Patent Application
20230227666
This application claims the priority to Chinese Application No. 202010526322.5, filed on Jun. 9, 2020, and entitled “PROTECTIVE COATING AND PREPARATION METHOD THEREOF”, and to Chinese Application No. 202010526684.4, filed on Jun. 9, 2020, and entitled “PROTECTIVE COATING AND PREPARATION METHOD THEREOF”, the contents of which are incorporated herein by reference in their entirety.
The present disclosure relates to the field of plasma chemistry, and more particularly, to a plasma polymerization protective coating and a preparation method thereof.
An organic polymer coating can effectively protect a surface of different materials. Among methods for preparing organic polymer coatings, the vapor deposition method is a mainstream method for preparing polymer protective coatings on a surface of a substrate, which is economical practical and easy to operate. In particular, the plasma chemical vapor deposition uses plasma to activate reaction monomer gas to deposit on a surface of a substrate, which is applicable for various substrates. In addition, the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, and it hardly has damage to the substrate surface as well as less effect on the substrate performance.
For plasma polymerization coatings, selection of plasma polymerization monomers has always been one of the important research topics. For example, organosiloxane can be used as a monomer to prepare a plasma polymerization coating, and a mixture of monofunctional unsaturated fluorocarbon resin and polyfunctional unsaturated hydrocarbon derivative can be used as monomer for plasma polymerization coating, which may result in a coating with a dense network structure that can protect metal and the like.
The specific embodiment of the present disclosure provides a new type of protective coating formed by plasma polymerization of monomer and a preparation method thereof, as illustrated in the following:
A protective coating II, which is a plasma polymerization coating formed on a surface of a substrate by contacting plasmas, wherein the plasmas include a plasma of a monomer α, and the monomer α includes an alicyclic epoxy structural unit shown in formula (1),
wherein, A is a three to twenty-membered alicyclic structure.
Optionally, the A is a five-membered alicyclic structure or a six-membered alicyclic structure.
Optionally, the monomer α further includes at least one selected from a group consisting of: a carbon-carbon double bond structural unit, a carbon-carbon triple bond structural unit, and an epoxy structural unit.
Optionally, the monomer α has a structure shown in formula (2),
wherein, R1, R2 and R3 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl;
and R4 is a connecting bond, a C1-C10 alkylene or a halogen-substituted C1-C10 alkylene.
Optionally, the R1, the R2 and the R3 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl; and R4 is a connecting bond, a methylene or an ethylidene.
Optionally, the monomer α has a structure shown in formula (3) or a structure shown in formula (4).
Optionally, the monomer α has a structure shown in formula (5),
wherein, R5 is a connecting bond, a C1-C10 alkylene or a halogen-substituted C1-C10 alkylene, and R6 has a structure selected from a group consisting of:
Optionally, the monomer α has a structure shown in formula (6) or a structure shown in formula (7).
Optionally, the monomer α has a structure shown in formula (8),
wherein, R7 and R9 are respectively and independently selected from a group consisting of: a connecting bond, a C1-C10 alkylene, and a halogen-substituted C1-C10 alkylene;
R8 is a C1-C10 alkylene or a halogen-substituted C1-C10 alkylene;
and X and Y are respectively and independently selected from a group consisting of: a connecting bond, an oxygen atom, a carbonyl, and an ester.
Optionally, the monomer α has a structure shown in formula (9) or a structure shown in formula (10).
Optionally, the plasmas also include a plasma of a monomer β, the monomer β includes a structural unit a;
and the structural unit a has a structure shown in formula (11);
wherein, R10, R11 and R12 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl.
Optionally, the monomer β also includes a structural unit b, and the structural unit b includes at least one selected from a group consisting of: a double bond structural unit, a triple bond structural unit, and an epoxy structural unit.
Optionally, the structural unit b has a structure shown in formula (12),
wherein, R13, R14 and R15 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl.
Optionally, the monomer β has a structure shown in formula (13),
wherein, R16 is a C2-C10 alkylene or a halogen-substituted C2-C10 alkylene, and n is an integer ranging from 1 to 10.
Optionally, the R10, R11, R12, R13, R14 and R15 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl.
Optionally, the substrate is selected from metal, plastic, fabric, glass, electrical assemblies, optical instruments or electrical components.
A preparation method of the aforementioned protective coating includes:
providing a substrate;
and contacting the substrate with plasmas to form a plasma polymerization coating on a surface of the substrate.
Optionally, the plasmas are excited in a pulse manner.
Optionally, a pulse frequency of the pulse manner ranges from 20 Hz to 80 kHz, a pulse duty cycle ranges from 0.1% to 80%, and an average pulse power density ranges from 0.001 W/m3 to 500 W/m3.
A device includes any of the aforementioned protective coating on at least part of the surface thereof.
A protective coating includes a coating I and a coating II deposited on a substrate,
and the coating II is any of the aforementioned protective coating II;
the coating I is a plasma polymerization coating formed on the coating II by contacting the coating II with a plasma including a monomer γ;
and the monomer γ includes one or more selected from a group consisting of: an alkane, a halogenated alkane, an alkene, a halogenated alkene, an alkyne, a halogenated alkyne, an acrylic ester, and a halogenated acrylic ester.
Optionally, the monomer γ has a structure shown in formula (14),
wherein, R17, R18 and R19 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl;
and R20 is a C1-C20 hydrocarbyl or a halogen-substituted C1-C20 hydrocarbyl.
Optionally, the R17, R18 and R19 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl; and R20 is a C4-C20 hydrocarbyl or a halogen-substituted C4-C20 hydrocarbyl.
Optionally, the monomer γ has a structure shown in formula (15),
wherein, R21 is a connecting bond, a C1-C10 alkylene, and a halogen-substituted C1-C10alkylene;
and B is an aromatic ring structure or a three to twenty-membered alicyclic structure.
Optionally, the R21 is a connecting bond, a methylene or an ethylidene, and B is a cyclohexyl or a cyclopentyl.
Optionally, the protective coating further includes a coating III, and the coating III is a plasma polymerization coating formed by contacting the substrate with a plasma including a monomer δ;
the coating II is a plasma polymerization coating formed on the coating III by contacting the coating III with a plasma including a monomer δ;
and the monomer δ includes a structural unit c and a structural unit d, and the structural unit c and the structural unit d both have a carbon-carbon double bond structure and an ester structure respectively.
Optionally, the structural unit c has a structure shown in formula (16),
wherein, R22, R23 and R24 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl.
Optionally, the structural unit d has a structure shown in formula (17),
wherein, R25, R26 and R27 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl.
Optionally, the monomer δ has a structure shown in formula (18),
wherein, R28 is a C2-C10 alkylene or a halogen-substituted C2-C10 alkylene, n is an integer ranging from 0 to 10, wherein R22, R23, R24, R25, R26 and R27 are respectively and independently selected from a group consisting of a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl.
Optionally, the R22, R23, R24, R25, R26 and R27 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl.
A preparation method of any of the aforementioned protective coating includes:
providing a substrate;
and forming the protective coating on the substrate by performing a plasma deposition.
Optionally, the plasma is a pulse plasma.
Optionally, the pulse plasma is generated by applying a pulse voltage discharge, wherein, a pulse power ranges from 20 W to 500 W, a pulse frequency ranges from 20 Hz to 80 kHz, a pulse duty cycle ranges from 0.1% to 80%, and a plasma discharge duration time ranges from 100 s to 20000 s.
A device includes any of the aforementioned protective coating on at least part of the surface thereof.
According to a specific embodiment of the present disclosure, the protective coating II is formed by plasma polymerization coating of monomers including alicyclic epoxy structural units, which is provided with a compact rigid molecular structure and a protective performance of which is improved. Further, the monomers including the alicyclic epoxy structural units have a multi-functional group site for combination, especially a multi-functional group monomer including an acrylate structure. A monomer including alicyclic epoxy structural unit can form a plurality of active sites to cross-link under plasma discharge to form a dense network structure, which has a high binding force with a substrate, especially metal, and can improve a corrosion resistance of the metal.
According to a specific embodiment of the present disclosure, an anticorrosive coating having a compact rigid molecular structure is formed by plasma polymerization coating of monomers including alicyclic epoxy structural units, and a hydrophobic coating is simultaneously formed by plasma polymerization coating on the anticorrosive coating, thus, coatings with excellent protective performance to the substrate are formed. Further, when a plasma monomer of the hydrophobic coating uses a monomer including alicyclic epoxy structural unit, the hydrophobic coating has a strong adhesion to the anti-corrosion coating, resulting in a better protective performance.
According to some specific embodiments of the present disclosure, a protective coating II is a plasma polymerization coating formed on a surface of a substrate when the substrate contacts plasmas, and the plasmas include a plasma of a monomer α, and the monomer α includes an alicyclic epoxy structural unit shown in formula (1),
wherein, A is a three to twenty-membered alicyclic structure.
According to some specific embodiments of the present disclosure, the alicyclic structure includes one or more substituents which may include alkyl such as methyl, ethyl, propyl, butyl, etc. The substituents may include halogen atom such as fluorine, chlorine, etc. The substituents may also include halogen-substituted alkyl such as fluorine-substituted methyl, chlorine-substituted methyl, fluorine-substituted ethyl, chlorine-substituted ethyl, fluorine-substituted propyl, chlorine-substituted propyl, fluorine-substituted butyl, chlorine-substituted butyl, etc.
According to some specific embodiments of the present disclosure, the A is a five-membered alicyclic structure or a six-membered alicyclic structure, which is rigid and stable.
According to some specific embodiments of the present disclosure, the monomer α further includes at least one selected from a group consisting of: a carbon-carbon double bond structural unit, a carbon-carbon triple bond structural unit, and an epoxy structural unit, which is conducive to forming a dense network structure by cross-linking multiple active sites. For example, the monomer α may be one or more selected from a group consisting of: a 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl formate, a 3,4-epoxycyclohexylmethyl methacrylate, a 3,4-epoxy cyclohexyl methacrylate, a 1,2-epoxy-4-vinyl cyclohexane, a bis (2,3-epoxycyclopentyl) ether, a 2,3-epoxycyclopentyl cyclopentyl ether, a vinyl cyclohexene diepoxide, a di-isoprene diepoxide, a bis ((3,4-epoxycyclohexyl) methyl) adipate, a 3,4-epoxy-6-methylcyclohexyl carboxylic acid-3′, 4′-epoxy-6′-methylcyclohexyl methyl ester, a dicyclopentadiene diepoxide, and the like. According to some specific embodiments of the present disclosure, the monomer α has a structure shown in formula (2),
wherein, R1, R2 and R3 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl, and R4 is a connecting bond, a C1-C10 alkylene or a halogen-substituted C1-C10 alkylene. Further, the R1, R2 and R3 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C4 alkyl, and a halogen-substituted C1-C10 alkyl, and the R4 is a connecting bond, a C1-C4 alkylene or a halogen-substituted C1-C10 alkylene. Further, the R1, R2 and R3 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl, and the R4 is a connecting bond, a methylene or an ethylidene. For example, the monomer α can be a 3,4-epoxycyclohexylmethyl methacrylate having a structure shown in formula (3), or can be a 3,4-epoxy cyclohexyl methacrylate having a structure shown in formula (4).
According to some specific embodiments of the present disclosure, the monomer α has a structure shown in formula (5),
wherein, R5 is a connecting bond, a C1-C10 alkylene or a halogen-substituted C1-C10 alkylene, and R6 has a structure selected from a group consisting of:
Further, R5 is a connecting bond, a C1-C4 alkylene or a halogen-substituted C1-C4 alkylene. For example, the monomer α can be a 1,2-epoxy-4-vinyl cyclohexane having a structure shown in formula (6), or can be a vinyl cyclohexene diepoxide having a structure shown in formula (7).
According to some specific embodiments of the present disclosure, the monomer α has a structure shown in formula (8),
wherein, R7 and R9 are respectively and independently selected from a group consisting of: a connecting bond, a C1-C10 alkylene, and a halogen-substituted C1-C10 alkylene. Further, R7 and R9 are respectively and independently selected from a group consisting of: a connecting bond, a C1-C4 alkylene, and a halogen-substituted C1-C4 alkylene. X and Y are respectively and independently selected from a group consisting of: a connecting bond, an oxygen atom, a carbonyl, and an ester. For example, the monomer α can be a 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl formate having a structure shown in formula (9), or can be a bis ((3,4-epoxycyclohexyl) methyl) adipate having a structure shown in formula (10).
According to some specific embodiments of the present disclosure, the plasmas only include a plasma of the monomer α. According to some specific embodiments of the present disclosure, in order to form a dense protective coating having a strong adhesion to the substrate, the plasmas include a plasma of the monomer α and a plasma of a monomer β, the monomer β includes a structural unit a, and the structural unit a has a structure shown in formula (11),
wherein, R10, R11 and R12 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl. For example, the monomer β may be one or more selected from a group consisting of: a acrylic acid, a hydroxyethyl acrylate, a hydroxypropyl acrylate, a methacrylic acid, a hydroxyethyl methacrylate, a hydroxypropyl methacrylate, a butyl acrylate, a 1,4-butanediol methacrylate, a 1,6-hexanediol diacrylate, a 1,6-hexanediol dimethacrylate, a ethylene glycol dimethacrylate, a diethylene glycol dimethacrylate, a triethylene glycol dimethacrylate, a tetraethylene glycol dimethacrylate, a 1,3-butanediol dimethacrylate, a neopentyl glycol dimethacrylate and the like. Further, the R10, R11 and R12 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C4 alkyl, and a halogen-substituted C1-C4 alkyl. Further, the R10, R11 and R12 are respectively and independently selected from a group consisting of: a hydrogen atom and a methyl. Further, the monomer β also includes a structural unit b, and the structural unit b includes at least one selected from a group consisting of a double bond structural unit, a triple bond structural unit, and an epoxy structural unit. Further, the structural unit b has a structure shown in formula (12),
wherein, R13, R14 and R15 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl. Further, the R13, R14 and R15 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C4 alkyl, and a halogen-substituted C1-C4 alkyl. Further, the R13, R14 and R15 are respectively and independently selected from a group consisting of: a hydrogen atom and a methyl. Further, the monomer β has a structure shown in formula (13),
wherein, R16 is a C2-C10 alkylene or a halogen-substituted C2-C10 alkylene, and n is an integer ranging from 1 to 10. For example, n is an integer of 1, R11 is a C2-C10 alkylene such as an ethylidene, a propylidene, a butylidene, a pentylidene, etc. For example, n is an integer of 1, R11 is a halogen-substituted C2-C10 alkylene such as a halogen-substituted ethylidene, a halogen-substituted propylidene, a halogen-substituted butylidene, a halogen-substituted pentylidene, etc. For example, n is an integer ranging from 2 to 10, R11 is an ethylidene or a propylidene. According to some specific embodiments of the present disclosure, bonding the monomer α including an alicyclic epoxy structural unit with the monomer β including an acrylate structure, especially with the monomer β including a diacrylate structure shown in formula (13), it is more conducive to forming a dense protective coating with strong adhesion force with the substrate after the plasma coating, and a corrosion resistance of the substrate is further improved.
According to some specific embodiments of the present disclosure, an addition amount of the monomer β and an addition amount of the monomer α can be adjusted according to the actual situation. Generally, a mass ratio of the monomer β to the monomer α ranges from 1:10 to 10:1, such as 1:1, 1:2, 1:3, 2:3, 1:4, 1:5, 2:1, 3:1, 3:2, 4:1, 5:1, etc.
According to some specific embodiments of the present disclosure, the substrate is a metal, such as iron, magnesium, aluminum, copper or an alloy thereof. According to some specific embodiments, the substrate is plastic, fabric, glass, electrical assemblies, or optical instruments. Specifically, the electrical assemblies can be printed circuit boards (PCB), electronic products or electronic assembly semi-finished products. The substrate can be an electronic product, for example, it is not limited to a mobile phone, a tablet, a keyboard, an e-reader, a wearable, a display, etc. The substrate can also be any suitable electrical component of the electrical assemblies. Specifically, the electrical component can be a resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch, LED, LED display, piezoelectric element, optoelectronic component or antenna or oscillator.
According to some specific embodiments of the present disclosure, a preparation method of the aforementioned protective coating II is provided. The preparation method includes: providing a substrate, and contacting the substrate with plasmas to form a plasma polymerization coating on a surface of the substrate. The plasmas and the substrate are described as above.
According to some specific embodiments of the present disclosure, for further enhancing an adhesion between the plasma coating and the substrate, the substrate for coating is pretreated by continuous plasma. For example, in an inert gas atmosphere, a plasma discharge power ranges from 20 W to 500 W, a discharge mode is continuous, and a duration time of discharge ranges from 1 min to 15 min. According to some specific embodiments, the substrate for coating is pretreated by means of heat, oxygen or high-energy radiation.
According to some specific embodiments of the present disclosure, the plasmas are excited by a continuous wave. According to some specific embodiments, the plasmas are excited in a pulse manner. The specific conditions of plasma coating can adopt the corresponding conditions in conventional technology. For example, the substrate is placed in a reaction chamber of a plasma chamber, the reaction chamber is vacuumized to 20 mTorr to 250 mTorr, and inert gases such as He, Ar, O2 or mixed gases thereof are introduced. A monomer for reacting is introduced into the chamber in the form of vapor, and the flow rate of the monomer ranges from 10 μL/min to 2000 μL/min. The power supply is turned on to generate plasma, so that a chemical vapor deposition occurs on the surface of the substrate. The temperature in the chamber is controlled in a range of 20° C. to 80° C., the monomer is gasified at a temperature ranging from 50° C. to 120° C. and under vacuum condition. The plasmas are excited in a continuous wave, a plasma discharge power ranges from 10 W to 180 W, and a discharge duration time ranges from 10 min to 600 min. Alternatively, the plasmas can be excited in a pulse mode, a pulse frequency in the pulse mode ranges from 20 Hz to 80 KHz, a duty cycle ranges from 0.1% to 80%, and an average pulse power density ranges from 0.001 W/m3 to 500 W/m3.
According to some specific embodiments of the present disclosure, the plasma discharge methods can be various conventional discharge methods, for example, electrodeless discharge (e.g. radio frequency inductively coupled discharge, microwave discharge), single-electrode discharge (e.g. corona discharge, plasma jet formed by single-electrode discharge), two-electrode discharge (e.g. dielectric barrier discharge, exposed electrode radio frequency glow discharge) and multi-electrode discharge (e.g. discharge using a floating electrode as the third electrode).
A device is also provided by some specific embodiments of the present disclosure. At least part of the surface of the device has any of the aforementioned protective coating II. According to some specific embodiments, only the aforementioned protective coating II is formed on part of or all of the surface of the device. According to some specific embodiments, the aforementioned protective coating II and other coating are formed on part of or all of the surface of the device.
A protective coating is also provided by some specific embodiments of the present disclosure, which includes a coating I and a coating II deposited on a substrate;
the coating II is the aforementioned protective coating II;
the coating I is a plasma polymerization coating formed on the coating II by contacting the coating II with a plasma including a monomer γ;
and the monomer γ includes one or more selected from a group consisting of: an alkane, a halogenated alkane, an alkene, a halogenated alkene, an alkyne, a halogenated alkyne, an acrylic ester, and a halogenated acrylic ester.
According to some specific embodiments of the present disclosure, the coating I is a plasma polymerization coating formed on the coating II by contacting the coating II with a plasma including a monomer γ shown in formula (14),
wherein, R17, R18 and R19 are respectively and independently selected from a group consisting of: a hydrogen atom, a C1-C10 alkyl, and a halogen-substituted C1-C10 alkyl, and R20 is a C1-C20 hydrocarbyl or a halogen-substituted C1-C20 hydrocarbyl. Further, for a better hydrophobicity, R20 is a C1-C20 hydrocarbyl or a halogen-substituted C4-C20 hydrocarbyl. Considering the effect of halogen elements on the environment, according to some specific embodiments, R17, R18 and R19 are respectively and independently selected from a group consisting of a hydrogen atom and a C1-C10 alkyl. Further, the R17, R18 and R19 are respectively and independently selected from a group consisting of a hydrogen atom and a methyl, and R20 is a C1-C20 hydrocarbyl, particularly the R20 is a C4-C20 hydrocarbyl. According to some specific embodiments of the present disclosure, the hydrocarbyl is a saturated alkyl, such as a methyl, an ethyl, a propyl, a butyl, a pentyl, a hexyl or an octadecyl, etc. According to some specific embodiments of the present disclosure, the hydrocarbyl is an unsaturated alkenyl, alkynyl or aromatic hydrocarbyl. For example, the monomer γ can be one or more selected from a group consisting of: a cyclohexyl methacrylate, an octadecyl acrylate, an isodecyl methacrylate, an allyl methacrylate, an isobornyl methacrylate, a tert-butyl methacrylate, a benzyl methacrylate, a phenyl methacrylate, an isopropyl methacrylate, and a 9-anthracene methyl methacrylate. According to some specific embodiments, the monomer γ has a structure shown in formula (15),
wherein, R21 is a connecting bond, a C1-C10 alkylene, and a halogen-substituted C1-C10 alkylene, and B is an aromatic ring structure or a three to twenty-membered alicyclic structure. Further, B is a five-membered alicyclic structure or is a six-membered alicyclic structure. Further, B is a cyclohexyl or a cyclopentyl. Considering the effect of halogen elements on the environment, according to some specific embodiments, R21 is a connecting bond or a C1-C10 alkylene, further, R21 is a connecting bond, a methylene or an ethylidene. When the monomer γ has a structure shown in formula (15) and B is an alicyclic structure, the coating I and the coating II both have an alicyclic structure which has a better bonding effect. Therefore, the combination of the coating I and the coating II result in a better protective performance.
According to some specific embodiments of the present disclosure, the protective coating further includes a coating III. The coating III is a plasma polymerization coating formed by contacting the substrate with a plasma including a monomer δ. The coating II is a plasma polymerization coating formed on the coating III by contacting the coating III with a plasma including a monomer δ. The monomer δ includes a structural unit c and a structural unit d, and the structural unit c and the structural unit d both have a carbon-carbon double bond structure and an ester structure respectively. The coating III formed by plasma chemical vapor deposition of the monomer δ with double unsaturated ester structure is conducive to improving the adhesion between the substrate and coating II, thereby improving the density and adhesion of the protective coating. For example, the monomer δ may be one or more selected from a group consisting of: a 1,4-butanediol methacrylate, a 1,6-hexanediol dimethacrylate, a ethylene glycol dimethacrylate, a diethylene glycol dimethacrylate, a triethylene glycol dimethacrylate, a tetraethylene glycol dimethacrylate, a 1,3-butanediol dimethacrylate, a neopentyl glycol dimethacrylate, a methacrylic anhydride, a 2-benzylidene malonic acid dipropyl-2-enyl ester, a diethyl diallyl malonate, a 1,4-butanediol diacrylate, a 1,4-butanediol dimethacrylate, and a 1,6-hexanediol diacrylate. According to some specific embodiments, the structural unit c has a structure shown in formula (16),
wherein, in some specific embodiments, R22, R23 and R24 are respectively and independently selected from a halogen-substituted C1-C10 alkyl, further selected from a halogen-substituted C1-C4 alkyl. Considering the effect of halogen elements on the environment, in some specific embodiments, R22, R23 and R24 are respectively and independently selected from a group consisting of a hydrogen atom and a C1-C10 alkyl, further selected from a group consisting of a hydrogen atom and a C1-C4 alkyl, and further selected from a group consisting of a hydrogen atom and a methyl. According to some specific embodiments, the structural unit d has a carbon-carbon double bond structure shown in formula (17),
wherein, in some specific embodiments, R25, R26 and R27 are respectively and independently selected from a halogen-substituted C1-C10 alkyl, further selected from a halogen-substituted C1-C4 alkyl. Considering the effect of halogen elements on the environment, in some specific embodiments, R25, R26 and R27 are respectively and independently selected from a group consisting of a hydrogen atom and a C1-C10 alkyl, further selected from a group consisting of a hydrogen atom and a C1-C4 alkyl, and further selected from a group consisting of a hydrogen atom and a methyl. In some specific embodiments, the monomer δ has a structure shown in formula (18).
wherein, in some specific embodiments, R28 is a halogen-substituted alkylene, and n is an integer ranging from 0 to 10. For example, n is an integer of 1, R28 is a halogen-substituted C2-C10 alkylene such as a halogen-substituted ethylidene, a halogen-substituted propylidene, a halogen-substituted butylidene, a halogen-substituted pentylidene, etc. Considering the effect of halogen elements on the environment, in some specific embodiments, R28 is a C2-C10 alkylene, and n is an integer ranging from 1 to 10. For example, n is an integer of 1, R28 is a C2-C10 alkylene such as an ethylidene, a propylidene, a butylidene, a pentylidene, etc. For example, n is an integer ranging from 2 to 10, R22 is an ethylidene or a propylidene and so on. The coating III, especially the coating III formed by the monomer δ including the diacrylate structure shown in formula (18), which is conducive to improving the adhesion between the substrate and coating II, thereby improving the density and adhesion of the protective coating.
In terms of plasma anti-corrosion coating, a common method is to use a perfluorinated monomer to plasma coat the substrate. For such coatings, there is a problem of poor adhesion to the substrate due to the perfluoro groups of the monomer, and fluoropolymers will release toxic substances such as perfluorooctyl carboxylate or perfluorooctane sulfonate to the environment, which will easily pollute the environment. In response, the United States Environmental Protection Agency (EPA) issued strict regulations to prohibit the use of fluoropolymers containing long carbon chains. The protective coating according to some specific embodiments of the present disclosure, on the one hand, has excellent adhesion force with the substrate, and on other hand, even without halogen F, has a better protective performance than the plasma coating formed by F-containing monomers.
Some specific embodiments of the present disclosure also provide a preparation method of the aforementioned protective coating. The method includes: providing a substrate, and forming the protective coating on the substrate by performing a plasma deposition. The plasmas and the substrate are described above.
According to some specific embodiments of the present disclosure, the specific conditions of the plasma coating can adopt the corresponding conditions in conventional technology. For example, the substrate is placed in a reaction chamber of a plasma chamber, the reaction chamber is vacuumized to 1 mTorr to 250 mTorr, and inert gases such as He, Ar, O2 or mixed gases thereof are introduced. Monomers for reacting are introduced into the chamber in the form of vapor, and the flow rate of the monomers ranges from 40 μL/min to 2000 μL/min. The power supply is turned on to generate plasma, so that a chemical vapor deposition occurs on the surface of the substrate and the coating III, the coating II, the coating I are formed respectively. The temperature in the chamber is controlled in a range of 20° C. to 80° C., the monomers are gasified at a temperature ranging from 70° C. to 150° C. and under vacuum condition. The plasmas are excited in a continuous wave, a plasma discharge power ranges from 10 W to 180 W, and a discharge duration time ranges from 100 s to 7200 s. Alternatively, the plasmas can be excited in a pulse mode, a pulse power ranges from 20 W to 500 W, a pulse frequency in the pulse mode ranges from 20 Hz to 80 KHz, a duty cycle ranges from 0.1% to 80%, and a discharge duration time ranges from 100 s to 20000 s.
The present disclosure is further described in the following specific embodiments.
Description of Test Method
5V salt water test: the test process was as follows: 1. 5V voltage was provided for circuit boards by a power supply; 2. the circuit boards were soaked in 3.6% salt water; 3. the current were detected by a computer; 4. the failure time (current >0.6 mA) was recorded.
Salt spray test: performing a test according to GB/T 2423.18-2000 environmental test method for electrical and electronic products.
High temperature and high humidity test: performing a test according to GB/T 2423.34-2012.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 80 mTorr, and a temperature in the chamber was 35° C.
(2) Argon gas was introduced at a flow rate of 10 sccm, and a radio frequency plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 100 W, and the discharge duration time was 80 s.
(3) A mixture of a monomer of triethylene glycol dimethacrylate and a monomer of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl formate (the mass ratio was 1:1) was introduced at a flow rate of 600 μl/min, and the temperature in the chamber was 60° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 100 μs, the pulse frequency was 100 Hz, the discharge power was 10 W, and the discharge duration time was 120 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 20 mTorr, and a temperature in the chamber was 45° C.
(2) Helium gas was introduced at a flow rate of 300 sccm, and a radio frequency plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 300 W, and the discharge duration time was 60 s.
(3) A mixture of a monomer of tetraethylene glycol dimethacrylate and a monomer of 3,4-epoxycyclohexylmethyl methacrylate (the mass ratio was 2:1) was introduced at a flow rate of 200 μl/min, and the temperature in the chamber was 65° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 200 μs, the pulse frequency was 100 Hz, the discharge power was 35 W, and the discharge duration time was 40 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 250 mTorr, and a temperature in the chamber was 45° C.
(2) Helium gas was introduced at a flow rate of 120 sccm, and a radio frequency plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 300 W, and the discharge duration time was 90 s.
(3) A mixture of a monomer of 1,6-hexanediol diacrylate and a monomer of 1,2-epoxy-4-vinyl cyclohexane (the mass ratio was 3:2) was introduced at a flow rate of 200 μl/min, and the temperature in the chamber was 70° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 200 μs, the pulse frequency was 50 Hz, the discharge power was 100 W, and the discharge duration time was 35 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 100 mTorr, and a temperature in the chamber was 80° C.
(2) Oxygen gas was introduced at a flow rate of 300 sccm, and a microwave plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 500 W, and the discharge duration time was 90 s.
(3) A mixture of a monomer of hydroxypropyl methacrylate and a monomer of bis ((3,4-epoxycyclohexyl) methyl) adipate (the mass ratio was 1:2) was introduced at a flow rate of 2000 μl/min, and the temperature in the chamber was 45° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 300 μs, the pulse frequency was 50 Hz, the discharge power was 180 W, and the discharge duration time was 15 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 100 mTorr, and a temperature in the chamber was 80° C.
(2) Helium gas was introduced at a flow rate of 180 sccm, and a microwave plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 120 W, and the discharge duration time was 600 s.
(3) A mixture of a monomer of 1,3-butanediol dimethacrylate and a monomer of vinyl cyclohexene diepoxide (the mass ratio was 2:1) was introduced at a flow rate of 800 μl/min, and the temperature in the chamber was 45° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 300 μs, the pulse frequency was 50 Hz, the discharge power was 300 W, and the discharge duration time was 20 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 80 mTorr, and a temperature in the chamber was 50° C.
(2) Helium gas was introduced at a flow rate of 160 sccm, and a microwave plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 180 W, and the discharge duration time was 300 s.
(3) A monomer of 1,2-epoxy-4-vinyl cyclohexane was introduced at a flow rate of 500 μl/min, and the temperature in the chamber was 85° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 500 μs, the pulse frequency was 20 Hz, the discharge power was 100 W, and the discharge duration time was 20 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
(1) A substrate Fe sheet (30*20*2 mm) and a substrate Mg sheet (30*20*2 mm) were placed in a 500 L plasma vacuum reaction chamber, the reaction chamber was vacuumized continuously to get the vacuum degree in the reaction chamber reach 80 mTorr, and a temperature in the chamber was 60° C.
(2) Helium gas was introduced at a flow rate of 140 sccm, and a microwave plasma discharge was turned on to pretreat the substrates. The discharge power in this pretreatment stage was 180 W, and the discharge duration time was 200 s.
(3) A monomer of ethylene glycol dimethacrylate was introduced at a flow rate of 70001/min, and the temperature in the chamber was 55° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was changed to pulse. The pulse width was 300 μs, the pulse frequency was 50 Hz, the discharge power was 80 W, and the discharge duration time was 40 min.
(4) After coating, air was introduced to restore the reaction chamber to normal pressure. The chamber was opened, and the Fe sheet and Mg sheet were taken out. A salt spray test and a high temperature and high humidity test were performed and the test results were listed in the following Table 1 and Table 2 respectively.
A circuit board, a Mg sheet and a Fe sheet were placed in a plasma chamber, the chamber was vacuumized continuously to 20 mTorr, and helium gas was introduced at a flow rate of 80 sccm. A radio frequency plasma discharge was turned on to pretreat the substrates, the discharge power in this pretreatment stage was 100 W, and the discharge duration time was 600 s.
Thereafter, a monomer of 1,4-butylene dimethacrylate was gasified at a gasification temperature of 100° C. and then was introduced into the chamber for plasma chemical vapor deposition, and the flow rate of the monomer was 150 μL/min. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 1000 Hz, the discharge power was 50 W, and the discharge duration time was 3600 s.
Thereafter, a mixture of a monomer of 1,6-hexanediol diacrylate and a monomer of 1,2-epoxy-4-vinyl cyclohexane (the mass ratio was 2:1) was introduced at a flow rate of 40 μl/min, and the gasification temperature of the monomers was 120° C. The plasma in the chamber was generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 1000 Hz, the discharge power was 10 W, and the discharge duration time was 7200 s.
Thereafter, a monomer vapor of octadecyl acrylate was introduced at a flow rate of 100 μl/min, and the gasification temperature of the monomer was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 1000 Hz, the discharge power was 180 W, and the discharge duration time was 7200 s. The coating process had been accomplished.
After coating, the compressed air was introduced to restore the reaction chamber to normal pressure. The circuit board, the Mg sheet and the Fe sheet were taken out. A salt water test and a salt spray test were performed and the test results were listed in the Table 3.
A circuit board, a Mg sheet and a Fe sheet were placed in a plasma chamber, the chamber was vacuumized continuously to 8 mTorr, and helium gas was introduced at a flow rate of 80 sccm. A radio frequency plasma discharge was turned on to pretreat the substrates, the discharge power in this pretreatment stage was 100 W, and the discharge duration time was 600 s.
Thereafter, a monomer of 1,6-hexanediol dimethacrylate was gasified at a gasification temperature of 100° C. and then was introduced into the chamber for plasma chemical vapor deposition, and the flow rate of the monomer was 150 μL/min. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 500 Hz, the discharge power was 50 W, and the discharge duration time was 3600 s.
Thereafter, a mixture of a monomer of 1,6-hexanediol dimethacrylate and a monomer of vinyl cyclohexene diepoxide (the mass ratio was 1:2) was introduced at a flow rate of 40 μl/min, and the gasification temperature of the monomers was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 500 Hz, the discharge power was 10 W, and the discharge duration time was 7200 s.
Thereafter, a monomer vapor of tert-butyl methacrylate was introduced at a flow rate of 100 μl/min, and the gasification temperature of the monomer was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 500 Hz, the discharge power was 25 W, and the discharge duration time was 7200 s. The coating process had been accomplished.
After coating, the compressed air was introduced to restore the reaction chamber to normal pressure. The circuit board, the Mg sheet and the Fe sheet were taken out. A salt water test and a salt spray test were performed and the test results were listed in the Table 3.
A circuit board, a Mg sheet and a Fe sheet were placed in a plasma chamber, the chamber was vacuumized continuously to 100 mTorr, and helium gas was introduced at a flow rate of 120 sccm. A radio frequency plasma discharge was turned on to pretreat the substrates, the discharge power in this pretreatment stage was 180 W, and the discharge duration time was 300 s.
Thereafter, a monomer of 1,6-hexanediol dimethacrylate was gasified at a gasification temperature of 110° C. and then was introduced into the chamber for plasma chemical vapor deposition, and the flow rate of the monomer was 220 μL/min. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 5000 Hz, the discharge power was 25 W, and the discharge duration time was 2200 s.
Thereafter, a mixture of a monomer of triethylene glycol dimethacrylate and a monomer of 3,4-epoxycyclohexylmethyl methacrylate (the mass ratio was 3:2) was introduced at a flow rate of 40 μl/min, and the gasification temperature of the monomers was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 5000 Hz, the discharge power was 10 W, and the discharge duration time was 7200 s.
Thereafter, a monomer vapor of isobornyl methacrylate was introduced at a flow rate of 100 μl/min, and the gasification temperature of the monomer was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 45%, the pulse frequency was 5000 Hz, the discharge power was 25 W, and the discharge duration time was 7200 s. The coating process had been accomplished.
After coating, the compressed air was introduced to restore the reaction chamber to normal pressure. The circuit board, the Mg sheet and the Fe sheet were taken out. A salt water test and a salt spray test were performed and the test results were listed in the Table 3.
A circuit board and a Mg sheet were placed in a plasma chamber, the chamber was vacuumized continuously to 80 mTorr, and helium gas was introduced at a flow rate of 120 sccm. A radio frequency plasma discharge was turned on to pretreat the substrates, the discharge power in this pretreatment stage was 180 W, and the discharge duration time was 300 s.
Thereafter, a monomer of 1,4-butanediol dimethacrylate was gasified at a gasification temperature of 110° C. and then was introduced into the chamber for plasma chemical vapor deposition, and the flow rate of the monomer was 120 μL/min. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge power was 20 W, and the discharge duration time was 3600 s.
Thereafter, a mixture of a monomer of 1,6-hexanediol dimethacrylate and a monomer of bis ((3,4-epoxycyclohexyl) methyl) adipate (the mass ratio was 2:1) was introduced at a flow rate of 150 μl/min, and the gasification temperature of the monomers was 120° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge power was 10 W, and the discharge duration time was 3600 s.
Thereafter, a monomer vapor of benzyl methacrylate was introduced at a flow rate of 150 μl/min, and the gasification temperature of the monomer was 150° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge power was 150 W, and the discharge duration time was 7200 s. The coating process had been accomplished.
After coating, the compressed air was introduced to restore the reaction chamber to normal pressure. The circuit board, the Mg sheet and the Fe sheet were taken out. A salt water test and a salt spray test were performed and the test results were listed in the Table 3.
A circuit board, a Mg sheet and a Fe sheet were placed in a plasma chamber, the chamber was vacuumized continuously to 80 mTorr, and helium gas was introduced at a flow rate of 120 sccm. A radio frequency plasma discharge was turned on to pretreat the substrates, the discharge power in this pretreatment stage was 180 W, and the discharge duration time was 300 s.
Thereafter, a monomer of 1,4-butanediol diacrylate was gasified at a gasification temperature of 110° C. and then was introduced into the chamber for plasma chemical vapor deposition, and the flow rate of the monomer was 120 μL/min. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge power was 20 W, and the discharge duration time was 3600 s.
Thereafter, a monomer of 2-(perfluorohexyl)ethyl methacrylate was introduced at a flow rate of 120 μl/min, and the gasification temperature of the monomer was 110° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge duration time was 3600 s, and the discharge power was 180 W.
Thereafter, a monomer vapor of 2-(perfluorododecyl)ethylacrylate was introduced at a flow rate of 160 μl/min, and the gasification temperature of the monomer was 110° C. The plasmas in the chamber were generated by a radio frequency discharge, and the output mode was pulse. The pulse duty cycle was 25%, the pulse frequency was 20 kHz, the discharge duration time was 7200 s, and the discharge power was 180 W. The coating process had been accomplished.
After coating, the compressed air was introduced to restore the reaction chamber to normal pressure. The circuit board, the Mg sheet and the Fe sheet were taken out. A salt water test and a salt spray test were performed and the test results were listed in the Table 3.
The results in above table 3 show that even without halogen F, the protective coating of the present disclosure has a better protective performance than the plasma coating formed by perfluorinated monomers.
Although the present disclosure has been disclosed above, the disclosure is not limited hereto. Those skilled in the art can modify and vary the embodiments without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure shall be subject to the scope defined in claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202010526322.5 | Jun 2020 | CN | national |
| 202010526684.4 | Jun 2020 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/094737 | 5/20/2021 | WO |
