CN111574818B - Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and carbon-hydrogen copper-clad plate prepared from polyarylether base composition - Google Patents
Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and carbon-hydrogen copper-clad plate prepared from polyarylether base composition Download PDFInfo
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- 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
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- B32B15/00—Layered products comprising a layer of metal
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention belongs to the field of communication materials, and particularly relates to a polyarylether-based composition containing reversible thermal shrinkage and cold expansion structural units, and a prepreg and a hydrocarbon copper-clad plate prepared from the polyarylether-based composition. The double-end vinyl type polyphenyl ether resin containing dibenzo eight-membered ring structural units is prepared firstly, and then the prepreg is prepared by taking the double-end vinyl type polyphenyl ether resin as matrix resin, and the prepreg is uniform in gel content, strong in resin adhesive force, smooth in surface, and appropriate in toughness and viscosity. And then, the carbon-hydrogen copper-clad plate is prepared by using the prepreg, and the carbon-hydrogen copper-clad plate has excellent dielectric property, high mechanical strength, high copper foil peeling strength and good uniformity of various properties. Particularly, the thermal expansion coefficient of the hydrocarbon copper clad laminate can be controllably reduced by adjusting the molecular weight of the double-end vinyl type polyphenyl ether resin containing the dibenzo eight-membered ring structural unit and the content of the double-end vinyl type polyphenyl ether resin in the prepreg, so that the composite material is suitable for manufacturing a multilayer board.
Description
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a polyarylether-based composition containing reversible thermal shrinkage and cold expansion structural units, and a prepreg and a carbon-hydrogen copper-clad plate prepared from the polyarylether-based composition.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, wearable equipment, communication base stations, satellites, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like, and is one of key materials in electronic communication and information industries. The traditional thermosetting resin represented by epoxy resin, phenolic resin and cyanate resin has high thermo-mechanical property, high quality, low price, convenient processing and strong universality, and is a common material for manufacturing copper-clad plate base materials. Researchers continuously search and optimize formulas and process parameters to prepare various thermosetting copper-clad plates with qualified comprehensive performance, and the most basic requirements of each subdivided field of the electronic communication industry on the copper-clad plates are met.
However, the dielectric constant and dielectric loss of the conventional thermosetting copper clad laminate are generally high, so that the conventional thermosetting copper clad laminate can only be used at low frequency and cannot meet the higher performance requirement of the substrate material in the field of high-frequency and high-speed communication. Later, people developed a polyphenyl ether-based thermosetting copper-clad plate, and the dielectric property of the plate in the high-frequency field is improved. At present, thermosetting polyphenyl ether resin can be divided into two main types of side vinyl modification and end vinyl modification. In the preparation process of the side vinyl modified polyphenyl ether, butyl lithium and other substances with strong reactivity, high risk and high toxicity are required to be used, the production process is complex, and no large-scale industrialized product is available at present; vinyl-terminated modified polyphenylene ethers have been commercialized.
In addition, electronic products are rapidly developing towards miniaturization, light weight, thinning and multi-functionalization, and copper-clad plates serving as main carriers of electronic components have higher and higher integration level and more obvious multi-layer trend, so that the copper-clad plates are required to have extremely low thermal expansion coefficients. The traditional idea is to introduce a large amount of inorganic filler into a plate matrix to inhibit the thermal expansion process of a polymer matrix, however, a significant limit value exists in the reduction effect of the thermal expansion coefficient of the copper-clad plate brought by the scheme. In addition, the introduction of excessive inorganic filler can cause problems such as poor dispersibility of materials in the matrix of the sheet material, poor uniformity and reliability of the sheet material properties, and the like.
In 2013, the Jennifer Lu subject group of the university of California and Wang Changchun subject group of the university of Compound Danzhou jointly discover that the polymer containing the dibenzo eight-membered ring structural unit has unique reversible thermal shrinkage and cold expansion characteristics, and the coefficient of thermal expansion of the polymer can be more than 1200ppm/K (nat. Chem., 2013, 5, 1035; chinese patent application 201710360230.2; chinese patent application 201910474075.6), which is derived from reversible conformation change of the dibenzo eight-membered ring structural unit from a twist boat type to a chair type.
Disclosure of Invention
The invention provides a polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units, and a prepreg and a carbon-hydrogen copper-clad plate prepared from the polyarylether base composition.
The preparation method comprises the steps of firstly preparing a double-end hydroxyl type polyphenylene oxide resin containing a dibenzo eight-membered ring structural unit, further modifying the double-end hydroxyl type polyphenylene oxide resin with the dibenzo eight-membered ring structural unit as a precursor to obtain a double-end vinyl type polyphenylene oxide resin containing the dibenzo eight-membered ring structural unit, then using the double-end hydroxyl type polyphenylene oxide resin as a matrix resin, adding a proper cross-linking agent, a proper modified resin, a proper filler, a proper flame retardant and a proper initiator, and preparing a prepreg containing the dibenzo eight-membered ring structural unit by processes of gluing, baking and the like. The prepreg has the advantages of uniform gel content, strong resin adhesive force, smooth surface, and proper toughness and viscosity. Furthermore, the carbon-hydrogen copper clad laminate prepared from the prepreg has excellent dielectric property, high mechanical strength, high copper foil peeling strength and good uniformity of various properties. Particularly, the thermal expansion coefficient of the carbon-hydrogen copper-clad plate can be controllably reduced to an extremely low range by adjusting the molecular weight of the double-end vinyl type polyphenyl ether resin containing the dibenzo eight-membered ring structural unit and the content of the double-end vinyl type polyphenyl ether resin in the prepreg, so that the prepared carbon-hydrogen copper-clad plate is suitable for manufacturing a multilayer copper-clad plate, and various performance requirements of the current high-frequency and high-speed communication field on the function diversification and the complication of the copper-clad plate material can be met.
The invention provides a polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units, which comprises more than six components of matrix resin, a cross-linking agent, modified resin, a filler, a flame retardant and an initiator; the matrix resin is double-end vinyl type polyarylether resin containing a structural unit with reversible thermal shrinkage and cold expansion characteristics, and the specific structure is as follows:
 |
wherein R1, R2, R3 and R4 each independently represent H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group and a halogen atom; r6, R7 and R8 each independently represent H, methyl and ethyl; a is more than or equal to 0; r is specifically one or a composite of two of the following structures:
the further preferred technical scheme is as follows: the specific preparation method of the double-end vinyl type polyarylether resin containing the structural unit with reversible thermal shrinkage and cold expansion characteristics, namely the dibenzo eight-membered ring, comprises the following steps:
step 1, adding a catalyst into a solution of a phenol derivative monomer, and uniformly stirring to obtain a reaction solution A; preparing a solution of a monomer I or a monomer II, and marking as a reaction solution B; setting the reaction temperature to be 20-60 ℃, slowly dropwise adding the reaction liquid A into the reaction liquid B under the condition of vigorous stirring and introducing oxygen-containing gas, and continuously reacting for 4-72h after dropwise adding is finished to obtain a product solution C; wherein, the monomer I or the monomer II can be prepared by the technical scheme of the Chinese patent application 201710360230.2 to obtain the corresponding dicarboxylic acid precursor, and then the dicarboxylic acid precursor is reacted with water vapor and oxygen at high temperature to prepare the dicarboxylic acid precursor
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| Monomer I | Monomer II |
step 3, preparing an organic solution E of the double-end hydroxyl type polyarylether resin with the concentration of 3 to 60wt%, adding alkali, stirring uniformly, slowly adding vinyl halide, and reacting for 30 to 150 o C, stirring and reacting for 1 to 72h to obtain a product solution F;
step 4, adding a poor solvent G of the polyarylether resin into the product solution F, uniformly stirring, standing until a polymer product is fully separated out and settled, and filtering, washing and drying to obtain a final product, namely the double-end vinyl type polyarylether resin with a main chain containing dibenzo eight-membered ring structural units;
the further preferred technical scheme is as follows: the phenol derivative monomer in the step 1 refers to one or a mixture of several compounds with the following chemical structures:
 |
wherein R9, R10, R11 and R12 each independently represent H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group and a halogen atom; preferred are 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-di-n-propylphenol, 2,6-diphenylphenol, 2,6-dimethylphenylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-methylphenylphenol, 2-methyl-6-bromophenol and 2-ethyl-6-chlorophenol; more preferred are 2,6-dimethylphenol, 2,3,6-trimethylphenol and 2-methyl-6-bromophenol; most preferred is 2,6-dimethylphenol;
the catalyst in the step 1 is a metal salt-amine complex;
the metal salt is one or a mixture of more of copper salt, manganese salt and chromium salt; preferred metal salts are copper halides, cuprous halides, cupric sulfate, cuprous sulfate, cupric nitrate, cuprous nitrate, cupric acetate, cuprous acetate, cupric propionate, cuprous propionate, cupric dodecanoate, cupric hexadecanoate, cuprous benzoate, and the corresponding manganese and chromium salts; besides the above metal salts, the corresponding metal salts or hydrates thereof can also be directly generated in the solution of the phenol derivative monomers by the reaction between copper, copper oxide, manganese oxide, chromium oxide, copper or manganese or chromium carbonate, copper or manganese or chromium hydroxide and organic acid or inorganic acid; cuprous halides are preferred;
the amine is one or a mixture of more of primary amine, secondary amine, tertiary amine, monoamine, diamine, polyamine and polymer with amino; preferred amines are dimethylamine, diethylamine, dipropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, diethanolamine, methylethylamine, N-methylisopropylamine, N-methylcyclohexylamine, N-ethylisopropylamine, N-benzylmethylamine, N-benzyl-1-phenylethylamine, N-dimethylbutylamine, N-dialkylethylenediamine and pyridine;
in the step 1, the solvent in the reaction solution A and the reaction solution B is one or a mixture of several of organic solvents capable of dissolving the polyarylether resin and the catalyst, or a mixture of the organic solvent capable of dissolving the polyarylether resin and the catalyst and water; preferred are aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, methylene chloride and dichlorobenzene, nitroaromatic compounds such as nitrobenzene, aliphatic hydrocarbons and ethers; more preferred are aromatic hydrocarbons such as benzene, toluene, xylene, etc.; most preferred is toluene;
the further preferred technical scheme is as follows: the poor solvent D in the step 2 is one or a mixture of more of alcohols, ethers and esters such as methanol, ethanol, isopropanol and butanol; preferred are alcohols such as methanol, ethanol, isopropanol, and butanol; most preferred is methanol;
the further preferred technical scheme is as follows: the alkali in the step 3 is one or a mixture of more of n-butyllithium, sec-butyllithium, tert-butyllithium, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate and potassium carbonate; the ratio of the mole number of the alkali to the mole number of the hydroxyl contained in the double-end hydroxyl type polyarylether resin is 3 to 1.02;
the vinyl halide in the step 3 is one or a mixture of several substances with the following chemical structures;
 |
wherein X represents Cl, br and I; r6, R7 and R8 each independently represent H, methyl and ethyl; the ratio of the mole number of the vinyl halide to the mole number of the hydroxyl contained in the dihydroxy polyarylether resin is 2 to 1.01;
in the step 3, the solvent of the organic solution E is one or a mixture of more of aprotic polar solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, or the aprotic polar solvent is added with one or a mixture of more of benzene, toluene, xylene and nitrobenzene; the water content of the solvent of the organic solution E is less than or equal to 0.1wt%;
the further preferred technical scheme is as follows: and 4, the poor solvent G in the step 4 is one or a mixture of more of methanol, ethanol, isopropanol, butanol, water, ether and ester.
The further preferred technical scheme is as follows: the cross-linking agent is one or a compound mixture of more of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), side vinyl modified polyarylether, polydiene and derivatives thereof; the dosage of the cross-linking agent accounts for 3-500wt% of the matrix resin; the number average molecular weight of the side vinyl modified polyarylether is between 400 and 13000, and a single side group or side chain of the side vinyl modified polyarylether at least contains 3 reactive vinyl functional groups in total; the number average molecular weight of the polydiene is 500 to 20000, and the side group or the side chain of a single polydiene polymer chain at least contains 3 reactive vinyl functional groups in total.
The further preferred technical scheme is as follows: the modified resin is a composite mixture of one or more of a diene-maleic anhydride copolymer and derivatives thereof and one or more of a styrene-maleic anhydride copolymer and derivatives thereof; wherein, the side group or side chain of the polydiene block of a single diolefin-maleic anhydride copolymer chain at least contains a reactive vinyl functional group, the number average molecular weight of the diolefin-maleic anhydride copolymer is between 500 and 150000, and the using amount of the diolefin-maleic anhydride copolymer accounts for 5 to 95wt% of the modified resin; the number average molecular weight of the styrene-maleic anhydride copolymer is 500 to 30000, and the dosage of the styrene-maleic anhydride copolymer accounts for 5 to 95wt% of the modified resin; the dosage of the modified resin accounts for 0-20wt% of the polyarylether-based composition containing the reversible thermal-shrinkage and cold-expansion structural unit.
The further preferred technical scheme is as follows: the filler is SiO 2 、Al 2 O 3 、TiO 2 、ZnO、MgO、Bi 2 O 3 、AlN、Si 3 N 4 、SiC、BN、Al(OH) 3 、Mg(OH) 2 、BaTiO 3 、SrTiO 3 、Mg 2 TiO 4 、Bi 2 (TiO 3 ) 3 、PbTiO 3 、NiTiO 3 、CaTiO 3 、ZnTiO 3 、Zn 2 TiO 4 、BaSnO 3 、Bi 2 (SnO 3 ) 3 、CaSnO 3 、PbSnO 3 、MgSnO 3 、SrSnO 3 、ZnSnO 3 、BaZrO 3 、CaZrO 3 、PbZrO 3 、MgZrO 3 、SrZrO 3 、ZnZrO 3 One or a mixture of more of inorganic fillers such as graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fibers, basalt fibers and carbon fibers, and also one or a mixture of more of organic fillers such as polytetrafluoroethylene pre-sintering materials, ultra-high molecular weight polyethylene fibers, kevlar fibers, polyimide, polyetherimide, polyether ether ketone, polyphenylene sulfide and the like; the amount of the filler accounts for 0-80wt% of the polyarylether-based composition containing the reversible thermal shrinkage and cold expansion structural unit.
The further preferred technical scheme is as follows: the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant, nitrogen flame retardant and derivatives thereof; the dosage of the flame retardant accounts for 0-60wt% of the polyarylether-based composition containing the reversible thermal shrinkage and cold expansion structural unit.
The further preferred technical scheme is as follows: the initiator is one or a mixture of more of radical initiators including peroxides, azo compounds and redox systems which can be dissolved in a solvent for uniformly dispersing the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit, and the dosage of the initiator accounts for 0.01 to 5wt% of the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit.
A prepreg prepared by adopting the polyarylether-based composition containing the reversible thermal shrinkage and cold expansion structural unit comprises the following specific steps:
(1) Preparing a uniform dispersion liquid of the polyarylether-based composition with the solid content of 20-75wt/v% and the reversible thermal shrinkage and cold expansion structural unit;
(2) And soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg.
The further preferred technical scheme is as follows: the solvent in the uniform dispersion liquid of the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit is one or a mixture of water and an organic solvent which can uniformly disperse the composition;
the fiber cloth is one of electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, kevlar, polyimide, polytetrafluoroethylene, polyester and the like;
the baking and drying are divided into two stages, wherein the baking and drying temperature in the first stage is 50 to 120 ℃, and the baking and drying time is 1 to 30min; the baking and drying temperature in the second stage is 150 to 350 ℃, and the time is 1 to 30min.
A carbon-hydrogen copper-clad plate manufactured by adopting the prepreg comprises the following specific steps: laminating a prepreg, a film and copper foil coated on the surface together, and preparing the carbon-hydrogen copper-clad plate through a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2;
the laminating temperature of the laminating process is 150 to 350 ℃, and the laminating pressure is 70 to 170kg/cm 2 The laminating time is 0.5 to 24h;
the film is one or a mixture of more of fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, cyanate resin, polycarbonate, polyurethane and polyformaldehyde and derivatives thereof;
the thickness of the hydrocarbon copper-clad plate is controlled to be 0.1-10mm.
Drawings
FIG. 1 is a GPC chart (THF phase) of a double-terminal hydroxyl group-containing polyphenylene ether resin containing a dibenzo eight-membered ring structural unit according to the present invention.
Detailed Description
The polyarylether-based composition containing reversible thermal shrinkage and cold expansion structural units and the prepreg and the carbon-hydrogen copper clad laminate prepared from the polyarylether-based composition are further described in detail by the following embodiments. However, this example is provided by way of illustration only and not as a limitation of the invention.
Example 3
Adding 120 parts (by mol) of 2,6-dimethylphenol into toluene, stirring, mixing and dissolving uniformly to obtain a reaction solution A with the concentration of 0.5mol/v per thousand; adding 1 part (mole) of copper bromide, 1 part (mole) of EDTA and 16 parts (mole) of monomer I into toluene, stirring, mixing and dissolving uniformly to obtain a reaction solution B with the concentration of the monomer I being 0.1mol/v per thousand; under the conditions that air is stably blown into the reaction liquid B, the mechanical stirring rotation speed is set to be 400rpm, and the oil bath temperature is 50 ℃, slowly dropwise adding the reaction liquid A into the reaction liquid B, and continuously stirring and reacting for 24 hours after dropwise adding is finished to obtain a product solution C; pouring the product solution C into a large amount of methanol for precipitation, performing operations such as filtration, methanol washing and the like for multiple times, and drying in a vacuum oven at 80 ℃ overnight to obtain the double-end hydroxyl type polyphenylene oxide resin containing the dibenzo eight-membered ring structural unit, wherein the GPC result is shown in the attached figure 1: number average molecular weight Mn =942, weight average molecular weight Mw =1727.
Setting the reaction temperature to be 30 ℃ and the mechanical stirring speed to be 200rpm, slowly dropwise adding 0.1mol/L tert-butyl lithium/n-pentane solution into 10wt/v% of methyl ethyl ketone solution of double-end hydroxyl type polyphenylene ether resin containing dibenzo eight-membered ring structural units, controlling the molar ratio of the total hydroxyl number contained in the double-end hydroxyl type polyphenylene ether resin to the tert-butyl lithium to be 1.02, after reacting for 20min, slowly dropwise adding 3-bromopropylene into the system, and continuing the reaction for 10h to obtain a product solution F; the product solution F is poured into a large amount of water for precipitation, filtered, washed with water for multiple times and mixed at 80 DEG o And C, drying in a vacuum oven overnight to prepare the double-end vinyl type polyphenylene ether resin containing the dibenzo eight-membered ring structural unit.
Taking 110 parts of double-end vinyl type polyphenylene ether containing dibenzo eight-membered ring structural unit, 20 parts of polybutadiene (g Lei Weili Ricon 154), 15 parts of TAIC and 22 parts of TiO 2 (Tianjin Zhongzheng Huamei science and technology), 25 parts of silicon oxide (New Yiyun Hongrun), 50 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 20 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang Huaxue) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 2.0 parts of dibenzoyl peroxide (Qin Feng chemical industry), and further stirring uniformly; dipping glue with 1080 glass fiber cloth, and baking and drying to obtain a prepreg, wherein the baking temperature of the first stage is 75 ℃ for 7min, and the baking temperature of the second stage is 250 ℃ for 15min; stacking 10 prepregs, respectively attaching loz copper foils to two sides of the prepregs under a pressure of 95-115kg/cm 2 At a temperature of 260 deg.C o And C, laminating for 8 hours under the condition of C to obtain the carbon-hydrogen copper-clad plate.
As mentioned above, the polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units comprises: double-terminal vinyl type polyphenylene ether, polybutadiene, TAIC, tiO of dibenzo eight-membered ring structural unit 2 Silicon oxide, flame retardant magnesium hydroxide, secondary flame retardant decabromodiphenylethane and dibenzoyl peroxideAnd (4) acyl.
Example 4
90 parts of the dibenzo eight-membered ring structural unit-containing double-terminal vinyl polyphenylene ether obtained in example 3, 15 parts of polybutadiene (g Lei Weili Ricon 154), 10 parts of TAIC, 4 parts of polybutadiene-maleic anhydride copolymer (g Lei Weili Ricon130MA 8), 3 parts of polystyrene-maleic anhydride copolymer (g Lei Weili SMA 1000), 35 parts of polytetrafluoroethylene pre-sinter (Shandong Yue), 10 parts of SiO 130MA8 2 (Xinyi macrorun), 30 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of secondary flame retardant decabromodiphenylethane (Shandonghai Wang Huaxue) and 450 parts of DMF solvent, stirring for 24 hours at 80 ℃, and fully dissolving and uniformly dispersing; cooling to room temperature, adding 2 parts of dibenzoyl peroxide (Qinfeng chemical industry), and further stirring uniformly; dipping glue by adopting 1080 glass fiber cloth, and then baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 DEG o C, the time is 7min, and the second stage baking temperature is 250 o C, the time is 15min; stacking 10 prepregs, respectively attaching loz copper foils to two sides of the prepregs under a pressure of 95 to 105kg/cm 2 And laminating for 8 hours at the temperature of 270 ℃ to obtain the carbon-hydrogen copper-clad plate.
As mentioned above, the polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units comprises: double-end vinyl type polyphenyl ether containing dibenzo eight-membered ring structural unit, polybutadiene, TAIC, polybutadiene-maleic anhydride copolymer, polystyrene-maleic anhydride copolymer, polytetrafluoroethylene pre-sintering material and SiO 2 Magnesium hydroxide as a flame retardant, decabromodiphenylethane as a secondary flame retardant and dibenzoyl peroxide.
Example 5
90 parts of the dibenzo eight-membered ring structure unit-containing double-terminal vinyl polyphenylene ether obtained in example 3, 15 parts of polybutadiene (g Lei Weili Ricon 156), 10 parts of TAIC, 5 parts of polydiene-styrene-divinylbenzene terpolymer (g Lei Weili Ricon 257), 4 parts of polybutadiene-maleic anhydride copolymer (g Lei Weili Ricon130MA 8), 6 parts of polystyrene-maleic anhydride copolymer (g Lei Weili SMA 1000), and 3 parts of styrene-maleic anhydride copolymer0 part of polytetrafluoroethylene pre-sintering material (Shandong Yue) 35 parts of flame retardant magnesium hydroxide (American Yabao MAGNIFIN H-5), 18 parts of secondary flame retardant decabromodiphenylethane (Shandong sea Wang Huaxue) and 450 parts of DMF solvent in 80 parts of o Stirring for 24 hours under C, fully dissolving and uniformly dispersing; cooling to room temperature, adding 2 parts of dibenzoyl peroxide (Qinfeng chemical industry), and further stirring uniformly; impregnating polytetrafluoroethylene fiber woven cloth, and baking and drying to obtain a prepreg, wherein the baking temperature in the first stage is 75 o C, the time is 7min, the baking temperature in the second stage is 250 ℃, and the time is 15min; stacking 10 prepregs, respectively attaching loz copper foils to two sides of the prepregs under a pressure of 100 to 120kg/cm 2 And laminating for 8 hours at the temperature of 260 ℃ to obtain the carbon-hydrogen copper-clad plate.
As mentioned above, the polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units comprises: the flame retardant comprises double-end vinyl type polyphenyl ether containing dibenzo eight-membered ring structural units, polybutadiene, TAIC, polydiene-styrene-divinylbenzene terpolymer, polybutadiene-maleic anhydride copolymer, polystyrene-maleic anhydride copolymer, polytetrafluoroethylene pre-sintering material, flame retardant magnesium hydroxide, secondary flame retardant decabromodiphenylethane and dibenzoyl peroxide.
Comparative example 1
The formulation and production process of comparative example 1 and example 3 are substantially identical except that "bis-styryl-terminated polyphenylene ether containing dibenzo eight-membered ring structural units" is replaced with commercial bis-styryl-terminated polyphenylene ether.
The overall performance of comparative example 1 is similar to that of example 3, except that the coefficient of thermal expansion of the former is 40 to 60ppm/K. In conclusion, the dibenzo eight-membered ring with reversible thermal shrinkage and cold expansion characteristics is introduced into the carbon-hydrogen copper-clad plate, so that the thermal expansion coefficient of the plate can be effectively reduced.
The above examples are not intended to limit the amount of the composition of the present invention. Any minor modifications, equivalent changes and modifications to the above embodiments in accordance with the technical spirit or composition ingredients or contents of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. A polyarylether base composition containing reversible thermal shrinkage and cold expansion structural units is characterized in that: comprises six components of matrix resin, cross-linking agent, modified resin, filler, flame retardant and initiator; the specific structure of the matrix resin is as follows:
wherein, R1, R2, R3 and R4 are any one of H, alkyl, substituted alkyl, aryl, substituted aryl and halogen atoms; r6, R7 and R8 are all H; a is more than 0; r is one or the compound of two of the following structures:
the specific preparation method of the matrix resin comprises the following steps:
step 1, adding a catalyst into a solution of a phenol derivative monomer, and uniformly stirring to obtain a reaction solution A; preparing a solution of a monomer I or a monomer II to obtain a reaction solution B; setting the reaction temperature to be 20-60 ℃, slowly dropwise adding the reaction liquid A into the reaction liquid B under the condition of stirring and introducing oxygen-containing gas, and continuing to react for 4-72h after dropwise adding is finished to obtain a product solution C;
step 2, adding a poor solvent D of the polyarylether resin into the product solution C, uniformly stirring, standing until the polyarylether resin product is fully separated out and settled, and then filtering, washing and drying to obtain the double-end hydroxyl type polyarylether resin;
step 3, preparing an organic solution E of the double-end hydroxyl polyarylether resin with the concentration of 3-60wt%, adding alkali, uniformly stirring, slowly adding vinyl halide, and reacting for 1-72h at the temperature of 30-150 ℃ under stirring to obtain a product solution F, wherein the vinyl halide is 3-bromopropylene;
step 4, adding a poor solvent G of the polyarylether resin into the product solution F, uniformly stirring, standing until a polymer product is fully separated out and settled, filtering, washing and drying to obtain a final product, namely the double-end vinyl type polyarylether resin with the main chain containing a dibenzo eight-membered ring structural unit,
the phenol derivative monomer in step 1 refers to one or a mixture of several of the following compounds:
wherein R9, R10, R11 and R12 are any one of H, alkyl, substituted alkyl, aryl, substituted aryl and halogen atoms;
the catalyst in the step 1 is a metal salt-amine complex; the metal salt is one or a mixture of more of copper salt, manganese salt and chromium salt; the amine is one or a mixture of more of primary amine, secondary amine, tertiary amine, monoamine, polyamine and polymer with amino;
in the step 1, the solvent in the reaction solution A and the reaction solution B is one or a mixture of several of organic solvents capable of dissolving the polyarylether resin and the catalyst, or a mixture of the organic solvents capable of dissolving the polyarylether resin and the catalyst and water.
2. The polyarylether based composition containing reversible thermal shrinkage and cold expansion structural units according to claim 1, wherein: the poor solvent D in the step 2 is one or a mixture of more of methanol, ethanol, isopropanol, butanol, ether and ester.
3. The polyarylether based composition containing reversible thermal shrinkage and cold expansion structural units according to claim 1, wherein: the alkali in the step 3 is one or a mixture of more of n-butyllithium, sec-butyllithium, tert-butyllithium, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate and potassium carbonate; the ratio of the mole number of the alkali to the mole number of the hydroxyl contained in the double-end hydroxyl type polyarylether resin is 3 to 1.02;
in the step 3, the solvent of the organic solution E is one or a mixture of more of aprotic polar solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, or the aprotic polar solvent is added with one or a mixture of more of benzene, toluene, xylene and nitrobenzene; the water content of the solvent of the organic solution E is less than or equal to 0.1wt%.
4. The polyarylether based composition containing reversible thermal shrinkage and cold expansion structural units according to claim 1, wherein: in the step 4, the poor solvent G is one or a mixture of more of methanol, ethanol, isopropanol, butanol, water, ether and ester.
5. The polyarylether based composition containing reversible thermal shrinkage and cold expansion structural units according to claim 1, wherein: the cross-linking agent is one or a compound mixture of more of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), side vinyl modified polyarylether and polydiene; the dosage of the cross-linking agent accounts for 3-500wt% of the matrix resin; the number average molecular weight of the side vinyl group modified polyarylether is between 400 and 13000, and a single side group or side chain of the side vinyl group modified polyarylether at least contains 3 reactive vinyl functional groups in total; the number average molecular weight of the polydiene is 500 to 20000, the side group or the side chain of a single polydiene polymer chain at least contains 3 reactive vinyl functional groups in total,
the modified resin is a composite mixture of one or more of diene-maleic anhydride copolymer and one or more of styrene-maleic anhydride copolymer; wherein, the side group or side chain of the polydiene block of a single diolefin-maleic anhydride copolymer chain at least contains a reactive vinyl functional group, the number average molecular weight of the diolefin-maleic anhydride copolymer is between 500 and 150000, and the using amount of the diolefin-maleic anhydride copolymer accounts for 5 to 95wt% of the modified resin; the number average molecular weight of the styrene-maleic anhydride copolymer is 500 to 30000, and the dosage of the styrene-maleic anhydride copolymer accounts for 5 to 95wt% of the modified resin; the dosage of the modified resin accounts for 0 to 20wt% of the polyarylether-based composition containing the reversible thermal shrinkage and cold expansion structural unit and is not 0,
the filler is SiO 2 、Al 2 O 3 、TiO 2 、ZnO、MgO、Bi 2 O 3 、AlN、Si 3 N 4 、SiC、BN、Al(OH) 3 、Mg(OH) 2 、BaTiO 3 、SrTiO 3 、Mg 2 TiO 4 、Bi 2 (TiO 3 ) 3 、PbTiO 3 、NiTiO 3 、CaTiO 3 、ZnTiO 3 、Zn 2 TiO 4 、BaSnO 3 、Bi 2 (SnO 3 ) 3 、CaSnO 3 、PbSnO 3 、MgSnO 3 、SrSnO 3 、ZnSnO 3 、BaZrO 3 、CaZrO 3 、PbZrO 3 、MgZrO 3 、SrZrO 3 、ZnZrO 3 One or a mixture of more of inorganic fillers such as graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass beads, hollow glass beads, glass fibers, basalt fibers and carbon fibers, and also one or a mixture of more of polytetrafluoroethylene pre-sintering materials, ultra-high molecular weight polyethylene fibers, kevlar fibers, polyimide, polyetherimide, polyether ether ketone and polyphenylene sulfide; the amount of the filler accounts for the polyarylether base containing the reversible thermal shrinkage and cold expansion structural unit0 to 80wt% of the composition and not 0,
the flame retardant is one or a mixture of more of aluminum-magnesium flame retardant, boron-zinc flame retardant, molybdenum-tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant and nitrogen flame retardant; the dosage of the flame retardant accounts for 0 to 60wt percent of the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit and is not 0,
the initiator is one or a mixture of more of radical initiators including peroxides, azo compounds and redox systems which can be dissolved in a solvent for uniformly dispersing the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit, and the dosage of the initiator accounts for 0.01 to 5wt% of the polyarylether base composition containing the reversible thermal shrinkage and cold expansion structural unit.
6. A prepreg prepared by using the polyarylether based composition containing the reversible thermal shrinkage and cold expansion structural unit as claimed in claim 1, wherein the prepreg is prepared by the following specific steps:
s1, preparing a uniform dispersion liquid of the polyarylether-based composition containing the reversible thermal shrinkage and cold expansion structural unit, wherein the solid content of the uniform dispersion liquid is 20-75wt/v%;
and S2, soaking the fiber cloth in the uniform dispersion liquid, and baking and drying to obtain a prepreg.
7. The prepreg according to claim 6, wherein the solvent in the uniform dispersion of the polyarylether based composition containing the reversible thermal shrinkage and cold expansion structural unit is one of water and an organic solvent or a mixture of water and an organic solvent which enables the composition to be uniformly dispersed;
the fiber cloth is one of electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, kevlar, polyimide, polytetrafluoroethylene and polyester;
the baking and drying are divided into two stages, wherein the baking and drying temperature in the first stage is 50 to 120 ℃, and the baking and drying time is 1 to 30min; the baking and drying temperature in the second stage is 150 to 350 ℃, and the time is 1 to 30min.
8. The carbon-hydrogen copper-clad plate manufactured by the prepreg according to claim 6 or 7 is characterized in that the specific preparation steps of the carbon-hydrogen copper-clad plate are as follows: laminating the prepreg, the film and the copper foil together, and preparing a carbon-hydrogen copper-clad plate by a laminating process; the number of the prepregs is more than or equal to 1, the number of the films is more than or equal to 0, and the number of the copper foils is 1 or 2;
the laminating temperature of the laminating process is 150 to 350 ℃, and the laminating pressure is 70 to 170kg/cm 2 The laminating time is 0.5 to 24h;
the film is made of one or a mixture of more of fluorine-containing polymer, polyimide, polyolefin, polyaromatic hydrocarbon, polyamide, polyether ketone, polyether ether ketone, polyaryl ether, polyaryl sulfide, polyaryl ether sulfone, polyaryl ether ketone, polyaryl sulfide ketone, polyether sulfone ketone, polyaryl ether nitrile sulfone, polyaryl sulfide nitrile sulfone, polyphenyl quinoxaline, phenolic resin, epoxy resin, cyanate resin, polycarbonate, polyurethane and polyformaldehyde;
the thickness of the hydrocarbon copper-clad plate is controlled to be 0.1-10mm.
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| CN114369268A (en) * | 2021-11-05 | 2022-04-19 | 常州中英科技股份有限公司 | Prepreg made of fluorine-containing resin mixture and low-thermal expansion type high-frequency copper-clad plate |
| CN114369239A (en) * | 2021-11-05 | 2022-04-19 | 常州中英科技股份有限公司 | Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof |
| CN116041759B (en) * | 2022-12-12 | 2024-04-19 | 电子科技大学 | High-heat-conductivity polyarylether nitrile interlayer dielectric film for flexible copper-clad plate and preparation method thereof |
| CN115975195B (en) * | 2023-03-03 | 2024-03-26 | 四川轻化工大学 | Polyphenylene sulfide nitrile and method for producing the same |
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| CN108752827A (en) * | 2018-05-17 | 2018-11-06 | 常州中英科技股份有限公司 | A kind of crosslinkable resin composition of high heat conduction and its prepreg and the heat curing type copper-clad plate of preparation |
| CN110605880A (en) * | 2019-08-07 | 2019-12-24 | 常州中英科技股份有限公司 | Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate |
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| CN108752827A (en) * | 2018-05-17 | 2018-11-06 | 常州中英科技股份有限公司 | A kind of crosslinkable resin composition of high heat conduction and its prepreg and the heat curing type copper-clad plate of preparation |
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