CN103484050B - 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
- Publication number
- CN103484050B CN103484050B CN201310469902.5A CN201310469902A CN103484050B CN 103484050 B CN103484050 B CN 103484050B CN 201310469902 A CN201310469902 A CN 201310469902A CN 103484050 B CN103484050 B CN 103484050B
- Authority
- CN
- China
- Prior art keywords
- temperature
- whipping speed
- epoxy
- low whipping
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
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 a kind of structural adhesive bonding primer and preparation method thereof.
Background technology
Structural adhesive bonding suppression corrosion primer has the effects such as the substrate surface after conservation treatment and the corrosion of suppression base material, is widely used in structural adhesive bonding field.Traditional structural adhesive bonding suppresses corrosion primer mostly to be solvent-borne type, 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 then can solve environmental problem that solvent-borne type primer brings and safety problem.
At present, commercially available water-based epoxy resin mostly is the low molecular weight liquid epoxy emulsion of the water-borne coatings being 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 have impact on 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 containing a small amount of solvent is 7 days, and the storage at normal temperature phase of not solvent-laden aqueous bottom glue is 30 days.The storage at normal temperature phase is too short, then require that primer must use low temperature to store in transportation, and power consumption is comparatively large, and too increases the urgency of construction, and it is very favourable for therefore extending the primer application of storage period to primer at normal temperatures.
Summary of the invention
The present invention be to solve the environmental pollution that existing solvent-borne type structural adhesive bonding suppresses corrosion primer to bring, problem that existing low VOC content suppresses corrosion primer storage period short and not good with the matching of the structural film adhesive of intermediate temperature setting, and provide a kind of structural adhesive bonding low VOC content and suppress corrosion primer and preparation method thereof.
A kind of structural adhesive bonding low VOC content of the present invention suppresses corrosion base rubber 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 suppression anticorrosion pigment and 10 ~ 100 parts of deionized waters.
A kind of structural adhesive bonding low VOC content of the present invention suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is under 500r/min ~ 1700r/min and nitrogen atmosphere protection be 100 DEG C ~ 160 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1000r/min ~ 2500r/min, temperature is 130 ~ 180 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 1h ~ 4h, obtains modified epoxy, wherein said epoxy resin and the mass ratio of chainextender are 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, mixture that is a kind of or wherein several composition in bisphenol f type epoxy resin and novolac epoxy, described chainextender is 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, mixture that is a kind of or wherein several composition in diethylaminoethanol,
(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 DEG C ~ 110 DEG C, then add catalyzer, low whipping speed is 700r/min ~ 1600r/min, temperature is react 1h ~ 3h at 145 ~ 185 DEG C, obtain 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 polyethers and step (1) obtain, and described catalyzer is the mixture that is a kind of or wherein several composition in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride;
(3) modified epoxy that step (1) obtains is added in reaction vessel, low whipping speed is under 400r/min ~ 800r/min be 90 DEG C ~ 140 DEG C by room temperature to temperature, then low whipping speed is under 1000r/min ~ 3500r/min, be that 0.06mL/min ~ 3mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 40 DEG C ~ 95 DEG C, and at temperature is 40 DEG C ~ 95 DEG C, 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 epoxy water dispersion, the quality of 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 modified epoxy that step (1) obtains and the emulsifying agent that step (2) obtains is 100:(4.6 ~ 30.7),
Two, by mass fraction take epoxy water dispersion that 9.7 ~ 21.1 parts of steps (1) obtain, 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 suppress anticorrosion pigment and 10 ~ 100 parts of deionized waters, be placed in whipping device, low whipping speed is stir 10min ~ 30min under 100/min ~ 900r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer; Wherein said solidifying agent is aromatic amine curing agent.
Suppressed by structural adhesive bonding low VOC content of the present invention corrosion primer brush or be sprayed in the test piece of aluminum base material, after test piece gluing, room temperature places 20min ~ 60min, and primer dry film weight is 4.5g/m
2~ 9.9g/m
2thickness 3.0 μm ~ 10.0 μm, then at 100 DEG C ~ 130 DEG C solidification 1h ~ 2h, primer layer after solidification can the wiping of resistance to butanone solvent, illustrate that structural adhesive bonding low VOC content of the present invention suppresses corrosion primer good to the wetting property of aluminum base material, bonding force is strong, effectively can strengthen the sticking power of structural film adhesive and metal base.
Structural adhesive bonding low VOC content of the present invention suppresses corrosion primer, volatile organic solvent (VOC) content < 1wt%, and it is good with glued membrane FM73MOST matching, simultaneously, by brand-new primer of the present invention (brand-new structural adhesive bonding low VOC content suppresses corrosion primer)+FM73MOST glued membrane and the primer+FM73MOST glued membrane of room temperature storage after 30 days are 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, carry out comprising pencil hardness to primer film according to related specifications, resistance to butanone solvent is cleaned, adhesive power, underlying membrane performance test and the fluid-resistant performances such as impact impedance and bending resistance folding endurance, 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.
Accompanying drawing explanation
Fig. 1 is the thermal gravimetric analysis curve figure of the structural adhesive bonding low VOC content suppression corrosion primer that embodiment 4 in test one, embodiment 5 and embodiment 6 obtain; Wherein a is embodiment 4, b be embodiment 5, c is embodiment 6;
Fig. 2 is 6) the structural adhesive bonding low VOC content that obtains of embodiment 6 suppresses the aging photo of salt spray resistance of corrosion primer in test four.
Embodiment
Embodiment one: a kind of structural adhesive bonding low VOC content of present embodiment suppresses corrosion base rubber 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 suppression anticorrosion pigment and 10 ~ 100 parts of deionized waters.
Embodiment two: present embodiment and embodiment one unlike: the preparation method that described epoxy resin is aqueous dispersion based is as follows:
One, epoxy water dispersion is prepared:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is under 500r/min ~ 1700r/min and nitrogen atmosphere protection be 100 DEG C ~ 160 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1000r/min ~ 2500r/min, temperature is 130 ~ 180 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 1h ~ 4h, obtains modified epoxy; Wherein said epoxy resin and the mass ratio of chainextender are 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, 1,4 one butyleneglycols, 1, the mixture that is a kind of or wherein several composition in 6 one hexylene glycols, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, diethylaminoethanol;
(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 DEG C ~ 110 DEG C, then add catalyzer, low whipping speed is 700r/min ~ 1600r/min, temperature is react 1h ~ 3h at 145 ~ 185 DEG C, obtain 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 polyethers and step (1) obtain, and described catalyzer is the mixture that is a kind of or wherein several composition in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride;
(3) modified epoxy that step (1) obtains is added in reaction vessel, low whipping speed is under 400r/min ~ 800r/min be 90 DEG C ~ 140 DEG C by room temperature to temperature, then low whipping speed is under 1000r/min ~ 3500r/min, be that 0.06mL/min ~ 3mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 40 DEG C ~ 95 DEG C, and at temperature is 40 DEG C ~ 95 DEG C, 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 epoxy water dispersion, the quality of 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 modified epoxy that step (1) obtains and the emulsifying agent that step (2) obtains is 100:(4.6 ~ 30.7), other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment two unlike: described epoxy resin is the mixture that is a kind of or wherein several composition in bisphenol A type epoxy resin, bisphenol f type epoxy resin and novolac epoxy.Other steps and parameter identical with embodiment one or two.
When epoxy resin in present embodiment is mixture, each component is mixed by any ratio.
Embodiment four: present embodiment and embodiment two or three unlike: described solidifying agent is aromatic amine curing agent.Other steps and parameter identical with embodiment two or three.
Embodiment five: one of present embodiment and embodiment two to four unlike: described aromatic amine curing agent is diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3'-diethyl-4,4' diaminodiphenylmethane, 3, mixture that is a kind of or wherein several composition in chloro-4, the 4' diaminodiphenylmethane of 3' bis-, diethyl toluene diamine and mphenylenediamine.Other steps and parameter identical with one of embodiment two to four.
When aromatic amine curing agent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment six: one of present embodiment and embodiment two to five unlike: described suppression anticorrosion pigment is the mixture that is a kind of or wherein several composition in chromic salt, molybdate and phosphoric acid salt.Other steps and parameter identical with one of embodiment two to five.
When suppression anticorrosion pigment in present embodiment is mixture, each component is mixed by any ratio.
Embodiment seven: one of present embodiment and embodiment two to six unlike: described filler is aerosil.Other steps and parameter identical with one of embodiment two to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: described auxiliary agent is the mixture that is a kind of or wherein several composition in silane coupling agent KH-560, KH-550 and Z-6040.Other steps and parameter identical with one of embodiment one to seven.
When auxiliary agent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: described solvent is the mixture that is a kind of or wherein several composition in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF).Other steps and parameter identical with one of embodiment one to eight.
When solvent in present embodiment is mixture, each component is mixed by any ratio.
Embodiment ten: a kind of structural adhesive bonding low VOC content of present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is under 500r/min ~ 1700r/min and nitrogen atmosphere protection be 100 DEG C ~ 160 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1000r/min ~ 2500r/min, temperature is 130 ~ 180 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 1h ~ 4h, obtains modified epoxy, wherein said epoxy resin and the mass ratio of chainextender are 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, mixture that is a kind of or wherein several composition in bisphenol f type epoxy resin and novolac epoxy, described chainextender is 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, mixture that is a kind of or wherein several composition in diethylaminoethanol,
(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 DEG C ~ 110 DEG C, then add catalyzer, low whipping speed is 700r/min ~ 1600r/min, temperature is react 1h ~ 3h at 145 ~ 185 DEG C, obtain 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 polyethers and step (1) obtain, and described catalyzer is the mixture that is a kind of or wherein several composition in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride;
(3) modified epoxy that step (1) obtains is added in reaction vessel, low whipping speed is under 400r/min ~ 800r/min be 90 DEG C ~ 140 DEG C by room temperature to temperature, then low whipping speed is under 1000r/min ~ 3500r/min, be that 0.06mL/min ~ 3mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 40 DEG C ~ 95 DEG C, and at temperature is 40 DEG C ~ 95 DEG C, 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 epoxy water dispersion, the quality of 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 modified epoxy that step (1) obtains and the emulsifying agent that step (2) obtains is 100:(4.6 ~ 30.7),
Two, by mass fraction take epoxy water dispersion that 9.7 ~ 21.1 parts of steps (1) obtain, 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 suppress anticorrosion pigment and 10 ~ 100 parts of deionized waters, be placed in whipping device, low whipping speed is stir 10min ~ 30min under 100/min ~ 900r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer; Wherein said solidifying agent is aromatic amine curing agent.
Embodiment 11: one of present embodiment and embodiment eight to ten are under 1000r/min and nitrogen atmosphere protection be 140 DEG C from room temperature to temperature unlike low whipping speed in: step one (1), then organic phosphine catalyzer is added, then low whipping speed is 1200r/min, temperature is 150 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 2.5h, low whipping speed is that to be warming up to temperature under 750r/min be 110 DEG C in step one (2), then catalyzer is added, low whipping speed is 950r/min, temperature is react 2h at 170 DEG C, low whipping speed is under 750r/min be 90 DEG C by room temperature to temperature in step one (3), then low whipping speed is under 2000r/min, be that 1mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 50 DEG C, and at temperature is 50 DEG C, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h.Other steps and parameter identical with one of embodiment eight to ten.
Embodiment 12: one of present embodiment and embodiment eight to ten one unlike: the solvent described in step one (3) is the mixture that is a kind of or wherein several composition in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF).Other steps and parameter identical with one of embodiment eight to ten one.
When solvent in present embodiment is mixture, each component is mixed by any ratio.
With following verification experimental verification beneficial effect of the present invention:
A kind of structural adhesive bonding low VOC content of embodiment 1, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 750r/min be 100 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.05g is added, low whipping speed is 1050r/min, temperature is react 2.5h at 135 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 800r/min be 90 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 950r/min, temperature is react 1.5h at 165 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 450r/min be 90 DEG C by room temperature to temperature, then low whipping speed is under 2000r/min, be that 1.2mL/min drips 12mL ethyl ester with rate of addition, add the emulsifying agent that 7.5g step (2) obtains again, being cooled to temperature after mixing is 45 DEG C, and at temperature is 45 DEG C, take stirring velocity as 1800r/min, rate of addition is that 1mL/min adds deionized water, condensation reaction 1h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 300r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the present embodiment step one (3) after condensation reaction 1h, in four-hole bottle, in emulsion, solid content is after 30wt%.
A kind of structural adhesive bonding low VOC content of embodiment 2, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 800r/min be 100 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.05g is added, low whipping speed is 1200r/min, temperature is react 2.5h at 135 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 800r/min be 90 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 1400r/min, temperature is react 1.5h at 165 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 600r/min be 100 DEG C by room temperature to temperature, then low whipping speed is under 2000r/min, be that 1.8mL/min drips 12mL ethyl ester with rate of addition, add the emulsifying agent that 10g step (2) obtains again, being cooled to temperature after mixing is 55 DEG C, and at temperature is 55 DEG C, take stirring velocity as 1800r/min, rate of addition is that 2mL/min adds deionized water, condensation reaction 1h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 500r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the step one (3) of the present embodiment after condensation reaction 1h, in four-hole bottle, in emulsion, solid content is after 30wt%.
A kind of structural adhesive bonding low VOC content of embodiment 3, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 800r/min be 110 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.08g is added, low whipping speed is 1200r/min, temperature is react 2.5h at 140 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 800r/min be 80 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 1400r/min, temperature is react 2h at 170 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 600r/min be 105 DEG C by room temperature to temperature, then low whipping speed is under 2000r/min, be that 1.8mL/min drips 15mL diacetone alcohol with rate of addition, add the emulsifying agent that 12g step (2) obtains again, being cooled to temperature after mixing is 55 DEG C, and at temperature is 55 DEG C, take stirring velocity as 900r/min, rate of addition is that 1mL/min adds deionized water, condensation reaction 1h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 500r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the step one (3) of the present embodiment after condensation reaction 1h, in four-hole bottle, in emulsion, solid content is after 40wt%.
A kind of structural adhesive bonding low VOC content of embodiment 4, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 700r/min be 110 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.1g is added, low whipping speed is 1100r/min, temperature is react 2.5h at 140 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 800r/min be 110 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 1300r/min, temperature is react 2h at 145 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 600r/min be 100 DEG C by room temperature to temperature, then low whipping speed is under 2000r/min, take rate of addition as the ethyl ester solvent that 1mL/min drips 14mL, add the emulsifying agent that 13g step (2) obtains again, being cooled to temperature after mixing is 50 DEG C, and at temperature is 50 DEG C, take stirring velocity as 900r/min, rate of addition is that 0.1mL/min adds deionized water, condensation reaction 0.8h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 550r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the step one (3) of the present embodiment after condensation reaction 0.8h, in four-hole bottle, in emulsion, solid content is after 40wt%.
A kind of structural adhesive bonding low VOC content of embodiment 5, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 1000r/min be 150 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.1g is added, low whipping speed is 1100r/min, temperature is react 2h at 140 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 800r/min be 80 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 850r/min, temperature is react 1.5h at 160 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 600r/min be 90 DEG C by room temperature to temperature, then low whipping speed is under 1500r/min, take rate of addition as the diacetone alcohol solvent that 1.7mL/min drips 10mL, add the emulsifying agent that 14.5g step (2) obtains again, being cooled to temperature after mixing is 65 DEG C, and at temperature is 65 DEG C, take stirring velocity as 1000r/min, rate of addition is that 0.12mL/min adds deionized water, condensation reaction 1h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 550r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the step one (3) of the present embodiment after condensation reaction 1h, in four-hole bottle, in emulsion, solid content is after 50wt%.
A kind of structural adhesive bonding low VOC content of embodiment 6, the present embodiment suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(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 under 1000r/min be 140 DEG C by room temperature to temperature, then the triphenylphosphine catalysis of 0.1g is added, low whipping speed is 1200r/min, temperature is react 2.5h at 150 DEG C, obtains modified epoxy;
(2) polyethers is joined in three mouthfuls of round-bottomed flasks with whipping appts, low whipping speed is under 750r/min be 110 DEG C by room temperature to temperature, then add Boron Trifluoride Ethylamine, low whipping speed is 950r/min, temperature is react 2h at 170 DEG C, obtain 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 polyethers and step (1) obtain;
(3) modified epoxy that 50g step (1) obtains is joined with agitator, reflux condensing tube, in the four-hole bottle of thermometer and constant pressure funnel, low whipping speed is under 750r/min be 90 DEG C by room temperature to temperature, then low whipping speed is under 2000r/min, take rate of addition as the diacetone alcohol solvent that 1mL/min drips 18mL, add the emulsifying agent that 15g step (2) obtains again, being cooled to temperature after mixing is 50 DEG C, and at temperature is 50 DEG C, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h, then room temperature is naturally cooled to, obtain epoxy water dispersion,
Two, 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 are taken by mass fraction, be placed in whipping device, low whipping speed is stir 20min under 560r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer.
In the step one (3) of the present embodiment after condensation reaction 1h, in four-hole bottle, in emulsion, solid content is after 30wt%.
Test one, structural adhesive bonding low VOC content embodiment 4, embodiment 5 and embodiment 6 obtained suppress each 6mg of corrosion primer, in condition of cure: then at room temperature placing dries in the air after 30min to be placed in 60 DEG C of baking ovens to surface drying and to dry 30min, then solidify under the condition of 120 DEG C of oven for curing 60min, then model is adopted to be DIAMOND-6300 thermal gravimetric analyzer, in a nitrogen atmosphere, with the speed that temperature rise rate is 10 DEG C/min, being warming up to temperature is 650 DEG C, carry out the test of thermostability, obtain thermal gravimetric analysis curve figure as shown in Figure 1.
Can draw from Fig. 1 (TG), in the temperature range interval that 350 DEG C ~ 500 DEG C epoxy main chains decompose, in three kinds of primers after solidification, the thermal weight loss rate of the primer that embodiment 6 obtains is minimum, has higher cross-linking density and better thermostability after its solidification is described.
Test two, suppress corrosion primer (hereinafter referred to as self-control primer) to carry out testing with the matching of glued membrane to the structural adhesive bonding low VOC content that embodiment 6 obtains, test process is as follows:
One, structural adhesive bonding low VOC content embodiment 6 obtained suppresses corrosion primer, fully rock and join in spray gun after evenly, be sprayed under pressure is 0.3MPa and carry out on the thick 2024-T3 aluminum alloy base material of surface-treated 0.5mm according to HB/Z197-91 " structural adhesive bonding aluminium alloy phosphoric acid technological specification ", then at room temperature placing dries in the air after 30min to be placed in 60 DEG C of baking ovens to surface drying and to dry 30min, then at 120 DEG C of oven for curing 60min, self-control primer film is obtained; Use film gauge is measured, and after solidification, the thickness of primer, measures ten times, average, and requires that the primer build after solidification is 3.0 μm ~ 10.0 μm.）
Two, the glued membrane FM73MOST aluminum alloy base material be bonded in step one of Cytec company is had in the self-control primer one side of this test, then at temperature is 120 DEG C, solidify 90min, obtain self-control primer film+FM73MOST glued membrane+aluminum alloy base material.
Adopt model to be INSTRON4467 universal testing machine to the self-control primer film+FM73MOST glued membrane+aluminum alloy base material of space management, 30 days salt fog burin-in process and 30 hydrothermal aging process and FM73MOST glued membrane+aluminum alloy base material to carry out mechanics properties testing, the results are shown in Table 1.
Primer film made by oneself by table 1 and glued membrane matching is tested
From table 1, self-control primer film and the glued membrane FM73MOST matching of embodiment 6 are good.
Test three, adopt the instruments and methods process in test two step one to mate system with FM73MOST glued membrane to the self-control primer film that embodiment 6 obtains respectively with the primer film of room temperature storage after 30 days to test, investigate storage period primer, test result is in table 2.
The package stability test of primer film made by oneself by table 2
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.
The step of test four, reference test two steps one and parameter, 1 is carried out to the self-control primer that embodiment 6 obtains) pencil hardness detection, 2) resistance to 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) thermal shock resistance detection, inspect on colligated-function is carried out to primer of the present invention, the results are shown in Table 3.
Except 2 in this test) other reference standards detected of detecting of resistance to butanone solvent wiping are BMS5-89;
2) resistance to butanone solvent wiping testing process is as follows: use and be moistened with the absorbent cotton of butanone or gauze carries out wiping to the primer film after solidification, observes whether absorbent cotton have to fade.
Table 3 primer film properties test result
Comprehensively above-mentioned every test to primer, the performance of determining to make by oneself primer can meet the requirement of related specifications to low VOC structural adhesive bonding suppression corrosion primer performance.
Primer room temperature storage, after 30 days, carries out above-mentioned every test again, all can meet the requirement test of related specifications.
Claims (6)
1. structural adhesive bonding low VOC content suppresses a corrosion primer, it is characterized in that a kind of structural adhesive bonding low VOC content suppresses corrosion base rubber 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 parts of suppression anticorrosion pigment and 10 ~ 100 parts of deionized waters; Epoxy resin in described epoxy water dispersion is the mixture that is a kind of or wherein several composition in bisphenol A type epoxy resin, bisphenol f type epoxy resin and novolac epoxy; Described solidifying agent is aromatic amine curing agent; Described aromatic amine curing agent is diaminodiphenylmethane, diaminodiphenylsulfone(DDS), 3,3'-diethyl-4, mixture that is a kind of or wherein several composition in 4' diaminodiphenylmethane, 3,3' bis-chloro-4,4' diaminodiphenylmethane, diethyl toluene diamine and mphenylenediamine; Described auxiliary agent is the mixture that is a kind of or wherein several composition in silane coupling agent KH-560, KH-550 and Z-6040;
The preparation method that described epoxy resin is aqueous dispersion based is as follows:
One, epoxy water dispersion is prepared:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is under 500r/min ~ 1700r/min and nitrogen atmosphere protection be 100 DEG C ~ 160 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1000r/min ~ 2500r/min, temperature is 130 ~ 180 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 1h ~ 4h, obtains modified epoxy; Wherein said epoxy resin and the mass ratio of chainextender are 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, 1,4 one butyleneglycols, 1, the mixture that is a kind of or wherein several composition in 6 one hexylene glycols, TriMethylolPropane(TMP), neopentyl glycol, sorbyl alcohol, diethylaminoethanol;
(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 DEG C ~ 110 DEG C, then add catalyzer, low whipping speed is 700r/min ~ 1600r/min, temperature is react 1h ~ 3h at 145 ~ 185 DEG C, obtain 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 polyethers and step (1) obtain, and described catalyzer is the mixture that is a kind of or wherein several composition in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride;
(3) modified epoxy that step (1) obtains is added in reaction vessel, low whipping speed is under 400r/min ~ 800r/min be 90 DEG C ~ 140 DEG C by room temperature to temperature, then low whipping speed is under 1000r/min ~ 3500r/min, be that 0.06mL/min ~ 3mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 40 DEG C ~ 95 DEG C, and at temperature is 40 DEG C ~ 95 DEG C, 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 epoxy water dispersion, the quality of 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 modified epoxy that step (1) obtains and the emulsifying agent that step (2) obtains is 100:(4.6 ~ 30.7).
2. structural adhesive bonding low VOC content according to claim 1 suppresses corrosion primer, it is characterized in that described suppression anticorrosion pigment is the mixture that is a kind of or wherein several composition in chromic salt, molybdate and phosphoric acid salt.
3. structural adhesive bonding low VOC content according to claim 1 suppresses corrosion primer, it is characterized in that described filler is aerosil.
4. a kind of structural adhesive bonding low VOC content as claimed in claim 1 suppresses the preparation method of corrosion primer, it is characterized in that a kind of structural adhesive bonding low VOC content suppresses the preparation method of corrosion primer to carry out according to the following steps:
One, epoxy water dispersion is prepared:
(1) epoxy resin and chainextender are joined in reaction vessel, pass into dry nitrogen, low whipping speed is under 500r/min ~ 1700r/min and nitrogen atmosphere protection be 100 DEG C ~ 160 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1000r/min ~ 2500r/min, temperature is 130 ~ 180 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 1h ~ 4h, obtains modified epoxy, wherein said epoxy resin and the mass ratio of chainextender are 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, mixture that is a kind of or wherein several composition in bisphenol f type epoxy resin and novolac epoxy, described chainextender is 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, mixture that is a kind of or wherein several composition in diethylaminoethanol,
(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 DEG C ~ 110 DEG C, then add catalyzer, low whipping speed is 700r/min ~ 1600r/min, temperature is react 1h ~ 3h at 145 ~ 185 DEG C, obtain 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 polyethers and step (1) obtain, and described catalyzer is the mixture that is a kind of or wherein several composition in Boron Trifluoride Ethylamine, triphenylphosphine and tin protochloride;
(3) modified epoxy that step (1) obtains is added in reaction vessel, low whipping speed is under 400r/min ~ 800r/min be 90 DEG C ~ 140 DEG C by room temperature to temperature, then low whipping speed is under 1000r/min ~ 3500r/min, be that 0.06mL/min ~ 3mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 40 DEG C ~ 95 DEG C, and at temperature is 40 DEG C ~ 95 DEG C, 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 epoxy water dispersion, the quality of 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 modified epoxy that step (1) obtains and the emulsifying agent that step (2) obtains is 100:(4.6 ~ 30.7),
Two, by mass fraction take epoxy water dispersion that 9.7 ~ 21.1 parts of steps (1) obtain, 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 parts suppress anticorrosion pigment and 10 ~ 100 parts of deionized waters, be placed in whipping device, low whipping speed is stir 10min ~ 30min under 100/min ~ 900r/min, obtains structural adhesive bonding low VOC content and suppresses corrosion primer; Wherein said solidifying agent is aromatic amine curing agent.
5. a kind of structural adhesive bonding low VOC content according to claim 4 suppresses the preparation method of corrosion primer, it is characterized in that in step one (1) that low whipping speed is under 1000r/min and nitrogen atmosphere protection is 140 DEG C from room temperature to temperature, then organic phosphine catalyzer is added, then low whipping speed is 1200r/min, temperature is 150 DEG C and nitrogen atmosphere protection lower condensing reflux reaction 2.5h, low whipping speed is that to be warming up to temperature under 750r/min be 110 DEG C in step one (2), then catalyzer is added, low whipping speed is 950r/min, temperature is react 2h at 170 DEG C, low whipping speed is under 750r/min be 90 DEG C by room temperature to temperature in step one (3), then low whipping speed is under 2000r/min, be that 1mL/min drips solvent with rate of addition, add the emulsifying agent that step (2) obtains again, being cooled to temperature after mixing is 50 DEG C, and at temperature is 50 DEG C, take stirring velocity as 1500r/min, rate of addition is that 0.3mL/min adds deionized water, condensation reaction 1h.
6. a kind of structural adhesive bonding low VOC content according to claim 4 suppresses the preparation method of corrosion primer, it is characterized in that the solvent described in described step one (3) is the mixture that is a kind of or wherein several composition in methyl alcohol, ethanol, butanols, diacetone alcohol, ethylene glycol, acetone, butanone, ethyl acetate and tetrahydrofuran (THF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310469902.5A CN103484050B (en) | 2013-10-10 | 2013-10-10 | Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310469902.5A CN103484050B (en) | 2013-10-10 | 2013-10-10 | Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103484050A CN103484050A (en) | 2014-01-01 |
| CN103484050B true CN103484050B (en) | 2015-02-04 |
Family
ID=49824663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310469902.5A Expired - Fee Related CN103484050B (en) | 2013-10-10 | 2013-10-10 | Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103484050B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176464A (en) * | 2015-08-19 | 2015-12-23 | 合肥市田源精铸有限公司 | Metal-to-metal adhesive with stable size |
| CN105368338B (en) * | 2015-12-21 | 2017-12-19 | 上海市合成树脂研究所有限公司 | A kind of preparation method of polyurethane Protection glue band |
| CN108610888A (en) * | 2018-03-14 | 2018-10-02 | 河北晨阳工贸集团有限公司 | A kind of metal surface sealing wax and preparation method thereof |
| CN108624002B (en) * | 2018-06-01 | 2020-04-07 | 黑龙江省科学院石油化学研究院 | High-temperature durable epoxy structure adhesive bonding system and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767176A (en) * | 1994-02-16 | 1998-06-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Aqueous dispersion composition containing microcrystalline cellulose and composition using the same |
| CN1506422A (en) * | 2002-11-29 | 2004-06-23 | ���չ�˾ | Aqueous epoxy slushing undercoat without chromate |
| CN101104770A (en) * | 2007-08-20 | 2008-01-16 | 维新环保涂料（深圳）有限公司 | Water-based epoxy intermediate paint |
| CN102559010A (en) * | 2011-12-26 | 2012-07-11 | 海洋化工研究院 | Chromium-free waterborne epoxy anticorrosion primer with excellent solvent oil resistant performance |
-
2013
- 2013-10-10 CN CN201310469902.5A patent/CN103484050B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767176A (en) * | 1994-02-16 | 1998-06-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Aqueous dispersion composition containing microcrystalline cellulose and composition using the same |
| CN1506422A (en) * | 2002-11-29 | 2004-06-23 | ���չ�˾ | Aqueous epoxy slushing undercoat without chromate |
| CN101104770A (en) * | 2007-08-20 | 2008-01-16 | 维新环保涂料（深圳）有限公司 | Water-based epoxy intermediate paint |
| CN102559010A (en) * | 2011-12-26 | 2012-07-11 | 海洋化工研究院 | Chromium-free waterborne epoxy anticorrosion primer with excellent solvent oil resistant performance |
Non-Patent Citations (1)
| Title |
|---|
| 贺曼罗编著.1.《环氧树脂胶粘剂》.中国石化出版社,2004,(第1版),第242-244页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103484050A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103484050B (en) | Corrosion-inhibiting primer with low VOC for structure glued joint and preparation method thereof | |
| CN104231863B (en) | The solvent free corrosion prevention corrosion-inhibiting coating composition that can solidify in the seawater | |
| CN103450725B (en) | A kind of Environment-friendlyfluorine/silicon-conheavyng fluorine/silicon-conheavyng heavyng anticorrosive epoxy resin paint and preparation method thereof | |
| CN101619201B (en) | Underwater epoxy adhesive and preparation method thereof | |
| CN103602220B (en) | A kind of Siloxane hybrid anticorrosive paint | |
| CN105838192B (en) | A kind of epoxy polysiloxane coating and preparation method | |
| CN104804633B (en) | A kind of low-temperature quick-drying type acroleic acid polyurethane coating and preparation method thereof | |
| CN102732130A (en) | High solid anticorrosive paint and preparation method thereof | |
| CN103145954A (en) | Anacardol glycidyl ether modified aliphatic amine hardener and preparation method thereof | |
| CN107267013A (en) | A kind of environment-friendly type road gage mark coating | |
| CN103965778A (en) | Ordinary temperature curing high-hardness organic-inorganic hybrid coating as well as preparation and use method thereof | |
| CN103242792A (en) | Primer for metal substrate structural bonding and preparation method thereof | |
| CN102977730B (en) | Metal antirust paint treating modified attapulgite as filler, and its preparation method | |
| CN106626652A (en) | Solvent-free composite PET/PE (Polyethylene Terephthalate/Polyethylene) film and preparation process thereof | |
| CN106317974B (en) | A kind of modified organic silicon aluminium organic solvent-resistant dual-component coating and preparation method | |
| CN106479327A (en) | A kind of vinyl ester resin glass flake plasticine coating | |
| CN104479505A (en) | Rapid curing high-tenacity epoxy anticorrosive coating for ship cabin and preparation method | |
| CN104004441B (en) | A kind of Single-component epoxy primer and preparation method thereof | |
| CN102741369B (en) | Surface coatings having anti-ice properties | |
| CN106543836A (en) | A kind of water-based anticorrosive paint | |
| CN107474722A (en) | A kind of heat radiation coating and preparation method thereof | |
| CN104532258A (en) | Preparation method of room-temperature curable nano sol hybridized polyalkylene oxide aluminum alloy surface preservative | |
| CN107722824A (en) | A kind of nano-graphene polysiloxanes composite coating and preparation method thereof | |
| CN105244455B (en) | A kind of soft package lithium battery anti-corrosion protective film and its preparation method and application | |
| CN107118659A (en) | A kind of preparation method of magnetic radiating waterborne epoxy coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150204 Termination date: 20191010 |