CN106905459A - A kind of epoxy resin modification polystyrene resin, preparation method and its usage - Google Patents
A kind of epoxy resin modification polystyrene resin, preparation method and its usage Download PDFInfo
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- CN106905459A CN106905459A CN201510980015.3A CN201510980015A CN106905459A CN 106905459 A CN106905459 A CN 106905459A CN 201510980015 A CN201510980015 A CN 201510980015A CN 106905459 A CN106905459 A CN 106905459A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
Abstract
The invention provides a kind of polystyrene resin of epoxy resin modification, preparation method and its usage.The epoxy resin modification polystyrene resin has the structure shown in formula (D).Be incorporated into epoxide group in polystyrene strand by the present invention, the superior dielectric performance of polystyrene chain segment offer had both been provided, simultaneously because the presence of epoxide group, the resin can not only arrange in pairs or groups with any epoxy resin, plate property can also be adjusted by different curing agent, be adapted to prepare the circuit substrate of high frequency electronic equipment.
Description
Technical field
The invention belongs to copper-clad plate technical field, it is related to a kind of epoxy resin modification polystyrene resin, prepares
A kind of method and application thereof, and in particular to epoxy resin modification polystyrene resin, preparation method and contain
Its prepreg, laminate and high-frequency circuit board.
Background technology
Be wirelessly transferred product flourish and high-frequency transmission technology leap, existing epoxy resin and phenol
The material of urea formaldehyde system cannot meet the demand of advanced application, particularly high frequency printed circuit board.Make
For the baseplate material of the printed circuit board (PCB) of low-dielectric loss has a fluorine-type resin, but this kind of resin high cost, plus
Work is difficult, using being confined to military and aerospace applications.In addition, polyphenylene oxide resin and band double bond polystyrene tree
Although fat increasingly becomes the base of high frequency printed circuit board with good mechanical property and superior dielectric performance
The first-selected resin material of plate, however, polystyrene (generally styrenebutadiene copolymer at present with double bond
Thing) and polyphenylene oxide be used for that to manufacture high-frequency high-speed sheet material to be by radical reaction, it is necessary to special production line,
And bonding sheet storage life is short, manufacturing condition regulation is difficult, high cost.
Polystyrene (PS) is the commodity polymer material of high comprehensive performance, and synthesis end or side chain are with work
The PS of property functional group, the functionalization of PS can be realized by appropriate reaction, so as to widen the use of PS significantly
On the way, the use value and economic worth of PS are improved.Active group is connected in polymer ends, its work(can be assigned
Can characteristic, according to the difference of functional group, the macromolecule of functionalization may participate in reversible ion association and its
On his oligomer or macromolecular chain can reactive group there is coupling reaction and trigger other monomers polymerization etc..
Additionally, polystyrene also has excellent dielectric properties.
Epoxy resin is one of widest resin of copper-clad plate sector application, and its processability is good, can be with difference
Resin and various functional group reactionses, the range of choice of curing agent are wide.Epoxy resin after solidification has good
Physics, chemical property, its surface to metal and nonmetallic materials have excellent adhesive strength, dielectricity
Can be good, deformation retract rate is small.
CN 101643525A disclose a kind of epoxy resin and preparation method thereof, and the epoxy resin has following
Structural formula：
Wherein R is：
The invention can be the mixture of 4-Vinyl phenol/styrol copolymer and epihalohydrin using one-step method
Thing is directly condensed to yield epoxy resin in the presence of alkali；Also two step method, i.e. para hydroxybenzene second first can be used
Alkene/styrol copolymer and epihalohydrin are etherified in the presence of catalyst, then the closed loop in the presence of alkali lye
Obtain epoxy resin.Methods described is required to two kinds of monomers (4-Vinyl phenol and styrene) copolymerization first
To copolymer, be introduced directly into epoxide group on copolymer afterwards, or after introducing ether on copolymer
Epoxidation.It is extremely difficult in the method that epoxide group is introduced directly on copolymer；And in copolymer
Process for epoxidation after upper introducing ether, is related to the problem of phenolic hydroxyl group conversion ratio and epoxy closed loop rate, if
Phenolic hydroxyl group conversion is not exclusively or epoxy closed loop can not exclusively cause dielectric properties to be greatly reduced, on the other hand
The side reaction reacted to each other between epoxide group can be caused in closed loop procedure again.
CN 102040713A disclose a kind of graft modified polymer material.The graft modified polymer material,
Obtained by polymer base material P grafted monomers A or monomer B, the molecular structure of monomer A includes at least one
Individual C=C double bonds and at least one epoxide group, the molecular structure of monomer B include that at least one C=C is double
Key and at least one anhydride group.The epoxy radicals or anhydride group that are carried on the graft modified polymer material surface and
The end modified DNA for having amino single-stranded terminal amino group carries out reacting the macromolecule for obtaining final product the absorption mercury ion
Material.The invention is that, by polystyrene plastics radiation grafting epoxy monomer, its effect is that mercury ion is reclaimed
And wastewater treatment.But the invention is that macromolecular material finished product is modified, be after completion of polymerization,
Irradiation grafting is carried out on microballoon, polymer film or the polymer fabrics for obtaining, by C=C double bonds, epoxy or acid
Acid anhydride grafting introduces macromolecular material finished product, and its reaction occurs on the surface of polymer end product, its interior molecules
Do not change.
The content of the invention
For the problem in prior art, an object of the present invention is to provide a kind of epoxy resin modification
Polystyrene resin, it combines the excellent processability of epoxy resin and the excellent dielectric properties of polystyrene,
Reduce for preparing processing technology difficulty during sheet material simultaneously, having reached process is simple can effectively reduce plate again
The purpose of material dielectric constant.Additionally, the polystyrene resin of the epoxy resin modification improves the resistance to leaching of sheet material
Weldering performance.
To achieve these goals, present invention employs following technical scheme：
A kind of polystyrene resin of epoxy resin modification, it has the structure shown in formula (D)：
R1Selected from-H or CH3, R2Selected from H, dodecyl,-OCH3、-CH3、In any one,It is selected from In it is any one
Kind, R4Selected from-H or CH3, m is 0,2,4 or 6, preferably 0,2 or 6, x/y=6~40, it is preferable that
X/y=8~30, further preferred x/y=10~25, the equal molecule of number of the epoxy resin modification polystyrene resin
Measure is 1000~50000.X/y of the present invention refers to the mol ratio of repeat unit.
Preferably, the polystyrene resin of the epoxy resin modification has any one in following structure：
In the present invention, wherein x>Y, x/y=6~40, such as 6,7,8,9,10,11,13,15,
17th, 19,20,21,22,23,25,27,28,29,31,33,35,37,39 or 40, when
When x/y is too small, polystyrene chain segment is not enough to provide excellent dielectric properties；When x/y is excessive, resin
Epoxide equivalent is too big, reactive functionality it is very few and cause reactivity it is too weak, usability is poor.Therefore, x/y values
When suitable, can both ensure sufficiently long polystyrene chain segment to provide excellent dielectric properties, while in molecule
The suitable epoxide group of quantity is introduced in chain, enables polystyrene resin and epoxy resin compatibility, so not
Can only be arranged in pairs or groups with any epoxy resin, moreover it is possible to plate property is adjusted by different curing agent, makes epoxy
The range of application of resin modified polystyrene resin is greatly increased, and improves performance of technical process, in industrial production
In have larger application value.Preferably, in the present invention, x/y=8~30, further preferred x/y=10~25.
The second object of the present invention is to provide a kind of polystyrene resin of epoxy resin modification as described above
Preparation method, the described method comprises the following steps：
With any one in alkenyl based epoxy resin, glycidol ether or glycidyl ester monomer and styrene
Class compound is monomer, by radical reaction synthetic epoxy resin modified polystyrene resin.
Being write of above-mentioned reaction equation be only easy for those skilled in the art and clearly understand this
The thinking and reaction principle of invention, described R1、R2、R3And R4Group and x and y and above-mentioned formula (D)
In restriction it is identical.
The preparation method that the present invention is provided directly is gathered with styrene monomer using the monomer with epoxy construction
Close, obtain the polymer with epoxy construction, methods described is simple, and yield is up to 98~100%, and purity is high,
Without purification.
Preferably, styrene compound and the alkenyl with formula (B) structure with formula (A) structure are made
Based epoxy resin, glycidol ether or glycidyl ester monomer initiator effect under, in solvent or solvent-free
In by radical reaction, obtain the polystyrene resin of the epoxy resin modification with formula (D) structure.
Preferably, the styrene compound with formula (A) structure has any in following structure
It is a kind of：
Preferably, the alkenyl based epoxy resin with formula (B) structure, glycidol ether or glycidol
Ester monomer has any one in following structure：
Preferably, the styrene compound with formula (A) structure, the alkenyl class with formula (B) structure
The mass ratio of epoxy, glycidol ether or glycidyl ester monomer and initiator is (4-30):1:(0.02-0.3),
The mass ratio is, for example, 5:1:0.025、8:1:0.025、10:1:0.035、13:1:0.035、14:1:0.045、
15:1:0.05、17:1:0.008、19:1:0.18、20:1:0.2、22:1:0.2、24:1:0.2 or 28:1:0.25, it is excellent
Elect as (5-20):1:(0.05-0.28), more preferably (7-19):1：(0.05-0.25).
Preferably, the radical reaction temperature be 60~160 DEG C, such as 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C,
85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、
140 DEG C, 145 DEG C, 150 DEG C or 155 DEG C, preferably 70~156 DEG C, further preferred 75~155 DEG C.
Preferably, the radical reaction time is 2~10 hours, such as 2 hours, 2.5 hours, it is 3 small
When, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours,
7.5 hours, 8 hours, 8.5 hours, 9 hours or 9.5 hours, preferably 2.4-9.4 hours, further preferably
2.8-8.8 hours.
Preferably, the initiator is radical initiator, and preferably organic peroxide or/and azo triggers
Agent.
Preferably, organic peroxide is the organic peroxide that 1 hour half-life period was 50-120 DEG C, is selected from
BPO, DCP, peroxide -3,5,5 Trimethylhexanoic acid tert-pentyl ester, 1,1- couple-(t-butyl peroxy) hexamethylene, 1,1-
Double-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- pair-(t-butyl peroxy) -3- hexins,
Single peroxy maleic acid tert-butyl ester, the monoperphthalic acid tert-butyl ester, 2,5- dimethyl -2,5- pair-(benzoyl mistake
Oxygen) hexane, peroxide heavy carbonic two-(2- Phenoxyethyls) ester, peroxidating disuccinic acid, 3,3,6,6,9,9- pregnancy
The oxygen cyclononane of base -1,2,4,5- four, benzoyl hydroperoxide tert-pentyl ester, 4,4- pair-(t-butyl peroxy) n-butyl pentanoate,
TBHP, TBHP+di-tert-butyl peroxide, t-butyl peroxybenzoate, mistake
Oxygen -2- methylbenzoates, 1,1- pair-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes, 3,3- pairs-(uncle
Butyl peroxy) ethyl butyrate, the peroxide -2- ethylhexyl carbonates tert-butyl ester, 2,5- dimethyl -2,5- be double-(tert-butyl group mistake
Oxygen) hexane, di isopropyl benzene hydroperoxide, 3- t-butyl peroxy -3- phenyl benzo (C) furanone, peroxide stearoyl carbonic acid
The tert-butyl ester, two-(2- tert-butylperoxyiso-propyls) benzene, peroxidating-two-(1- hydroxy-cyclohexyls), peroxidating February
Osmanthus acyl, cumyl hydroperoxide (cumyl hydroperoxide), di t-amyl peroxide (two t-amyl peroxy compounds),
Di-tert-butyl peroxide, peroxide heavy carbonic dicyclohexyl maleate, peroxide heavy carbonic diisopropyl ester, peroxide diethyl
Tert-butyl acetate, peroxide -2 ethyl hexanoic acid tert-butyl ester, peroxide heavy carbonic di-secondary butyl ester, peroxide heavy carbonic two-(2-
Ethylhexyl) ester, 2,5- dimethyl -2,5- be double-(peroxidating -2- ethyl hexanoyls) hexane, peroxide heavy carbonic two positive third,
Peroxide heavy carbonic two-(4- tert-butylcyclohexyls) ester, the capric acid of peroxidating two, the positive decoyl of peroxidating two, peroxide -2-
Thylhexoic acid tert-pentyl ester t-butyl peroxyneodecanoate, 1,1,3,3- tetramethyls peroxide -2 ethyl hexanoic acid butyl ester, mistake
Oxygen heavy carbonic two (cetyl) ester, the myristin of peroxide heavy carbonic two (peroxide heavy carbonic two (myristyl) ester)
Or in the positive nonanoyl of peroxidating two any one or at least two mixture.The mixture such as BPO
With the mixture of DCP, peroxide -3,5,5- tri-methyl hexanoic acid tert-pentyl esters and 1,1- pair-(t-butyl peroxy) hexamethylene
Mixture, 1,1- double-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes and 2,5- dimethyl -2,5- is double-(tert-butyl group
Peroxide) -3- hexins mixture, the mixing of single peroxy maleic acid tert-butyl ester and the monoperphthalic acid tert-butyl ester
Thing, 2,5- dimethyl -2,5- is double-(benzoyl peroxide) hexane, peroxide heavy carbonic two-(2- Phenoxyethyls) ester and
The mixture of peroxidating disuccinic acid, 3,3,6,6,9,9- vegolysens, 2,4,5- tetra- oxygen cyclononane, benzoyl hydroperoxide
The mixture of tert-pentyl ester, 4,4- pair-(t-butyl peroxy) n-butyl pentanoate and TBHP, the tert-butyl group
Hydrogen peroxide, di-tert-butyl peroxide, t-butyl peroxybenzoate, peroxide -2- methylbenzoates,
The mixing of 1,1- pairs-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes and 3,3- pairs-(t-butyl peroxy) ethyl butyrate
Thing, the peroxide -2- ethylhexyl carbonates tert-butyl ester, 2,5- dimethyl -2,5- pairs-(t-butyl peroxy) hexane, peroxidating
The mixing of hydrogen pinane, 3- t-butyl peroxies -3- phenyl benzo (C) furanone and peroxide stearoyl t-butyl carbonate
Thing, two-(2- tert-butylperoxyiso-propyls) benzene, peroxidating-two-(1- hydroxy-cyclohexyls), dilauroyl peroxide,
The mixing of cumyl hydroperoxide (cumyl hydroperoxide) and di t-amyl peroxide (two t-amyl peroxy compounds)
Thing, di-t-butyl peroxide (di-tert-butyl peroxide, peroxide heavy carbonic dicyclohexyl maleate, peroxide heavy carbonic two
The mixture of isopropyl ester, the peroxide diethacetic acid tert-butyl ester and peroxide -2 ethyl hexanoic acid tert-butyl ester, peroxide weight carbon
Sour di-secondary butyl ester, peroxide heavy carbonic two-(2- ethylhexyls) ester, 2,5- dimethyl -2,5- pair-(peroxidating -2- ethyls
Hexanoyl) hexane, peroxide heavy carbonic two positive third, peroxide heavy carbonic two-(4- tert-butylcyclohexyls) ester and peroxidating two
The mixture of capric acid, the positive decoyl of peroxidating two, peroxide -2 ethyl hexanoic acid tert-pentyl ester t-butyl peroxyneodecanoate,
1,1,3,3- tetramethyls peroxide -2 ethyl hexanoic acid butyl ester, peroxide heavy carbonic two (cetyl) ester, peroxide heavy carbonic
The mixture of two myristins (peroxide heavy carbonic two (myristyl) ester) and the positive nonanoyl of peroxidating two.
Preferably, the azo-initiator is different selected from azodiisobutyronitrile, ABVN or azo two
In valeronitrile any one or at least two mixture.The mixture such as ABVN and idol
The mixture of the mixture of nitrogen diisoamyl nitrile, azodiisobutyronitrile and 4,6- tri-butyl benzene oxygen radical, it is even
The mixture of the different heptonitrile of nitrogen two and azodiisobutyronitrile, AMBN and 4,6- tri-butyl benzene oxygen freedom
The mixture of base, the mixture of ABVN, AMBN and azodiisobutyronitrile, azo two
The mixture of isobutyronitrile, 4,6- tri-butyl benzenes oxygen radical and ABVN.
Preferably, methods described includes the step of reaction uses the solid content of solvent adjustment resin after terminating.
Preferably, the solid content solvent for use of regulation resin is any one in toluene, dimethylbenzene or butanone
Or any two kinds of mixture.The mixture of the mixture such as toluene and dimethylbenzene, toluene and butanone
Mixture, the mixture of dimethylbenzene and butanone, the mixture of toluene, dimethylbenzene and butanone.The solvent
The solid content of epoxy resin modification polystyrene resin of the regulation with formula (D) structure is 40-70%, preferably
60-65%.
The third object of the present invention is to provide a kind of resin combination, and the resin combination includes as above institute
The epoxy resin modification polystyrene resin with formula (D) structure stated.
In addition to the above-mentioned epoxy resin modification polystyrene resin with formula (D) structure, the resin combination
Thing can also include other components, and other components assign the resin combination different characteristics.For example, institute
Stating resin combination can also include other epoxy resin, curing agent, curing accelerator, inorganic filler and resistance
Combustion agent etc..
Preferably, described other epoxy resin are selected from phenol novolak type epoxy, methylphenol phenol aldehyde type ring
Oxygen tree fat, bisphenol A-type novolac epoxy resin, DCPD-containing epoxy resin, biphenyl epoxy resin, naphthalene system
Epoxy resin, phosphorous epoxy resin, containing epoxy silicone, diglycidyl ether type epoxy resin, alicyclic ring
Same clan's epoxy resin, polyglycol type epoxy resins, the glycidol ether of four phenol ethane four or triphenol methane type
A kind of in epoxy resin or at least two mixture.
Preferably, the curing agent is selected from anhydride curing agent or/and active ester curing agent.
Preferably, the anhydride curing agent is common selected from maleic anhydride of styrene, methyl vinyl ether-maleic acid
Polymers, methyl hexahydrophthalic anhydride, HHPA, phenylsuccinic acid acid anhydride, succinic anhydride, oxa- acid anhydrides, diformazan
Base maleic anhydride, glutaric anhydride, 2- methyl succinics acid anhydrides, phthalic anhydride, ENB dianhydride,
The acid anhydride of benzene four, 1,2- cyclohexyl dicarboxylic acids acid anhydride, 4- difluorophthalic anhydrides, 3- difluorophthalic anhydrides, 2,2- diformazans
Base succinyl oxide, 1,1- cyclohexanediacetic acids acid anhydride, phenyl cis-butenedioic anhydride, citraconic anhydride, 1,8- naphthalic anhydrides, 4,4 '
- biphenyl ether dianhydride, 3,3'4,4'- bibenzene tetracarboxylic dianhydrides, equal benzene dianhydride, 3,3'4,4'- dianhydrides diphenyl ether, 4,4'- (six
Fluorine isopropyl alkene) two anhydride phthalic acids, 1,2,3,4- cyclobutanetetracarboxylics dianhydride, 3,3'4,4'- benzophenone tetracarboxylic dianhydrides,
1,4,5,8- benzene tetracarboxylic acid Gan, perylene -1,4,9,10- tetrabasic carboxylic acids acetic anhydride, 3,4,5,6- THPAs or cis- 1,2,3,6- tetrahydrochysenes
In phthalic anhydride any one or at least two mixture.
Preferably, the active ester is by a kind of phenolic compound, two officials connected by aliphatic acyclic hydrocarbon structure
Energy degree carboxylic acid aromatic compound or acid halides and a kind of monohydroxy compound react and obtain, for example Japan
The HPC-8000-65T of DIC.
Preferably, the curing accelerator is selected from glyoxaline compound, preferably 2-methylimidazole, 2- ethyls -4-
In methylimidazole, 2- phenylimidazoles or 2- undecyl imidazoles any one or at least two mixture.
Preferably, the inorganic filler be selected from aluminium hydroxide, boehmite, silica, talcum powder, mica,
Barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, shepardite, diatomite, bentonite or float stone
In powder any one or at least two mixture.
Preferably, the fire retardant is selected from any in halogenated flame retardant, phosphorus flame retardant or inorganic combustion inhibitor
It is a kind of or at least two combination.
Preferably, the fire retardant is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl)
Miscellaneous -10- phosphines phenanthrene -10- the oxides of -9,10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10-
Phenyl -9, the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- dihydro-9-oxies, phenoxyphosphazene compound, Firebrake ZB, nitrogen phosphorus
It is any one in series expansion type, organic polymer fire retardant, phosphorus containing phenolic resin or phosphorous BMI
Kind or at least two mixture.
As the preparation method of one of resin combination of the present invention, can be coordinated by known method,
Stir, mix the described epoxy resin modification polystyrene resin with formula (D) structure, optionally its
His epoxy resin, curing agent, curing accelerator, inorganic filler and fire retardant etc. are stirred and prepare.
The fourth object of the present invention is to provide a kind of resin adhesive liquid, and it is by resin combination as described above
It is dissolved or dispersed in solvent and obtains.As the solvent in the present invention, it is not particularly limited, as concrete example,
Can enumerate the alcohols such as methyl alcohol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether,
The ethers such as carbitol, butyl carbitol, acetone, butanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), hexamethylene
The ketones such as ketone, toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon, ethoxyethyl acetate, acetic acid
The esters such as ethyl ester, DMF, DMA, METHYLPYRROLIDONE etc.
Nitrogen-containing solvent.Above-mentioned solvent can be used alone one kind, it is also possible to two kinds or it is two or more be used in mixed way,
It is preferred that the aromatic hydrocarbon solvent such as toluene, dimethylbenzene and acetone, butanone, methyl ethyl ketone, methyl tert-butyl
The ketone flux such as base ketone, cyclohexanone is used in mixed way.Usage amount those skilled in the art of the solvent can be with
Experience according to oneself is selected, so as to get resin adhesive liquid reach the viscosity being adapted in use to.
During resin combination as described above is dissolved or dispersed in solvent, emulsifying agent can be added.
Disperseed by emulsifying agent, inorganic filler etc. can be made to be uniformly dispersed in glue.
The fifth object of the present invention is to provide a kind of prepreg, and it is that reinforcing material infiltration is as described above
After resin adhesive liquid, it is dried to obtain.
The reinforcing material such as carbon fiber, glass fabric or aramid fibre and non-woven fabrics.Carbon fiber
For example there are T300, T700, T800 of toray company, aromatic polyamide fibre such as Kevlar fibers,
Exemplary glass fabric is such as：7628 glass-fiber-fabrics, 2116 glass-fiber-fabrics.
The sixth object of the present invention is to provide a kind of copper-clad plate, and the copper-clad plate contains at least one as above institute
The prepreg stated.Copper-clad plate is prepared as prior art, and those skilled in the art completely has the ability basis
The technology of preparing of the copper-clad plate disclosed in prior art, prepares copper-clad plate of the present invention.This is covered
When copper coin is applied to the preparation of printed circuit board (PCB), with superior electrical properties, it meets high speed and high frequency
The demand of change.
The seventh object of the present invention is to provide a kind of insulation board, and the insulation board contains at least one as above institute
The prepreg stated.
The eighth object of the present invention is to provide a kind of high-frequency circuit board, the high-frequency circuit board contain to
A few prepreg as described above.
Compared with prior art, the present invention has the advantages that：
(1) be incorporated into epoxide group in polystyrene strand by the present invention, both remains polystyrene chain segment
The superior dielectric performance of offer, simultaneously because the presence of epoxide group, the resin not only can be with any epoxy
Resin is arranged in pairs or groups, moreover it is possible to is adjusted plate property by different curing agent, is made the application model of polystyrene resin
Enclose and greatly increase；
(2) due to containing epoxide group in epoxy resin modification polystyrene resin, double bond is solved by certainly
The technological problemses solidified by base, improve performance of technical process, in the industrial production with larger application value；
(3) arranged in pairs or groups with other epoxy resin using epoxy resin modification polystyrene resin of the present invention and made
Standby high-frequency circuit board dielectric properties are excellent, are adapted to prepare the circuit substrate of high frequency electronic equipment, with tradition
Low dielectric resin is compared, and cost is greatly reduced.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
By 1040g styrene and 71g GMAs in equipped with agitator, condensing reflux pipe,
Stirred in the reactor of thermometer and wireway (logical nitrogen), maintaining nitrogen purge 0.5-1 hours removing reactor
In air, be subsequently adding 12g benzoyl peroxides, be to slowly warm up to 85 DEG C after dissolving to be mixed to whole,
10 DEG C were raised every 15 minutes, until temperature is increased to 155 DEG C, and temperature 0.5h is maintained at.Reaction knot
Butanone is added to adjust the solid content of resin after beam under agitation.
Embodiment 2
By 1040g styrene and 142g GMAs in equipped with agitator, condensing reflux pipe,
Stirred in the reactor of thermometer and wireway (logical nitrogen), maintaining nitrogen purge 0.5-1 hours removing reactor
In air, be subsequently adding 10g benzoyl peroxides, be to slowly warm up to 70 DEG C after dissolving to be mixed to whole,
10 DEG C were raised every 15 minutes, until temperature is increased to 155 DEG C, and temperature 0.5h is maintained at.Reaction knot
Butanone is added to adjust the solid content of resin after beam under agitation.
Embodiment 3
By 1040g styrene and 57g allyl glycidyl ethers in equipped with agitator, condensing reflux pipe, temperature
Stirred in the reactor of degree meter and wireway (logical nitrogen), in maintaining nitrogen purge 0.5-1 hours removing reactor
Air, be subsequently adding 13g and cross azodiisobutyronitrile, be to slowly warm up to 80 DEG C after dissolving to be mixed to whole,
15 DEG C were raised every 15 minutes, until temperature is increased to 155 DEG C, and temperature 0.5h is maintained at.Reaction knot
Butanone is added to adjust the solid content of resin after beam under agitation.
Embodiment 4
Prepare resin a：
By 624g styrene and 142g GMAs in equipped with agitator, condensing reflux pipe,
Stirred in the reactor of thermometer and wireway (logical nitrogen), maintaining nitrogen purge 0.5-1 hours removing reactor
In air, be subsequently adding 10g benzoyl peroxides, be to slowly warm up to 70 DEG C after dissolving to be mixed to whole,
10 DEG C were raised every 15 minutes, until temperature is increased to 155 DEG C, and temperature 0.5h is maintained at.Reaction knot
Butanone is added to adjust the solid content of resin after beam under agitation.
Embodiment 5
Prepare resin b：
By 1040g styrene and 35.5g GMAs in equipped with agitator, condensing reflux
Stirred in the reactor of pipe, thermometer and wireway (logical nitrogen), removed within maintaining nitrogen purge 0.5-1 hours anti-
The air in kettle is answered, 10g benzoyl peroxides are subsequently adding, is to slowly warm up to after dissolving to be mixed to whole
70 DEG C, 10 DEG C were raised every 15 minutes, until temperature is increased to 155 DEG C, and be maintained at temperature 0.5h.
Reaction adds butanone to adjust the solid content of resin under agitation after terminating.
Embodiment 6-9
Prepare resin c：
The polystyrene epoxy resin that to be obtained by different styrene and GMA ratio with
EF40 maleic anhydride of styrene is dissolved in butanone or toluene, and accelerator is made with 2E4MI, is made solid content
The glue of 55-65%.After glass-fiber-fabric is impregnated by glue, in 155 DEG C of oven for drying solvents, that is, prepreg is obtained.
The thick Copper Foils of 0.5OZ are covered with gained prepreg two sides, solidification lamination procedure is 200 DEG C, and 90min is obtained final product
To copper-clad laminate.
Embodiment 10
Prepare resin d：
By epoxy resin modification polystyrene resin and HPC-8000-65T active ester crosslinking agents be dissolved in butanone or
In toluene, accelerator is made with DMAP, be made the glue of solid content 55-65%.Glass-fiber-fabric is impregnated by glue
Afterwards, in 155 DEG C of oven for drying solvents, that is, prepreg is obtained.It is thick 0.5OZ to be covered with gained prepreg two sides
Copper Foil, solidification lamination procedure be 200 DEG C, 90min obtains copper-clad laminate.
Embodiment 11
By epoxy resin modification polystyrene resin, 7200-H dicyclopentadiene types novolac epoxy resin and benzene second
Alkene maleic anhydride is dissolved in butanone or toluene, and accelerator is made with 2E4MI, is made the glue of solid content 55-65%
Liquid.After glass-fiber-fabric is impregnated by glue, in 155 DEG C of oven for drying solvents, that is, prepreg is obtained.It is pre- in gained
Leaching material two sides is covered with the thick Copper Foils of 0.5OZ, and solidification lamination procedure is 200 DEG C, and 90min obtains covering Copper Foil
Laminate.
Embodiment 12
By epoxy resin modification polystyrene resin, NC3000-H biphenyl types novolac epoxy resin and styrene horse
Carry out acid anhydrides to be dissolved in butanone or toluene, accelerator is made with 2E4MI, be made the glue of solid content 55-65%.
After glass-fiber-fabric is impregnated by glue, in 155 DEG C of oven for drying solvents, that is, prepreg is obtained.In gained prepreg
Two sides is covered with the thick Copper Foils of 0.5OZ, and solidification lamination procedure is 200 DEG C, and 90min obtains copper foil covered pressure
Plate.
Comparative example 1
7200-H dicyclopentadiene types novolac epoxy resin and maleic anhydride of styrene are dissolved in butanone or toluene
In, accelerator is made with 2E4MI, it is made the glue of solid content 55-65%.After glass-fiber-fabric is impregnated by glue,
In 155 DEG C of oven for drying solvents, that is, obtain prepreg.The thick copper of 0.5OZ is covered with gained prepreg two sides
Paper tinsel, solidification lamination procedure is 200 DEG C, and 90min obtains copper-clad laminate.
Comparative example 2
During NC3000-H biphenyl types novolac epoxy resin and maleic anhydride of styrene are dissolved in into butanone or toluene,
Accelerator is made with 2E4MI, the glue of solid content 55-65% is made.After glass-fiber-fabric is impregnated by glue, at 155 DEG C
Oven for drying solvent, that is, obtain prepreg.The thick Copper Foils of 0.5OZ, solidification are covered with gained prepreg two sides
Lamination procedure is 200 DEG C, and 90min obtains copper-clad laminate.
Comparative example 3
7200-H dicyclopentadiene types novolac epoxy resin is dissolved in HPC-8000-65T active ester crosslinking agents
In butanone or toluene, accelerator is made with DMAP, be made the glue of solid content 55-65%.Glass-fiber-fabric is by glue
After immersion stain, in 155 DEG C of oven for drying solvents, that is, prepreg is obtained.0.5OZ is covered with gained prepreg two sides
Thick Copper Foil, solidification lamination procedure is 200 DEG C, and 90min obtains copper-clad laminate.
The copper-clad plate the performance test results of embodiment 6~12 and comparative example 1~5 are as shown in Tables 1 and 2：
Table 1
Table 2
Note：Each component content is all solids content parts by weight in Tables 1 and 2.
The material that Tables 1 and 2 is enumerated is specific as follows：
Synthetic resin a:Styrene is 4.4 with GMA mass ratio:1 epoxy resin modification
Polystyrene tree, embodiment 4.
Synthetic resin b:Styrene is 7.3 with GMA mass ratio:1 epoxy resin modification
Polystyrene tree, embodiment 2.
Synthetic resin c:Styrene is 14.5 with GMA mass ratio:1 epoxy resin changes
Property polystyrene tree, embodiment 1.
Synthetic resin d:Styrene is 29.3 with GMA mass ratio:1 epoxy resin changes
Property polystyrene tree, embodiment 5.
NC-3000H：Biphenyl type novolac epoxy resin (Japanese chemical drug).
7200-H：Dicyclopentadiene type novolac epoxy resin (Japanese DIC).
HPC-8000-65T：Active ester crosslinking agent (Japanese DIC).
EF40：SMA curing agent (U.S.'s Sartomer).
DMAP：Curing accelerator, DMAP (wide Rong Huaxue).
2E4MI：Curing accelerator, 2-ethyl-4-methylimidazole (Japanese four countries' chemical conversion).
The laminate that embodiment 5-10 and comparative example 1-5 is obtained is tested using following methods：
(1) glass transition temperature (Tg)：Tested using DSC, according to IPC-TM-6502.4.25 institutes
The DSC method of testings of regulation are measured.
(2) dielectric constant and dielectric loss factor：Method according to IPC-TM-6502.5.5.13 is tested,
Test frequency is 10GHz.
(3) resistance to dip solderability evaluation：By copper-clad laminate be immersed in the tin stove that temperature is 288 DEG C until
Plate material lamination bubbles, and writes down the time of plate material lamination foaming, and this is the resistance to dip solderability limit of the sheet material.
(4) peel strength：Method according to IPC-TM-6502.4.8 is tested.
(5) heat decomposition temperature (Td)：According to thermogravimetry (TGA), according to IPC-TM-6502.4.24
The TGA methods of defined are measured.
Embodiment 6-9 shows the epoxy resin modification polystyrene resin synthesized by the present invention, its styrene list
Body ratio is higher, and the dielectric properties of sheet material are better, but visible sheet material Tg and peel strength are relatively low simultaneously, and this is
Because panel body resin structure is polystyrene, Tg is relatively low in itself for polystyrene, and polarity is also low, therefore table
Reveal poor peel strength.
Embodiment 10-12 and comparative example 1-3 show epoxy resin modification polystyrene resin of the invention by with
Other epoxy composites or the epoxy hardener using different structure, had both remained epoxy resin modification polyphenyl
Vinyl excellent dielectric properties and heat resistance, also cause that the Tg and peel strength of sheet material are greatly improved, from
And obtain excellent combination property.
Therefore, the epoxy resin modification polystyrene resin synthesized by the present invention has excellent dielectric properties,
The dielectric constant and dielectric loss of sheet material can not only be effectively reduced, while can also substantially reduce board cost.
Claims (10)
1. a kind of polystyrene resin of epoxy resin modification, it has the structure shown in formula (D)：
R1Selected from-H or CH3, R2Selected from H, dodecyl,-OCH3、-CH3、In any one,It is selected from In any one, R4Selected from-H or-CH3, m be 0,2,4 or 6, preferably 0,2 or
6, x/y=6~40, it is preferable that x/y=8~30, further preferred x/y=10~25；The epoxy resin modification
The number-average molecular weight of polystyrene resin is 1000~50000.
2. epoxy resin modification polystyrene resin as claimed in claim 1, it is characterised in that the ring
The resin modified polystyrene resin of oxygen has any one in following structure：
X/y=6~40；
Preferably, x/y=8~30, further preferred x/y=10~25.
3. a kind of preparation method of the polystyrene resin of epoxy resin modification as claimed in claim 1 or 2,
The described method comprises the following steps：
With any one in alkenyl based epoxy resin, glycidol ether or glycidyl ester monomer and styrene
Class compound is monomer, the polystyrene resin being modified by radical reaction synthetic epoxy resin.
4. method as claimed in claim 3, it is characterised in that make the styrene with formula (A) structure
Class compound and the alkenyl based epoxy resin, glycidol ether or glycidyl ester monomer with formula (B) structure
Under initiator effect, solvent or it is solvent-free in by radical reaction, obtain with formula (D) structure
Epoxy resin modification polystyrene resin；
Preferably, the styrene compound with formula (A) structure has any in following structure
It is a kind of：
Preferably, the alkenyl based epoxy resin with formula (B) structure, glycidol ether or glycidol
Ester monomer has any one in following structure：
Preferably, the styrene compound with formula (A) structure, the alkenyl class with formula (B) structure
The mass ratio of epoxy, glycidol ether or glycidyl ester monomer and initiator is (4-30):1:(0.02-0.3),
Preferably (5-20):1:(0.05-0.28), more preferably (7-19):1：(0.05-0.25)；
Preferably, the radical reaction temperature be 60~160 DEG C, preferably 70~156 DEG C, further preferably
75~155 DEG C；
Preferably, the radical reaction time is 2~10 hours, preferably 2.4-9.4 hours, further excellent
Select 2.8-8.8 hours；
Preferably, the initiator is radical initiator, and preferably organic peroxide or/and azo triggers
Agent；
Preferably, organic peroxide is the organic peroxide that 1 hour half-life period was 50-120 DEG C, is selected from
BPO, DCP, peroxide -3,5,5 Trimethylhexanoic acid tert-pentyl ester, 1,1- couple-(t-butyl peroxy) hexamethylene, 1,1-
Double-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- pair-(t-butyl peroxy) -3- hexins,
Single peroxy maleic acid tert-butyl ester, the monoperphthalic acid tert-butyl ester, 2,5- dimethyl -2,5- pair-(benzoyl mistake
Oxygen) hexane, peroxide heavy carbonic two-(2- Phenoxyethyls) ester, peroxidating disuccinic acid, 3,3,6,6,9,9- pregnancy
The oxygen cyclononane of base -1,2,4,5- four, benzoyl hydroperoxide tert-pentyl ester, 4,4- pair-(t-butyl peroxy) n-butyl pentanoate,
TBHP, TBHP+di-tert-butyl peroxide, t-butyl peroxybenzoate, mistake
Oxygen -2- methylbenzoates, 1,1- pair-(t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes, 3,3- pairs-(uncle
Butyl peroxy) ethyl butyrate, the peroxide -2- ethylhexyl carbonates tert-butyl ester, 2,5- dimethyl -2,5- be double-(tert-butyl group mistake
Oxygen) hexane, di isopropyl benzene hydroperoxide, 3- t-butyl peroxy -3- phenyl benzo (C) furanone, peroxide stearoyl carbonic acid
The tert-butyl ester, two-(2- tert-butylperoxyiso-propyls) benzene, peroxidating-two-(1- hydroxy-cyclohexyls), peroxidating February
Osmanthus acyl, cumyl hydroperoxide (cumyl hydroperoxide), di t-amyl peroxide (two t-amyl peroxy compounds),
Di-tert-butyl peroxide, peroxide heavy carbonic dicyclohexyl maleate, peroxide heavy carbonic diisopropyl ester, peroxide diethyl
Tert-butyl acetate, peroxide -2 ethyl hexanoic acid tert-butyl ester, peroxide heavy carbonic di-secondary butyl ester, peroxide heavy carbonic two-(2-
Ethylhexyl) ester, 2,5- dimethyl -2,5- be double-(peroxidating -2- ethyl hexanoyls) hexane, peroxide heavy carbonic two positive third,
Peroxide heavy carbonic two-(4- tert-butylcyclohexyls) ester, the capric acid of peroxidating two, the positive decoyl of peroxidating two, peroxide -2-
Thylhexoic acid tert-pentyl ester t-butyl peroxyneodecanoate, 1,1,3,3- tetramethyls peroxide -2 ethyl hexanoic acid butyl ester, mistake
Oxygen heavy carbonic two (cetyl) ester, the myristin of peroxide heavy carbonic two (peroxide heavy carbonic two (myristyl) ester)
Or in the positive nonanoyl of peroxidating two any one or at least two mixture；
Preferably, the azo-initiator is different selected from azodiisobutyronitrile, ABVN or azo two
In valeronitrile any one or at least two mixture；
Preferably, methods described includes the step of reaction uses the solid content of solvent adjustment resin after terminating；
Preferably, the solid content solvent for use of regulation resin is any one in toluene, dimethylbenzene or butanone
Or any two kinds of mixture.
5. a kind of resin combination, the resin combination includes asphalt mixtures modified by epoxy resin as claimed in claim 1 or 2
The modified polystyrene resin of fat.
6. a kind of resin adhesive liquid, its be resin combination as claimed in claim 5 is dissolved or dispersed in it is molten
Obtained in agent.
7. a kind of prepreg, it is after reinforcing material is infiltrated into resin adhesive liquid as claimed in claim 6, to do
It is dry to obtain.
8. a kind of copper-clad plate, the copper-clad plate contains at least one prepreg as claimed in claim 7.
9. a kind of insulation board, the insulation board contains at least one prepreg as claimed in claim 7.
10. a kind of high-frequency circuit board, the high-frequency circuit board contains at least one such as claim 7 institute
The prepreg stated.
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| CN201510980015.3A CN106905459A (en) | 2015-12-22 | 2015-12-22 | A kind of epoxy resin modification polystyrene resin, preparation method and its usage |
| PCT/CN2016/099124 WO2017107584A1 (en) | 2015-12-22 | 2016-09-14 | Epoxy resin modified polystyrene resin, preparation method therefor, and uses thereof |
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| CN107652570A (en) * | 2017-09-01 | 2018-02-02 | 安徽省德邦瓷业有限公司 | A kind of preparation technology of ceramic drying plant resistant material |
| CN113025037A (en) * | 2021-02-09 | 2021-06-25 | 林州致远电子科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
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