CN104672371B - 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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- CN104672371B CN104672371B CN201410799691.6A CN201410799691A CN104672371B CN 104672371 B CN104672371 B CN 104672371B CN 201410799691 A CN201410799691 A CN 201410799691A CN 104672371 B CN104672371 B CN 104672371B
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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 double-component aqueous acrylic resin of feature, specially fluorine-containing block propylene acid resin (group
Part A) and firming agent containing organosilicon (component B) preparation method.
Background introduction
Acrylic polymer has excellent combination property, such as film property, heat stability, chemical stability and antioxidation
Property is all fairly good, and its raw material be easy to get, it is with low cost, therefore be widely used in the aspects such as coating, but it is in water-oil resistance, resistance to
The aspect such as high and low temperature and pollution resistance is poor.On the one hand, poly- third can be obtained by introducing fluoro-containing group in acrylic resin side chain
Olefin(e) acid fluoroalkyl, fluorine-containing side chain forms " shielding protection " to main chain and interior molecules, can improve the stability of carbon-carbon bond, makes
Fluorinated acrylate polymer stable physical property, also improves weather resisteant, water-oil resistance, the pollution resistance of coating.On the other hand,
Organosilicon is introduced in firming agent and forms siliceous firming agent, after siliceous firming agent and acrylic resin film-forming siliceous segment to
Coating surface is migrated, so as to the high temperature resistant for improving coating, water-fast, pollution resistance.
The content of the invention
It is an object of the invention to provide a kind of system of the double-component aqueous acrylic resin of high durable, resistant, heat-resisting quantity
Preparation Method.In the resin, component A is that fluorine-containing construction unit is present on main chain with block form and fluorine element is in side chain end
End, this strengthens fluorine element to resin and Air Interface travel motion, improves fluorine element utilization ratio, reduces fluorine-containing list in polymer
Body consumption, reduces cost, and reach same performance, such as weatherability, water-oil resistance, soil resistance；Component B is to be with organosilicon
Bridging agent end is polyisocyanate-based firming agent, on the one hand, the polyisocyanate-based crosslink density that can improve coating makes
The resistance to water of coating, hardness increase, on the other hand, due to the good high-low temperature resistant of organosilicon, weatherability, hydrophobicity, physiology it is lazy
Property and many excellent performances such as electric insulation, improve the water-fast, weather-proof of coating, heat-resisting quantity.
The technical scheme is that：
The preparation method of the double-component aqueous acrylic resin of high durable, resistant, heat-resisting quantity, comprises the steps：
(1) medicine purification：The purification of (methyl) acrylate:(methyl) acrylate 30mL is added in separatory funnel,
The NaOH solution for being subsequently adding the 10% of equivalent is washed according to a conventional method to liquid colorless.Then during deionized water is washed till
Property.Appropriate anhydrous sodium sulfate water suction is added to stand, filter.By there-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump group
Load.Clean monomer is placed in there-necked flask, addition Cu-lyt. 0.1g turn on pump evacuation, heated and stirred, collection 40～
4l DEG C of fraction obtains pure (methyl) acrylate；
(2) synthesis of fluoroacrylic resin (component A)：By a certain amount of catalyst, methacrylic acid, (methyl) third
The mixing of olefin(e) acid ester monomer, cross-linking (methyl) acrylate functional monomer and organic solvent A is added in 100ml there-necked flasks,
Under condensation reflux unit, 90-110 DEG C is warming up to, reacts 3-4h, Deca fluorinated acrylate monomer and a small amount of catalyst, protected
Warm 90-110 DEG C is continued to react 2-3h；After experiment terminates, room temperature is cooled to, obtains cross-linking fluoroacrylic resin (component A)；
(3) synthesis of firming agent containing organosilicon (component B)：By a certain amount of catalyst, isocyanate trimer and organic
Solvent B is added in there-necked flask, and temperature is risen to into a certain amount of end hydroxyl silicone oil of 48-50 DEG C of Deca, 3-4h is reacted, when NCO reaches
Terminate during to theoretical value, obtain organosilicon firming agent (component B).
(methyl) acrylate described in step (1) and (2) is acrylic acid methyl ester., methyl methacrylate, acrylic acid second
It is several in ester, ethyl methacrylate, n-butyl acrylate, n-propyl, isobornyl methacrylate；
Cross-linking (methyl) acrylate functional monomer described in step (2) is 2-(Acryloyloxy)ethanol, hydroxyethyl methacrylate
At least one in ethyl ester, Hydroxypropyl acrylate；
Solvent orange 2 A described in step (2) is at least one in toluene, Ketohexamethylene, N,N-dimethylformamide (DMF)；
Catalyst described in step (2) is at least one in azo-bis-isobutyl cyanide, benzoyl peroxide；
Fluorine-containing (methyl) acrylate monomer described in step (2) is (methyl) dodecafluorhe-ptylacrylate, (methyl) third
At least one in olefin(e) acid hexafluoro butyl ester or (methyl) acrylic acid trifluoro ethyl ester；
Catalyst 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, butyl acetate, butanone, tetrahydrofuran；
Isocyanate trimer described in step (3) is TDI trimers, HDI biurets, TDI-HDI trimers, HDI tri-
Aggressiveness, IPDI trimers are 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：React by more than, synthesize a kind of preparation side of the acrylic resin of high surface energy
Method, because fluorochemical monomer is continuously to add in the later stage in component A, makes fluorochemical monomer be linked at polymer ends, fluorine as much as possible
Atom is easier to surface migration, obtains the acrylic resin of low-surface-energy；Component B silicone segments not only can improve coating
Heat-resisting quantity, can with to Air Interface migration reduce coating surface energy.The double-component aqueous acrylic resin can be used extensively
In the surface with the antifouling requirement of high-weatherability such as plastics, thin film, door and window, eyeglass.
Specific embodiment
Embodiment 1
Medicine is purified：Methyl methacrylate 30mL is added in separatory funnel, the 10% of equivalent is subsequently adding
NaOH solution is washed according to a conventional method to liquid colorless.Then deionized water is washed till neutrality.Add appropriate anhydrous slufuric acid
Sodium water suction stands, filters.There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump group are loaded.By clean monomer
In being placed in there-necked flask, Cu-lyt. 0.1g turn on pump evacuation, heated and stirred, the fraction for collecting 40～4l DEG C is added to obtain pure
Methyl methacrylate；The purification of 2-(Acryloyloxy)ethanol:Vacuum distillation in aforementioned manners obtains pure 2-(Acryloyloxy)ethanol；Third
The purification of olefin(e) acid butyl ester:Cleaned with 10% NaOH and obtain pure butyl acrylate；
The synthesis of fluoroacrylic resin (component A)：By 30g methyl methacrylates, the 20g acrylic acid of purification in (1)
Butyl ester, 10g 2-(Acryloyloxy)ethanols and 0.6g azo-bis-isobutyl cyanides are uniformly mixed and obtain component 1, are subsequently adding Dropping funnel
In；By 60ml dimethylbenzene and mixed solution (volume ratio=1 of butyl acetate:2) in adding the there-necked flask of 250ml, stirring, plus
Heat heats up 80 DEG C, is slowly added dropwise component 1, and 2h is dripped, after completion of dropwise addition, insulation reaction 3h；Then 0.15g azos two are added different
Fourth cyanogen and with the speed Deca 15g dodecafluoroheptyl methacrylate of 2-3s/ drops, completion of dropwise addition, insulation reaction 3h obtains fluorine-containing
Acrylic resin (component A)；
The synthesis of firming agent containing organosilicon (component B)：By 0.008 dibutyl tin laurate, 10.3gHDI trimers and
12g acetone is added in there-necked flask, and temperature is risen to into 50 DEG C of Deca 20gSF-8427 end hydroxyl silicone oils, 3-4h is reacted, when NCO reaches
Terminate during to theoretical value, obtain organosilicon firming agent (component B).
Embodiment 2
Medicine is purified：Methyl methacrylate 30mL is added in separatory funnel, the 10% of equivalent is subsequently adding
NaOH solution is washed according to a conventional method to liquid colorless.Then deionized water is washed till neutrality.Add appropriate anhydrous slufuric acid
Sodium water suction stands, filters.There-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump group are loaded.By clean monomer
In being placed in there-necked flask, Cu-lyt. 0.1g turn on pump evacuation, heated and stirred, the fraction for collecting 40～4l DEG C is added to obtain pure
Methyl methacrylate；The purification of 2-(Acryloyloxy)ethanol:Vacuum distillation in aforementioned manners obtains pure 2-(Acryloyloxy)ethanol；Propylene
The purification of acid butyl ester:Cleaned with 10% NaOH and obtain pure butyl acrylate；
The synthesis of fluoroacrylic resin (component A)：By 30g methyl methacrylates, the 20g acrylic acid of purification in (1)
Butyl ester, 10g 2-(Acryloyloxy)ethanols and 0.6g benzoyl peroxides are uniformly mixed and obtain component 1, are subsequently adding Dropping funnel
In；By 60ml dimethylbenzene and mixed solution (volume ratio=1 of butyl acetate:2) in adding the there-necked flask of 250ml, stirring, plus
Heat heats up 110 DEG C, is slowly added dropwise component 1, and 2h is dripped, after completion of dropwise addition, insulation reaction 3h；Then 0.15g peroxidating is added
Benzoyl and with the speed Deca 20g Hexafluorobutyl mathacrylate of 2-3s/ drops, completion of dropwise addition, insulation reaction 3h obtains fluorine-containing
Acrylic resin (component A)；
The synthesis of firming agent containing organosilicon (component B)：By 0.008 dibutyl tin laurate, 10.3gHDI trimers and
12g acetone is added in there-necked flask, and temperature is risen to into 50 DEG C of Deca 24g OFX-3667 end hydroxyl silicone oils, reacts 3-4h, works as NCO
Terminate when reaching theoretical value, obtain organosilicon firming agent (component B).
Claims (2)
1. a kind of high durable, the preparation method of the double-component aqueous acrylic resin of antifouling, heat-resisting quantity, its characterization step is：
(1) medicine purification：The purification of (methyl) acrylate:(methyl) acrylate 30mL is added in separatory funnel, then
The NaOH solution for adding the 10% of equivalent is washed according to a conventional method to liquid colorless；Then deionized water is washed till neutrality；
Appropriate anhydrous sodium sulfate water suction is added to stand, filter；By there-necked flask, agitator, spherical condensation tube, thermometer, vacuum pump assembling
Get up；Clean monomer is placed in there-necked flask, adds Cu-lyt. 0.1g turn on pump evacuation, heated and stirred to collect 40～4l
DEG C fraction obtain pure (methyl) acrylate；
(2) synthesis of fluoroacrylic resin (component A)：By a certain amount of catalyst, methacrylic acid, (methyl) acrylate
The mixing of monomer, cross-linking (methyl) acrylate functional monomer and organic solvent A is added in 100mL there-necked flasks, is being condensed back
Under stream device, 90-110 DEG C is warming up to, reacts 3-4h, fluorine-containing (methyl) acrylate of Deca and a small amount of catalyst, be incubated 90-
110 DEG C are continued to react 2-3h；After experiment terminates, room temperature is cooled to, obtains cross-linking fluoroacrylic resin (component A)；
(3) synthesis of firming agent containing organosilicon (component B)：By a certain amount of catalyst, isocyanate trimer and organic solvent B
In adding there-necked flask, temperature is risen to into a certain amount of end hydroxyl silicone oil of 48-50 DEG C of Deca, 3-4h is reacted, when NCO reaches theory
Terminate during value, obtain organosilicon firming agent (component B).
2. as claimed in claim 1 a kind of high durable, the preparation side of the double-component aqueous acrylic resin of antifouling, heat-resisting quantity
Method, it is characterised in that：
(methyl) acrylate described in step (1) and (2) is acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, first
It is several in base ethyl acrylate, n-butyl acrylate, n-propyl, isobornyl methacrylate；
Cross-linking (methyl) acrylate functional monomer described in step (2) be 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate,
At least one in Hydroxypropyl acrylate；
Solvent orange 2 A described in step (2) is at least one in toluene, Ketohexamethylene, N,N-dimethylformamide (DMF)；
Catalyst described in step (2) is at least one in azodiisobutyronitrile, benzoyl peroxide；
Fluorine-containing (methyl) acrylate monomer described in step (2) is (methyl) dodecafluorhe-ptylacrylate, (methyl) acrylic acid
At least one in hexafluoro butyl ester or (methyl) acrylic acid trifluoro ethyl ester；
Catalyst 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, butyl acetate, butanone, tetrahydrofuran；
Isocyanate trimer described in step (3) be TDI trimers, HDI biurets, TDI-HDI trimers, HDI trimer,
IPDI trimers are 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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| CN201410799691.6A CN104672371B (en) | 2014-12-19 | 2014-12-19 | Method for preparing weather-resisting, antifouling and heat-resisting two-component aqueous acrylic resin |
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| CN107722185B (en) * | 2017-09-15 | 2020-12-18 | 浙江大学 | Low-surface-energy fluorine-silicon antifouling resin and preparation method thereof |
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| CN101942192B (en) * | 2010-09-14 | 2014-09-24 | 江南大学 | Method for preparing siloxane and nano silicon dioxide double modified ultraviolet curing aqueous polyurethane dispersion |
| CN102020917B (en) * | 2010-11-18 | 2013-03-13 | 青岛德鑫汽车涂料有限公司 | Water-based two-component acrylic acid polyurethane automobile paint and preparation method thereof |
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