CN102732208A - Modified 250 DEG C high temperature resistant cyanate ester/benzoxazine resin adhesive and preparation method thereof - Google Patents
Modified 250 DEG C high temperature resistant cyanate ester/benzoxazine resin adhesive and preparation method thereof Download PDFInfo
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- CN102732208A CN102732208A CN2012102340780A CN201210234078A CN102732208A CN 102732208 A CN102732208 A CN 102732208A CN 2012102340780 A CN2012102340780 A CN 2012102340780A CN 201210234078 A CN201210234078 A CN 201210234078A CN 102732208 A CN102732208 A CN 102732208A
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Abstract
The invention relates to a 250 DEG C high temperature resistant cyanate ester/benzoxazine resin adhesive and a preparation method thereof, and is characterized in that the adhesive comprises the following components: cyanate ester resin, bismaleimide resin, diallyl bisphenol A, benzoxazine resin and some solvents. The 250 DEG C high temperature resistant adhesive is prepared by adopting a fusion mixing method and a solution mixing method. When the 250 DEG C high temperature resistant adhesive is thermally cured, a co-curing reaction is carried out and a high temperature resistant adhesive in a co-curing structure is obtained. The adhesive has the advantages of excellent mechanical property, heat resistance and dielectric property. The adhesive has an irreplaceable action in production of an aviation power supply, and can be popularized to high temperature insulation aspects of aviation, ships, weapons, nuclear industry and high-speed electric locomotives and production of composites and copper-clad plates. The preparation method of the adhesive has the characteristics of wide applicability, simple operation process, and the like.
Description
Technical field
The present invention relates to anti-250 ℃ of high temperature adhesives of a kind of modified cyanic acid ester/benzoxazine colophony and preparation method; Be that a kind of employing contains bi-maleimide modified cyanate ester resin as matrix; Mix as modified filler with dilution benzoxazine colophony and diallyl bisphenol, can be widely used in high-tech areas such as aerospace, electric power, electronics.
Background technology
Developed time of decades at home and abroad for high-temperature resistance adhesive, the above tackiness agent of wherein high temperature resistant 250 degree has polyimides adhesive, polybenzimidazole adhesive, thermostable epoxy resin adhesive, modified phenolic resin adhesive and organic silicon adhesive etc.But above-mentioned tackiness agent exists following shortcoming in special places such as Aeronautics and Astronautics bonding: the fragility of (1) above-mentioned tackiness agent is generally all bigger, causes cracking in the following process after bonding easily; (2) solidification value of above-mentioned tackiness agent is generally all higher, in solidification process, because the thermal expansivity and the thermal stresses of tackiness agent and punching are prone to cause bonding cracking.Therefore, domestic and international in recent years, in the stable on heating while of improving tackiness agent, toughness, the curing process property of high-temperature resistance adhesive conducted a research as main direction.In the U.S. and Japan,, obtained bigger progress with novel long-chain monomer and the toughness and the manufacturability of end amino silane compounds modified polyimide tackiness agent to raising fire resistant polyimide resin.High temperature resistant in order to prepare (more than or equal to 250 degree), high cohesive force, good toughness, low-dielectric loss, the tackiness agent of low-temperature curing carries out bonding, to improve tackiness agent reliability of applying at high temperature.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes anti-250 ℃ of high temperature adhesives of a kind of modified cyanic acid ester/benzoxazine colophony and preparation method; Irreplaceable effect is not only arranged in the manufacturing of airplane power source, but also can be generalized to the high-temperature insulation aspect of space flight, boats and ships, weapons, nuclear industry and electric express locomotive and the manufacturing of matrix material and copper-clad plate.
Technical scheme
The anti-250 ℃ of high temperature adhesives of a kind of cyanate/benzoxazine colophony is characterized in that component is: the solvent of 5～30 parts of 20～50 parts of cyanate ester resins, 10～40 parts of bimaleimide resins, 5～20 parts of benzoxazine colophonies, diallyl bisphenol and 10～40 parts; Said part is weight part.
Said cyanate ester resin be in bisphenol A cyanate ester resin, phenolic cyanate ester resin, bis-phenol M type cyanate ester resin or the line style phenolic cyanate ester resin any, or multiple mixture.
Said bimaleimide resin is any in ditane type bismaleimides, a penylene bismaleimides, diphenyl ether type bismaleimides, diallyl type bismaleimides, the diamino-anthraquinone bismaleimides Huo oxadiazole structure to prolong type bimaleimide resin, or multiple mixture.
Said benzoxazine colophony is bisphenol A-type benzoxazine colophony and bis-phenol M type benzoxazine colophony or both mixtures.
Said solvent is any or the multiple mixture in absolute ethyl alcohol, N, YLENE, pimelinketone, N,N-DIMETHYLACETAMIDE, toluene or the trieline.
A kind of method for preparing the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony is characterized in that step is following:
Step 1:, obtain B component cyanate/bimaleimide resin with 20～50 parts of cyanate ester resins and 10～40 parts of bimaleimide resins fusion and copolymer-1 0min～100min under 120～200 ℃ temperature;
Step 2: the solvent of 5～30 parts diallyl bisphenols, 5～20 parts of benzoxazine colophonies and 10～40 parts is at room temperature stirred, it is dissolved fully obtain the C component;
Step 3: reduce the temperature of temperature to 80～130 ℃, the C component is poured into carries out condensing reflux in the B component, and fusion copolymerization 20min～100min, promptly obtain the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony.
A kind of curing of weighing the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony is characterized in that: curing process is 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, last 250 ℃/4h of aftertreatment.
Beneficial effect
Anti-250 ℃ of high temperature adhesives of a kind of modified cyanic acid ester/benzoxazine colophony and preparation method that the present invention proposes, advantage is: the monomeric consistency of CE monomer and BMI is good, and forms cyanate/bimaleimide resin, i.e. B component.Diallyl bisphenol and benzoxazine colophony are joined in the B system, play when strengthening toughness reinforcing effect, also can not reduce the dielectric properties of prepolymerization system significantly; The adding of diallyl bisphenol and benzoxazine colophony can further impel the formation of the toughness group in the B system.Owing to the excellent heat resistance of each material that adds, the group of formation has good thermotolerance simultaneously, thereby improves each item performance of tackiness agent.And then the cf-that under high speed rotating, produces of the blade that can satisfy airplane power source, the development of Aeronautics and Astronautics is had very high use value.
Embodiment
Combine embodiment that the present invention is further described at present:
Embodiment 1
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 20 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 40 parts of N, N '-N, 10 parts of diallyl bisphenols and 5 parts of benzoxazine colophonies mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
Embodiment 2
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 20 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 20 parts of N, N '-N, 20 parts of YLENE, 20 parts of diallyl bisphenols and 5 parts of benzoxazine colophonies mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
Embodiment 3
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 30 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 20 parts of N, N '-N, 10 parts of YLENE, 10 parts of pimelinketone and 20 parts of benzoxazine colophonies mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
Embodiment 4:
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 30 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 20 parts of N, N '-N, 10 parts of YLENE, 10 parts of pimelinketone, 20 parts of diallyl bisphenols and 5 parts of benzoxazine colophonies mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
Embodiment 5:
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 30 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 20 parts of N, N '-N, 10 parts of YLENE, 10 parts of pimelinketone, 30 parts of diallyl bisphenols and 10 parts of benzoxazine colophonies mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
Embodiment 6:
Take by weighing 40 parts of bisphenol A cyanate esters (BADCy) in there-necked flask, be heated to fusion, add 30 part 4 then, 4 '-ditane type bismaleimides heated and stirred gets the B component, at 120～200 ℃ of reaction 10min～100min; With 20 parts of N, N '-N, 10 parts of YLENE, 10 parts of pimelinketone and 30 parts of diallyl bisphenols mix stirring and obtain diluting the C component; Adjust the temperature to 80～130 ℃ then, under this temperature, the C component is poured into condensing reflux in the B component of there-necked flask, and fusion copolymerization 20min～100min, the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony promptly obtained.Its curing process is: 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, and last 250 ℃/4h of aftertreatment.
The performance index of the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony after smear solidifies of this enforcement preparation are following:
Under the normal temperature condition: tensile shear strength>=18MPa; Room temperature shearing impact intensity (steel)>=15kJ/m
2Specific inductivity (50HZ)≤3.6; Dielectric loss factor (50HZ)≤0.011;
Under 250 ℃ of hot conditionss: tensile shear strength>=10MPa; Specific inductivity (50HZ)≤3.3; Dielectric loss factor (50HZ)≤0.009;
Sample is immersed in 130 ℃ of RP-3 Aviation Fuels behind the 100h, at room temperature tests shearing resistance >=15MPa then;
Sample is immersed in 200 ℃ of 4050 lubricating oil behind the 100h, tests shearing resistance >=14MPa under the room temperature;
Viscosity≤22s;
Solids content >=50%;
Storage period >=6 month.
Claims (7)
1. anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony is characterized in that component is: the solvent of 5～30 parts of 20～50 parts of cyanate ester resins, 10～40 parts of bimaleimide resins, 5～20 parts of benzoxazine colophonies, diallyl bisphenol and 10～40 parts; Said part is weight part.
2. according to the anti-250 ℃ of high temperature adhesives of the said cyanate/benzoxazine colophony of claim 1; It is characterized in that: said cyanate ester resin be in bisphenol A cyanate ester resin, phenolic cyanate ester resin, bis-phenol M type cyanate ester resin or the line style phenolic cyanate ester resin any, or multiple mixture.
3. according to the anti-250 ℃ of high temperature adhesives of the said cyanate/benzoxazine colophony of claim 1; It is characterized in that: said bimaleimide resin is any in ditane type bismaleimides, a penylene bismaleimides, diphenyl ether type bismaleimides, diallyl type bismaleimides, the diamino-anthraquinone bismaleimides Huo oxadiazole structure to prolong type bimaleimide resin, or multiple mixture.
4. according to the anti-250 ℃ of high temperature adhesives of the said cyanate/benzoxazine colophony of claim 1, it is characterized in that: said benzoxazine colophony is bisphenol A-type benzoxazine colophony and bis-phenol M type benzoxazine colophony or both mixtures.
5. according to the anti-250 ℃ of high temperature adhesives of the said cyanate/benzoxazine colophony of claim 1, it is characterized in that: said solvent is any or the multiple mixture in absolute ethyl alcohol, N, YLENE, pimelinketone, N,N-DIMETHYLACETAMIDE, toluene or the trieline.
6. method for preparing the anti-250 ℃ of high temperature adhesives of each said cyanate/benzoxazine colophony of claim 1～5 is characterized in that step is following:
Step 1:, obtain B component cyanate/bimaleimide resin with 20～50 parts of cyanate ester resins and 10～40 parts of bimaleimide resins fusion and copolymer-1 0min～100min under 120～200 ℃ temperature;
Step 2: the solvent of 5～30 parts diallyl bisphenols, 5～20 parts of benzoxazine colophonies and 10～40 parts is at room temperature stirred, it is dissolved fully obtain the C component;
Step 3: reduce the temperature of temperature to 80～130 ℃, the C component is poured into carries out condensing reflux in the B component, and fusion copolymerization 20min～100min, promptly obtain the anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony.
7. the curing of the prepared anti-250 ℃ of high temperature adhesives of cyanate/benzoxazine colophony of a claim 6 is characterized in that: curing process is 100 ℃/2h+150 ℃/2h+180 ℃/2h+220 ℃/2h, last 250 ℃/4h of aftertreatment.
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| CN103074027A (en) * | 2013-01-11 | 2013-05-01 | 西北工业大学 | Phenolphthalein cyanate/benzoxazine resin adhesive resistant to 250 DEG C and preparation method |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
| CN106280449A (en) * | 2016-08-19 | 2017-01-04 | 大连理工大学 | A kind of high tenacity, low viscous benzimidazole dihydrochloride/diallyl diphenol/BMI blending resin and preparation method thereof |
| CN108264875A (en) * | 2018-02-12 | 2018-07-10 | 成都理工大学 | A kind of resistance to 150 DEG C of high temperature adhesives and preparation method thereof |
| CN111500249A (en) * | 2020-05-20 | 2020-08-07 | 山东金宝电子股份有限公司 | Low-dielectric-property low-water-absorption halogen-free copper-clad plate and preparation method thereof |
| CN115584025A (en) * | 2022-12-07 | 2023-01-10 | 四川泸天化创新研究院有限公司 | Modified BT resin and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074027A (en) * | 2013-01-11 | 2013-05-01 | 西北工业大学 | Phenolphthalein cyanate/benzoxazine resin adhesive resistant to 250 DEG C and preparation method |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
| CN106280449A (en) * | 2016-08-19 | 2017-01-04 | 大连理工大学 | A kind of high tenacity, low viscous benzimidazole dihydrochloride/diallyl diphenol/BMI blending resin and preparation method thereof |
| CN108264875A (en) * | 2018-02-12 | 2018-07-10 | 成都理工大学 | A kind of resistance to 150 DEG C of high temperature adhesives and preparation method thereof |
| CN111500249A (en) * | 2020-05-20 | 2020-08-07 | 山东金宝电子股份有限公司 | Low-dielectric-property low-water-absorption halogen-free copper-clad plate and preparation method thereof |
| CN115584025A (en) * | 2022-12-07 | 2023-01-10 | 四川泸天化创新研究院有限公司 | Modified BT resin and preparation method thereof |
| CN115584025B (en) * | 2022-12-07 | 2023-09-26 | 四川泸天化创新研究院有限公司 | Modified BT resin and preparation method thereof |
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Application publication date: 20121017 |