CN113105622B - Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof - Google Patents

Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof Download PDF

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CN113105622B
CN113105622B CN202110427187.3A CN202110427187A CN113105622B CN 113105622 B CN113105622 B CN 113105622B CN 202110427187 A CN202110427187 A CN 202110427187A CN 113105622 B CN113105622 B CN 113105622B
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polyphenyl ether
polyphenylene ether
thermosetting
solvent
double bonds
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CN113105622A (en
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阮文红
廖凌元
章明秋
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention discloses modified polyphenyl ether, which has a structure shown as a formula (I). The modified polyphenyl ether contains unsaturated double bonds, can further react with other substances for crosslinking to form a thermosetting material, and improves the solvent resistance and the dimensional stability of the material. The invention also discloses a preparation method of the modified polyphenyl ether, which is simple, high in repeatability and applicable to industrial application. The invention also discloses a thermosetting polyphenyl ether composition, wherein the organic siloxane in the thermosetting polyphenyl ether composition contains double bonds and methoxyl/ethoxyl groups, and can perform a crosslinking reaction with the double bonds and residual hydroxyl groups of the modified polyphenyl ether, so that on one hand, the polyphenyl ether can be converted into thermosetting, and on the other hand, the content of residual polar hydroxyl groups of the polyphenyl ether can be reduced. The invention also discloses a resin glue solution, a prepreg and a high-frequency printed circuit board substrate, and application of the thermosetting polyphenyl ether composition in preparation of the resin glue solution, the prepreg and the high-frequency printed circuit board substrate.

Description

Modified polyphenyl ether, thermosetting polyphenyl ether composition and application thereof
Technical Field
The invention relates to the technical field of macromolecules, and in particular relates to a modified polyphenyl ether and thermosetting polyphenyl ether composition and application thereof.
Background
With the development of higher frequency communication technology, miniaturization and higher integration of electronic devices, and larger information capacity, electronic devices have been required to have higher performance of circuit boards, such as low dielectric constant (Dk), low dielectric loss (Df), low moisture absorption, dimensional stability, and heat resistance. Printed Circuit Boards (PCBs) using phenolic resins and epoxy resins as base materials are being eliminated because their dielectric properties cannot meet the requirements of high-speed, low-dielectric-loss transmission of signals, and copper-clad board base materials with high speed, high frequency and low dielectric loss are being researched, wherein polyphenylene oxide is also called polyphenylene oxide or polyphenylene ether, the main chain of the polyphenylene oxide or polyphenylene ether is P-pi-conjugated by phenol aromatic ring, two methyl groups block active sites at ortho-positions of phenol groups, benzene ring and oxygen atom, and the flexibility of ether bond is reduced by the influence of benzene ring and methyl group. The polyphenyl ether polymer chain has no obvious polar group and hydrolytic group, so the dielectric constant is lower than 2.5(10GHz), the dielectric loss is lower than 0.0009(10GHz), the hygroscopicity is low, and the mechanical strength is good. Because of these characteristics, polyphenylene ether has natural advantages for use in high frequency Printed Circuit Boards (PCBs), but polyphenylene ether has some disadvantages when used as a substrate for high frequency printed circuit boards, such as (1) polyphenylene ether is a thermoplastic material and has poor resistance to solvents such as aromatic hydrocarbons and halogenated hydrocarbons, (2) polyphenylene ether has a thermal linear expansion coefficient of about 60-120 ppm/c, which is greater than that of copper foil (18 ppm/c), and mismatch of the thermal linear expansion coefficients is likely to cause cracking of the copper foil and failure, and (3) thermoplastic polyphenylene ether has insufficient heat resistance and cannot meet the temperature requirements of a dip soldering process and a drilling process in the PCB manufacturing process.
In view of the above problems, thermoplastic polyphenylene ethers are generally converted into thermosetting resins, and patent document No. 201711470773.6 discloses a method of preparing a thermosetting material by reacting a low molecular weight bishydroxypolyphenylene ether with a dicarboxylic acid halide or dicarboxylic acid or the like, and then mixing with an epoxy resin. Although the method can obtain the thermosetting polyphenyl ether material, the introduced acyl halide, carboxylic acid and epoxy have polarity, and the prepared polyphenyl ether material has higher dielectric constant and dielectric loss.
The patent document 201910181506.X discloses a preparation process of thermosetting allyl (ether) functionalized polyphenylene ether, and the preparation process adopts the steps that firstly, hydroxyl-terminated polyphenylene ether reacts with sodium hydroxide, and then, the hydroxyl-terminated polyphenylene ether and chloropropene are etherified under the action of a phase transfer catalyst to obtain the polyphenylene ether with an allyl end. The patent application No. 201910638310.9 discloses an organosilicon modified polyphenylene ether resin, its preparation method and application, wherein hydroxy-terminated polyphenylene ether is reacted with organosiloxane such as vinyltrimethoxysilane, vinyltriethoxysilane, etc., and active reaction groups are attached to both ends of polyphenylene ether.
In both the two technologies, active groups are connected to two ends of polyphenylene oxide, but due to the fact that the polyphenylene oxide molecular chain is high in rigidity, large in steric hindrance and difficult in chain movement, the active groups on the polyphenylene oxide chain are difficult to contact with each other to generate effective reaction, the polyphenylene oxide is insufficient in crosslinking degree, and the dielectric constant and the dielectric loss of the material are increased due to the fact that a large number of the remaining active groups exist. In addition, none of the above techniques improves the thermal stability of polyphenylene ether when modifying polyphenylene ether.
Disclosure of Invention
In order to solve the problems of low crosslinking degree, high dielectric constant and dielectric loss and insufficient thermal stability of polyphenylene oxide in the thermosetting modification of polyphenylene oxide in the prior art, one of the purposes of the invention is to provide a thermosetting polyphenylene oxide material with high crosslinking degree, low dielectric constant and dielectric loss and good thermal stability. Specifically, the technical scheme adopted by the invention is as follows: a modified polyphenylene ether has a structure shown in formula (I):
Figure BDA0003026173120000021
wherein R is1～R5At least one of the groups is a group containing a carbon-carbon double bond, the rest groups are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) straight-chain alkyl group and a substituted or unsubstituted C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) branched-chain alkyl group, and m is 30-60.
In the modified polyphenylene ether, the molecular weight contained therein is a distribution of molecular weights having a large or small value, and in a strict sense, the values of m for different molecular weights are different and are a range rather than a value. In the laboratory, the molecular weight of the polymer is generally determined by gel chromatography GPC, and the molecular weight Mn or the weight average molecular weight Mw is obtained as data. The m value is too high, namely the modified polyphenyl ether has low content of terminal double bonds and insufficient crosslinking; the m value is too small, the terminal hydroxyl groups are too many, the polarity of the material is large, and the dielectric constant and the dielectric loss are increased.
Preferably, the modified polyphenylene ether has a structural formula represented by the formulae (II) and (III):
Figure BDA0003026173120000031
another object of the present invention is to provide a process for producing the modified polyphenylene ether, which comprises the steps of:
s1, dissolving 100 parts by weight of polyphenyl ether in 250-350 parts by weight of solvent A, adding 0.2-0.5 part by weight of initiator and 5-10 parts by weight of monohydric phenol containing double bonds, and stirring at 70-95 ℃ for 3-4 hours to obtain a mixed solution;
s2, adding the mixed solution obtained in the step S1 into a solvent B, filtering, washing and drying to obtain the modified polyphenyl ether;
the solvent A is at least one of toluene, xylene, carbon tetrachloride, chlorobenzene and dichlorobenzene; the solvent B is at least one of methanol, ethanol and acetone.
Preferably, in step S1, the polyphenylene ether has a number average molecular weight of 16000 to 30000, which is referred to as the starting polyphenylene ether, a typical but non-limiting example of which is Asahi Kasei commercial name PPO S201A.
Preferably, the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and lauroyl peroxide. Preferably, the monohydric phenol having a double bond is at least one of 2-allylphenol, 3-allylphenol, 4- (prop-1-en-2-yl) phenol, 4- (3-buten-1-yl) phenol, and 2-allyl-4-methylphenol.
The invention also aims to provide a thermosetting polyphenyl ether composition, which comprises the following components in parts by weight: 100 parts of modified polyphenyl ether, 10-25 parts of organic siloxane and 0.2-0.5 part of peroxide free radical initiator;
the structural formula of the organic siloxane is shown as the formula (IV):
Figure BDA0003026173120000041
wherein y is 5 to 15, y is a natural number (5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or the like), and R is6And R7At least one of which is a group containing a carbon-carbon unsaturated double bond and the remainder being a hydrogen atom or a methyl group, R8And R9Independently selected from C1-C6 (e.g., C1, C2, C3, C4, C5 or C6) alkyl and phenyl, R10Is methyl or ethyl.
The double bond and the methoxyl group on the organic siloxane can respectively react with the double bond and the residual hydroxyl group on the modified polyphenyl ether, so that the modified polyphenyl ether is promoted to be cured into organic siloxane modified thermosetting polyphenyl ether, and meanwhile, the residual hydroxyl group of the modified polyphenyl ether can be consumed, and the polarity is reduced.
Preferably, the peroxide radical initiator is at least one of cumene hydroperoxide, dicumyl peroxide and tert-butyl hydroperoxide.
Preferably, the preparation method of the organosiloxane comprises the following steps: adding dialkoxysilane containing double bonds, silicon glycol, a solvent and barium hydroxide monohydrate into the mixture, stirring the mixture at the temperature of between 60 and 80 ℃, introducing nitrogen, reacting for 12 to 24 hours, and filtering to obtain organosiloxane; the mass ratio of the dialkoxysilane containing double bonds to the silicon diol is: dialkoxysilanes containing a double bond: 1.2-1.6% of silicon glycol: 1.
preferably, the dialkoxysilane containing a double bond is methylvinyldimethoxysilane and/or methylvinyldiethoxysilane.
Preferably, the silicon diol is at least one of tert-butyl methyl silicon diol, diphenyl silicon diol, methyl phenyl silicon diol and cyclohexyl methyl silicon diol. Preferably, the solvent is at least one of toluene, n-hexane, and carbon tetrachloride. The amount of the solvent to be used may be selected by those skilled in the art based on their own experience, and the reaction may be carried out smoothly. Preferably, the ratio of the amounts of the substance of barium hydroxide monohydrate and silicon glycol is: 0.01-0.03: 1.
the thermosetting polyphenylene ether composition further comprises a powder filler and an additive. The additives may be antioxidants, antistatic agents, lubricants, colorants, and the like.
The fourth object of the present invention is to provide a resin cement obtained by dissolving or dispersing the thermosetting polyphenylene ether composition described above in a solvent.
The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The solvent may be used singly or in combination of two or more, and preferably an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene is used in combination with a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. The amount of the solvent to be used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue solution has a viscosity suitable for use.
The present invention also provides a prepreg obtained by impregnating a glass fiber cloth with the resin glue solution and then drying the resin glue solution. Preferably, the weight ratio of the glass fiber cloth to the modified polyphenylene ether composition is: 10: 6-3. According to different requirements of plate thickness, different types of glass fiber cloth can be selected. Exemplary fiberglass cloth such as: 7628 fiberglass cloth, 2116 fiberglass cloth.
The sixth object of the present invention is to provide a high-frequency printed circuit board substrate made of the prepreg.
Preferably, the high-frequency printed circuit board substrate is prepared by the following method: and overlapping at least one prepreg, placing copper foils on two sides of the prepreg, and performing lamination molding to obtain the composite material.
The seventh purpose of the invention is to provide the application of the thermosetting polyphenyl ether composition in the preparation of resin glue solution, prepreg and high-frequency printed circuit board substrates.
The term "high frequency" as used herein means a frequency greater than 100 MHz.
The invention has the beneficial effects that: the modified polyphenyl ether contains unsaturated double bonds, can further react with other substances for crosslinking to form a thermosetting material, and improves the solvent resistance and the dimensional stability of the material.
The invention also provides a preparation method of the modified polyphenyl ether, the modified polyphenyl ether is obtained by reacting monohydric phenol containing double bonds with polyphenyl ether with high molecular weight, the preparation method is simple, the repeatability is high, and the modified polyphenyl ether can be applied industrially.
The invention also provides a thermosetting polyphenyl ether composition, wherein the organic siloxane in the thermosetting polyphenyl ether composition contains double bonds and methoxyl/ethoxyl groups, and can perform a crosslinking reaction with the double bonds and residual hydroxyl groups of the modified polyphenyl ether, so that on one hand, the polyphenyl ether can be converted into thermosetting, and on the other hand, the content of residual polar hydroxyl groups of the polyphenyl ether can be reduced.
The invention also provides a resin glue solution, a prepreg and a high-frequency printed circuit board substrate, and application of the thermosetting polyphenyl ether composition in preparation of the resin glue solution, the prepreg and the high-frequency printed circuit board substrate.
Drawings
FIG. 1 is a nuclear magnetic resonance H spectrum of the modified polyphenylene ether of example 1.
FIG. 2 is a nuclear magnetic resonance H spectrum of the modified polyphenylene ether of example 2.
FIG. 3 is a NMR H spectrum of the organosiloxane cross-linking agent of example 3.
FIG. 4 is a nuclear magnetic resonance H spectrum of the organosiloxane cross-linking agent of example 4.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Unless otherwise specified, the materials and reagents used in the examples of the present invention were obtained from the market, wherein polyphenylene ether was obtained from Asahi Kasei publication No. PPO S201A, and the number average molecular weight Mn was 19000; glass fiber cloth: 7628 glass fiber cloth, available from intelligent electronic technology ltd, guangzhou city.
Example 1
In one embodiment of the modified polyphenylene ether of the present invention, the structural formula of the modified polyphenylene ether of this embodiment is represented by formula (II):
Figure BDA0003026173120000071
the preparation method of the modified polyphenylene ether described in this example includes the following steps: dissolving 100 parts by weight of polyphenylene oxide (PPO S201A) in 300 parts by weight of toluene, adding 0.2 part by weight of benzoyl peroxide and 10 parts by weight of 2-allyl phenol, and stirring at 70 ℃ for 3 hours to obtain a uniform solution; and dripping the obtained solution into methanol to precipitate a solid, and filtering, washing and drying to obtain the modified polyphenyl ether. The NMR H spectrum of the modified polyphenylene ether of example 1 is shown in FIG. 1.
Example 2
In one embodiment of the modified polyphenylene ether of the present invention, the structural formula of the modified polyphenylene ether of this embodiment is represented by formula (III):
Figure BDA0003026173120000072
the preparation method of the modified polyphenylene ether described in this example includes the following steps: dissolving 100 parts by weight of polyphenylene oxide (PPO S201A) in 300 parts by weight of carbon tetrachloride, adding 0.5 part by weight of azobisisobutyronitrile and 5 parts by weight of 2-allyl-4-methylphenol, and stirring at 90 ℃ for 4 hours to obtain a mixed solution; and dripping the obtained mixed solution into acetone to precipitate a solid, and filtering, washing and drying to obtain the modified polyphenyl ether.
The NMR H spectrum of the modified polyphenylene ether of example 2 is shown in FIG. 2.
Example 3
This example is a method of preparing an organosiloxane, the method comprising: adding 1.2mol of methylvinyldimethoxysilane, 1mol of diphenylsilanediol, 0.02mol of barium hydroxide monohydrate and 4mol of toluene into a three-neck flask, stirring at 80 ℃ for reaction, continuously introducing nitrogen gas during the reaction process to carry out a side product out, reacting for 12 hours, filtering the reaction solution to remove barium hydroxide monohydrate, and drying to remove toluene to obtain the organosiloxane. FIG. 3 is a NMR H spectrum of the organosiloxane of example 3.
Example 4
This example is a method of preparing an organosiloxane, the method comprising: adding 1.6mol of methylvinyldiethoxysilane, 1mol of diphenylsilanediol, 0.02mol of barium hydroxide monohydrate and 6mol of toluene into a three-neck flask, stirring at 60 ℃ for reaction, continuously introducing nitrogen gas during the reaction process to carry out a by-product out, reacting for 24 hours, filtering the reaction solution to remove the barium hydroxide monohydrate, and drying to remove the toluene to obtain the organosiloxane. FIG. 4 is a NMR H spectrum of the organosiloxane of example 4.
Examples 5 to 8
The compositions of the thermosetting polyphenylene ether compositions of examples 5 to 8 are shown in Table 1.
TABLE 1
Figure BDA0003026173120000081
Figure BDA0003026173120000091
The thermosetting polyphenyl ether composition in the embodiment 5-8 is respectively prepared into a substrate of a high-frequency printed circuit board, and the preparation method comprises the following steps: mixing the thermosetting polyphenyl ether composition, and adding toluene to obtain a prepreg, wherein the weight percentage of the thermosetting polyphenyl ether composition in the prepreg is 20%; impregnating a prepreg into glass fiber cloth, volatilizing a solvent to obtain a prepreg, stacking 8 prepregs to obtain a cured sheet group, covering copper foils on the upper surface and the lower surface of the cured sheet group, placing in a hot press, and heating at 60kg/cm2Hot pressing for 1h at the temperature of 260 ℃ to obtain the high-frequency printed circuit board substrate.
Comparative example 1
Dissolving polyphenylene oxide (PPO S201A) in toluene to prepare a prepreg with the weight percentage of 20%, impregnating the prepreg in glass fiber cloth, volatilizing the solvent to obtain a prepreg, stacking 8 prepregs to obtain a cured sheet group, covering copper foils on the upper and lower surfaces of the cured sheet group, placing the cured sheet group in a hot press, and heating at 60kg/cm2Hot pressing for 1h at the temperature of 260 ℃ to obtain the circuit board substrate.
Examples of effects
The performance of the high-frequency printed circuit board substrate prepared from the thermosetting polyphenylene ether composition in example 5-8 was tested by the following test method:
the dielectric constant and the dielectric loss of 10GHz are tested according to the method of IEC 61189-2-721;
the temperature at 5% weight loss (Td 5%. degree. C.) was measured by IPC-TM-6502.4.24.6;
the thermal expansion coefficient is measured according to the IPC-TM-6502.4.24 standard test method, and the temperature range is 50-200 ℃;
glass transition temperature (Tg, DSC method) was measured according to IPC-TM-6502.4.25 method;
solvent resistance: and (3) measuring and soaking for 24 hours by using chloroform as a solvent medium, drying and weighing, and measuring the mass loss condition of the sample before and after soaking.
The test results are shown in Table 2.
TABLE 2
Figure BDA0003026173120000101
As can be seen from the results of the performance tests in Table 2, the circuit board substrates made of the thermosetting polyphenylene ether composition containing the modified polyphenylene ether and the organosiloxane cross-linking agent as main components are remarkably improved in heat resistance and solvent resistance, reduced in thermal expansion coefficient, dielectric constant and dielectric loss, and suitable for use as high-frequency printed circuit substrates.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. A thermosetting polyphenylene ether composition is characterized by comprising the following components in parts by weight: 100 parts of modified polyphenyl ether, 10-25 parts of organic siloxane and 0.2-0.5 part of peroxide radical initiator,
the modified polyphenyl ether is characterized in that the structure is shown as the formula (I):
Figure FDA0003541994290000011
wherein R is1～R5At least one of the groups is a group containing a carbon-carbon double bond, and the rest groups are independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 straight-chain alkyl group and a substituted or unsubstituted C1-C8 branched-chain alkyl group, wherein m is 30-60;
the structural formula of the organic siloxane is shown as the formula (IV):
Figure FDA0003541994290000012
wherein y is 5-15, R6And R7At least one is a group containing unsaturated double bonds, the rest is a hydrogen atom or a methyl group, R8And R9Independently selected from C1-C6 alkyl and phenyl, R10Is methyl or ethyl;
the thermosetting polyphenylene ether composition is characterized in that the preparation method of the organic siloxane comprises the following steps: adding dialkoxysilane containing double bonds, silicon glycol, a solvent and a catalyst into the mixture, stirring the mixture at the temperature of between 60 and 80 ℃, introducing nitrogen, reacting for 12 to 24 hours, and filtering to obtain organosiloxane; the mass ratio of the dialkoxysilane containing double bonds to the silicon diol is: dialkoxysilanes containing a double bond: 1.2-1.6% of silicon glycol: 1, the dialkoxysilane containing double bonds is methyl vinyl dimethoxy silane and/or methyl vinyl diethoxy silane.
2. The process for producing a thermosetting polyphenylene ether composition according to claim 1, comprising the steps of:
s1, dissolving 100 parts by weight of polyphenyl ether in 250-350 parts by weight of solvent A, adding 0.2-0.5 part by weight of initiator and 5-10 parts by weight of monohydric phenol containing double bonds, and stirring at 70-95 ℃ for 3-4 hours to obtain a mixed solution;
s2, adding the mixed solution obtained in the step S1 into a solvent B to precipitate a solid, filtering, washing and drying to obtain the modified polyphenylene ether;
the solvent A is at least one of toluene, xylene, carbon tetrachloride, chlorobenzene and dichlorobenzene; the solvent B is at least one of methanol, ethanol and acetone.
3. The process for producing a thermosetting polyphenylene ether composition according to claim 2, further comprising at least one of the following (a) to (c):
(a) in step S1, the number average molecular weight of the polyphenylene ether is 16000-30000;
(b) the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and lauroyl peroxide;
(c) the monohydric phenol containing double bonds is at least one of 2-allyl phenol, 3-allyl phenol, 4- (prop-1-ene-2-yl) phenol, 4- (3-butene-1-yl) phenol and 2-allyl-4-methyl phenol.
4. The thermosetting polyphenylene ether composition according to claim 1, further comprising at least one of the following (d) to (e):
(d) the silicon diol is at least one of tert-butyl methyl silicon diol, diphenyl silicon diol, methyl phenyl silicon diol and cyclohexyl methyl silicon diol;
(e) the solvent is at least one of toluene, n-hexane and carbon tetrachloride.
5. A resin cement obtained by dissolving or dispersing the thermosetting polyphenylene ether composition according to any one of claims 1 to 4 in a solvent.
6. A prepreg obtained by impregnating a glass fiber cloth with the resin paste according to claim 5 and drying the impregnated cloth.
7. A high-frequency printed circuit board substrate characterized in that it is made of the prepreg according to claim 6.
8. Use of the thermosetting polyphenylene ether composition according to any one of claims 1 to 4 for the preparation of resin glues, prepregs and high frequency printed circuit board substrates.
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