CN104211847A - Terpolymer and thermosetting resin composition thereof - Google Patents
Terpolymer and thermosetting resin composition thereof Download PDFInfo
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- CN104211847A CN104211847A CN201410389721.6A CN201410389721A CN104211847A CN 104211847 A CN104211847 A CN 104211847A CN 201410389721 A CN201410389721 A CN 201410389721A CN 104211847 A CN104211847 A CN 104211847A
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Abstract
The invention provides a terpolymer containing structural units represented by a general formula (I), a general formula (II) and a general formula (III). The invention also provides a thermosetting resin composition containing the terpolymer and epoxy resin. The composition has low dielectric constant, low dielectric loss tangent, and excellent heat resistance, processing manufacturability and storage performance. The invention also provides a prepreg and a laminate prepared from the thermosetting resin composition, and the thermosetting resin composition can be used in printed circuit substrate material and printed circuit board.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to a kind of terpolymer and compositions of thermosetting resin thereof, and the prepreg using this resin combination to make and veneer sheet, belong to technical field of electronic materials.
Background technology
In prior art, be must have good thermotolerance, insulativity, processibility and the advantage such as with low cost by the material prepared of the compositions of thermosetting resin of composition with epoxy resin and solidifying agent thereof, therefore be widely used in, in the electronic material such as semi-conductor, printed circuit board, having become starting material main in printed circuit board.
In recent years, along with the continuous propelling of information processing and information transmission high-speed high frequency technology, in dielectric properties, more and more higher requirement is proposed to tellite material.In simple terms, namely tellite material require possesses lower specific inductivity and dielectric loss tangent, the delay of signal during to reduce high-speed transfer, distortion and loss, and the interference between signal.Therefore, expect to provide a kind of compositions of thermosetting resin, the printed circuit board material using this compositions of thermosetting resin to make can show fully low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
Styrene-maleic anhydride copolymer has good reactivity worth, and the composition epoxy resin after its solidification has excellent dielectric properties, and therefore, the composition epoxy resin of its solidification is often used to the printed circuit board material making high-frequency high-speed field.When but anhydride type curing agent and epoxy composite use, there is a reactive problem: when not adding promotor, severe reaction conditions, requires that temperature of reaction is higher, but under interpolation promotor, normal-temperature reaction is very fast, and processing technology and storage all receive and have a strong impact on.
Mention in patent CN101845199A, use and there is the modification agent of hydroxyl and styrene-maleic anhydride copolymer reacts, generate a kind of terpolymer solidifying agent.But, this patent utilizes the hydroxyl on hydroxyl modification agent or the rear newly-generated carboxyl of upgrading reaction as solidification functional group cured epoxy resin, such meeting produces secondary hydroxyl in the process of solidification, make the dielectric properties deterioration of cured article, namely dielectricity constant and dielectric loss increase, and are unfavorable for its application in high-frequency high-speed printed circuit board material.
Therefore, the present invention have developed a kind of terpolymer, there is suitable reactive behavior thus improve processing technology and the storage of the composition of itself and epoxy resin, there are excellent dielectric properties simultaneously, be suitable for the application in high-frequency high-speed printed circuit board material field.
Summary of the invention
The object of this invention is to provide a kind of terpolymer and compositions of thermosetting resin thereof, and the prepreg using this resin combination to make and veneer sheet.
To achieve the above object of the invention, the present invention be introduce in styrene-maleic anhydride copolymer there is reactive behavior active ester as the 3rd structural unit, thus obtain and a kind of there is acid anhydrides and the active ester terpolymer as epoxy hardener simultaneously.The structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III represent;
(I)
, in formula, x is positive integer, R in formula
1for the alkyl of hydrogen atom, C1 ~ C5, R
2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C5;
(II)
, in formula, y is positive integer, R
3, R
4respective independence, can be identical or different, is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
(III)
, in formula, z is positive integer, R
3', R
4' independent separately, can be identical or different, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R
5, R
6respective independence, can be identical or different, can be following group,
,
,
,
,
,
,
,
,
,
,
,
,
, wherein R
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5, be preferably hydrogen atom, R
0for alkyl, the cycloalkyl of C1 ~ C8, the phenylalkyl of C7 ~ C10, the alkylene of C3 ~ C10 of C1 ~ C5, but R
5or R
6in have at most a group to be
.
In technique scheme, the R in described terpolymer
5or R
6group, preferred maleimide phenoxyl, can obtain good resistance toheat, preferably
or
, good flame retardant properties can be obtained.
In technique scheme, in described terpolymer, x is 1:1 ~ 15:1 with the proportional range of (y+z), and preferred proportion scope is 1:1 ~ 10:1, more has the proportional range of choosing to be 1:1 ~ 5:1.
In technique scheme, in described terpolymer, the ratio of y and z is 1:10 ~ 10:1, and preferred proportion is 1:5 ~ 5:1.
In technique scheme, the number-average molecular weight of described terpolymer is 1500 ~ 50000g/mol, and preferably 2000 ~ 35000 g/mol, are more preferably 3000 ~ 30000 g/mol.
In technique scheme, described terpolymer can obtain by the following method: first maleic anhydride or toxilic acid and phenolic hydroxyl-compounds or phenol sulfhydryl compound or hydroxylamine compound are carried out esterification under catalyst action and obtain micromolecular active ester, then this small molecule active ester, maleic anhydride, vinylbenzene are carried out radical polymerization under certain condition according to a certain percentage and obtains.Described catalyzer can be an acidic catalyst or basic catalyst, and an acidic catalyst can be phosphoric acid, sulfonic acid, Lewis acid etc., and basic catalyst can be sodium hydroxide, potassium hydroxide, DMAP, amine etc.
The present invention provides a kind of compositions of thermosetting resin simultaneously, comprising:
(1) epoxy resin;
(2) terpolymer,
The structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III are;
(I)
, in formula, x is positive integer, R in formula
1for the alkyl of hydrogen atom, C1 ~ C5, R
2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ 5;
(II)
, in formula, y is positive integer, R
3, R
4respective independence, can be identical or different, is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
(III)
, in formula, z is positive integer, R
3', R
4' independent separately, can be identical or different, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R
5, R
6respective independence, can be identical or different, can be following group:
,
,
,
,
,
,
,
,
,
,
,
,
, wherein R
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5, be preferably hydrogen atom, R
0for alkyl, the cycloalkyl of C1 ~ C8, the phenylalkyl of C7 ~ C10, the alkylene of C3 ~ C10 of C1 ~ C5, but a group in R5 or R6, is had at most to be
; In its epoxy group and terpolymer, the molar ratio of acid anhydrides and ester group total amount is 1:5 ~ 4:1, and preferred proportion is 3:5 ~ 2:1.
In technique scheme, in described terpolymer, x is 1:1 ~ 15:1 with the proportional range of (y+z), and preferred proportion scope is 1:1 ~ 10:1, more has the proportional range of choosing to be 1:1 ~ 5:1.
In technique scheme, in described terpolymer, the ratio of y and z is 1:10 ~ 10:1, and preferred proportion is 1:5 ~ 5:1.
In technique scheme, the number-average molecular weight of described terpolymer is 1500 ~ 50000g/mol, and preferably 2000 ~ 35000 g/mol, are more preferably 3000 ~ 30000 g/mol.
In technique scheme, described component (1) epoxy resin can be selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, in glycidyl ester type epoxy resin one or more.
Preferably, described component (1) epoxy resin is selected from one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, phosphorous epoxy resin.
In technique scheme, compositions of thermosetting resin can also comprise the solidifying agent such as amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate as co-curing agent.Specifically, amine system solidifying agent can be diaminodiphenyl-methane, diaminodiphenylsulfone(DDS), diethylenetriamine, bismaleimides, two carboxyl phthalic imidine, imidazoles etc.; Acid amides based compound can be Dyhard RU 100, Versamid etc.; Acid anhydrides based compound can be Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenated phthalic anhydride, carbic anhydride etc.; Phenol system compound can be phosphorus containing phenolic resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol novolacs, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, Pehanorm resin, benzoxazine colophony etc.
Preferably, the co-curing agent in the compositions of thermosetting resin of technique scheme is selected from following resin: bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
Preferably, add cyanate ester resin in the compositions of thermosetting resin of technique scheme further as co-curing agent, and the weight ratio of cyanate ester resin and component (1) epoxy resin is 100:20 ~ 100:300, preferred proportion is 100:50 ~ 100:200.Described cyanate ester resin can be selected from one or more in bisphenol A cyanate ester resin, Bisphenol F cyanate ester resin, bis-phenol M cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy resin, phenol type cyanate ester resin.
Preferably, bimaleimide resin is added as co-curing agent in the compositions of thermosetting resin of technique scheme, and the weight ratio of bimaleimide resin and component (2) terpolymer is 100:20 ~ 100:200, preferred proportion is 100:50 ~ 100:150, wherein the R of terpolymer
5or R
6be preferably maleimide phenoxyl.Described bimaleimide resin is allyl group modified bismaleimide resin, and its number-average molecular weight is 1000 ~ 8000g/mol, preferably 2000 ~ 5000g/mol.
In technique scheme, described compositions of thermosetting resin can further include toughner, fire retardant, mineral filler and curing catalyst.
Described toughner can be high molecular phenoxy resin, rubber etc.
Described fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, organic metal salt fire retardant, inorganic flame retardant etc.Wherein, bromide fire retardant can be decabromodiphynly oxide, TDE, brominated styrene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be the general organophosphorus based compounds and 9 such as inorganic phosphorus, phosphate compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound, organic system Nitrogen-and Phosphorus-containing compound, 10-dihydro-9 oxa--10-phosphine is mixed phenanthrene-10-oxide compound, 10-(2,5 dihydroxy phenyls)-9, mix phenanthrene-10-oxide compound, 10-phenyl-9,10-dihydro-9-oxy of 10-dihydro-9 oxa--10-phosphine is mixed the organophosphorus compound of the DOPO structures such as-10-phosphine phenanthrene-10-oxide compound and the derivative etc. that uses itself and the compound such as epoxy resin, resol to react.Nitrogenated flame retardant can be triaizine compounds, cyanuric acid compound, isocyanic acid compound, thiodiphenylamine etc.Organic silicon fibre retardant can be organic silicone oil, organo-silicone rubber, silicone resin etc.Organo-metallic fire retardant can be ferrocene, acetylacetone metal complex, organo-metallic carbonyl compound etc.Inorganic flame retardant can be aluminium hydroxide, magnesium hydroxide, aluminum oxide, barium oxide etc.
The content of described mineral filler amounts to 100 weight parts relative to compositions of thermosetting resin, is 5 ~ 300 weight parts, is preferably 5 ~ 80 weight parts.Described mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanate, barium titanate, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, mica, tetrafluoroethylene.
Described curing catalyst adds use according to practical situation, can be selected from dimethyl aminopyridine, tertiary amine and salt thereof, imidazoles, organic metal salt, triphenylphosphine Ji Qi phosphonium salt etc.
In technique scheme, in described compositions of thermosetting resin, can also add according to actual feelings additives such as using silane coupling agent, pigment, emulsifying agent, dispersion agent.
Above-mentioned compositions of thermosetting resin, may be used for manufacturing semiconductor-encapsulating material, lamination adhering film, binding agent, resin cast material, conductive paste etc.
Present invention also offers the prepreg adopting above-mentioned resin combination to make, above-mentioned resin combination dissolution with solvents is made glue, then strongthener is immersed in above-mentioned glue; After flooding after strongthener heat drying, described prepreg can be obtained.
One or more in described solvent selected from acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or inorganic fabric.
Be immersed in by strongthener in glue, then heat drying, heat drying 1-30 minute at the temperature of 100-200 degree, makes it semicure usually.
Present invention also offers the veneer sheet adopting above-mentioned resin combination to make, be covered with tinsel at one by the single or double of above-mentioned prepreg, or after being superposed at least 2 by above-mentioned prepreg, be covered with tinsel at its single or double, hot compacting, can obtain described veneer sheet.
The quantity of described prepreg is that laminate thickness is as requested determined, available one or more.Described tinsel, as long as the material used in electrically insulating material purposes, is not particularly limited, and can be Copper Foil, also can be aluminium foil, and their thickness is not particularly limited.In addition, molding condition is applicable electrically insulating material veneer sheet and multiple-plate method such as, such as can use multiple deck press, multi-layer vacuum press, continuous molding, hot compacting machine etc., temperature 100-250 DEG C, pressure 2-100kg/cm2, the scope internal shaping of 0.1-5 hour heat-up time.
Beneficial effect of the present invention: resin combination of the present invention not only has excellent dielectric properties, and there is excellent complete processing controllability, have suitable reactive behavior when adding promotor, compared with prior art, the operability in the course of processing significantly improves.The veneer sheet obtained by compositions of thermosetting resin of the present invention has excellent dielectric properties, compared with prior art, specific inductivity and dielectric loss all decline to a great extent, and can show fully low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
Embodiment
To be further described by specific embodiment below.But should be appreciated that specific embodiment only for explaining the present invention, the protection domain be not intended to limit the present invention.Instrument, equipment, reagent, method etc. used in the application, as do not specialized, are instrument, equipment, reagent and method that this area is conventional.When without special instruction, " part " representative " weight part ", " % " representative " % by weight ".Embodiment 1 ~ 4 is synthesis of terpolymer of the present invention, and comparative example 1 is the synthesis of phenolic hydroxyl group group terpolymer, and embodiment 5 ~ 10 and comparative example 2 ~ 3 are preparation and the evaluation of physical property of compositions of thermosetting resin.Hereinafter without special instruction, " part " representative " weight part ", " % " representative " % by weight ".
Embodiment 1
Maleic anhydride 49g, dicyclohexylcarbodiimide 110g, phenol 100g are fully dissolved in ethyl acetate to be placed in three neck reaction flasks and fully to mix, then the DMAP of 1.0g is under agitation added, after reacting 4 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, is then distilled by obtained product, purifying obtains toxilic acid diphenyl ester.Then, obtained above toxilic acid diphenyl ester 80g, vinylbenzene 830g, maleic anhydride 175g are fully dissolved in butanone, add 45g benzoyl peroxide initiator and 100g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-1) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 7000g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ）
，（Ⅱ）
，（Ⅲ）
，
In formula, x, y, z is positive integer, and the ratio that x is 3.8:1, y and z with the ratio of (y+z) is 6:1, R1, R2, R3, R4 are hydrogen atom, and R5, R6 are phenoxy group.
Embodiment 2
Maleic anhydride 49g, dicyclohexylcarbodiimide 110g, phenol 100g are fully dissolved in ethyl acetate to be placed in three neck reaction flasks and fully to mix, then the DMAP of 1.5g is under agitation added, after reacting 4 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, is then distilled by obtained product, purifying obtains toxilic acid diphenyl ester.Then, obtained above toxilic acid diphenyl ester 400g, vinylbenzene 1040g, maleic anhydride 33g are fully dissolved in butanone, add 50g benzoyl peroxide initiator and 100g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-2) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 11000g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ）
，（Ⅱ）
，（Ⅲ）
，
In formula, x, y, z is positive integer, and the ratio that x is 5.5:1, y and z with the ratio of (y+z) is 1:5, R1, R2, R3, R4 are hydrogen atom, and R5, R6 are phenoxy group.
Embodiment 3
By maleic anhydride 49g, dicyclohexylcarbodiimide 110g, 3-hydroxyl-1,2,3-phentriazine-4 (3H)-one 170g is fully dissolved in ethyl acetate and is placed in three neck reaction flasks and fully mixes, then 2.0g4-Dimethylamino pyridine is under agitation added, after reacting 8 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, is then distilled by obtained product, purifying obtains toxilic acid diphenyl ester.Then, obtained above maleic acid diester 267g, vinylbenzene 312g, maleic anhydride 33g are fully dissolved in butanone, add 20g benzoyl peroxide initiator and 50g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-3) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 14000g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ）
，（Ⅱ）
，（Ⅲ）
，
In formula, x, y, z is positive integer, and the ratio that x is 3:1, y and z with the ratio of (y+z) is 2:1, R1, R2, R3, R4 are hydrogen atom, and R5, R6 are:
。
Embodiment 4
Maleic anhydride 49g, dicyclohexylcarbodiimide 110g, N-(4-hydroxy phenyl) maleimide 200g are fully dissolved in ethyl acetate to be placed in three neck reaction flasks and fully to mix, then under agitation add the DMAP of 5.0.g, react separating-purifying after 10 hours under room temperature and obtain toxilic acid diphenyl ester.Then, obtained above maleic acid diester 150g, vinylbenzene 208g, maleic anhydride 67g are fully dissolved in butanone, add 15g benzoyl peroxide initiator and 35g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-3) under 70 ~ 90 DEG C of conditions, its number-average molecular weight is 21000g/mol, comprises following three kinds of structural units in its structural formula:
（Ⅰ）
，（Ⅱ）
，（Ⅲ）
，
In formula, x, y, z is positive integer, and the ratio that x is 2:1, y and z with the ratio of (y+z) is 2:1, R1, R2, R3, R4 are hydrogen atom, and R5, R6 are: 4-maleimide phenoxyl.
Embodiment 5
Maleic anhydride 49g, dicyclohexylcarbodiimide 110g, phenol 50g are fully dissolved in ethyl acetate to be placed in three neck reaction flasks and fully to mix, then 0.5g4-Dimethylamino pyridine is under agitation added, react 4 hours under room temperature, under agitation add 16g methyl alcohol afterwards, react separating-purifying after 6 hours and obtain maleic acid diester.Then, obtained above maleic acid diester 103g, vinylbenzene 104g, maleic anhydride 49g are fully dissolved in butanone, add 10g benzoyl peroxide initiator and 25g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-1) under 70 ~ 90 DEG C of conditions, its number-average molecular weight is 4800g/mol, comprises following three kinds of structural units in its structural formula:
（Ⅰ）
，（Ⅱ）
，（Ⅲ）
，
In formula, x, y, z is positive integer, and the ratio that x is 1:1, y and z with the ratio of (y+z) is 1:1, R1, R2, R3, R4 are hydrogen atom, and R5 is phenoxy group, and R6 is methoxyl group.
Comparative example 1
Be 4:1 with toluene by the ratio of styrene-maleic anhydride copolymer resin 250g(vinylbenzene and maleic anhydride) be placed in after three neck reaction flasks dissolve completely with the third diphenol 120g, 0.5g second two base aniline is added under stirring, then 70 ~ 80 DEG C of reactions 4 hours are warming up to, namely obtain the styrene-maleic anhydride copolymer resin B-1 that the third diphenol is modified, its structural formula is as follows:
In formula, n is the integer of 1 ~ 30, and x, y are integer and the ratio of x and y is 4:1; R group is
。
Embodiment 5 ~ 10 and comparative example 2 ~ 3
According to the formula that table 1 is recorded, all components is mixed with the resin adhesive liquid that solid content is 60%, curing catalyst adds according to the amount of 0.5phr.
Then on gelation time tester, test the reactivity of gelation time in order to evaluating resin composition of glue, thus evaluating resin is combined in processing performance in the course of processing, test condition is 171 DEG C.
Then veneer sheet is made under the following conditions, and by following method evaluation flame retardant resistance, wet-hot aging performance and dielectric characteristics.The results are shown in table 1.
< veneer sheet manufacturing conditions >
Base material: ordinary electronic level 2116 glass-fiber-fabric;
The number of plies: 5;
Shaping rear sheet metal thickness: 1.0mm;
Preimpregnation semicure condition: 165 DEG C/5min;
Condition of cure: 150 DEG C/60min+190 DEG C/120min;
< thermotolerance > second-order transition temperature (Tg) characterizes thermotolerance, according to dsc, measures according to the DSC method of IPC-TM-650 2.4.25 defined.
The mensuration > specific inductivity of < specific inductivity and dielectric loss tangent uses flat band method according to IPC-TM-650 2.5.5.9, measures the specific inductivity under 1GHz; Dielectric loss tangent: use flat band method according to IPC-TM-650 2.5.5.9, measures the dielectric loss factor under 1GHz.
< flame retardant resistance > measures according to UL94 method.Not fire-retardantly to represent with " No ".
Table 1
The explanation of table 1:
A-1: terpolymer (A-1) obtained in embodiment 1;
A-2: terpolymer (A-2) obtained in embodiment 2;
A-3: terpolymer (A-3) obtained in embodiment 3;
A-4: terpolymer (A-4) obtained in embodiment 4;
A-5: terpolymer (A-5) obtained in embodiment 4;
B-1: terpolymer (B-1) obtained in comparative example 1;
SMA: self-control styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 3:1;
Epoxy resin 1: dicyclopentadiene type resol, chemical drug, epoxy equivalent (weight) 265g/eq;
Epoxy resin 2: phosphorous epoxy resin, CHIN YEE PE-315, epoxy equivalent (weight) 240g/eq, phosphorus content 3.5%wt;
Equivalence ratio: the equivalence ratio of active ester groups in epoxy group(ing) and upgrading type Zelan 338;
Cyanate: bisphenol A cyanate ester resin, Lonza, BA-3000S;
Bismaleimides: self-control allyl group modified BMI resin prepolymer, synthetic method is by 100 parts of bimaleimide resins and 50 parts of allylic cpds, at 130 DEG C of temperature, react 85min, be cooled to room temperature after reaction terminates and obtain, its number-average molecular weight is 3500g/mol;
Phosphorus-containing phenolic aldehyde: Dow 92741 phosphorus content 9.2%wt;
Toughner: nucleocapsid particles toughner, EVONIK;
Curing catalyst: 2-methyl-4-ethyl imidazol(e);
Filler: silicon-dioxide.
From upper table 1, what embodiment 5 ~ 11 adopted is terpolymer cured epoxy resin in the present invention, compare the comparative example 2 using phenolic hydroxyl group styrene-maleic anhydride copolymer cured epoxy resin, significantly reduce the low-k after epoxy resin cure, low-dielectric loss tangent.Embodiment 5 ~ 11 and comparative example 3 compare, and have suitable gelation time, show that resin system has suitable reactivity, are conducive to the improvement of processing technology and storage.Embodiment 9 with the addition of the resin system of cyanate ester resin as co-curing agent, compares embodiment 5 ~ 8, have more excellent resistance toheat and dielectric properties.Embodiment 10 with the addition of the resin system of bimaleimide resin as co-curing agent, compares embodiment 5 ~ 8, have more excellent resistance toheat and dielectric properties.
Claims (10)
1. a terpolymer, is characterized in that, the structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III represent;
(I)
, in formula, x is positive integer, R in formula
1for the alkyl of hydrogen atom, C1 ~ C5, R
2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C5;
(II)
, in formula, y is positive integer, R
3, R
4respective independence, can be identical or different, is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
(III)
, in formula, z is positive integer, R
3', R
4' independent separately, can be identical or different, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R
5, R
6respective independence, can be identical or different, is selected from following group:
,
,
,
,
,
,
,
,
,
,
,
,
, wherein R
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5; R
0for the alkylene of the alkyl of C1 ~ C5, the cycloalkyl of C1 ~ C8, the phenylalkyl of C7 ~ C10 or C3 ~ C10, but R
5or R
6in have at most a group to be
, the number-average molecular weight of described terpolymer is 1500 ~ 50000g/mol.
2. terpolymer according to claim 1, is characterized in that, the ratio that in described terpolymer, x and the ratio of (y+z) are 1:1 ~ 15:1, y and z is 1:10 ~ 10:1.
3. terpolymer according to claim 1, is characterized in that, described R
5or R
6group be maleimide phenoxyl,
or
.
4. a compositions of thermosetting resin, comprising:
(1) epoxy resin;
(2) terpolymer described in any one of claim 1-3,
In its epoxy group and terpolymer, the molar ratio of acid anhydrides and ester group total amount is 1:5 ~ 4:1.
5. compositions of thermosetting resin according to claim 4, it is characterized in that, described compositions of thermosetting resin also comprises co-curing agent, described co-curing agent is selected from amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate, preferably at least one in bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
6. compositions of thermosetting resin according to claim 5, is characterized in that, described co-curing agent is cyanate ester resin, and the weight ratio of cyanate ester resin and epoxy resin is 100:20 ~ 100:300.
7. compositions of thermosetting resin according to claim 5, is characterized in that, described co-curing agent is bimaleimide resin, and the weight ratio of bismaleimides and terpolymer is 100:20 ~ 100:200.
8. the compositions of thermosetting resin according to any one of claim 4 ~ 7, is characterized in that, also comprises toughner, fire retardant, mineral filler and curing catalyst.
9. a prepreg, is characterized in that, the resin combination dissolution with solvents described in any one of claim 4 ~ 8 is made glue, is then immersed in by strongthener in above-mentioned glue; After the strongthener heat drying after dipping, described prepreg can be obtained.
10. a veneer sheet, is characterized in that, is covered with tinsel at the single or double of a prepreg according to claim 9, or after at least 2 prepregs superpositions according to claim 9, be covered with tinsel at its single or double, hot compacting, described veneer sheet can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389721.6A CN104211847B (en) | 2014-08-08 | A kind of terpolymer and compositions of thermosetting resin thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410389721.6A CN104211847B (en) | 2014-08-08 | A kind of terpolymer and compositions of thermosetting resin thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN104211847A true CN104211847A (en) | 2014-12-17 |
| CN104211847B CN104211847B (en) | 2017-01-04 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221126A (en) * | 2016-08-29 | 2016-12-14 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN106243626A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN106336662A (en) * | 2016-08-29 | 2017-01-18 | 苏州生益科技有限公司 | Thermosetting resin composition and prepreg and laminated board manufactured from same |
| CN109943047A (en) * | 2019-01-25 | 2019-06-28 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN113402500A (en) * | 2021-06-30 | 2021-09-17 | 长沙新材料产业研究院有限公司 | Polyimide modifier and resin composition containing same |
| CN114149684A (en) * | 2021-10-29 | 2022-03-08 | 航天特种材料及工艺技术研究所 | Low-temperature curing low-dielectric high-toughness cyanate ester resin and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221126A (en) * | 2016-08-29 | 2016-12-14 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN106243626A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN106336662A (en) * | 2016-08-29 | 2017-01-18 | 苏州生益科技有限公司 | Thermosetting resin composition and prepreg and laminated board manufactured from same |
| CN109943047A (en) * | 2019-01-25 | 2019-06-28 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its preparation |
| CN109943047B (en) * | 2019-01-25 | 2022-02-08 | 苏州生益科技有限公司 | Thermosetting resin composition, and prepreg and laminated board prepared from thermosetting resin composition |
| CN113402500A (en) * | 2021-06-30 | 2021-09-17 | 长沙新材料产业研究院有限公司 | Polyimide modifier and resin composition containing same |
| CN113402500B (en) * | 2021-06-30 | 2022-07-12 | 长沙新材料产业研究院有限公司 | Polyimide modifier and resin composition containing same |
| CN114149684A (en) * | 2021-10-29 | 2022-03-08 | 航天特种材料及工艺技术研究所 | Low-temperature curing low-dielectric high-toughness cyanate ester resin and preparation method thereof |
| CN114149684B (en) * | 2021-10-29 | 2023-05-09 | 航天特种材料及工艺技术研究所 | Low-temperature-cured low-dielectric high-toughness cyanate resin and preparation method thereof |
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