CN104448821A - Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg - Google Patents
Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg Download PDFInfo
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- 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
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a resin material for a prepreg, the prepreg, a preparation method thereof, and a meta-material substrate and a meta-material containing the prepreg. The resin material for the prepreg comprises by weight: 40-100 parts of cyanate ester and 0 to 60 parts of an organic modifier; the organic modifier comprises one or more selected from epoxy group, double bond group or amide group. According to the resin material, cyanate ester is subjected to reaction for the formation of a low molecular weight prepolymer with good fluidity; and the organic modifier capable of adjusting network crosslink density is further added, so that while self accumulation of the cyanate ester, can be conducted pre polymerization reaction between the cyanate ester and the organic modifier, and between the organic modifier and the organic modifier; the produced cyanate ester prepolymer is impregnated into the enhanced material to form the prepreg, which has long storage time, is easy to transport, simple and practical for usage, and can effectively reduce the costs of storage and transportation.
Description
Technical field
The present invention relates to prepreg field, in particular to a kind of prepreg resin material, prepreg, they preparation method and comprise metamaterial substrate and the Meta Materials of prepreg.
Background technology
Prepreg refers to the matrix material of the prepreg of the even rule formed after certain resin impregnation by the strongthener such as carbon fiber bundle, glass fiber material, the cohesiveness that this material is good and snappiness, layer paving moulding process can be applicable to, the manufacture of baroque composite product can be directly used in, be widely used in aerospace cause and military equipment, particularly properller and wing, the material of fuselage and some important bodies etc.The method of producing prepreg mainly contains dry method and wet method.
Current wet processing is exactly use the most widely at present, so-called wet method just refers to that carbon fiber or other fiber-like use thinner in certain gumming device and resin-phase combination, then through a kind of method of baking and curing final molding.Such as, wet method prepreg and the laminating material of a kind of cyanate and composition epoxy resin is disclosed in the patent CN102532801A enjoyed in Shengyi Science and Technology Co., Ltd, Guangdong.Although it is fairly simple in process engineering for wet method prepreg, carries out needing in winding process again by curing oven, the assorted remaining compositions such as thinner wherein used to be volatilized in the later stage, affect environment, also waste solvent.
And adopting the hot-melting type prepreg of dry process, it has unique advantage, and the material intermediate gap defect of preparation is little, prepreg volatile content is very low, mechanical property is better, and prepreg has good cohesiveness, goes for the multiple moulding processs such as the layer paving in later stage.Hot-melting type epoxy prepreg carries out direct impregnation and obtains under its hot melt state, and the follow-up shaping work personality of the prepreg prepared of this method is lived.The resin that current hot-melting type prepreg adopts is epoxy resin mostly.Such as, disclose a kind of epoxy matrix resin, prepreg and preparation method thereof and the device preparing prepreg employing in the patent CN102108185A that Institute of Petrochemistry, HLJ Academy of Science enjoys.It is very short that this hot-melting type epoxy prepreg has the shorter viscosity shelf lives, pot life at room temperature about 1 month, brings very large difficulty to storage, transport and use.In order to extend shelf life, have to take low temperature (be generally ~ 18 DEG C) to store and transport, adding difficulty in process thereupon, also substantially increase the manufacturing cost of matrix material.
Summary of the invention
The present invention aim to provide a kind of prepreg resin material, prepreg, they preparation method and comprise metamaterial substrate and the Meta Materials of prepreg, to extend the memory period of prepreg.
To achieve these goals, one aspect of the present invention, provide a kind of prepreg resin material, this prepreg resin material is prepared from by the prepolymerization of resin material raw material, resin material raw material comprises by weight: the cyanate of 40 ~ 100 parts, and the organic modifiers of 0 ~ 60 part, organic modifiers comprise in epoxide group, double bond group or amide group one or more.
Further, above-mentioned prepreg resin material raw material comprises by weight: the cyanate of 40 ~ 95 parts, and the organic modifiers of 5 ~ 60 parts.
Further, in above-mentioned prepreg resin material, cyanate is aromatic base cyanate or fatty group cyanate; Preferably, cyanate is one or more in bisphenol A cyanate ester, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin, bisphenol E-type cyanate, tetramethyl-p-Xylol type cyanate, tetramethyl-bisphenol-f type cyanate, biphenyl type cyanate and p-Xylol type cyanate.
Further, in above-mentioned prepreg resin material organic modifiers be epoxy resin, one or more in resin containing sub-amide group, span cyanate resin, preferably, epoxy resin is biphenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, biphenyl type epoxy resin, one or more in naphthalene type epoxy resin; Preferably, the resin containing sub-amide group is maleimide and/or bismaleimides; More preferably, the resin containing sub-amide group is N-methylphenylmaleimide and/or 4, and 4 '-span carrys out phthalimide base ditane.
Further, in above-mentioned prepreg resin material, resin material raw material also comprises the modified filler of 1 ~ 30 part, modified filler is polyphenylene oxide or elastomerics, and preferably, elastomerics is one or more in epoxy-terminated paracril, nbr carboxyl terminal and chloroprene rubber.
Further, in above-mentioned prepreg resin material, resin material raw material also comprises the phenol catalysis agent of 1 ~ 10 part, preferably, phenol catalysis agent is nonyl phenol, more preferably, resin material raw material also comprises the organometallic salt catalysts by cyanate mole 5 ~ 800ppm, and preferably, organometallic salt catalysts is one or more in zinc octoate, manganese octoate, dibutyl tin laurate or second phthalein acetone cobalt.
Another aspect of the present invention, provide a kind of preparation method of prepreg resin material, comprise the following steps: by cyanate, organic modifiers, optional modified filler mixing, add optional phenol catalysis agent and/or optional organo-metallic salt catalyzer under heated and stirred, keep thermotonus 1 ~ 3h to obtain prepreg resin material.
Further, above-mentioned preparation method comprises the following steps: it is 50 DEG C ~ 250 DEG C that cyanate, organic modifiers, optional modified filler are joined temperature, be preferably 100 DEG C ~ 200 DEG C, be more preferably in the oil bath of 100 DEG C ~ 180 DEG C, optional phenol catalysis agent and/or optional organo-metallic salt catalyzer is added under the condition stirred, Keep agitation 1min ~ 120min, be preferably 5 ~ 60min, be more preferably 10 ~ 30min, keep temperature prepolymerization 1 ~ 3h to obtain prepreg resin material.
Another aspect of the present invention, provides a kind of prepreg, is formed after resin material impregnation by strongthener, and resin material is above-mentioned prepreg resin material.
Another aspect of the present invention, provides a kind of preparation method of prepreg, comprises the following steps: prepare above-mentioned prepreg resin material according to aforesaid method, and glued membrane is made in the heating of prepreg resin material; Prepreg resin material is covered on strongthener, exerts pressure to the heating of prepreg resin material, make prepreg resin material be impregnated in strongthener, make prepreg.
Further, the Heating temperature preparing glued membrane in above-mentioned preparation method is 50 DEG C ~ 160 DEG C, is preferably 50 DEG C ~ 140 DEG C, is more preferably 50 DEG C ~ 120 DEG C; The Heating temperature preparing prepreg is 120 DEG C ~ 250 DEG C, is preferably 140 DEG C ~ 220 DEG C, is more preferably 140 DEG C ~ 180 DEG C; Prepare the applying pressure position 5 ~ 50kg/cm of prepreg
2, be preferably 5 ~ 40kg/cm2, be more preferably 5 ~ 30kg/cm
2.
Another aspect of the present invention, provides a kind of metamaterial substrate, comprises prepreg material layer, and this prepreg material layer is formed by above-mentioned cyanate prepreg solidification.
Further, in above-mentioned metamaterial substrate, prepreg material layer is solidified by above-mentioned cyanate prepreg and forms at 180 DEG C ~ 250 DEG C.
Another aspect of the present invention, provides a kind of Meta Materials, and the conduction geometry comprising substrate and arrange on the substrate, described substrate is above-mentioned metamaterial substrate.
Beneficial effect of the present invention: prepreg resin material of the present invention, prepreg, they preparation method and comprise metamaterial substrate and the Meta Materials of prepreg.Wherein prepreg resin material has excellent mechanical behavior under high temperature by adopting cyanate (CE), extremely low specific inductivity (2.8 ~ 3.2) and tangent of the dielectric loss angle value (0.002 ~ 0.008), and the performed polymer by making polyisocyanate reactant form molecular weight, and there is good mobility, and can the organic modifiers of regulating networks cross-linking density by add further, while cyanate carries out autohemagglutination, make between cyanate and organic modifiers, and can prepolymerization be carried out between organic modifiers and organic modifiers, the generation of this prepolymerization can make cyanate prepolymer can be impregnated into the prepreg formed in strongthener, with the mechanical property of strongthener and thermal property, mode further by heating cure forms matrix material.This prepreg is longer for storage time, be convenient to conveying, and using method is simple and practical, effectively can reduce storage and transportation cost.
Embodiment
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
Environment is affected in order to solve wet method prepreg solvent evaporates, and the problem that hot-melting type prepreg storage period is short, provide a kind of prepreg resin material in the present invention, this prepreg resin material is applicable to hot-melting type prepreg, it is prepared from by the prepolymerization of resin material raw material, resin material raw material comprises by weight: the cyanate of 40 ~ 100 parts, and the organic modifiers of 0 ~ 60 part, organic modifiers comprise in epoxide group, double bond group or amide group one or more.
The English full name of the cyanate used in prepreg resin material of the present invention is Triazine A resin, TA resin, Cyanateresin, is abbreviated as CE.It is the novel hot setting resin containing at least one cyanate functional group (-OCN) in a kind of molecular structure.This cyanate (CE) has excellent mechanical behavior under high temperature, and flexural strength and tensile strength are all high than bifunctional epoxy resin; Extremely low water-intake rate (<1.5%); Molding shrinkage is low, good stability of the dimension; Good heat resistance, second-order transition temperature is at 240 ~ 260 DEG C, and most high energy reaches 400 DEG C, modified can 170 DEG C of solidifications; Humidity resistance, flame retardant resistance, cohesiveness are all fine, and the adhesiveproperties of the strongthener such as glass, carbon fibre, silica fiber, whisker is good; Excellent electrical property, has extremely low specific inductivity (2.8 ~ 3.2) and tangent of the dielectric loss angle value (0.002 ~ 0.008), and the change of dielectric properties to temperature and wave frequency all shows distinctive stability.Use this material making prepreg can improve mechanical property, the electric property of prepreg, especially can reduce specific inductivity and the tangent loss of prepreg.
Simultaneously, performed polymer in the present invention by making cyanate prepolymerization form molecular weight, and there is good mobility, and can the organic modifiers of regulating networks cross-linking density by add further, while cyanate carries out autohemagglutination, make can carry out prepolymerization between cyanate and organic modifiers and between organic modifiers and organic modifiers, the cyanate prepolymer formed can be impregnated into the prepreg formed in strongthener, can form matrix material by the mode of heating cure.This prepreg is longer for storage time, be convenient to conveying, and using method is simple and practical, effectively can reduce storage and transportation cost.
Preferably, in this prepreg resin material above-mentioned, resin material raw material comprises by weight: the cyanate of 40 ~ 95 parts, and the organic modifiers of 5 ~ 60 parts, organic modifiers comprise in epoxide group, double bond group or amide group one or more.
The cyanate used in prepreg resin material of the present invention includes but not limited to aromatic base cyanate or fatty group cyanate; Preferably, this cyanate is one or more in bisphenol A cyanate ester, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin, bisphenol E-type cyanate, tetramethyl-p-Xylol type cyanate, tetramethyl-bisphenol-f type cyanate, biphenyl type cyanate and p-Xylol type cyanate.
The organic modifiers used in prepreg resin material of the present invention preferably include but be not limited in epoxy resin, resin containing sub-amide group, span cyanate resin one or more.The spendable epoxy resin of the present invention does not have particular requirement to molecular weight or oxirane value, as long as containing epoxide group, preferably, this epoxy resin is biphenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, biphenyl type epoxy resin, one or more in naphthalene type epoxy resin; Preferably, the resin containing sub-amide group is maleimide and/or bismaleimides; More preferably, the described resin containing sub-amide group is N-methylphenylmaleimide and/or 4,4 '--and span carrys out phthalimide base ditane.
This prepreg resin material provided by the present invention is formed by the prepolymerization of resin material raw material, and in this pre-polymerization process, contingent reaction is as follows:
(1) when added organic modifiers is the epoxy resin containing epoxide group, resin material raw material prepolymerization process comprises:
The first auto-polymerization of cyanate forms first prepolymer with following structural formula (1),
First prepolymer with structural formula (1) reacts as follows with the epoxy resin containing epoxide group:
The prepreg resin material obtained by above-mentioned reaction is by first forming the reticulated structure be made up of triazine ring, there is excellent dielectric properties and thermotolerance, react with epoxy resin again, it is made at room temperature to be less likely to occur solidification, the flowing property of resin material can be improved, extend the storage time of prepreg.
(2), described organic modifiers is resin containing sub-amide group and/or span cyanate resin, and resin material raw material prepolymerization process comprises:
The first auto-polymerization of cyanate forms first prepolymer with following structural formula (2),
N≡C-O-Ar
1-O-C≡N （2）。
Resin containing sub-amide group and/or bimaleimide resin are substantially identical with the reaction of the cyanate containing two cyanate groups, and the reaction formula that the following is the first prepolymer and the bismaleimides with structural formula (2) is as follows:
As can be seen from above-mentioned reaction formula, the first prepolymer and its reaction of bismaleimides with structural formula (2) can be diversification, at least can form as above (I) to (IV) four kind of structure.Containing the resin of sub-amide group and/or the interpolation of span cyanate resin in above-mentioned reaction, what can continue carries out polyreaction with first prepolymer with structure above (2), avoid the solidification of cyanate, and then make formed prepolymer be easy to flowing, in the extender storage time, the prepreg simultaneously formed by this prepolymer has good mechanical property (such as improving toughness, tensile strength, bending strength) and electric property (such as reducing dielectric loss).
At prepreg resin material of the present invention with the modified filler also comprising 1 ~ 30 part in resin material raw material, the interpolation of this modified filler can increase the mechanical property of prepared prepreg.Preferably, modified filler is polyphenylene oxide or elastomerics, and especially preferably this elastomerics is epoxy-terminated paracril, one or more in nbr carboxyl terminal and chloroprene rubber.
The reactive hydrogen class catalyzer also comprising 1 ~ 10 part with resin material raw material in prepreg resin material of the present invention, preferably, this reactive hydrogen class catalyzer includes but not limited to phenol catalysis agent.Especially preferably, this phenol catalysis agent is nonyl phenol.Phenol catalysis agent used in the present invention can occur to react as follows with cyanate group, and the triple bond between C and N can be disassembled formation double bond by this reaction, and double bond is disassembled as single key structure further, carries out accelerating to form the resin structure wanted required for the present invention.
The organometallic salt catalysts also comprised in the resin material raw material of prepreg resin material of the present invention, the preferable amount of this organometallic salt catalysts is by cyanate mole 5 ~ 800ppm, is preferably by cyanate mole 20 ~ 300ppm.
Preferably, described organometallic salt catalysts is one or more in zinc octoate, manganese octoate, dibutyl tin laurate or second phthalein acetone cobalt.
As long as above-mentioned prepreg resin material provided by the present invention impels its resin material raw material to carry out prepolymerization and forms prepreg resin material, provide a kind of preparation method of prepreg resin material in the present invention, comprise the following steps: by cyanate, organic modifiers, optional modified filler mixing, add optional phenol catalysis agent and/or optional organo-metallic salt catalyzer under heated and stirred, keep temperature prepolymerization 1 ~ 3h to obtain prepreg resin material.
In the preferred embodiment of the present invention, preparation method comprises the following steps: it is 50 DEG C ~ 250 DEG C that cyanate, organic modifiers, optional modified filler are joined temperature, be preferably 100 DEG C ~ 200 DEG C, be more preferably in the oil bath of 100 DEG C ~ 180 DEG C, optional phenol catalysis agent and/or optional organo-metallic salt catalyzer is added under the condition stirred, Keep agitation 1min ~ 120min, be preferably 5 ~ 60min, be more preferably 10 ~ 30min, keep temperature prepolymerization 1 ~ 3h to obtain prepreg resin material.
Additionally provide a kind of prepreg in the present invention, formed by strongthener after resin material impregnation, described resin material is above-mentioned prepreg resin material.This prepreg is long for storage time, is easy to transport, can reduces transportation cost.
Additionally provide a kind of preparation method of prepreg in the present invention, comprise the following steps: prepare prepreg resin material of the present invention according to aforesaid method, glued membrane is made in the heating of prepreg resin material; Prepreg resin material is covered on strongthener, exerts pressure to described prepreg resin material heating, prepreg resin material is impregnated in described strongthener, makes prepreg.Wherein strongthener preferably includes but is not limited to glass fibre, aramid fiber or silica fiber.
The Heating temperature preparing glued membrane in above-mentioned preparation method is 50 DEG C ~ 160 DEG C, is preferably 50 DEG C ~ 140 DEG C, is more preferably 50 DEG C ~ 120 DEG C; The Heating temperature preparing prepreg is 120 DEG C ~ 250 DEG C, is preferably 140 DEG C ~ 220 DEG C, is more preferably 140 DEG C ~ 180 DEG C; Prepare the applying pressure position 5 ~ 50kg/cm of prepreg
2, be preferably 5 ~ 40kg/cm
2, be more preferably 5 ~ 30kg/cm
2.
Additionally provide a kind of metamaterial substrate in the present invention, this metamaterial substrate comprises this prepreg material layer of prepreg material layer and is formed by above-mentioned cyanate prepreg solidification.Preferably, prepreg material layer is solidify to form at 180 DEG C ~ 250 DEG C by above-mentioned cyanate prepreg.In actually operating, this metamaterial substrate is formed by prepreg being covered hot pressing on conductive metallic material layer.Wherein conductive metallic material layer preferably includes but is not limited to Copper Foil, aluminium foil or silver pool.This matrix material provided by the present invention has good mechanical property, electric property etc.
Additionally provide a kind of Meta Materials in the present invention, the conduction geometry that this metamaterial substrate comprises substrate and arranges on the substrate, this substrate is above-mentioned metamaterial substrate.
Further illustrate their preparation method of this prepreg resin below with reference to embodiment 1 to 6 and comprise the metamaterial substrate of prepreg and the beneficial effect of Meta Materials.
Embodiment 1
Raw materials: bisphenol A cyanate ester 80 parts, oxirane value are the biphenyl aralkyl-type epoxy resin 5 parts of 0.36mol/100g, paracril 5 parts, the nonyl phenol of 10 parts and the dibutyl tin laurate by cyanate mole 160ppm/mol.
The preparation method of prepreg resin material: by bisphenol A cyanate ester, epoxy resin, paracril is in the oil bath of 110 DEG C, add nonyl phenol and dibutyl tin laurate again, stir 30min, prepolymerization 2 hours under 110 DEG C of conditions, be cooled to room temperature, obtain the resin material being used as prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 90 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener glass fibre, glued membrane and the pre-dipping machine infiltration of strongthener are prepared prepreg, and pre-dipping machine infiltration temperature is 140 DEG C, and pressure is 10kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 180 DEG C) compacting obtains cyanate substrate in 3 hours.
Embodiment 2
Raw materials: Cyclopeutadiene type cyanate 50 parts, oxirane value are 0.29mol/100g biphenyl type epoxy resin 15 parts, bismaleimides 30 parts, paracril 5 parts, dibutyl tin laurate by cyanate mole 160Ppm/mol.
The preparation method of prepreg resin material: Cyclopeutadiene type cyanate, epoxy resin, bismaleimides, paracril are stirred melting in the oil bath of 200 DEG C, add the catalyzer of dibutyl tin laurate as the cruel esterification of cyanic acid, stir 1min, prepolymerization 2 hours under 120 DEG C of conditions, be cooled to room temperature, be used as the resin material of prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 100 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener aramid fiber, glued membrane and the pre-dipping machine infiltration of strongthener aramid fiber are prepared prepreg, and pre-dipping machine infiltration temperature is 140 DEG C, and pressure is 10kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 250 DEG C) compacting obtains cyanate substrate in 3 hours.
Embodiment 3
Raw materials: Cyclopeutadiene type cyanate 75 parts, bismaleimides 20 parts, epoxy-terminated paracril 5 parts, by the dibutyl tin laurate of cyanate mole 160Ppm/mol.
The preparation method of prepreg resin material: by Cyclopeutadiene type cyanate, bismaleimides, epoxy-terminated paracril stirs melting in the oil bath of 120 DEG C, add the catalyzer of tin as the cruel esterification of cyanic acid, stir 15min, prepolymerization 2 hours under 120 DEG C of conditions, be cooled to room temperature, be used as the resin material of prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 100 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener aramid fiber, glued membrane and the pre-dipping machine infiltration of strongthener aramid fiber are prepared prepreg, and pre-dipping machine infiltration temperature is 140 DEG C, and pressure is 10kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 250 DEG C) compacting obtains cyanate substrate in 3 hours.
Embodiment 4
Raw materials: Cyclopeutadiene type cyanate 95 parts, 5 parts of nonyl phenols and the second phthalein acetone cobalt by cyanate mole 800Ppm/mol.
The preparation method of prepreg resin material: Cyclopeutadiene type cyanate is stirred melting in the oil bath of 100 DEG C, add nonyl phenol and the second phthalein acetone cobalt catalyzer as the cruel esterification of cyanic acid, stir 10min, prepolymerization 2 hours under 100 DEG C of conditions, be cooled to room temperature, be used as the resin material of prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 50 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener silica fiber, glued membrane and the pre-dipping machine infiltration of strongthener silica fiber are prepared prepreg, and pre-dipping machine infiltration temperature is 130 DEG C, and pressure is 10kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 180 DEG C) compacting obtains cyanate substrate in 3 hours.
Embodiment 5
Raw materials: tetramethyl-p-Xylol type cyanate 40 parts, oxirane value are biphenyl aralkyl-type epoxy resin 40 parts, the N-methylphenylmaleimide 20 parts of 0.42mol/100g, nbr carboxyl terminal 1 part, the nonyl phenol of 1 part and the dibutyl tin laurate by cyanate mole 60ppm/mol.
The preparation method of prepreg resin material: by tetramethyl-p-Xylol type cyanate, biphenyl aralkyl-type epoxy resin, N ~ methylphenylmaleimide, nbr carboxyl terminal stirs melting in the oil bath of 180 DEG C, add nonyl phenol and the dibutyl tin laurate catalyzer as the cruel esterification of cyanic acid, stir 20min, prepolymerization 1 hour under 180 DEG C of conditions, be cooled to room temperature, be used as the resin material of prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 120 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener silica fiber, glued membrane and the pre-dipping machine infiltration of strongthener silica fiber are prepared prepreg, and pre-dipping machine infiltration temperature is 180 DEG C, and pressure is 5kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 200 DEG C) compacting obtains cyanate substrate in 3 hours.
Embodiment 6
Raw materials: bisphenol A cyanate ester 40 parts, oxirane value are naphthols aralkyl-type epoxy resin 5 parts, the bismaleimides, 4 of 0.38mol/100g, and 4 '-span comes phthalimide base ditane 5 parts, nbr carboxyl terminal 30 parts, the nonyl phenol of 10 parts and the dibutyl tin laurate by cyanate mole 5ppm/mol.
The preparation method of prepreg resin material: by bisphenol A cyanate ester, naphthols aralkyl-type epoxy resin, bismaleimides, 4,4 '-span comes phthalimide base ditane, nbr carboxyl terminal and stir melting in the oil bath of 120 DEG C, add nonyl phenol and the dibutyl tin laurate catalyzer as the cruel esterification of cyanic acid, stir 20min, prepolymerization 2 hours under 120 DEG C of conditions, be cooled to room temperature, be used as the resin material of prepreg processed.
The preparation method of prepreg: roller prepreg resin material being put into film-making machine pricks heating 50 DEG C on axle, makes glued membrane; Covered by prepreg resin material on strongthener silica fiber, glued membrane and the pre-dipping machine infiltration of strongthener silica fiber are prepared prepreg, and pre-dipping machine infiltration temperature is 150 DEG C, and pressure is 2kg/cm
2.
The preparation method of matrix material: cover on surfaces of the copper foil by prepreg surface, hot pressing (0.5 ~ 10Mpa, 220 DEG C) compacting obtains cyanate substrate in 3 hours.
Test:
Prepreg prepared by embodiment 1-6 and matrix material are carried out following test.
Testing method:
Mechanic property test method: tensile strength testing method is GB/T1447; Flexural strength testing method is GB/T9341 ~ 2008.
The testing method of electric property: evanescent wave resonance test method (Japanese AET high-frequency dielectric constant tester).
The testing method of viscosity or mobility: meet ISO 10933:1997 standard.
Test result: as shown in table 1.
Table 1
Can find out that the prepreg prepared by the present invention obtains larger improvement compared to the prepreg that existing pot life at room temperature is 1 month by data in table 1, prepreg provided by the present invention all can be greater than 8 months storage time, this makes this prepreg be convenient to conveying, and using method is simple and practical, effectively can reduce storage and transportation cost, and the cyanate substrate prepared by prepreg of the present invention has lower specific inductivity and dielectric tangent loss, good mechanical property (tensile strength and bending strength), it is made to be more suitable for aerospace cause and military equipment
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (14)
1. a prepreg resin material, it is characterized in that, described prepreg resin material is prepared from by the prepolymerization of resin material raw material, described resin material raw material comprises by weight: the cyanate of 40 ~ 100 parts, and the organic modifiers of 0 ~ 60 part, described organic modifiers comprise in epoxide group, double bond group or amide group one or more.
2. prepreg resin material according to claim 1, is characterized in that, described resin material raw material comprises by weight: the cyanate of 40 ~ 95 parts, and the organic modifiers of 5 ~ 60 parts.
3. prepreg resin material according to claim 1 and 2, is characterized in that, described cyanate is aromatic base cyanate or fatty group cyanate; Preferably, described cyanate is one or more in bisphenol A cyanate ester, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin, bisphenol E-type cyanate, tetramethyl-p-Xylol type cyanate, tetramethyl-bisphenol-f type cyanate, biphenyl type cyanate and p-Xylol type cyanate.
4. prepreg resin material according to claim 1 and 2, it is characterized in that, described organic modifiers is epoxy resin, one or more in resin containing sub-amide group, span cyanate resin, preferably, described epoxy resin is biphenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin, biphenyl type epoxy resin, one or more in naphthalene type epoxy resin; Preferably, the described resin containing sub-amide group is maleimide and/or bismaleimides; More preferably, the described resin containing sub-amide group is N-methylphenylmaleimide and/or 4, and 4 '-span carrys out phthalimide base ditane.
5. prepreg resin material according to any one of claim 1 to 4, it is characterized in that, described resin material raw material also comprises the modified filler of 1 ~ 30 part, described modified filler is polyphenylene oxide or elastomerics, preferably, described elastomerics is one or more in epoxy-terminated paracril, nbr carboxyl terminal and chloroprene rubber.
6. prepreg resin material according to any one of claim 1 to 5, it is characterized in that, described resin material raw material also comprises the phenol catalysis agent of 1 ~ 10 part, preferably, described phenol catalysis agent is nonyl phenol, and more preferably, described resin material raw material also comprises the organometallic salt catalysts by cyanate mole 5 ~ 800ppm, preferably, described organometallic salt catalysts is one or more in zinc octoate, manganese octoate, dibutyl tin laurate or second phthalein acetone cobalt.
7. a preparation method for prepreg resin material according to any one of claim 1 to 6, is characterized in that, comprise the following steps:
By cyanate, organic modifiers, optional modified filler mixing, add optional phenol catalysis agent and/or optional organo-metallic salt catalyzer under heated and stirred, keep thermotonus 1 ~ 3h to obtain described prepreg resin material.
8. preparation method according to claim 7, is characterized in that, described preparation method specifically comprises the following steps:
By the heating temperatures of described cyanate, described organic modifiers, optional described modified filler to 50 DEG C ~ 250 DEG C, be preferably 100 DEG C ~ 200 DEG C, be more preferably 100 DEG C ~ 180 DEG C, described optional phenol catalysis agent and/or optional organo-metallic salt catalyzer is added under the condition stirred, Keep agitation 1min ~ 120min, be preferably 5 ~ 60min, be more preferably 10 ~ 30min, keep thermotonus 1 ~ 3h to obtain described prepreg resin material.
9. a prepreg, is formed by strongthener, it is characterized in that after resin material impregnation, the prepreg resin material of described resin material according to any one of claim 1 to 6.
10. a preparation method for prepreg, is characterized in that, comprises the following steps:
Method according to claim 7 or 8 prepares the prepreg resin material according to any one of claim 1 to 6,
Glued membrane is made in described prepreg resin material heating;
Described prepreg resin material is covered on strongthener, exerts pressure to described prepreg resin material heating, described prepreg resin material is impregnated in described strongthener, makes prepreg.
11. preparation methods according to claim 10, is characterized in that,
The Heating temperature preparing described glued membrane is 50 DEG C ~ 160 DEG C, is preferably 50 DEG C ~ 140 DEG C, is more preferably 50 DEG C ~ 120 DEG C;
The Heating temperature preparing described prepreg is 120 DEG C ~ 250 DEG C, is preferably 140 DEG C ~ 220 DEG C, is more preferably 140 DEG C ~ 180 DEG C;
Prepare the applying pressure position 5 ~ 50kg/cm of described prepreg
2, be preferably 5 ~ 40kg/cm
2, be more preferably 5 ~ 30kg/cm
2.
12. 1 kinds of metamaterial substrate, comprise prepreg material layer, it is characterized in that, described prepreg material layer is formed by the cyanate prepreg solidification described in claim 10 or 11.
13. metamaterial substrate according to claim 10, is characterized in that, described prepreg material layer is solidified by described cyanate prepreg and forms at 180 DEG C ~ 250 DEG C.
14. 1 kinds of Meta Materials, the conduction geometry comprising substrate and arrange on the substrate, it is characterized in that, described substrate is the metamaterial substrate described in claim 12 or 13.
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| CN108822543A (en) * | 2018-05-16 | 2018-11-16 | 西北工业大学 | A kind of cyanate resin base wave-penetrating composite material and preparation method thereof |
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