CN104211845B - A kind of terpolymer and its compositions of thermosetting resin - Google Patents
A kind of terpolymer and its compositions of thermosetting resin Download PDFInfo
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- CN104211845B CN104211845B CN201410388442.8A CN201410388442A CN104211845B CN 104211845 B CN104211845 B CN 104211845B CN 201410388442 A CN201410388442 A CN 201410388442A CN 104211845 B CN104211845 B CN 104211845B
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Abstract
The invention provides a kind of terpolymer, the terpolymer contains（a）Formula（Ⅰ）The construction unit of expression,（b）Formula（Ⅱ）The construction unit of expression,（c）Formula（Ⅲ）The construction unit of expression, wherein, present invention also offers the compositions of thermosetting resin comprising above-mentioned terpolymer and epoxy resin, this composition has relatively low dielectric constant and low-dielectric loss tangent, while with excellent heat resistance.Present invention also offers the prepreg prepared using this compositions of thermosetting resin and laminate, can be used as tellite material and printed circuit board (PCB) etc..
Description
Technical field
The invention belongs to technical field of electronic materials, more particularly to a kind of terpolymer and comprising the ter-polymers
Compositions of thermosetting resin, and the prepreg that made using the resin combination and laminate.
Background technology
In prior art, with material prepared by the compositions of thermosetting resin that epoxy resin and its curing agent are required composition
There is good heat resistance, insulating properties, processability and with low cost, be therefore widely used in semiconductor, printed circuit
In the electronic materials such as plate, main raw material in printed circuit board are become.
In recent years, with information processing and the continuous propulsion of information transfer high-speed high frequency technology, to tellite
Material proposes higher and higher requirement in terms of dielectric properties.In simple terms, i.e., tellite material need to have relatively low
Dielectric constant and dielectric loss tangent, to reduce the delay of signal during high-speed transfer, between distortion and loss, and signal
Interference.Accordingly, it is desired to provide a kind of compositions of thermosetting resin, the printed circuit made using this compositions of thermosetting resin
Plate material can show low-k and low-dielectric loss tangent in the signals transmission of high speed, high frequency.
Styrene-maleic anhydride copolymer has good reactivity worth, and the composition epoxy resin after which solidifies has
Excellent dielectric properties, therefore, its composition epoxy resin for solidifying is commonly used for the printed circuit for making high-frequency high-speed field
Plate material.
Mention in patent BE627887, styrene-maleic anhydride copolymer is used as the curing agent of epoxy resin, but
Be composition epoxy resin after solidification glass transition temperature degree very low, can neither meet during materials'use to heat-resisting
The requirement of performance, is also unsatisfactory in process under unleaded trend more wanting high heat resistant requirements.
Mention in patent TW552280B, using the monomer modified phenylethylene-maleic anhydride of N- substituent maleimides
Copolymer, the modified resin is used for after cured epoxy resin so that the glass transition temperature of composition epoxy resin
Increase substantially.But the substituent on the modified monomer N- substituent maleimides which uses, otherwise with hydroxyl or
Carboxyl, so can produce secondary hydroxyl during cured epoxy resin so that the dielectric properties deterioration of solidfied material, i.e. dielectric
Property constant and dielectric loss increase, or with the ester group for not having reactivity, so that crosslinking points reduce, limit heat-resisting
The further raising of performance.
Therefore, the present invention have developed a kind of terpolymer so as to which the composition epoxy resin of solidification has concurrently excellent simultaneously
Dielectric properties and heat resistance.
Content of the invention
For solving thermosetting resin poor heat resistance that prior art provides, dielectricity is poor or can not be provided simultaneously with good
The problems such as electricity saving performance and heat resistance, the invention provides a kind of new terpolymer and its compositions of thermosetting resin,
And the prepreg that made using the resin combination and laminate.
For solving the above problems, the present invention is introducing N- substituent maleimides in styrene-maleic anhydride copolymer
Amine monomers, the substituent on the N- substituent maleimide monomers are the active ester groups with reactivity, so as to obtain one
Plant terpolymer.The terpolymer contains（a）Formula（Ⅰ）The construction unit of expression,（b）Formula（Ⅱ）The structure of expression
Unit,（c）Formula（Ⅲ）The construction unit of expression；
（Ⅰ）, in formula x be positive integer, R in formula1For hydrogen atom or the alkyl of C1～C5, R2Former for hydrogen
The aliphatic alkyl of son, aromatic hydrocarbyl or C1～C5；
（Ⅱ）, in formula y be positive integer, R3、R4Each independent, be hydrogen atom, aromatic hydrocarbyl or
The alkyl of C1～C8；
（Ⅲ）Or, in formula z be positive integer, R3’、R3”、R4’、R4" each solely
Vertical, it is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1～C8, R5Cycloalkylidene or sub- benzene for the alkyl or C1-C8 of C1-C5
Base, R6It is selected from following group：
、、、、、、、、、、、, wherein R7Former for hydrogen
The aliphatic alkyl of son, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, R7Preferably hydrogen atom, R8For hydrogen atom,
The aryl alkyl of the alkyl of C1-C8, the alkylaryl of C7-C15 or C7-C15, R8Preferably methyl.
In above-mentioned technical proposal, the R of the terpolymer6Group, preferably maleimide phenoxyl can be obtained
Preferable heat resistance, preferably
OrPreferable fire resistance can be obtained.
The number-average molecular weight of above-mentioned terpolymer is 1500～50000g/mol, preferably 3000～30000g/
Mol, more preferably 5000～20000g/mol.
In above-mentioned technical proposal, in terpolymer x with（y+z）Ratio be 1：1～15:1, it is preferably in a proportion of 1：1～
10:1, more preferably ratio:1：1～5:1.
In above-mentioned technical proposal, in terpolymer, the ratio of y and z is 1:10～10:1, it is preferably in a proportion of 1:5～5:1.
In above-mentioned technical proposal, the terpolymer can be obtained by the following method：First with phenol replacement
The maleimide and carboxylic acid of base carries out esterification under catalyst action and the maleimide that active ester replaces is obtained, or
Person is with maleimide and phenolic hydroxyl-compounds or phenol sulfhydryl compound or hydroxylamine compound with carboxylic acid substituent in catalysis
Carry out esterification and the maleimide that active ester replaces be obtained under agent effect.Then, by styrene, maleic anhydride, activity
Three kinds of monomer copolymerizables of maleimide that ester replaces are obtained terpolymer.The carboxylic acid can be aliphatic carboxylic acid, fragrance
Race's carboxylic acid.Described catalyst can be acidic catalyst or base catalyst, and acidic catalyst can be phosphoric acid, sulfonic acid, road
Lewis acid etc., base catalyst can be NaOH, potassium hydroxide, DMAP, amine etc..
Present invention simultaneously provides a kind of compositions of thermosetting resin, including：
（1）Epoxy resin；
（2）Terpolymer,
The terpolymer contains（a）Formula（Ⅰ）The construction unit of expression,（b）Formula（Ⅱ）The construction unit of expression,
（c）Formula（Ⅲ）The construction unit of expression；
（Ⅰ）, in formula x be positive integer, R in formula1For hydrogen atom or the alkyl of C1～C5, R2Former for hydrogen
The aliphatic alkyl of son, aromatic hydrocarbyl or C1～C5；
（Ⅱ）, in formula y be positive integer, R3、R4Each independent, be hydrogen atom, aromatic hydrocarbyl or
The alkyl of C1～C8；
（Ⅲ）Or, in formula z be positive integer, R3’、R3”、R4’、R4" each solely
Vertical, it is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1～C8, R5Cycloalkylidene or sub- benzene for the alkyl or C1-C8 of C1-C5
Base, R6It is selected from following group：
、、、、、、、、、、、, wherein R7Former for hydrogen
The aliphatic alkyl of son, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, R8For hydrogen atom, the alkyl of C1-C8, C7-
The aryl alkyl of the alkylaryl or C7-C15 of C15；In its epoxy group and terpolymer acid anhydrides and ester group total amount mole
Ratio is 1:5～4:1, it is preferably in a proportion of 3:5～2:1.The number-average molecular weight of the terpolymer is 1500～50000g/
Mol, preferably 3000～30000g/mol, more preferably 5000～20000g/mol.
In above-mentioned technical proposal, in terpolymer x with（y+z）Ratio be 1：1～15:1, it is preferably in a proportion of 1：1～
10:1, more preferably ratio is 1：1～5:1.In above-mentioned technical proposal, in terpolymer, the ratio of y and z is 1:10～10:1,
It is preferably in a proportion of 1:5～5:1.
In above-mentioned technical proposal, the component（1）Epoxy resin can be selected from bisphenol A epoxide resin, Bisphenol F epoxy tree
Fat, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy
Resin, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene
Ring-like epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin,
In alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin one or more.
Preferably, the component（1）Epoxy resin selected from biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, bicyclic penta 2
One or more in ene-type epoxy resin, aralkyl novolac epoxy resin, phosphorous epoxy resin.
In above-mentioned technical proposal, compositions of thermosetting resin can also include amine compound, acid amides based compound, acid anhydrides
The curing agent such as based compound, phenol system compound, cyanate are used as co-curing agent.Specifically, amine system curing agent can be diamino
Base diphenyl methane, DADPS, diethylenetriamines, BMI, double carboxyl phthalimides, imidazoles
Deng；Acid amides based compound can be dicyandiamide, Versamid etc.；Acid anhydrides based compound can be phthalic anhydride, partially
Benzenetricarboxylic acid acid anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenated phthalic anhydride, carbic anhydride etc.；Phenol system compound can
Being that phosphorus containing phenolic resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol novolacs, naphthol novolac resin, biphenyl change
Property phenolic resin, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl
Base resin, Pehanorm resin, benzoxazine resins etc..
Preferably, the co-curing agent in the compositions of thermosetting resin of above-mentioned technical proposal is selected from following resin：Span comes
Imide resin, cyanate ester resin, naphthol novolac resin, biphenyl phenol-formaldehyde resin modified, biphenyl modification naphthol resin, bicyclic penta 2
Alkene phenol add-on type resin, phosphorus containing phenolic resin.
Preferably, add cyanate ester resin in the compositions of thermosetting resin of above-mentioned technical proposal as co-curing agent, and
Cyanate ester resin and component（1）The weight ratio of epoxy resin is 100:20～100:300, it is preferably in a proportion of 100:50～100:
200.The cyanate ester resin can be selected from bisphenol A cyanate ester resin, Bisphenol F cyanate ester resin, bis-phenol M cyanate ester resins,
One or more in dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy resin, phenol type cyanate ester resin.
Preferably, add bimaleimide resin in the compositions of thermosetting resin of above-mentioned technical proposal as co-curing
Agent, and bimaleimide resin and component（2）The weight ratio of terpolymer is 100:20～100:300, it is preferably in a proportion of
100:50～100:150, wherein R in terpolymer6Group is preferably maleimide phenoxyl.The bismaleimide
Polyimide resin be pi-allyl modified bismaleimide resin, its number-average molecular weight be 1000～8000g/mol, preferably 2000～
5000g/mol.
In above-mentioned technical proposal, the compositions of thermosetting resin can further include toughener, fire retardant, inorganic
Filler and curing accelerator.
The toughener can be HMW phenoxy resin, rubber etc..
The fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, You Jijin
Category salt fire retardant, inorganic flame retardant etc..Wherein, bromide fire retardant can be deca-BDE, TDE, bromination benzene
Ethene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be Phos, phosphate compound, phosphinic acid compounds, secondary phosphine
General organic phosphorus series compound such as nitrogenous phosphorus compound of acid compound, phosphine oxide compound, organic system and 9,10- dihydros -9
Miscellaneous phenanthrene -10- the oxides of oxa- -10- phosphines, 10-（2,5 dihydroxy phenyls）Miscellaneous phenanthrene -10- the oxidations of -9 oxa- -10- phosphines of -9,10- dihydros
The organophosphorus compound of DOPO structures and the uses such as the miscellaneous -10- phosphines phenanthrene -10- oxides of thing, 10- phenyl -9,10- dihydro-9-oxies
Its derivative reacted with compounds such as epoxy resin, phenolic resin etc..Nitrogenated flame retardant can be triaizine compounds, cyanogen
Uric acid compound, isocyanide acid compound, phenthazine etc..Organic silicon fibre retardant can be organic silicone oil, organic silicon rubber, organosilicon
Resin etc..Organic metal fire retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyls etc..Nothing
Machine flame retardant can be aluminium hydroxide, magnesium hydroxide, aluminum oxide, barium monoxide etc..
The content of the inorganic filler amounts to 100 weight portions relative to compositions of thermosetting resin, is 5～300 weight portions,
Preferably 5～80 weight portions.The inorganic filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, oxygen
Change aluminium, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanates, barium titanate, barium sulfate, talcum powder, calcium silicates, carbonic acid
One or more in calcium, mica, polytetrafluoroethylene (PTFE).
The curing accelerator according to actual conditions add use, can be selected from dimethyl aminopyridine, tertiary amine and its salt,
Imidazoles, organic metal salt, triphenylphosphine and its salt etc..
In above-mentioned technical proposal, can be silane coupled to be used according to the interpolation of actual feelings in the compositions of thermosetting resin
The additives such as agent, pigment, emulsifying agent, dispersant.
Above-mentioned compositions of thermosetting resin, can be used for manufacturing semiconductor-encapsulating material, lamination adhering film, bonding
Agent, resin cast material, conductive paste etc..
Present invention also offers the prepreg made using above-mentioned resin combination, by above-mentioned resin combination solvent
Glue is made in dissolving, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, you can
Arrive the prepreg.
Described solvent selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N- dimethyl second
One or more in acid amides, EGME, propylene glycol monomethyl ether.Described reinforcing material refers to the prepreg of the present invention
Base material, can be suitable for the well known materials that may use in various laminate, such as natural fiber, organic synthetic fibers, have woven
Thing or inorganic fabric, and their mixture.
Reinforcing material is immersed in glue, then heat drying, heat drying 1- generally at a temperature of the 100-200 degree
30 minutes, it is allowed to semi-solid preparation.
Present invention also offers the laminate made using above-mentioned resin combination, at one by above-mentioned prepreg
Single or double is covered with metal forming, or will at least 2 be superimposed by above-mentioned prepreg after, be covered with metal in its single or double
Paper tinsel, hot forming, you can obtain the laminate.
The quantity of the prepreg is laminate thickness as requested determining, can be with one or more.The gold
Category paper tinsel, as long as the material used in electrically insulating material purposes, is not particularly limited, can be Copper Foil, or
Aluminium foil, and their thickness is not particularly limited.In addition, for example applicable electrically insulating material laminate of molding condition and many
The method of laminate, for example, can use multidaylight press, multi-layer vacuum press, progressive forming, hot forming machine etc., in temperature 100-
250 DEG C, pressure 2-100kg/cm2, shape in the range of heat time 0.1-5 hour.
Beneficial effects of the present invention：The resin combination of the present invention not only has excellent dielectric properties, but also has
Excellent heat resistance.Laminate obtained in the compositions of thermosetting resin of the present invention has excellent dielectric properties, and existing
There is technology to compare, dielectric constant and dielectric loss decline to a great extent, can show in the signals transmission of high speed, high frequency
Substantially low low-k and low-dielectric loss tangent.
Specific embodiment
To be further described by specific embodiment below.It should be appreciated, however, that specific embodiment is only used for solving
The present invention is released, the protection domain being not intended to limit the present invention.The instrument for arriving use herein, equipment, reagent, method etc. as
Do not specialize, be instrument commonly used in the art, equipment, reagent and method.In the case of without special instruction, " part " represents
" weight portion ", " % " representative " weight % ".Embodiment 1～5 is the synthesis of terpolymer of the present invention, and embodiment 6～7 is band carboxyl
Or not having the synthesis of the polymer of the ester group of reactivity, embodiment 8～13 and embodiment 14～15 are thermosetting resin combinations
The preparation of thing and performance evaluation.
Embodiment 1
By N-（4 hydroxy phenyls）Maleimide 95g（0.5mol）, dicyclohexylcarbodiimide 110g（0.53mol）, second
Sour 30g（0.5mol）It is placed in after being substantially soluble in ethyl acetate in three neck reaction bulbs and is sufficiently mixed, then adds under agitation
1.20g4- dimethylamino naphthyridines, to react under room temperature and cool down one under the low temperature environment that reaction solution is placed in 0～5 DEG C for 6 hours afterwards
Section and then filters to isolate solid impurity at the time, then will obtained product distills, purifying is obtained to dimaleoyl imino benzene second
Ester.Then, will above obtained dimaleoyl imino phenethyl ester 78g（0.33mol）, styrene 830g（8.0mol）, maleic acid
Acid anhydride 176g（1.80mol）It is substantially dissolved in butanone, adds 50g benzoyl peroxides initiator and 80g amylene chain-transferring agents,
React 3 hours under the conditions of 70～90 DEG C and terpolymer is obtained（A-1）, measuring its number-average molecular weight using GPC method is
4900g/mol, includes following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 3.8:1, y and z ratio is 5.5:1, R1, R2,
R3, R4, R3 ", R4 " is hydrogen atom, and R8 is methyl.
Embodiment 2
Dimaleoyl imino phenethyl ester is obtained as in Example 1.Then, will above obtained dimaleoyl imino benzene second
Ester 350g（1.50mol）, styrene 1040g（10.0mol）, maleic anhydride 33g（0.33mol）It is substantially dissolved in butanone, plus
Enter 55g benzoyl peroxides initiator and 120g amylene chain-transferring agents, react 4 hours under the conditions of 70～90 DEG C and ternary is obtained
Copolymer（A-2）, measure its number-average molecular weight for 7500g/mol using GPC method, its structure with embodiment 1, x with（y+z）Ratio
Example is 5.5:1, y and z ratio is 1:5.
Embodiment 3
By N-（4 carboxyl phenyls）Maleimide 108g（0.5mol）, dicyclohexylcarbodiimide 110g（0.53mol）、
Phenol 50g（0.53mol）It is placed in after being substantially soluble in ethyl acetate in three neck reaction bulbs and is sufficiently mixed, then adds under agitation
2.0g4- dimethylamino naphthyridines, after reacting 6 hours, reaction solution are placed under 0～5 DEG C of low temperature environment and cool down one section under room temperature
Then time filter to isolate solid impurity, and then the distillation of obtained product, purifying are obtained to maleimide yl benzoic acid
Phenol ester.Then, will be above obtained to dimaleoyl imino phenylamino benzoic acid phenolic ester 193g（0.66mol）, styrene 312g
（3.0mol）, maleic anhydride 33g（0.33mol）It is substantially dissolved in butanone, adds 20g benzoyl peroxides initiator and 50g
Amylene chain-transferring agent, reacts 5 hours under the conditions of 70～90 DEG C and terpolymer is obtained（A-3）, which is measured using GPC method count
Average molecular weight is 11500g/mol, includes following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 3:1, y and z ratio is 1:2, R1, R2, R3, R4,
R3 ', R4 ' are hydrogen atom, and R5 is phenylene, and R6 is phenoxy group.
Embodiment 4
By N-（4 carboxyl phenyls）Maleimide 108g（0.5mol）, dicyclohexylcarbodiimide 110g（0.53mol）、
3- hydroxyl -1,2,3- phentriazine -4 (3H) -one 85g（0.52mol）It is placed in after being substantially soluble in ethyl acetate in three neck reaction bulbs
Be sufficiently mixed, then add 5.0g4- dimethylamino naphthyridines under agitation, 8 hours are reacted under room temperature afterwards, reaction solution is put
Under 0～5 DEG C of low temperature environment, then cooling a period of time filters to isolate solid impurity, then obtained product is distilled,
Purifying is obtained to maleimidobenzoate.Then, will be above obtained to maleimidobenzoate 120g
（0.33mol）, styrene 208g（2.0mol）, maleic anhydride 66g（0.67mol）It is substantially dissolved in butanone, adds 15g peroxides
Change benzoyl initiator and 35.0g amylene chain-transferring agents, react 5 hours under the conditions of 70～90 DEG C and terpolymer is obtained
（A-4）, its number-average molecular weight is measured for 15400g/mol using GPC method, include following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 2:1, y and z ratio is 2:1, R1, R2, R3, R4,
R3 ', R4 ' are hydrogen atom, and R5 is phenylene, and R6 is.
Embodiment 5
By N-（4 carboxyl phenyls）Maleimide 108g（0.5mol）, dicyclohexylcarbodiimide 110g（0.53mol）、
N-（4 hydroxy phenyls）Maleimide 95g（0.52mol）It is placed in after being substantially soluble in ethyl acetate in three neck reaction bulbs and fully mixes
Close, then add 3.0g4- dimethylamino naphthyridines under agitation, 8 hours are reacted under room temperature afterwards, reaction solution is placed in 0～5
DEG C low temperature environment under cooling a period of time then filter to isolate solid impurity, then by obtained product distill, purifying system
Must be to maleimidobenzoate.Then, will be above obtained to maleimidobenzoate 194g
（0.50mol）, styrene 104g（5mol）, maleic anhydride 49g（0.50mol）It is substantially dissolved in butanone, adds 10g peroxides
Change benzoyl initiator and 25.0g lauryl mercaptan chain-transferring agents, react 7 hours under the conditions of 70～90 DEG C and ternary polymerization is obtained
Thing（A-5）, its number-average molecular weight is measured for 20500g/mol using GPC method, include following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 1:1, y and z ratio is 1:1, R1, R2, R3, R4,
R3 ', R4 ' are hydrogen atom, and R5 is phenylene, R6 maleimide phenoxyls.
Embodiment 6
Take styrene 104g（1mol）, maleic anhydride 49g（0.5mol）、N-（4 carboxyl phenyls）Maleimide 108g
（0.5mol）It is substantially dissolved in butanone, adds 9.8g benzoyl peroxides initiator and 25.0g amylene chain-transferring agents, 70～
React 6 hours under the conditions of 90 DEG C and terpolymer is obtained（B-1）, its number-average molecular weight is measured for 8000g/ using GPC method
Mol, includes following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 1:1, y and z ratio is 1:1, R1, R2, R3, R4,
R3 ', R4 ' are hydrogen atom, and R5 is phenylene, and R6 is hydroxyl.
Embodiment 7
By N-（4 carboxyl phenyls）Maleimide 108g（0.5mol）, dicyclohexylcarbodiimide 110g（0.53mol）、
Methyl alcohol 16g（0.50mol）It is placed in after being substantially soluble in ethyl acetate in three neck reaction bulbs and is sufficiently mixed, then adds under agitation
The DMAP of 1.20g, reacts 6 hours afterwards, reaction solution is placed in cold under 0～5 DEG C of low temperature environment under room temperature
But a period of time then filter to isolate solid impurity, then will obtained product distill, purifying be obtained to dimaleoyl imino
Benzoic ether..Then, will be above obtained to dimaleoyl imino methyl benzoate 77g（0.33mol）, styrene 70g
（0.67mol）, maleic anhydride 33g（0.33mol）Be substantially dissolved in butanone, add 6.5g benzoyl peroxides initiators and
20.0g amylene chain-transferring agents, react 7 hours under the conditions of 70～90 DEG C and terpolymer are obtained（B-2）, surveyed using GPC method
It is 10000g/mol to obtain its number-average molecular weight, includes following three kinds of construction units in its structural formula：
（Ⅰ）,（Ⅱ）,（Ⅲ）,
In formula, x, y, z is positive integer, x with（y+z）Ratio be 1:1, y and z ratio is 1:1, R1, R2, R3, R4,
R3 ', R4 ' are hydrogen atom, and R5 is phenylene, and R6 is methoxyl group.
Embodiment 8-15
According to the formula that table 1 is recorded, all components are configured to the resin adhesive liquid that solid content is 60%, curing accelerator is pressed
Amount according to 0.5phr is added.
Then make laminate under the following conditions, and anti-flammability, wet-hot aging performance and dielectric is evaluated by following methods
Characteristic.As a result table 1 is shown in.
<Laminate manufacturing conditions>
Base material：2116 glass-fiber-fabric of ordinary electronic level；
The number of plies：5；
Sheet metal thickness after shaping：1.0mm；
Pre-preg semi-solid preparation condition：165℃/5min；
Condition of cure：150℃/60min+200℃/120min；
<Heat resistance>Heat resistance is characterized with glass transition temperature (Tg), according to differential scanning calorimetry, according to IPC-
The DSC method of TM-650 2.4.25 defineds is measured.
<Dielectric constant and the measure of dielectric loss tangent>Dielectric constant uses flat board according to IPC-TM-650 2.5.5.9
Method, determines the dielectric constant under 1GHz；Dielectric loss tangent：Flat band method is used according to IPC-TM-650 2.5.5.9, is determined
Dielectric loss factor under 1GHz.
<Anti-flammability>Determine according to UL94 methods.Not fire-retardant use " No " represents.
Table 1
The explanation of table 1：
A-1：Obtained terpolymer in embodiment 1（A-1）；
A-2：Obtained terpolymer in embodiment 2（A-2）；
A-3：Obtained terpolymer in embodiment 3（A-3）；
A-4：Obtained terpolymer in embodiment 4（A-4）；
A-5：Obtained terpolymer in embodiment 5（A-5）；
B-1：Obtained terpolymer in embodiment 6（B-1）；
B-2：Obtained terpolymer in embodiment 7（B-2）；
Epoxy resin 1：Dicyclopentadiene type phenolic resin, chemical drug, epoxide equivalent 265g/eq；
Epoxy resin 2：Phosphorous epoxy resin, CHIN YEE PE-315, epoxide equivalent 300g/eq, phosphorus content 3.5%wt；
Equivalent proportion：The equivalent proportion of active ester groups in epoxy radicals and modification type styrene maleic anhydride copolymer；
Cyanate：Bisphenol A cyanate ester resin, Lonza, BA-3000S；
BMI：Self-control pi-allyl modified BMI resin prepolymer, synthetic method is by 100 parts of bismaleimides
Polyimide resin and 50 parts of allyl compounds, react 85min at a temperature of 130 degree, and reaction is cooled to room temperature and obtains after terminating, its
Number-average molecular weight is 3500g/mol；
Phosphorus-containing phenolic aldehyde：92741 phosphorus content 9.2%wt of Dow；
Toughener：Nucleocapsid particles toughener, EVONIK；
Curing accelerator：2- methyl -4- ethyl imidazol(e)s；
Filler：Silica.
From upper table 1, embodiment 8～13 uses the terpolymer cured epoxy resin in the present invention, compares
Embodiment using the modified styrene-maleic anhydride copolymer cured epoxy resin of the N- substituent maleimides with carboxyl
14, hence it is evident that reduce the low-k after epoxy resin cure, low-dielectric loss tangent.Embodiment 8～13 and use are with general
The embodiment 15 of the modified styrene-maleic anhydride copolymer cured epoxy resin of the N- substituent maleimides of logical ester group,
There is higher glass transition temperature, obtain excellent heat resistance.Embodiment 12 is to the addition of cyanate ester resin conduct
The resin system of co-curing agent, compares embodiment 8～11, with more excellent heat resistance and dielectric properties.Embodiment 13 is
Bimaleimide resin be with the addition of as the resin system of co-curing agent, embodiment 8～11 is compared, with more excellent heat-resisting
Performance and dielectric properties.
Claims (12)
1. a kind of terpolymer, it is characterised in that the terpolymer contain the construction unit that (a) formula (I) represents,
The construction unit that b construction unit that () formula (II) is represented, (c) formula (III) are represented；
In formula x be positive integer, R in formula1For hydrogen atom or the alkyl of C1～C5, R2For hydrogen atom,
Aromatic hydrocarbyl or the aliphatic alkyl of C1～C5；
In formula y be positive integer, R3、R4Each independent, can with identical or different, be hydrogen atom,
Aromatic hydrocarbyl or the alkyl of C1～C8；
OrIn formula z be positive integer, R3’、R3”、R4’、R4" each independent,
It is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1～C8, R5For the cycloalkylidene or phenylene of the alkyl or C1-C8 of C1-C5, R6
It is selected from following group：
Wherein R7Former for hydrogen
The aliphatic alkyl of son, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, R8For hydrogen atom, the alkyl of C1-C8, C7-
The aryl alkyl of the alkylaryl or C7-C15 of C15；The number-average molecular weight of the terpolymer is 1500～50000g/mol,
And the x of the terpolymer is 1 with the ratio of (y+z):1～15:The ratio of 1, the y and z is 1:10～10:1.
2. terpolymer according to claim 1, it is characterised in that the R7 is hydrogen atom.
3. terpolymer according to claim 1, it is characterised in that the R6For maleimide phenoxyl,
4. a kind of compositions of thermosetting resin, including：
(1) epoxy resin；
(2) terpolymer described in any one of claim 1-3,
Its epoxy group is 1 with the molar ratio of acid anhydrides and ester group total amount in terpolymer:5～4:1.
5. resin combination according to claim 4, it is characterised in that：The epoxy resin is selected from biphenyl type epoxy tree
In fat, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, phosphorous epoxy resin
One or more.
6. compositions of thermosetting resin according to claim 4, it is characterised in that the compositions of thermosetting resin is also wrapped
Co-curing agent is included, the co-curing agent is modified selected from bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl
At least one of phenolic resin, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
7. compositions of thermosetting resin according to claim 6, it is characterised in that the co-curing agent is cyanate resin
Fat, and cyanate ester resin is 100 with the weight ratio of epoxy resin:20～100:300.
8. compositions of thermosetting resin according to claim 6, it is characterised in that the co-curing agent is bismaleimide
Polyimide resin, and bimaleimide resin is 100 with the weight ratio of terpolymer:20～100:300.
9. resin combination according to claim 8, it is characterised in that：Described bimaleimide resin is pi-allyl
Modified span imide resin, its number-average molecular weight are 2000～5000g/mol.
10. the compositions of thermosetting resin according to any one of claim 4～9, it is characterised in that also include toughener,
Fire retardant, inorganic filler and curing accelerator.
11. a kind of prepregs, it is characterised in that will be molten with solvent for the resin combination described in any one of claim 4～10
Solution makes glue, and then reinforcing material is immersed in above-mentioned glue；After reinforcing material heat drying after by dipping, you can
Arrive the prepreg.
12. a kind of laminates, it is characterised in that be covered with gold in the single or double of the prepreg described in a claim 11
Category paper tinsel, or after the prepreg described at least 2 claims 11 is superimposed, metal forming is covered with its single or double, heat
Pressing formation, you can obtain the laminate.
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