WO2019037442A1 - Preparation method for organosilicon nano-protective coating - Google Patents

Abstract

A preparation method for an organosilicon nano-protective coating, belonging to the field of plasma technology. In the method, the vacuum degree within a reaction chamber is adjusted to 10-200 mTorr, an inert gas is introduced, a movement mechanism is turned on so that a base material moves, a monomer vapour is introduced into the reaction chamber for chemical vapour deposition, and an organosilicon nano-coating is prepared via chemical vapour deposition on a surface of the base material. The monomer vapour component is a mixture of at least one organosilicon monomer containing a double bond, Si-Cl, Si-O-C, Si-N-Si or Si-O-Si structure or an annular structure and at least one polyfunctional unsaturated hydrocarbon or hydrocarbon derivative. The present invention replaces traditional carbon/hydrogen/oxygen organic compound monomers with the organosilicon monomer, wherein each silicon atom at least provides 1-4 active sites for higher activity. The coating thickness may be precisely controlled from nanometres to microns via the plasma deposition method, and it is not necessary to use a solvent. The present invention also prevents defects such as waste water, waste liquid and waste gas produced by liquid phase organosilicon coating methods.

Description

Method for preparing silicone nano protective coating Technical field

The invention belongs to the technical field of plasma chemical vapor deposition, and in particular relates to a preparation method of a nano protective coating.

Background technique

Corrosive environments are the most common factor in the destruction of electronic devices. Corrosion of solid materials in electronic devices due to environmental corrosion, reduced conductor/semiconductor insulation, and short-circuit, open circuit, or poor contact. At present, in the products of high-tech industries such as national defense and aerospace, the proportion of electronic components is increasing, and the requirements for moisture, mildew and corrosion resistance of electronic products are becoming more and more strict. In the field of communication, with the continuous advancement of technology, the communication frequency is constantly increasing, and the requirements for the heat dissipation of communication equipment and the stability and reliability of signal transmission are also increasing. Therefore, a reliable method is needed to effectively protect the circuit board and electronic components without affecting normal heat dissipation and signal transmission.

Polymer coatings are often used for material surface protection due to their economical, easy-to-coat and wide application range, which can give materials good physical and chemical durability. Based on the barrier properties of polymer coatings, the protective film formed on the surface of electronic appliances and circuit boards can effectively isolate the circuit board, and protect the circuit from corrosion and damage in a corrosive environment, thereby improving the reliability of the electronic device. Increased safety factor and guaranteed service life are used as anti-corrosion coatings.

Conformal coating is a process of applying a specific material to a PCB to form an insulating protective layer conforming to the shape of the object to be coated. It is a commonly used circuit board waterproofing method, which can effectively isolate the circuit board. And protect the circuit from the erosion and damage of harsh environments. At present, there are some problems and disadvantages in the preparation process of the conformal coating: the solvent in the liquid phase method is easy to damage the circuit board device; the high temperature of the heat curing coating is likely to cause damage to the device; the photocurable coating is difficult to be sealed inside the device. . HZO Company of the United States has developed a conformal parylene coating. Parylene coating is a para-xylene polymer with low water, gas permeability and high barrier effect to achieve moisture, water and rust resistance. , the role of acid and alkali corrosion resistance. It has been found that parylene is deposited under vacuum and can be applied to fields that cannot be covered by liquid coatings such as high frequency circuits and extremely weak current systems. The thickness of the polymer film coating is the main reason for the protection failure of the para-xylene vapor-deposited conformal coating. The polymer film coating of the printed circuit board component is prone to local rust failure at a thickness of 3 to 7 microns without affecting the high. The coating thickness should be ≥ 30 μm in the case of frequency dielectric loss. Parylene coating requires high pretreatment of printed circuit boards that need protection, such as conductive components, signal transmission components, RF components, etc., in the vapor deposition of conformal coatings, it is necessary to pre-mask the circuit board components to avoid Affects component performance. This drawback has brought great limitations to the application of parylene coating. Pyrene coatings have high cost of raw materials, harsh coating preparation conditions (high temperature, high vacuum requirements), low film formation rate, and are difficult to be widely used. In addition, thick coatings are prone to problems such as poor heat dissipation, signal transmission barriers, and increased coating defects.

Plasma chemical vapor deposition (PCVD) is a technique in which a reactive gas is excited by a plasma to promote a chemical reaction on a surface of the substrate or in a near surface space to form a solid film. Plasma chemical vapor deposition coatings have the following advantages:

(1) It is a dry process that produces a uniform film without pinholes.

(2) The plasma polymerization film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance.

(3) The plasma polymerization film has good adhesion to the substrate.

(4) A uniform film can also be formed on the surface of the substrate having irregular irregularities.

(5) The coating preparation temperature is low, and can be carried out under normal temperature conditions, thereby effectively avoiding damage to temperature sensitive devices.

(6) The plasma process can not only prepare a coating having a thickness of a micron order but also can prepare an ultra-thin nano-scale coating.

In the preparation process of the existing plasma chemical vapor deposition coating, the substrate is fixed, and the motion state of the substrate is not related to the discharge energy of the plasma; the stationary substrate is treated by the continuous discharge method. The activated chain scission in the monomer is generally formed into a film by simple stacking under the action of continuous discharge, and the obtained plating layer generally has a loose structure and even a high degree of pulverization, which is disadvantageous to the formation of a microscopic dense structure of the coating layer. Waterproof, moisture-proof, corrosion-resistant, solvent-resistant and other protective properties are poor.

Due to the different regional differences in plasma density and chemical material density in the reaction chamber, the stationary state of the substrate may result in slow deposition of coatings in some regions, low production efficiency, and a large difference in uniformity and compactness.

In addition, most of the current plasma coatings are traditional hydrocarbon-hydrogen organic compounds. Compared with these traditional organic coatings, silicone coatings are environmentally friendly, have high hardness, good wear resistance, and good insulation properties. The product industry is becoming more and more widely used. The silicone monomer itself is non-toxic and does not decompose into toxic and harmful substances. After polymerization of the monomer, the polymer coating has high silicon due to silicon oxide bond or inorganic SiO ₂ nanoparticles formed in the coating. Hardness, good insulation and heat resistance. However, most silicone coatings are currently obtained by the liquid phase method. The silicone monomer is hydrolyzed in solution to form a sol. The sol is applied to the sample to be processed and finally thermally cured to form a dense coating on the surface of the sample. The thickness of the coating is usually from several micrometers to several tens of micrometers. Liquid-phase silicone coating technology, although more environmentally friendly than traditional liquid-phase coating technology, has many shortcomings:

(1) It is necessary to use water or organic matter as a solvent, which adversely affects electronic products;

(2) The presence of wastewater, waste liquid and waste gas requires post-treatment;

(3) The thickness of the coating is poorly controllable and difficult to control to the nanometer level.

Summary of the invention

The present invention provides a method for preparing a silicone nano protective coating in order to solve the above technical problems. In the preparation process, the movement characteristics of the substrate and the plasma discharge energy are combined, and the plasma discharge energy is output while the substrate remains in a moving state. Additional monomeric components with a polyfunctional crosslinked structure are introduced by plasma energy to introduce additional crosslinking sites to form a crosslinked structure. The plasma discharge generates a plasma, and by controlling the relationship between the plasma discharge energy and the bond energy of the monomer, the effective activation of the higher energy active group in the monomer component by the low temperature plasma is obtained, and at the same time, The additional active sites introduced are cross-linked and polymerized in a plasma environment to form a dense network structure.

In addition, the present invention replaces a conventional hydrocarbon-hydrogen organic compound monomer with a silicone monomer, and since the functional group attached to the silicon in the silicone monomer is liable to undergo hydrolysis or alcoholysis, the obtained structure is very susceptible to condensation reaction and mutual Cross-linking, each silicon atom provides at least 1-4 active sites and has high activity. Therefore, it is easier to generate free radicals and cross-linking reaction under low temperature plasma to form dense cross-linking compounds and improve protection. performance. The plasma deposition method can achieve precise and controllable coating thickness from nanometer to micrometer, and does not require the use of solvents, and also avoids the shortage of wastewater, waste liquid, exhaust gas, etc. by the liquid phase silicone coating method.

The technical solutions adopted by the present invention are as follows:

A method for preparing a silicone nano protective coating, comprising: the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 to 200 mTorr, and an inert gas of He, Ar or He and Ar is introduced. Mixing the gas, opening the moving mechanism to cause the substrate to move in the reaction chamber;

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 30-300 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

At least one silicone monomer containing a double bond, Si-Cl, Si-OC, Si-N-Si, Si-O-Si structure or cyclic structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative a mixture of substances, wherein the monomeric vapor has a mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives of 15 to 65%;

The monomer steam is introduced into the reaction chamber by atomizing, volatilizing and introducing the monomer into the reaction chamber by a low pressure of 10 to 200 mTorr, and the flow rate of the monomer vapor is 10 to 1000 μL/min;

(3) Post-processing:

Stop the monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber for 10~200 mTorr for 1~5min, then pass the air to an atmospheric pressure, stop the movement of the substrate, and then take out the substrate. Yes;

Alternatively, the introduction of the monomer vapor is stopped while the plasma discharge is stopped, and the reaction chamber is filled with air or an inert gas to a pressure of 2000-5000 mTorr, and then evacuated to 10-200 mTorr for the above aeration and evacuation steps. At least once, pass air to an atmospheric pressure, stop the movement of the substrate, and then remove the substrate.

In the low-vacuum plasma discharge environment, by the effective output of energy, the chemical bonds in the active monomer are controlled to break, forming higher-activity free radicals, excited free radicals and surface activation groups of mobile phones and other products. The group initiates polymerization to form a nanometer waterproof film by chemical bonding, and forms a silicone nano coating on the surface of the substrate. In addition, since the group attached to the silicon in the silicone monomer has high activity, radicals are more likely to be generated and cross-linking reaction occurs in the case of low-temperature plasma to form a dense cross-linking compound.

In the step (1), the substrate generates motion in the reaction chamber, and the substrate moves in the form of a linear reciprocating motion or a curved motion of the substrate relative to the reaction chamber, the curved motion including circular motion, elliptical motion, planetary motion, Curved motion of spherical motion or other irregular routes.

The substrate in the step (1) is a solid material, and the solid material is an electronic product, an electrical component, an electronic assembly semi-finished product, a PCB board, a metal plate, a polytetrafluoroethylene plate or an electronic component, and the surface of the substrate After preparation of the silicone nano-coating, any interface can be exposed to water environment, mold environment, acid, alkaline solvent environment, acid, alkaline salt spray environment, acidic atmospheric environment, organic solvent soaking environment, cosmetic environment, sweat environment, Use in cold or hot cycle impact environment or wet heat alternating environment.

In the step (1), the reaction chamber is a rotating body chamber or a cubic chamber, the volume is 50-1000 L, the temperature of the reaction chamber is controlled at 30-60 ° C, and the flow rate of the inert gas is 5-300 sccm. .

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process during the deposition process includes low power continuous discharge, pulse discharge or periodic alternating discharge.

The plasma discharge process during the deposition process is a low power continuous discharge, specifically including the following deposition process at least once:

The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600 W, the continuous discharge time is 60-450 s, and then enters the coating stage. The plasma discharge power is adjusted to 10 to 150 W, and the continuous discharge time is 600 to 3600 s. .

The plasma discharge process during the deposition is a pulse discharge, specifically including the following deposition process at least once:

The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power of the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage. The coating stage is pulse discharge, the power is 10 to 300 W, and the time is 600 s to 3600 s. The frequency of the pulse discharge is 1 to 1000 Hz, and the duty ratio of the pulse is 1:1 to 1:500.

The plasma discharge process during the deposition process is a periodic alternating discharge, specifically including the following deposition process at least once:

The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage. The plasma in the coating stage is a periodic alternating discharge output with a power of 10 to 300 W. The time is 600s~3600s, the frequency conversion rate is 1-1000Hz, and the plasma cycle alternately changes. The discharge output waveform is a sawtooth waveform, a sinusoidal waveform, a square wave waveform, a full-wave rectified waveform or a half-wave rectified waveform.

The silicone monomer containing a double bond, a Si—Cl, a Si—O—C, a Si—N—Si, a Si—O—Si structure or a ring structure includes:

Silicone monomer containing double bond structure: allyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethyl silane, 3-butenyl trimethyl silane, vinyl tributyl ketone fluorenyl Silane, tetramethyldivinyldisiloxane, 1,2,2-trifluorovinyltriphenylsilane;

Silicone monomer containing Si-Cl bond: triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane , tributylchlorosilane, benzyldimethylchlorosilane;

Silicone monomer containing Si-OC structure: tetramethoxysilane, trimethoxyhydrogensiloxane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyltris(2-methoxy Ethyl ethoxy) silane, triethyl vinyl silane, hexaethylcyclotrisiloxane, 3-(methacryloyloxy)propyl trimethoxy silane, phenyl tris(trimethyl siloxane group Silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, n-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane;

Silicone monomer containing Si-N-Si or Si-O-Si structure: hexamethyldisilazide, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;

Silicone monomer containing cyclic structure: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenyl ring Tetrasiloxane, triphenylhydroxysilane, diphenyldihydroxysilane, bis(tritylsilyl) chromate, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4 -tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, γ - glycidyloxypropyltrimethoxysilane;

The polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives include:

1,3-butadiene, isoprene, 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol divinyl ether or neopentyl glycol diacrylate.

In the step (2), the plasma discharge mode is radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electric spark discharge, and the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or bipolar pulses. The radio frequency plasma is a plasma generated by discharge of a high frequency electromagnetic field. The microwave method utilizes the energy of the microwave to excite the plasma, and has the advantages of high energy utilization efficiency. At the same time, since the electrodeless discharge and the plasma are pure, it is an excellent method for high-quality, high-rate, large-area preparation.

During the preparation of the coating, the motion characteristics of the substrate and the plasma discharge energy are combined. During the plasma discharge during the preparation process, the substrate generates motion, improves the deposition efficiency of the coating, and improves the uniformity and compactness of the coating thickness.

The prepared coating has waterproof, moisture proof, mold proof, acid resistance, alkaline solvent, acid resistance, alkaline salt spray, acid resistance atmosphere, organic solvent immersion resistance, cosmetics resistance, sweat resistance, cold and heat cycle impact resistance (-40 ° C ~ +100 ° C), resistance to heat and humidity (humidity 75% to 95%) and other characteristics. For electronic products (mobile phones, earphones, smart bracelets, etc.), drones, etc., the coatings have the above-mentioned protective performance, and the thickness of the radio frequency communication signal in the range of 10M to 8G in the range of 1 to 1000 nm The effect is less than 5%, and the coating does not affect the original heat dissipation performance of the electronic product and the current continuity requirement of the electronic product itself.

The above technical solution of the present invention has the following advantages compared with the prior art:

1. The plasma chemical vapor deposition method is more environmentally friendly than the liquid phase three-coating coating method; and the deposition temperature is lower, the speed is faster, and the coating structure and composition are controllable compared to the vapor deposition parylene method. Strong, the monomer is highly selective.

2. The substrate moves in the reaction chamber, so that the coating thickness of the substrate at different positions tends to be uniform, which solves the problem that the thickness of the coating on the surface of the substrate is not uniform due to the difference in monomer density in different regions of the reaction chamber. During the preparation process, the combination of the motion characteristics of the substrate and the plasma discharge energy, while the discharge energy is output, the substrate moves, and the deposition efficiency is improved, so that the denseness of the obtained silicone nano protective coating is remarkably improved. At the same time, due to the increase of deposition efficiency, the amount of chemical monomer raw materials used in monomer steam is only 10% to 15% of the amount in other prior art, thereby reducing emissions of exhaust gas, making it more environmentally friendly and improving actual production efficiency. It has great significance.

3. General plasma polymerization uses a monofunctional hydrocarbon-hydrogen organic compound monomer to obtain a coating having a certain cross-linking structure. The crosslinked structure is formed by a plurality of active sites formed by chain scission of a monomer during plasma discharge by cross-linking. However, this crosslinked structure is relatively loose, contains more linear components, and is resistant to solution penetration and solubility.

Compared with the conventional monofunctional organic monomer, under the plasma condition, the silicon-bonded functional groups in the silicone monomer can undergo a condensation reaction with each other, and therefore, a three-dimensional network can occur between the monomer and the monomer. Cross-linking can further improve the compactness, wear resistance and corrosion resistance of the coating.

(1) Replacing a conventional monofunctional hydrocarbon-hydrogen organic compound monomer with a silicone monomer containing a double bond, Si-Cl, Si-OC, Si-N-Si, Si-O-Si structure or a cyclic structure Under the plasma condition, since the functional groups linked to silicon have high reactivity, these organosilicon monomers have more crosslinkable active sites;

(2) An additional crosslinking point is introduced by introducing other monomer components having a polyfunctional crosslinked structure to form a crosslinked structure. During plasma discharge, under the action of low temperature plasma, the active group with higher energy in the monomer component is broken to form an active point by effective control and output of energy, and the additional active point introduced is in the plasma environment. They cross-link and polymerize to form a dense network structure.

Compared with the coating structure with loose linear components, the mesh structure has better compactness and can effectively improve the corrosion-resistant environment of the film. In the plasma environment, the surface of the coated substrate is activated to obtain a plurality of active sites. The active sites are combined with the active radicals of the plasma-excited monomeric material with strong chemical bonds, and various forms of primitives are generated. The reaction makes the nano film of the base material have excellent bonding force and mechanical strength. By controlling the mixing mode of different monomers and controlling different process conditions at the same time, the effective control of the corrosion-resistant environment of the material surface is realized, and the structure with large roughness of the underlying dense surface layer with special microstructure is obtained, and the comprehensive performance of environmental corrosion resistance is obtained. Increased by 45% to 60%. In particular, the hardness of the silicone coating of the same thickness is 1-2 grades higher than that of the conventional coating, and the salt spray resistance is increased by 30-50%.

4. By introducing other monomers of the crosslinked structure, controlling the monomer ratio, according to the difference of molecular bond energy, bond length and vaporization temperature of different monomers, the corresponding energy output and effective changes of process parameters are given to the device. The composite nano-coating with a composite structure and a gradual structure not only ensures the hydrophobicity of the film, but also improves the environmental corrosion resistance of products such as electronic products.

Electronic equipment in daily life is extremely vulnerable to corrosion by corrosive environments, and is basically in a corrosive environment during use. In the long run, it will cause irreparable damage to electronic equipment. The coating method of the patent of the invention greatly increases the significance of the nanometer in improving the actual production efficiency. The service life of the coating in a corrosive environment increases the protection of the product. Mainly used in the following products:

(1) Portable device keyboard: The portable keyboard has the characteristics of small and light, and is often used in computers, mobile phones and the like. It makes it easy for users to work on the journey. However, when it encounters the contamination of common liquids, such as the accidental overturn of the water cup, the soaking of rain and sweat, the inside of the keyboard is easily short-circuited and damaged. After coating with this type of nano-coating, it can ensure that the surface of the keyboard is easy to clean and function properly after being exposed to water, so that the keyboard can adapt to a more severe environment.

(2) LED display: LED display has merchandise promotion, store decoration, lighting, warning and other purposes. Some of its uses need to face the harsh environment of rain or dust, such as the rainy day, the open-air LED advertising screen of the mall, the LED display control panel of the production workshop, the road warning light, the LED light module of the trademark logo, these harsh environments lead to LED The screen is out of order, and it is easy to accumulate dust and is difficult to clean. After using the nano-coating, the above problems can be effectively solved.

(3) Intelligent fingerprint lock: Fingerprint lock is a smart lock. It integrates computer information technology, electronic technology, mechanical technology and modern hardware technology. It is widely used in public security criminal investigation and judicial field. However, after it meets water, its internal circuit is short-circuited, difficult to repair, and requires violent de-locking. This coating can be used to avoid this problem.

(4) Hearing aids, Bluetooth headsets, VR/AR glasses: After using this coating, users can use them in a water environment for a certain period of time, such as bathing, raining, and the equipment will not be damaged by rain infiltration. . At the same time, after the coating is applied, the product has a certain salt spray resistance and sweat resistance function, ensuring that the user can normally use the product even when sweating during exercise.

(5) Some sensors: Some sensors need to work in a liquid environment, such as water pressure, oil pressure sensors, and sensors used in underwater equipment, as well as sensors that often encounter water in the working environment. These sensors use the coating. After that, it can guarantee that the sensor will not malfunction due to the liquid invading the internal structure of the mechanical device.

(6) Most 3C products: such as mobile phones, computers, tablets, digital cameras, PSPs, etc.

(7) UAV products (agricultural/civil/police): UAVs will encounter different weather conditions during normal work. Corrosive gas environment, rainy days and humid environments are inevitable, even with some pesticide reagents. s contact. After the coating is used, the drone can effectively protect it from normal use in rainy days or even in the environment of water, without the phenomenon that the circuit board is short-circuited or the flight control fails.

(8) Other equipment that needs to be waterproof: including equipment that needs to work in a humid environment, or may encounter unexpected situations such as liquid spills, which may affect the normal operation of the internal weak current line.

The silicone nano-coating prepared by the method can also be applied to the following different environments and related products:

Waterproof, moisture proof, moldproof:

1 House interior: bathroom top, wallpaper, chandeliers, curtains, screens. 2 daily necessities: mosquito nets, table lamp covers, chopsticks, car rearview mirrors. 3 Cultural relics and works of art: copybooks, antiques, woodcarving, leather, bronze, silk, costumes, ancient books. 4 Electronic components and electronic products: sensors (working in wet or dusty environments), chips of various electronic products (electronic sphygmomanometers, smart watches), circuit boards, mobile phones, LED screens, hearing aids. 5 precision instruments and optical equipment: mechanical watches, microscopes. 6 agricultural / police / civilian drones.

Acid and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere:

1 housing interior parts: wallpaper, tiles. 2 protective equipment: acid (alkali) gloves, acid (alkali) protective clothing. 3 Mechanical equipment and pipelines: flue desulfurization equipment, seals (acid/alkaline lubricants), pipes, valves, large-diameter sea pipelines, etc. 4 various reactors, reactors. 5 chemical production, storage; sewage treatment, aeration tank; 6 other: acid and alkali workshop, anti-alkali aerospace, energy and power, steel and metallurgy, petrochemical, medical and other industries, storage containers, statues (reduced acid rain Corrosion), sensor (acid/alkaline environment).

Soaked with organic solvents, resistant to cosmetics, sweat resistant:

1 such as paraffin, olefin, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenated hydrocarbon, terpene olefin, halogenated hydrocarbon, heterocyclic compound, nitrogen-containing compound and sulfur compound solvent; 2 cosmetic packaging container ; 3 fingerprint lock, headphones.

Resistance to cold and heat cycle (-40 ° C ~ +100 ° C), resistance to heat and humidity (humidity 75% ~ 95%), electrical, electronic, automotive electrical, such as aviation, automotive, home appliances, scientific research and other fields of equipment.

Detailed ways

The invention will be described in detail below with reference to specific embodiments, but the invention is not limited to the specific embodiments.

Example 1

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 mTorr, and an inert gas Ar is introduced to open the moving mechanism. , causing the substrate to generate motion in the reaction chamber;

The substrate in the step (1) is a solid material, and the solid material is a block-shaped polytetrafluoroethylene sheet.

In the step (1), the reaction chamber is a rotating body chamber, the volume of the reaction chamber is 50 L, the temperature of the reaction chamber is controlled at 30 ° C, and the flow rate of the inert gas is 5 sccm.

In the step (1), the substrate moves in the reaction chamber, and the substrate moves in the form of a circular motion of the substrate relative to the reaction chamber at a rotation speed of 1 rpm.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 30 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of a silicone monomer having a double bond structure and two polyfunctional unsaturated hydrocarbons and a hydrocarbon derivative, the mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor 15%;

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process:

The deposition process includes the pretreatment stage and the coating stage. The plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage. The plasma discharge power is adjusted to 150W and the continuous discharge time is 600s.

In step (2):

Passing monomer steam to atomize and volatilize the monomer through the feed pump, and introduce the reaction chamber into the reaction chamber by a low pressure of 10 mTorr, and the flow rate of the monomer vapor is 1000 μL/min;

The silicone monomer containing a double bond structure is: vinyl triethoxysilane;

The two polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,3-butadiene, ethylene glycol diacrylate;

The plasma discharge mode in the step (2) is a radio frequency discharge.

(3) Post-processing:

Stop the monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber at 10 mTorr for 1 min, then pass the air to an atmospheric pressure, stop the movement of the substrate, and then take out the substrate.

The obtained polytetrafluoroethylene plate deposited with a silicone nano coating was tested for antifungal properties according to GJB150.10A-2009, and the effects were as follows:

Example 2

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 60 mTorr, and an inert gas He is introduced to start the moving mechanism. Moving the substrate;

The substrate in the step (1) is a solid material, and the solid material is a bulk aluminum alloy anodized material.

In the step (1), the reaction chamber is a cubic chamber, the volume of the reaction chamber is 250 L, the temperature of the reaction chamber is controlled at 40 ° C, and the flow rate of the inert gas is 15 sccm.

In the step (1), the substrate is subjected to planetary motion, the revolution speed is 1 rpm, and the rotation speed is 1.5 rpm.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 110 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of two Si-Cl-containing organosilicon monomers and three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives, the mass of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor The score is 29%;

In the step (2): plasma discharge, chemical vapor deposition, the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process three times:

The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power of the pretreatment stage is 600 W, the discharge time is 60 s, and then enters the coating stage. The plasma discharge power is adjusted to 10 W and the continuous discharge time is 3600 s.

In step (2):

The monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 60 mTorr, and the flow rate of the monomer vapor is 700 μL/min;

The two Si-Cl-containing silicone monomers are: triphenylchlorosilane and trifluoropropylmethyldichlorosilane.

The three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, polyethylene glycol diacrylate;

The plasma discharge mode in the step (2) is an intermediate frequency discharge.

(3) Post-processing:

Stop the monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber at 80 mTorr, and then pass the air to an atmospheric pressure after 2 min, then take out the substrate.

After preparing the silicone coating on the surface of the bulk aluminum alloy anodized material, it is tested for acid and alkali resistance in an acid and alkali test environment, and the effects are as follows:

Example 3

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is drawn to 130 mTorr, and a mixture of inert gases Ar and He is introduced. a gas that activates a moving mechanism to move the substrate;

The substrate in the step (1) is a solid material, and the solid material is a bulk alloy steel plate material and a PC plastic plate.

In the step (1), the reaction chamber is a rotating body chamber, the volume of the reaction chamber is 480 L, the temperature of the reaction chamber is controlled at 50 ° C, and the flow rate of the inert gas is 60 sccm.

In the step (1), the substrate was subjected to circular motion at a rotation speed of 3 rpm.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 170 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of three Si-OC structured silicone monomers and a polyfunctional unsaturated hydrocarbon and a hydrocarbon derivative, the mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor 42%;

Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is pulse discharge, specifically including the following deposition process three times:

The deposition process includes pretreatment stage and coating stage. The plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage. The coating stage is pulse discharge, power 300W, time 600s, pulse discharge frequency is 1HZ, pulse The duty cycle is 1:1.

In step (2):

The monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 130 mTorr, and the flow rate of the monomer vapor is 550 μL/min;

The three Si-O-C structure-containing silicone monomers are: phenyltriethoxysilane, triethylvinylsilane, hexaethylcyclotrisiloxane;

The polyfunctional unsaturated hydrocarbon derivative is: 1,6-hexanediol diacrylate;

In the step (2), the plasma discharge mode is a high frequency discharge, and the waveform of the high frequency discharge is a bipolar pulse.

(3) Stop the flow of monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber at 160 mTorr, and then pass air to an atmospheric pressure after 3 min, then take out the substrate.

After depositing the silicone coating on the above alloy steel plate material and PC plastic plate, the organic solvent resistance is tested by immersing in an organic solvent, and the effects are as follows:

Example 4

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 160 mTorr, and an inert gas He is introduced to start the moving mechanism. Moving the substrate;

In the step (1), the substrate is a solid material, and the solid material is a bulk aluminum material and a PCB board.

The volume of the reaction chamber in the step (1) was 680 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 160 sccm.

In the step (1), the substrate is linearly reciprocated at a moving speed of 20 mm/min.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 210 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of two organosilicon monomers containing Si-N-Si or Si-O-Si structures and four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives, said polyfunctional unsaturated hydrocarbons in said monomer vapors and The hydrocarbon derivative accounts for 65% by mass;

Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is pulse discharge, specifically including the following deposition process:

The deposition process includes pretreatment stage and coating stage. The plasma discharge power of the pretreatment stage is 600W, the discharge time is 60s, and then enters the coating stage. The coating stage is pulse discharge, power 10W, time 3600s, pulse discharge frequency is 1000HZ, pulse The duty cycle is 1:500.

In step (2):

The monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 160 mTorr, and the flow rate of the monomer vapor is 220 μL/min;

The two silicone monomers containing Si-N-Si or Si-O-Si structure are: hexamethylcyclotrisilylamino, hexamethyldisilazane;

The four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate ;

The plasma discharge mode in the step (2) is microwave discharge.

(3) Post-processing:

Stop the monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber at 200 mTorr, and then pass air to an atmospheric pressure after 5 min, then take out the substrate.

The above-mentioned coated aluminum material and PCB board are exposed to the cold and heat cycle test environment for the thermal cycle test. The test results are as follows:

Example 5

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 200 mTorr, and an inert gas Ar is introduced to start the moving mechanism. Moving the substrate;

The substrate in the step (1) is a solid material, and the solid material is an electronic component.

The volume of the reaction chamber in the step (1) was 1000 L, the temperature of the reaction chamber was controlled at 60 ° C, and the flow rate of the inert gas was 300 sccm.

In the step (1), the substrate was subjected to a curve reciprocating motion at a speed of 100 mm/min.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 300 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of three cyclic-containing organosilicon monomers and five polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives, the mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor 52%;

Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is alternating periodic, specifically including the following deposition process four times:

The deposition process includes the pretreatment stage and the coating stage. The plasma discharge power of the pretreatment stage is 150W, the continuous discharge time is 450s, and then enters the coating stage. The plasma in the coating stage is the periodic alternating discharge output, power 300W, time 600s, alternating frequency At 1 Hz, the plasma cycle alternately changes the discharge output waveform to a sawtooth waveform;

In step (2):

The monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 200 mTorr, and the flow rate of the monomer vapor is 10 μL/min;

The three kinds of silicone-containing monomers having a cyclic structure are: octaphenylcyclotetrasiloxane, bis(tritylsilyl) chromate, tetramethyltetravinylcyclotetrasiloxane;

The five polyfunctional unsaturated hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol Divinyl ether;

The plasma discharge mode in the step (2) is a spark discharge.

(3) Post-processing:

Stop the introduction of monomer vapor while stopping the plasma discharge, fill the reaction chamber with inert gas to a pressure of 2000 mTorr, then evacuate to 10 mTorr, perform the above aeration and vacuum steps once, and introduce air to an atmospheric pressure. Stop the movement of the substrate and then remove the substrate. The above-mentioned coated electronic components were tested for their resistance to moisture and heat exchange when exposed to a damp heat test environment. The test results are as follows:

Example 6

A method for preparing a silicone nano protective coating comprises the following steps:

(1) Pre-processing:

The substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 180 mTorr, and an inert gas Ar is introduced to start the moving mechanism. Moving the substrate;

Step (1) The substrate is a solid material, and the solid material is an electrical component.

The volume of the reaction chamber in the step (1) was 880 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 200 sccm.

In the step (1), the substrate was subjected to a curve reciprocating motion at a speed of 200 mm/min.

(2) Preparation of silicone coating:

Passing monomer vapor into the reaction chamber to a vacuum of 250 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

The monomer vapor component is:

a mixture of four Si-OC-containing organosilicon monomers and three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives, the mass of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor The score is 57%;

Plasma discharge, chemical vapor deposition, plasma discharge process is a periodic alternating discharge during deposition, specifically including the following deposition process:

The deposition process includes the pretreatment stage and the coating stage. The plasma discharge power of the pretreatment stage is 600W, the continuous discharge time is 60s, and then enters the coating stage. The plasma in the coating stage is the cycle alternating discharge output, power 10W, time 3600s, alternating frequency For 1000 Hz, the plasma cycle alternately changes the discharge output waveform to a full-wave rectified waveform;

In step (2):

The monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 180 mTorr, and the flow rate of the monomer vapor is 35 μL/min;

The four Si-OC structure-containing silicone monomers are: hexaethylcyclotrisiloxane, diphenyldiethoxysilane, dodecyltrimethoxysilane, 3-chloropropyltrimethoxy Silane

The three polyfunctional unsaturated hydrocarbon derivatives are: polyethylene glycol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate.

In the step (2), the plasma discharge mode is an intermediate frequency discharge, and the waveform of the intermediate frequency discharge is sinusoidal.

(3) Post-processing:

Stop the monomer vapor, stop the plasma discharge, fill the reaction chamber with air to a pressure of 5000 mTorr, then evacuate to 200 mTorr, perform the above aeration and vacuum steps 12 times, and introduce air to an atmospheric pressure. Stop the movement of the substrate and then remove the substrate. The above-mentioned coated electrical components are tested for underwater resistance and underwater immersion resistance under the environment described in International Industrial Waterproofing Standard IPX7. The experimental results are as follows:

The following table tests the time taken for the coating prepared in this example to reach 1 mA at different voltages:

Voltage	3.8V	5V	12.5V
time	>48h	>48h	>48h

The obtained IPX 7 waterproof rating test (underwater 1m immersion test for 30 minutes) of the electrical component deposited with the waterproof and electrical breakdown coating is as follows:

Claims (10)

1. A method for preparing a silicone nano protective coating, comprising: the following steps:

   (1) Pre-processing:

   The substrate is placed in a reaction chamber of the nano-coating preparation device, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 to 200 mTorr, and an inert gas of He, Ar or He and Ar is introduced. Mixing the gas, opening the moving mechanism to cause the substrate to move in the reaction chamber;

   (2) Preparation of silicone coating:

   Passing monomer vapor into the reaction chamber to a vacuum of 30-300 mTorr, plasma discharge is started, chemical vapor deposition is performed, and a silicone nano-coating is prepared by chemical vapor deposition on the surface of the substrate;

   The monomer vapor component is:

   At least one silicone monomer containing a double bond, Si-Cl, Si-OC, Si-N-Si, Si-O-Si structure or cyclic structure and at least one polyfunctional unsaturated hydrocarbon and hydrocarbon derivative a mixture of substances, wherein the monomeric vapor has a mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives of 15 to 65%;

   The flow rate of the monomer vapor is 10 to 1000 μL/min;

   (3) Post-processing:

   Stop the monomer vapor, stop the plasma discharge, continue to vacuum, keep the vacuum of the reaction chamber for 10~200 mTorr for 1~5min, then pass the air to an atmospheric pressure, stop the movement of the substrate, and then take out the substrate. Yes;

   Alternatively, the introduction of the monomer vapor is stopped while the plasma discharge is stopped, and the reaction chamber is filled with air or an inert gas to a pressure of 2000-5000 mTorr, and then evacuated to 10-200 mTorr for the above aeration and evacuation steps. At least once, pass air to an atmospheric pressure, stop the movement of the substrate, and then remove the substrate.
2. The method for preparing a silicone nano-protective coating according to claim 1, wherein in the step (1), the substrate is moved in the reaction chamber, and the substrate is moved in the form of a substrate relative to the reaction chamber. A linear reciprocating motion or a curved motion is performed, the curved motion including circular motion, elliptical circumferential motion, planetary motion, spherical motion, or other irregularly curved motion.
3. The method for preparing a silicone nano protective coating according to claim 1, wherein the substrate in the step (1) is a solid material, and the solid material is an electronic product, an electrical component, or an electronic assembly semi-finished product. , PCB board, metal plate, PTFE sheet or electronic component, and any interface of the substrate after the preparation of the silicone nano-coating can be exposed to water environment, mold environment, acid, alkaline solvent environment, Acid, alkaline salt spray environment, acidic atmospheric environment, organic solvent soaking environment, cosmetic environment, sweat environment, hot and cold cycle impact environment or wet heat alternating environment.
4. The method for preparing a silicone nano protective coating according to claim 1, wherein in the step (1), the reaction chamber is a rotating body chamber or a cubic chamber, and the volume thereof is 50 to 1000 L. The temperature of the reaction chamber is controlled at 30 to 60 ° C, and the flow rate of the inert gas is 5 to 300 sccm.
5. The method for preparing a silicone nano protective coating according to claim 1, wherein in the step (2): plasma discharge, chemical vapor deposition, and plasma discharge process during deposition includes low power Continuous discharge, pulse discharge or periodic alternating discharge.
6. The method for preparing a silicone nano-protective coating according to claim 5, wherein the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process at least once:

   The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600 W, the continuous discharge time is 60-450 s, and then enters the coating stage. The plasma discharge power is adjusted to 10 to 150 W, and the continuous discharge time is 600 to 3600 s. .
7. The method for preparing a silicone nano-protective coating according to claim 5, wherein the plasma discharge process during the deposition is a pulse discharge, specifically comprising the following deposition process at least once:

   The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power of the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage. The coating stage is pulse discharge, the power is 10 to 300 W, and the time is 600 s to 3600 s. The frequency of the pulse discharge is 1 to 1000 Hz, and the duty ratio of the pulse is 1:1 to 1:500.
8. The method for preparing a silicone nano-protective coating according to claim 5, wherein the plasma discharge process during the deposition is a periodic alternating discharge, specifically comprising the following deposition process at least once:

   The deposition process includes a pretreatment stage and a coating stage. The plasma discharge power in the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage. The plasma in the coating stage is a periodic alternating discharge output with a power of 10 to 300 W. The time is 600s~3600s, the frequency conversion rate is 1-1000Hz, and the plasma cycle alternately changes. The discharge output waveform is a sawtooth waveform, a sinusoidal waveform, a square wave waveform, a full-wave rectified waveform or a half-wave rectified waveform.
9. The method for preparing a silicone nano protective coating according to claim 1, wherein:

   The silicone monomer containing a double bond, a Si—Cl, a Si—O—C, a Si—N—Si, a Si—O—Si structure or a ring structure includes:

   Silicone monomer containing double bond structure: allyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethyl silane, 3-butenyl trimethyl silane, vinyl tributyl ketone fluorenyl Silane, tetramethyldivinyldisiloxane, 1,2,2-trifluorovinyltriphenylsilane;

   Silicone monomer containing Si-Cl bond: triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane , tributylchlorosilane, benzyldimethylchlorosilane;

   Silicone monomer containing Si-OC structure: tetramethoxysilane, trimethoxyhydrogensiloxane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyltris(2-methoxy Ethyl ethoxy) silane, triethyl vinyl silane, hexaethylcyclotrisiloxane, 3-(methacryloyloxy)propyl trimethoxy silane, phenyl tris(trimethyl siloxane group Silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, n-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane;

   Silicone monomer containing Si-N-Si or Si-O-Si structure: hexamethyldisilazide, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;

   Silicone monomer containing cyclic structure: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenyl ring Tetrasiloxane, triphenylhydroxysilane, diphenyldihydroxysilane, bis(tritylsilyl) chromate, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4 -tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, γ - glycidyloxypropyltrimethoxysilane;

   The polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives include:

   1,3-butadiene, isoprene, 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol divinyl ether or neopentyl glycol diacrylate.
10. The method for preparing a silicone nano protective coating according to claim 1, wherein in the step (2), the plasma discharge mode is radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electricity. The spark discharge, the waveform of the high frequency discharge and the intermediate frequency discharge is a sinusoidal or bipolar pulse.