency discharge, penning discharge or electric spark discharge.
  19. 根据权利要求11所述含硅共聚物纳米涂层的制备方法，其特征在于，所述步骤(2)中，所述沉积用等离子体放电方式为微波放电。The method for preparing a silicon-containing copolymer nano-coating according to claim 11, wherein in the step (2), the plasma discharge method for deposition is microwave discharge.
  20. 根据权利要求19所述含硅共聚物纳米涂层的制备方法，其特征在于，所述微波放电的频率为500MHz-200KMHz。The method for preparing a silicon-containing copolymer nano-coating according to claim 19, wherein the frequency of the microwave discharge is 500MHz-200KMHz.
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