CN115677983A - Method for modifying parylene, parylene modified material and waterproof coating - Google Patents

Abstract

The present application relates to the technical field of waterproof materials, in particular, to a method for modifying parylene, a modified parylene material and a waterproof coating. The method for modifying p-parylene includes: mixing raw materials in the presence of oxygen; the raw materials include free radical precursors, parylene particles and modified substances; and the modified substances include a first modifier. The modification method provided by the application can efficiently introduce hydroxyl or isocyanate groups into the skeleton of parylene molecules and effectively increase the ratio of hydroxyl or isocyanate groups introduced on the skeleton of parylene molecules, so that the modified poly The waterproof performance of p-xylene is improved and can be used as a waterproof material, which is beneficial to realize the full recycling of the parylene stripped from the deposition chamber.

Description

Modification method of parylene, parylene modified material and waterproof coating

technical field

The present application relates to the technical field of waterproof materials, in particular, to a method for modifying parylene, a modified parylene material and a waterproof coating.

Background technique

Compared with ordinary conformal coatings, parylene protective materials have more excellent protective performance, uniform film-forming performance and continuous film-forming ability, making parylene protective materials one of the most common protective materials in the electronics industry .

However, there is a big difference between the preparation process of the parylene protective material and the common three-proof paint, and the parylene protective material can only be deposited on the target device by vapor deposition after pyrolysis of parylene under vacuum conditions ( For example, the surface of electronic devices, etc.) is formed. Moreover, the preparation of the parylene protective material needs to be carried out in the deposition chamber, resulting in a large amount of parylene being deposited and attached to other areas outside the target device in the deposition chamber.

The parylene sheet stripped from the deposition chamber has poor waterproof performance and cannot be directly used as a waterproof material, and cannot be fully recycled, resulting in a large amount of waste of parylene.

Contents of the invention

The purpose of this application is a modification method of parylene, a parylene modified material and a waterproof coating, which aims to improve the existing problem that the parylene stripped from the deposition chamber cannot be fully recycled. technical problem.

In the first aspect, the present application provides a method for modifying parylene, comprising: mixing raw materials in the presence of oxygen; raw materials include free radical precursors, parylene particles and modified substances; modified substances include first modifier.

Wherein, the structural formula of the active ingredient in the free radical precursor is as follows:

R ₁ , R ₂ and R ₃ are each independently selected from an alkyl group having 2-4 C atoms.

The structural formula of the first modifying agent is as follows:

m is a natural number ≥ 0, R ₄ is a hydroxyl group or an isocyanate group.

In the present application, the free radical precursor, the parylene particles and the modifying substance including the first modifying agent are mixed. In the presence of oxygen, oxygen can be inserted between the boron (B) atom of the radical precursor and the alkyl group (i.e., _R1 group, _R2 group or _R3 group) and homolytically split to form an alkoxyl radical, The formed alkoxy radicals have better hydrogen-absorbing ability, and the alkoxy radicals can effectively capture the hydrogen on the molecular structure of parylene, so that the parylene molecules can be combined with the acrylic acid in the first modifier molecule The carbon-carbon double bond of ester group is covalently bonded, and then can effectively introduce _R group (being hydroxyl or isocyanate group) on the skeleton of parylene molecule, effectively improves the R that introduces on the skeleton of parylene molecule The ratio of ₄ groups improves the waterproof performance of the modified parylene and can be used as a waterproof material, which is beneficial to fully recycle the parylene stripped from the deposition chamber.

In some embodiments of the first aspect of the present application, the modified substance also includes a second modifier, and the structural formula of the second modifier is as follows:

n is a natural number ≥ 0, and R ₅ is a hydroxyl group or an isocyanate group.

The raw material includes a first material and a second material; the first material includes a radical precursor, parylene particles and a first modifier; the second material includes a second modifier.

The step of mixing the raw materials includes: firstly performing the first mixing on the first material, and then performing the second mixing on the first mixed system and the second material.

Wherein, R in the first modifier is _a hydroxyl group, and R in the second modifier is an isocyanate group; or _, R _in the first modifier is an isocyanate group, and R in the second modifier is _an isocyanate group For hydroxyl.

First, the first material is first mixed, so that the _R group can be effectively introduced into the skeleton of the parylene molecule, and then the first mixed system is mixed with the second material containing the second modifier, and the polymer Part of the R group on the skeleton of the p-xylene molecule can be covalently bonded _with the _R group in the second modifier to carry out hydroxyl and isocyanate groups, and then make the acrylate group in the second modifier also Can be introduced into the skeleton of the parylene molecule, that is, the skeleton of the whole modified parylene molecule contains R _group and acrylate group at the same time, which is beneficial to further improve the modified parylene waterproof performance.

Optionally, the second material further includes a catalyst, and the catalyst includes N-methylmorpholine or proline.

The use of the catalyst is beneficial to promote the covalent bonding reaction of the R ₄ group and the R ₅ group.

In some embodiments of the first aspect of the present application, the first modifier and the second modifier are each independently selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isocyanoethyl methacrylate At least one of ester and isocyanate ethyl acrylate.

Optionally, the first modifier is hydroxyethyl acrylate, and the second modifier is isocyanate ethyl acrylate; or, the first modifier is isocyanate ethyl acrylate, and the second modifier is hydroxyethyl acrylate.

Under the above circumstances, it is beneficial to further improve the waterproof performance of the modified parylene.

In some embodiments of the first aspect of the present application, the first material further includes a plasticizer; and/or, the second material further includes a plasticizer.

The first material and/or the second material contains a plasticizer, which is beneficial to enable the first mixing and/or the second mixing to form a relatively uniform mixture shape, which is convenient for subsequent further reaction and processing, and is conducive to further improving the modification. After the parylene waterproof performance.

Optionally, the plasticizer is a mixture comprising diethylene glycol dibenzoate and dipropylene glycol dibenzoate.

In some embodiments of the first aspect of the present application, the active ingredient is selected from triethylboron, tripropylboron or tributylboron.

The active ingredient is selected from triethyl boron, tripropyl boron or tributyl boron, which can form alkoxyl radicals with strong hydrogen-absorbing ability, which is conducive to further improving the R ₄ introduced on the skeleton of parylene molecules. The proportion of the group further improves the waterproof performance of the modified parylene.

Optionally, the free radical precursor includes at least one of triethylboron-1,6-hexanediamine complex and triethylboron-1,3-propanediamine complex; the raw material also includes Complexing agent.

Due to the flammability of triethyl boron, it is not easy to store and transport directly. In order to ensure safety, triethyl boron is generally stored in the form of complexes. When the free radical precursor is selected from the complexes of triethyl boron When it is necessary to add a decomplexing agent, so that during the mixing process of raw materials, triethyl boron can be released from the complex system to form ethoxy radicals.

Optionally, the decomplexing agent includes at least one of an organic acid or a substance containing isocyanate groups.

The above-mentioned substances can effectively release triethylboron from the complex system.

Optionally, the organic acid includes at least one of methacrylic acid, acrylic acid, lactic acid and acetic acid.

Optionally, the isocyanate group-containing substance includes at least one of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.

In some embodiments of the first aspect of the present application, the particle size of the parylene particles is 0.1-40 μm.

The particle diameter of the parylene particles is 0.1-40 μm, which is convenient to make sufficient mixing and contact between the raw materials, and is conducive to improving the modification group (R ₄ group, or R ₄ group) introduced in the parylene molecular skeleton. group and acrylate group), which in turn is beneficial to further improve the waterproof performance of the modified parylene.

In some embodiments of the first aspect of the present application, the preparation method of parylene particles includes: first pulverizing the parylene initial material to a particle size of 1-20 nm, and then grinding to a particle size of 0.1-40 μm; wherein , adding antioxidants during the grinding process.

First, the initial parylene is crushed to a particle size of 1-20nm, which is convenient for subsequent grinding to form particles with a particle size of 0.1-40μm; due to the small size after crushing, friction between parylene particles during the grinding process And the collision is relatively intense, which will cause the temperature of the grinding system to rise. Adding an antioxidant during the grinding process is beneficial to avoid thermal oxygen degradation of parylene during the grinding process.

Optionally, the antioxidant includes at least one of phenolic antioxidants, amine antioxidants, phosphite antioxidants and thioether antioxidants.

Optionally, the antioxidants include phenolic antioxidants and thioether antioxidants.

Antioxidants include phenolic antioxidants and thioether antioxidants, which are beneficial to further improve the ability of parylene to resist thermal oxygen degradation during grinding.

Optionally, phenolic antioxidants include tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, 1,3,5-tris(3,5-di-tert Butyl-4-hydroxybenzyl)-1,3,5-triazinane-2,4,6-trione, tris(4-tert-butyl-3-hydroxy-2,6-diisocyanurate Tolyl) ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, octadecyl 3-(3,5 -at least one of di-tert-butyl-4-hydroxyphenyl)propionate and 4,6-bis(octylthiomethyl)o-cresol.

Optionally, the thioether antioxidant includes at least A sort of.

Optionally, the grinding time is ≤30min.

The grinding time is ≤30min, which is beneficial to avoid the effect of the system temperature rising due to the long grinding time, which will affect the antioxidant's ability to fully exert its resistance to thermal oxygen degradation, resulting in a decrease in the resistance to thermal oxygen degradation.

In some embodiments of the first aspect of the present application, the first mixing is by stirring and mixing, the time of the first mixing is 0.5-5min, and the rotation speed of the first mixing is 1500-2500rpm; and/or, the second mixing is by stirring and mixing, The time of the second mixing is 0.5-5min, and the rotational speed of the second mixing is 1500-2500rpm.

Under the above conditions, it is beneficial to realize sufficient mixing, and then improve the modification effect of the parylene.

In the second aspect, the present application provides a modified parylene material, which is prepared by the method for modifying parylene provided in the first aspect above.

The modified parylene material provided by this application has better waterproof performance, and can be used as a waterproof material to improve the waterproof effect of waterproof coatings.

In a third aspect, the present application provides a waterproof coating, including the parylene modified material provided in the second aspect above.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the accompanying drawings used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, so It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.

Fig. 1 shows the flowchart of the modification method of p-parylene provided by the present application.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

The application provides a modification method of p-parylene, and Fig. 1 shows the flow chart of the modification method of p-parylene provided by the application, please refer to Fig. 1, the modification of p-parylene Methods include:

S10, performing micronization treatment on the parylene initial material to obtain parylene particles.

Before introducing modifying groups (i.e. hydroxyl or isocyanate groups) into the skeleton of p-parylene, the particle size of parylene is controlled to 0.1-40 μm, which is convenient for the raw materials to be fully mixed and contacted in the subsequent mixing process , which is beneficial to increase the ratio of the modified groups introduced into the molecular skeleton of parylene, and further helps to improve the waterproof performance of the modified parylene.

As an example, the particles of parylene may be 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 20 μm, 25 μm or 40 μm and so on.

Further, the preparation method of the parylene particles includes: first pulverizing the parylene initial material to a particle size of 1-20 nm, and then grinding to a particle size of 0.1-40 μm; and adding an antioxidant during the grinding process.

Due to the large size of the parylene initial material, it is not easy to directly form particles with a particle size of 0.1-40 μm, and in the process of directly forming particles with a particle size of 0.1-40 μm, it may occur that the friction between the particles will make the system The higher temperature will cause thermal oxygen degradation of part of the parylene, which is not conducive to the effect of subsequent modification.

First, the initial parylene is crushed to a particle size of 1-20nm, which is convenient for subsequent grinding to form particles with a particle size of 0.1-40μm; due to the small size after crushing, friction between parylene particles during the grinding process And the collision is more intense, which will lead to an increase in the temperature of the grinding system. Adding an antioxidant during the grinding process is beneficial to avoid thermal oxygen degradation of parylene due to the high temperature of the system during the grinding process.

As an example, in this application, the parylene starting material is a parylene sheet that is directly peeled off from the deposition chamber, which is beneficial to fully recycle the parylene peeled off from the deposition chamber.

In this application, the mass ratio of the pulverized parylene to the antioxidant added during the grinding process is 1: (0.005-0.01). Under the above conditions, it is beneficial to further effectively avoid thermal oxygen degradation of parylene.

In the present application, the antioxidant includes at least one of phenolic antioxidants, amine antioxidants, phosphite antioxidants and thioether antioxidants.

Phenolic antioxidants and amine antioxidants are mainly used as proton donors to achieve antioxidant effects; phosphite antioxidants and thioether antioxidants are mainly produced during the thermal oxidation of parylene The peroxide is reduced to achieve the protective effect on parylene. Moreover, phenolic antioxidants, amine antioxidants, phosphite antioxidants, and thioether antioxidants all have certain high temperature resistance properties, which is beneficial to avoid failures due to insufficient heat resistance of the antioxidant itself. Fully protective parylene case.

As an example, the phenolic antioxidants include tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (Irganox 1010, CAS No.: 6683-19-8), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazinane-2,4,6-trione (Irganox 3114, CAS No.: 27676 -62-6), tris(4-tert-butyl-3-hydroxy-2,6-xylyl)isocyanurate (Irganox 1790, CAS No.: 40601-76-1), 1,3,5 -Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (Irganox 1330, CAS No.: 1709-70-2), octadecyl 3-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, CAS No.: 2082-79-3) and 4,6-di(octylthiomethyl) o-cresol (Irganox1520, CAS No.: 110553-27-0) at least one.

Amine antioxidants include 4,4'-bis(phenylisopropyl)diphenylamine (CAS No.: 10081-67-1), OCTAMINE (CAS No.: 37338-62-8), Antioxidant 5057 (Antioxidant 5057 , CAS No.: 68411-46-1) and at least one of the reaction product of 2-acetone diphenylamine (CAS No.: 68412-48-6).

Phosphite antioxidants include tris(2,4-di-tert-butylphenyl)phosphite (CAS No.: 31570-04-4), (2,4-di-tert-butylphenyl)pentaerythritol Diphosphite (Irgafos 126, CAS No.: 26741-53-7), Tris(nonylphenol) phosphite (CAS No.: 26523-78-4) and Dioctadecylpentaerythritol Diphosphite (CAS No.: 3806-34-6) at least one.

Thioether antioxidants include didodecanyl thiodipropionate (Irganox PS800, CAS No.: 123-28-4), distearyl thiodipropionate (Naugard DSTDP, CAS No.: 693- 36-7) and at least one of pentaerythritol tetraester (β-lauryl thiopropionate) (Naugard 412S, CAS No.: 29598-76-3).

All of the above-mentioned substances can have a good protective effect against thermal and oxygen degradation of parylene.

In the present application, the antioxidant is selected from phenolic antioxidants and thioether antioxidants. Among them, the phenolic antioxidant is used as the main antioxidant; the high temperature resistance of the thioether antioxidant is better than that of the phosphite antioxidant, so the thioether antioxidant is selected as the auxiliary antioxidant ; The mutual cooperation of phenolic antioxidants and thioether antioxidants can further improve the resistance to thermal oxygen degradation of parylene in the grinding process.

Further, the antioxidant is selected from phenolic antioxidants and thioether antioxidants, and the phenolic antioxidant is selected from at least one of Irganox3114, Irganox 1790, Irganox 1330 and Irganox 1076, and the thioether antioxidant The agent is selected from Naugard 412S, and the above-mentioned substances can further improve the protection effect of parylene against thermal and oxygen degradation.

Further, the phenolic antioxidant is selected from at least one of Irganox 3114, Irganox 1790 and Irganox 1330, and the above-mentioned substances have an isocyanate ring and a benzene ring as the central ring of the antioxidant, and have higher heat resistance and resistance oxygen performance.

In the present application, the antioxidant is selected from phenolic antioxidants and thioether antioxidants, and the mass ratio of phenolic antioxidants to thioether antioxidants is 0.5:1.5-1.5:0.5. As an example, the mass ratio of the phenolic antioxidant to the thioether antioxidant is 1:1.

As an example, the above pulverization process may adopt a cutting pulverization method or a jaw pulverization method. The above-mentioned grinding process can adopt ultra-centrifugal pulverization, knife mixing grinding, mortar grinding, disc vibration grinding or hybrid grinding; further, the above grinding process can be hybrid grinding or mortar grinding.

Furthermore, the grinding time ≤ 30 minutes is beneficial to avoid the effect of the temperature rise of the system due to the long grinding time, which will affect the full performance of the anti-oxidant degradation resistance of the antioxidant, resulting in a decrease in the anti-thermal oxidative degradation effect.

In this application, plasticizer is also added during the grinding process, which is beneficial to make the parylene particle shape after grinding have a higher uniformity, and is beneficial to be more fully mixed with other raw materials in the subsequent mixing process.

As an example, the plasticizer added during the milling process is a mixture containing diethylene glycol dibenzoate and dipropylene glycol dibenzoate (eg, benzoflex 2088).

Further, in this application, the mass ratio of the pulverized parylene to the plasticizer added during the grinding process is no more than 1:0.1. As an example, the mass ratio of the pulverized parylene to the plasticizer added during the grinding process is 1:0.005.

S20, in the presence of oxygen, first mix the first material containing the parylene particles, the free radical precursor and the first modifier to obtain a first mixed system.

Wherein, the structural formula of the active ingredient in the free radical precursor is as follows:

R ₁ , R ₂ and R ₃ are each independently selected from an alkyl group having 2-4 C atoms.

Exemplarily, R ₁ , R ₂ and R ₃ are each independently selected from ethyl, propyl and butyl.

Wherein, the structural formula of the first modifying agent is as follows:

m is a natural number ≥ 0, R ₄ is a hydroxyl group or an isocyanate group.

As an example, the value of m may be 0, 1, 2 or 3 and so on.

In the present application, the free radical precursor, the parylene particles and the modifying substance including the first modifying agent are mixed. In the presence of oxygen, oxygen can be inserted between the boron (B) atom of the radical precursor and the alkyl group (i.e., _R1 group, _R2 group or _R3 group) and homolytically split to form an alkoxyl radical, The formed alkoxyl radical has better hydrogen-absorbing ability, and the alkoxyl radical can effectively grab the hydrogen on the molecular structure of parylene, so that the parylene molecule can be combined with the acrylic acid in the first modifier molecule The carbon-carbon double bond of ester group is covalently bonded, and then can effectively introduce _R group (being hydroxyl or isocyanate group) on the skeleton of parylene molecule, effectively improves the R that introduces on the skeleton of parylene molecule The ratio of ₄ groups improves the waterproof performance of the modified parylene and can be used as a waterproof material, which is beneficial to fully recycle the parylene stripped from the deposition chamber.

In addition, when preparing parylene protective materials, γ-methacryloxypropyltrimethoxysilane (A174, adhesion promoter) is usually added to parylene during the polymerization process to improve the protection. Adhesion of the material as a whole to the target device. However, A174 has a silanol structure. The carbon-oxygen-silicon bond in the silanol structure is easily hydrolyzed and unstable, and silanol is very prone to self-polymerization to produce siloxane, which makes parylene protective materials difficult to cooperate with conventional waterproof materials. to achieve a protective effect. This application introduces hydroxyl groups or isocyanate groups on the skeleton of parylene, which is conducive to enabling parylene to interact and cooperate with conventional waterproof systems to form waterproof coatings, so as to achieve better waterproof effects of waterproof coatings .

In this application, the active ingredient in the free radical precursor is selected from triethyl boron, tripropyl boron or tributyl boron, which can form alkoxyl radicals with strong hydrogen abstraction ability, which is beneficial to further improve poly The ratio of the R ₄ group introduced on the skeleton of the p-xylylene molecule further improves the waterproof performance of the modified parylene.

Further, the active ingredient in the radical precursor is selected from triethylboron, which can form an ethoxy radical with a strong hydrogen-absorbing ability, which is beneficial to further improve the _R4 group introduced on the skeleton of the parylene molecule. The proportion of clusters further improves the waterproof performance of the modified parylene.

Since triethyl boron is flammable and difficult to store and transport directly, in order to ensure safety, triethyl boron is generally stored in the form of complexes. Therefore, when the active ingredient in the free radical precursor is selected from triethyl boron, the free radical precursor is selected from triethyl boron complexes.

When the radical precursor is selected from triethylboron complexes, the first material also includes a decomplexing agent. The addition of the decomplexing agent can make triethyl boron be released from the complex system to form ethoxy radicals during the mixing process of the raw materials.

In the present application, the free radical precursor includes at least one of triethylboron-1,6-hexanediamine complex and triethylboron-1,3-propanediamine complex. Further, the free radical precursor is selected from triethylboron-1,3-propanediamine complex, and the active ingredient in the triethylboron-1,3-propanediamine complex is triethylboron, which can Produces ethoxyl radicals with good hydrogen-absorbing ability, which in turn helps to increase the ratio of _R4 groups introduced on the skeleton of parylene molecules, and can effectively avoid triethylboron from easily occurring due to the nature of complexes. Inflammable and explosive phenomenon is conducive to improving the safety of operation.

In the present application, the decomplexing agent includes at least one of an organic acid or a substance containing an isocyanate group. The above-mentioned substances can effectively release triethylboron from the complex system.

Further, the organic acid includes at least one of methacrylic acid, acrylic acid, lactic acid and acetic acid; the material containing isocyanate group includes toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI) at least one. The above substances can further improve the decomplexing effect on the triethylboron complex. Still further, the organic acid is selected from methacrylic acid; the substance containing isocyanate group is selected from IPDI.

In the present application, the first modifier is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isocyanoethyl methacrylate and isocyanate ethyl acrylate. The above substances can effectively improve the waterproof performance of the modified parylene.

Further, the first modifying agent is selected from at least one of hydroxyethyl acrylate and isocyanate ethyl acrylate, which is beneficial to further improve the waterproof performance of the modified parylene.

In this application, the first material also includes a plasticizer, which is beneficial to form a relatively uniform mixture after the first mixing, which is convenient for subsequent further reaction and processing, and is beneficial to further improve the modified parylene waterproof performance.

As an example, the plasticizer in the first material is a mixture containing diethylene glycol dibenzoate and dipropylene glycol dibenzoate (for example, benzoflex 2088).

In the present application, in the first material, the mass ratio of parylene particles, free radical precursor, decomplexing agent, first modifier and plasticizer is 100:(2-7):(2- 7):(2-8):(5-15). As an example, in the first material, the mass ratio of the parylene particles, the free radical precursor, the decomplexing agent, the first modifier and the plasticizer is 100:2:2:5:10.

In this application, the first mixing adopts agitation and mixing, the time of the first mixing is 0.5-5min, and the rotation speed of the first mixing is 1500-2500rpm; under the above conditions, it is beneficial to realize sufficient mixing, and then improve the paraxylene modification effect.

In this application, after the first mixing, it is necessary to stand still at room temperature for 0.5-24 hours, so that the modification can be fully carried out. Further, after the first mixing, it needs to stand at room temperature for 2-3 hours.

S30, performing second mixing on the first mixing system and the second material containing the second modifying agent.

The structural formula of the second modifying agent is as follows:

n is a natural number ≥ 0, and R ₅ is a hydroxyl group or an isocyanate group.

As an example, the value of m may be 0, 1, 2 or 3 and so on.

Wherein, when R in the first modifying agent in the S20 step _is a hydroxyl group, _R in the second modifying agent in the S30 step is an isocyanate group; or, when R in the first modifying agent in the S20 step When R ₄ is an isocyanate group, R ₅ in the second modifier in step S30 is a hydroxyl group.

The first material is first mixed (i.e. step S20), which can effectively introduce the _R group on the skeleton of the parylene molecule, and then combine the first mixed system with the second modifying agent. The two materials are mixed (i.e. S30 step), and part of the R group on the skeleton of the parylene molecule can carry out the covalent bonding of the _hydroxyl group and the _isocyanate group with the R group in the second modifying agent, thereby making the second The acrylate group in the modifying agent can also be introduced into the skeleton of the parylene molecule, that is, the skeleton of the whole modified parylene molecule contains R _group and acrylate group at the same time, which is beneficial to Further improve the waterproof performance of the modified parylene.

In this application, the first modifier is hydroxyethyl acrylate, and the second modifier is isocyanate ethyl acrylate; or, the first modifier is isocyanate ethyl acrylate, and the second modifier is hydroxyethyl acrylate . Under the above circumstances, it is beneficial to further improve the waterproof performance of the modified parylene.

Further, the second material also includes a catalyst for promoting the covalent bonding reaction between the R ₄ group and the R ₅ group. Exemplarily, the catalyst is selected from N-methylmorpholine or proline.

It should be noted that, in other feasible embodiments, the catalyst may also be a cyclic compound containing N element.

The second material also includes a plasticizer, which is beneficial to form a relatively uniform mixture after the second mixing, which is convenient for subsequent further reaction and processing.

As an example, the plasticizer in the second material is a mixture containing diethylene glycol dibenzoate and dipropylene glycol dibenzoate (for example, benzoflex 2088).

In the present application, the second mixing adopts stirring and mixing, the time of the second mixing is 0.5-5min, and the speed of the second mixing is 1500-2500rpm; under the above conditions, it is beneficial to realize sufficient mixing, and then improve the paraxylene modification effect.

In this application, after the second mixing, it is necessary to stand at room temperature for 0.5-24 hours, so that the modification can be fully carried out. Further, after the second mixing, it needs to stand at room temperature for 2-3 hours.

It should be noted that, in this application, step S20 and step S30 may be performed continuously or intermittently, or only step S20 may be performed without performing step S30. Compared with the scheme of "carrying out both step S20 and step S30", the waterproof performance of the modified parylene can be further improved.

The present application also provides a modified parylene material, which is prepared by the method for modifying parylene as provided above.

The modified parylene material provided by this application has better waterproof performance, and can be used as a waterproof material to improve the waterproof effect of waterproof coatings.

The present application also provides a waterproof coating, including the modified parylene material as provided in the second aspect above.

The waterproof coating provided by the application has better waterproof effect.

Example 1

This embodiment provides a parylene modified material and its preparation method, which is prepared by the following steps:

(1) Cut 200 g of parylene film into rectangular blocks with a size of 17 cm*20 cm. Put the cut block sample into a cutter grinder, grind it for 5 minutes, and sieve the parylene pulverized matter of 5 mm or less.

(2) Put the 190g parylene pulverized matter obtained in step (1) into a disc vibration grinder, and add 1.9g antioxidant package (the antioxidant package is benzoflex2088 of 0.95g, Irganox 1790 of 0.475g , 0.475g of Naugard 412S), the grinding time is 20min, and the parylene particles of 25μm and below are sieved.

(3) 100g of parylene particles obtained in step (2), 2g of triethylboron-1,6-hexamethylenediamine complex, 2g of methacrylic acid, 5g of hydroxyethyl acrylate, 10g The benzoflex 2088 was placed in a planetary mixer, stirred and mixed at a rate of 2000rpm for 2min, and then allowed to stand at room temperature for 2h.

(4) Add 6.1 g of ethyl isocyanate acrylate and 0.1 g of N-methylmorpholine to the mixing system in step (3), stir and mix in a planetary mixer at a speed of 2000 rpm for 2 min, and then stand at room temperature for 2 h.

Example 2

This embodiment provides a parylene modified material and a preparation method thereof. The difference between this embodiment and Embodiment 1 is that step (4) is not performed.

Example 3

This example provides a parylene modified material and its preparation method. The difference between this example and Example 1 is that 5 g of hydroxyethyl acrylate in step (3) is replaced by 6.1 g of isocyanate ethyl acrylate , and step (4) is not performed.

Example 4

This embodiment provides a parylene modified material and a preparation method thereof. The difference between this embodiment and Embodiment 1 is that the isocyanate ethyl acrylate in step (4) is replaced with isocyanoethyl methacrylate.

Example 5

This embodiment provides a parylene modified material and its preparation method. The difference between this embodiment and Embodiment 1 is that the hydroxyethyl acrylate in step (3) is replaced with hydroxybutyl acrylate.

Example 6

This example provides a parylene modified material and its preparation method. The difference between this example and Example 1 is that the 25 μm in step (2) is changed to 50 μm.

Example 7

This example provides a parylene modified material and its preparation method. The difference between this example and Example 1 is that Naugard 412S in step (2) is replaced with Irgafos 126.

Example 8

This example provides a parylene modified material and its preparation method. The difference between this example and Example 1 is that Irganox 1790 in step (2) is replaced with OCTAMINE.

Comparative example 1

This comparative example provides a parylene modified material and a preparation method thereof, which is prepared by the following steps:

(1) Cut 200 g of parylene film into rectangular blocks with a size of 17 cm*20 cm. Put the cut block sample into a cutter grinder, grind it for 5 minutes, and sieve the parylene pulverized matter of 5 mm or less.

(2) Put the 190g parylene pulverized matter obtained in step (1) into a disc vibration grinder, and add 1.9g antioxidant package (the antioxidant package is benzoflex2088 of 0.95g, Irganox 1790 of 0.475g , 0.475g of Naugard 412S), the grinding time is 20min, and the parylene particles of 25μm and below are sieved.

(3) Place 100g of parylene particles obtained in step (2), 2g of benzoyl peroxide, 5g of hydroxyethyl acrylate, and 10g of benzoflex 2088 in a planetary agitator, and stir and mix at a speed of 2000rpm 2min. Then use a dispersing disk to stir, and add 0.5 g of N,N-dimethyl-p-toluidine, and stir for 2 hours.

Comparative example 2

This comparative example provides a parylene modified material and its preparation method. The difference between this comparative example and Example 1 is that step (3) and step (4) are not performed.

Test case

The parylene modified materials prepared in Examples 1-8 and Comparative Examples 1-2 were used to prepare waterproof coatings, and the salt spray resistance, water vapor transmission coefficient and dielectric constant of the prepared waterproof coatings were tested. The test results are shown in Table 1.

Wherein, the preparation method of waterproof coating is: under normal temperature, the Irgacure 1173 (CAS No. : 7473-98-5), 0.15g of 2,6-di-tert-butyl-p-cresol (BHT), 0.05g of benzoquinone, and 2g of acrylate phosphate were stirred and mixed evenly.

The method of salt spray resistance is as follows: apply waterproof paint on the surface of the copper plate with a coating thickness of 100 μm, test the salt spray resistance according to ASTM B117, after 1000 hours, take the copper plate out of the salt spray test, and immediately Clean the copper plate with hot water, wash and dry the surface of the copper plate, and observe the appearance of the copper plate according to ASTM D714-87.

Table 1

Note: In Table 1, the degree of bubbles: more bubbles>bubbles>slight bubbles>no bubbles.

As can be seen from Table 1, the water vapor transmission rate of the waterproof coating prepared by the parylene modified material prepared in Examples 1-8 is lower than that of the prepared parylene modified material prepared in Comparative Example 1-2. The water vapor transmission rate of the coating shows that the modification method provided by the application is compared with the method of modification with benzoyl peroxide in Comparative Example 1 and the method of Comparative Example 2 without group modification of parylene particles This method can effectively reduce the water vapor transmission rate of the waterproof coating, thereby improving the waterproof effect.

Through the comparison of Examples 1-3, it can be seen that compared with Example 2, which only carried out the modification of hydroxyl groups and Example 3, which only carried out the modification of isocyanate groups, Example 1 carried out the modification of hydroxyl groups and isocyanate groups in sequence, which is beneficial to further Reduce the water vapor transmission rate of waterproof coatings. Compared with Example 2, which only modified the hydroxyl group, when Example 3 only modified the isocyanate group, the isocyanate ethyl acrylate has a post-curing effect, and the isocyanate group (-NCO) is finally transformed under the action of water vapor. It has become a polyurea structure with better waterproof performance.

Through the comparison of Example 1 and Example 4, it can be seen that the selection of isocyanate ethyl acrylate in Example 1 is compared to the selection of isocyanoethyl methacrylate in Example 4, which is conducive to further reducing the water vapor transmission rate of the waterproof coating; The reason is that the curing effect of the acrylate group in the isocyanate ethyl acrylate of Example 1 is better than that of the methacrylate group in the isocyanoethyl methacrylate of Example 4 under the same light curing conditions.

From the comparison of Example 1 and Example 5, it can be seen that the selection of hydroxyethyl acrylate in Example 1 can slightly reduce the water vapor transmission rate of the waterproof coating compared with the selection of hydroxybutyl acrylate in Example 5.

Through the comparison of Example 1 and Example 6, it can be seen that the particle size of the parylene particles in Example 1 is lower than that of the Parylene particles in Example 6, making the waterproof coating prepared in Example 1 more compact , which is conducive to further reducing the water vapor transmission rate of waterproof coatings.

Through the comparison of Example 1 and Example 7-8, it can be seen that Naugard 412S can further reduce the water vapor transmission rate of waterproof coatings compared with Irgafos 126 and Irganox 1790 compared with OCTAMINE, indicating that Naugard 412S has excellent high temperature resistance and oxidation resistance. The high temperature resistance and oxidation resistance of Irgafos 126 and Irganox 1790 are better than OCTAMINE. During the process of grinding parylene pulverized products, it can effectively avoid the decomposition of parylene thermal oxygen aging, which is beneficial to improve the overall Water resistance.

In summary, the modification method provided by this application can effectively introduce modified groups into the skeleton of the parylene molecule, thereby improving the waterproof performance of the modified parylene and being able to be used as a waterproof material. It is beneficial to fully recycle the parylene stripped from the deposition chamber.

The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, there may be various modifications and changes in the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included within the protection scope of this application.

Claims (10)

1. a method for modifying parylene, characterized in that, comprising: In the presence of oxygen, the raw materials are mixed; the raw materials include free radical precursors, parylene particles, and modified substances; the modified substances include a first modifier; Wherein, the structural formula of the active ingredient in the free radical precursor is as follows:

R ₁ , R ₂ and R ₃ are each independently selected from alkyl groups with 2-4 C atoms; The structural formula of the first modifying agent is as follows:

m is a natural number ≥ 0, R ₄ is a hydroxyl group or an isocyanate group. 2. modification method according to claim 1, is characterized in that, The modified substance also includes a second modifier, and the structural formula of the second modifier is as follows:

n is a natural number ≥ 0, R ₅ is a hydroxyl group or an isocyanate group; The raw material includes a first material and a second material; the first material includes the free radical precursor, the parylene particles and the first modifier; the second material includes the first Secondary modifier; The step of mixing the raw materials includes: firstly performing the first mixing on the first material, and then performing the second mixing on the first mixed system and the second material; Wherein, R in the first modifier is a hydroxyl group, and _R in the second modifier is an isocyanate group; or _{, R} in the first modifier is an isocyanate group, and the In the second modifier, R ₅ is a hydroxyl group; Optionally, the second material further includes a catalyst selected from N-methylmorpholine or proline. 3. modification method according to claim 2, is characterized in that, described first modifying agent and described second modifying agent are independently selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate At least one of ester, isocyanoethyl methacrylate and isocyanate ethyl acrylate; Optionally, the first modifier is hydroxyethyl acrylate, and the second modifier is ethyl isocyanate acrylate; or, the first modifier is ethyl isocyanate acrylate, and the second modifier is The neutralizing agent is hydroxyethyl acrylate. 4. The modification method according to claim 2, characterized in that, the first material also includes a plasticizer; and/or, the second material also includes a plasticizer; Optionally, the plasticizer is a mixture containing diethylene glycol dibenzoate and dipropylene glycol dibenzoate. 5. The modification method according to claim 1, wherein the active ingredient is selected from triethylboron, tripropylboron or tributylboron; Optionally, the radical precursor includes at least one of triethylboron-1,6-hexanediamine complex and triethylboron-1,3-propanediamine complex; the The raw material also includes a decomplexing agent; Optionally, the decomplexing agent includes at least one of an organic acid or a substance containing an isocyanate group; Optionally, the organic acid includes at least one of methacrylic acid, acrylic acid, lactic acid and acetic acid; Optionally, the isocyanate group-containing substance includes at least one of toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate. 6. The modification method according to claim 1, characterized in that, the particle diameter of the parylene particles is 0.1-40 μm. 7. The modification method according to claim 6, characterized in that, the preparation method of the parylene particles comprises: first pulverizing the parylene initial material to a particle size of 1-20 nm, and then grinding to a particle size of 1-20 nm. The diameter is 0.1-40 μm; wherein, an antioxidant is added during the grinding process; Optionally, the antioxidant includes at least one of phenolic antioxidants, amine antioxidants, phosphite antioxidants and thioether antioxidants; Optionally, the antioxidants include phenolic antioxidants and thioether antioxidants; Optionally, the phenolic antioxidants include tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol, 1,3,5-tris(3,5- Di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazinane-2,4,6-trione, Tris(4-tert-butyl-3-hydroxy-2,6-isocyanurate -xylyl) ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, octadecyl 3-(3 , at least one of 5-di-tert-butyl-4-hydroxyphenyl) propionate and 4,6-bis(octylthiomethyl)-o-cresol; Optionally, the thioether antioxidants include didodecyl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetraester (β-lauryl thiopropionate). at least one of Optionally, the grinding time is ≤30min. 8. The modification method according to claim 2, characterized in that, the first mixing adopts stirring and mixing, the time of the first mixing is 0.5-5min, and the rotating speed of the first mixing is 1500-2500rpm; And/or, the second mixing adopts agitation and mixing, the time of the second mixing is 0.5-5min, and the rotation speed of the second mixing is 1500-2500rpm. 9. A modified parylene material, characterized in that, the modified parylene material is obtained by the modification method of the parylene as described in any one of claims 1-8 . 10. A waterproof coating, characterized in that it comprises the modified parylene material according to claim 9.

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