阅读说明：本技术 一种液晶高分子材料表面改性方法 (Surface modification method for liquid crystal polymer material ) 是由 赵长稳 魏伟 许斌 范红军 廖伟亮 李宏 周臻纶 孟庆国 周文 于 2021-09-14 设计创作，主要内容包括：本发明涉及一种液晶高分子的表面改性方法,本发明的液晶高分子的表面改性方法包括以下步骤：第一步,将含氨基硅烷偶联剂溶液涂布于液晶高分子的表面,并且照射紫外光,得到表面偶联硅氧烷基团的改性液晶高分子；第二步,将表面偶联硅氧烷基团的改性液晶高分子在酸性水溶液中浸泡,得到表面羟基化改性液晶高分子,并进一步将表面羟基化改性液晶高分子浸入含有双键的硅烷偶联剂溶液中,得到表面双键化的液晶高分子。本发明改性条件温和、速度快、不影响液晶高分子本体性能,能够有效改善液晶高分子材料和含有双键的树脂之间的界面结合性能。(The invention relates to a surface modification method of a liquid crystal polymer, which comprises the following steps: firstly, coating the amino-containing silane coupling agent solution on the surface of a liquid crystal polymer, and irradiating ultraviolet light to obtain a modified liquid crystal polymer with a siloxane group coupled on the surface; and secondly, soaking the modified liquid crystal polymer with the surface coupled with the siloxane groups in an acidic aqueous solution to obtain a surface hydroxylated modified liquid crystal polymer, and further soaking the surface hydroxylated modified liquid crystal polymer into a silane coupling agent solution containing double bonds to obtain a surface double-bonded liquid crystal polymer. The invention has mild modification condition and high speed, does not influence the performance of the liquid crystal polymer body, and can effectively improve the interface bonding performance between the liquid crystal polymer material and the resin containing double bonds.)

1. A surface modification method of a liquid crystal high polymer material is characterized by comprising the following steps: the method comprises the following steps:

(1) coating the amino-containing silane coupling agent solution on the surface of the fluorine-containing polymer, and irradiating ultraviolet light to obtain a modified liquid crystal polymer with a siloxane group coupled on the surface;

(2) soaking the modified liquid crystal polymer with the surface coupled with siloxane groups in an acidic aqueous solution with the pH value of 1-6 for 10-240 minutes to obtain a surface hydroxylated modified liquid crystal polymer;

(3) and immersing the surface hydroxylation modified liquid crystal polymer into a silane coupling agent solution containing double bonds for 5-240 minutes to obtain the surface double-bond liquid crystal polymer.

2. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the amino-containing silane coupling agent is selected from 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (piperazinylethyl) -3-aminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-divinyltriaminopropyltrimethoxysilane, N-propyltrimethoxysilane, N-propylmethyldimethoxysilane, N-propyl-methyl-dimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, N-S-N-S-N-S-N-S-N-S-N-S-N-, N-benzyl-N' - [3- (trimethoxysilyl) propyl ] ethylenediamine hydrochloride, N- (2-dimethylaminoethyl) -3-aminopropylmethyldimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, n- (N-butyl) -3-aminopropyltriethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, bis (3-triethoxysilylpropyl) amine, and bis (3-trimethoxysilylpropyl) amine.

3. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the solvent in the amino-containing silane coupling agent solution is at least one selected from water, sulfoxides, amides, ketones and cyclic ethers.

4. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the content of the amino-containing silane coupling agent in the amino-containing silane coupling agent solution is 10-80 wt%.

5. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the irradiation intensity of the ultraviolet light is 5000-30000 mu W/cm²The irradiation time is 1-60 minutes.

6. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the double bond-containing silane coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, a 3-methacryloxypropyltrimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethoxysilane, a vinyltrimethoxysilane, a 3-methacryloxypropyltrimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethacrylate, a vinyltrimethoxysilane, a vinyltriethoxysilane, a vinyltriethoxysilane, a vinylsubstrate, a vinyltriethoxysilane, a substrate, at least one of vinyltrichlorosilane and methylvinyldichlorosilane.

7. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the solvent of the double-bond-containing silane coupling agent solution is at least one selected from alcohols, ketones and hydrocarbons.

8. The method for modifying the surface of a liquid crystal polymer material according to claim 1, wherein: the content of the double-bond-containing silane coupling agent in the double-bond-containing silane coupling agent solution is 1-80 wt%.

Technical Field

The invention belongs to the field of material modification treatment, and particularly relates to a surface modification method of LCP (liquid crystal polymer) materials.

Background

The Liquid Crystal Polymer (LCP) has the advantages of high temperature resistance, high mechanical strength, good chemical stability, low thermal expansion coefficient, low hygroscopicity, low dielectric constant and loss and the like, and has wide application prospect in the fields of electronic and electric appliances, automobile industry, aerospace, medical materials and the like. However, LCP materials also have the characteristic of low surface energy, and show the problems of poor hydrophilicity, difficult adhesion and the like in practical use.

Some documents have proposed solutions to improve the surface energy and adhesion of LCP. For example, CN 111497379A is used for surface modification of LCP film by plasma treatment, which increases the surface roughness and improves the peeling strength of LCP film and copper foil under the same process conditions. CN 112647065A discloses a method for roughening LCP by introducing ozone into potassium persulfate solution and under the action of ultrasonic waves, wherein the surface roughness of the LCP material is obviously increased after treatment, and the bonding strength with a plating layer is good after further copper plating. CN 112281118A realizes the surface metallization of LCP through high-energy ion beam treatment and combined ion beam deposition method, the deposition effect is good, and the bonding force with the metal layer is high. However, the above-mentioned method also has certain problems: the plasma treatment method has shallow modification depth and poor modification timeliness, and the treated sample is difficult to store for a long time; the wet chemical treatment method usually relates to toxic and harmful reagents such as strong oxidant, strong acid, strong alkali and the like, and has the disadvantages of large environmental pollution and long treatment time; high-energy ion beam treatment equipment is complex and expensive, has higher requirements on treatment environment and lower production efficiency.

Therefore, it is important to develop a new LCP material modification method in view of safety, environmental protection, low production cost, and simple process.

Disclosure of Invention

In view of the above-mentioned defects in the prior art, the technical problem to be solved by the present invention is to provide a method for modifying the surface of LCP material with mild reaction conditions, simple equipment and process, and low cost.

The purpose of the invention is realized by the following technical scheme.

A surface modification method for a liquid crystal high polymer material comprises the following steps:

(1) coating the amino-containing silane coupling agent solution on the surface of the fluorine-containing polymer, and irradiating ultraviolet light to obtain a modified liquid crystal polymer with a siloxane group coupled on the surface;

(2) soaking the modified liquid crystal polymer with the surface coupled with siloxane groups in an acidic aqueous solution with the pH value of 1-6 for 10-240 minutes to obtain a surface hydroxylated modified liquid crystal polymer;

(3) and immersing the surface hydroxylation modified liquid crystal polymer into a silane coupling agent solution containing double bonds for 5-240 minutes to obtain the surface double-bond liquid crystal polymer.

The amino-containing silane coupling agent is selected from 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (piperazinylethyl) -3-aminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-divinyltriaminopropyltrimethoxysilane, N-propyltrimethoxysilane, N-propylmethyldimethoxysilane, N-propyl-methyl-dimethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, N-S-N-S-N-S-N-S-N-S-N-S-N-, N-benzyl-N' - [3- (trimethoxysilyl) propyl ] ethylenediamine hydrochloride, N- (2-dimethylaminoethyl) -3-aminopropylmethyldimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, n- (N-butyl) -3-aminopropyltriethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, bis (3-triethoxysilylpropyl) amine, and bis (3-trimethoxysilylpropyl) amine.

The solvent in the amino-containing silane coupling agent solution is at least one selected from water, sulfoxides, amides, ketones and cyclic ethers.

The content of the amino-containing silane coupling agent in the amino-containing silane coupling agent solution is 10-80 wt%.

The irradiation intensity of the ultraviolet light is 5000-30000 mu W/cm²The irradiation time is 1-60 minutes.

The double bond-containing silane coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltris (trimethylsiloxy) silane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, a 3-methacryloxypropyltrimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethoxysilane, a vinyltrimethoxysilane, a 3-methacryloxypropyltrimethoxysilane, a vinyltrimethoxysilane, a vinylmethyldimethacrylate, a vinyltrimethoxysilane, a vinyltriethoxysilane, a vinyltriethoxysilane, a vinylsubstrate, a vinyltriethoxysilane, a substrate, at least one of vinyltrichlorosilane and methylvinyldichlorosilane.

The solvent in the double-bond-containing silane coupling agent solution is at least one selected from alcohols, ketones and hydrocarbons.

The content of the double-bond-containing silane coupling agent in the double-bond-containing silane coupling agent solution is 1-80 wt%.

Through the implementation of the technical scheme, the invention can obtain the following technical effects:

according to the modification method, the specific amino-containing silane coupling agent reacts with the ester bond on the surface of the LCP material under the irradiation of ultraviolet light, so that the siloxane groups can be quickly introduced into the surface of the LCP material, and then are converted into hydroxyl groups through hydrolysis, and the quick hydroxylation of the LCP surface is realized. The hydroxylated surface can be conveniently reacted with a coupling agent containing bis-silane, thereby realizing double-bonding modification of the LCP surface. The modification method of the invention uses a general ultraviolet light source, has simple equipment, does not relate to the use of high-toxicity and strong-oxidizing agent, and has weak ultraviolet light penetrability, so that the modification reaction does not influence the bulk performance of the LCP material. Meanwhile, the method has the advantages of high reaction speed and simple process, and is suitable for continuous production.

Detailed Description

The present invention will be described in further detail with reference to examples. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.

The starting materials and reagents used in the following examples and comparative examples are commercially available. Unless otherwise specified, "part" means "part by weight" and "%" means "% by weight" hereinafter.

Example 1:

uniformly spreading a 60% N, N' -dimethylformamide solution of 3-aminopropyltriethoxysilane on the surface of LCP fiber cloth, illuminating for 5min by using a high-pressure mercury lamp under the light intensity of 15000 microwatts per square centimeter, ultrasonically cleaning for 20min by using ethanol, and drying by using nitrogen to obtain the siloxane modified LCP fiber cloth. The silicone modified LCP fiber cloth was immersed in water at pH 4 for 4h, rinsed with water after removal, and oven dried at 80 degrees for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into a 3% vinyl trichlorosilane toluene solution for 10min, cleaning the film with ethanol, and drying the film with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

Comparative example 1:

uniformly spreading a 60% N, N' -dimethylformamide solution of 3-aminopropyltriethoxysilane on the surface of LCP fiber cloth, standing at 25 ℃ for 5min, ultrasonically cleaning with ethanol for 20min, blow-drying with nitrogen, immersing the LCP fiber cloth in water with pH of 4 for 4h, taking out, washing with water, and drying in an oven at 80 ℃ for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into a 3% vinyl trichlorosilane toluene solution for 10min, cleaning the film with ethanol, and drying the film with nitrogen to obtain the LCP fiber cloth.

Comparative example 2:

irradiating the surface of the LCP fiber cloth for 5min under the light intensity of 15000 microwatts per square centimeter by using a high-pressure mercury lamp, then ultrasonically cleaning the LCP fiber cloth for 20min by using ethanol, drying the LCP fiber cloth by using nitrogen, then soaking the LCP fiber cloth into water with the pH value of 4 for 4h, taking out the LCP fiber cloth, washing the LCP fiber cloth by using the water, and drying the LCP fiber cloth by using an oven at 80 ℃ for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into a 3% vinyl trichlorosilane toluene solution for 10min, cleaning the film with ethanol, and drying the film with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

Example 2:

uniformly spreading 10% 3-aminopropyltrimethoxysilane aqueous solution on the surface of the LCP fiber cloth, illuminating for 3min by using a high-pressure mercury lamp under the light intensity of 20000 microwatts/square centimeter, ultrasonically cleaning for 20min by using ethanol, and drying by using nitrogen to obtain the siloxane modified LCP fiber cloth. The silicone modified LCP fiber cloth was immersed in water at pH 2 for 1h, rinsed with water after removal, and oven dried at 80 degrees for 0.5 h. And (3) after the membrane is cooled to room temperature, putting the membrane into a 10% 3-acetoxypropyl trimethoxy silane ethanol solution for 1h, cleaning the membrane with ethanol, and drying the membrane with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

Example 3:

uniformly spreading a dimethyl sulfoxide solution of 50% N-2-aminoethyl-3-aminopropyltrimethoxysilane on the surface of the LCP fiber cloth, illuminating for 20min by using a high-pressure mercury lamp under the light intensity of 8000 microwatts/square centimeter, ultrasonically cleaning for 20min by using ethanol, and drying by using nitrogen to obtain the siloxane modified LCP fiber cloth. The siloxane modified LCP fiber cloth is immersed in water with pH value of 1 for 0.5h, taken out, washed by water and dried in an 80-degree oven for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into 20% vinyl trimethoxy silane ethanol solution for 2 hours, cleaning the film with ethanol, and drying the film with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

Example 4:

uniformly spreading a 10% acetone solution of 3-diethylenetriaminopropylmethyldimethoxysilane on the surface of the LCP fiber cloth, illuminating for 10min by using a high-pressure mercury lamp under the light intensity of 10000 microwatts/square centimeter, ultrasonically cleaning for 20min by using ethanol, and drying by using nitrogen to obtain the siloxane modified LCP fiber cloth. The siloxane modified LCP fiber cloth is immersed in water with pH 4 for 2h, taken out, washed with water and dried in an 80-degree oven for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into 50% vinyl trimethoxy silane acetone solution for 10min, cleaning the film with ethanol, and drying the film with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

Example 5:

uniformly spreading a dioxane solution of 20% 3-aminopropylmethyldimethoxysilane on the surface of the LCP fiber cloth, illuminating for 4min by using a high-pressure mercury lamp under the light intensity of 18000 microwatts/square centimeter, ultrasonically cleaning for 20min by using ethanol, and drying by using nitrogen to obtain the siloxane modified LCP fiber cloth. The siloxane modified LCP fiber cloth is immersed in water with pH 4 for 2h, taken out, washed with water and dried in an 80-degree oven for 0.5 h. And (3) after the film is cooled to room temperature, putting the film into a 10% vinyl trichlorosilane toluene solution for 5min, cleaning the film with ethanol, and drying the film with nitrogen to obtain the surface double-bonded modified LCP fiber cloth.

The treated LCP fiber cloth and the unmodified LCP fiber cloth obtained in examples 1-5 and comparative examples 1-2 were impregnated with resin glues, and prepregs were prepared, wherein the glues consisted of 60 parts of allyl modified polyphenylene ether resin (SA9000), 20 parts of styrene-butadiene resin (Ricon100), 20 parts of triallyl isocyanurate, 1 part of 1, 4-di-tert-butylperoxyisopropyl benzene, and 30 parts of silica filler, and the solvent was xylene. And (3) laminating the prepared prepregs together to prepare a laminated board, covering copper foils on two sides of the laminated board, and curing and laminating to prepare the copper-clad plate, wherein the curing conditions are as follows: the curing temperature is 180 ℃, the curing time is 30min, the temperature is increased to 210 ℃, the curing time is 90min, and the laminating pressure is 600psi.

Table 1: and (3) a performance parameter table of copper-clad plates made of different LCP fiber cloths.

As can be seen from Table 1, the dielectric properties of the copper-clad plate prepared by using the modified LCP fiber cloth obtained in the embodiments 1 to 5 are equivalent to those of the unmodified LCP fiber cloth, which indicates that the dielectric properties of the LCP fiber cloth body are not damaged by the modification treatment. Compared with a comparative example and unmodified LCP fiber cloth, the dip-soldering resistance of the copper-clad plate prepared from the modified LCP fiber cloth is obviously improved.