CN102423673A - Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof - Google Patents
Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof Download PDFInfo
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- CN102423673A CN102423673A CN2011102143769A CN201110214376A CN102423673A CN 102423673 A CN102423673 A CN 102423673A CN 2011102143769 A CN2011102143769 A CN 2011102143769A CN 201110214376 A CN201110214376 A CN 201110214376A CN 102423673 A CN102423673 A CN 102423673A
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Abstract
The invention relates to a latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and a preparation method of an adhesive thereof. The latent microcapsule curing agent is technically characterized in that the high-activity medium temperature curing agent is taken as a core material, thermoplastic high polymer microspheres are taken as a wall material, the solvent evaporation technology is adopted for preparing the latent microcapsule curing agent with better curing performance and latent performance, and the latent microcapsule curing agent can be applied to an epoxy resin system for preparing the single-component medium temperature curing epoxy resin adhesive. Microcapsules prepared by the method are high in capsule core content, smooth in surfaces, narrow in particle size distribution and good in compatibility with matrix epoxy resin and can be better dispersed in the epoxy resin; and the prepared single component adhesive can realize curing at the medium temperature, the storage period at room temperature is longer and the tensile shear strength performance can be further improved.
Description
Technical field
The present invention relates to a kind of latency microcapsules curing agent that thermosetting epoxy resin solidifies that causes, can be used for preparing cured article with superior physical properties and low viscosity and superior workability.
Background technology
But epoxy resin is at aspect excellent performances such as cementability, corrosion resistance, mechanical performance, hot property and electrical properties, its by a large amount of be widely used as adhesive, coating, printing ink, laminate, casted article, moulded work and electronic isolation material etc.The epoxy resin gluing agent that is used for these aspects can be one-component system or two component system.
The most widely used epoxy adhesive is a bicomponent system, and it is made up of epoxy resin and curing agent etc., and the two is a separate storage.Therefore, two component adhesives not only need the packing accumulating, bring many runnings and environmental issue, and error in dipping and mix inhomogeneously during mixed preparing, are prone to cause the fluctuation of important performances such as product adhesive strength.Glue preparation back constantly increases with the system viscosity that carries out of chemical reaction, and its working life is limited, is not suitable for automatic novel technique for bonding, also is prone to cause and scraps.Thereby operating procedure simplify, easy to implement, environmental pollution is little, help product comprehensive quality improves, is applicable to that the research and development of the monocomponent epoxide-resin rubber adhesive of new technology are paid close attention to by people always.
The design that focuses on the curing agent molecule and the selection of research and development at present, the establishment of corresponding process conditions reaches the improvement to combination property, and wherein the research and development of latent curing agent are the most active and important.This type curing agent mainly is through temporary transient sealing or some reactivity height of passivation and the active group and the structure of the curing agent of poor storage stability are implemented.But because curing agent directly contacts with the substrate ring epoxy resins; Physical-chemical reaction can take place in two component epoxy adhesive by such latent curing agent preparation usually in storage process; Cause the storage life (working life) of this two component epoxy adhesive to descend, and then influence the performance of adhesive effectiveness.Simultaneously, in the index of adhesive, normally a pair of contradiction of the storage life of solidification temperature and adhesive: promptly select the curing agent of low solidification temperature for use, longer relatively by the storage life of the adhesive of its preparation; Select the curing agent of high solidification temperature for use, shorter relatively by the storage life of the adhesive of its preparation.For solving problem as above, we have prepared a kind of novel latent curing agent---microcapsules curing agent.
The microcapsules curing agent is meant curing agent is coated and can stop itself and matrix resin (being generally epoxy resin) at room temperature to react with microcapsules technology; Improve the room temperature storage phase of resin and prepreg thereof; Then under certain condition (temperature or pressure etc.); Microcapsules rupture discharges a kind of novel curing agent that curing agent is accomplished curing reaction.Compare with general curing agent, microcapsules curing agent storage period is longer, and it can block the interaction of curing agent and matrix resin, thereby reaches the purpose that control is solidified.And owing to selected the agent of high activity intermediate temperature setting for use, the problem of solidification temperature has also obtained solution.
The one-component adhesive, but because its working life is long, error in dipping is little, join the stable ready access upon use, efficient and convenient of colloid amount, and then can enhance productivity greatly.Be applied to many industrial departments at present, bonding like auto production line entrance door flanging, the structure of case is bonding before and after the car, the electronic component embedding on the electronics industry, the production of electronic product etc.The particularly application of single-component epoxy adhesive on the electric elements streamline, rising greatly.At present, the latent curing system that is obtained by the microcapsules curing agent is the effective ways that solve contradiction during epoxy low-temperature setting and the longer room temperature storage, also is the main developing direction of polymer matrix composites with latent curing agent.
In epoxy-resin systems, introduce the microcapsules curing agent, being prepared into the one-component adhesive is one of focus of studying in recent years.At present domestic on preparation one-component adhesive, the main method of directly adding latent curing agent that adopts prolongs its storage life, and adopts the report of latency microcapsules curing agent less.Diaminodiphenyl-methane after with modification such as Xing Suli is a core, 2, and the 2-toluene di-isocyanate(TDI) is a wall material monomer, adopts the interfacial polymerization technology to prepare the novel polyurea microcapsules of particle diameter narrow distribution.Prepared microcapsule curing agent average grain diameter is 2.54 μ m, and wall thickness is about 100nm.This microcapsules curing agent not only can successfully be realized the curing of E-51 epoxy resin, and itself and E-51 epoxy-resin systems have the good performance of hiding at normal temperatures, and the room temperature storage phase can reach more than 6 months.Tong Suling etc. disperse water-insoluble 2-ethyl-4-methylimidazole (EMI) pre-reaction thing in water, make the carbamide prepolymer make epoxy resin cure promoter microcapsules in its surface in situ polymerization then.This capsule is used for the preparation of epoxy adhesive tape, and gained adhesive tape storge quality and outward appearance are good, and microcapsules are solidified with better facilitation to adhesive tape.Yuan Yan is superfine to have prepared multi-thiol micro-capsule through situ aggregation method in n-octyl alcohol.Core is liquid polythiol, and the wall material is melamine formaldehyde resin, methylated melamine-formaldehyde resin, urea-formaldehyde resin or its mixture, and core material/wall material weight ratio is 1: 5～1: 6, diameter 1 μ m～1mm, wall thickness 100nm～10 μ m.Prepare in the process few part core at capsule and be consumed a part that forms cyst wall with wall material generation cross-linking reaction, most of core polythiol can keep it to be coated preceding activity.This multi-thiol micro-capsule has enough mechanical strengths, can stand the external force effect in the composite process of manufacture.It is core that Xu Hongxia etc. have prepared 2-phenylimidazole (2PZ) through the S/O/W solvent evaporated method, and poly-methyl methacrylate vinegar (PMMA) is the microcapsules of wall material.This microcapsules particle diameter is about 10 μ m, and wherein the embedding rate of 2PZ is about 10wt%.And the system storage life at room temperature is more than 6 months for EP/Micro20 (20 parts of 100 parts/microcapsules of epoxy), and the EP/2PZ system that curing agent is not coated just has cured after at room temperature 7 days.Xing Suli etc. adopt emulsion-solvent evaporation technique, are core with the 2-ethyl-4-methylimidazole of modification, are the wall material with the PEI, have successfully prepared the spherical microcapsule curing agent.This microcapsules particle diameter narrow distribution, average grain diameter is about 25 μ m.Prepared curing agent microcapsules have good curing activity, release performance and the performance of hiding, E-51 epoxy resin is solidified in 2h and the room temperature storage phase more than 3 months.
The report of microcapsules curing agent is then comparatively active abroad, and Japanese, the U.S. is annual to have a large amount of patents to occur aspect the microcapsules curing agent.Shigeaki F etc. then adopts the epoxy resin modification glyoxal ethyline, after grinding, obtains micron-sized amine addition product, makes it and 4, and the reaction of 4-methyl diphenylene diisocyanate has made the glyoxal ethyline microcapsules that polyureas coats.And with the bisphenol A type epoxy resin of 67 parts (mass fractions), 33 parts microcapsules curing agent has made the microcapsules resin system.Record its solidification temperature between 115～120 ℃ with DSC, after storing 30 days under 40 ℃, record its viscosity growth rate with E type viscosimeter and be less than 50%.Taketoshi U etc. has adopted similar method to synthesize the glyoxal ethyline microcapsules that polyureas coats, and the microcapsules solidification temperature that makes is between 100～130 ℃.Different is that it has adopted new method mensuration microcapsules resin system incubation period: promptly after suitable pre-treatment (removing fugitive constituent etc.), store 3 days down at 50 ℃, adopt FT-IR method mensuration epoxy radicals (914cm
-1The place) survival rate before and after 3 days, and compare, the incubation period of microcapsules resin system can be analyzed qualitatively with this.Masuko etc. adopt situ aggregation method to make the low temperature curing agent of anti-the solvent microcapsule in No. 1 kerosene of day mark level, and core is the addition product of epoxy resin and 2-ethyl-4-methylimidazole, and the wall material is the addition product of polyfunctionality isocyanates and ethyl cellulose.The microcapsule-type curing agent particle diameter that makes when adopting this microcapsules curing agent cured epoxy resin, records the exothermic peak corresponding temperature about 120 ℃ about 5 μ m.In addition, because the isocyanates and the ethyl cellulose degree of depth are crosslinked, make these microcapsules have solvent resistance preferably again.
At present; Preparation method at microcapsules mainly concentrates on situ aggregation method, the interfacial polymerization both at home and abroad; The reaction time length, the polymerization rate that exist chemical process to bring wait problem more slowly, have shortcomings such as consersion unit complicacy, material requested preparation cost height simultaneously.
Summary of the invention
The technical problem that solves
For fear of the weak point of prior art, the present invention proposes a kind of latency microcapsules curing agent of thermosetting epoxy resin curing and preparation method of adhesive thereof of under middle temperature, causing.
Technical scheme
A kind of preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing is characterized in that step is following:
Step 1: in the container of electric mixer is housed, add 0.1～2wt% aqueous dispersant, 50～100mL, 0.1～2wt% emulsifier aqueous solution, 50～100mL disperses 30～60min to obtain water under the mechanical agitation of 500～1000r/min; Said emulsifying agent is one or more among neopelex, lauryl sodium sulfate and tween and the Si Ban; Said dispersant is one or more in gelatin or the polyvinyl alcohol;
Step 2: in 25～50mL volatile solvent is housed, add respectively 0.2～2g of core and wall material, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5～10min, oil phase is added drop-wise to the prepared aqueous phase of step 1 gradually; Above-mentioned water be 100～200 mass parts, oil phase be 50～100 mass parts, water oil be in a ratio of 1: 2～2: 1; Said core is one or more in boron trifluoride and amine complex compound thereof, aromatic polyamine, polyamines salt, aliphatic cyclic amine, organic acid hydrazides etc.; Said wall material is one or more in polyethylene base class microballoon, polystyrene type microballoon, the polyacrylate microballoon; Said volatile solvent is one or more in carrene, chloroform or the acetone;
Step 3: stirring and emulsifying 30～60min, 3～5h is stirred in rising reaction temperature to 30～35 ℃, is warming up to 38～40 ℃ again and stirs above suspension is centrifugal to the volatile solvent volatilization, the distilled water washing of 3～5h, is drying to obtain product microcapsules curing agent.
Said boron trifluoride and amine complex compound thereof are one or more in boron triflouride-mono aminoethane, boron trifluoride-n-butylamine, boron trifluoride-Bian amine, boron trifluoride-chloroaniline, boron trifluoride-dimethylaniline, boron trifluoride-diphenylamines, boron trifluoride-aniline, boron trifluoride-para-totuidine, boron trifluoride-ortho-aminotoluene, boron trifluoride-n-butylamine, boron trifluoride-ethamine or the boron trifluoride-piperidines.
Said aromatic polyamine is one or more in MDA, diaminourea dimethoxy diphenyl-methane, diamino-dicyclohexyl methane, diaminourea dichloro diphenyl methane, m-phenylene diamine (MPD) or the DADPS.
In the Phenylphosphine hydrochlorate that said polyamines salt is o-phenylenediamine, m-phenylene diamine (MPD), aniline, MDA, p-phenylenediamine (PPD), m-xylene diamine, piperazine, benzylamine or ethylenediamine one or more.
Said aliphatic cyclic amine is N-amine ethyl piperazidine, different fluorine that ketone diamines, 1, two (aminomethyl) cyclohexanes, 4 of 3-, one or more in 4-diamino-dicyclohexyl methane or two (4-amino-3-methylcyclohexyl) methane.
Said organic acid hydrazides is one or more in propionic acid hydrazides, butyric acid hydrazides, caproic acid hydrazides, sad hydrazides, adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, salicylic acid hydrazides or the phenyl amino propionic acid hydrazides.
Said polyethylene base class is one or more in polyvinyl acetate, polyvinyl alcohol or the Pioloform, polyvinyl acetal.
Said polystyrene type is one or more in polystyrene, SAN, styrene-methylmethacrylate copolymer or the styrene diethylene benzene copoly mer.
Said polyacrylic is polymethyl methacrylate, methyl methacrylate and styrol copolymer, gather methyl or gather in the Mecrilate one or more.
A kind ofly utilize the above-mentioned method that latency microcapsules curing agent that thermosetting epoxy resin solidifies prepares intermediate temperature setting single-component epoxy resin adhesive that under middle temperature, causes; It is characterized in that the latency microcapsules curing agent and 1～20 mass parts filler that the thermosetting polyfunctional epoxy resin, 5～100 mass parts non-activated thinners, 1～100 mass parts that under the 100 mass parts room temperatures are liquid state are caused thermosetting epoxy resin curing under middle temperature mix, and obtain long latency intermediate temperature setting single-component epoxy resin adhesive; Said thermosetting polyfunctional epoxy resin is one or more in bisphenol-A glycidol ether or the Bisphenol F glycidol ether; Said non-activated thinner is one or more in acetone, MEK, cyclohexanone, ethanol or the toluene; Said filler is one or more in nano silicon, nano-calcium carbonate, aluminium oxide or the potter's clay powder.
Beneficial effect
A kind of latency microcapsules curing agent of thermosetting epoxy resin curing and preparation method of adhesive thereof of under middle temperature, causing that the present invention proposes adopts solvent evaporation method simple and easy to control to prepare microcapsules.In addition, compare with similar approach, the alternative capsule-core cyst material of this method institute is more; The microcapsules capsule-core content height of preparation, smooth surface, particle diameter narrow distribution, good with substrate ring epoxy resins compatibility can be disperseed in epoxy resin preferably; Can under middle temperature, be realized solidifying by the one-component adhesive of its preparation, the room temperature storage phase is longer, and the tensile shear strength performance increases.
To sum up; The present invention is a core with the agent of high activity intermediate temperature setting, and thermoplastic high polymer micro balloons is the wall material, adopts the solvent evaporates technology; Prepared the curing performance and the performance latency microcapsules curing agent preferably of hiding, and applied it to and be prepared into one-component intermediate temperature setting resin adhesive in the resin system.Prepared microcapsule curing agent smooth surface of the present invention, particle diameter narrow distribution, average grain diameter are at 10～20 μ m, and wall material thickness is about 0.5～1.0 μ m, and core content is 20～50wt%.One-component adhesive by microcapsules curing agent and epoxy resin preparation; Have good curing performance, the performance of hiding; Can in 100～150 ℃ of following 30min～1h, realize solidifying; The room temperature storage phase is about 40～60d, and tensile shear strength increases than two component adhesives of direct interpolation curing agent.In addition; The present invention characterizes through infrared spectrometer (FT-IR), thermogravimetric analyzer (TGA), SEM (SEM) and differential scanning calorimeter (DSC) chemical constitution, core content, surface topography and the curing performance etc. to the microcapsules curing agent, has convincingly demonstrated the successful preparation of microcapsules curing agent.
The advantage that the present invention compares traditional two component adhesives is:
1, preparation method's (solvent evaporation method) is simple, is beneficial to batch process, adapts to modern streamline production.
2, prepared microcapsule curing agent particle diameter narrow distribution has good curing performance and hides performance, and temperature is solidified down fast in can realizing.
3, the one-component adhesive that is prepared from the microcapsules curing agent can be blocked the interaction of curing agent and substrate ring epoxy resins, thereby reaches the purpose that control is solidified.And once join glue and can use for a long time, but its error in dipping little, join the stable ready access upon use, efficient and convenient of colloid amount, thereby enhance productivity greatly.
Description of drawings
Fig. 1 is an infrared spectrum: (a) DDM (b) DDM-PMMA microcapsules (c) PMMA microballoon;
Fig. 2 is TGA and DTG curve: (a) DDM (b) PMMA microballoon (c) DDM-PMMA microcapsules;
Fig. 3 is a stereoscan photograph: (a) PMMA microballoon (b) DDM-PMMA microcapsules (c) DDM-PMMA microcapsules crushing appearance;
Fig. 4 is the DSC curve: (a) E-51/DDM-PMMA microcapsules system (c) E-51/DDM system.
The specific embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
With diaminodiphenyl-methane (DDM) is core, and polymethyl methacrylate (PMMA) microballoon is that the microcapsules curing agent of wall material is that example characterizes explanation.
1, analytical method
(1) microcapsules are formed
Sample is dissolved in obtains settled solution in the carrene, dip in a small amount of above-mentioned solution with glass rod and be coated in equably on the KBr compressing tablet and form liquid film, place to be baked to the methylene chloride volatilization under the infrared lamp fully.The KBr compressing tablet that is covered with liquid film is placed Fourier transformation infrared spectrometer, and setting is swept parameter and is scanned, and obtains infrared spectrogram.
(2) core content
Weighing 10mg left and right sides prepared microcapsule curing agent or wall material microballoon particulate place crucible, and the adjustment thermogravimetric analyzer is to desirable experimental state, and protective gas is N
2, nitrogen flow is 100mL/min, begins to be warming up to 800 ℃ of microcapsules with 20 ℃/min from room temperature and decomposes fully, stops experiment.
(3) microcapsules pattern
Sample powder is scattered in the absolute ethyl alcohol, and on silicon chip, the dry back metal spraying of waiting to be evenly distributed places under the SEM and observes with hanging drop.
(4) curing performance
Adopt the TAInstrument-2910 type DSC appearance of U.S. Waters-TA company, N
2Atmosphere, example weight is about 5mg, and heating rate is 10 ℃/min, and temperature range is 25～300 ℃, adopts TA Universal Analysis software that curve is handled.
(5) performance of hiding
Microcapsules curing agent, curing agent and wall material mixture, curing agent are processed resin system respectively, place on the testing stand, the room temperature lower body is bound the room temperature storage phase of the time of piece, be used for characterizing its performance of hiding as system.
2, raw material sources
Core: diaminodiphenyl-methane, chemical pure, Chemical Reagent Co., Ltd., Sinopharm Group; Wall material: polymethyl methacrylate, self-control; Emulsifying agent: neopelex (SDBS), chemical pure, Chemical Reagent Co., Ltd., Sinopharm Group; Dispersant: gelatin, chemical pure, the huge chemical reagent of Tianjin Dongli District factory; Solvent: carrene, analyze pure, Tianjin Fu Yu Fine Chemical Co., Ltd; Decentralized medium: distilled water, self-control; E-51 (WSR618): technical grade, Wuxi Resin Factory of Blue Star New Chemical Material Co., Ltd.; Absolute ethyl alcohol, analyze pure, Tianjin Fu Yu Fine Chemical Co., Ltd.
Embodiment 1: be dispersant with the gelatin, neopelex is an emulsifying agent, and carrene is a solvent
In fume hood; 50mL 0.5wt% aqueous gelatin solution 100mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 500r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 1g MDA, 1g polymethyl methacrylate respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 38 ℃ again and stirs more than the 3h complete to the carrene volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 2～10 μ m.
100 parts of 50 parts in 20 parts in microcapsules curing agent, acetone, E-54 epoxy resin, the nano silicon of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 120 ℃ of following 1h, and the room temperature storage phase reached more than 46 days.
Embodiment 2: be dispersant with the polyvinyl alcohol, neopelex is an emulsifying agent, and carrene is a solvent
In fume hood; 40mL 0.2wt% polyvinyl alcohol water solution 80mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 1000r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 1g N-amine ethyl piperazidine, 2g polystyrene respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 35 ℃ again and stirs more than the 3h complete to the carrene volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 2～11 μ m.
100 parts of 40 parts of 15 parts in microcapsules curing agent, MEKs, CYDF-170 epoxy resin, the nano-calcium carbonate of gained are evenly mixed for 2 parts, promptly get single-component epoxy resin adhesive.It can realize solidifying in 120 ℃ of following 30min, and the room temperature storage phase reached more than 42 days.
Embodiment 3: be dispersant with the gelatin, tween and Si Ban are emulsifying agent, and carrene is a solvent
In fume hood; 50mL 0.3wt% aqueous gelatin solution, 90mL 0.1wt% tween and Si Ban (1: the 1) aqueous solution are directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 700r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 2g m-phenylene diamine (MPD), 1g styrene-methylmethacrylate copolymer respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 40 ℃ again and stirs more than the 3h complete to the carrene volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 0.5～12 μ m.
100 parts of 60 parts of 30 parts in microcapsules curing agent, cyclohexanone, E-51 epoxy resin, the aluminium oxide of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 100 ℃ of following 30min, and the room temperature storage phase reached more than 45 days.
Embodiment 4: be dispersant with the polyvinyl alcohol, tween and Si Ban are emulsifying agent, and carrene is a solvent
In fume hood; 40mL 0.3wt% polyvinyl alcohol water solution, 100mL 0.2wt% tween and Si Ban (1: the 1) aqueous solution are directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 800r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 0.5g p-phenylenediamine (PPD), 1g styrene diethylene benzene copoly mer respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 32 ℃ stirring 3h is warming up to 37 ℃ again and stirs more than the 3h complete to the carrene volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 1～12 μ m.
100 parts of 40 parts in 40 parts in microcapsules curing agent, acetone, CYDF-180 epoxy resin, the potter's clay powder of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 100 ℃ of following 30min, and the room temperature storage phase reached more than 45 days.
Embodiment 5: be dispersant with the gelatin, neopelex is an emulsifying agent, and chloroform is a solvent
In fume hood; 50mL 0.2wt% aqueous gelatin solution 80mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 600r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL chloroform is housed, add 1g propionic acid hydrazides, 1g polymethyl methacrylate respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 38 ℃ again and stirs more than the 3h complete to the chloroform volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 2～10 μ m.
60 parts of 30 parts in microcapsules curing agent, MEKs, E-44 epoxy resin, the nano silicon of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 150 ℃ of following 1h, and the room temperature storage phase reached more than 52 days.
Embodiment 6: be dispersant with the polyvinyl alcohol, neopelex is an emulsifying agent, and chloroform is a solvent
In fume hood; 30mL 0.1wt% polyvinyl alcohol water solution 60mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 900r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL chloroform is housed, add 2g boron triflouride-mono aminoethane, 1g polystyrene respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 40 ℃ again and stirs more than the 3h complete to the chloroform volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 2.5～10 μ m.With 20 parts in the microcapsules curing agent of gained, 50 parts in acetone, the bisphenol-A glycidol ether evenly mixes for 100 parts, promptly gets single-component epoxy resin adhesive.
100 parts of 50 parts of 40 parts in microcapsules curing agent, cyclohexanone, NPEF-170 epoxy resin, the nano-calcium carbonate of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 120 ℃ of following 1h, and the room temperature storage phase reached more than 45 days.
Embodiment 7: be dispersant with the gelatin, tween and Si Ban are emulsifying agent, and chloroform is a solvent
In fume hood; 40mL 0.2wt% aqueous gelatin solution, 100mL 0.2wt% tween and Si Ban (1: the 1) aqueous solution are directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 700r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL chloroform is housed, add 1g butyric acid hydrazides, 1g styrene-methylmethacrylate copolymer respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 32 ℃ stirring 3h is warming up to 39 ℃ again and stirs more than the 3h complete to the chloroform volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 0.5～12 μ m.
100 parts of 40 parts in 20 parts in microcapsules curing agent, acetone, E-42 epoxy resin, the aluminium oxide of gained are evenly mixed for 2 parts, promptly get single-component epoxy resin adhesive.It can realize solidifying in 150 ℃ of following 1h, and the room temperature storage phase reached more than 50 days.
Embodiment 8: be dispersant with the polyvinyl alcohol, tween and Si Ban are emulsifying agent, and chloroform is a solvent
In fume hood; 50mL 0.2wt% polyvinyl alcohol water solution, 100mL 0.1wt% tween and Si Ban (1: the 1) aqueous solution are directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 800r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL chloroform is housed, add 1g aniline, 0.5g styrene diethylene benzene copoly mer respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 38 ℃ again and stirs more than the 3h complete to the chloroform volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 3～13 μ m.
100 parts of 40 parts of 25 parts in microcapsules curing agent, MEKs, EP-4901 epoxy resin, the potter's clay powder of gained are evenly mixed for 1 part, promptly get single-component epoxy resin adhesive.It can realize solidifying in 100 ℃ of following 30min, and the room temperature storage phase reached more than 45 days.
Comparative Examples 1: do not add the dispersant gelatin
In fume hood, 100mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 500r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 1g MDA, 1g polymethyl methacrylate respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slow rising reaction temperature to 30 ℃ stirring 3h is warming up to 38 ℃ again and stirs more than the 3h complete to the carrene volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 0.5～25 μ m.
50 parts in 50 parts in microcapsules curing agent, acetone, E-51 epoxy resin 100 parts of even, 1 part of mixing of nano silicon with gained promptly get single-component epoxy resin adhesive.It can realize solidifying in 120 ℃ of following 1h, and the room temperature storage phase reached more than 42 days.
Comparative Examples 2: directly heat up
In fume hood; 40mL 0.2wt% polyvinyl alcohol water solution 80mL 0.2wt% sodium dodecyl benzene sulfonate aqueous solution is directly joined in the 500ml there-necked flask that electric mixer, condenser pipe and thermometer are housed, under the mechanical agitation of 1000r/min, disperse 30min to obtain the stabilized uniform water; In two beakers that the 20mL carrene is housed, add 1gN-amine ethyl piperazidine, 2g polystyrene respectively, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5min, oil phase is added drop-wise in the there-necked flask gradually.Further stirring about 30min makes oil phase, water form uniform and stable emulsion.Slowly rising reaction temperature to 38 ℃ stirring 6h is complete to the chloroform volatilization.Suspension is centrifugal, distilled water washs, is drying to obtain the microcapsules curing agent that the product particle diameter is 0.5～18 μ m.
100 parts of 40 parts of 15 parts in microcapsules curing agent, MEKs, EP-4930 epoxy resin, the nano-calcium carbonate of gained are evenly mixed for 2 parts, promptly get single-component epoxy resin adhesive.It can realize solidifying in 120 ℃ of following 30min, and the room temperature storage phase reached more than 40 days.
Can know by Comparative Examples, not add dispersant or direct intensification and all can cause the microcapsules distribution to broaden, be unfavorable for that microcapsules disperse in the one-component adhesive, also influence the room temperature storage phase of one-component adhesive to a certain extent.
Combine accompanying drawing, embodiment and table 1 and table 2 to analyze at present:
Fig. 1 is the infrared spectrum of DDM, DDM-PMMA microcapsules and PMMA microballoon.Spectral line (b) is the infrared line of DDM-PMMA microcapsules, and spectral line (c) is the infrared line of PMMA, all can see from spectral line (b) with (c): at 2997cm
-1, 2953cm
-1Neighbouring is the vibration absorption peak of C-H, 1730cm
-1The place is-C=O stretching vibration absworption peak 1241cm
-1, 1150cm
-1The place is promptly to exist wall material PMMA in the microcapsules by the stretching vibration absworption peak of C-O.Spectral line (a) is the infrared line of epoxy curing agent DDM, 3443cm
-1Near the stretching vibration peak of N-H when, 1628cm
-1, 1514cm
-1, 1431cm
-1Near be the stretching vibration bands of a spectrum of C=C on the skeleton of phenyl ring, 1280cm
-1Near be the stretching vibration peak of C-N, 900cm
-1～766cm
-1Near be the out-of-plane bending vibration peak of N-H.In spectral line (b) the DDM-PMMA microcapsules, at 3443cm
-1, 1628cm
-1, 1514cm
-1, 1431cm
-1Non-existent characteristic peak among spectral line (c) PMMA has appearred at the place, and these characteristic peaks characteristic peak of spectral line (a) core curing agent DDM just.In sum, contain curing agent DDM among the DDM-PMMA really.
Constituent analysis from the DDM-PMMA microcapsules among Fig. 2 can be known, contains core materials DDM in the prepared microcapsule really.In order further to obtain the accurate content of DDM, we adopt thermogravimetric analysis to quantize this content, and the result is as shown in Figure 2.Analysis-by-synthesis can be known: curve (a) is the thermogravimetric curve of core curing agent DDM, and it decomposes to since about 180 ℃ and decomposes about 300 ℃ fully; Curve (b) is the thermogravimetric curve of capsule casing material PMMA, and its decomposition range is for being roughly 180～420 ℃; Curve (c) is the thermal weight loss and the differential curve of DDM-PMMA microcapsules; Different with simple core wall material, its decomposition curve has demonstrated two and has significantly decomposed step, and this also can be confirmed from its DTG curve; First DTG peak occurs about 283 ℃; Owing to the decomposition of DDM, and the temperature that another DTG peak occurs is about 431 ℃, is the decomposition region of PMMA capsule casing material.This research thinks that DDM decomposes end when PMMA begins to decompose in the DDM-PMMA microcapsules, and the content that can calculate core DDM in the DDM-PMMA microcapsules thus is about 49.82wt%.
The pattern of PMMA microballoon and DDM-PMMA microcapsules characterizes (Fig. 4) through SEM among Fig. 3.Can know by Fig. 3 (a) and 3 (b); PMMA microballoon and DDM-PMMA microcapsules are regular spherical, and the PMMA microspherulite diameter is about 2.65 μ m, and the DDM-PMMA microcapsules are then about 6.57 μ m; Surface both is all very smooth, and DDM-PMMA microcapsules particle diameter is significantly greater than the PMMA microballoon.Simultaneously, can know by Fig. 3 (b), DDM-PMMA microcapsules particle diameter distribution relative narrower, this has guaranteed that to a certain extent the microcapsules curing agent can disperse equably in epoxy resin, thereby better plays a role.
In addition, Fig. 3 (c) grinds the back with the DDM-PMMA microcapsules fully to wash the sample that makes after the drying with DDM good solvent ethanol.Can know that from Fig. 4 (c) there is capsule-core cyst wall structure in the DDM-PMMA microcapsules.Can know that to sum up the DDM-PMMA microcapsules are to be nuclear with DDM, PMMA is the core-shell type microcapsules of shell.
Among Fig. 4 DDM curing agent, DDM-PMMA microcapsules are prepared into one-component adhesive system as shown in table 1, and measure DSC respectively, study its curing reaction characteristic, the result is as shown in Figure 4.Can know by figure: the peak temperature (T of E-51/DDM-PMMA microcapsules system
p) be about 180 ℃, lag behind about 10 ℃ than E-51/DDM system, the curing agent that microcapsules coat in this explanation E-51/DDM-PMMA microcapsules system has reacted the effect that postpones to epoxy resin cure.This be because: in the E-51/DDM system, DDM is directly to contact with epoxy resin, and the curing reaction generation time does not have obstacle physically; And in E-51/DDM-PMMA microcapsules system, curing agent DDM is covered by in the PMMA container, can't contact with epoxy resin, has only that DDM permeate away just and can be in contact with it through the hole on the film when PMMA is softening, thus the generation curing reaction.
Stable storage is a big advantage of microcapsules curing agent under the uniform temperature, and therefore, the performance of hiding also is an important performance indexes must investigating.At ambient temperature, according to proportioning shown in the table 1 (mass fraction), DDM-PMMA microcapsules, DDM are processed E-51/DDM-PMMA, E-51/DDM one-component adhesive with epoxy resin E-51 respectively; After stirring; Place on the testing stand, treat its curing, measure its room temperature storage phase.Because the existence of wall material; Make in the DDM-PMMA microcapsules that effectively the amount of cure component is about 49.82wt% (by 50%), so the consumption (56phr) of microcapsules curing agent is 2 times of hardener dose in the E-51/DDM system (28phr) in the E-51/DDM-PMMA microcapsules system.
Can know that by table 1 the room temperature storage phase of E-51/DDM-PMMA one-component adhesive system is the longest, is about about 50 days; And common E-51/DDM/PMMA, E-51/DDM resin system are only through 5 days just most of curing only.Be the room temperature storage phase that prepared DDM-PMMA microcapsules curing agent can prolong the DDM curing agent widely, explain that microencapsulation coats the isolation that can realize active component (curing agent) effectively.Anatomizing contrast E-51/DDM/PMMA, E-51/DDM resin system can also find; The E-51/DDM/PMMA resin system storage life is longer slightly, and this possibly be because the PMMA that adds can hinder DDM to a certain extent cross-linking reaction and then curing to take place at ambient temperature.
Prepared two kinds of single-component adhesives according to proportioning shown in the table 1 and carried out adhesive test, under 100 ℃/30min and condition, be cured, gained tensile shear strength value has been listed in the table 2 with the stove cooling.
As shown in table 2, the tensile shear strength mean value of E-51/DDM-PMMA one-component adhesive is 15.56MPa, than the high 0.93MPa of tensile shear strength mean value of the two component adhesives of the E-51/2PZ of direct interpolation curing agent.This is that promptly prepared E-51/DDM-PMMA one-component adhesive has good adhesive property because the PMMA in the E-51/DDM-PMMA one-component adhesive component has played toughening effect.
The room temperature storage phase of each one-component adhesive of table 1
The tensile shear strength of each adhesive of table 2
Claims (10)
1. preparation method who under middle temperature, causes the latency microcapsules curing agent that thermosetting epoxy resin solidifies is characterized in that step is following:
Step 1: in the container of electric mixer is housed, add 0.1～2wt% aqueous dispersant, 50～100mL, 0.1～2wt% emulsifier aqueous solution, 50～100mL disperses 30～60min to obtain water under the mechanical agitation of 500～1000r/min; Said emulsifying agent is one or more among neopelex, lauryl sodium sulfate and tween and the Si Ban; Said dispersant is one or more in gelatin or the polyvinyl alcohol;
Step 2: in 25～50mL volatile solvent is housed, add respectively 0.2～2g of core and wall material, and in Ultrasound Instrument, be uniformly dispersed to its dissolving and obtain oil phase, in 5～10min, oil phase is added drop-wise to the prepared aqueous phase of step 1 gradually; Above-mentioned water be 100～200 mass parts, oil phase be 50～100 mass parts, water oil be in a ratio of 1: 2～2: 1; Said core is one or more in boron trifluoride and amine complex compound thereof, aromatic polyamine, polyamines salt, aliphatic cyclic amine, organic acid hydrazides etc.; Said wall material is one or more in polyethylene base class microballoon, polystyrene type microballoon, the polyacrylate microballoon; Said volatile solvent is one or more in carrene, chloroform or the acetone;
Step 3: stirring and emulsifying 30～60min, 3～5h is stirred in rising reaction temperature to 30～35 ℃, is warming up to 38～40 ℃ again and stirs above suspension is centrifugal to the volatile solvent volatilization, the distilled water washing of 3～5h, is drying to obtain product microcapsules curing agent.
2. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: said boron trifluoride and amine complex compound thereof are one or more in boron triflouride-mono aminoethane, boron trifluoride-n-butylamine, boron trifluoride-Bian amine, boron trifluoride-chloroaniline, boron trifluoride-dimethylaniline, boron trifluoride-diphenylamines, boron trifluoride-aniline, boron trifluoride-para-totuidine, boron trifluoride-ortho-aminotoluene, boron trifluoride-n-butylamine, boron trifluoride-ethamine or the boron trifluoride-piperidines.
3. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: said aromatic polyamine is one or more in MDA, diaminourea dimethoxy diphenyl-methane, diamino-dicyclohexyl methane, diaminourea dichloro diphenyl methane, m-phenylene diamine (MPD) or the DADPS.
4. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: one or more in the Phenylphosphine hydrochlorate that said polyamines salt is o-phenylenediamine, m-phenylene diamine (MPD), aniline, MDA, p-phenylenediamine (PPD), m-xylene diamine, piperazine, benzylamine or ethylenediamine.
5. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1; It is characterized in that: said aliphatic cyclic amine is N-amine ethyl piperazidine, different fluorine that ketone diamines, 1; Two (aminomethyl) cyclohexanes, 4 of 3-, one or more in 4-diamino-dicyclohexyl methane or two (4-amino-3-methylcyclohexyl) methane.
6. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: said organic acid hydrazides is one or more in propionic acid hydrazides, butyric acid hydrazides, caproic acid hydrazides, sad hydrazides, adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, salicylic acid hydrazides or the phenyl amino propionic acid hydrazides.
7. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: said polyethylene base class is one or more in polyvinyl acetate, polyvinyl alcohol or the Pioloform, polyvinyl acetal.
8. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent of thermosetting epoxy resin curing of claim 1, it is characterized in that: said polystyrene type is one or more in polystyrene, SAN, styrene-methylmethacrylate copolymer or the styrene diethylene benzene copoly mer.
9. according to the said preparation method who under middle temperature, causes the latency microcapsules curing agent that thermosetting epoxy resin solidifies of claim 1, it is characterized in that: said polyacrylic is polymethyl methacrylate, methyl methacrylate and styrol copolymer, gather methyl or gather in the Mecrilate one or more.
10. one kind is utilized said any of claim 1～9 under middle temperature, to cause the method that latency microcapsules curing agent that thermosetting epoxy resin solidifies prepares intermediate temperature setting single-component epoxy resin adhesive; It is characterized in that the latency microcapsules curing agent and 1～20 mass parts filler that the thermosetting polyfunctional epoxy resin, 5～100 mass parts non-activated thinners, 1～100 mass parts that under the 100 mass parts room temperatures are liquid state are caused thermosetting epoxy resin curing under middle temperature mix, and obtain long latency intermediate temperature setting single-component epoxy resin adhesive; Said thermosetting polyfunctional epoxy resin is one or more in bisphenol-A glycidol ether or the Bisphenol F glycidol ether; Said non-activated thinner is one or more in acetone, MEK, cyclohexanone, ethanol or the toluene; Said filler is one or more in nano silicon, nano-calcium carbonate, aluminium oxide or the potter's clay powder.
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