CN103756550A - Methods for preparing mono-component hybridized aqueous anti-icing coating material and coating layer thereof and application of coating material - Google Patents
Methods for preparing mono-component hybridized aqueous anti-icing coating material and coating layer thereof and application of coating material Download PDFInfo
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Abstract
The invention provides a mono-component hybridized aqueous anti-icing coating material. The mono-component hybridized aqueous anti-icing coating material mainly contains a hybridization emulsion, wherein the hybridization emulsion is a nanoparticle modified polymer emulsion preferably. The invention further provides a coating layer containing the coating material, a preparation method of the coating material, a coating method of the coating layer and a method for forming an anti-icing coating layer on the surface of a base material. As water serves as a dispersion medium, the mono-component hybridized aqueous anti-icing coating material provided by the invention is environment-friendly; after cured to form a film, the coating layer can have excellent wear resistance and prolonged service life; through coating the surfaces of base materials, such as metal, glass and macromolecular engineering materials, with the anti-icing coating layer, the ice adhesion strength of the surfaces of the base materials can be lowered, so that compared with the other similar materials, the material has the following advantages of simple process, wide applicable range, easiness in large-area construction, excellent anti-icing performance, excellent mechanical properties and easiness in coating layer repair.
Description
Technical field
The invention belongs to chemistry, chemical industry, material technology field, relate to preparation method and the application of the hybridized aqueous anti-icing paint of a kind of single component and coating thereof.
Background technology
The weather such as sleet, frosting, snowfall cause inconvenience to people's life.Serious is that this class weather often causes the equipment surface generation icing such as road, vehicle, boats and ships, aircraft, transmitting line facility, communications service, aerogenerator, dam, offshore platform and radar scanner and radome.This icing phenomenon, not only can cause damage and the malfunctioning financial loss that causes of equipment, facility, more can cause the loss of life and personal injury that causes of major disaster.As the snow disaster of southern china in 2008, the direct economic loss causing is up to 15,000,000,000 yuans.And for example aircraft wing icing phenomenon once caused repeatedly air crash accident.
The ice-covering-proof method of physics normally adopts electric heating method to heat substrate surface, can effectively prevent substrate surface icing or frosting, but energy consumption is too large.The ice-covering-proof method of chemistry is applied to the ice-covering-proof field of aircraft surfaces conventionally, normally at the icing inhibitor of its surface-coated.This class inhibitor that freezes is generally organic liquid, and on the one hand, this class I liquid I can not be stablized, long-term existence is in aircraft surfaces, and duration of service is short, need to repeatedly construct; On the other hand, the liquid of loss can be to environment.In recent years, there is report to think that hydrophobic or super hydrophobic material is surperficial and can be used in ice-covering-proof field, yet this class material can only play the effect that delays icing or frosting to a certain extent, the mechanical property of this class material surface is not good in addition, thereby in use surface tissue is easily destroyed, loses the effect that delays to freeze.
All in all, the ice-covering-proof method extensively adopting at present, the deficiencies such as ubiquity energy consumption is large, efficiency is low, easy contaminate environment, therefore urgently develop a kind of easy construction, less energy-consumption, high-level efficiency, free of contamination ice-covering-proof approach.
Summary of the invention
The object of the present invention is to provide hybridized aqueous anti-icing paint of a kind of single component and preparation method thereof.
The present invention also aims to provide a kind of ice-covering-proof coating and preparation method thereof.
The present invention also aims to provide the application of the hybridized aqueous anti-icing paint of a kind of single component and coating thereof.
The present invention is achieved through the following technical solutions:
The hybridized aqueous anti-icing paint of single-component, mainly comprises hybridisation emulsion.
According to the present invention, described coating is comprised of hybridisation emulsion, and its massfraction is 70-100%, is preferably 80-95%.
According to the present invention, described hybridisation emulsion is nanometer particle-modified polymer emulsion.
According to the present invention, described nanometer particle-modified polymer emulsion is selected from: the co-mixing system that nano particle emulsion or aqueous dispersion and polymer emulsion physical blending form, nanoparticle carries out the copolymerization system of chemical modification formation to polymkeric substance, as nano particle grafting polymkeric substance modification by copolymerization or by polymkeric substance by nanoparticle embedding modification by copolymerization.
According to the present invention, described nanoparticle, its massfraction is the 0-20% of polymer emulsion quality, is preferably 1-15%, more preferably 2-10%.
According to the present invention, described nanoparticle is selected from inorganic mineral nano particle, as silicon-dioxide, diatomite etc., also comprise clay nano particle, as polynite, kaolin etc., also comprise metal oxide nanoparticles, as titanium dioxide, aluminum oxide, zinc oxide etc., also comprise other inorganic nano-particles, as carbon black, Graphene, graphene oxide, carbon nanotube etc.
According to the present invention, described polymer emulsion can be that molecular weight is greater than the non-crosslinked type polymer emulsion that 10000 waterborne polymeric is dispersed in water formation.Described polymer emulsion is selected from one or more in aqueous polyurethane, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon, for example above-mentioned two or more blend or multipolymer.
Described multipolymer can, by a kind of polymkeric substance wherein, form multipolymer with other raw material grafting or block.For example in urethane, add acrylate monomer graft polymerization to form polyurethane-polyacrylate multipolymer.
According to the present invention, described polymer emulsion can also select the free uV curable polymer emulsion that is dispersed in water formation with waterborne polymeric and the water-soluble photoinitiator of two keys.Wherein, the described waterborne polymeric with two keys can be with one or several blend or the multipolymer in the aqueous polyurethane of two keys, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon etc. in molecular chain.Described water-soluble photoinitiator is the conventional aquosity ultraviolet light initiator of this area, as water-based acetophenones, water-based benzophenone photoinitiator.
According to the present invention, described polymer emulsion, can also be to be dispersed in water by the waterborne polymeric with active group and water-based latent curing agent the cross-linkable solidifying polymer emulsion forming.The described waterborne polymeric with active group can be with one or several blend or the multipolymer in the aqueous polyurethane of epoxy group(ing), two key, hydroxyl, amino groups, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon etc. in molecular chain.Latent curing agent is the conventional latent curing agent of this area, as the modified amine water-based crosslinking and curing agent for cross-linked epoxy base, as the masked isocyanate emulsion for crosslinked hydroxyl, amino, as the metal catalyst for crosslinked two keys.
According to the present invention, described polymer emulsion, can also be in above-mentioned non-crosslinked type polymer emulsion, uV curable polymer emulsion, cross-linkable solidifying polymer emulsion two or three form.
According to the present invention, described coating also comprises that hybridisation emulsion adds auxiliary agent, as the conventional auxiliary agent of this areas such as wetting agent, flow agent, defoamer, film coalescence aid, thickening material, anti-aging agent, and pigment and filler etc.
According to the present invention, the add-on of described auxiliary agent: wetting agent 0-1%; Defoamer 0-2%; Flow agent 0-4%; Film coalescence aid 0-6%; Thickening material 0-1%; Anti-aging agent 0-1%; Filler 0-30%, pigment 0-20%.
The present invention also provides the preparation method of the hybridized aqueous anti-icing paint of a kind of single component, it is characterized in that, described method comprises optional above-mentioned hybridisation emulsion is directly formed, or adds auxiliary agent composition anti-icing paint.
According to the present invention, described anti-icing paint is directly comprised of hybridisation emulsion.
According to the present invention, described anti-icing paint can also add hybridisation emulsion interpolation auxiliary agent by hybridisation emulsion and form, and wherein, the mass percent of each raw material is:
Described hybridisation emulsion massfraction is 70-100%, is preferably 80-95%;
The addition that hybridisation emulsion adds auxiliary agent is wetting agent 0-1%; Defoamer 0-2%; Flow agent 0-4%; Film coalescence aid 0-6%; Filler 0-30%, pigment 0-20%.
The present invention also provides a kind of single-component hybridized aqueous ice-covering-proof coating, it is characterized in that, described coating comprises above-mentioned anti-icing paint and base material.
According to the present invention, the metal or alloy such as described base material chosen from Fe, carbon steel, stainless steel, red copper, aluminium alloy, the inorganic materials such as glass, pottery, and the engineering materials such as macromolecular material.
The present invention also provides a kind of preparation method of ice-covering-proof coating, it is characterized in that, above-mentioned anti-icing paint is coated in to substrate surface, and film-forming obtains ice-covering-proof coating under suitable condition.
According to the present invention, described coating method comprises one or more in the forms of construction work such as brushing, roller coat, spraying or dip-coating.
According to the present invention, described film-forming, can be anti-icing paint convection drying film forming, can be also ultraviolet light polymerization film forming, can also be crosslinking curing film forming, can also be with one or more film-formings in above-mentioned three kinds of thin film-forming methods.
According to the present invention, described convection drying film forming, refers to the anti-icing paint being comprised of non-crosslinked type polymer emulsion, at room temperature or under heating condition, only by moisture evaporation film forming, forms coating.
According to the present invention, described ultraviolet light polymerization film forming, refer to the anti-icing paint that comprises uV curable polymer emulsion, under ultraviolet light polymerization condition, the two keys in polymer molecular chain crosslinking curing, moisture evaporation film forming under the effect of light trigger form coating.
According to the present invention, described crosslinking curing film forming, refers to the anti-icing paint that comprises cross-linkable solidifying polymer emulsion, and under the conditions such as heating, oxidation, radiation, crosslinking curing, moisture evaporation film forming form coating.
Preferably, described method comprises: described anti-icing paint is coated in to substrate surface in modes such as brushing, roller coat, spraying or dip-coatings, and film-forming, obtains ice-covering-proof coating under suitable condition.
The present invention also provides a kind of above-mentioned anti-icing paint and the application of coating in preventing base material icing thereof.
According to the present invention, described anti-icing paint and coating thereof, can be applicable to the field that any needs such as Aeronautics and Astronautics, boats and ships, vehicle, road, bridge, transmitting line, electrical network, power station, dam, interchanger, refrigerator prevent surperficial icing.
The present invention also provides a kind of method that prevents substrate surface icing, and described method comprises above-mentioned anti-icing paint is coated in to substrate surface in modes such as brushing, roller coat, spraying and dip-coatings.Preferably, described method also comprises the anti-icing paint that is coated in substrate surface is formed to coating through film-forming.
The hybridized aqueous anti-icing paint of single component of the present invention and coating thereof, compare other analogous materials and have the following advantages:
(1) technique is simple: preparation is simple for anti-icing paint of the present invention, as by as described in polymer emulsion and water nano particle emulsion blending just can obtain anti-icing paint; The construction technology of described anti-icing paint is simple, can be coated in substrate surface by the mode of brushing, roller coat, spraying or dip-coating.
(2) applied widely, be easy to large-area construction: described anti-icing paint can be widely used in metal and the alloy surfaces such as stainless steel, aluminium, aluminium alloy, the inorganic material surfaces such as pottery, and the substrate surface such as macromolecular material, and can carry out large-area construction by the mode of brushing, roller coat, spraying or dip-coating.
(3) anti-icing performance is excellent: described anti-icing paint forms coating at substrate surface, can reduce on the one hand the roughness of substrate surface, and coatingsurface has lower ice addisive strength on the other hand, and the self falling or the deicing that are easy to ice sheet are easy.
(4) mechanical property is superior: described anti-icing paint is comprised of hybridized polymer emulsion, and rigidity nanoparticle wherein can improve the mechanical property of coating, extends coating work-ing life.
(5) coating is easily repaired: described ice-covering-proof coating, and for the surface fracture occurring in life-time service process or come off, only need to again apply this anti-icing paint in region damaged or that come off and form coating, can realize the reparation of coating.
By anti-icing paint of the present invention, be coated in the ice-covering-proof coating that substrate surface forms, can reach～30-60kPa of its ice addisive strength.
accompanying drawing explanation
Fig. 1: the ice viscosity intensity on the aluminum alloy base material surface in test examples 1;
Fig. 2: the ice viscosity intensity on the aluminum alloy base material surface in test examples 2;
Fig. 3: the ice viscosity intensity on the aluminum alloy base material surface in test examples 3;
Fig. 4: the ice viscosity intensity on the aluminum alloy base material surface in test examples 4.
embodiment
Below in conjunction with embodiment, the present invention is described further.It should be noted that, embodiment can not, as limiting the scope of the invention, those skilled in the art will recognize that any improvement of doing on basis of the present invention and change within protection scope of the present invention.
Embodiment 1
(1) 90 parts of water-based polyurethane-acrylate emulsions are mixed with 10 parts of water-based nano silicon dioxide emulsions, stir, obtain the hybridized aqueous anti-icing paint of single component.
(2) above-mentioned coating is coated in to aluminum alloy base material surface in the mode of brushing, drying and forming-film under room temperature, obtains ice-covering-proof coating.
Embodiment 2
(1) by the water-base epoxy-acrylic ester emulsion of certain mass and etc. stoichiometric modified imidazole class resting form waterborne curing agent, by homogenizer, fully mix.
(2) 95 parts of above-mentioned emulsions that mix and 5 parts of water-based nano silicon dioxide emulsions are mixed, obtain the anti-icing paint of cross-linkable solidifying.
(3) above-mentioned anti-icing paint is coated to aluminum alloy base material surface in the mode of brushing, 220 ℃ of film-formings, obtain ice-covering-proof coating.
Embodiment 3
(1) by polyethylene glycol adipate glycol (M
n=1000,65g), isophorone diisocyanate (31g), dimethylol propionic acid (6.7g) joins in there-necked flask, be heated to 80 ℃ and stirring, under nitrogen protection, react extremely-NCO group content and reach theoretical value, according to system viscosity size, add proper amount of acetone reduction viscosity; Add stoichiometric encapsulant hexanolactam, reacting the p-NCO of 2h at 80 ℃ carries out end-blocking, to-NCO primitive reaction is complete; Be cooled to 40 ℃, add triethylamine (5g), in and 15min, obtain base polyurethane prepolymer for use as; By adjustment, stir, base polyurethane prepolymer for use as is distributed in deionized water, obtain cross-linkable solidifying aqueous polyurethane emulsion.
(2) 95 parts of above-mentioned aqueous polyurethane emulsions and 5 parts of water-based nano silicon dioxide emulsions are mixed, obtain cross-linkable solidifying anti-icing paint.
(3) above-mentioned anti-icing paint is coated to aluminum alloy base material surface in the mode of brushing, drying and forming-film at 180 ℃, obtains ice-covering-proof coating.
Embodiment 4
(1) by polyoxyethylene glycol (M
n=1000,65g), tolylene diisocyanate (26g) joins in there-necked flask, is heated to 80 ℃ and stirring, under nitrogen protection, reacts 2h; Add again dimethylol propionic acid (6.7g), 80 ℃ of reaction 2h; Cool to 60 ℃, add hydroxyethyl methylacrylate (1.5g) and Resorcinol (0.5g), reaction 2h; Be cooled to 40 ℃, add triethylamine to carry out neutralization reaction 0.5h, obtain base polyurethane prepolymer for use as; By high-speed stirring, base polyurethane prepolymer for use as is distributed in deionized water, obtain photo curable polyaminoester emulsion.
(3) by 95 parts of polyaminoester emulsions and 5 parts of water-based nano silicon dioxide emulsions with two keys, and appropriate water-soluble photoinitiator mixes, and obtains photo curable water-based anti-icing paint.
(4) in the mode of brushing, above-mentioned anti-icing paint is brushed to aluminum alloy base material surface, room temperature or 60 ℃ of drying and forming-films, recycling UV-light is irradiated 5min to filming and is carried out photocuring, obtains ice-covering-proof coating.
Embodiment 5
(1) by polyethylene glycol adipate glycol (M
n=1000), isophorone diisocyanate (37g), dimethylol propionic acid (6.7g) joins in there-necked flask, is heated to 80 ℃ and stirring, under nitrogen protection, react extremely-NCO group content and reach theoretical value, according to system viscosity size, add proper amount of acetone and reduce viscosity; Add hydroxyethyl methylacrylate (1.8g), 80 ℃ of reaction 1h; Add stoichiometric encapsulant methyl ethyl ketoxime, react 2h at 80 ℃, unreacted-NCO is carried out to end-blocking, to-NCO primitive reaction is complete; Be cooled to 40 ℃, add triethylamine, in and 15min, obtain base polyurethane prepolymer for use as; By adjustment, stir, base polyurethane prepolymer for use as is distributed in deionized water, obtain the aqueous polyurethane emulsion of can heat-ultraviolet dual cure.
(2) by 95 parts of above-mentioned aqueous polyurethane emulsions and 5 parts of water-based nano silicon dioxide emulsions with two keys, and appropriate water-soluble photoinitiator mixes, and obtains the anti-icing paint of can heat-ultraviolet dual cure.
(3) above-mentioned anti-icing paint is coated to aluminum alloy base material surface in the mode of brushing, crosslinking curing film forming 3h at 150 ℃, then carry out photocuring with UV-irradiation 5min, obtain ice-covering-proof coating.
Test examples 1
Under the condition that the aluminum alloy base material that the surface-coated of preparation in above-described embodiment 1 is had to a described anti-icing paint is 20% in humidity for-5 ℃, humidity, carry out the test of ice addisive strength.To freeze, balance is after 5 hours under test condition for sample, and the ice addisive strength recording as shown in Figure 1.
On the aluminum alloy base material surface that there is no ice-covering-proof coating, ice viscosity intensity is up to 1180kPa, and has the substrate surface of ice-covering-proof coating, and ice addisive strength significantly reduces, and 45kPa only has an appointment.
Test examples 2
Under the condition that the aluminum alloy base material that the surface-coated of preparation in above-described embodiment 2 is had to a described anti-icing paint is 60% in temperature for-10 ℃, humidity, carry out the test of ice addisive strength.To freeze, balance is after 5 hours under test condition for sample, and the ice addisive strength recording as shown in Figure 2.
On the aluminum alloy base material surface that there is no ice-covering-proof coating, ice adhesiveness intensity is up to 1180kPa, and has the substrate surface of ice-covering-proof coating, and ice addisive strength significantly reduces, and 54kPa only has an appointment.
Test examples 3
Under the condition that the aluminum alloy base material that the surface-coated of preparation in above-described embodiment 5 is had to a described anti-icing paint is 40% in temperature for-15 ℃, humidity, carry out the test of ice addisive strength.To freeze, balance is after 5 hours under test condition for sample, and the ice addisive strength recording as shown in Figure 3.
On the aluminum alloy base material surface that there is no ice-covering-proof coating, ice viscosity intensity is up to 1180kPa, and has the substrate surface of ice-covering-proof coating, and ice addisive strength significantly reduces, and 32kPa only has an appointment.
Test examples 4
To the surface-coated of preparation in above-described embodiment 4, there is the aluminum alloy base material of described anti-icing paint in differing temps, to carry out the test of the sticky intensity of ice.The ice addisive strength recording as shown in Figure 4.
In temperature, during higher than-40 ℃, the ice addisive strength of coatingsurface is very low, only has 44kPa left and right.Along with temperature further drops to-50 ℃～-60 ℃, there is the trend increasing in ice addisive strength.Now, the effect of ice-covering-proof coating is no longer remarkable.
Claims (10)
1. the hybridized aqueous anti-icing paint of single-component, mainly comprises hybridisation emulsion.
Preferably, described hybridisation emulsion is nanometer particle-modified polymer emulsion.
Preferably, described inorganic nano-particle addition is the 0-20% of hybridisation emulsion quality, is preferably 1-15%, more preferably 2-10%.
Preferably, described nanoparticle is selected from inorganic mineral nano particle, as silicon-dioxide, diatomite etc., also comprise clay nano particle, as polynite, kaolin etc., also comprise metal oxide nanoparticles, as titanium dioxide, aluminum oxide, zinc oxide etc., also comprise other inorganic nano-particles, as carbon black, Graphene, graphene oxide, carbon nanotube etc.
2. according to the anti-icing paint of claim 1, it is characterized in that, described nanometer particle-modified polymer emulsion is selected from: the co-mixing system that nano particle emulsion or aqueous dispersion and polymer emulsion physical blending form, nanoparticle carries out the copolymerization system of chemical modification formation to polymkeric substance, as nano particle grafting polymkeric substance modification by copolymerization or by polymkeric substance by nanoparticle embedding modification by copolymerization.
3. according to the anti-icing paint of claim 1 or 2, it is characterized in that, described coating is mainly comprised of hybridisation emulsion, and its massfraction is 70-100%, is preferably 80-95%.
4. according to the anti-icing paint of claim 1-3 any one, it is characterized in that, described coating also comprises that hybridisation emulsion adds auxiliary agent, as the conventional auxiliary agent of this areas such as wetting agent, flow agent, defoamer, film coalescence aid, thickening material, anti-aging agent, and pigment and filler etc.
Preferably, the add-on of described auxiliary agent: wetting agent 0-1%; Defoamer 0-2%; Flow agent 0-4%; Film coalescence aid 0-6%; Thickening material 0-1%; Anti-aging agent 0-1%; Filler 0-30%, pigment 0-20%.
5. according to the anti-icing paint of claim 1-4 any one, it is characterized in that, described polymer emulsion is selected from molecular weight and is greater than the non-crosslinked type polymer emulsion that 10000 waterborne polymeric is dispersed in water formation.Described polymer emulsion is selected from one or more in aqueous polyurethane, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon, for example above-mentioned two or more blend or multipolymer; Or,
Described polymer emulsion can also select the free uV curable polymer emulsion that is dispersed in water formation with waterborne polymeric and the water-soluble photoinitiator of two keys.Wherein, the described waterborne polymeric with two keys can be with one or several blend or the multipolymer in the aqueous polyurethane of two keys, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon etc. in molecular chain.Described water-soluble photoinitiator is the conventional aquosity ultraviolet light initiator of this area, as water-based acetophenones, water-based benzophenone photoinitiator; Or,
Described polymer emulsion can also be to be dispersed in water by the waterborne polymeric with active group and water-based latent curing agent the cross-linkable solidifying polymer emulsion forming.The described waterborne polymeric with active group can be with one or several blend or the multipolymer in the aqueous polyurethane of epoxy group(ing), two key, hydroxyl, amino groups, water-and acrylate, aqueous epoxy resins, water polyolefin, waterborne organic silicon etc. in molecular chain.Latent curing agent is the conventional latent curing agent of this area, as the modified amine water-based crosslinking and curing agent for cross-linked epoxy base, as the masked isocyanate emulsion for crosslinked hydroxyl, amino, as the metal catalyst for crosslinked two keys.
Or described polymer emulsion can also be in above-mentioned non-crosslinked type polymer emulsion, uV curable polymer emulsion, cross-linkable solidifying polymer emulsion two or three forms.
6. a preparation method for the hybridized aqueous anti-icing paint of single component of claim 1-5 any one, is characterized in that, described method comprises: by optional above-mentioned hybridisation emulsion, optionally add auxiliary agent with hybridisation emulsion and form anti-icing paint.
7. the hybridized aqueous ice-covering-proof coating of single-component, is characterized in that, described coating comprises anti-icing paint and the base material of claim 1-5 any one.
The metal or alloy such as described base material chosen from Fe, carbon steel, stainless steel, red copper, aluminium alloy, the inorganic materials such as glass, pottery, and the engineering materials such as macromolecular material.
8. a method that forms ice-covering-proof coating at substrate surface, described method comprises: the anti-icing paint of claim 1-5 any one is coated in to substrate surface, preferably, in modes such as brushing, roller coat, spraying or dip-coatings, film-forming, obtains ice-covering-proof coating under suitable condition.
Preferably, described film-forming, can be anti-icing paint convection drying film forming, can be also ultraviolet light polymerization film forming, can also be crosslinking curing film forming, can also be with one or more film-formings in above-mentioned three kinds of thin film-forming methods.
9. the anti-icing paint of a claim 1-5 any one or the application of the ice-covering-proof coating of claim 7 in preventing base material icing.
Preferably, described anti-icing paint or coating, can be applicable to the field that any needs such as Aeronautics and Astronautics, boats and ships, vehicle, road, bridge, transmitting line, electrical network, power station, dam, interchanger, refrigerator prevent surperficial icing.
10. prevent a method for substrate surface icing, described method comprises the anti-icing paint of claim 1-5 any one is coated in to substrate surface in modes such as brushing, roller coat, spraying and dip-coatings.
Preferably, described method also comprises and will be coated in the coating of the anti-icing paint of substrate surface through film-forming formation claim 7.
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