CN110951235A - Methacrylate polyphenyl ether resin and preparation method and application thereof - Google Patents
Methacrylate polyphenyl ether resin and preparation method and application thereof Download PDFInfo
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- 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
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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
- 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
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
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- 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
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- 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
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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
- 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
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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
- 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
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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
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- 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
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- 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
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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 structure of the methacrylate polyphenyl ether is shown as a formula I, wherein R is cycloalkyl, m + n is 18-26, and the number average molecular weight Mn is2800～3200。
Description
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 substrate 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 can have the above characteristics, and thus the epoxy resin is the most commonly used resin 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 polyphenylene ether resin compositions have the advantages of low dielectric constant and dissipation factor, however, the existing polyphenylene ether resins still cannot 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 be used to prepare a laminate having 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 low dissipation factor.
A 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,
40-60 parts of cyanate ester resin;
the structure of the methacrylate polyphenyl ether is shown as the following formula I:
I
wherein R is cycloalkyl, m + n is 18-26, and the number average molecular weight Mn is 2800-3200.
The methacrylate polyphenyl ether resin composition has good solubility in organic solvents, is very convenient to apply, and the 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.
In one embodiment, the paint further comprises 100 to 200 parts by weight of a 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 dimethyl sulfoxide (DMSO). Preferably, the solvent is toluene.
In one embodiment, the hydrocarbon resin is butadiene-styrene copolymer, and the number average molecular weight is 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 eastern Material technology DEF 409.
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 hours.
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 distributivity and high solvent selectivity.
The reaction formula for synthesizing methacrylate polyphenylene ether is shown below:
in one embodiment, the polyphenylene ether has the structure shown in formula II below:
II
in one embodiment, the polyphenylene ether is prepared by the following method:
preparing an intermediate: sulfuric acid, dehydrating agent, 2, 6-dimethylphenol and a catalyst containing CH2Cl2Mixing the Hexane, adding the alkanone, controlling the reaction temperature to be 65-75 ℃, reacting for 20-28 h, adding the alkali for neutralizingAdding CH2Cl2Extracting, 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, methylbutanone or ethylbutanone. 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; and adding a 2, 6-dimethylphenol solution into the pre-reaction solution under the condition of introducing oxygen, and reacting for 6-8 hours to obtain the polyphenyl ether. Preferably, the molar ratio of the 2, 6-dimethylphenol to the toluene used for preparing the 2, 6-dimethylphenol solution is (3-16): 1. Preferably, the metal catalyst is CuCl2。
In one embodiment, the reaction step in the polyphenylene ether production method further comprises the following steps:
removing impurities: adding an EDTA aqueous solution to adsorb a metal catalyst, mixing for 8-12 h at 20-30 ℃, heating to 50-60 ℃, mixing for 1-3h, layering, and keeping a 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 the rotating speed of 3000-4000 rpm, and separating out a product.
And (3) drying: filtering, and placing the solid product at 75-85 ℃ for vacuum drying for 14-18 h.
Wherein the structure of the polyphenylene ether intermediate is shown as the following formula III:
r is cycloalkyl, and the cycloalkyl is cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl or 3, 5-dimethylcyclohexyl.
The reaction formula for synthesizing polyphenylene ether is shown below:
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 ester and cycloaliphatic aromatic cyanate ester. Preferably, the cyanate ester resin is selected from Bismaleimide (BMI) phenolic resin.
In one embodiment, the paint further comprises 0.05-50 parts by weight of an additive selected from the group consisting of: one or more of flame retardant, accelerator, 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 which is prepared from the raw materials comprising the methacrylate polyphenylene ether 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 substrate, 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 7-9 prepregs, laminating 1oz copper foil on each of two sides of the laminate, and hot pressing, where the hot pressing conditions are as follows: 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/cm2(initial pressure 12kg/cm2) 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 a chart of an infrared spectrum of the 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 showing 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 a chart showing an infrared spectrum of a methacrylate polyphenylene ether in example 4;
Detailed Description
To facilitate an understanding of the invention, a more complete description of the invention will be given below in terms of preferred embodiments. 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 specification of glass transition temperature test 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 autoclave retort test (PCT) was performed, in which the laminate was placed in a pressure vessel and tested for high humidity resistance at 121 ℃, saturation humidity (100% r.h.) 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 × 3mm2The 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, i.e., the thermal decomposition temperature, is measured by a thermogravimetric analyzer (TGA).
(10) And (3) toughness testing: 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 (25.4mm) of width. MIL-P-55110E specifies a 1oz copper foil substrate and a pass standard of 4 lb/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:
the flame retardant is prepared by mixing butadiene-styrene copolymer (number average molecular weight is 1000-2500), methacrylate polyphenylene oxide, Bismaleimide (BMI) phenolic resin, flame retardant of Yabao 8010, silane dispersant and toluene in the proportions shown in Table 1, and mixing for 2-4 hours at room temperature by using a stirrer.
The methacrylate polyphenyl ether is prepared by the following method:
100g R of a cyclohexyl polyphenylene ether and 300g of toluene were sequentially charged into a 500mL three-necked round bottom flask and stirred at room temperature (about 20 ℃ C.) for about 30 min. After the polyphenylene oxide was dissolved, 17.33g of methacryloyl chloride was pre-dissolved in 52g of toluene and stirred (molar ratio 8: 1), and then added to the flask in portions, and after 20min, the reaction was continued for 30 min. Then 25.18g of triethylamine (molar ratio of triethylamine to methacryloyl chloride 1.5: 1) was pre-dissolved in 75.5g of toluene and stirred, and added to the flask in portions. 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 polyphenylene ether is shown as the following formula IV:
wherein m + n is 26-30, and the number average molecular weight Mn is 2800-3200.
The polyphenyl ether with the cyclohexyl R is prepared by the following method:
preparing an intermediate: controlling the reflux condensation temperature to 0 ℃, and adding 600mL of CH-containing solution into a 1000mL four-mouth bottle2Cl2Adding 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 into the mixture 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 CH2Cl2Extraction 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 and controllingStirring at 150-200 rpm, adding 1.3L of toluene and 30g of CuCl2120g of Tri-ethyl amine (triethylamine), continuously introducing oxygen, and adding 280g of the polyphenylene oxide intermediate until the polyphenylene oxide intermediate is completely dissolved; dissolving 800g of 2, 6-dimethylphenol in 1L of toluene, and pouring 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. And 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 continuing stirring for 2 hours. The toluene layer solution was collected, 2.4L of 1% hydrochloric acid was added thereto, stirred for 2 hours, and allowed to stand for 24 hours. Collecting the toluene layer solution, adding 10L of methanol to separate out a large amount of precipitate, continuously stirring at room temperature for at least 1 hour, filtering the precipitate product, and drying in a vacuum oven (80 ℃, 16hrs) to obtain 850-950 g of light gray powder.
The structure of the polyphenylene oxide intermediate is shown as a formula V:
the structure of the polyphenylene ether is shown as a formula VI:
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 is different from that of example 1 in that, in the preparation of a methacrylate polyphenylene ether, 9.2g of cyclohexanone is replaced by 7.8g of cyclopentanone, and R is a cyclopentyl group, to give 84g of a pale gray powder, where m + n is 24 to 28, and the number average molecular weight Mn is 2400 to 3000.
The methacrylate polyphenylene ether has the following structure formula VII:
the structure of the polyphenylene oxide intermediate involved in the preparation process is shown as a formula VIII:
the structure of the polyphenylene oxide involved in the preparation process is shown as formula IX:
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 represented by the 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 polyphenylene ether resin composition is different from that in example 1 in that raw materials for preparing the methacrylate polyphenylene ether resin composition further comprise a flame retardant of Yabao 8010 and a silane dispersing agent, wherein the dosage of the flame retardant of Yabao 8010 is 20 parts by weight, and the dosage 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)
Application examples
Laminates were made 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 of glass fiber cloth with the methacrylate polyphenylene ether resin composition, wherein the mass ratio of the methacrylate polyphenylene ether resin composition to the glass fiber cloth is 43%, placing the coated glass fiber cloth in a dryer, and heating and drying the coated glass fiber cloth 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/cm2(initial pressure 12kg/cm2) 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 the examples and comparative examples are shown in Table 2:
TABLE 2 laminate Properties
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.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification 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, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The methacrylate polyphenylene oxide resin composition is characterized by comprising the following raw materials in parts by weight:
40-60 parts of hydrocarbon resin,
80-180 parts of methacrylate polyphenyl ether,
40-60 parts of cyanate ester resin;
the structure of the methacrylate polyphenyl ether is shown as the following formula I:
wherein R is cycloalkyl, m + n is 18-26, and the number average molecular weight Mn is 2800-3200.
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, wherein the hydrocarbon resin is a butadiene-styrene copolymer and has a number average molecular weight of 1000 to 2500.
4. The methacrylate polyphenylene ether resin composition according to claim 1, wherein R in the methacrylate polyphenylene ether is cyclopentyl, cyclohexyl, cycloheptyl, 3-methylcyclohexyl, 3-methylcycloheptyl, or 3, 5-dimethylcyclohexyl.
5. The methacrylate polyphenylene ether resin composition according to claim 1, wherein the cyanate ester resin is selected from the group consisting of: one or more than two of bismaleimide-triazine, bismaleimide phenolic resin, bisphenol A cyanate ester and cycloaliphatic aromatic cyanate ester.
6. The methacrylate polyphenylene ether resin composition according to any one of claims 1 to 5, 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.
7. A method for producing a methacrylate polyphenylene ether resin composition according to any one of claims 1 to 6, comprising the steps of: weighing the raw materials, adding a solvent, and uniformly mixing to obtain the methacrylate polyphenylene oxide resin composition.
8. A prepreg prepared from a raw material comprising the methacrylate polyphenylene ether resin composition according to any one of claims 1 to 6.
9. A method for preparing a laminated plate is characterized by comprising the following steps:
preparing a prepreg: coating the methacrylate polyphenylene ether resin composition as defined in any one of claims 1 to 6 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 body, and hot-pressing to obtain the copper foil-coated laminated plate.
10. A laminate produced by the method of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911213232.4A CN110951235B (en) | 2019-12-02 | 2019-12-02 | Methacrylate polyphenyl ether resin and preparation method and application thereof |
| TW109105945A TW202122490A (en) | 2019-12-02 | 2020-02-25 | Methacrylate polyphenyl ether resin, preparation method thereof and application thereof |
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| CN201911213232.4A CN110951235B (en) | 2019-12-02 | 2019-12-02 | Methacrylate polyphenyl ether resin and preparation method and application thereof |
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|---|---|---|---|---|
| JPH07268205A (en) * | 1994-04-04 | 1995-10-17 | Asahi Chem Ind Co Ltd | Resin composition for conductive heat-resistant ic member |
| CN102838864A (en) * | 2012-09-20 | 2012-12-26 | 苏州生益科技有限公司 | Resin composition and prepreg and laminate manufactured by using same |
| CN104341766A (en) * | 2013-08-09 | 2015-02-11 | 台光电子材料(昆山)有限公司 | Low-dielectric resin composition, as well as copper foil substrate and printed circuit board applying same |
| US20170260364A1 (en) * | 2016-03-10 | 2017-09-14 | Elite Material Co., Ltd. | Resin composition, copper-clad laminate using the same, and printed circuit board using the same |
| CN109971152A (en) * | 2017-12-28 | 2019-07-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composition, prepreg, laminate and printed wiring board |
| US20190300649A1 (en) * | 2016-12-28 | 2019-10-03 | Shengyi Technology Co., Ltd. | Flame-retardant polyphenylene ether resin composition |
-
2019
- 2019-12-02 CN CN201911213232.4A patent/CN110951235B/en active Active
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2020
- 2020-02-25 TW TW109105945A patent/TW202122490A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268205A (en) * | 1994-04-04 | 1995-10-17 | Asahi Chem Ind Co Ltd | Resin composition for conductive heat-resistant ic member |
| CN102838864A (en) * | 2012-09-20 | 2012-12-26 | 苏州生益科技有限公司 | Resin composition and prepreg and laminate manufactured by using same |
| CN104341766A (en) * | 2013-08-09 | 2015-02-11 | 台光电子材料(昆山)有限公司 | Low-dielectric resin composition, as well as copper foil substrate and printed circuit board applying same |
| US20150044485A1 (en) * | 2013-08-09 | 2015-02-12 | Elite Electronic Material (Kunshan) Co., Ltd. | Low-dielectric resin composition and copper-clad laminate and printed circuit board using the same |
| US20170260364A1 (en) * | 2016-03-10 | 2017-09-14 | Elite Material Co., Ltd. | Resin composition, copper-clad laminate using the same, and printed circuit board using the same |
| US20190300649A1 (en) * | 2016-12-28 | 2019-10-03 | Shengyi Technology Co., Ltd. | Flame-retardant polyphenylene ether resin composition |
| CN109971152A (en) * | 2017-12-28 | 2019-07-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composition, prepreg, laminate and printed wiring board |
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| TW202122490A (en) | 2021-06-16 |
| CN110951235B (en) | 2022-12-20 |
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