WO2020082675A1 - 一种高粘附性耐老化纳米涂层及其制备方法 - Google Patents

一种高粘附性耐老化纳米涂层及其制备方法 Download PDF

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WO2020082675A1
WO2020082675A1 PCT/CN2019/079109 CN2019079109W WO2020082675A1 WO 2020082675 A1 WO2020082675 A1 WO 2020082675A1 CN 2019079109 W CN2019079109 W CN 2019079109W WO 2020082675 A1 WO2020082675 A1 WO 2020082675A1
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monomer
nano
reaction chamber
discharge
plasma
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PCT/CN2019/079109
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French (fr)
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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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    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/58—Polymerisation initiated by direct application of electric current
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen

Definitions

  • the invention relates to the technical field of plasma chemical vapor deposition, in particular to a high-adhesion aging-resistant nano protective coating and a preparation method thereof.
  • Fluorine-containing olefin polymers have excellent chemical stability, electrical insulation, self-lubricity, non-combustibility, aging resistance, UV resistance, etc., and are widely used in military and daily life.
  • PTFE is one of the best corrosion-resistant materials in the world today, and it is known as the "plastic king".
  • Teflon products such as Teflon seals, gaskets, and gaskets have played an important role in the national economic fields such as chemical, machinery, electronics, electrical appliances, military, aerospace, environmental protection, and bridges.
  • the surface energy of commonly used fluorocarbon materials is generally very low, resulting in poor wetting properties between the materials, which cannot be well bonded to the substrate chemically.
  • the adsorption on the surface of the substrate mainly depends on the van der Waals force between the molecules. Moreover, due to the highly symmetrical structure of the fluorocarbon material and low molecular structure polarity, the van der Waals force cannot form a strong orientation force and an inducing force, but only forms a weak dispersion force, so that the coating is easily peeled off from the surface of the substrate.
  • the current solution is mainly to modify the surface and synthesize new adhesives, surface modification methods such as chemical treatment, high temperature melting, radiation grafting, etc .; the synthesis of new adhesives such as the development of new epoxy resin adhesives, fluorine-containing polymerization Adhesives, etc.
  • the former often requires the use of special energy-intensive special processes; the latter is more difficult to develop new adhesives, and the use of the adhesive also often brings a significant cost increase to the enterprise.
  • these two methods are not suitable for the process of preparing nano-scale coatings by plasma vapor deposition.
  • the plasma vapor deposition method generally needs to perform surface cleaning and plasma etching treatment on the substrate in advance, and then directly deposit the fluorocarbon material on the surface of the substrate to form a nanometer-thick coating.
  • the object of the present invention is to provide a high-adhesion aging-resistant nano-coating and a preparation method thereof to solve the problems of poor adhesion between the coating and the surface of the substrate and being easily peeled off.
  • a high-adhesion aging-resistant nano-coating which exposes the substrate to the atmosphere of monomer vapor, and forms a protective coating by plasma discharge on the surface of the substrate through chemical reaction;
  • the monomer vapor is vaporized monomer 1 and / or monomer 2 and / or monomer 3; that is, the monomer vapor includes one of vaporized monomer 1, monomer 2 and monomer 3 Species or several species, the "several species" refers to any two kinds of monomers or three kinds of monomers; several kinds of gases can be passed separately or simultaneously, or any two kinds of monomers can be passed first, and then Access to the third monomer;
  • the monomer 1 has the structure represented by formula (I):
  • the monomer 2 has a structure represented by formula (II):
  • the monomer 3 has a structure represented by formula (III):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 are the groups connected to the double bond, which can be It is independently selected from hydrophobic groups such as hydrogen, alkyl, aryl, halogen, haloalkyl or haloaryl.
  • n is an integer of 1-20
  • j and k are integers of 0-10 and cannot be 0 at the same time.
  • R 14 is a bridging group in the middle of divinyl ether, including polar groups and non-polar groups, specifically, it can be a bond, -CO-, -COO-, -O-, arylene, Alicycloalkyl subunit or hydroxy substituted fatty alkyl subunit.
  • the deposition rate of the film can be increased; the presence of fluorine substituents can improve the hydrophobic performance of the film.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 are independently selected from hydrogen, methyl or fluorine.
  • a suitable number of fluorinated alkyl carbon atoms can ensure that the melting point and boiling point of the monomer are within an appropriate range, and the monomer is easily vaporized into the vacuum reaction chamber.
  • n is an integer of 1-8.
  • j and k are integers of 1-4, respectively.
  • R 14 may be a bond, an alicyclic alkylene subunit or a hydroxyl substituted fatty alkyl subunit .
  • the monomer 1 is a liquid at normal temperature and pressure; and / or the monomer 3 is a liquid at normal temperature and pressure.
  • monomer 2 is a short carbon chain fluorinated olefin, which is a gas at normal temperature and pressure.
  • the coating protects the surfaces of different substrates against aging and hydrophobicity.
  • the substrates may be solid materials such as metals, optical instruments, clothing fabrics, electronic devices, and medical devices.
  • the present invention also discloses a method for preparing the above nano-coating, including the following steps:
  • the plasma source gas is introduced to start the plasma discharge for deposition; the monomer vapor is introduced into the reaction chamber for chemical vapor deposition;
  • the monomer vapor includes monomer 1, monomer 2 and monomer 3;
  • any two of the monomer 1, the monomer 2 and the monomer 3 are simultaneously passed into the reaction chamber, and then the third monomer of the monomer 1, the monomer 2 and the monomer 3 are passed Into the reaction chamber.
  • the steams of monomer 1, monomer 2, and monomer 3 can be passed separately, or simultaneously, or any two monomers can be passed first, and then the third monomer, because monomer 2 It is a gas, which can also pass directly into the reaction chamber.
  • the monomer vapor includes at least monomer 1; the mole percentage of monomer 1 in the total flux of the monomer vapor is not less than 20%.
  • the monomer vapor introduced contains monomer 1, monomer 1 accounts for not less than 20% of the total monomer vapor flux, and monomer 2 and monomer 3 may not be introduced.
  • the volume of the reaction chamber of the plasma chamber is 50-1000L.
  • the temperature of the reaction chamber of the plasma chamber is controlled at 30-60 ° C; the flow rate of the plasma source gas is 5-300 sccm.
  • the monomer vapor is introduced into the reaction chamber at 0.1-1000 mTorr, and the flow rate of the monomer vapor is 10-1000 ⁇ L / min;
  • a plasma discharge step for pretreatment of the substrate is further included.
  • step (2) after the plasma source gas is introduced, the substrate is subjected to plasma discharge pretreatment. After the pretreatment phase ends, it enters the deposition phase (the plasma discharge for pretreatment is converted to plasma discharge for deposition). At this time, the plasma discharge mode or parameters may or may not be changed.
  • 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 is electric spark discharge; plasma discharge frequency is 20Hz-20KHz, pulse width is 5 ⁇ s-50ms, discharge time is 100s- 20000s.
  • the present invention combines the performance of different monomers to construct the structure of the coating.
  • the use of monomers containing multiple ether oxygen in the main chain, the bond between ether oxygen and the substrate is generally strong, which improves the adhesion of the coating;
  • the use of fluorine-containing olefin monomer polymer anti-UV properties improves the coating
  • the use of a strong hydrophobic coating formed with fluoroalkyl monomers greatly improves the waterproof performance of the composite coating.
  • the coating prepared by the method of the present application does not compromise on various properties, and obtains a technical effect that takes into account many excellent properties.
  • the monomer 3a is introduced first, and then the monomer 2a is introduced, and finally the monomer 1a is introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the three monomers in the preparation process of the coating is 150 ⁇ L / min, the lead-in time is 500 s, 200 s and 300 s, respectively.
  • the plasma discharge for pretreatment is converted to the plasma discharge for deposition.
  • the discharge time of the electrical discharge in this deposition stage is 1000 s .
  • the device for plasma discharge for pretreatment and the device for plasma discharge for 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 base material, so as to facilitate the quick connection with the coating process after pretreatment;
  • the plasma discharge device for deposition can be arranged in the reaction chamber It is placed outside and away from the reaction chamber, so that the negative impact of plasma discharge on the substrate during the coating process can be selectively or as far as possible avoided.
  • the monomer 3b is introduced first, and then the monomer 2b is introduced, and finally the monomer 1a is introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the three monomers in the coating preparation process is 150 ⁇ L / min, the passing time is 500 s, 500 s and 500 s, respectively.
  • the plasma discharge for pretreatment is converted to the plasma discharge for deposition, and the discharge time in this deposition stage is 1500 s.
  • the magnesium alloy is placed in a 2000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum of 100 mtorr.
  • start EDM plasma discharge for pretreatment that is, start EDM-type plasma discharge for pretreatment
  • the discharge frequency in the pretreatment stage is 50 kHz
  • the pulse width is 50 ⁇ s
  • the discharge time For 100s.
  • the monomer 3c is introduced first, and after the end, the monomer 2c and the monomer 1c are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the three monomers in the coating preparation process is 200 ⁇ L / min
  • the lead-in time is 1500 s and 2500 s (2c and 1c), respectively
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the discharge time of this deposition stage is 4000s.
  • start EDM plasma discharge for pretreatment that is, start EDM-type plasma discharge for pretreatment
  • the discharge frequency in the pretreatment phase is 2000 Hz
  • pulse width is 80 ⁇ s
  • discharge time 200s is 200 Hz.
  • the monomer 3d is introduced first, then the monomer 2d is introduced, and finally the monomer 1d is introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the three monomers in the coating preparation process is 200 ⁇ L / min, the passing time is 500 s, 500 s and 800 s, respectively.
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the discharge time in the deposition stage is 1800s.
  • start EDM plasma discharge for pretreatment that is, start EDM pretreatment plasma discharge
  • the discharge frequency in the pretreatment stage is 50kHz
  • the pulse width is 80 ⁇ s
  • the discharge time 200s is 200s.
  • the monomer 3e is introduced first, and after the end, the monomer 2e and the monomer 1e are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the flow rate of the three monomers during the preparation of the coating is 250 ⁇ L / min, and the inflow time is 2500 s and 2500 s, respectively.
  • the plasma discharge for pretreatment is adjusted to the plasma discharge for deposition.
  • the discharge time in the deposition stage is 5000s.
  • step (3) the three monomers are replaced with 1000s, 800s, and 900s, and the discharge time is correspondingly replaced with 2700s, and other conditions remain unchanged.
  • reaction chamber in step (1) was continuously evacuated to a vacuum of 10 mtorr, and other conditions remained unchanged.
  • Example 7 Compared with Example 7, the discharge frequency of the spark plasma in step (2) was changed to 1000 Hz, and other conditions remained unchanged.
  • step (3) monomer 1a is not passed, and other conditions remain unchanged.
  • the monomers 2a and 3a are not introduced, the monomer 1a introduction time is 2700s, the discharge time is also 2700s, and other conditions remain unchanged.
  • Example 7 Compared with Example 7, in the step (3), the monomers 1a and 3a are not fed, the monomer 2a is introduced for 2700s, the discharge time is also 2700s, and other conditions remain unchanged.
  • the monomers 1a and 2a are not introduced, the monomer 3a introduction time is 2700s, the discharge time is also 2700s, and other conditions remain unchanged.
  • step (3) the monomer 3c is not fed, the monomer 2c and 1c are simultaneously fed for 4000 s, the discharge time is also 4000 s, and other conditions remain unchanged.
  • the substrate after plating in the above embodiments is subjected to coating thickness, water contact angle, xenon lamp aging test, ultraviolet aging test, and adhesion test.
  • the thickness of the nano-coating is tested using the Filmetrics F20-UV-thickness film thickness measuring instrument.
  • Nano-coating water contact angle is tested according to GB / T 30447-2013 standard.
  • Xenon lamp aging test is tested according to GB / T 16422.2-2014 standard.
  • the ultraviolet aging test is tested according to GB / T16422.3-2014 standard.
  • Adhesion test method according to GB / T 9286-1998 standard for 100 grid knife scratch test.
  • a nano-coating with multiple protective properties can be obtained.
  • the coatings of different functions are mainly superimposed to make the thickness more than tens of hundreds of microns, which often leads to the signal transmission, electrical conductivity and thermal conductivity of some electronic devices becoming very difference.
  • nano-coatings have almost no effect on the above properties due to their thickness at the nanoscale. Using plasma to deposit coating materials with different functions at the same time solves the disadvantage of poor adhesion between coatings.

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Abstract

一种高粘附性耐老化纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层，单体蒸汽为汽化的单体1、和/或单体2和/或单体3，单体1、2和3分别如式(I)、式(II)、式(III)所示。涂层的制备方法为将基材置于等离子体室的反应腔体内，通入等离子体源气体，开启沉积用等离子体放电，将单体蒸汽通入反应腔体内，进行化学气相沉积，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，打开反应腔体，取出基材。

Description

一种高粘附性耐老化纳米涂层及其制备方法 技术领域
本发明涉及等离子体化学气相沉积技术领域，具体涉及到一种高粘附性耐老化纳米防护涂层及其制备方法。
背景技术
含氟烯烃的聚合物，具有优异的化学稳定性、电绝缘性、自润滑性、不燃性、耐老化性、抗紫外等，广泛应用于军事和日常生活中。如聚四氟乙烯是当今世界上耐腐蚀最佳材料之一，有“塑料王”之称。聚四氟乙烯密封件、垫圈、垫片等聚四氟乙烯制品已在化工、机械、电子、电器、军工、航天、环保和桥梁等国民经济领域中起到了举足轻重的作用。但常用的氟碳材料表面能一般很低，导致材料间润湿性能差，不能很好地与基材化学键粘接，吸附在基材表面主要靠分子间的范德华力起作用。且该范德华力由于氟碳材料结构高度对称，分子结构极性低，不能形成较强的取向力和诱导力，仅仅形成较弱的色散力，使涂层容易从基材表面被剥离出来。目前解决的办法主要是对表面进行改性和合成新型胶粘剂，表面改性方法如化学处理、高温熔融、辐射接枝等；新型胶粘剂的合成如开发新型的环氧树脂粘接剂、含氟聚合物粘接剂等。前者往往需要采用耗能严重的特殊工序；后者新型胶粘剂的研发比较困难，且使用该胶粘剂往往也给企业带来成本的大幅上升。另外，这两种方法不适合 于利用等离子体气相沉积制备纳米级涂层的工艺。等离子体气相沉积方法一般需预先对基材进行表面清洗和等离子体刻蚀处理，然后再将氟碳材料直接沉积在基材表面形成纳米级厚度的涂层。如何通过分子结构的调控和不同功能涂层之间复合，达到既保持含氟烯烃聚合物的化学惰性、抗紫外等防护能力，又保证涂层与基材之间足够的结合力，是目前等离子体纳米涂层研究的重要方向之一。
发明内容
本发明的目的在于提供一种高粘附性耐老化纳米涂层及其制备方法，解决涂层与基材表面粘接性差、容易被剥离的问题。
本发明是通过以下技术方案实现的：
一种高粘附性耐老化纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层；
所述单体蒸汽为汽化的单体1和/或单体2和/或单体3；也就是说，所述单体蒸汽包括汽化的单体1、单体2和单体3中的一种或者若干种，所述“若干种”是指任两种单体或者三种单体；若干种气体可以先后分别通入，也可以同时通入，或者先通入任两种单体，再通入第三种单体；
所述单体1具有式(I)所示结构：
Figure PCTCN2019079109-appb-000001
所述单体2具有式(II)所示结构：
Figure PCTCN2019079109-appb-000002
所述单体3具有式(III)所示的结构：
Figure PCTCN2019079109-appb-000003
其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13是与双键相连的基团，可独立地选自氢、烷基、芳基、卤素、卤代烷基或卤代芳基等疏水性基团。
m为0-5的整数，n为1-20的整数，j、k分别为0-10的整数且不能同时为0。
R 14是双乙烯基醚中间的桥联基团，包括是极性基团和非极性基团，具体地，可以是键、-CO-、-COO-、-O-、芳亚基、脂环烷亚基或羟基取代的脂肪烷基亚基。
不饱和键上的基团为H、短碳链烷基时，可以提高膜层的沉积速度；氟取代基的存在则可以提高膜层的疏水性能。
优选地，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13独立地选自氢、甲基或氟。
合适的氟化烷基碳原子数可以保证单体的熔点、沸点在适当的范围内，单体容易被汽化引入真空反应腔体。
优选地，m为0-2的整数，n为1-8的整数。j、k分别为1-4的整数。
环状结构利于降低聚合物的结晶度，含有羟基基团利于提高涂层与基材的粘接性，优选地，R 14可以是键、脂环烷亚基或羟基取代的脂肪烷基亚基。
优选地，单体1在常温常压下是一种液体；和/或，单体3在常 温常压下是一种液体。
优选地，单体2是一种短碳链氟化烯烃，在常温常压下是一种气体。
所述涂层对不同基材的表面进行耐老化疏水进行防护，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。
另外，本发明还公开了一种上述纳米涂层的制备方法，包括以下步骤：
(1)将基材置于等离子体室的反应腔体内，反应腔体内的真空度为0.1-1000毫托；
(2)通入等离子体源气体，开启沉积用等离子体放电；将单体蒸汽通入反应腔体内，进行化学气相沉积；
(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，打开反应腔体，取出基材。
优选地，所述单体蒸汽包括单体1、单体2和单体3；
所述单体1、单体2和单体3的蒸汽分别先后通入反应腔体；
或者，所述单体1、单体2和单体3的蒸汽同时通入反应腔体；
或者，先将所述单体1、单体2和单体3中的任意两种同时通入反应腔体，再所述单体1、单体2和单体3中第三种单体通入反应腔体。
即，单体1、单体2、单体3的蒸汽可以先后分别通入，也可以同时通入，或者先通入任两种单体，再通入第三种单体，由于单体2是气体，其也可以直接通入反应腔体中。
优选地，所述单体蒸汽至少包括单体1；单体1占所述单体蒸汽的总通入量的摩尔百分数不低于20％。当通入的单体蒸汽中包含单体1时，单体1占单体蒸汽的总通入量摩尔百分数不低于20％，单体2、单体3可以不通入。
优选地，等离子体室反应腔体的容积为50-1000L。
优选地，步骤(2)中，等离子体室反应腔室的温度控制在30-60℃；等离子体源气体的流量为5-300sccm。
优选地，步骤(3)中，单体蒸汽在0.1-1000毫托引入反应腔体，所述通入单体蒸汽的流量为10-1000μL/min；
优选地，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。
步骤(2)中，通入所述等离子体源气体后对基材进行等离子体放电预处理。预处理阶段结束后进入沉积阶段(预处理用等离子体放电转换为沉积用等离子体放电)，此时等离子体放电方式或参数可以改变也可以不改变。
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)方式为射频放电、微波放电、中频放电、潘宁放电或电火花放电。
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)为电火花放电；等离子体放电频率为20Hz-20KHz，脉宽为5μs-50ms，放电时间为100s-20000s。
相比于现有技术，本发明结合不同单体的性能，对涂层的结构进行了构造。使用主链含有多个醚氧健的单体，醚氧健一般与基材的结合力较强，提高了涂层的附着力；利用含氟烯烃单体聚合物的抗紫外特性，提高了涂层抗紫外老化的能力；利用具有氟烷基单体形成的强疏水涂层，使复合涂层的防水性能大大提高。而且，采用本申请的方法制备的涂层，各种性能之间没有顾此失彼，获得了兼 顾多项性能优良的技术效果。
具体实施方式
实施例1
本发明中高粘附性耐老化纳米涂层的制备方法中，经过如下步骤：
(1)将电子器件的PCB板放置于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30毫托。
(2)通入氮气，流量为20sccm，开启电火花等离子体放电对PCB板进行预处理(即开启电火花式的预处理用等离子体放电)，预处理阶段放电频率在500Hz，脉宽200μs，放电时间为100s。
(3)先通入单体3a，结束后，再通入单体2a，最后通入单体1a，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种单体流量均为150μL/min，通入时间分别为500s、200s和300s，预处理用等离子体放电转换为沉积用等离子体放电，该沉积阶段电火花放电时间为1000s。
(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，取出电子器件的PCB板。
Figure PCTCN2019079109-appb-000004
Figure PCTCN2019079109-appb-000005
其中，预处理用等离子体放电的装置和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；沉积用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。
实施例2
本发明中高粘附性耐老化纳米涂层的制备方法中，经过如下步骤：
(1)将汽车后视镜片放置于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5毫托。
(2)通入氩气，流量为50sccm，开启电火花等离子体放电进行预处理(即开启电火花方式的预处理用等离子体放电)，预处理阶段放电频率在1000Hz，脉宽20μs，放电时间为100s。
(3)先通入单体3b，结束后，再通入单体2b，最后通入单体1a，在基材表面进行化学气相沉积制备纳米涂层，。涂层制备过程中三种单体流量均为150μL/min，通入时间分别为500s、500s和500s，预处理用等离子体放电转换为沉积用等离子体放电，该沉积阶段放电时间为1500s。
(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，取出汽车后视镜片。
Figure PCTCN2019079109-appb-000006
实施例3
本发明中高粘附性耐老化纳米涂层的制备方法中，经过如下步骤：
(1)将镁合金放置于2000L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100毫托。
(2)通入氩气，流量为10sccm，开启电火花等离子体放电进行预处理(即开启电火花式的预处理用等离子体放电)，预处理阶段放电频率在50kHz，脉宽50μs，放电时间为100s。
(3)先通入单体3c，结束后，再同时通入单体2c和单体1c，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种单体流量均为200μL/min，通入时间分别为1500s、2500s(2c和1c)，预处理用等离子体放电调整为沉积用等离子体放电。该沉积阶段放电时间为4000s。
(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，取出镁合金。
Figure PCTCN2019079109-appb-000007
实施例4
本发明中高粘附性耐老化纳米涂层的制备方法中，经过如下步骤：
(1)将汽车后视镜片放置于1800L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。
(2)通入氩气，流量为40sccm，开启电火花等离子体放电进行预处理(即开启电火花式的预处理用等离子体放电)，预处理阶段放电频率在2000Hz，脉宽80μs，放电时间为200s。
(3)先通入单体3d，结束后，再通入单体2d，最后通入单体1d，在基材表面进行化学气相沉积制备纳米涂层，。涂层制备过程中三种单体流量均为200μL/min，通入时间分别为500s、500s和800s，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 段放电时间为1800s。
(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，取出汽车后视镜片。
Figure PCTCN2019079109-appb-000008
实施例5
本发明中高粘附性耐老化纳米涂层的制备方法中，经过如下步骤：
(1)将保温杯放置于3500L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200毫托。
(2)通入氩气，流量为10sccm，开启电火花等离子体放电进行预处理(即开启电火花式的预处理用等离子体放电)，预处理阶段放电频率在50kHz，脉宽80μs，放电时间为200s。
(3)先通入单体3e，结束后，再同时通入单体2e和单体1e，在基材表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种 单体流量均为250μL/min，通入时间分别为2500s、2500s，预处理用等离子体放电调整为沉积用等离子体放电。沉积阶段放电时间为5000s。
(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，取出保温杯。
Figure PCTCN2019079109-appb-000009
实施例6
与实施例1相比，将步骤(3)三种单体流量均更换为200μL/min,其他条件不变。
实施例7
与实施例1相比，将步骤(3)中，三种单体通入时间分别更换为1000s、800s、900s，放电时间相应的更换为2700s，其他条件不变。
实施例8
与实施例7相比，将步骤(1)中反应腔体连续抽真空使真空度达到10毫托，其他条件不变。
实施例9
与实施例7相比，将步骤(2)中电火花等离子体放电频率更换为1000Hz，其他条件不变。
实施例10
与实施例7相比，在步骤(3)中，不通入单体1a，其他条件不变。
实施例11
与实施例7相比，在步骤(3)中，不通入单体2a、3a，单体1a通入时间为2700s，放电时间也为2700s，其他条件不变。
实施例12
与实施例7相比，在步骤(3)中，不通入单体1a、3a，单体2a通入时间为2700s，放电时间也为2700s，其他条件不变。
实施例13
与实施例7相比，在步骤(3)中，不通入单体1a、2a，单体3a通入时间为2700s，放电时间也为2700s，其他条件不变。
实施例14
与实施例3相比，在步骤(3)中，不通入单体3c，单体2c、1c同时通入时间为4000s，放电时间也为4000s，其他条件不变。
上述各实施例施镀后的基材，进行涂层厚度、水接触角、氙灯老化试验、紫外老化试验、附着力测试。
纳米涂层厚度，使用美国Filmetrics F20-UV-薄膜厚度测量仪进行检测。
纳米涂层水接触角，根据GB/T 30447-2013标准进行测试。
氙灯老化试验，根据GB/T 16422.2-2014标准进行测试。
紫外老化试验，根据GB/T 16422.3-2014标准进行测试。
附着力测试方法，根据GB/T 9286-1998标准进行百格刀划格试验。
表1
Figure PCTCN2019079109-appb-000010
采用本发明的技术，可获得具有多重防护性能的纳米涂层。常规技术手段为了获得多重功能涂层，主要通过将不同功能的涂层进行叠加，使厚度达几十上百微米以上，这往往会导致一些电子器件的信号传输、导电性、导热性变得很差。与此相比，纳米涂层由于其厚度处于纳米尺度，对上述性能几乎不产生任何影响。利用等离子体将不同功能的涂层材料同时沉积，解决了涂层之间的粘附性差的缺点。
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。

Claims (14)

  1. 一种高粘附性耐老化纳米涂层，将基材暴露于单体蒸汽氛围中，通过等离子体放电在基材表面发生化学反应形成保护涂层；
    所述单体蒸汽为汽化的单体1、和/或单体2、和/或单体3；
    所述单体1具有式(I)所示结构：
    Figure PCTCN2019079109-appb-100001
    所述单体2具有式(II)所示结构：
    Figure PCTCN2019079109-appb-100002
    所述单体3具有式(III)所示的结构：
    Figure PCTCN2019079109-appb-100003
    其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13独立地选自氢、烷基、芳基、卤素、卤代烷基或卤代芳基；
    m为0-5的整数，n为1-20的整数，j、k分别为0-10的整数且不能同时为0；
    R 14是键、-CO-、-COO-、芳亚基、脂环烷亚基或羟基取代的脂肪烷基亚基。
  2. 根据权利要求1所述的纳米涂层，其特征在于，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12、R 13独立地选自氢、甲基或氟。
  3. 根据权利要求1所述的纳米涂层，其特征在于，m为0-2的整数，n为1-8的整数，j、k分别为1-4的整数。
  4. 根据权利要求1所述的一种纳米涂层制备方法，其特征在于，所述R 14是键、脂环烷亚基或羟基取代的脂肪烷基亚基。
  5. 根据权利要求1所述的纳米涂层制备方法，其特征在于，所述单体1在常温常压下是一种液体和/或单体3在常温常压下是一种液体，和/或单体2在常温常压下是一种气体。
  6. 根据权利要求1所述的纳米涂层，其特征在于，所述基材为金属、光学仪器、衣服织物、电子器件或医疗器械。
  7. 一种权利要求1-6任一项所述高粘附性耐老化纳米涂层的制备方法，其特征在于，其包括以下步骤：
    (1)将基材置于等离子体室的反应腔体内，反应腔体内真空度为0.1-1000毫托；
    (2)通入等离子体源气体，开启沉积用等离子体放电，将单体蒸汽通入反应腔体内，进行化学气相沉积；
    (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，打开反应腔体，取出基材。
  8. 根据权利要求7所述的纳米涂层的制备方法，其特征在于，所述单体蒸汽包括单体1、单体2和单体3；
    所述单体1、单体2和单体3的蒸汽分别先后通入反应腔体；
    或者，所述单体1、单体2和单体3的蒸汽同时通入反应腔体；
    或者，先将所述单体1、单体2和单体3中的任意两种同时通入反应腔体，再所述单体1、单体2和单体3中第三种单体通入反应腔体。
  9. 根据权利要求7或者8所述的纳米涂层的制备方法，其特征在于，所述单体蒸汽至少包括单体1；单体1占所述单体蒸汽的总通入量的摩尔百分数不低于20％。
  10. 根据权利要求7所述的纳米涂的层制备方法，其特征在于，步骤(2)中，等离子体室反应腔体的温度控制在30-60℃；
    通入反应腔体的等离子体源气体的流量为5-300sccm。
  11. 根据权利要求7所述的纳米涂层的制备方法，其特征在于，所述单体蒸汽包括单体1和/或单体3；
    步骤(3)中，利用加料泵将单体1和/或单体3雾化和挥发后通入所述反应腔体；
    所述单体蒸汽在0.1-1000毫托压力下引入反应腔体；
    所述单体蒸汽通入反应腔体时的流量为10-1000μL/min。
  12. 根据权利要求7所述的纳米涂层的制备方法，其特征在于，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。
  13. 根据权利要求7或12所述的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。
  14. 根据权利要求7或12所述的纳米涂层的制备方法，所述等离子体放电为电火花放电；等离子体放电频率为20Hz-20KHz，脉宽为5μs-50ms，放电时间为100s-20000s。
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