CN102676112A - Low-temperature curing cyanate ester adhesive and preparation method thereof - Google Patents
Low-temperature curing cyanate ester adhesive and preparation method thereof Download PDFInfo
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- CN102676112A CN102676112A CN201210187060XA CN201210187060A CN102676112A CN 102676112 A CN102676112 A CN 102676112A CN 201210187060X A CN201210187060X A CN 201210187060XA CN 201210187060 A CN201210187060 A CN 201210187060A CN 102676112 A CN102676112 A CN 102676112A
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Abstract
The invention discloses a low-temperature curing cyanate ester adhesive and a preparation method thereof, which relate to an adhesive and a preparation method thereof and solve the technical problems of high curing temperature and short room-temperature storage period of the existing cyanate ester adhesive. The adhesive disclosed by the invention is manufactured by adopting cyanate ester resin, a catalyst, modified resin, organic nano particles, inorganic nano particles, a thinning agent and a toughening agent. The preparation method comprises the following steps that: firstly, a mixture A is prepared; secondly, the toughening agent is added into the mixture A to obtain a mixture B; thirdly, the modified resin and the thinning agent are added into the mixture B and are stirred and mixed uniformly, the catalyst is added into the mixture to obtain a substrate, and then the substrate and quartz fiber fabric are subjected to hot melting to be combined into a low-temperature curing cyanate ester carrier adhesive film, so the low-temperature curing cyanate ester adhesive is obtained. The curing temperature of the low-temperature curing cyanate ester adhesive prepared by the preparation method provided by the invention is low, the low-temperature curing cyanate ester adhesive can be cured at a temperature of 120-140 DEG C, and the room-temperature storage period of the low-temperature curing cyanate ester adhesive is as long as 20 days, and meanwhile, the low-temperature curing cyanate ester adhesive has high bonding strength and excellent heat-resistant performance and is suitable for bonded materials which cannot resist to high temperature.
Description
Technical field
The present invention relates to a kind of tackiness agent and preparation method thereof.
Background technology
Cyanate (CE) tackiness agent is as sqtructural adhesive kind of new generation; Combine the high thermal resistance of bimaleimide resin and the good process property of epoxy resin resin; Have simultaneously excellent mechanical property, wet-hot aging performance and dielectric properties again, have a wide range of applications at numerous areas such as aerospace, electronics.The cyanate tackiness agent is mainly used in the printed substrate of aerospace structural members, the stealthy structure of aircraft, the advanced radome of high-performance, satellite arm and high-frequency high-speed communication electronics etc. at present.
The characteristics of cyanate curing reaction are that solidification value is higher; Set time is long; Under the situation that does not add catalyzer; Under comparatively high temps (more than 200 ℃), carry out the curing of long period (more than the 7h), transformation efficiency is merely 90%, and reach higher transformation efficiency then needs longer time and the temperature of Geng Gao.Therefore, select effective catalyst particularly important for the room temperature placement and the curing of cyanate tackiness agent.Being used for cyanate solidified catalyzer at present mainly contains: 1, transition metal complex/alcohols catalyzer (US4608434); Transition metal complex/NP mixture catalyzer (US4604452, US4785075 and US4847233) 2, phenols and amine (US5385989) etc. contain the compound of reactive hydrogen; 3. organo-tin compound catalyzer (CN1467244A).Research shows that these several types of catalyzer commonly used at present all can not well be taken into account latent and catalytic activity or dielectric properties are influenced problems such as bigger.As, transition metal complex/NP effectively catalysis cyanate solidifies, but the dielectric properties of cured resin are descended, and the minimum solidification value of resin system is 177 ℃; Organic amine compound still has a strong impact on the room temperature storage phase of resin system to the katalysis highly significant of cyanate/epoxy systems.
Summary of the invention
The present invention is in order to solve the technical problem that existing cyanate adhesive curing temperature is high, the room temperature storage phase is short, a kind of low-temperature curing cyanate tackiness agent and preparation method thereof to be provided.
Low-temperature curing cyanate tackiness agent is processed by 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight.
The preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight;
Two, under 40 ℃～100 ℃ conditions; Cyanate ester resin, inorganic nano-particle and organic nano particle are mixed the back stir 20～50min with 60～300r/min speed; In impeller, disperse 20～60min then, obtain mixture A with 700～1500r/min speed;
Three, in mixture A, add the toughner that step 1 takes by weighing, under 100 ℃～150 ℃ condition, be stirred to dissolving fully, obtain mixture B with 60～300r/min speed;
Four, under 100 ℃～150 ℃ conditions, in mixture B, add modified resin and thinner, mix; Reduce temperature to 40 ℃～90 ℃; Add the catalyzer that step 1 takes by weighing, mix, promptly obtain low temperature modification cyanate adhesive matrix; Again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
Said cyanate ester resin is one or more the combination in dihydroxyphenyl propane cyanate, bisphenol b cyanate, bis-phenol E cyanate, bis-phenol M cyanate, phenolic cyanate, dicyclopentadiene type ethylene rhodanate and the cardanol ethylene rhodanate resin.
Said modified resin is bisphenol A type epoxy resin E-54; Bisphenol A type epoxy resin E-51; Bisphenol A type epoxy resin E-44; Bisphenol A type epoxy resin E-42; Bisphenol A type epoxy resin E-35; Bisphenol A type epoxy resin E-31; Bisphenol A type epoxy resin E-20; Bisphenol A type epoxy resin E-14; Bisphenol A type epoxy resin E-12; Bisphenol A type epoxy resin E-06; Bisphenol A type epoxy resin E-04; Bisphenol A type epoxy resin E-03; Novolac epoxy resin F-51; Novolac epoxy resin F-44; Novolac epoxy resin F-46; Bisphenol f type epoxy resin; Bisphenol-s epoxy resin; Resorcinol diglycidyl ether epoxy resin; Organosilicon epoxy resin 665; A kind of or wherein several kinds combination in organotitanium epoxy resin and the organic silicon-boron modified epoxy.
Said organic nano particle is polyacrylic ester nanoparticle, ZGK 5 nanoparticle or polyurethane nano particle.
Said inorganic nano-particle is one or more the combination in nano silicon, nano imvite, nano kaoline and the nano titanium oxide.
Said thinner is Tri Ethyleneglycol dimethacrylate, ethoxyquin bisphenol a dimethacrylate or polyethylene glycol dimethacrylate.
Said toughner is one or more the combination in paracril, carboxy terminated polybutadiene vinyl cyanide, polysulfones, polyethersulfone, polyetheretherketone and the polyetherimide.
Said catalyzer is made up of bisphenol cpd, active hydrogen compounds and transition metal complex;
Wherein the mass ratio of bisphenol cpd and active hydrogen compounds is 5～45: 6, and the mass ratio of active hydrogen compounds and transition metal complex is 1～45: 15;
Said bisphenol cpd is 2-chavicol, diallyl bisphenol, dihydroxyphenyl propane, bisphenol b, bisphenol-c, bis-phenol E, bis-phenol M, bisphenol S, Bisphenol F, bisphenol AF, bisphenol-ap or bisphenol b P;
Said active hydrogen compounds is 2-methylphenol, pyrocatechol, o-sec-butyl phenol or NP.
Said transition metal complex is an acetylacetone copper; Acetylacetone cobalt (cobalt is divalence or trivalent); Zinc acetylacetonate; Manganese acetylacetonate; Ferric acetyl acetonade; Methyl ethyl diketone is plumbous; Aluminium acetylacetonate; Vanadium acetylacetonate; Copper naphthenate; Cobalt naphthenate; Zinc naphthenate; Manganese naphthenate; Iron naphthenate; Aluminum napthenate; Lead naphthenate; The naphthenic acid vanadium; New certain herbaceous plants with big flowers acid copper; New certain herbaceous plants with big flowers acid cobalt; New certain herbaceous plants with big flowers acid zinc; New certain herbaceous plants with big flowers acid manganese; New certain herbaceous plants with big flowers acid iron; New certain herbaceous plants with big flowers lead plumbate; New certain herbaceous plants with big flowers acid bismuth; Isocaprylic acid copper; Cobalt iso-octoate; Isocaprylic acid zinc; Manganese iso-octoate; Isocaprylic acid iron; Isocaprylic acid is plumbous; Isocaprylic acid aluminium; The isocaprylic acid vanadium; Sad chromium or dibutyl tin laurate.
The solidification value of the low-temperature curing cyanate tackiness agent of the present invention preparation is low, can reach 20 days 120～140 ℃ of curing, room temperature storage phases, has high-adhesive-strength and excellent heat resisting simultaneously, be applicable to non-refractory by adhesives.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment low-temperature curing cyanate tackiness agent is processed by 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight;
Said cyanate ester resin is one or more the combination in dihydroxyphenyl propane cyanate, bisphenol b cyanate, bis-phenol E cyanate, bis-phenol M cyanate, phenolic cyanate, dicyclopentadiene type ethylene rhodanate and the cardanol ethylene rhodanate resin;
Said modified resin is bisphenol A type epoxy resin E-54; Bisphenol A type epoxy resin E-51; Bisphenol A type epoxy resin E-44; Bisphenol A type epoxy resin E-42; Bisphenol A type epoxy resin E-35; Bisphenol A type epoxy resin E-31; Bisphenol A type epoxy resin E-20; Bisphenol A type epoxy resin E-14; Bisphenol A type epoxy resin E-12; Bisphenol A type epoxy resin E-06; Bisphenol A type epoxy resin E-04; Bisphenol A type epoxy resin E-03; Novolac epoxy resin F-51; Novolac epoxy resin F-44; Novolac epoxy resin F-46; Bisphenol f type epoxy resin; Bisphenol-s epoxy resin; Resorcinol diglycidyl ether epoxy resin; Organosilicon epoxy resin 665; A kind of or wherein several kinds combination in organotitanium epoxy resin and the organic silicon-boron modified epoxy;
Said organic nano particle is polyacrylic ester nanoparticle, ZGK 5 nanoparticle or polyurethane nano particle;
Said inorganic nano-particle is one or more the combination in nano silicon, nano imvite, nano kaoline and the nano titanium oxide;
Said thinner is Tri Ethyleneglycol dimethacrylate, ethoxyquin bisphenol a dimethacrylate or polyethylene glycol dimethacrylate;
Said toughner is one or more the combination in paracril, carboxy terminated polybutadiene vinyl cyanide, polysulfones, polyethersulfone, polyetheretherketone and the polyetherimide;
Said catalyzer is made up of bisphenol cpd, active hydrogen compounds and transition metal complex;
Wherein the mass ratio of bisphenol cpd and active hydrogen compounds is 5～45: 6, and the mass ratio of active hydrogen compounds and transition metal complex is 1～45: 15;
Said bisphenol cpd is 2-chavicol, diallyl bisphenol, dihydroxyphenyl propane, bisphenol b, bisphenol-c, bis-phenol E, bis-phenol M, bisphenol S, Bisphenol F, bisphenol AF, bisphenol-ap or bisphenol b P;
Said active hydrogen compounds is 2-methylphenol, pyrocatechol, o-sec-butyl phenol or NP;
Said transition metal complex is an acetylacetone copper; Acetylacetone cobalt (II); Acetylacetone cobalt (III); Zinc acetylacetonate; Manganese acetylacetonate; Ferric acetyl acetonade; Methyl ethyl diketone is plumbous; Aluminium acetylacetonate; Vanadium acetylacetonate; Copper naphthenate; Cobalt naphthenate; Zinc naphthenate; Manganese naphthenate; Iron naphthenate; Aluminum napthenate; Lead naphthenate; The naphthenic acid vanadium; New certain herbaceous plants with big flowers acid copper; New certain herbaceous plants with big flowers acid cobalt; New certain herbaceous plants with big flowers acid zinc; New certain herbaceous plants with big flowers acid manganese; New certain herbaceous plants with big flowers acid iron; New certain herbaceous plants with big flowers lead plumbate; New certain herbaceous plants with big flowers acid bismuth; Isocaprylic acid copper; Cobalt iso-octoate; Isocaprylic acid zinc; Manganese iso-octoate; Isocaprylic acid iron; Isocaprylic acid is plumbous; Isocaprylic acid aluminium; The isocaprylic acid vanadium; Sad chromium or dibutyl tin laurate.
When cyanate ester resin described in this embodiment is compsn between each composition for arbitrarily than;
When modified resin described in this embodiment is compsn between each composition for arbitrarily than;
When organic nano particle described in this embodiment is compsn between each composition for arbitrarily than;
When inorganic nano-particle described in this embodiment is compsn between each composition for arbitrarily than;
When thinner described in this embodiment is compsn between each composition for arbitrarily than;
When toughner described in this embodiment is compsn between each composition for arbitrarily than;
When catalyzer described in this embodiment is compsn between each composition for arbitrarily than.
Embodiment two: the preparation method of this embodiment low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight;
Two, under 40 ℃～100 ℃ conditions; Cyanate ester resin, inorganic nano-particle and organic nano particle are mixed the back stir 20～50min with 60～300r/min speed; In impeller, disperse 20～60min then, obtain mixture A with 700～1500r/min speed;
Three, in mixture A, add the toughner that step 1 takes by weighing, under 100 ℃～150 ℃ condition, be stirred to dissolving fully, obtain mixture B with 60～300r/min speed;
Four, under 100 ℃～150 ℃ conditions, in mixture B, add modified resin and thinner, mix; Reduce temperature to 40 ℃～90 ℃; Add the catalyzer that step 1 takes by weighing, mix, promptly obtain low temperature modification cyanate adhesive matrix; Again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
Embodiment three: this embodiment and embodiment two are different is that cyanate ester resin described in the step 1 is one or more the combination in dihydroxyphenyl propane cyanate, bisphenol b cyanate, bis-phenol E cyanate, bis-phenol M cyanate, phenolic cyanate, dicyclopentadiene type ethylene rhodanate and the cardanol ethylene rhodanate resin.Other is identical with embodiment two.
When cyanate ester resin described in this embodiment is compsn between each composition for arbitrarily than.
Embodiment four: what this embodiment was different with embodiment two or three is that modified resin described in the step 1 is bisphenol A type epoxy resin E-54; Bisphenol A type epoxy resin E-51; Bisphenol A type epoxy resin E-44; Bisphenol A type epoxy resin E-42; Bisphenol A type epoxy resin E-35; Bisphenol A type epoxy resin E-31; Bisphenol A type epoxy resin E-20; Bisphenol A type epoxy resin E-14; Bisphenol A type epoxy resin E-12; Bisphenol A type epoxy resin E-06; Bisphenol A type epoxy resin E-04; Bisphenol A type epoxy resin E-03; Novolac epoxy resin F-51; Novolac epoxy resin F-44; Novolac epoxy resin F-46; Bisphenol f type epoxy resin; Bisphenol-s epoxy resin; Resorcinol diglycidyl ether epoxy resin; Organosilicon epoxy resin 665; A kind of or wherein several kinds combination in organotitanium epoxy resin and the organic silicon-boron modified epoxy.Other is identical with embodiment two or three.
When modified resin described in this embodiment is compsn between each composition for arbitrarily than.
Embodiment five: what this embodiment was different with one of embodiment two to four is that organic nano particle described in the step 1 is polyacrylic ester nanoparticle, ZGK 5 nanoparticle or polyurethane nano particle.Other is identical with one of embodiment two to four.
Embodiment six: this embodiment is different with one of embodiment two to five is that inorganic nano-particle described in the step 1 is one or more the combination in nano silicon, nano imvite, nano kaoline and the nano titanium oxide.Other is identical with one of embodiment two to five.
When inorganic nano-particle described in this embodiment is compsn between each composition for arbitrarily than.
Embodiment seven: what this embodiment was different with one of embodiment two to six is that thinner described in the step 1 is Tri Ethyleneglycol dimethacrylate, ethoxyquin bisphenol a dimethacrylate or polyethylene glycol dimethacrylate.Other is identical with one of embodiment two to six.
Embodiment eight: this embodiment is different with one of embodiment two to seven is that toughner described in the step 1 is one or more the combination in paracril, carboxy terminated polybutadiene vinyl cyanide, polysulfones, polyethersulfone, polyetheretherketone and the polyetherimide.Other is identical with one of embodiment two to seven.
When toughner described in this embodiment is compsn between each composition for arbitrarily than.
Embodiment nine: what this embodiment was different with one of embodiment two to eight is that catalyzer described in the step 1 is made up of bisphenol cpd, active hydrogen compounds and transition metal complex;
Wherein the mass ratio of bisphenol cpd and active hydrogen compounds is 5～45: 6, and the mass ratio of active hydrogen compounds and transition metal complex is 1～45:15;
Said bisphenol cpd is 2-chavicol, diallyl bisphenol, dihydroxyphenyl propane, bisphenol b, bisphenol-c, bis-phenol E, bis-phenol M, bisphenol S, Bisphenol F, bisphenol AF, bisphenol-ap or bisphenol b P;
Said active hydrogen compounds is 2-methylphenol, pyrocatechol, o-sec-butyl phenol or NP;
Said transition metal complex is an acetylacetone copper; Acetylacetone cobalt (cobalt is divalence or trivalent); Zinc acetylacetonate; Manganese acetylacetonate; Ferric acetyl acetonade; Methyl ethyl diketone is plumbous; Aluminium acetylacetonate; Vanadium acetylacetonate; Copper naphthenate; Cobalt naphthenate; Zinc naphthenate; Manganese naphthenate; Iron naphthenate; Aluminum napthenate; Lead naphthenate; The naphthenic acid vanadium; New certain herbaceous plants with big flowers acid copper; New certain herbaceous plants with big flowers acid cobalt; New certain herbaceous plants with big flowers acid zinc; New certain herbaceous plants with big flowers acid manganese; New certain herbaceous plants with big flowers acid iron; New certain herbaceous plants with big flowers lead plumbate; New certain herbaceous plants with big flowers acid bismuth; Isocaprylic acid copper; Cobalt iso-octoate; Isocaprylic acid zinc; Manganese iso-octoate; Isocaprylic acid iron; Isocaprylic acid is plumbous; Isocaprylic acid aluminium; The isocaprylic acid vanadium; Sad chromium or dibutyl tin laurate.Other is identical with one of embodiment two to eight.
Embodiment ten: this embodiment is different with one of embodiment two to nine be in the step 4 under 120 ℃ of conditions, in mixture B, add modified resin and thinner, mix, reduce temperature to 50 ℃.Other is identical with one of embodiment two to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
The preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 85 parts of bis-phenol E cyanates, 10 parts of dihydroxyphenyl propanes, 0.03 part of acetylacetone cobalt (II), 2 parts of NPs, 15 parts of bisphenol A type epoxy resin E-51,10 parts of polyacrylic ester nanoparticles, 2 parts of nano silicons, 5 parts of ethoxyquin bisphenol a dimethacrylate, 10 parts of polyethersulfones by weight;
Two, under 40 ℃ of conditions, bis-phenol E cyanate, nano silicon and polyacrylic ester nanoparticle are mixed the back stir 20min with 60r/min speed, in impeller, disperse 20min then with 800r/min speed, obtain mixture A;
Three, in mixture A, add the polyethersulfone that step 1 takes by weighing, under 100 ℃ condition, be stirred to dissolving fully, obtain mixture B with 60r/min speed;
Four, under 100 ℃ of conditions; In mixture B, add bisphenol A type epoxy resin E-51 and ethoxyquin bisphenol a dimethacrylate; Mix, reduce temperature to 40 ℃, add dihydroxyphenyl propane, NP and acetylacetone cobalt (cobalt is a divalence) that step 1 takes by weighing; Mix; Promptly obtain low temperature modification cyanate adhesive matrix, again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
Experiment two:
The preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 70 parts of dihydroxyphenyl propane cyanates, 30 parts of bisphenol A type epoxy resin E-51,2 parts of nano silicons, 10 parts of polyacrylic ester nanoparticles, 10 parts of polyethersulfones, 5 parts of ethoxyquin bisphenol a dimethacrylate, 15 parts of bis-phenol M, 2 parts of NPs and 0.03 part of acetylacetone cobalt (II) by weight;
Two, under 40 ℃ of conditions, dihydroxyphenyl propane cyanate, nano silicon and polyacrylic ester nanoparticle are mixed the back stir 20～50min with 60r/min speed, in impeller, disperse 20min then with 900r/min speed, obtain mixture A;
Three, in mixture A, add the polyethersulfone that step 1 takes by weighing, under 100 ℃ condition, be stirred to dissolving fully, obtain mixture B with 60r/min speed;
Four, under 100 ℃ of conditions; In mixture B, add bisphenol A type epoxy resin E-51 and ethoxyquin bisphenol a dimethacrylate; Mix, reduce temperature to 40 ℃, add bis-phenol M, NP and acetylacetone cobalt (cobalt is a divalence) that step 1 takes by weighing; Mix; Promptly obtain low temperature modification cyanate adhesive matrix, again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
Experiment three:
The preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 70 parts of bis-phenol E cyanates, 15 parts of dihydroxyphenyl propane cyanates, 15 parts of bisphenol A type epoxy resin E-51,2 parts of nano silicons, 10 parts of polyacrylic ester nanoparticles, 10 parts of polyethersulfones, 5 parts of ethoxyquin bisphenol a dimethacrylate, 5 parts of dihydroxyphenyl propanes, 5 parts of bis-phenol M, 2 parts of NPs and 0.02 part of acetylacetone copper by weight;
Two, under 50 ℃ of conditions; Bis-phenol E cyanate, dihydroxyphenyl propane cyanate, nano silicon and polyacrylic ester nanoparticle are mixed the back stir 30min with 80r/min speed; In impeller, disperse 30min then, obtain mixture A with 800r/min speed;
Three, in mixture A, add the polyethersulfone that step 1 takes by weighing, under 140 ℃ condition, be stirred to dissolving fully, obtain mixture B with 100r/min speed;
Four, under 120 ℃ of conditions, in mixture B, add bisphenol A type epoxy resin E-51 and ethoxyquin bisphenol a dimethacrylate, mix; Reduce temperature to 50 ℃; Add dihydroxyphenyl propane, bis-phenol M, NP and acetylacetone copper that step 1 takes by weighing, mix, promptly obtain low temperature modification cyanate adhesive matrix; Again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
Experiment four:
The preparation method of cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 85 parts of bis-phenol E cyanates, 15 parts of bisphenol A type epoxy resin E-51,2 parts of nothings by weight
Machine nanoparticle, 10 parts of polyacrylic ester nanoparticles, 10 parts of polyethersulfones, 5 parts of ethoxyquin bisphenol a dimethacrylate and 15 parts of bis-phenol M;
Two, under 50 ℃ of conditions, bis-phenol E cyanate, nano silicon and polyacrylic ester nanoparticle are mixed the back stir 30min with 80r/min speed, in impeller, disperse 30min then with 1000r/min speed, obtain mixture A;
Three, in mixture A, add the polyethersulfone that step 1 takes by weighing, under 140 ℃ condition, be stirred to dissolving fully, obtain mixture B with 100r/min speed;
Four, under 120 ℃ of conditions, in mixture B, add bisphenol A type epoxy resin E-51 and ethoxyquin bisphenol a dimethacrylate, mix; Reduce temperature to 50 ℃; Add the bis-phenol M that step 1 takes by weighing, mix, promptly obtain the cyanate adhesive matrix; Again with cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain the cyanate tackiness agent.
Experiment five:
The preparation method of cyanate tackiness agent carries out according to the following steps:
The preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 85 parts of bis-phenol E cyanates, 15 parts of bisphenol A type epoxy resin E-51,2 parts of nano silicons, 10 parts of polyacrylic ester nanoparticles, 10 parts of polyethersulfones, 5 parts of ethoxyquin bisphenol a dimethacrylate, 2 parts of NPs and 0.14 part of acetylacetone cobalt (II) by weight;
Two, under 60 ℃ of conditions, bis-phenol E cyanate, nano silicon and polyacrylic ester nanoparticle are mixed the back stir 40min with 100r/min speed, in impeller, disperse 30min then with 1000r/min speed, obtain mixture A;
Three, in mixture A, add the polyethersulfone that step 1 takes by weighing, under 120 ℃ condition, be stirred to dissolving fully, obtain mixture B with 100r/min speed;
Four, under 130 ℃ of conditions, in mixture B, add bisphenol A type epoxy resin E-51 and ethoxyquin bisphenol a dimethacrylate, mix; Reduce temperature to 60 ℃; Add NP and acetylacetone cobalt (cobalt is a divalence) that step 1 takes by weighing, mix, promptly obtain the cyanate adhesive matrix; Again with cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain the cyanate tackiness agent.
The shearing resistance of the cyanate tackiness agent of test experiments one to experiment five preparations (is tested with reference to HB5164 tensile shear strength TP sample material: LY12CZ duraluminum.), stripping strength (test with reference to 90 ° of peeling strength test methods of GJB446-88 tackiness agent, sample material: LY12CZ duraluminum.) and storage period (glued membrane has the property of pasting on by adhesives), test result such as following table:
Table 1
Curing process: 135 ℃/4h
By shown in the table 1.With catalyst modification amine or or compare through increasing the method that the traditional catalyst consumption reduces cyanate system solidification value; The present invention adopts dihydroxyphenyl propane/active hydrogen compounds/transition metal complex system modified cyanic acid ester; The adhesive solidification temperature of preparation is low, can be 135 ℃ of curing; Storage period is long, and room temperature can be placed 16～20 days; Adhesiveproperties is high, and the shearing resistance of normal temperature and 150 ℃ is higher than 20MPa, and the normal temperature stripping strength can reach 5.8N/mm; Good Heat-resistance is placed 200h at 150 ℃, and adhesiveproperties does not descend basically.
Claims (10)
1. low-temperature curing cyanate tackiness agent is characterized in that low-temperature curing cyanate tackiness agent processed by 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight;
Said cyanate ester resin is one or more the combination in dihydroxyphenyl propane cyanate, bisphenol b cyanate, bis-phenol E cyanate, bis-phenol M cyanate, phenolic cyanate, dicyclopentadiene type ethylene rhodanate and the cardanol ethylene rhodanate resin;
Said modified resin is bisphenol A type epoxy resin E-54; Bisphenol A type epoxy resin E-51; Bisphenol A type epoxy resin E-44; Bisphenol A type epoxy resin E-42; Bisphenol A type epoxy resin E-35; Bisphenol A type epoxy resin E-31; Bisphenol A type epoxy resin E-20; Bisphenol A type epoxy resin E-14; Bisphenol A type epoxy resin E-12; Bisphenol A type epoxy resin E-06; Bisphenol A type epoxy resin E-04; Bisphenol A type epoxy resin E-03; Novolac epoxy resin F-51; Novolac epoxy resin F-44; Novolac epoxy resin F-46; Bisphenol f type epoxy resin; Bisphenol-s epoxy resin; Resorcinol diglycidyl ether epoxy resin; Organosilicon epoxy resin 665; A kind of or wherein several kinds combination in organotitanium epoxy resin and the organic silicon-boron modified epoxy;
Said organic nano particle is polyacrylic ester nanoparticle, ZGK 5 nanoparticle or polyurethane nano particle;
Said inorganic nano-particle is one or more the combination in nano silicon, nano imvite, nano kaoline and the nano titanium oxide;
Said thinner is Tri Ethyleneglycol dimethacrylate, ethoxyquin bisphenol a dimethacrylate or polyethylene glycol dimethacrylate;
Said toughner is one or more the combination in paracril, carboxy terminated polybutadiene vinyl cyanide, polysulfones, polyethersulfone, polyetheretherketone and the polyetherimide;
Said catalyzer is made up of bisphenol cpd, active hydrogen compounds and transition metal complex, and wherein the mass ratio of bisphenol cpd and active hydrogen compounds is 5～45: 6, and the mass ratio of active hydrogen compounds and transition metal complex is 1～45: 15;
Said bisphenol cpd is 2-chavicol, diallyl bisphenol, dihydroxyphenyl propane, bisphenol b, bisphenol-c, bis-phenol E, bis-phenol M, bisphenol S, Bisphenol F, bisphenol AF, bisphenol-ap or bisphenol b P;
Said active hydrogen compounds is 2-methylphenol, pyrocatechol, o-sec-butyl phenol or NP;
Said transition metal complex is an acetylacetone copper; Acetylacetone cobalt; Zinc acetylacetonate; Manganese acetylacetonate; Ferric acetyl acetonade; Methyl ethyl diketone is plumbous; Aluminium acetylacetonate; Vanadium acetylacetonate; Copper naphthenate; Cobalt naphthenate; Zinc naphthenate; Manganese naphthenate; Iron naphthenate; Aluminum napthenate; Lead naphthenate; The naphthenic acid vanadium; New certain herbaceous plants with big flowers acid copper; New certain herbaceous plants with big flowers acid cobalt; New certain herbaceous plants with big flowers acid zinc; New certain herbaceous plants with big flowers acid manganese; New certain herbaceous plants with big flowers acid iron; New certain herbaceous plants with big flowers lead plumbate; New certain herbaceous plants with big flowers acid bismuth; Isocaprylic acid copper; Cobalt iso-octoate; Isocaprylic acid zinc; Manganese iso-octoate; Isocaprylic acid iron; Isocaprylic acid is plumbous; Isocaprylic acid aluminium; The isocaprylic acid vanadium; Sad chromium or dibutyl tin laurate.
2. the preparation method of the said low-temperature curing cyanate of claim 1 tackiness agent is characterized in that the preparation method of low-temperature curing cyanate tackiness agent carries out according to the following steps:
One, takes by weighing 70～100 parts of cyanate ester resins, 2～20 parts of catalyzer, 5～40 parts of modified resin, 3～15 parts of organic nano particles, 0.5～5 part of inorganic nano-particle, 1～5 part of thinner and 5～15 parts of toughner by weight;
Two, under 40 ℃～100 ℃ conditions; Cyanate ester resin, inorganic nano-particle and organic nano particle are mixed the back stir 20～50min with 60～300r/min speed; In impeller, disperse 20～60min then, obtain mixture A with 700～1500r/min speed;
Three, in mixture A, add the toughner that step 1 takes by weighing, under 100 ℃～150 ℃ condition, be stirred to dissolving fully, obtain mixture B with 60～300r/min speed;
Four, under 100 ℃～150 ℃ conditions, in mixture B, add modified resin and thinner, mix; Reduce temperature to 40 ℃～90 ℃; Add the catalyzer that step 1 takes by weighing, mix, promptly obtain low temperature modification cyanate adhesive matrix; Again with low temperature modification cyanate adhesive matrix and silica fiber cloth hot melt compound be low-temperature curing cyanate carrier glued membrane, promptly obtain low-temperature curing cyanate tackiness agent.
3. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that cyanate ester resin described in the step 1 is one or more the combination in dihydroxyphenyl propane cyanate, bisphenol b cyanate, bis-phenol E cyanate, bis-phenol M cyanate, phenolic cyanate, dicyclopentadiene type ethylene rhodanate and the cardanol ethylene rhodanate resin.
4. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that modified resin described in the step 1 is a kind of or wherein several kinds the combination in bisphenol A type epoxy resin E-54, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-42, bisphenol A type epoxy resin E-35, bisphenol A type epoxy resin E-31, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-14, bisphenol A type epoxy resin E-12, bisphenol A type epoxy resin E-06, bisphenol A type epoxy resin E-04, bisphenol A type epoxy resin E-03, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-46, bisphenol f type epoxy resin, bisphenol-s epoxy resin, resorcinol diglycidyl ether epoxy resin, organosilicon epoxy resin 665, organotitanium epoxy resin and the organic silicon-boron modified epoxy.
5. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that organic nano particle described in the step 1 is polyacrylic ester nanoparticle, ZGK 5 nanoparticle or polyurethane nano particle.
6. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that inorganic nano-particle described in the step 1 is one or more the combination in nano silicon, nano imvite, nano kaoline and the nano titanium oxide.
7. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that thinner described in the step 1 is Tri Ethyleneglycol dimethacrylate, ethoxyquin bisphenol a dimethacrylate or polyethylene glycol dimethacrylate.
8. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that toughner described in the step 1 is one or more the combination in paracril, carboxy terminated polybutadiene vinyl cyanide, polysulfones, polyethersulfone, polyetheretherketone and the polyetherimide.
9. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent; It is characterized in that catalyzer described in the step 1 is made up of bisphenol cpd, active hydrogen compounds and transition metal complex; Wherein the mass ratio of bisphenol cpd and active hydrogen compounds is 5～45: 6, and the mass ratio of active hydrogen compounds and transition metal complex is 1～45: 15;
Said bisphenol cpd is 2-chavicol, diallyl bisphenol, dihydroxyphenyl propane, bisphenol b, bisphenol-c, bis-phenol E, bis-phenol M, bisphenol S, Bisphenol F, bisphenol AF, bisphenol-ap or bisphenol b P;
Said active hydrogen compounds is 2-methylphenol, pyrocatechol, o-sec-butyl phenol or NP;
Said transition metal complex is an acetylacetone copper; Acetylacetone cobalt; Zinc acetylacetonate; Manganese acetylacetonate; Ferric acetyl acetonade; Methyl ethyl diketone is plumbous; Aluminium acetylacetonate; Vanadium acetylacetonate; Copper naphthenate; Cobalt naphthenate; Zinc naphthenate; Manganese naphthenate; Iron naphthenate; Aluminum napthenate; Lead naphthenate; The naphthenic acid vanadium; New certain herbaceous plants with big flowers acid copper; New certain herbaceous plants with big flowers acid cobalt; New certain herbaceous plants with big flowers acid zinc; New certain herbaceous plants with big flowers acid manganese; New certain herbaceous plants with big flowers acid iron; New certain herbaceous plants with big flowers lead plumbate; New certain herbaceous plants with big flowers acid bismuth; Isocaprylic acid copper; Cobalt iso-octoate; Isocaprylic acid zinc; Manganese iso-octoate; Isocaprylic acid iron; Isocaprylic acid is plumbous; Isocaprylic acid aluminium; The isocaprylic acid vanadium; Sad chromium or dibutyl tin laurate.
10. according to the preparation method of the said low-temperature curing cyanate of claim 2 tackiness agent, it is characterized in that in the step 4 under 120 ℃ of conditions, in mixture B, adding modified resin and thinner, mix, reduce temperature to 50 ℃.
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