CN103965824B - 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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- CN103965824B CN103965824B CN201410208713.7A CN201410208713A CN103965824B CN 103965824 B CN103965824 B CN 103965824B CN 201410208713 A CN201410208713 A CN 201410208713A CN 103965824 B CN103965824 B CN 103965824B
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- 0 C*(CCC(*(C(C)*1*(C)c2cccc(C=C)c2)(C(C)=O)C1=O)=O)C(CC(C1(C(*2c3cc(C=C)ccc3)=O)C2=O)=O)C1=C Chemical compound C*(CCC(*(C(C)*1*(C)c2cccc(C=C)c2)(C(C)=O)C1=O)=O)C(CC(C1(C(*2c3cc(C=C)ccc3)=O)C2=O)=O)C1=C 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N Nc(cc1)ccc1Oc(cc1)ccc1N Chemical compound Nc(cc1)ccc1Oc(cc1)ccc1N HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N O=C(c(c1c2)ccc2-c2cccc(C(O3)=O)c2C3=O)OC1=O Chemical compound O=C(c(c1c2)ccc2-c2cccc(C(O3)=O)c2C3=O)OC1=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N O=C(c(c1c2)ccc2Oc(cc2)cc(C(O3)=O)c2C3=O)OC1=O Chemical compound O=C(c(c1c2)ccc2Oc(cc2)cc(C(O3)=O)c2C3=O)OC1=O QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N O=C(c(cc1)c2cc1-c(cc1)cc(C(O3)=O)c1C3=O)OC2=O Chemical compound O=C(c(cc1)c2cc1-c(cc1)cc(C(O3)=O)c1C3=O)OC2=O WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
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 ester adhesive and preparation method thereof.
Background technology
Tackiness agent is 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, thus proposes new demand to the temperature resistant grade of macromolecular material.Meanwhile, in order to promote the wave penetrate capability of Airborne Radome, requirements at the higher level are proposed to the dielectric properties of the macromolecular material comprising tackiness agent, as required the dielectric characterization at GHz band display 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 non-volatility low-molecular material produces in the curing process simultaneously.Therefore, as above-mentioned adhesive material, generally adopt the cyanate tackiness agent with good workability and dielectric properties.But causing material fragility comparatively large due to cross-linking density high after ethylene rhodanate resin curing, the existence of C-H bond and ehter bond in cyanate structure simultaneously, causes adverse influence to the resistance toheat of material, significantly limit 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 adhesive material toughness can be improved, to also reduce use temperature simultaneously.Therefore, in order to entirety improves toughness and the heat aging performance of cyanate, generally adopt thermosetting resin to its modification: to adopt epoxy resin modification cyanate, though have good mechanical property and adhesiveproperties after solidification, its thermotolerance is poor; Adopt bimaleimide resin modified cyanic acid ester, form cyanate resin (bismaleimide triazine is called for short BT resin) after solidification 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 matrix fragility larger, and adhesiveproperties is poor, is difficult to improve cyanate ester material toughness.
Prior art adopts epoxy resin, bimaleimide resin and allylic compound modified cyanate ester resin that the resistance toheat of tackiness agent is declined; Catalytic effect is solidified with to cyanate simultaneously, affects process window and shelf lives; In order to avoid prior art is not enough, 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 ester adhesive 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, the process window keeping it wider and suitable gel time.Simultaneously because ethynyl polyimide and cyanate have similar solidification value interval, thus synchronously solidify; On the other hand, the crosslinking reaction due to ethynyl polyimide does not affect triazine ring and is formed, thus little on the dielectric properties impact of system.
Present invention employs ethynyl polyimide containing soft segment as the matrix resin of sizing agent, the introducing of its acetylene end group has higher cross-linking density after making 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, it is interval that acetylene end group polyimide and cyanate have similar solidification value, both can synchronously solidify and not have cross-linking set to occur each other, the complete inierpeneirating network structure formed can either keep the dielectric properties that cyanate is good, can embody again thermal stability and the toughness of material of polyimide excellence.
Present invention employs in backbone structure the polyimide of bit architecture and ether ketone structure between containing, make it have good solubility energy in lower softening temperature and organic solvent, give the better adhesiveproperties of tackiness agent and mechanical property simultaneously; By controlling diamines/dianhydride kind and the ingredient proportion of ethynyl polyimide, controlling polymericular weight and backbone structure, thus reaching the object to cyanate ester resin/ethynyl polyimide toughening modifying.
The polyimide modified cyanate ester adhesive tool of ethynyl adopting the present invention to prepare has the following advantages:
(1) there is superior heat resistance energy, 5% heat decomposition temperature >=410 DEG C;
(2) there is lower dielectric loss and specific inductivity: ε < 3.3, tan δ < 0.015;
(3) adhesiveproperties is higher, shearing resistance and high temperature conservation rate high, its room temperature shearing resistance >=15MPa, its 350 DEG C of down cut intensity >=10MPa;
(4) manufacturability is better, and gel time is long, the moderate viscosity of sizing agent.
The present invention fills a prescription rationally, prepared tackiness agent has good resistance toheat, mechanical property, adhesiveproperties, can be used for splicing thermal characteristics and dielectric properties being required to higher metal or composite material structural member, thus widen 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, with the requirement of satisfied aerospace high-performance wave transparent tackiness agent of new generation.
Summary of the invention
The present invention is to solve the poor heat stability of existing cyanate ester adhesive existence, the problem of toughness deficiency, providing polyimide modified cyanate ester adhesive of a kind of ethynyl and preparation method thereof.
The polyimide modified cyanate ester adhesive 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 arbitrarily than the mixture formed; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed.
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, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, 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 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained 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, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.
The preparation method of the polyimide modified cyanate ester adhesive 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 DEG C;
Two, 1 ~ 100 part of ethynyl polyimide resin is joined in the polar solvent of 50 ~ 200 parts, be warming up to 130 ~ 160 DEG C, and stirring and dissolving 30min, obtain mixture, then temperature is kept to add in cyanate ester resin by mixture, at 120 ~ 140 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 1 ~ 5 part of mineral filler properties-correcting agent under 90 ~ 120 DEG C of whipped states, after stirring 10 ~ 30min, namely obtain tackiness agent;
Cyanate ester resin described in step one is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by arbitrarily than the mixture formed;
Polar solvent described in step 2 is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by arbitrarily than the mixture formed;
Mineral filler properties-correcting agent described in step 3 is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed.
The present invention includes following beneficial effect:
Accompanying drawing explanation
Fig. 1 is the thermogravimetric curve figure of tackiness agent prepared by embodiment 1 and comparative example 1.
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 ester adhesive 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 arbitrarily than the mixture formed; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed.
Embodiment two: present embodiment and embodiment one unlike: 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 and embodiment one or two unlike: described ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N, N-N,N-DIMETHYLACETAMIDE, in a nitrogen atmosphere, to N, aromatic dianhydride is added in N-N,N-DIMETHYLACETAMIDE, add aromatic diamines after 1 hour to be mixed, 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 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained 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, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.Other is identical with embodiment one or two.
Embodiment four: the preparation method of the polyimide modified cyanate ester adhesive of the ethynyl described in embodiment one, carry out according to the following steps:
One, by weight, 100 parts of cyanate ester resins are heated to 115 ~ 120 DEG C;
Two, 1 ~ 100 part of ethynyl polyimide resin is joined in the polar solvent of 50 ~ 200 parts, be warming up to 130 ~ 160 DEG C, and stirring and dissolving 30min, obtain mixture, then temperature is kept to add in cyanate ester resin by mixture, at 120 ~ 140 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 1 ~ 5 part of mineral filler properties-correcting agent under 90 ~ 120 DEG C of whipped states, after stirring 10 ~ 30min, namely obtain tackiness agent;
Cyanate ester resin described in step one is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by arbitrarily than the mixture formed;
Polar solvent described in step 2 is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by arbitrarily than the mixture formed;
Mineral filler properties-correcting agent described in step 3 is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed;
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, 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 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained 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, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.
Embodiment five: present embodiment and embodiment four unlike: be warming up to 140 ~ 150 DEG C in step 2.Other is identical with embodiment four.
Embodiment six: present embodiment and embodiment four or five unlike: 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 and embodiment four or five unlike: 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 ester adhesive 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 DEG C;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 100 parts, be warming up to 160 DEG C, and stirring and dissolving 30min, obtain mixture, then keep temperature to add in cyanate ester resin by mixture, at 120 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 4 parts of aerosils under 100 DEG C of whipped states, after stirring 30min, namely obtain tackiness agent;
Polar solvent described in step 2 is made up 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, in a nitrogen atmosphere, to N, 31.02g (0.1mol) 2 is added in N-N,N-DIMETHYLACETAMIDE, 3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride, 16.02g (0.08mol) 3 is added after 1 hour to be mixed, 4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; Acetylenylaniline between 4.68g (0.04mol) is added, stirring reaction 3 hours in mixing solutions; Then add 50mL toluene, be warming up to 125 DEG C of back flow reaction 4 hours; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 140 DEG C of oven dry, obtained ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
Be cured the polyimide modified cyanate ester adhesive of ethynyl prepared by the present embodiment, curing process is: 130 DEG C/1h+200 DEG C/2h, aftertreatment 260 DEG C/2h.
Embodiment 2:
The preparation method of the polyimide modified cyanate ester adhesive 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 DEG C;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 100 parts, be warming up to 160 DEG C, and stirring and dissolving 30min, obtain mixture, then keep temperature to add in cyanate ester resin by mixture, at 120 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 4 parts of aerosils under 100 DEG C of whipped states, after stirring 30min, namely obtain tackiness agent;
Polar solvent described in step 2 is made up 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, in a nitrogen atmosphere, to N, 31.02g (0.1mol) 2 is added in N-N,N-DIMETHYLACETAMIDE, 3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride, 10.01g (0.05mol) 3 is added after 1 hour to be mixed, 4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; Acetylenylaniline between 11.71g (0.1mol) is added, stirring reaction 3 hours in mixing solutions; Then add 50mL toluene, be warming up to 125 DEG C of back flow reaction 4 hours; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 140 DEG C of oven dry, obtained ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
Be cured the polyimide modified cyanate ester adhesive of ethynyl prepared by the present embodiment, curing process is: 130 DEG C/1h+200 DEG C/2h, aftertreatment 260 DEG C/2h.
Embodiment 3:
The preparation method of the polyimide modified cyanate ester adhesive 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 DEG C;
Two, 70 parts of ethynyl polyimide resins are joined in the polar solvent of 150 parts, be warming up to 160 DEG C, and stirring and dissolving 30min, obtain mixture, then keep temperature to add in cyanate ester resin by mixture, at 120 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 4 parts of aerosils under 100 DEG C of whipped states, after stirring 30min, namely obtain tackiness agent;
Polar solvent described in step 2 is made up 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, in a nitrogen atmosphere, to N, 29.42g (0.1mol) 3 is added in N-N,N-DIMETHYLACETAMIDE, 3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 16.02g (0.08mol) 3 is added after 1 hour to be mixed, 4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; Acetylenylaniline between 4.68g (0.04mol) is added, stirring reaction 3 hours in mixing solutions; Then add 50mL toluene, be warming up to 125 DEG C of back flow reaction 4 hours; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 140 DEG C of oven dry, obtained ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
Be cured the polyimide modified cyanate ester adhesive of ethynyl prepared by the present embodiment, curing process is: 130 DEG C/1h+200 DEG C/2h, aftertreatment 260 DEG C/2h.
Embodiment 4:
The preparation method of the polyimide modified cyanate ester adhesive 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 DEG C;
Two, 50 parts of ethynyl polyimide resins are joined in the polar solvent of 150 parts, be warming up to 160 DEG C, and stirring and dissolving 30min, obtain mixture, then keep temperature to add in cyanate ester resin by mixture, at 120 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 4 parts of aerosils under 100 DEG C of whipped states, after stirring 30min, namely obtain tackiness agent;
Polar solvent described in step 2 is made up 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, in a nitrogen atmosphere, to N, 29.42g (0.1mol) 2 is added in N-N,N-DIMETHYLACETAMIDE, 3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 16.02g (0.08mol) 3 is added after 1 hour to be mixed, 4 '-diaminodiphenyl oxide, stirs 3 hours, obtains mixing solutions; Acetylenylaniline between 4.68g (0.04mol) is added, stirring reaction 3 hours in mixing solutions; Then add toluene, be warming up to 125 DEG C of back flow reaction 4 hours; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 140 DEG C of oven dry, obtained ethynyl polyimide resin.
The structural formula of the ethynyl polyimide resin of preparation is:
Be cured the polyimide modified cyanate ester adhesive of ethynyl prepared by the present embodiment, curing process is: 130 DEG C/1h+200 DEG C/2h, aftertreatment 260 DEG C/2h.
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 DEG C in beaker, under 100 DEG C of whipped states, add 4 parts of aerosils, stir after 30min stirs and namely obtain tackiness agent.The solidification process of tackiness agent is identical with embodiment 1-4.
Tackiness agent after solidifying embodiment 1 and comparative example 1 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 tackiness agent prepared by embodiment 1 and comparative example 1, wherein curve a is the thermogravimetric curve of the polyimide modified cyanate ester adhesive of ethynyl prepared by embodiment 1, the thermogravimetric curve of the tackiness agent that curve b provides for comparative example 1.
Tackiness agent after the solidification prepare above-mentioned 5 embodiments has carried out the test of second-order transition temperature, thermostability, shearing resistance, stripping strength and dielectric properties, and 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 DEG C/min; Measurement 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 is tested under adopting waveguide short method 9.8GHz condition.
Table 1: the performance comparison table of embodiment and comparative example
Embodiment, compared to comparative example, has good resistance toheat, 600 DEG C of carbon yields especially under air, and embodiment is all far above comparative example; The high temperature bonding intensity of embodiment is higher than comparative example simultaneously, and does not produce considerable influence to dielectric properties, is applicable to the application of high-temperature resistance adhesive field.
The explanation of above embodiment just understands method of the present invention for helping.It should be pointed out that for those skilled in the art, under or else departing from the prerequisite of the principle of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (5)
1. the polyimide modified cyanate ester adhesive 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 arbitrarily than the mixture formed; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed;
The structural formula of described ethynyl polyimide resin is:
wherein polymerization degree n is 1 ~ 9, Ar
1for
Described ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, 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 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained 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, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.
2. the preparation method of the polyimide modified cyanate ester adhesive of ethynyl as claimed in claim 1, is characterized in that the method is carried out according to the following steps:
One, by weight, 100 parts of cyanate ester resins are heated to 115 ~ 120 DEG C;
Two, 1 ~ 100 part of ethynyl polyimide resin is joined in the polar solvent of 50 ~ 200 parts, be warming up to 130 ~ 160 DEG C, and stirring and dissolving 30min, obtain mixture, then temperature is kept to add in cyanate ester resin by mixture, at 120 ~ 140 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;
Three, multipolymer is added 1 ~ 5 part of mineral filler properties-correcting agent under 90 ~ 120 DEG C of whipped states, after stirring 10 ~ 30min, namely obtain tackiness agent;
Cyanate ester resin described in step one is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by arbitrarily than the mixture formed;
Polar solvent described in step 2 is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by arbitrarily than the mixture formed;
Mineral filler properties-correcting agent described in step 3 is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed;
Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, 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 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained 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, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.
3. the preparation method of the polyimide modified cyanate ester adhesive of ethynyl according to claim 2, is characterized in that being warming up to 140 ~ 150 DEG C in step 2.
4. the preparation method of the polyimide modified cyanate ester adhesive of the ethynyl according to Claims 2 or 3, is characterized in that the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.8:0.4.
5. the preparation method of the polyimide modified cyanate ester adhesive of the ethynyl according to Claims 2 or 3, is characterized in that the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5:1.
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| DE102015008496A1 (en) * | 2015-07-03 | 2017-01-05 | Airbus Defence and Space GmbH | Cyanate ester / arylethynyl polyimide resins for composites |
| CN109957373A (en) * | 2019-04-08 | 2019-07-02 | 宁海县新佳塑料制品有限公司 | Moisture-proof seamless removable seamless viscose glue of high intensity of one kind and preparation method thereof |
| CN114891479B (en) * | 2022-05-24 | 2023-05-26 | 广东硕成科技股份有限公司 | Heat-resistant pressure-resistant sizing material, and preparation method and application thereof |
| CN115181419A (en) * | 2022-07-14 | 2022-10-14 | 重庆工商大学 | Method for modifying cyanate ester by vinyl mesoporous silica and polyimide |
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