CN103131008B - A kind of BMI prepolymer and synthetic method thereof - Google Patents
A kind of BMI prepolymer and synthetic method thereof Download PDFInfo
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- CN103131008B CN103131008B CN201310025380.XA CN201310025380A CN103131008B CN 103131008 B CN103131008 B CN 103131008B CN 201310025380 A CN201310025380 A CN 201310025380A CN 103131008 B CN103131008 B CN 103131008B
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- 0 CC(C)(C)CCCc1cc(Oc(cc2C=CCC(CC(N3*N(C(CC4C(C)(C)C)=O)C4=O)=O)C3=Cl)ccc2O)ccc1O Chemical compound CC(C)(C)CCCc1cc(Oc(cc2C=CCC(CC(N3*N(C(CC4C(C)(C)C)=O)C4=O)=O)C3=Cl)ccc2O)ccc1O 0.000 description 2
Abstract
The invention provides a kind of prepolymer synthetic method for BMI. It is raw material that the method is selected BMI and diallyl bisphenol compound, and three grades of phosphines are that catalyst is specifically to add synthesis modification BMI resin on opportunity. The modified BMI resin of method manufacture has specific molecular structure and molecular weight distribution thus; Solution dissolubility at DMF or acetone, butanone is good; Storage life is not less than 180 days, within this storage life, and does not have resin to separate out or gelatin phenomenon appearance. The copper-clad plate that resin is made thus has larger bending strength, impact strength and peel strength, and higher glass transition temperature, heat decomposition temperature and good humidity resistance, can be used in high temperature resistant and high multilayer circuit.
Description
Technical field
The present invention relates to the field of chemical synthesis, relate in particular to a kind of BMI prepolymer, its synthetic method, Qi ShuOil/fat composition and the prepreg made from it and laminate.
Background technology
BMI (BMI) resin can meet the requirement of manufacturing high-speed figure and high frequency printed circuit boards base material,Be usually used in making high-performance multilayer plate. Bimaleimide resin monomer reactivity is high, when polymerization, discharges without molecule, and end properties is steadyFixed, can in wide temperature range, keep higher physical and mechanical properties. The Tg that bimaleimide resin tool is higher, widerTemperature range in its dipolar loss little, therefore electrical property is very good, have dielectric constant compared with low, dielectric loss is little, volumeThe advantages such as resistance is large. These performances still can remain on higher level in wider temperature and frequency range. But span carrys out acylThat imide resin exists is poorly soluble, the storage life is short, forming temperature is high, solidfied material fragility is large, uses thereby limited it, therefore needsTo carry out modification to it.
What current bi-maleimide modified aspect was used morely has aromatic diamine modification, epoxy resin modification, allylBased compound modification, modified rubber, cyanate modified, polyphenyl ether modified, thermoplastic resin modified etc.
1984, Giby-Geigy exited Xu292 resin, had started Allylphenyl Compounds modified bismaleimideThe new method of resin. The BMI resin system of this method modification is soluble in acetone, butanone equal solvent, the adhesiveness of prepregGood, system good toughness after solidifying, temperature classification is high, humidity resistance good, dielectric properties, mechanical performance are excellent and cause that people's is generalAll over paying close attention to. Described in patent CN03134502.6, use allyl compound modified bismaleimide resin, mention 130～Polymerase 10～60min at 150 DEG C; Patent CN101735456A and CN1200970C mention BMI and epoxy resin and allylBased compound Hybrid Heating is carried out pre-polymerization; Patent CN200910264756.6 and CN101775139A mention BMI and allylBased compound and organosilicon and water one react, in order to prepare MODIFIED BMI; Patent CN201110088156.6 mentions BMIWith allyl compound pre-polymerization 20～120min at 120～160 DEG C; In patent CN1213084C, mention BMI, pi-allylThe polymerization of the Hybrid Heating such as compound, epoxy acrylate; In CN1200015C, mention, with nanometer particle-modified BMI and pi-allylThe performed polymer of compound; CN1279110C mentions with thermoplastic resin modified BMI and allyl compound in order to prepare microballoon.All patents are all just mentioned the simple pre-polymerization of DABPA and BMI and other resin above, do not mention in synthetic resin processCatalyst problem. CN101735611A mentions BMI and DABPA is reacted to 2h at 130 DEG C, then by this prepolymer and moltenAgent, catalyst, epoxy resin etc. mix at normal temperatures. Do not mention by prepolymer under catalyst existence condition 130～160At DEG C, react a period of time, generate the performed polymer of new construction 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 Chinese scholars paper has all been avoided the storage of resinSustainability problem, just mechanical property or the dielectric properties to resin are set forth. In CN101768269A, mention with rare earth goldGenus oxide is catalyst, the pre-polymerization of catalysis BMI and allyl compound, the storage life to 100 day that can improve resin. But itsDo not mention the structure of synthesized resin and the molecular weight distribution situation of performed polymer, do not mention the modification of gained prepolymer resin yetAfter hot property, mechanical property and dielectric properties.
In this area, need stability better, the prepolymer of the BMI of the storage of being more convenient for.
Summary of the invention
The object of the present invention is to provide a kind of new method of prepolymer of synthetic BMI, described method is syntheticThe prepolymer going out has specified molecular weight and distributes and in solvent, have the storage life that is not less than 180 days.
In a first aspect of the present invention, a kind of BMI prepolymer of star structure is provided, it is characterized in that,The structural formula of described prepolymer is as follows:
Wherein: R1For
Wherein R3Be phenyl or carbon number 1～3 independently of one anotherAlkyl; R2For N1, n2 in formula I, 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 25%-65% and molecular weight2000～5000 is 11%-64%.
In a second aspect of the present invention, provide closing of BMI (BMI) prepolymer as described in first aspectOne-tenth method, it comprises the compound of formula II is contacted with catalyst:
Wherein: R1And R2As defined in claim 1, the positive integer that n4 is 1～42.
The synthetic method of described BMI prepolymer of the present invention can comprise:
(1) diallyl bisphenol compound is mixed in solvent with BMI or by bismaleimideAmine joins in hot diallyl bisphenol compound and mixes, with 120～160 DEG C, and preferably 140-160 DEG C, reaction 1～5 hours, preferably within 2～4 hours, obtain the compound of formula II; With
(2) under the reaction temperature of step (1), add described catalyst to react 1～3 hour with described formula II, preferred1.5-2.5 hour, obtains described BMI prepolymer formula I;
Wherein, the amount of substance of described bismaleimide compound and described diallyl bisphenol compound preferablyRatio be 1.2:1-4:1, be more preferably 1.5:1-3:1, be most preferably 2:1;
Preferably the consumption of described catalyst is described bismaleimide compound and described diallyl bisphenols0.05～1.9% of the mixture quality of compound, more preferably 0.5-1.5%.
In the synthetic method of described BMI prepolymer of the present invention, described catalyst can be three grades of phosphines,Being preferably triaryl phosphine or trialkyl phosphine, is more preferably in triphenylphosphine, trimethyl-phosphine, tri-n-butyl phosphine and tricyclohexyl phosphineOne or more mixture.
In the synthetic method of described BMI prepolymer of the present invention, the molecule knot of described BMIStructure can beWherein R1As defined in first aspect, be preferably diphenyl-methane bismaleimideThe mixture of one or more in amine, Diphenyl Ether Bismaleimide and diphenyl sulphone (DPS) BMI.
In the synthetic method of described BMI prepolymer of the present invention, described diallyl bisphenol compoundIt 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, provide the resin combination that comprises the prepolymer as described in first aspect, preferablyThe described resin combination in ground comprises described BMI prepolymer, epoxy resin, amine curing agent and promoter, more preferablyGround BMI prepolymer, epoxy resin, amine curing agent, promoter, fire retardant and filler, further preferably comprise100 parts of described BMI prepolymers, 20～100 parts of epoxy resin, 2～20 parts of amine curing agents, promoter 0～0.75Part, 0～300 part of 0～20 part of fire retardant and filler;
Wherein preferably epoxy resin is to have the ring more than two or more epoxide groups in 1 molecule resinEpoxy resins, for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclicBased epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group ringAt least one in epoxy resins and phenol aldehyde type epoxy resin;
Preferably amine curing agent is aromatic diamines, for example p-phenylenediamine (PPD), m-phenylene diamine (MPD), diphenylmethane diamine, 4,4`-bis-Amido diphenyl ether, 3,4`-diaminodiphenyl ether, 4,4`-bis-amido diphenyl methanes, 3,3`-dimethyl-4,4`-bis-amidos twoPhenylmethane, 4,4`-DADPS, 4,4`-diaminourea-hexichol Oxy-1 ", 4 " and-benzene, 4,4`-diaminourea-hexichol oxygenBase-1 ", 3 "-benzene, 3,3`-diaminourea-hexichol Oxy-1 ", 3 " and-benzene, diamino-diphenyl ether isopropyl diphenyl (base) and diethylAt least one in base toluenediamine;
More preferably amine curing agent is p-phenylenediamine (PPD), m-phenylene diamine (MPD), diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 4,At least one in 4`-DADPS and diethyl toluene diamine;
Preferably, promoter be 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 miaowAt least one in azoles, 1-1-cyanoethyl-2-methylimidazole, Boron Trifluoride Ethylamine, triethylamine and benzyl dimethylamine;
Preferred fire retardant is bromide fire retardant, is tetrabromobisphenol-A, HBCD, deca-BDE, ten bromines twoAt least one in vinylbenzene, octa-BDE and pentabromotoluene; Be more preferably TDE and HBCDIn at least one;
Preferably, filler is organic or inorganic filler, is preferably powder, mono-crystlling fibre, glass or short fiber, Qi ZhongsuoState powder and be preferably aluminium hydroxide, magnesium hydroxide, kaolin, hydrotalcite, titanium oxide, calcium silicates, beryllium oxide, boron nitride, glassPowder, Firebrake ZB, aluminium nitrogen compound, silicon nitride, carborundum, magnesia, zirconia, mullite, titanium dioxide, potassium titanate, hollowGlass microballoon, polytetrafluorethylepowder powder, polystyrene or polyphenylene oxide powder, described mono-crystlling fibre be preferably potassium titanate, carborundum,Silicon nitride or alumina single crystal fiber, and wherein said silicon powder can be spherical silica, fused silica or knotCrystallinity silica.
In a fourth aspect of the present invention, a kind of prepreg is provided, it comprises according to the resin combination described in the third aspectThing and at least one reinforcing material, wherein said reinforcing material is inorganic or organic material, preferably described inorganic material comprisesThe woven fabric of glass fabric, carbon fiber, boron fibre, metal or nonwoven or paper; Preferably organic material comprises polyester, poly-The fabric of amine, polyacrylic acid, polyimides, aramid fiber, polytetrafluoroethylene (PTFE) or syndiotactic polytyrene or nonwoven or paper.
In a fifth aspect of the present invention, provide the prepreg being made by the prepreg described in fourth aspect, preferablyDescribed prepreg is printed circuit bonding sheet.
In a sixth aspect of the present invention, a kind of laminate is provided, it comprises the prepreg as described in the 5th aspectAt least one deck conductive seed layer, preferably described conductive seed layer be Copper Foil and preferably described laminate be printed circuit board (PCB)Use copper-clad laminate.
Beneficial effect of the present invention:
1, method of the present invention is simple to operate, and reaction condition gentleness is raw materials usedly easily obtained, and is easy to large-scale production;
2, the synthetic BMI prepolymer of method of the present invention has specified molecular weight distribution and tool in solventThere is the storage life that is not less than 180 days;
3, the synthetic BMI prepolymer of method of the present invention does not have gel time to shorten or coagulating between the storage lifeGlue, the situation of separating out occur;
4, adopt the synthetic prepared copper-clad plate of BMI prepolymer of method of the present invention to have larger curvedQu Qiangdu, impact strength and peel strength, higher glass transition temperature, heat decomposition temperature and good wet-heat resistingProperty, can be used in high temperature resistant and high multilayer circuit.
Brief description of the drawings
Fig. 1 shows the infrared spectrum of the prepolymer that catalyst joining day difference obtains.
Detailed description of the invention
Below by specific embodiment, the present invention is elaborated, but and do not limit the present invention in any way.
Embodiment 1
36 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 164 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 155 DEG C, and at this temperature, react 5 littleTime, then add 3.8 grams of triphenylphosphines, and at this temperature, react and after 1 hour, stop reaction, and shift out rapidly and be cooled to chamberTemperature, obtains reddish brown solid.
Embodiment 2
36 grams of diallyl bisphenol Ss and 67 grams of 1-METHYLPYRROLIDONEs (NMP) are heated to 100 DEG C in there-necked flask,Then add 164 grams of diphenyl methane dimaleimides, at this temperature, stir 30min, it is mixed. Then be warmed up to155 DEG C, and at this temperature, react 5 hours, then add 3 grams of triphenylphosphines, and at this temperature, react after 2 hours, stop anti-Should, and shift out rapidly and cool to room temperature, obtain blackish green look liquid.
Embodiment 3
45 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 155 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 150 DEG C, and at this temperature, react 3 littleTime, then add 2.2 grams of triphenylphosphines, and at this temperature, react and after 3 hours, stop reaction, and shift out rapidly and be cooled to chamberTemperature, obtains reddish brown solid.
Embodiment 4
73 grams of diallyl bisphenols and 67 grams of DMAC are heated to 100 DEG C in there-necked flask, then add 127 gram twoPhenylmethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 145 DEG C, and in this temperatureThe lower reaction of degree 4 hours, then adds 1.4 grams of triphenylphosphines, and at this temperature, reacts and after 3 hours, stop reaction, and moves rapidlyGo out and cool to room temperature, obtain blackish green viscous liquid.
Embodiment 5
51 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 149 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 145 DEG C, and at this temperature, react 3 littleTime, then add 1 gram of triphenylphosphine, and at this temperature, react and after 3 hours, stop reaction, and shift out rapidly and be cooled to chamberTemperature, obtains reddish brown solid.
Embodiment 6
51 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 149 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 155 DEG C, and in this temperatureLower reaction 2 hours. Then after adding 0.92 gram of triphenylphosphine, continue reaction 1 hour, stop reaction, and shift out rapidly and be cooled toRoom temperature, obtains blackish green liquid.
Embodiment 7
60 grams of diallyl Bisphenol F are heated to 100 DEG C in there-necked flask, then add 140 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 135 DEG C, and at this temperature, react 4 littleTime, then add 0.8 gram of trimethyl-phosphine, and at this temperature, react and after 2 hours, stop reaction, and shift out rapidly and be cooled to chamberTemperature, obtains light brown viscous shape liquid.
Embodiment 8
60 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 140 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 130 DEG C, and in this temperatureLower reaction 2 hours, then adds 0.7 gram of tri-n-butyl phosphine, and at this temperature, reacts and after 2 hours, stop reaction, and moves rapidlyGo out and cool to room temperature, obtain light brown viscous shape liquid.
Embodiment 9
63 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 127 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 130 DEG C, and at this temperature, react 2 littleTime, then add 0.6 gram of triphenylphosphine, and at this temperature, react and after 2 hours, stop reaction, and shift out rapidly and be cooled to chamberTemperature, obtains softening point and is the reddish brown solid of 90 DEG C.
Embodiment 10
63 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 127 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 155 DEG C, and in this temperatureLower reaction 3 hours, then adds 0.4 gram of tricyclohexyl phosphine, and at this temperature, reacts and after 2 hours, stop reaction, and moves rapidlyGo out and cool to room temperature, obtain bronzing liquid.
Embodiment 11
106 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 94 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 150 DEG C, and in this temperatureLower reaction 5 hours, then adds 0.2 gram of triphenylphosphine, and at this temperature, reacts and after 2 hours, stop reaction, and shifts out rapidlyAnd cool to room temperature, obtain light brown viscous shape liquid.
Embodiment 12
106 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 94 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 145 DEG C, and in this temperatureLower reaction 5 hours, then adds 0.1 gram of triphenylphosphine, and at this temperature, reacts and after 1 hour, stop reaction, and shifts out rapidlyAnd cool to room temperature, obtain light brown viscous shape liquid.
Comparative example 1
106 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 94 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 155 DEG C, and at this temperature, react 5 littleTime after stop reaction, and shift out rapidly and cool to room temperature, obtain brown color brittle solid.
Comparative example 2
84 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 116 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 155 DEG C, and in this temperatureLower reaction stops reaction after 6.5 hours, and shifts out rapidly and cool to room temperature, obtains brown color liquid.
Comparative example 3
63 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 127 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 155 DEG C, and in this temperatureLower reaction stops reaction after 4 hours, and shifts out rapidly and cool to room temperature, obtains brown color liquid.
Comparative example 4
60 grams of diallyl bisphenols and 67 grams of DMF are heated to 100 DEG C in there-necked flask, then add 140 grams of hexicholMethane BMI stirs 30min at this temperature, and it is mixed. Then be warmed up to 155 DEG C, and in this temperatureLower reaction stops reaction after 5 hours, and shifts out rapidly and cool to room temperature, obtains brown color liquid.
Comparative example 5
51 grams of diallyl bisphenols are heated to 100 DEG C in there-necked flask, then add 149 grams of diphenyl-methane spansCarry out acid imide, at this temperature, stir 30min, it is mixed. Then be warmed up to 130 DEG C, and at this temperature, react 3 littleTime after stop reaction, and shift out rapidly and cool to room temperature, obtain brown color transparent solid.
Embodiment 13～17:
BMI resin synthetic in embodiment 6 is prepared according to the following formulation, first by BMI resin and the linear phenolic aldehyde epoxy of bisphenol-AResin fully dissolves in solvent DMF, mixes. Then add the diethyl toluene diamine and the 2-benzene that are dissolved in advance in DMFBase-4-methylimidazole, mixes it. Then add fire retardant, make to add filler molten silicon micro mist and solvent after its dispersion,Making mixed system solid content is 70%, and high-speed stirred is after 20 minutes, with 2116 glass cloth gluings, and dries 2 in 155 DEG C of baking ovens～10 minutes, make prepreg, then cover Copper Foil with 8 prepreg two sides, at 210 DEG C, vacuum pressed is solidified 200 pointsClock. Obtain following plate property:
Embodiment 18 Performance Detection
By prepolymer prepared in embodiment 1-5 and comparative example 1-5 taking identical formulated as resin combination,And the physicochemical property of each resin combination is carried out to parallel contrast, described formula is the synthetic BMI:375g of each embodiment; Bisphenol A-typeLinear 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, solidifies and makes copper-clad plate, its performance by same programTest result is in table 1:
Table 1 the performance test results
Embodiment 19
First, by the performed polymer 100g in embodiment 1,32g High Bromine epoxy Resin A (epoxide equivalent 400g/mol, solid content61%), 14g isocyanate modified epoxy resin B (epoxide equivalent 360g/mol, solid content 76%), 20gDMF, stir about half is littleTime, 303g aluminium oxide is fully mixed with 80gDMF, then resin is mixed with filler, the evenly rear gluing of above mixture, pressesSame program solidifies makes copper-clad plate A.
Afterwards, by the performed polymer 100g in comparative example 5,32g High Bromine epoxy Resin A (epoxide equivalent 400g/mol, solid content61%), 14g isocyanate modified epoxy resin B (epoxide equivalent 360g/mol, solid content 76%), 0.05g triphenylphosphine,20gDMF, stir about half an hour, fully mixes 303g aluminium oxide with 80gDMF, then resin is mixed with filler, more than mixedThe evenly rear gluing of compound, solidifies and makes copper-clad plate B by same program.
The copper-clad plate that adopts different performed polymers to make is carried out to Performance Ratio, the results are shown in Table 2.
Table 2 the performance test results
Embodiment 20 examination of infrared spectrum
Prepare BMI prepolymer according to the method described in embodiment 5 above, wherein said catalyst exists respectivelyStep 1, step 2 (completely according to preparation method of the present invention) add or do not add catalyst. And by obtained mixingRaw material and three kinds of prepolymers that prepolymerization reaction does not occur uniformly carry out examination of infrared spectrum, and it the results are shown in Figure 1.
Spectrogram explanation: this spectrogram is BMI (BMI) and the diallyl bisphenol with phase jljl amount ratio(DABPA), mix (A) to react initial raw material, do not add catalyst (B), initially add catalyst (C), add and urge midwayThe infrared spectrum of agent (D), with BMI at 1154cm-1Characteristic absorption peak is reference peak, makes its peak height identical. By contrast996cm-1The two key characteristic absorption of end group at place, can know, relative initial mixing, do not add catalyst and add catalysis midwayGreatly weakening of agent absorption herein, and after initially adding catalyst reaction, substantially do not have change in the absorption of this wave number, explanationDo not add catalyst or add catalyst that first step pre-polymerization has all occurred midway, generated formula II. And comparison 1186cm-1Peak height feelingsCondition, the Catalysis Principles of three grades of phosphines of contrast, can reflect thus and add after three grades of phosphine catalysts midway, can be formed in a large number by formula IIThe trimerical pentacyclic tertiary carbon of BMI, thus the star performed polymer formula I having generated as in claim reflected.
Applicant's statement, the present invention illustrates detailed features of the present invention and method by above-described embodiment, but thisBright above-mentioned detailed features and the method for being not limited to, does not mean that the present invention must rely on above-mentioned detailed features and methodCould implement. Person of ordinary skill in the field should understand, any improvement in the present invention, to the selected material of the present inventionWith the selection of the equivalence replacement of step and the increase of auxiliary material and step, concrete mode etc., all drop on protection of the present inventionWithin scope and open scope.
Claims (35)
1. a BMI prepolymer for star structure, is characterized in that, the structural formula of described prepolymer is as follows:
Wherein: R1For
Wherein R3Be the alkyl of phenyl or carbon number 1～3 independently of one another; R2For-S-、-SO-、-SO2-,-O-orN1, n2 in formula I, n3Be the integer of 0-42 independently of one another, wherein at least one is not 0;
The molecular weight distribution of wherein said prepolymer is: molecular weight 300～500 is 25%-65% and molecular weight 2000～5000For 11%-64%, molecular weight > 5000 is 0%.
2. the synthetic method of BMI prepolymer as claimed in claim 1, it comprises the compound of formula II and urgesAgent contact:
Wherein: R1And R2As defined in claim 1, n4 is greater than 1 to be less than or equal to 42 positive integer; Described catalyst isThree grades of phosphines;
Particularly, described method comprises:
(1) diallyl bisphenol compound is mixed in solvent with BMI or BMI is addedEnter in hot diallyl bisphenol compound and mix, with 120～160 DEG C, react 1～5 hour, obtain the change of formula IICompound, described bismaleimide compound is 1.2:1-4 with the ratio of the amount of substance of described diallyl bisphenol compound:1; With
(2) under the reaction temperature of step (1), add described catalyst to react 1～3 hour with described formula II, obtain described twoMaleimide prepolymer formula I.
3. synthetic method as claimed in claim 2, step (1) reaction temperature is 140～160 DEG C.
4. synthetic method as claimed in claim 2, step (1) reaction time is 2～4 hours.
5. synthetic method as claimed in claim 2, step (2) reaction time is 1.5～2.5 hours.
6. synthetic method as claimed in claim 2, described bismaleimide compound and described diallyl bisphenolsThe ratio of the amount of substance of compound is 1.5:1-3:1.
7. synthetic method as claimed in claim 6, described bismaleimide compound and described diallyl bisphenolsThe ratio of the amount of substance of compound is 2:1.
8. synthetic method as claimed in claim 2, the consumption of described catalyst is described bismaleimide compound and instituteState diallyl bisphenol compound mixture quality 0.05～1.9%.
9. synthetic method as claimed in claim 8, the consumption of described catalyst is described bismaleimide compound and instituteState the 0.5-1.5% of the mixture quality of diallyl bisphenol compound.
10. method as claimed in claim 2, described catalyst is triaryl phosphine or trialkyl phosphine.
11. as the method for claim 10, described catalyst be a kind of in triphenylphosphine, trimethyl-phosphine or tri-n-butyl phosphine orTwo or more mixtures.
12. methods as described in any one in claim 2-3, is characterized in that the molecular structure of described BMIForWherein R1As definition in claim 1.
13. methods as claimed in claim 12, is characterized in that, described BMI is diphenyl-methane bismaleimideThe mixture of one or more in amine, Diphenyl Ether Bismaleimide and diphenyl sulphone (DPS) BMI.
14. methods as described in any one in claim 2-5, is characterized in that, described diallyl bisphenol compound isThe mixture of one or more in diallyl bisphenol, diallyl Bisphenol F and diallyl bisphenol S.
15. resin combinations that comprise prepolymer as claimed in claim 1, described resin combination comprises described span and carrys out acylImines prepolymer, epoxy resin, amine curing agent and promoter.
16. resin combinations as claimed in claim 15, described resin combination comprises BMI prepolymer, epoxyResin, amine curing agent, promoter, fire retardant and filler.
17. resin combinations as claimed in claim 16, described resin combination comprises described BMI prepolymer100 parts, 20～100 parts of epoxy resin, 2～20 parts of amine curing agents, 0～0.75 part of promoter, 0～20 part of fire retardant and filler0～300 part.
18. resin combinations as claimed in claim 15, epoxy resin for to have more than two epoxy in 1 molecule resinThe epoxy resin of group, is specially bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene class epoxyResin, alicyclic based epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin,At least one in four-functional group epoxy resin and phenol aldehyde type epoxy resin.
19. resin combinations as claimed in claim 15, amine curing agent is aromatic diamines, is specially p-phenylenediamine (PPD), isophthalicDiamines, diphenylmethane diamine, 4,4`-diaminodiphenyl ether, 3,4`-diaminodiphenyl ether, 4,4`-bis-amido diphenyl methanes,3,3`-dimethyl-4,4`-bis-amido diphenyl methanes, 4,4`-DADPS, 4,4`-diaminourea-hexichol Oxy-1,4-Benzene, 4,4`-diaminourea-hexichol Oxy-1,3-benzene, 3,3`-diaminourea-hexichol Oxy-1, in 3-benzene and diethyl toluene diamineAt least one.
20. resin combinations as claimed in claim 15, amine curing agent is p-phenylenediamine (PPD), m-phenylene diamine (MPD), diphenyl-methane twoAmine, 4,4`-diaminodiphenyl ether, 4, at least one in 4`-DADPS and diethyl toluene diamine.
21. resin combinations as claimed in claim 15, promoter is glyoxal ethyline, 2-ethyl-4 methylimidazole, 2-benzeneBase imidazoles, 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 benzyl dimethylamineIn at least one.
22. resin combinations as claimed in claim 16, fire retardant is bromide fire retardant, is tetrabromobisphenol-A, hexabromo ring tenAt least one in dioxane, deca-BDE, TDE, octa-BDE and pentabromotoluene.
23. resin combinations as claimed in claim 22, fire retardant be in TDE and HBCD extremelyFew a kind of.
24. resin combinations as claimed in claim 16, filler is organic or inorganic filler.
25. resin combinations as claimed in claim 24, filler is powder, mono-crystlling fibre or glass.
26. resin combinations as claimed in claim 24, filler is short fiber.
27. resin combinations as claimed in claim 25, described powder is aluminium hydroxide, magnesium hydroxide, kaolin, neatlyStone, calcium silicates, beryllium oxide, boron nitride, glass dust, Firebrake ZB, aluminium nitrogen compound, silicon nitride, carborundum, magnesia, zirconia,Mullite, titanium dioxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene or polyphenylene oxide powder.
28. 1 kinds of prepregs, it comprises according to the resin combination one of claim 15-27 Suo Shu and at least one enhancing materialMaterial, wherein said reinforcing material is inorganic or organic material.
29. prepregs as claimed in claim 28, described inorganic material is the machine of glass fibre, carbon fiber, boron fibre, metalWoven fabric or nonwoven or paper.
30. prepregs as claimed in claim 28, organic material is polyester, polyamine, polyacrylic acid, polyimides, aramid fiber, poly-The fabric of tetrafluoroethene or syndiotactic polytyrene or paper.
31. prepregs as claimed in claim 28, organic material is polyester, polyamine, polyacrylic acid, polyimides, aramid fiber, poly-The nonwoven of tetrafluoroethene or syndiotactic polytyrene.
32. prepreg that made by the prepreg one of claim 28-31 Suo Shu.
33. prepreg as claimed in claim 32, described prepreg is printed circuit bonding sheet.
34. 1 kinds of laminates, it comprises the prepreg as described in one of claim 32-33 and at least one deck conduction is subLayer.
35. laminates as claimed in claim 34, described conductive seed layer is that Copper Foil and described laminate are printing electricityRoad plate copper-clad laminate.
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| CN104610678A (en) * | 2015-02-13 | 2015-05-13 | 芜湖市伟华泡塑有限公司 | Heat-resistant high-tenacity polystyrene resin foamed plastic |
| KR20190035731A (en) * | 2016-08-05 | 2019-04-03 | 닛뽄 가야쿠 가부시키가이샤 | Maleimide resin composition, prepreg, cured product thereof, and semiconductor device |
| CN107353855B (en) * | 2017-08-01 | 2019-03-29 | 烟台德邦科技有限公司 | A kind of chip adhesive agent and preparation method thereof that low resin is precipitated |
| CN109503839B (en) * | 2018-10-31 | 2021-03-23 | 陕西硕博电子材料有限公司 | Bismaleimide resin prepolymer and preparation method thereof |
| CN109628001A (en) * | 2018-11-09 | 2019-04-16 | 李梅 | A kind of sPS glue film and preparation method thereof for FPC industry |
| CN112679357B (en) * | 2020-12-22 | 2023-02-17 | 广东盈骅新材料科技有限公司 | Modified allyl compound, modified bismaleimide prepolymer 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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