CN103484050A - Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof - Google Patents
Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof Download PDFInfo
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Abstract
A corrosion-inhibiting primer with low VOC for structure glued joint and a preparation method thereof. The invention relates to a primer for structure glued joint and a preparation method thereof. The invention aims to solve the problems in the prior art, such as environmental pollution caused by a solvent-type corrosion-inhibiting primer for structure glued joint, and short storage period and poor compatibility with an intermediate temperature solidified structure glue membrane of a corrosion-inhibiting primer with low VOC. The corrosion-inhibiting primer with low VOC for structure glued joint provided by the invention is prepared from an epoxy aqueous dispersion, a curing agent, a filling material, an auxiliary agent, a corrosion-inhibiting pigment and water. The preparation method is as below: 1, preparing the epoxy aqueous dispersion; and 2, stirring the epoxy aqueous dispersion prepared in the step 1, the curing agent, the filling material, the auxiliary agent, the corrosion-inhibiting pigment and water to obtain the corrosion-inhibiting primer with low VOC for structure glued joint. The primer provided by the invention has low VOC, good storage stability and compatibility with structure glue membrane, and can be applied to the field of metal base material structure glued joint.
Description
Technical field
The present invention relates to primer and preparation method thereof for a kind of structural adhesive bonding.
Background technology
Structural adhesive bonding has the substrate surface after conservation treatment and suppresses the effect such as base material corrosion with suppressing the corrosion primer, in the structural adhesive bonding field, is widely used.Traditional structural adhesive bonding mostly is solvent-borne type with suppressing the corrosion primer, and its volatile organic solvent (VOC) content is up to 80～90wt%, and environmental pollution is serious.Use the water-based system of low VOC content to replace traditional solvent-based system can solve environmental problem and safety problem that the solvent-borne type primer brings.
At present, commercially available water-based epoxy resin mostly is the low molecular weight liquid epoxy emulsion of the water-borne coatings that is applicable to ambient cure, excessive, the poor toughness of cross-linking density after its film-forming, not good with the matching of the sqtructural adhesive of intermediate temperature setting, and storage period is short, just may carry out partial reaction with solidifying agent at normal temperature, greatly affect package stability.
The package stability of primer is the importance of the application performance of primer, the traditional solvent-borne type primer of relevant Boeing standard-required at normal temperatures storage period be 3 days, the storage at normal temperature phase of the aqueous bottom glue that contains a small amount of solvent is 7 days, and the storage at normal temperature phase of solvent-laden aqueous bottom glue is not 30 days.The storage at normal temperature phase is too short, requires primer must use the low temperature storage in transportation, consume energy larger, and increased the urgency of construction, so to extend primer storage period at normal temperatures is very favourable to the application of primer.
Summary of the invention
The present invention will solve existing solvent-borne type structural adhesive bonding to suppress short and not good with the matching of the structural film adhesive of intermediate temperature setting problem corrosion primer storage period with suppressing environmental pollution, existing low VOC content that the corrosion primer brings, and provides low VOC content for a kind of structural adhesive bonding to suppress to corrode primer and preparation method thereof.
It is to be prepared from by 9.7～21.1 parts of epoxy water dispersions, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters by mass fraction that a kind of structural adhesive bonding of the present invention suppresses the corrosion primer with low VOC content.
The preparation method that a kind of structural adhesive bonding of the present invention suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is that to be warming up to temperature from room temperature under the protection of 500r/min～1700r/min and nitrogen atmosphere be 100 ℃～160 ℃, then add the organic phosphine catalyzer, then low whipping speed is that 1000r/min～2500r/min, temperature are 130～180 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 1h～4h, obtains modified epoxy, the mass ratio of wherein said epoxy resin and chainextender is 100:(5～37), the mass ratio of described epoxy resin and organic phosphine catalyzer is 100:(0.1～2), described epoxy resin is bisphenol A type epoxy resin, a kind of in bisphenol f type epoxy resin and novolac epoxy or the mixture of several compositions wherein, described chainextender is the 2-imidazolidone, quinhydrones one or two (β mono-hydroxyethyl) ether, 2, 2-bis-(4-hydroxy phenyl) propane, 1, 4 one butyleneglycols, 1, 6 one hexylene glycols, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, a kind of in diethylaminoethanol or the mixture of several compositions wherein,
(2) polyethers is joined in reaction vessel, low whipping speed is that to be warming up to temperature under 600r/min～1200r/min be 80 ℃～110 ℃, then add catalyzer, low whipping speed is that 700r/min～1600r/min, temperature are to react 1h～3h under 145～185 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is (0.4～2.7): 1, the quality of described catalyzer is 0.1%～0.25% of the modified epoxy total mass that obtains of polyethers and step (1), and described catalyzer is a kind of in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride or the mixture of several compositions wherein;
(3) modified epoxy step (1) obtained adds in reaction vessel, low whipping speed is that to be warming up to temperature by room temperature under 400r/min～800r/min be 90 ℃～140 ℃, then low whipping speed is under 1000r/min～3500r/min, the rate of addition of take drips solvent as 0.06mL/min～3mL/min, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 40 ℃～95 ℃, and be under 40 ℃～95 ℃ in temperature, take stirring velocity as 500r/min～2500r/min, rate of addition is that 0.1mL/min～1.5mL/min adds deionized water, condensation reaction 0.5h～1h, naturally cool to room temperature, obtain the epoxy water dispersion, the quality of the modified epoxy that wherein said step (1) obtains is (2～7) g:1mL with the ratio of the volume of solvent, and the mass ratio of the emulsifying agent that the modified epoxy that step (1) obtains and step (2) obtain is 100:(4.6～30.7),
Two, take by mass fraction epoxy water dispersion, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters that 9.7～21.1 parts of steps (1) obtain, be placed in whipping device, low whipping speed is to stir 10min～30min under 100/min～900r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content; Wherein said solidifying agent is aromatic amine curing agent.
Structural adhesive bonding of the present invention is suppressed to the corrosion primer with low VOC content and brush or be sprayed in the test piece of aluminum base material, after the test piece gluing, room temperature is placed 20min～60min, and primer dry film weight is 4.5g/m
2～9.9g/m
2thickness 3.0 μ m～10.0 μ m, then at 100 ℃～130 ℃ curing 1h～2h, primer layer after solidifying can anti-butanone solvent wiping, illustrate that structural adhesive bonding of the present invention suppresses the corrosion primer with low VOC content good to the wetting property of aluminum base material, bonding force is strong, can effectively strengthen the sticking power of structural film adhesive and metal base.
Structural adhesive bonding of the present invention suppresses the corrosion primer with low VOC content, volatile organic solvent (VOC) content<1wt%, and good with glued membrane FM73MOST matching, simultaneously, by by new system primer of the present invention (low VOC content suppresses the corrosion primer for the new system structural adhesive bonding)+FM73MOST glued membrane and room temperature storage, the primer after 30 days+FM73MOST glued membrane is contrasted, show that self-control primer package stability of the present invention is good, the performance of storage at normal temperature primer after 30 days remains unchanged substantially, in addition, according to related specifications, the primer film has been carried out comprising pencil hardness, anti-butanone solvent is cleaned, adhesive power, the performance test of the underlying membrane such as impact impedance and anti-bending and fluid-resistant performance, the salt spray resistance aging resistance, wet and heat ageing resistant, the durability test of the glued membrane such as resistance toheat and thermal shock resistance, show that primer room temperature storage of the present invention is after 30 days, still possesses good performance.
The accompanying drawing explanation
Fig. 1 suppresses the thermogravimetric analysis graphic representation of corrosion primer for the structural adhesive bonding that in test one, embodiment 4, embodiment 5 and embodiment 6 obtain with low VOC content; Wherein a is embodiment 4, and b is embodiment 5, and c is embodiment 6;
Fig. 2 is 6) test structural adhesive bonding that in four, embodiment 6 obtains and suppress the aging photo of salt spray resistance of corrosion primer with low VOC content.
Embodiment
Embodiment one: it is to be prepared from by 9.7～21.1 parts of epoxy water dispersions, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters by mass fraction that a kind of structural adhesive bonding of present embodiment suppresses the corrosion primer with low VOC content.
Embodiment two: present embodiment is different from embodiment one: the aqueous dispersion based preparation method of described epoxy resin is as follows:
One, prepare the epoxy water dispersion:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is that to be warming up to temperature from room temperature under the protection of 500r/min～1700r/min and nitrogen atmosphere be 100 ℃～160 ℃, then add the organic phosphine catalyzer, then low whipping speed is that 1000r/min～2500r/min, temperature are 130～180 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 1h～4h, obtains modified epoxy; The mass ratio of wherein said epoxy resin and chainextender is 100:(5～37), the mass ratio of described epoxy resin and organic phosphine catalyzer is 100:(0.1～2), described chainextender is 2-imidazolidone, quinhydrones one or two (β mono-hydroxyethyl) ether, 2,2-bis-(4-hydroxy phenyl) propane, 1, a kind of in 4 one butyleneglycols, 1,6 one hexylene glycol, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, diethylaminoethanol or the mixture of several compositions wherein;
(2) polyethers is joined in reaction vessel, low whipping speed is that to be warming up to temperature under 600r/min～1200r/min be 80 ℃～110 ℃, then add catalyzer, low whipping speed is that 700r/min～1600r/min, temperature are to react 1h～3h under 145～185 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is (0.4～2.7): 1, the quality of described catalyzer is 0.1%～0.25% of the modified epoxy total mass that obtains of polyethers and step (1), and described catalyzer is a kind of in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride or the mixture of several compositions wherein;
(3) modified epoxy step (1) obtained adds in reaction vessel, low whipping speed is that to be warming up to temperature by room temperature under 400r/min～800r/min be 90 ℃～140 ℃, then low whipping speed is under 1000r/min～3500r/min, the rate of addition of take drips solvent as 0.06mL/min～3mL/min, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 40 ℃～95 ℃, and be under 40 ℃～95 ℃ in temperature, take stirring velocity as 500r/min～2500r/min, rate of addition is that 0.1mL/min～1.5mL/min adds deionized water, condensation reaction 0.5h～1h, naturally cool to room temperature, obtain the epoxy water dispersion, the quality of the modified epoxy that wherein said step (1) obtains is (2～7) g:1mL with the ratio of the volume of solvent, and the mass ratio of the emulsifying agent that the modified epoxy that step (1) obtains and step (2) obtain is 100:(4.6～30.7), other steps and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment two: described epoxy resin is a kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin and novolac epoxy or the mixture of several compositions wherein.Other steps and parameter are identical with embodiment one or two.
When the epoxy resin in present embodiment is mixture, each component is mixed by any ratio.
Embodiment four: present embodiment is different from embodiment two or three: described solidifying agent is aromatic amine curing agent.Other steps and parameter are identical with embodiment two or three.
Embodiment five: present embodiment is different from one of embodiment two to four: described aromatic amine curing agent is diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3'-diethyl-4,4' diaminodiphenylmethane, 3,3' bis-is chloro-4, a kind of in 4' diaminodiphenylmethane, diethyl toluene diamine and mphenylenediamine or the mixture of several compositions wherein.Other steps and parameter are identical with one of embodiment two to four.
When the aromatic amine curing agent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment six: present embodiment is different from one of embodiment two to five: described inhibition corrosion pigment is a kind of in chromic salt, molybdate and phosphoric acid salt or the mixture of several compositions wherein.Other steps and parameter are identical with one of embodiment two to five.
When the inhibition corrosion pigment in present embodiment is mixture, each component is mixed by any ratio.
Embodiment seven: present embodiment is different from one of embodiment two to six: described filler is aerosil.Other steps and parameter are identical with one of embodiment two to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: described auxiliary agent is a kind of in silane coupling agent KH-560, KH-550 and Z-6040 or the mixture of several compositions wherein.Other steps and parameter are identical with one of embodiment one to seven.
When the auxiliary agent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment nine: present embodiment is different from one of embodiment one to eight: described solvent is a kind of in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF) or the mixture of several compositions wherein.Other steps and parameter are identical with one of embodiment one to eight.
When the solvent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment ten: the preparation method that a kind of structural adhesive bonding of present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is that to be warming up to temperature from room temperature under the protection of 500r/min～1700r/min and nitrogen atmosphere be 100 ℃～160 ℃, then add the organic phosphine catalyzer, then low whipping speed is that 1000r/min～2500r/min, temperature are 130～180 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 1h～4h, obtains modified epoxy, the mass ratio of wherein said epoxy resin and chainextender is 100:(5～37), the mass ratio of described epoxy resin and organic phosphine catalyzer is 100:(0.1～2), described epoxy resin is bisphenol A type epoxy resin, a kind of in bisphenol f type epoxy resin and novolac epoxy or the mixture of several compositions wherein, described chainextender is the 2-imidazolidone, quinhydrones one or two (β mono-hydroxyethyl) ether, 2, 2-bis-(4-hydroxy phenyl) propane, 1, 4 one butyleneglycols, 1, 6 one hexylene glycols, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, a kind of in diethylaminoethanol or the mixture of several compositions wherein,
(2) polyethers is joined in reaction vessel, low whipping speed is that to be warming up to temperature under 600r/min～1200r/min be 80 ℃～110 ℃, then add catalyzer, low whipping speed is that 700r/min～1600r/min, temperature are to react 1h～3h under 145～185 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is (0.4～2.7): 1, the quality of described catalyzer is 0.1%～0.25% of the modified epoxy total mass that obtains of polyethers and step (1), and described catalyzer is a kind of in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride or the mixture of several compositions wherein;
(3) modified epoxy step (1) obtained adds in reaction vessel, low whipping speed is that to be warming up to temperature by room temperature under 400r/min～800r/min be 90 ℃～140 ℃, then low whipping speed is under 1000r/min～3500r/min, the rate of addition of take drips solvent as 0.06mL/min～3mL/min, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 40 ℃～95 ℃, and be under 40 ℃～95 ℃ in temperature, take stirring velocity as 500r/min～2500r/min, rate of addition is that 0.1mL/min～1.5mL/min adds deionized water, condensation reaction 0.5h～1h, naturally cool to room temperature, obtain the epoxy water dispersion, the quality of the modified epoxy that wherein said step (1) obtains is (2～7) g:1mL with the ratio of the volume of solvent, and the mass ratio of the emulsifying agent that the modified epoxy that step (1) obtains and step (2) obtain is 100:(4.6～30.7),
Two, take by mass fraction epoxy water dispersion, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters that 9.7～21.1 parts of steps (1) obtain, be placed in whipping device, low whipping speed is to stir 10min～30min under 100/min～900r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content; Wherein said solidifying agent is aromatic amine curing agent.
Embodiment 11: present embodiment is different from one of embodiment eight to ten: low whipping speed is that to be warming up to temperature from room temperature under 1000r/min and nitrogen atmosphere protection be 140 ℃ in step 1 (1), then add the organic phosphine catalyzer, then low whipping speed is 1200r/min, temperature is 150 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 2.5h, low whipping speed is that to be warming up to temperature under 750r/min be 110 ℃ in step 1 (2), then add catalyzer, low whipping speed is 950r/min, temperature is to react 2h under 170 ℃, low whipping speed is that to be warming up to temperature by room temperature under 750r/min be 90 ℃ in step 1 (3), then low whipping speed is under 2000r/min, take rate of addition as 1mL/min dropping solvent, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 50 ℃, and be under 50 ℃ in temperature, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h.Other steps and parameter are identical with one of embodiment eight to ten.
Embodiment 12: present embodiment is different from one of embodiment eight to 11: the solvent described in step 1 (3) is a kind of in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF) or the mixture of several compositions wherein.Other steps and parameter are identical with one of embodiment eight to 11.
When the solvent in present embodiment is mixture, each component is mixed by any ratio.
With following verification experimental verification beneficial effect of the present invention:
The preparation method that a kind of structural adhesive bonding of embodiment 1, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 100g epoxy resin E-51 and 17g2-imidazolidone are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 750r/min be 100 ℃, then the triphenylphosphine catalyzer that adds 0.05g, low whipping speed is that 1050r/min, temperature are to react 2.5h under 135 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 90 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 950r/min, temperature are to react 1.5h under 165 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 0.8: 1, and the quality of described Boron Trifluoride Ethylamine is 0.1% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 450r/min be 90 ℃, then low whipping speed is under 2000r/min, take rate of addition as 1.2mL/min dropping 12mL ethyl ester, the emulsifying agent that adds again 7.5g step (2) to obtain, being cooled to temperature after mixing is 45 ℃, and be under 45 ℃ in temperature, take stirring velocity as 1800r/min, rate of addition is that 1mL/min adds deionized water, condensation reaction 1h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.7 parts of diethyl toluene diamines, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of deionized waters by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 300r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 1h of the present embodiment step 1 (3), after in four-hole bottle, in emulsion, solid content is 30wt%.
The preparation method that a kind of structural adhesive bonding of embodiment 2, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 100g bisphenol A type epoxy resin E-51 and 17g2-imidazolidone are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 100 ℃, then the triphenylphosphine catalyzer that adds 0.05g, low whipping speed is that 1200r/min, temperature are to react 2.5h under 135 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 90 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 1400r/min, temperature are to react 1.5h under 165 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 1: 1, and the quality of described Boron Trifluoride Ethylamine is 0.1% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 600r/min be 100 ℃, then low whipping speed is under 2000r/min, take rate of addition as 1.8mL/min dropping 12mL ethyl ester, the emulsifying agent that adds again 10g step (2) to obtain, being cooled to temperature after mixing is 55 ℃, and be under 55 ℃ in temperature, take stirring velocity as 1800r/min, rate of addition is that 2mL/min adds deionized water, condensation reaction 1h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.7 parts of diethyl toluene diamines, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of water by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 500r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 1h of the step 1 of the present embodiment (3), after in four-hole bottle, in emulsion, solid content is 30wt%.
The preparation method that a kind of structural adhesive bonding of embodiment 3, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 60g bisphenol A type epoxy resin E-51,40g novolac epoxy DEN438 and 19g2-imidazolidone are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 110 ℃, then the triphenylphosphine catalyzer that adds 0.08g, low whipping speed is that 1200r/min, temperature are to react 2.5h under 140 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 80 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 1400r/min, temperature are to react 2h under 170 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 1: 1, and the quality of described Boron Trifluoride Ethylamine is 0.17% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 600r/min be 105 ℃, then low whipping speed is under 2000r/min, take rate of addition as 1.8mL/min dropping 15mL diacetone alcohol, the emulsifying agent that adds again 12g step (2) to obtain, being cooled to temperature after mixing is 55 ℃, and be under 55 ℃ in temperature, take stirring velocity as 900r/min, rate of addition is that 1mL/min adds deionized water, condensation reaction 1h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.7 parts of diethyl toluene diamines, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of water by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 500r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 1h of the step 1 of the present embodiment (3), after in four-hole bottle, in emulsion, solid content is 40wt%.
The preparation method that a kind of structural adhesive bonding of embodiment 4, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 70g bisphenol A type epoxy resin E-51,30g novolac epoxy DEN438 and 20g2-imidazolidone are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 700r/min be 110 ℃, then the triphenylphosphine catalyzer that adds 0.1g, low whipping speed is that 1100r/min, temperature are to react 2.5h under 140 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 110 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 1300r/min, temperature are to react 2h under 145 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 1: 1, and the quality of described Boron Trifluoride Ethylamine is 0.2% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 600r/min be 100 ℃, then low whipping speed is under 2000r/min, the rate of addition of take drips the ethyl ester solvent of 14mL as 1mL/min, the emulsifying agent that adds again 13g step (2) to obtain, being cooled to temperature after mixing is 50 ℃, and be under 50 ℃ in temperature, take stirring velocity as 900r/min, rate of addition is that 0.1mL/min adds deionized water, condensation reaction 0.8h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.7 parts of diaminodiphenylsulfone(DDS)s, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of water by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 550r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 0.8h of the step 1 of the present embodiment (3), after in four-hole bottle, in emulsion, solid content is 40wt%.
The preparation method that a kind of structural adhesive bonding of embodiment 5, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 50g bisphenol A type epoxy resin E-51,50g bisphenol A type epoxy resin DER669 and 12g diethylaminoethanol are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 1000r/min be 150 ℃, then the triphenylphosphine catalyzer that adds 0.1g, low whipping speed is that 1100r/min, temperature are to react 2h under 140 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 800r/min be 80 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 850r/min, temperature are to react 1.5h under 160 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 1: 1, and the quality of described Boron Trifluoride Ethylamine is 0.1% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 600r/min be 90 ℃, then low whipping speed is under 1500r/min, the rate of addition of take drips the diacetone alcohol solvent of 10mL as 1.7mL/min, the emulsifying agent that adds again 14.5g step (2) to obtain, being cooled to temperature after mixing is 65 ℃, and be under 65 ℃ in temperature, take stirring velocity as 1000r/min, rate of addition is that 0.12mL/min adds deionized water, condensation reaction 1h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.7 parts of diaminodiphenylsulfone(DDS)s, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of water by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 550r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 1h of the step 1 of the present embodiment (3), after in four-hole bottle, in emulsion, solid content is 50wt%.
The preparation method that a kind of structural adhesive bonding of embodiment 6, the present embodiment suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) 50g bisphenol A type epoxy resin E-51,20g bisphenol A type epoxy resin DER669,30g novolac epoxy DEN438 and 15g diethylaminoethanol are joined in the four-hole bottle with agitator, reflux condensing tube and thermometer, pass into dry nitrogen, low whipping speed is that to be warming up to temperature by room temperature under 1000r/min be 140 ℃, then the triphenylphosphine catalyzer that adds 0.1g, low whipping speed is that 1200r/min, temperature are to react 2.5h under 150 ℃, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is that to be warming up to temperature by room temperature under 750r/min be 110 ℃, then add Boron Trifluoride Ethylamine, low whipping speed is that 950r/min, temperature are to react 2h under 170 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is 1: 1, and the quality of described Boron Trifluoride Ethylamine is 0.2% of the modified epoxy total mass that obtains of polyethers and step (1);
(3) modified epoxy 50g step (1) obtained joins with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is that to be warming up to temperature by room temperature under 750r/min be 90 ℃, then low whipping speed is under 2000r/min, the rate of addition of take drips the diacetone alcohol solvent of 18mL as 1mL/min, the emulsifying agent that adds again 15g step (2) to obtain, being cooled to temperature after mixing is 50 ℃, and be under 50 ℃ in temperature, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h, then naturally cool to room temperature, obtain the epoxy water dispersion,
Two, take 10 parts of epoxy water dispersions, 1.2 parts of diethyl toluene diamines, 0.45 part of aerosil, 0.5 part of silane coupling agent and 1 part of strontium yellow and 89 parts of water by mass fraction, be placed in whipping device, low whipping speed is to stir 20min under 560r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content.
After the middle condensation reaction 1h of the step 1 of the present embodiment (3), after in four-hole bottle, in emulsion, solid content is 30wt%.
For test one, structural adhesive bonding that embodiment 4, embodiment 5 and embodiment 6 are obtained, low VOC content suppresses each 6mg of corrosion primer, in condition of cure: dry in the air after at room temperature placing 30min and then be placed in 60 ℃ of baking ovens and dry 30min to surface drying, then in 120 ℃ of baking ovens, under the condition of curing 60min, solidify, then adopting model is the DIAMOND-6300 thermal gravimetric analyzer, under nitrogen atmosphere, take the speed of temperature rise rate as 10 ℃/min, being warming up to temperature is 650 ℃, carry out the test of thermostability, obtain thermogravimetric analysis graphic representation as shown in Figure 1.
From Fig. 1 (TG), can draw, in the temperature range interval of decomposing at 350 ℃～500 ℃ epoxy resin main chains, in three kinds of primers after solidifying, the thermal weight loss rate of the primer that embodiment 6 obtains is minimum, illustrates after it solidifies higher cross-linking density and better thermostability are arranged.
Test two, the structural adhesive bonding that embodiment 6 is obtained suppress corrosion primer (being designated hereinafter simply as the self-control primer) with low VOC content and carry out testing with the matching of glued membrane, and test process is as follows:
One, structural adhesive bonding embodiment 6 obtained suppresses the corrosion primer with low VOC content, fully rock after evenly and join in spray gun, at pressure, be under 0.3MPa, to be sprayed at according to HB/Z197-91 " structural adhesive bonding aluminium alloy phosphoric acid technological specification ", to carry out on 2024-T3 aluminum alloy base material that surface-treated 0.5mm is thick, then at room temperature placing after 30min dries in the air is placed in 60 ℃ of baking ovens and dries 30min to surface drying, then solidify 60min in 120 ℃ of baking ovens, obtain making by oneself the primer film; The use film gauge is measured, and after solidifying, the thickness of primer, measure ten times, averages, and the primer build after requiring to solidify is 3.0 μ m～10.0 μ m.）
Two, the aluminum alloy base material glued membrane FM73MOST of Cytec company is bonded in step 1 has the self-control primer of this test simultaneously to go up, and in temperature, is then to solidify 90min under 120 ℃, obtains making by oneself primer film+FM73MOST glued membrane+aluminum alloy base material.
The self-control primer film that to adopt model be the INSTRON4467 universal testing machine processes space management, 30 days salt fog burin-in process and 30 hydrothermal agings+FM73MOST glued membrane+aluminum alloy base material and FM73MOST glued membrane+aluminum alloy base material carry out the mechanical property detection, the results are shown in Table 1.
Table 1 self-control primer film and the test of glued membrane matching
From table 1, self-control primer film and the glued membrane FM73MOST matching of embodiment 6 are good.
Self-control primer film and the primer film of room temperature storage after 30 days that instrument in test three, employing test two step 1 and procedure obtain embodiment 6 are tested with FM73MOST glued membrane coupling system respectively, primer is investigated storage period, and test result is in Table 2.
The package stability test of table 2 self-control primer film
From table 2, self-control primer package stability is good, and the performance of storage at normal temperature primer after 30 days remains unchanged substantially.
Step and the parameter of test four, reference test two step 1, the self-control primer that embodiment 6 is obtained carries out 1) pencil hardness detection, 2) anti-butanone solvent wiping detection, 3) adhesive power detection, 4) impact impedance detection, 5) fluid-resistant Performance Detection, 6) salt spray resistance aging resistance, 7) wet and heat ageing resistant detection, 8) resistance toheat detection, 9) the thermal shock resistance detection, primer of the present invention is carried out to the over-all properties detection, the results are shown in Table 3.
In this test except 2) reference standard of other detections of detecting of anti-butanone solvent wiping is BMS5-89;
Whether 2) anti-butanone solvent wiping testing process is as follows: use the absorbent cotton or the gauze that are moistened with butanone to carry out wiping to the primer film after solidifying, observe on absorbent cotton and have and fade.
Table 3 primer film properties test result
Comprehensive above-mentioned every test to primer, determine that the performance of self-control primer can meet related specifications to the requirement that suppresses corrosion primer performance for low VOC structural adhesive bonding.
After primer room temperature storage 30 days, again carry out above-mentioned every test, all can meet the requirement test of related specifications.
Claims (10)
1. a structural adhesive bonding suppresses the corrosion primer with low VOC content, it is characterized in that it is to be prepared from by 9.7～21.1 parts of epoxy water dispersions, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters by mass fraction that a kind of structural adhesive bonding suppresses the corrosion primer with low VOC content.
2. low VOC content suppresses the corrosion primer for a kind of structural adhesive bonding according to claim 1, it is characterized in that epoxy resin in described epoxy water dispersion is a kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin and novolac epoxy or the mixture of several compositions wherein.
3. a kind of structural adhesive bonding according to claim 1 and 2 suppresses the corrosion primer with low VOC content, it is characterized in that described solidifying agent is aromatic amine curing agent.
4. a kind of structural adhesive bonding according to claim 3 suppresses the corrosion primer with low VOC content, it is characterized in that described aromatic amine curing agent is diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3'-diethyl-4,4' diaminodiphenylmethane, 3,3' bis-is chloro-4, a kind of in 4' diaminodiphenylmethane, diethyl toluene diamine and mphenylenediamine or the mixture of several compositions wherein.
5. low VOC content suppresses the corrosion primer for structural adhesive bonding according to claim 3, it is characterized in that described inhibition corrosion pigment is a kind of in chromic salt, molybdate and phosphoric acid salt or the mixture of several compositions wherein.
6. structural adhesive bonding according to claim 3 suppresses the corrosion primer with low VOC content, it is characterized in that described filler is aerosil.
7. low VOC content suppresses the corrosion primer for structural adhesive bonding according to claim 3, it is characterized in that described auxiliary agent is a kind of in silane coupling agent KH-560, KH-550 and Z-6040 or the mixture of several compositions wherein.
8. a kind of structural adhesive bonding as claimed in claim 1 suppresses the preparation method of corrosion primer with low VOC content, it is characterized in that the preparation method that a kind of structural adhesive bonding suppresses the corrosion primer with low VOC content carries out according to the following steps:
One, prepare the epoxy water dispersion:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is that to be warming up to temperature from room temperature under the protection of 500r/min～1700r/min and nitrogen atmosphere be 100 ℃～160 ℃, then add the organic phosphine catalyzer, then low whipping speed is that 1000r/min～2500r/min, temperature are 130～180 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 1h～4h, obtains modified epoxy, the mass ratio of wherein said epoxy resin and chainextender is 100:(5～37), the mass ratio of described epoxy resin and organic phosphine catalyzer is 100:(0.1～2), described epoxy resin is bisphenol A type epoxy resin, a kind of in bisphenol f type epoxy resin and novolac epoxy or the mixture of several compositions wherein, described chainextender is the 2-imidazolidone, quinhydrones one or two (β mono-hydroxyethyl) ether, 2, 2-bis-(4-hydroxy phenyl) propane, 1, 4 one butyleneglycols, 1, 6 one hexylene glycols, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, a kind of in diethylaminoethanol or the mixture of several compositions wherein,
(2) polyethers is joined in reaction vessel, low whipping speed is that to be warming up to temperature under 600r/min～1200r/min be 80 ℃～110 ℃, then add catalyzer, low whipping speed is that 700r/min～1600r/min, temperature are to react 1h～3h under 145～185 ℃, obtains emulsifying agent; The mol ratio of the modified epoxy that wherein said polyethers and step (1) obtain is (0.4～2.7): 1, the quality of described catalyzer is 0.1%～0.25% of the modified epoxy total mass that obtains of polyethers and step (1), and described catalyzer is a kind of in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride or the mixture of several compositions wherein;
(3) modified epoxy step (1) obtained adds in reaction vessel, low whipping speed is that to be warming up to temperature by room temperature under 400r/min～800r/min be 90 ℃～140 ℃, then low whipping speed is under 1000r/min～3500r/min, the rate of addition of take drips solvent as 0.06mL/min～3mL/min, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 40 ℃～95 ℃, and be under 40 ℃～95 ℃ in temperature, take stirring velocity as 500r/min～2500r/min, rate of addition is that 0.1mL/min～1.5mL/min adds deionized water, condensation reaction 0.5h～1h, naturally cool to room temperature, obtain the epoxy water dispersion, the quality of the modified epoxy that wherein said step (1) obtains is (2～7) g:1mL with the ratio of the volume of solvent, and the mass ratio of the emulsifying agent that the modified epoxy that step (1) obtains and step (2) obtain is 100:(4.6～30.7),
Two, take by mass fraction epoxy water dispersion, 1.2～5.1 parts of solidifying agent, 0.3～0.9 part of filler, 0.1～1.5 part of auxiliary agent, 1.0～5.0 parts of inhibition corrosion pigment and 10～100 parts of deionized waters that 9.7～21.1 parts of steps (1) obtain, be placed in whipping device, low whipping speed is to stir 10min～30min under 100/min～900r/min, obtains structural adhesive bonding and suppresses the corrosion primer with low VOC content; Wherein said solidifying agent is aromatic amine curing agent.
9. a kind of structural adhesive bonding according to claim 8 suppresses the preparation method of corrosion primer with low VOC content, it is characterized in that in step 1 (1) that low whipping speed is that to be warming up to temperature from room temperature under 1000r/min and nitrogen atmosphere protection be 140 ℃, then add the organic phosphine catalyzer, then low whipping speed is 1200r/min, temperature is 150 ℃ and the lower condensing reflux reaction of nitrogen atmosphere protection 2.5h, low whipping speed is that to be warming up to temperature under 750r/min be 110 ℃ in step 1 (2), then add catalyzer, low whipping speed is 950r/min, temperature is to react 2h under 170 ℃, low whipping speed is that to be warming up to temperature by room temperature under 750r/min be 90 ℃ in step 1 (3), then low whipping speed is under 2000r/min, take rate of addition as 1mL/min dropping solvent, the emulsifying agent that adds again step (2) to obtain, being cooled to temperature after mixing is 50 ℃, and be under 50 ℃ in temperature, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h.
10. a kind of structural adhesive bonding according to claim 8 or claim 9 suppresses the preparation method of corrosion primer with low VOC content, it is characterized in that the solvent described in described step 1 (3) is a kind of in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF) or the mixture of several compositions wherein.
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