CN104672371A - Method for preparing weather-resisting, antifouling and heat-resisting two-component aqueous acrylic resin - Google Patents
Method for preparing weather-resisting, antifouling and heat-resisting two-component aqueous acrylic resin Download PDFInfo
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- CN104672371A CN104672371A CN201410799691.6A CN201410799691A CN104672371A CN 104672371 A CN104672371 A CN 104672371A CN 201410799691 A CN201410799691 A CN 201410799691A CN 104672371 A CN104672371 A CN 104672371A
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Abstract
The invention discloses a method for preparing a weather-resisting, antifouling and heat-resisting two-component aqueous acrylic resin. In the resin, the component A is a fluorine-containing structure unit which exists on the main chain in a block form while the fluorine element is on the side chain end, the fluorine element is reinforced to move towards the resin and the air interface, the utilization efficiency of the fluorine element is increased, the fluorine-containing monomer dosage in the polymer is reduced, the cost is reduced and the performances such as weather fastness, water and oil resistance and antifouling property can be obtained; the component B is a curing agent by taking an organic silicon as a bridging fiber and a polyisocyanate group on the end; on the one hand, the polyisocyanate group is capable of increasing the crosslinking density of the coating so as to increase the water resistance and the hardness of the coating, on the other hand, because the organic silicon has many excellent performances such as temperature resistance, weather fastness, hydrophobic property, physiological inertia and electric insulativity, the water resistance, the weather fastness and the temperature resistance of the coating are improved.
Description
Technical field
The present invention relates to a kind of functional double-component aqueous acrylic resin, be specially fluorine-containing block propylene acid resin (component A) and the preparation method containing organosilicon solidifying agent (component B).
Background introduction
Acrylic polymer has excellent over-all properties, as film-forming properties, thermostability, chemical stability and oxidation-resistance are all fairly good, and its raw material be easy to get, with low cost, therefore be widely used in the aspects such as coating, but it is poor in water-oil resistance, resistant of high or low temperature and pollution resistance etc.On the one hand; polyacrylic acid fluoroalkyl can be obtained by introducing fluoro-containing group at acrylic resin side chain; fluorine-containing side chain forms " shielding protection " to main chain and interior molecules; the stability of carbon-carbon bond can be improved; make fluorinated acrylate polymer stable physical property, also improve the weather resisteant of coating, water-oil resistance, pollution resistance.On the other hand, introduced by organosilicon in solidifying agent and form siliceous solidifying agent, after siliceous solidifying agent and acrylic resin film-forming, siliceous segment moves to coatingsurface, thus improves high temperature resistant, water-fast, the pollution resistance of coating.
Summary of the invention
The object of the present invention is to provide the preparation method of the double-component aqueous acrylic resin of a kind of high durable, resistant, high thermal resistance.In this resin, to be fluorine-containing structural unit with block form be present on main chain component A and fluorine element is in side chain terminal, this strengthens fluorine element to resin and Air Interface locomotory movement, improve fluorine element utilising efficiency, reduce fluorochemical monomer consumption in polymkeric substance, reduce costs, and reach same performance, as weathering resistance, water-oil resistance, didirtresistance; Component B is take organosilicon as bridging agent end is polyisocyanate-based solidifying agent, on the one hand, the polyisocyanate-based cross-linking density that can improve coating makes the water tolerance of coating, hardness increases, on the other hand, due to the performance of many excellences such as high-low temperature resistant, weathering resistance, hydrophobicity, physiological inertia and electrical isolation that organosilicon is good, water-fast, weather-proof, the high thermal resistance of coating are improved.
Technical scheme of the present invention is:
The preparation method of the double-component aqueous acrylic resin of high durable, resistant, high thermal resistance, comprises the steps:
(1) medicine is purified: the purification of (methyl) acrylate: add (methyl) acrylate 30mL in separating funnel, the NaOH solution then adding 10% of equivalent is washed according to a conventional method to liquid colorless.Then neutrality is washed till with deionized water.Add the water suction of appropriate anhydrous sodium sulphate to leave standstill, filter.There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump are assembled.Clean monomer is placed in there-necked flask, adds cuprous chloride 0.1g turn on pump and vacuumize, heated and stirred, the cut collecting 40 ~ 4l DEG C obtains pure (methyl) acrylate;
(2) synthesis of fluoroacrylic resin (component A): the mixing of a certain amount of catalyzer, methacrylic acid, (methyl) acrylate monomer, crosslinkable (methyl) acrylate functional monomer and organic solvent A is added in 100ml there-necked flask, under condensation reflux unit, be warming up to 90-110 DEG C, reaction 3-4h, drip fluorinated acrylate monomer and a small amount of catalyzer, be incubated 90-110 DEG C and continue reaction 2-3h; After experiment terminates, be cooled to room temperature, obtain crosslinkable fluoroacrylic resin (component A);
(3) containing the synthesis of organosilicon solidifying agent (component B): a certain amount of catalyzer, isocyanate trimer and organic solvent B are added in there-necked flask, temperature is risen to 48-50 DEG C and drip a certain amount of end hydroxyl silicone oil, reaction 3-4h, terminate when NCO reaches theoretical value, obtain organosilicon solidifying agent (component B).
(methyl) acrylate described in step (1) and (2) is several in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, n-butyl acrylate, n-propyl, isobornyl methacrylate;
Crosslinkable (methyl) acrylate functional monomer described in step (2) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate;
Solvent orange 2 A described in step (2) is at least one in toluene, pimelinketone, DMF (DMF);
Catalyzer described in step (2) is at least one in azo-bis-isobutyl cyanide, benzoyl peroxide;
Fluorine-containing (methyl) described in step (2) acrylate monomer is at least one in (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid hexafluoro butyl ester or (methyl) vinylformic acid trifluoro ethyl ester;
Catalyzer described in step (3) is at least one in dibutyl tin laurate, stannous octoate;
Solvent B described in step (3) is at least one in acetone, butylacetate, butanone, tetrahydrofuran (THF);
Isocyanate trimer described in step (3) is TDI tripolymer, HDI biuret, TDI-HDI tripolymer, HDI tripolymer, IPDI tripolymer at least one;
End hydroxyl silicone oil described in step (3) is at least one in DOW CORNING SF-8427, OFX-3667, BY16-004;
The invention has the beneficial effects as follows: by above reaction, synthesize a kind of preparation method of acrylic resin of high surface energy, because fluorochemical monomer in component A adds continuously in the later stage, fluorochemical monomer is made to be linked at polymer ends as much as possible, fluorine atom is easier to surface transport, obtains the acrylic resin of low surface energy; Component B silicone segments not only can improve the high thermal resistance of coating, can also reduce coatingsurface energy to Air Interface migration.This double-component aqueous acrylic resin can be widely used in the surface that plastics, film, door and window, eyeglass etc. have the antifouling requirement of high-weatherability.
Embodiment
Embodiment 1
Medicine is purified: in separating funnel, add methyl methacrylate 30mL, the NaOH solution then adding 10% of equivalent is washed according to a conventional method to liquid colorless.Then neutrality is washed till with deionized water.Add the water suction of appropriate anhydrous sodium sulphate to leave standstill, filter.There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump are assembled.Clean monomer is placed in there-necked flask, adds cuprous chloride 0.1g turn on pump and vacuumize, heated and stirred, the cut collecting 40 ~ 4l DEG C obtains pure methyl methacrylate; The purification of Hydroxyethyl acrylate: obtain pure Hydroxyethyl acrylate with aforesaid method underpressure distillation; The purification of butyl acrylate: obtain pure butyl acrylate with the NaOH cleaning of 10%;
The synthesis of fluoroacrylic resin (component A): the 30g methyl methacrylate of purifying in (1), 20g butyl acrylate, 10g Hydroxyethyl acrylate and 0.6g azo-bis-isobutyl cyanide are uniformly mixed and obtain component 1, then add in dropping funnel; The mixing solutions (volume ratio=1:2) of 60ml dimethylbenzene and N-BUTYL ACETATE is added in the there-necked flask of 250ml, stirs, heat temperature raising 80 DEG C, slowly drip component 1,2h and drip, drip after terminating, insulation reaction 3h; Then add 0.15g azo-bis-isobutyl cyanide and drip 15g dodecafluoroheptyl methacrylate with the speed that 2-3s/ drips, drip and terminate, insulation reaction 3h, obtains fluoroacrylic resin (component A);
Synthesis containing organosilicon solidifying agent (component B): 0.008 dibutyl tin laurate, 10.3gHDI tripolymer and 12g acetone are added in there-necked flask, temperature is risen to 50 DEG C and drip 20gSF-8427 end hydroxyl silicone oil, reaction 3-4h, terminate when NCO reaches theoretical value, obtain organosilicon solidifying agent (component B).
Embodiment 2
Medicine is purified: in separating funnel, add methyl methacrylate 30mL, the NaOH solution then adding 10% of equivalent is washed according to a conventional method to liquid colorless.Then neutrality is washed till with deionized water.Add the water suction of appropriate anhydrous sodium sulphate to leave standstill, filter.There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump are assembled.Clean monomer is placed in there-necked flask, adds cuprous chloride 0.1g turn on pump and vacuumize, heated and stirred, the cut collecting 40 ~ 4l DEG C obtains pure methyl methacrylate; The purification of Hydroxyethyl acrylate: obtain pure Hydroxyethyl acrylate with aforesaid method underpressure distillation; The purification of butyl acrylate: obtain pure butyl acrylate with the NaOH cleaning of 10%;
The synthesis of fluoroacrylic resin (component A): the 30g methyl methacrylate of purifying in (1), 20g butyl acrylate, 10g Hydroxyethyl acrylate and 0.6g benzoyl peroxide are uniformly mixed and obtain component 1, then add in dropping funnel; The mixing solutions (volume ratio=1:2) of 60ml dimethylbenzene and N-BUTYL ACETATE is added in the there-necked flask of 250ml, stirs, heat temperature raising 110 DEG C, slowly drip component 1,2h and drip, drip after terminating, insulation reaction 3h; Then add 0.15g benzoyl peroxide and drip 20g Hexafluorobutyl mathacrylate with the speed that 2-3s/ drips, drip and terminate, insulation reaction 3h, obtains fluoroacrylic resin (component A);
Synthesis containing organosilicon solidifying agent (component B): 0.008 dibutyl tin laurate, 10.3gHDI tripolymer and 12g acetone are added in there-necked flask, temperature is risen to 50 DEG C and drip 24g OFX-3667 end hydroxyl silicone oil, reaction 3-4h, terminate when NCO reaches theoretical value, obtain organosilicon solidifying agent (component B).
Claims (2)
1. a preparation method for high durable, resistant, the double-component aqueous acrylic resin of high thermal resistance, its characterization step is:
(1) medicine is purified: the purification of (methyl) acrylate: add (methyl) acrylate 30mL in separating funnel, the NaOH solution then adding 10% of equivalent is washed according to a conventional method to liquid colorless; Then neutrality is washed till with deionized water; Add the water suction of appropriate anhydrous sodium sulphate to leave standstill, filter; There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump are assembled; Clean monomer is placed in there-necked flask, adds cuprous chloride 0.1g turn on pump and vacuumize, heated and stirred, the cut collecting 40 ~ 4l DEG C obtains pure (methyl) acrylate;
(2) synthesis of fluoroacrylic resin (component A): the mixing of a certain amount of catalyzer, methacrylic acid, (methyl) acrylate monomer, crosslinkable (methyl) acrylate functional monomer and organic solvent A is added in 100ml there-necked flask, under condensation reflux unit, be warming up to 90-110 DEG C, reaction 3-4h, drip fluorinated acrylate monomer and a small amount of catalyzer, be incubated 90-110 DEG C and continue reaction 2-3h; After experiment terminates, be cooled to room temperature, obtain crosslinkable fluoroacrylic resin (component A);
(3) containing the synthesis of organosilicon solidifying agent (component B): a certain amount of catalyzer, isocyanate trimer and organic solvent B are added in there-necked flask, temperature is risen to 48-50 DEG C and drip a certain amount of end hydroxyl silicone oil, reaction 3-4h, terminate when NCO reaches theoretical value, obtain organosilicon solidifying agent (component B).
2. the preparation method of a kind of high durable as claimed in claim 1, resistant, the double-component aqueous acrylic resin of high thermal resistance, is characterized in that:
(methyl) acrylate described in step (1) and (2) is several in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, n-butyl acrylate, n-propyl, isobornyl methacrylate;
Crosslinkable (methyl) acrylate functional monomer described in step (2) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate;
Solvent orange 2 A described in step (2) is at least one in toluene, pimelinketone, DMF (DMF);
Catalyzer described in step (2) is at least one in azo-bis-isobutyl cyanide, benzoyl peroxide;
Fluorine-containing (methyl) described in step (2) acrylate monomer is at least one in (methyl) dodecafluorhe-ptylacrylate, (methyl) vinylformic acid hexafluoro butyl ester or (methyl) vinylformic acid trifluoro ethyl ester;
Catalyzer described in step (3) is at least one in dibutyl tin laurate, stannous octoate;
Solvent B described in step (3) is at least one in acetone, butylacetate, butanone, tetrahydrofuran (THF);
Isocyanate trimer described in step (3) is TDI tripolymer, HDI biuret, TDI-HDI tripolymer, HDI tripolymer, IPDI tripolymer at least one;
End hydroxyl silicone oil described in step (3) is at least one in DOW CORNING SF-8427, OFX-3667, BY16-004.
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| CN106085187A (en) * | 2016-08-23 | 2016-11-09 | 上海海事大学 | A kind of high adhesion force low-surface-energy carries silver antifouling paint and preparation method thereof |
| CN107722185A (en) * | 2017-09-15 | 2018-02-23 | 浙江大学 | A kind of low surface energy fluorine silicon antifouling resin and preparation method thereof |
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| CN106085187A (en) * | 2016-08-23 | 2016-11-09 | 上海海事大学 | A kind of high adhesion force low-surface-energy carries silver antifouling paint and preparation method thereof |
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