CN110951235B - Methacrylate polyphenyl ether resin and preparation method and application thereof - Google Patents

Methacrylate polyphenyl ether resin and preparation method and application thereof Download PDF

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CN110951235B
CN110951235B CN201911213232.4A CN201911213232A CN110951235B CN 110951235 B CN110951235 B CN 110951235B CN 201911213232 A CN201911213232 A CN 201911213232A CN 110951235 B CN110951235 B CN 110951235B
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methacrylate
resin composition
polyphenylene ether
ether resin
polyphenyl ether
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CN110951235A (en
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郑煇颖
江胜宗
林仁宗
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Zhuhai Epoxy Base Electronic Material Co ltd
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Zhuhai Epoxy Base Electronic Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • 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
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention provides a methacrylate polyphenyl ether resin composition and a preparation method and application thereof, and relates to the technical field of high polymer materials. The methacrylate polyphenyl ether resin composition comprises the following raw materials in parts by weight: 40-60 parts of hydrocarbon resin, 80-180 parts of methacrylate polyphenyl ether and 40-60 parts of cyanate ester resin; the methacrylate polyphenyl ether has a structure shown in a formula I, wherein R is cycloalkyl, m + n = 18-26, and the number average molecular weight Mn is 2800-3200.
Figure DDA0002298741170000011

Description

Methacrylate polyphenyl ether resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to methacrylate polyphenyl ether and a preparation method and application thereof.
Background
A Printed Circuit Board (PCB) is a circuit board of an electronic device, and the PCB carries other electronic components and is electrically connected to the components, so as to provide a stable circuit working environment. A common printed circuit board is a Copper Clad Laminate (CCL) mainly composed of resin, reinforcing material, and copper foil, the common resin includes epoxy resin, phenol resin, polyamine formaldehyde, silicone, teflon, and the like, and the common reinforcing material includes glass fiber cloth, glass fiber mat, insulating paper, linen, and the like.
In consideration of the back-end electronic processing procedure, the printed circuit board is fabricated considering its properties such as heat resistance, dimensional stability, chemical stability, workability, toughness, and mechanical strength. In general, a printed circuit board prepared using an epoxy resin has the above-mentioned characteristics, and thus the epoxy resin is most commonly used in the industry. However, printed circuit boards made of epoxy resin often have relatively high dielectric constant (Dk) and dissipation factor (Df). The transmission speed of signal is approximately inversely proportional to the square root of Dk, and a high Dk tends to slow down the signal transmission rate of the laminate; df is critical to the signal transmission quality, and the higher Df is the higher the proportion of signal lost in the laminate material due to material resistance. Therefore, it is an object of the present invention to provide a laminate having good physical and chemical properties and low Dk and Df.
Printed circuit boards prepared from the polyphenylene ether resin composition have the advantages of low dielectric constant and dissipation factor, however, the prior polyphenylene ether resin can not meet the requirements of printed circuit board industry in certain characteristics, such as fire resistance, heat resistance and the like.
Disclosure of Invention
In view of the above, there is a need to provide a methacrylate polyphenylene ether resin composition, which can provide a laminate having excellent physical and electrical properties, such as high glass transition temperature (Tg), low water absorption, good solder dip resistance, good flame retardancy, and low dielectric constant and dissipation factor.
A methacrylate polyphenyl ether resin composition comprises the following raw materials in parts by weight:
40 to 60 portions of hydrocarbon resin,
80-180 parts of methyl acrylate polyphenyl ether,
40-60 parts of cyanate ester resin;
the structure of the methacrylate polyphenyl ether is shown as the following formula I:
Figure BDA0002298741150000011
I
wherein R is cycloalkyl, m + n = 18-26, and the number average molecular weight Mn is 2800-3200.
The methacrylate polyphenyl ether resin composition has good solubility in organic solvents and extremely convenient application, and a laminated plate prepared from the methacrylate polyphenyl ether resin composition has excellent physicochemical properties and electrical properties, such as high glass transition temperature (Tg), low water absorption, good dip soldering resistance, good flame retardancy, low dielectric constant and dissipation factor.
In one embodiment, the paint also comprises 100 to 200 parts by weight of solvent. Preferably, the weight part of the solvent is 150 parts.
In one embodiment, the solvent is selected from: one or more of toluene, methyl Ethyl Ketone (MEK), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO). Preferably, the solvent is toluene.
In one embodiment, the hydrocarbon resin is butadiene-styrene copolymer with number average molecular weight of 1000-2500. It is also possible to select a hydrocarbon resin with a solids content of 50% to 80% whose main component is a butadiene-styrene copolymer, such as DONGSTE TECHNOLOGY DEF409.
In one embodiment, R in the methacrylate polyphenylene ether is cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl, or 3, 5-dimethylcyclohexyl. Preferably, R is cyclopentyl or cyclohexyl.
In one embodiment, the preparation method of the methacrylate polyphenylene ether comprises the following steps:
and (3) substitution reaction: mixing toluene, triethylamine, methacryloyl chloride and polyphenyl ether, heating and reacting to obtain the methacrylate polyphenyl ether.
In one embodiment, in the substitution reaction step, the heating temperature is 40-60 ℃, and the reaction time is 6-8 h.
In one embodiment, the substitution reaction step further comprises the following steps:
neutralizing: adding acid for neutralization; preferably, hydrochloric acid is added for neutralization;
and (3) precipitation: adding toluene for extraction, reserving a toluene layer, adding methanol into a toluene solution, stirring to separate out a solid, and performing vacuum drying to obtain refined methacrylate polyphenyl ether; preferably, the drying temperature is 120 ℃.
The methacrylate polyphenyl ether prepared by the method has the advantages of small molecular weight, good distribution and high solvent selectivity.
The reaction formula for synthesizing methacrylate polyphenylene ether is shown below:
Figure BDA0002298741150000021
in one embodiment, the polyphenylene ether has the structure shown in formula II below:
Figure BDA0002298741150000022
II
in one embodiment, the polyphenylene ether is prepared by the following method:
preparing an intermediate: sulfuric acid, dehydrating agent, 2, 6-dimethylphenol, compound containing CH 2 Cl 2 Mixing the mixture, adding the keton, controlling the reaction temperature to be 65-75 ℃, reacting for 20-28 h, adding the alkali for neutralization, and adding the CH 2 Cl 2 Extracting, and adding Hexane to precipitate solid to obtain the refined polyphenyl ether intermediate. The alkanone is selected from: one of cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclohexanone, 3-methylcycloheptanone, 3, 5-dimethylcyclohexanone, methylethylketone, methylacetone, ethylacetone, propylacetone, methyl butanone or ethyl butanone. Preferably, the dehydrating agent is magnesium sulfate.
Reaction: mixing toluene, a metal catalyst, triethylamine and the polyphenyl ether intermediate to obtain pre-reaction liquid; dissolving 2, 6-dimethylphenol in toluene to obtain a 2, 6-dimethylphenol solution; adding 2, 6-dimethylphenol solution into the pre-reaction solution under the condition of introducing oxygen, and reacting for 6-8 h to obtain the polyphenyl ether. Preferably, the 2, 6-dimethylphenol solution is prepared with a molar ratio of 2, 6-dimethylphenol to toluene of (3-16): 1. Preferably, the metal catalyst is CuCl 2 。
In one embodiment, the reaction step in the polyphenylene ether production method further comprises the following steps:
removing impurities: adding EDTA aqueous solution to adsorb metal catalyst, mixing at 20-30 deg.C for 8-12 hr, heating to 50-60 deg.C, mixing for 1-3 hr, layering, and keeping toluene solution layer.
Neutralizing: adding acid for neutralization, mixing for 20-40 min, layering, and reserving a toluene solution layer. Preferably, the acid is hydrochloric acid.
And (3) precipitation: adding methanol, stirring at 3000-4000 rpm to separate out the product.
And (3) drying: filtering, and vacuum drying the solid product at 75-85 deg.c for 14-18 hr.
Wherein the structure of the polyphenylene ether intermediate is shown as the following formula III:
Figure BDA0002298741150000031
r is cycloalkyl, which is cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl, or 3, 5-dimethylcyclohexyl.
The reaction formula for synthesizing polyphenylene ether is shown below:
Figure BDA0002298741150000032
in one embodiment, the cyanate ester resin (CE resin) is selected from: one or more of bismaleimide-triazine (BT resin), bismaleimide (BMI) phenolic resin, bisphenol A cyanate, and cyclic ester (37706). Preferably, the cyanate ester resin is selected from Bismaleimide (BMI) phenolic resin.
In one embodiment, the paint further comprises 0.05 to 50 parts by weight of an additive selected from the group consisting of: one or more than two of flame retardant, accelerant, dispersant and flexibilizer.
The invention also provides a preparation method of the methacrylate polyphenylene ether resin composition, which comprises the following steps: weighing the raw materials, adding a solvent, and uniformly mixing to obtain the methacrylate polyphenylene oxide resin composition.
The invention also provides a prepreg prepared from the raw material comprising the methacrylate polyphenylene oxide resin composition.
The invention also provides a preparation method of the laminated plate, which is characterized by comprising the following steps:
preparing a prepreg: coating the methacrylate polyphenyl ether resin composition on a base material, and drying to obtain a prepreg;
hot pressing: laminating a plurality of prepregs, laminating copper foils on two sides of the laminated body, and hot-pressing to obtain the copper foil-coated laminated plate.
In one embodiment, the substrate may be one selected from glass fiber cloth (e.g., glass fabric, glass paper, glass mat), kraft paper, short fiber cotton paper, natural fiber cloth, and organic fiber cloth.
In the step of preparing the prepreg, the glass fiber cloth is 7628, the mass ratio of the methacrylate polyphenylene ether resin to the glass fiber cloth is 40% -45%, and preferably the mass ratio of the methacrylate polyphenylene ether resin to the glass fiber cloth is 43%; and heating and drying at 170-180 ℃ for 2-10 min to obtain the prepreg. Preferably the drying temperature is 175 ℃.
In one embodiment, the hot pressing step specifically includes laminating 7 to 9 prepregs, laminating one copper foil of 1oz on each of two sides of the laminate, and hot pressing under the following conditions: heating to 200 deg.C at a heating rate of 2.0 deg.C/min, and at 200 deg.C under full pressure of 25kg/cm 2 (initial pressure 12kg/cm 2 ) Hot pressing for 80-100 min.
The invention also provides a laminated plate prepared by the method. The laminate has excellent physical and chemical properties and electrical properties, such as high glass transition temperature (Tg), low water absorption, good solder dip resistance, good flame retardancy, and low dielectric constant and dissipation factor.
Compared with the prior art, the invention has the following beneficial effects:
the methacrylate polyphenyl ether resin composition has good solubility in organic solvents, is very convenient to apply, and a laminated plate prepared from the methacrylate polyphenyl ether resin composition has excellent physical and chemical properties and electrical properties, such as high glass transition temperature (Tg), low water absorption, good dip soldering resistance, good flame retardancy, low dielectric constant and dissipation factor.
Drawings
FIG. 1 is a hydrogen spectrum of a polyphenylene ether intermediate in example 1;
FIG. 2 is a carbon spectrum of the polyphenylene ether intermediate of example 1;
FIG. 3 is a chart of the infrared spectrum of the polyphenylene ether intermediate in example 1;
FIG. 4 is an infrared spectrum of a polyphenylene ether in example 1;
FIG. 5 is an infrared spectrum of a methacrylate polyphenylene ether in example 1;
FIG. 6 is a hydrogen spectrum of the polyphenylene ether intermediate in example 4;
FIG. 7 is a carbon spectrum of the polyphenylene ether intermediate of example 4;
FIG. 8 is a chart of an infrared spectrum of a polyphenylene ether intermediate in example 4;
FIG. 9 is an infrared spectrum of a polyphenylene ether in example 4.
FIG. 10 is an infrared spectrum of a methacrylate polyphenylene ether in example 4;
Detailed Description
In order that the invention may be more fully understood, preferred embodiments will now be given. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples, comparative examples and application examples relate to the following test methods and apparatus:
(1) Nuclear Magnetic Resonance (NMR) analysis: a nuclear magnetic resonance spectrometer (model: mercury-VX200 MHz) from Varian.
(2) Infrared spectrum analysis: infrared spectrometer (model: FTS-3000) from Bio-RAD.
(3) Differential Scanning Calorimetry (DSC) analysis: differential scanning calorimeter (model: DSC 7) from Perkin-Elmer.
(4) Gel chromatography (GPC) analysis: a colloid chromatograph (model: waters 600) from Waters corporation.
(5) Glass transition temperature test: the glass transition temperature (Tg) was measured using a Dynamic Mechanical Analyzer (DMA). The testing specification of glass transition temperature adopts The Electronic circuit interconnection and Packaging society (IPC) IPC-TM-650.2.4.25C and No. 24C detection method.
(6) Dielectric constant and dissipation factor measurements: dielectric constant (Dk) and dissipation factor (Df) were calculated according to ASTM D150 specification at an operating frequency of 1 megahertz (GHz).
(7) Water absorption test: the high Pressure Cooker (PCT) test was performed by placing the laminate in a pressure vessel and testing the laminate for high humidity resistance at 121 ℃, saturation humidity (100%) and 2 atm for 2 hours.
(8) Thermal expansion coefficient test and expansion rate in the Z-axis direction: measuring with thermal expansion analyzer of TA 2940 model of TA instrument company at 50-260 deg.C, heating rate of 5 deg.C/min, and measuring sample size of 3 × 3mm 2 The thermal expansion coefficient in the thickness direction (Z-axis direction) and the expansion rate in the Z-axis direction of the laminate sample were measured.
(9) Thermal decomposition temperature test: the temperature at which the mass is reduced by 5% compared to the initial mass, that is, the thermal decomposition temperature, is measured by a thermogravimetric analyzer (TGA).
(10) And (3) testing toughness: the laminated plate is horizontally placed on a plane jig, a cross-shaped metal jig is vertically contacted with the surface of the laminated plate, then vertical pressure is applied, the cross-shaped jig is removed, cross-shaped traces on the laminated plate are observed, the surface of the laminated plate is inspected, if no white crease occurs, the laminated plate is judged to be good, if no white crease occurs, the laminated plate is general, and if cracks or fractures occur, the laminated plate is inferior.
(11) And (3) testing the tearing strength: the peel strength refers to the adhesion of the copper foil to the substrate, and is usually expressed in terms of the amount of force required to peel the copper foil from the surface of the substrate vertically per inch (25.4 mm) of width. MIL-P-55110E specifies a 1oz copper foil substrate and a pass standard of 4lb/in.
(12) Dip soldering resistance test: after soaking the dried laminate in a soldering bath at 288 ℃ for a certain period of time, it is observed whether defects appear, for example as determined by delamination or blistering of the laminate.
Example 1
A methacrylate polyphenylene ether resin composition is prepared by the following method:
butadiene-styrene copolymer (number average molecular weight 1000 to 2500), methacrylate polyphenylene ether, bismaleimide (BMI) phenol resin, yabao 8010 flame retardant, silane dispersant, and toluene were mixed in the proportions shown in table 1, and were mixed at room temperature for 2 to 4 hours using a stirrer.
The methacrylate polyphenyl ether is prepared by the following method:
100g of polyphenylene ether in which R is cyclohexyl and 300g of toluene were sequentially charged into a 500mL three-necked round-bottomed flask, and stirred at room temperature (about 20 ℃ C.) for about 30min. After the polyphenylene ether was dissolved, 17.33g of methacryloyl chloride was pre-dissolved in 52g of toluene and stirred (molar ratio 8. Then 25.18g of triethylamine (molar ratio of triethylamine to methacryloyl chloride: 1.5). The reaction was terminated by heating to 50 ℃ and stirring for 5 hours. Neutralizing with hydrochloric acid, extracting with toluene, retaining toluene layer, adding methanol to precipitate solid, filtering, and vacuum drying to obtain 90g light gray powder.
The structure of the obtained methacrylate polyphenyl ether is shown as the following formula IV:
Figure BDA0002298741150000061
wherein m + n =26 to 30, and the number average molecular weight Mn =2800 to 3200.
The polyphenyl ether with the cyclohexyl R is prepared by the following method:
preparing an intermediate: controlling the reflux condensation temperature to be 0 ℃, and adding 600mL of CH-containing solution into a 1000mL four-mouth bottle 2 Cl 2 Adding 57.3g of 2, 6-dimethylphenol into Hexane (normal Hexane), 0.8g of sulfuric acid and 2g of dehydrating agent magnesium sulfate, then adding 9.2g of cyclohexanone in batches, controlling the reaction temperature to be 70 ℃, and reacting for 24 hours to obtain a primary product. Adding sodium bicarbonate water solution into the initial product for neutralization, and adding CH 2 Cl 2 Extraction was carried out, and Hexane was added to precipitate a solid, whereby 18.1g of a purified product was obtained.
Reaction: taking a 5L four-neck round-bottom bottle, controlling the stirring speed to be 150-200 rpm, adding 1.3L of toluene and 30g of CuCl 2 120g of Tri-ethyl amine (triethylamine), continuously introducing oxygen, and adding 280g of the polyphenylene oxide intermediate until the polyphenylene oxide intermediate is completely dissolved; 800g of 2, 6-dimethylphenol is dissolved in 1L of toluene and poured into a liquid adding funnel; adding the 2, 6-dimethylphenol solution into a four-neck round-bottom bottle, continuing stirring for 7 hours, and stopping introducing oxygen after stirring. Transferring the reaction solution into a 12L round-bottom bottle, adding 820mL0.1N EDTA aqueous solution, stirring at room temperature for 6 hours, heating to 50-60 ℃, and continuously stirring for 2 hours. The toluene layer solution was collected, 2.4l of 1% hydrochloric acid was added thereto, stirred for 2 hours, and left to stand for 24 hours. The toluene layer solution was collected, 10L of methanol was added to precipitate a large amount of precipitate, which was continuously stirred at room temperature for at least 1 hour, and then the precipitated product was filtered and dried in a vacuum oven (80 ℃ C., 16 hrs) to obtain 850-950 g of light gray powder.
The structure of the polyphenylene oxide intermediate is shown as a formula V:
Figure BDA0002298741150000071
the structure of the polyphenylene ether is shown as a formula VI:
Figure BDA0002298741150000072
the results of the hydrogen spectrum, carbon spectrum and infrared spectrum of the polyphenylene ether intermediate represented by the formula V are shown in FIGS. 1 to 3; the melting point of this compound was tested to be 202.23 ℃. The infrared spectrum of the polyphenylene ether represented by the formula VI is shown in FIG. 4. The infrared spectrum of the methacrylate polyphenylene ether represented by the formula VI is shown in FIG. 5. The detection proves that the polyphenyl ether and the methacrylate polyphenyl ether have good dissolubility for benzenes, ketones, amides, pyridine and the like.
Example 2
A methacrylate polyphenylene ether resin composition was distinguished from example 1 in that a methacrylate polyphenylene ether was used in an amount of 80 parts by weight.
Example 3
A methacrylate polyphenylene ether resin composition was distinguished from example 1 in that the methacrylate polyphenylene ether was used in an amount of 180 parts by weight.
Example 4
A methacrylate polyphenylene ether resin composition, which is different from example 1 in that 9.2g of cyclohexanone was replaced with 7.8g of cyclopentanone and R was a cyclopentyl group, to prepare a methacrylate polyphenylene ether, to finally obtain 84g of light gray powder, m + n =24 to 28, and number average molecular weight Mn =2400 to 3000.
The methacrylate polyphenylene ether has the following structure formula VII:
Figure BDA0002298741150000073
the structure of the polyphenylene oxide intermediate involved in the preparation process is shown as a formula VIII:
Figure BDA0002298741150000081
the structure of the polyphenylene oxide involved in the preparation process is shown as formula IX:
Figure BDA0002298741150000082
the results of the hydrogen, carbon and infrared spectra of the polyphenylene ether intermediate represented by formula VIII are shown in FIGS. 6-8; the melting point of this compound was determined to be 176.4 ℃. The infrared spectrum of the polyphenylene ether shown in formula IX is shown in FIG. 9. The infrared spectrum of the methacrylate polyphenylene ether represented by the formula VII is shown in FIG. 10. The detection proves that the polyphenyl ether and the methacrylate polyphenyl ether have good dissolubility for benzenes, ketones, amides, pyridine and the like.
Example 5
A methacrylate polyphenyl ether resin composition is different from that in example 1, raw materials for preparing the methacrylate polyphenyl ether resin composition further comprise a Yabao 8010 flame retardant and a silane dispersing agent, wherein the usage amount of the Yabao 8010 flame retardant is 20 parts by weight, and the usage amount of the silane dispersing agent is 0.2 part by weight.
Comparative example 1
A methacrylate polyphenylene ether resin composition was distinguished from example 1 in that the methacrylate polyphenylene ether was used in an amount of 60 parts by weight.
Comparative example 2
A methacrylate polyphenylene ether resin composition was distinguished from example 1 in that a methacrylate polyphenylene ether was used in an amount of 200 parts by weight.
The kinds and amounts of raw materials for preparing methacrylate polyphenylene ethers in the above examples and comparative examples are shown in Table 1:
TABLE 1 raw materials and amounts (parts by weight)
Figure BDA0002298741150000083
Figure BDA0002298741150000091
Application examples
A laminate was prepared using the methacrylate polyphenylene ether resin compositions of examples and comparative examples, respectively, the preparation method comprising the steps of:
preparing a prepreg: coating 7628 mass ratio of the methacrylate polyphenylene oxide resin composition to the glass fiber cloth is 43%, placing the coated methacrylate polyphenylene oxide resin composition and the glass fiber cloth in a dryer, and heating and drying at 180 ℃ for 2-5 min to obtain a prepreg;
hot pressing: laminating 8 prepregs, laminating a 1oz copper foil on each side of the laminate, and hot pressing under the following conditions: heating to 200 deg.C at a heating rate of 2.0 deg.C/min, and at 200 deg.C under full pressure of 25kg/cm 2 (initial pressure 12 kg/cm) 2 ) Hot pressing for 90min under the pressure of the pressure to obtain the copper foil coated laminated board.
The results of the performance tests of the laminates made from the methacrylate polyphenylene ether resin compositions of examples and comparative examples are shown in table 2:
TABLE 2 laminate Properties
Figure BDA0002298741150000092
Figure BDA0002298741150000101
As can be seen from Table 2, the laminated sheets obtained from the resin compositions of the examples of the present invention all had better glass transition temperature, water absorption, thermal expansion coefficient and excellent electrical characteristics (low Dk and Df). In comparative example 1, the addition amount of the methacrylate polyphenylene oxide is small, the Tg is obviously low, the heat resistance is poor, and the expansion coefficient is large, while in comparative example 2, the addition amount of the methacrylate polyphenylene oxide is large, and the toughness of the plate is obviously poor.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (7)

1. A methacrylate polyphenyl ether resin composition is characterized by comprising the following raw materials in parts by weight:
40 to 60 portions of hydrocarbon resin,
80 to 120 portions of methyl acrylate polyphenyl ether,
40-60 parts of bismaleimide phenolic resin;
the methacrylate polyphenyl ether has the structure as follows:
Figure FDA0003921732300000011
wherein m + n = 18-26, and the number average molecular weight Mn is 2800-3200;
the hydrocarbon resin is butadiene-styrene copolymer with number average molecular weight of 1000-2500.
2. The methacrylate polyphenylene ether resin composition according to claim 1, further comprising 100 to 200 parts by weight of a solvent; the solvent is selected from: one or more than two of toluene, butanone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
3. The methacrylate polyphenylene ether resin composition according to claim 1 or 2, further comprising 0.05 to 50 parts by weight of an additive selected from the group consisting of: one or more of flame retardant, hardening accelerator, dispersant and flexibilizer.
4. A method for producing a methacrylate polyphenylene ether resin composition according to any one of claims 1 to 3, comprising the steps of: weighing the raw materials, adding a solvent, and uniformly mixing to obtain the methacrylate polyphenyl ether resin composition.
5. A prepreg prepared from a raw material comprising the methacrylate polyphenylene ether resin composition according to any one of claims 1 to 3.
6. A method for preparing a laminated plate is characterized by comprising the following steps:
preparing a prepreg: coating the methacrylate polyphenylene ether resin composition according to any one of claims 1 to 3 on a substrate, and drying to obtain a prepreg;
hot pressing: laminating a plurality of prepregs, laminating copper foils on two sides of the laminated material, and hot-pressing to obtain the laminated plate coated with the copper foils.
7. A laminate produced by the method of claim 6.
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