CN103131008A - Bismaleimide prepolymer and synthesis method thereof - Google Patents
Bismaleimide prepolymer and synthesis method thereof Download PDFInfo
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- CN103131008A CN103131008A CN201310025380XA CN201310025380A CN103131008A CN 103131008 A CN103131008 A CN 103131008A CN 201310025380X A CN201310025380X A CN 201310025380XA CN 201310025380 A CN201310025380 A CN 201310025380A CN 103131008 A CN103131008 A CN 103131008A
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Abstract
The invention provides a bismaleimide prepolymer and a synthesis method of the bismaleimide prepolymer. According to the synthesis method, bismaleimide (BMI) and diallyl bisphenol compounds are chosen to be raw materials, and tertiary phosphine used as a catalytic agent is added at an opportune moment for synthesizing modified BMI resin. The modified BMI resin produced through the synthesis method has a specific molecular structure and specific molecular weight distribution and is good in solubility in a solution of dimethyl formamide (DMF) or a solution of acetone or a solution of butanone, the storage life of the modified BMI resin is longer than 180 days, and within the storage life, no resin precipitation phenomenon or gelation phenomenon happens. A copper-clad laminate (CCL) produced with the modified BMI resin has pretty high bending strength, impact strength and peel strength, a pretty high glass transition temperature, a pretty high thermal decomposition temperature and a good heat and humidity resistance property, and can be used in high-temperature resistant and high multi-layer circuits.
Description
Technical field
The present invention relates to the field of chemical synthesis, relate in particular to a kind of bismaleimides prepolymer, its synthetic method, its resin combination and with its prepreg of making and veneer sheet.
Background technology
Bismaleimides (BMI) resin can satisfy the requirement of making high-speed figure and high frequency printed circuit boards base material, is usually used in making the high-performance multilayer plate.The bimaleimide resin monomer reactivity is high, discharges without molecule during polymerization, and end properties is stable, can keep higher physical and mechanical properties in wide temperature range.The Tg that the bimaleimide resin tool is higher, its dipolar loss is little in wide temperature range, so electrical property is very good, has the advantages such as specific inductivity is lower, dielectric loss is little, volume resistance is large.These performances still can remain on higher level in wider temperature and range of frequency.But that bimaleimide resin exists is poorly soluble, the shelf lives is short, mold temperature is high, cured article fragility is large, thereby has limited its use, therefore need to carry out modification to it.
Present bi-maleimide modified aspect is used morely aromatic diamine modification, epoxy resin modification, allylic cpd modification, modified rubber, cyanate modified, polyphenyl ether modified, thermoplastic resin modified etc.
1984, Giby-Geigy withdrawed from the Xu292 resin, had started the novel method of Allylphenyl Compounds modified bismaleimide resin.The BMI resin system of this method modification is soluble in acetone, butanone equal solvent, and the adhesivity of prepreg is good, and system good toughness after solidifying, temperature classification is high, humidity resistance good, dielectric properties, mechanical property is excellent and cause people's common concern.Described in patent CN03134502.6, use the allylic cpd modified bismaleimide resin, mention at 130 ~ 150 ℃ of lower polymerase 10 ~ 60min; Patent CN101735456A and CN1200970C mention BMI and epoxy resin and allylic cpd Hybrid Heating are carried out pre-polymerization; Patent CN200910264756.6 and CN101775139A mention BMI and allylic cpd and organosilicon and water one are reacted, in order to prepare MODIFIED BMI; Patent CN201110088156.6 mentions BMI and allylic cpd at 120 ~ 160 ℃ of lower pre-polymerization 20 ~ 120min; Mention in patent CN1213084C Hybrid Heating polymerizations such as BMI, allylic cpd, epoxy acrylates; Mention in CN1200015C, with the performed polymer of nanometer particle-modified BMI and allylic cpd; CN1279110C mentions with thermoplastic resin modified BMI and allylic cpd in order to prepare microballoon.Above all patents are all just mentioned the simple pre-polymerization of DABPA and BMI and other resin, do not mention the catalyzer problem in the synthetic resins process.CN101735611A mentions BMI and DABPA are reacted 2h under 130 ℃, then this prepolymer is mixed at normal temperatures with solvent, catalyzer, epoxy resin etc.Do not mention prepolymer is being reacted for some time under the catalyzer existence condition under 130 ~ 160 ℃, generate the performed polymer of new texture and do not mention the storage situation of performed polymer in solution that generate.But for now, also there are a lot of deficiencies in the stability of resin prepolymer, and the Chinese scholars paper has all been avoided the storage characteristics problem of resin, just mechanical property or the dielectric properties of resin is set forth.Mention take rare-earth oxide as catalyzer the pre-polymerization of catalysis BMI and allylic cpd, the shelf lives to 100 day that can improve resin in CN101768269A.But it does not mention the structure of institute's synthetic resins and the molecular weight distribution situation of performed polymer, does not mention thermal characteristics, mechanical property and dielectric properties after the modification of gained prepolymer resin yet.
Need stability better in this area, the prepolymer of the bismaleimides of being more convenient for storing.
Summary of the invention
The object of the present invention is to provide a kind of novel method of prepolymer of synthetic bismaleimides, the prepolymer that described method synthesizes has specified molecular weight and distributes and have in solvent and be not less than the shelf lives of 180 days.
In a first aspect of the present invention, a kind of bismaleimides prepolymer of star structure is provided, it is characterized in that, the structural formula of described prepolymer is as follows:
Wherein: R
1For
R wherein
3Be the alkyl of phenyl or carbon number 1 ~ 3 independently of one another; R
2For
N1 in the formula I, n2, n3 are the integer of 0-42 independently of one another, and wherein at least one is not 0;
Wherein preferably the molecular weight distribution of described prepolymer is: molecular weight 300 ~ 500 is that 25%-65% and molecular weight 2000 ~ 5000 are 11%-64%.
In a second aspect of the present invention, the synthetic method of bismaleimides as described in first aspect (BMI) prepolymer is provided, it comprises that the compound with formula II contacts with catalyzer:
Wherein: R
1And R
2As defined in claim 1, n4 is 1 ~ 42 positive integer.
The synthetic method of described bismaleimides prepolymer of the present invention can comprise:
(1) with the diallyl bisphenol compound and bismaleimides mixes in solvent or with bismaleimides join heat the diallyl bisphenol compound in mix, with 120 ~ 160 ℃, preferred 140-160 ℃, reacted the compound of preferred 2 ~ 4 hours acquisition formula II 1 ~ 5 hour; With
(2) under the temperature of reaction of step (1), add described catalyzer and described formula II reaction 1 ~ 3 hour, preferred 1.5-2.5 hour, obtain described bismaleimides prepolymer formula I;
Wherein, preferably described bismaleimide compound is 1.2:1-4:1 with the ratio of the amount of substance of described diallyl bisphenol compound, is more preferably 1.5:1-3:1, is most preferably 2:1;
Preferably the consumption of described catalyzer be described bismaleimide compound and described diallyl bisphenol compound mixture quality 0.05 ~ 1.9%, 0.5-1.5% more preferably.
In the synthetic method of described bismaleimides prepolymer of the present invention, described catalyzer can be three grades of phosphines, being preferably triaryl phosphine or trialkyl phosphine, is more preferably one or more the mixture in triphenylphosphine, trimethyl-phosphine, tri-n-butyl phosphine and tricyclohexyl phosphine.
In the synthetic method of described bismaleimides prepolymer of the present invention, the molecular structure of described bismaleimides can for
R wherein
1As defining in first aspect, be preferably one or more the mixture in diphenyl methane dimaleimide, Diphenyl Ether Bismaleimide and sulfobenzide bismaleimides.
In the synthetic method of described bismaleimides prepolymer of the present invention, described diallyl bisphenol compound can be one or more the mixture in diallyl bisphenol, diallyl Bisphenol F and diallyl bisphenol S.
In a third aspect of the present invention, the resin combination that comprises as the described prepolymer of first aspect is provided, preferably described resin combination comprises described bismaleimides prepolymer, epoxy resin, amine curing agent and promotor, more preferably bismaleimides prepolymer, epoxy resin, amine curing agent, promotor, fire retardant and filler further preferably comprise 0 ~ 300 part of 100 parts of described bismaleimides prepolymers, 20 ~ 100 parts of epoxy resin, 2 ~ 20 parts of amine curing agents, 0 ~ 0.75 part of promotor, 0 ~ 20 part of fire retardant and filler;
Wherein preferably epoxy resin for have epoxy resin more than two or more epoxide groups in 1 molecule resin, at least a in bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and phenol aldehyde type epoxy resin for example;
Preferably amine curing agent is aromatic diamines, for example Ursol D, mphenylenediamine, diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 3,4`-diaminodiphenyl ether, 4,4`-two amido ditans, 3,3`-dimethyl-4,4`-two amido ditans, 4,4`-diaminodiphenylsulfone(DDS), 4,4`-diamino-hexichol Oxy-1 ", 4 "-benzene, 4,4`-diamino-hexichol Oxy-1 "; 3 "-benzene, 3,3`-diamino-hexichol Oxy-1 ", 3 "-at least a in benzene, diamino-diphenyl ether isopropyl diphenyl (base) and diethyl toluene diamine;
More preferably amine curing agent is Ursol D, mphenylenediamine, diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 4, at least a in 4`-diaminodiphenylsulfone(DDS) and diethyl toluene diamine;
Preferably, promotor is at least a in glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2 isopropyl imidazole, 2-phenyl-4-methylimidazole, 2-dodecyl imidazoles, 1-1-cyanoethyl-2-methylimidazole, Boron Trifluoride Ethylamine, triethylamine and benzyldimethylamine;
Preferred fire retardant is bromide fire retardant, at least a in tetrabromobisphenol-A, hexabromocyclododecane, decabromodiphynly oxide, TDE, octa-BDE and pentabromotoluene; Be more preferably at least a in TDE and hexabromocyclododecane;
preferably, filler is the organic or inorganic filler, be preferably powder, single crystal fibre, glass or staple fibre, wherein said powder is preferably aluminium hydroxide, magnesium hydroxide, kaolin, hydrotalcite, titanium oxide, Calucium Silicate powder, beryllium oxide, boron nitride, glass powder, zinc borate, the aluminium nitrogen compound, silicon nitride, silicon carbide, magnesium oxide, zirconium white, mullite, titanium dioxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene or polyphenylene oxide powder, described single crystal fibre is preferably potassium titanate, silicon carbide, silicon nitride or alumina single crystal fiber, and wherein said silicon powder can be spherical silica, fused silica or crystallinity silicon-dioxide.
In a fourth aspect of the present invention, a kind of prepreg is provided, it comprises resin combination described according to the third aspect and at least a strongthener, wherein said strongthener is inorganic or organic materials, and preferably described inorganic materials comprises woven fabric or non-woven fabrics or the paper of glasscloth, carbon fiber, boron fibre, metal; Preferably organic materials comprises fabric or non-woven fabrics or the paper of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene.
In a fifth aspect of the present invention, the prepreg that is made by the described prepreg of fourth aspect is provided, preferably described prepreg is the printed electronic circuit bonding sheet.
In a sixth aspect of the present invention, a kind of laminate is provided, it comprises as the 5th described prepreg in aspect and one deck conductive seed layer at least, preferably described conductive seed layer be Copper Foil and preferably described laminate be the use in printed circuit board copper-clad laminate.
Beneficial effect of the present invention:
1, method of the present invention is simple to operate, and reaction conditions is gentle, raw materials usedly easily obtains, and is easy to scale operation;
2, the synthetic bismaleimides prepolymer of method of the present invention has specified molecular weight and distributes and have in solvent and be not less than the shelf lives of 180 days;
3, the synthetic bismaleimides prepolymer of method of the present invention does not have gel time to shorten or the gel between the shelf lives, the situation of separating out occur;
4, adopt the synthetic prepared copper-clad plate of bismaleimides prepolymer of method of the present invention to have larger flexural strength, shock strength and peel strength, higher second-order transition temperature, heat decomposition temperature and good humidity resistance can be used in high temperature resistant and high multilayer circuit.
Description of drawings
Fig. 1 shows the infrared spectrum of the prepolymer that catalyzer joining day difference obtains.
Embodiment
Below by specific embodiment, the present invention is elaborated, but and do not limit the present invention in any way.
36 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 164 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and reaction 5 hours at this temperature, then add 3.8 gram triphenylphosphines, and at the stopped reaction after 1 hour of reaction at this temperature, and shift out rapidly and cool to room temperature, the reddish brown solid obtained.
Embodiment 2
36 gram diallyl bisphenol Ss and 67 gram N-Methyl pyrrolidone (NMP) are heated to 100 ℃ in there-necked flask, then add 164 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and reaction 5 hours at this temperature, then add 3 gram triphenylphosphines, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, blackish green look liquid obtained.
Embodiment 3
45 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 155 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 150 ℃, and reaction 3 hours at this temperature, then add 2.2 gram triphenylphosphines, and at the stopped reaction after 3 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, the reddish brown solid obtained.
Embodiment 4
73 gram diallyl bisphenols and 67 gram DMAC are heated to 100 ℃ in there-necked flask, then add 127 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 145 ℃, and reaction 4 hours at this temperature, then add 1.4 gram triphenylphosphines, and at the stopped reaction after 3 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, blackish green viscous liquid obtained.
Embodiment 5
51 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 149 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 145 ℃, and reaction 3 hours at this temperature, then add 1 gram triphenylphosphine, and at the stopped reaction after 3 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, the reddish brown solid obtained.
Embodiment 6
51 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 149 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and reacted 2 hours at this temperature.Then continue reaction 1 hour after adding 0.92 gram triphenylphosphine, stopped reaction, and shift out rapidly and cool to room temperature, obtain blackish green liquid.
Embodiment 7
60 gram diallyl Bisphenol F are heated to 100 ℃ in there-necked flask, then add 140 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 135 ℃, and reaction 4 hours at this temperature, then add 0.8 gram trimethyl-phosphine, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, light brown viscous shape liquid obtained.
Embodiment 8
60 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 140 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 130 ℃, and reaction 2 hours at this temperature, then add 0.7 gram tri-n-butyl phosphine, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, light brown viscous shape liquid obtained.
Embodiment 9
63 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 127 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 130 ℃, and reaction 2 hours at this temperature, then add 0.6 gram triphenylphosphine, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, obtain softening temperature and be the reddish brown solid of 90 ℃.
Embodiment 10
63 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 127 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and reaction 3 hours at this temperature, then add 0.4 gram tricyclohexyl phosphine, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, sorrel liquid obtained.
Embodiment 11
106 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 94 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 150 ℃, and reaction 5 hours at this temperature, then add 0.2 gram triphenylphosphine, and at the stopped reaction after 2 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, light brown viscous shape liquid obtained.
Embodiment 12
106 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 94 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 145 ℃, and reaction 5 hours at this temperature, then add 0.1 gram triphenylphosphine, and at the stopped reaction after 1 hour of reaction at this temperature, and shift out rapidly and cool to room temperature, light brown viscous shape liquid obtained.
Comparative Examples 1
106 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 94 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and at the stopped reaction after 5 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, the brown color brittle solid obtained.
Comparative Examples 2
84 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 116 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and at the stopped reaction after 6.5 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, brown color liquid obtained.
Comparative Examples 3
63 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 127 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and at the stopped reaction after 4 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, brown color liquid obtained.
Comparative Examples 4
60 gram diallyl bisphenols and 67 gram DMF are heated to 100 ℃ in there-necked flask, then add 140 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 155 ℃, and at the stopped reaction after 5 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, brown color liquid obtained.
Comparative Examples 5
51 gram diallyl bisphenols are heated to 100 ℃ in there-necked flask, then add 149 gram diphenyl methane dimaleimides, stir 30min at this temperature, it is mixed.Then be warmed up to 130 ℃, and at the stopped reaction after 3 hours of reaction at this temperature, and shift out rapidly and cool to room temperature, the brown color transparent solid obtained.
Embodiment 13 ~ 17:
BMI resin synthetic in embodiment 6 is prepared according to the following formulation, and the first fully dissolving in solvent DMF with BMI resin and dihydroxyphenyl propane linear phenolic epoxy resin mixes.Then add the diethyl toluene diamine and the 2-phenyl-4-methylimidazole that are dissolved in advance in DMF, it is mixed.Then add fire retardant, after being disperseed, it adds filler molten silicon micro mist and solvent, making the mixed system solid content is 70%, and high-speed stirring is after 20 minutes, with 2116 woven fiber glass gluings, and dried by the fire 2 ~ 10 minutes in 155 ℃ of baking ovens, make prepreg, then cover Copper Foil with 8 prepreg two sides, solidified 200 minutes in 210 ℃ of lower vacuum pressed.Obtain following plate property:
Embodiment 18 Performance Detection
Prepolymer prepared in embodiment 1-5 and Comparative Examples 1-5 take identical formulated as resin combination, and is carried out parallel contrast to the physicochemical property of each resin combination, and described formula is the synthetic BMI:375g of each embodiment; Bisphenol A-type linear phenolic epoxy resin: 300g; Diethyl toluene diamine: 37.2g; 2-phenyl-4-methylimidazole: 0.5g; Fire retardant: 68g; Molten silicon micro mist: 125g; DMF:250g, the evenly rear gluing of above mixture is solidified by same program and is made copper-clad plate, and its performance test results sees Table 1:
Table 1 the performance test results
Embodiment 19
At first, with the performed polymer 100g in embodiment 1,32g High Bromine epoxy Resin A(epoxy equivalent (weight) 400g/mol, solid content 61%), 14g isocyanate modified epoxy resin B(epoxy equivalent (weight) 360g/mol, solid content 76%), 20gDMF, stir about half an hour, the 303g aluminum oxide is fully mixed with 80gDMF, then resin is mixed with filler, the evenly rear gluing of above mixture is solidified by same program and is made copper-clad plate A.
Afterwards, with the performed polymer 100g in Comparative Examples 5,32g High Bromine epoxy Resin A(epoxy equivalent (weight) 400g/mol, solid content 61%), 14g isocyanate modified epoxy resin B(epoxy equivalent (weight) 360g/mol, solid content 76%), 0.05g triphenylphosphine, 20gDMF, stir about half an hour, the 303g aluminum oxide is fully mixed with 80gDMF, then resin is mixed with filler, the evenly rear gluing of above mixture is solidified by same program and is made copper-clad plate B.
The copper-clad plate of adopting different performed polymers to make is carried out Performance Ratio, the results are shown in Table 2.
Table 2 the performance test results
Embodiment 20 examination of infrared spectrum
Prepare the bismaleimides prepolymer according to the described method of embodiment 5 above, wherein said catalyzer respectively at step 1, step 2(namely fully according to preparation method of the present invention) add or do not add catalyzer.And the raw material that prepolymerization reaction does not occur that mixes and the three kinds of prepolymers that obtain are carried out examination of infrared spectrum, it the results are shown in Figure 1.
The spectrogram explanation: this spectrogram is the bismaleimides (BMI) and diallyl bisphenol (DABPA) with phase jljl amount ratio, mix (A) to react initial raw material, do not add catalyzer (B), initially add catalyzer (C), the infrared spectra that adds catalyzer (D) midway, with BMI at 1154cm
-1Charateristic avsorption band is the reference peak, makes its peak height identical.By contrast 996cm
-1The two key characteristic absorbance of the end group at place, know, relative initial mixing, do not add catalyzer and add greatly weakening of catalyzer absorption herein midway, absorption in this wave number there is not change substantially after catalyst reaction and initially add, illustrate not add catalyzer or add catalyzer that the first step pre-polymerization has all occured midway, generated formula II.And comparison 1186cm
-1The peak height situation, the contrast three grades of phosphines Catalysis Principles, can reflect thus add three grades of phosphine catalysts midway after, can form the trimerical pentacyclic tertiary carbon of a large amount of BMI by formula II, thereby reflect the star performed polymer formula I that has generated as on claim.
Applicant's statement, the present invention illustrates detailed features of the present invention and method by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and method, does not mean that namely the present invention must rely on above-mentioned detailed features and method could be implemented.The person of ordinary skill in the field should understand; any improvement in the present invention; to the increase of the equivalence replacement of the selected material of the present invention and step and subsidiary material and step, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. the bismaleimides prepolymer of a star structure, is characterized in that, the structural formula of described prepolymer is as follows:
Wherein: R
1For
R wherein
3Be the alkyl of phenyl or carbon number 1 ~ 3 independently of one another; R
2For
N1 in the formula I, n2, n3 are the integer of 0-42 independently of one another, and wherein at least one is not 0;
Wherein preferably the molecular weight distribution of described prepolymer is: molecular weight 300 ~ 500 is that 25%-65% and molecular weight 2000 ~ 5000 are 11%-64%.
2. the synthetic method of bismaleimides prepolymer as claimed in claim 1, it comprises that the compound with formula II contacts with catalyzer:
Wherein: R
1And R
2As defined in claim 1, n4 is 1 ~ 42 positive integer.
3. synthetic method as claimed in claim 2, described method comprises:
(1) with the diallyl bisphenol compound and bismaleimides mixes in solvent or with bismaleimides join heat the diallyl bisphenol compound in mix, with 120 ~ 160 ℃, preferred 140-160 ℃, reacted the compound of preferred 2 ~ 4 hours acquisition formula II 1 ~ 5 hour; With
(2) under the temperature of reaction of step (1), add described catalyzer and described formula II reaction 1 ~ 3 hour, preferred 1.5-2.5 hour, obtain described bismaleimides prepolymer formula I;
Wherein, preferably described bismaleimide compound is 1.2:1-4:1 with the ratio of the amount of substance of described diallyl bisphenol compound, is more preferably 1.5:1-3:1, is most preferably 2:1;
Preferably the consumption of described catalyzer be described bismaleimide compound and described diallyl bisphenol compound mixture quality 0.05 ~ 1.9%, 0.5-1.5% more preferably.
4. as the method for claim 2 or 3, wherein, described catalyzer is three grades of phosphines, is preferably triaryl phosphine or trialkyl phosphine, is more preferably one or more the mixture in triphenylphosphine, trimethyl-phosphine, tri-n-butyl phosphine and tricyclohexyl phosphine.
5. method as described in any one in claim 3-4, is characterized in that, the molecular structure of described bismaleimides is
R wherein
1As definition in claim 1, be preferably one or more the mixture in diphenyl methane dimaleimide, Diphenyl Ether Bismaleimide and sulfobenzide bismaleimides.
6. method as described in any one in claim 2-5, is characterized in that, described diallyl bisphenol compound is one or more the mixture in diallyl bisphenol, diallyl Bisphenol F and diallyl bisphenol S.
7. the resin combination that comprises prepolymer as claimed in claim 1, preferably described resin combination comprises described bismaleimides prepolymer, epoxy resin, amine curing agent and promotor, more preferably bismaleimides prepolymer, epoxy resin, amine curing agent, promotor, fire retardant and filler further preferably comprise 0 ~ 300 part of 100 parts of described bismaleimides prepolymers, 20 ~ 100 parts of epoxy resin, 2 ~ 20 parts of amine curing agents, 0 ~ 0.75 part of promotor, 0 ~ 20 part of fire retardant and filler;
Wherein preferably epoxy resin for have epoxy resin more than two or more epoxide groups in 1 molecule resin, at least a in bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and phenol aldehyde type epoxy resin for example;
Preferably amine curing agent is aromatic diamines, for example Ursol D, mphenylenediamine, diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 3,4`-diaminodiphenyl ether, 4,4`-two amido ditans, 3,3`-dimethyl-4,4`-two amido ditans, 4,4`-diaminodiphenylsulfone(DDS), 4,4`-diamino-hexichol Oxy-1 ", 4 "-benzene, 4,4`-diamino-hexichol Oxy-1 "; 3 "-benzene, 3,3`-diamino-hexichol Oxy-1 ", 3 "-at least a in benzene, diamino-diphenyl ether isopropyl diphenyl (base) and diethyl toluene diamine;
More preferably amine curing agent is Ursol D, mphenylenediamine, diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 4, at least a in 4`-diaminodiphenylsulfone(DDS) and diethyl toluene diamine;
Preferably, promotor is at least a in glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2 isopropyl imidazole, 2-phenyl-4-methylimidazole, 2-dodecyl imidazoles, 1-1-cyanoethyl-2-methylimidazole, Boron Trifluoride Ethylamine, triethylamine and benzyldimethylamine;
Preferred fire retardant is bromide fire retardant, at least a in tetrabromobisphenol-A, hexabromocyclododecane, decabromodiphynly oxide, TDE, octa-BDE and pentabromotoluene; Be more preferably at least a in TDE and hexabromocyclododecane;
preferably, filler is the organic or inorganic filler, be preferably powder, single crystal fibre, glass or staple fibre, wherein said powder is preferably aluminium hydroxide, magnesium hydroxide, kaolin, hydrotalcite, titanium oxide, Calucium Silicate powder, beryllium oxide, boron nitride, glass powder, zinc borate, the aluminium nitrogen compound, silicon nitride, silicon carbide, magnesium oxide, zirconium white, mullite, titanium dioxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene or polyphenylene oxide powder, described single crystal fibre is preferably potassium titanate, silicon carbide, silicon nitride or alumina single crystal fiber, and wherein said silicon powder can be spherical silica, fused silica or crystallinity silicon-dioxide.
8. prepreg, it comprises resin combination according to claim 7 and at least a strongthener, wherein said strongthener is inorganic or organic materials, and preferably described inorganic materials comprises woven fabric or non-woven fabrics or the paper of glasscloth, carbon fiber, boron fibre, metal; Preferably organic materials comprises fabric or non-woven fabrics or the paper of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene.
9. the prepreg that is made by prepreg claimed in claim 8, preferably described prepreg is the printed electronic circuit bonding sheet.
10. laminate, it comprises prepreg as claimed in claim 9 and one deck conductive seed layer at least, preferably described conductive seed layer be Copper Foil and preferably described laminate be the use in printed circuit board copper-clad laminate.
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| CN115926181A (en) * | 2022-12-05 | 2023-04-07 | 苏州太湖电工新材料股份有限公司 | Polyimide modified epoxy resin and application thereof |
| CN115926181B (en) * | 2022-12-05 | 2023-11-17 | 苏州太湖电工新材料股份有限公司 | Polyimide modified epoxy resin and application thereof |
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