CN103965824A - Acetenyl polyimide modified cyanate ester adhesive and preparation method thereof - Google Patents
Acetenyl polyimide modified cyanate ester adhesive and preparation method thereof Download PDFInfo
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- CN103965824A CN103965824A CN201410208713.7A CN201410208713A CN103965824A CN 103965824 A CN103965824 A CN 103965824A CN 201410208713 A CN201410208713 A CN 201410208713A CN 103965824 A CN103965824 A CN 103965824A
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Abstract
The invention provides an acetenyl polyimide modified cyanate ester adhesive and a preparation method thereof, and relates to a cyanate ester adhesive and a preparation method thereof, aiming at solving the problems of poor heat stability and insufficient toughness of the existing cyanate ester adhesive. The adhesive comprises cyanate ester resin, acetenyl polyimide resin and an inorganic filler modifier. The method comprises the following steps: 1, heating cyanate ester resin; 2, adding acetenyl polyimide resin to a polar solvent, heating, agitating to dissolve to obtain a mixture, maintaining the temperature and adding the mixture to cyanate ester resin, agitating, and then performing reduced pressure distillation to remove a solvent to obtain a copolymer; and 3, adding the inorganic filler modifier to the copolymer under the agitating state, and then agitating to obtain the adhesive. The adhesive is high in heat stability and toughness, and applicable to the field of adhesives.
Description
Technical field
The present invention relates to a kind of cyanate tackiness agent and preparation method thereof.
Background technology
Tackiness agent has been widely used in every profession and trade, and adhesive bonding technique has become one of three large interconnection techniques.Along with the development of the industry research such as aerospace and utilisation technology, high-speed aircraft Mach number increases year by year, thereby the temperature resistant grade of macromolecular material is proposed to new demand.Meanwhile, in order to promote the wave penetrate capability of Airborne Radome, to comprising that the dielectric properties of the macromolecular material of tackiness agent have proposed requirements at the higher level, as require the dielectric characterization at GHz wave band region demonstration low-k and low-dielectric loss tangent.
Because cyanate ester resin can generate triazine ring structure under heat or catalyst action, the cyanate of this structure not only has low, the minimum dielectric loss angle tangent of specific inductivity, low rate of moisture absorption and good processing technology, and in solidification process, non-volatility low-molecular material produces simultaneously.Therefore,, as above-mentioned adhesive material, generally adopt the cyanate tackiness agent with good workability and dielectric properties.Yet because cross-linking density high after ethylene rhodanate resin curing causes material fragility larger, the existence of hydrocarbon key and ehter bond in cyanate structure simultaneously, causes adverse influence to the resistance toheat of material, has greatly limited its application in fields such as aerospace.
Adopt rubber elastomer (as active end group fluid rubber, macromole isoprene-isobutylene rubber etc.) or thermoplastic engineering plastic (as polysulfones, polyethersulfone, polyetherimide etc.) although can improve adhesive material toughness, also reduced use temperature simultaneously.Therefore,, for integral body improves toughness and the heat aging performance of cyanate, generally adopt thermosetting resin to its modification: adopt epoxy resin modification cyanate, though have good mechanical property and adhesiveproperties after solidifying, its thermotolerance is poor; Adopt bimaleimide resin modified cyanic acid ester, after solidifying, form cyanate resin (bismaleimide triazine is called for short BT resin) and there is low-dielectric energy and water-intake rate, but cured article fragility is large, stripping strength is low, and bismaleimide resin heat aging performance is not good simultaneously; Though aryl ethane has the advantages such as good resistance to ablation and high glass transition temperature, many benzene ring structures of aryl ethane and high crosslink density cause that matrix fragility is larger, and adhesiveproperties is poor, is difficult to improve cyanate toughness of material.
Summary of the invention
The present invention is the poor heat stability in order to solve existing cyanate tackiness agent existence, the problem of toughness deficiency, and polyimide modified cyanate tackiness agent of a kind of ethynyl and preparation method thereof is provided.
The polyimide modified cyanate tackiness agent of ethynyl of the present invention comprises 100 parts of cyanate ester resins, 1～100 part of ethynyl polyimide resin and 1～10 part of mineral filler properties-correcting agent by weight; Wherein said cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming.
The structural formula of described ethynyl polyimide resin is:
, wherein polymerization degree n is 1～9, Ar
1for
ar
2for
Described ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, under nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after stirring 1 hour, add aromatic diamines, stir 1～5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1～5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5～0.9:0.2～1; Then add toluene, be warming up to 120～130 ℃ of back flow reaction 1～4 hour; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 130～140 ℃ of oven dry, obtains ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3, the amino benzoxazole of 4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-.
The preparation method of the polyimide modified cyanate tackiness agent of above-mentioned ethynyl, carries out according to the following steps:
One, by weight, 100 parts of cyanate ester resins are heated to 115～120 ℃;
Two, 1～100 part of ethynyl polyimide resin is joined in the polar solvent of 50～200 parts, be warming up to 130～160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120～140 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 90～120 ℃ of whipped states to 1～5 part of mineral filler properties-correcting agent, after stirring 10～30min, make tackiness agent;
Described in step 1, cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming;
Described in step 2, polar solvent is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by any mixtures than forming;
Described in step 3, mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming.
The present invention includes following beneficial effect:
Prior art adopts epoxy resin, bimaleimide resin and the compound modified cyanate ester resin of allylic that the resistance toheat of tackiness agent is declined; Cyanate is solidified with to catalytic effect simultaneously, affects process window and shelf lives; Not enough for fear of prior art, compared with former modification technology, the present invention adopts cyanate ester resin/ethynyl polyimide mixture as matrix resin, take mineral filler as properties-correcting agent, has prepared the polyimide modified cyanate tackiness agent of a kind of ethynyl.
The present invention does not adopt the resin (as bismaleimides, allylic cpd, epoxy resin etc.) cyanate ester resin to catalytic crosslinking effect, on the one hand, do not affect the curing process of cyanate ester resin, keep its wider process window and suitable gel time.The solidification value interval that while is similar because ethynyl polyimide and cyanate have, thus synchronously solidify; On the other hand, because not affecting triazine ring, the crosslinking reaction of ethynyl polyimide do not form, thus little on the dielectric properties impact of system.
The present invention has adopted and has contained the ethynyl polyimide of soft segment as the matrix resin of sizing agent, the introducing of its acetylene end group makes to have higher cross-linking density after polyimide curing on the one hand, more than second-order transition temperature, there is good modulus to keep, improve resistance toheat and the bonding strength of tackiness agent; On the other hand, acetylene end group polyimide has similar solidification value interval to cyanate, both can synchronously solidify and not have each other cross-linking set to occur, the complete inierpeneirating network structure forming can either keep the dielectric properties that cyanate is good, can embody again thermal stability and the toughness of material of polyimide excellence.
The present invention has adopted the polyimide that contains a bit architecture and ether ketone structure in backbone structure, makes it have good solubility energy in lower softening temperature and organic solvent, gives the better adhesiveproperties of tackiness agent and mechanical property simultaneously; By controlling diamines/dianhydride kind and the ingredient proportion of ethynyl polyimide, control polymericular weight and backbone structure, thereby reach the object to cyanate ester resin/ethynyl polyimide toughening modifying.
The polyimide modified cyanate tackiness agent of the ethynyl tool that adopts the present invention to prepare has the following advantages:
(1) there is superior heat resistance energy, 5% heat decomposition temperature >=410 ℃;
(2) there is lower dielectric loss and specific inductivity: ε < 3.3, tan δ < 0.015;
(3) adhesiveproperties is higher, and shearing resistance and high temperature conservation rate are high, its room temperature shearing resistance >=15MPa, its 350 ℃ of down cut intensity >=10MPa;
(4) manufacturability is better, and gel time is long, and the viscosity of sizing agent is moderate.
The present invention fills a prescription rationally, prepared tackiness agent has good resistance toheat, mechanical property, adhesiveproperties, can be used for metal that thermal characteristics and dielectric properties are had relatively high expectations or the splicing of composite material structural member, thereby widened the application of high-temperature resistance adhesive in fields such as aerospace.Tackiness agent of the present invention is keeping on the dielectric properties of cyanate ester resin excellence, good processing performance basis, improves heat-resisting, mechanical property and the thermal oxidation of tackiness agent, to meet the requirement of high-performance wave transparent tackiness agent for aerospace of new generation.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric curve figure of the tackiness agent of embodiment 1 and comparative example 1 preparation.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the polyimide modified cyanate tackiness agent of present embodiment ethynyl comprises 100 parts of cyanate ester resins, 1～100 part of ethynyl polyimide resin and 1～10 part of mineral filler properties-correcting agent by weight; Wherein said cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming.
Embodiment two: present embodiment is different from embodiment one: the structural formula of described ethynyl polyimide resin is:
, wherein polymerization degree n is 1～9, Ar
1for
ar
2for
other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: described ethynyl polyimide resin is prepared in the steps below: add N in three-necked bottle, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, to N, in N-N,N-DIMETHYLACETAMIDE, add aromatic dianhydride, after stirring 1 hour, add aromatic diamines, stir 1～5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1～5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5～0.9:0.2～1; Then add toluene, be warming up to 120～130 ℃ of back flow reaction 1～4 hour; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 130～140 ℃ of oven dry, obtains ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3, the amino benzoxazole of 4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-.Other is identical with embodiment one or two.
Embodiment four: the preparation method of the polyimide modified cyanate tackiness agent of ethynyl described in embodiment one, carries out according to the following steps:
One, by weight, 100 parts of cyanate ester resins are heated to 115～120 ℃;
Two, 1～100 part of ethynyl polyimide resin is joined in the polar solvent of 50～200 parts, be warming up to 130～160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120～140 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 90～120 ℃ of whipped states to 1～5 part of mineral filler properties-correcting agent, after stirring 10～30min, make tackiness agent;
Described in step 1, cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming;
Described in step 2, polar solvent is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by any mixtures than forming;
Described in step 3, mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming;
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, under nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after stirring 1 hour, add aromatic diamines, stir 1～5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1～5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5～0.9:0.2～1; Then add toluene, be warming up to 120～130 ℃ of back flow reaction 1～4 hour; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 130～140 ℃ of oven dry, obtains ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3, the amino benzoxazole of 4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-.
Embodiment five: present embodiment is different from embodiment four: be warming up to 140～150 ℃ in step 2.Other is identical with embodiment four.
Embodiment six: present embodiment is different from embodiment four or five: the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.8:0.4.Other is identical with embodiment four or five.
Embodiment seven: present embodiment is different from embodiment four or five: the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5:1.Other is identical with embodiment four or five.
Embodiment 1:
The preparation method of the polyimide modified cyanate tackiness agent of the present embodiment ethynyl, carries out according to the following steps:
One, by weight, 100 parts of Novolac Cyanate Ester Resins are heated to 120 ℃;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 100 parts, be warming up to 160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 100 ℃ of whipped states to 4 parts of aerosils, after stirring 30min, make tackiness agent;
Described in step 2, polar solvent is comprised of 50 parts of DMFs and 50 parts of N,N-dimethylacetamide.
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add 160mLN, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, to N, in N-N,N-DIMETHYLACETAMIDE, add 31.02g (0.1mol) 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride, after stirring 1 hour, add 16.02g (0.08mol) 3,4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; In mixing solutions, add acetylenylaniline between 4.68g (0.04mol), stirring reaction 3 hours; Then add 50mL toluene, be warming up to 125 ℃ of back flow reaction 4 hours; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 140 ℃ of oven dry, obtains ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
The polyimide modified cyanate tackiness agent of ethynyl prepared by the present embodiment is cured, and curing process is: 130 ℃/1h+200 ℃/2h, and 260 ℃/2h of aftertreatment.
Embodiment 2:
The preparation method of the polyimide modified cyanate tackiness agent of the present embodiment ethynyl, carries out according to the following steps:
One, by weight, 100 parts of Novolac Cyanate Ester Resins are heated to 120 ℃;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 100 parts, be warming up to 160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 100 ℃ of whipped states to 4 parts of aerosils, after stirring 30min, make tackiness agent;
Described in step 2, polar solvent is comprised of 50 parts of DMFs and 50 parts of N,N-dimethylacetamide.
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add 162mLN, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, to N, in N-N,N-DIMETHYLACETAMIDE, add 31.02g (0.1mol) 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride, after stirring 1 hour, add 10.01g (0.05mol) 3,4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; In mixing solutions, add acetylenylaniline between 11.71g (0.1mol), stirring reaction 3 hours; Then add 50mL toluene, be warming up to 125 ℃ of back flow reaction 4 hours; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 140 ℃ of oven dry, obtains ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
The polyimide modified cyanate tackiness agent of ethynyl prepared by the present embodiment is cured, and curing process is: 130 ℃/1h+200 ℃/2h, and 260 ℃/2h of aftertreatment.
Embodiment 3:
The preparation method of the polyimide modified cyanate tackiness agent of the present embodiment ethynyl, carries out according to the following steps:
One, by weight, 100 parts of Novolac Cyanate Ester Resins are heated to 120 ℃;
Two, 70 parts of ethynyl polyimide resins are joined in the polar solvent of 150 parts, be warming up to 160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 100 ℃ of whipped states to 4 parts of aerosils, after stirring 30min, make tackiness agent;
Described in step 2, polar solvent is comprised of 75 parts of DMFs and 75 parts of N,N-dimethylacetamide.
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add 160mLN, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, to N, in N-N,N-DIMETHYLACETAMIDE, add 29.42g (0.1mol) 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, after stirring 1 hour, add 16.02g (0.08mol) 3,4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; In mixing solutions, add acetylenylaniline between 4.68g (0.04mol), stirring reaction 3 hours; Then add 50mL toluene, be warming up to 125 ℃ of back flow reaction 4 hours; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 140 ℃ of oven dry, obtains ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
The polyimide modified cyanate tackiness agent of ethynyl prepared by the present embodiment is cured, and curing process is: 130 ℃/1h+200 ℃/2h, and 260 ℃/2h of aftertreatment.
Embodiment 4:
The preparation method of the polyimide modified cyanate tackiness agent of the present embodiment ethynyl, carries out according to the following steps:
One, by weight, 100 parts of Novolac Cyanate Ester Resins are heated to 120 ℃;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 150 parts, be warming up to 160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 100 ℃ of whipped states to 4 parts of aerosils, after stirring 30min, make tackiness agent;
Described in step 2, polar solvent is comprised of 75 parts of DMFs and 75 parts of N,N-dimethylacetamide.
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add 160mLN, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, to N, in N-N,N-DIMETHYLACETAMIDE, add 29.42g (0.1mol) 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, after stirring 1 hour, add 16.02g (0.08mol) 3,4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; In mixing solutions, add acetylenylaniline between 4.68g (0.04mol), stirring reaction 3 hours; Then add toluene, be warming up to 125 ℃ of back flow reaction 4 hours; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 140 ℃ of oven dry, obtains ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
The polyimide modified cyanate tackiness agent of ethynyl prepared by the present embodiment is cured, and curing process is: 130 ℃/1h+200 ℃/2h, and 260 ℃/2h of aftertreatment.
Comparative example 1:
The preparation method of the tackiness agent of this comparative example carries out in the steps below: by weight, 100 parts of Novolac Cyanate Ester Resins are slowly heated to 120 ℃ in beaker, under 100 ℃ of whipped states, add 4 parts of aerosils, stir after 30min stirs and make tackiness agent.The solidification process of tackiness agent is identical with embodiment 1-4.
Tackiness agent after embodiment 1 and comparative example 1 solidified carries out heat treated, test thermal weight loss performance in its air, result is with reference to Fig. 1, Fig. 1 is the thermogravimetric curve figure of the tackiness agent of embodiment 1 and comparative example 1 preparation, wherein curve a is the thermogravimetric curve of the polyimide modified cyanate tackiness agent of ethynyl of embodiment 1 preparation, the thermogravimetric curve of the tackiness agent that curve b provides for comparative example 1.
Prepared by above-mentioned 5 embodiment solidify after tackiness agent carried out second-order transition temperature, thermostability, shearing resistance, stripping strength and dielectric properties test, as shown in table 1, the test condition of properties is with reference to following standard (method):
1, thermostability: test adopts thermal gravimetric analyzer (TGA).Temperature rise rate: 10 ℃/min; Test atmosphere: air.
2, shearing resistance: test is with reference to GB/T7124-2008 tackiness agent tensile shear strength test method.Material: LY12CZ aluminium alloy.
3, dielectric properties: test adopts under waveguide short method 9.8GHz condition and tests.
The performance comparison table of table 1: embodiment and comparative example
Embodiment, than comparative example, has good resistance toheat, 600 ℃ of carbon yields under air especially, and embodiment is all far above comparative example; Simultaneously the high temperature bonding intensity of embodiment is higher than comparative example, and dielectric properties are not produced to considerable influence, is applicable to the application of high-temperature resistance adhesive field.
The explanation of above embodiment is just for helping to understand method of the present invention.It should be pointed out that for those skilled in the art, or else depart under the prerequisite of the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (7)
1. the polyimide modified cyanate tackiness agent of ethynyl, is characterized in that this tackiness agent comprises 100 parts of cyanate ester resins, 1～100 part of ethynyl polyimide resin and 1～10 part of mineral filler properties-correcting agent by weight; Wherein said cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming.
2. the polyimide modified cyanate tackiness agent of a kind of ethynyl according to claim 1, is characterized in that the structural formula of described ethynyl polyimide resin is:
, wherein polymerization degree n is 1～9, Ar
1for
ar
2for
3. the polyimide modified cyanate tackiness agent of a kind of ethynyl according to claim 1 and 2, ethynyl polyimide resin described in it is characterized in that is prepared in the steps below: in three-necked bottle, add N, N-N,N-DIMETHYLACETAMIDE, under nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after stirring 1 hour, add aromatic diamines, stir 1～5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1～5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5～0.9:0.2～1; Then add toluene, be warming up to 120～130 ℃ of back flow reaction 1～4 hour; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 130～140 ℃ of oven dry, obtains ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3, the amino benzoxazole of 4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-.
4. the preparation method of the polyimide modified cyanate tackiness agent of ethynyl as claimed in claim 1, is characterized in that the method carries out according to the following steps:
One, by weight, 100 parts of cyanate ester resins are heated to 115～120 ℃;
Two, 1～100 part of ethynyl polyimide resin is joined in the polar solvent of 50～200 parts, be warming up to 130～160 ℃, and stirring and dissolving 30min, obtain mixture, then keep temperature that mixture is added in cyanate ester resin, at 120～140 ℃, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added under 90～120 ℃ of whipped states to 1～5 part of mineral filler properties-correcting agent, after stirring 10～30min, make tackiness agent;
Described in step 1, cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by any mixtures than forming;
Described in step 2, polar solvent is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by any mixtures than forming;
Described in step 3, mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by any mixtures than forming;
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, under nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after stirring 1 hour, add aromatic diamines, stir 1～5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1～5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5～0.9:0.2～1; Then add toluene, be warming up to 120～130 ℃ of back flow reaction 1～4 hour; Solution is down to after room temperature, is added drop-wise in dehydrated alcohol, and precipitating was filtered after 1 hour, and precipitation, after the absolute ethanol washing of 80 ℃ 3 times, 130～140 ℃ of oven dry, obtains ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3, the amino benzoxazole of 4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-.
5. the preparation method of the polyimide modified cyanate tackiness agent of ethynyl according to claim 4, is characterized in that being warming up to 140～150 ℃ in step 2.
6. according to the preparation method of the polyimide modified cyanate tackiness agent of the ethynyl described in claim 4 or 5, the mol ratio that it is characterized in that aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.8:0.4.
7. according to the preparation method of the polyimide modified cyanate tackiness agent of the ethynyl described in claim 4 or 5, the mol ratio that it is characterized in that aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5:1.
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| EP3115396A1 (en) * | 2015-07-03 | 2017-01-11 | Airbus Defence and Space GmbH | Cyanate ester/aryl ethynyl polyimide resins for composite materials |
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| US7819938B2 (en) * | 2004-12-22 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Highly aromatic compounds and polymers as precursors to carbon nanotube and metal nanoparticle compositions in shaped solids |
| CN101560371B (en) * | 2008-04-18 | 2012-08-08 | 中国科学院化学研究所 | High temperature resistant thermosetting polyimide adhesive and preparation method thereof |
| JP2010047704A (en) * | 2008-08-22 | 2010-03-04 | Fujifilm Corp | Resin composition and film or coating film formed using resin the composition |
| CN102618206B (en) * | 2012-03-28 | 2013-12-04 | 黑龙江省科学院石油化学研究院 | Polyimide adhesive |
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