CN102190951A - High-weather-resistance high-wear-resistance acrylic polyurethane coating and preparation method thereof - Google Patents
High-weather-resistance high-wear-resistance acrylic polyurethane coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-weather-resistance high-wear-resistance acrylic polyurethane coating. The high-weather-resistance high-wear-resistance acrylic polyurethane coating is prepared by mixing hydroxyl-containing nano silicon dioxide (SiO2) modified acrylate resin and an isocyano-containing hexamethyl diisocyanate prepolymer curing agent. The coating has an inorganic-organic interpenetrating network polymer structure formed by the nano SiO2, acrylic ester and a hexamethylene diisocyanate (HDI) prepolymer, and can obviously improve weather resistance, wear resistance, hardness, scratch resistance and the like. The coating can be applied to decorating paper and thin films such as a polyvinyl chloride (PVC) film, a polyethylene terephthalate (PET) film, a biaxially-oriented polypropylene (BOPP) film and the like, and can also be applied to decorating and protecting the surfaces of materials with high wear resistance and wear resistance requirements.
Description
Technical field
The present invention relates to a kind of coating and preparation method thereof, particularly a kind of acroleic acid polyurethane coating and preparation method thereof.
Background technology
The method for adhering film that a kind of alternative paint is used for household electrical appliances, furniture, floor, indoor and outdoor decoration, movable plank house etc. quietly rises, the film and the iron plate stickup that will have decorative coveringn can be made appliance shell, can make furniture, floor with the plank stickup, can also carry out various decorations, the finishing of indoor and outdoor and fit.The material of main part that has the film of decorative coveringn is plastics films such as paper, PVC film, PET film, BOPP film, and decorative coveringn commonly used mostly is polyurethane coating.This coating in the market exists too many defective at aspects such as wear-resisting, damage resistant, resistant, weathering resistancies, and the utmost point needs a kind of high-grade coating of high weather-proof high abrasion, so that class of raising such as furniture, household electrical appliances, house ornamentations.
More as the coating variety of timber, metal, plastics, ceramic surface decoration in the market, and the coating that is used for plastics films decorations such as paper, PVC film, PET film, BOPP film is of less types, mostly exist of poor quality, performance is low, problem such as not weather-proof, not wear-resisting, does not adapt to social growing needs.
The execution of coating processing range is than broad, and general spraying, dip-coating, brushing can both normal constructions under multiple situation, and the construction technology scope of coating is very narrow, it be toilet roll open with plastics film on carry out roller coat.Industrialized production is to be coated with coating machine, with let off roll toilet roll is opened earlier or the plastics film expansion, with upper glue roller the coating glue is uniformly applied on the base material, come out through tens meters drying tunnels, with paper or plastics film rolling, rolling is placed on the decorating film that spontaneous curing one-tenth and base material under the room temperature constitute one again with wind-up roll.In order to prevent that paper and plastics film are not out of shape by high bake, temperature in the drying tunnel must be controlled under the heat-drawn wire of base material, the time of the substrate passed drying tunnel generally has only several seconds to tens seconds, come out to require 1. from drying tunnel that solvent will volatilize totally, can produce bubble otherwise be clipped in the rolling plastic material; 2. the glue levelling property will be got well; 3. glue is wanted surface drying, and is not sticking mutually mutually, can rolling.The singularity of coating process and base material has constituted the singularity of coating prod structure, and this is the crucial part with the coating difference.
The nanometer material science technology develops very fast at home now, some has the uvioresistant additive of the nano inoganic particle of ultraviolet screener performance as macromolecular material, be the focus of research, the present invention has also utilized the property of nano material to solve some problem of coating.Nanometer SiO
2The ability of shielding ultraviolet rays is strong, is transparent at visible-range, if it is added in the coating as the uvioresistant additive, has advantages such as nontoxic, heat-resisting, weather-proof, wear-resisting, long-acting, can also solve other problems of coating simultaneously.
How nano material is added in the macromolecular material, the performance that different adding methods shows is not quite similar, and the method for suitability for industrialized production adding nano material is simple and easy to do, to adapt to requirements of large-scale production.The method that present domestic many enterprises generally adopt is earlier with nanopowder high speed dispersion or static the dispersion, again with resin ground blended method.
CN1412261A discloses a kind of various nanometers slurry of making earlier and has added the method for preparing nano uvioresistant polyurethane paint in the resin again, and the feature of this method is the coating that the nanoparticle ground and mixed is formed in resin.
CN1931938A discloses and has a kind ofly made organic functional base on the band of nano material termination with organo-silicon coupling agent, again with the organic active substance polymerization, nano material and polymkeric substance is coupled together, and forms the method for good nanometer stable dispersion.
The present invention proposes the another kind of method that adds nano material, with nanometer SiO
2Dispersion liquid joins in the radical polymerization of acrylate, utilizes nanometer SiO
2A large amount of unsaturated residual bond that the surface exists and acrylate monomer react, and have prevented the secondary agglomeration of nano material effectively, disperse more even, stable better.
The present invention also utilizes the microcosmic surface performance of nano silicon, the method that a kind of and acrylate and urethane can both carry out chemical bonding has been proposed, inorganic-organic interpenetrating net polymer the structure that constitutes has improved the weathering resistance and the wear resistance of coating greatly.
The present invention has also utilized the premium properties of silicone resin, with hydroxy-terminated polysiloxane modification HDI prepolymer, the add-on of control hydroxy-terminated polysiloxane, has improved flexibility, lower temperature resistance, weathering resistance and the wear resistance of coating effectively.
Summary of the invention
The object of the present invention is to provide a kind of acroleic acid polyurethane coating and preparation method thereof.
The technical solution used in the present invention is:
A kind of high weather-proof high abrasion acroleic acid polyurethane coating is by hydroxyl nanometer SiO
2Modified acrylic ester resin mixes with the hexamethylene-diisocyanate prepolymer cures agent of band isocyano.
Preferably, hydroxyl nanometer SiO
2The preparation method of modified acrylic ester resin may further comprise the steps:
1) with nanometer SiO
2Become the nanometer slurry with the vinylformic acid of band difunctionality base and acrylate monomer are wetting;
2) in the nanometer slurry, add organic solvent and dispersion agent, be uniformly dispersed, obtain nanometer SiO
2Dispersion liquid;
3) ptfe micropowder wax and organic solvent and dispersant is even, obtain fluorine wax powder dispersion liquid;
4) the nanometer SiO that in reactor, adds organic solvent and initiator and make
2Dispersion liquid mixes, and is warming up to 50～80 ℃, drips the acrylate mixing monomer that contains initiator, and the control dropping time is 3～5 hours, and dropping temperature is 60～90 ℃;
5) dropwise after, 70～100 ℃ of reactions 3～5 hours, add lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid, stir, cooling discharge obtains hydroxyl nanometer SiO
2Modified acrylic ester resin.
The preparation method of the hexamethylene-diisocyanate prepolymer cures agent of band isocyano may further comprise the steps:
1) in reactor, adds HDI and organic solvent, stir;
2) add linear hydroxyl-terminated polysiloxane, stir, be warming up to 60～100 ℃ of reactions 3～6 hours;
3) be cooled to 50～70 ℃, drip the mixed solution that TriMethylolPropane(TMP) and organic solvent are formed, 60～80 ℃ of dropping temperatures dripped off in 2～3 hours, insulation reaction 1～2 hour;
4) be warming up to 80～100 ℃ of reactions 5～9 hours;
5) cooling adds organic solvent, stirs, and discharging must be with the HDI prepolymer cures agent of NCO base.
Hydroxyl nanometer SiO2 modified acrylic ester resin is made by radical polymerization in acrylate mixing monomer by nanometer SiO2 dispersion liquid, and the proportioning of its reactant is:
Methyl methacrylate 100 mass parts
Hydroxy acryl acid ester 5.5～19 mass parts
Butyl acrylate 12～34 mass parts
Isooctyl acrylate monomer 0～15 mass parts
Butyl methacrylate 1～19 mass parts
Methacrylic acid 0～2 mass parts
Vinylformic acid 0～1.5 mass parts
Nanometer SiO2 1～5.5 mass parts.
The HDI prepolymer cures agent of band isocyano is formed by linear hydroxyl-terminated polysiloxane, TriMethylolPropane(TMP) and HDI pre-polymerization, and the proportioning of reactant is:
Linear hydroxyl-terminated polysiloxane 115～250 mass parts
TriMethylolPropane(TMP) 57～67 mass parts
HDI 300 mass parts.
Hydroxyl nanometer SiO
2Modified acrylic ester resin also is added with the initiators for polymerization of reactant gross weight 0.1～1% in preparation process, 0.06～0.14% molecular weight regulator lauryl mercaptan, 0.6～1% dispersion agent, 1～2.5% product performance conditioning agent ptfe micropowder wax.
Preferably, dispersion agent is at least a among polymer molecule dispersion agent Disperbyk163, Disperebyk2000, Disperes610S, Dispers630S, EFKA4010, the EKA6220.
Preferably, initiator of polyreaction is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
Acroleic acid polyurethane coating of the present invention, behind paper, PET film, BOPP film coating drying and forming-film, the film surface drying that obtains is soft and smooth, bright and clean has no time, good hand touch, rolling can adhesion.In the coating, nanometer SiO
2With inorganic-organic interpenetrating net polymer structure that acrylate and HDI prepolymer form, can significantly improve the performances such as weathering resistance, wear resistance, hardness, scratch-resistant of coating.The adding of fluorine wax powder has further improved self lubricity, chemical proofing and the coating process of coating.Acroleic acid polyurethane coating of the present invention not only can be used as the coating of films such as decor paper, PVC film, PET film, BOPP film, also can be used for other surface decoration that requires high weather-proof high abrasion resisting material and protection.
Preparation method of the present invention, nanometer SiO
2Powder with acrylate monomer mixing process in, participated in the radical polymerization in the system, mix more fully, be more evenly distributed stable very good in resin system; Rigidity nanometer SiO
2Particle has suppressed the generation of ultra-high molecular weight to the inhibition of long chain molecule motion, and product viscosity is low, helps making the product of high solids content; The low viscosity of resin component and solidifying agent component helps the carrying out of coating process.
Embodiment
A kind of high weather-proof high abrasion acroleic acid polyurethane coating is by hydroxyl nanometer SiO
2Modified acrylic ester resin mixes with the hexamethylene-diisocyanate prepolymer cures agent of band isocyano.
Preferably, hydroxyl nanometer SiO
2The preparation method of modified acrylic ester resin may further comprise the steps:
1) with nanometer SiO
2Become the nanometer slurry with the vinylformic acid of band difunctionality base and acrylate monomer are wetting;
2) in the nanometer slurry, add organic solvent and dispersion agent, be uniformly dispersed, obtain nanometer SiO
2Dispersion liquid;
3) ptfe micropowder wax and organic solvent and dispersant is even, obtain fluorine wax powder dispersion liquid;
4) the nanometer SiO that in reactor, adds organic solvent and initiator and make
2Dispersion liquid mixes, and is warming up to 50～80 ℃, drips the acrylate mixing monomer that contains initiator, and the control dropping time is 3～5 hours, and dropping temperature is 60～90 ℃;
5) dropwise after, 70～100 ℃ of reactions 3～5 hours, add lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid, stir, cooling discharge obtains hydroxyl nanometer SiO
2Modified acrylic ester resin.
The preparation method of the hexamethylene-diisocyanate prepolymer cures agent of band isocyano may further comprise the steps:
1) in reactor, adds HDI and organic solvent, stir;
2) add linear hydroxyl-terminated polysiloxane, stir, be warming up to 60～100 ℃ of reactions 3～6 hours;
3) be cooled to 50～70 ℃, drip the mixed solution that TriMethylolPropane(TMP) and organic solvent are formed, 60～80 ℃ of dropping temperatures dripped off in 2～3 hours, insulation reaction 1～2 hour;
4) be warming up to 80～100 ℃ of reactions 5～9 hours;
5) cooling adds organic solvent, stirs, and discharging must be with the HDI prepolymer cures agent of NCO base.
Hydroxyl nanometer SiO2 modified acrylic ester resin is made by radical polymerization in acrylate mixing monomer by nanometer SiO2 dispersion liquid, and the proportioning of its reactant is:
Methyl methacrylate 100 mass parts
Hydroxy acryl acid ester 5.5～19 mass parts
Butyl acrylate 12～34 mass parts
Isooctyl acrylate monomer 0～15 mass parts
Butyl methacrylate 1～19 mass parts
Methacrylic acid 0～2 mass parts
Vinylformic acid 0～1.5 mass parts
Nanometer SiO2 1～5.5 mass parts.
The HDI prepolymer cures agent of band isocyano is formed by linear hydroxyl-terminated polysiloxane, TriMethylolPropane(TMP) and HDI pre-polymerization, and the proportioning of reactant is:
Linear hydroxyl-terminated polysiloxane 115～250 mass parts
TriMethylolPropane(TMP) 57～67 mass parts
HDI 300 mass parts.
Hydroxyl nanometer SiO
2Modified acrylic ester resin also is added with the initiators for polymerization of reactant gross weight 0.1～1% in preparation process, 0.06～0.14% molecular weight regulator lauryl mercaptan, 0.6～1% dispersion agent, 1～2.5% product performance conditioning agent ptfe micropowder wax.
Preferably, dispersion agent is at least a among polymer molecule dispersion agent Disperbyk163, Disperebyk2000, Disperes610S, Dispers630S, EFKA4010, the EKA6220.
Preferably, initiator of polyreaction is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
The organic solvent that uses in the preparation process is common solvent vinyl acetic monomer, N-BUTYL ACETATE, toluene, dimethylbenzene, butanone, pimelinketone, ethylene glycol ether acetate, propylene glycol monomethyl ether acetate, N, one or more in the dinethylformamide.Those skilled in the art can select appropriate organic solvent according to actual needs.
The present invention has utilized nanometer SiO
2There is the hydroxyl of a large amount of unsaturated residual bonds and different bonding states in the surface, can both carry out the characteristics that chemical bond combines with the unsaturated double-bond of acrylate and the NCO base of HDI prepolymer, the complete chemical bonding of nano inorganic material and polymkeric substance is integral, form a kind of inorganic-coating of organic interpenetrating net polymer structure, improved the performance such as weathering resistance, wear resistance, hardness, scratch-resistant of coating significantly.The adding of fluorine wax powder has further improved self lubricity, chemical proofing and the coating process of coating.
The present invention prepares the agent of HDI prepolymer cures, select the polyvalent alcohol of linear hydroxy-terminated polysiloxane as modification HDI symmetrical structure, can improve the soft and smooth property of low temperature flexibility, feel of coating, the tack-free property in dried back, wear resistance and coating processing fluidity etc., the not xanthochromia weather resistance with HDI is complementary simultaneously.
Nanometer SiO of the present invention
2Particle diameter below 100nm, much smaller than wavelength of visible light (400～750nm), in abundant dispersive resin system, nanometer SiO
2Particle can not produce coating and hide phenomenon, the nanometer SiO that obtains
2Modified acrylic ester resin has the extraordinary transparency.
Below in conjunction with embodiment, further specify the present invention.
In following examples:
Solid content detects the mensuration by National Standard GB/T 2793-1995 tackiness agent non-volatile content " carry out;
Viscosity measurements is by the mensuration of National Standard GB/T2794-1995 tackiness agent viscosity " carry out;
The OH content detection of resin is undertaken by " mensuration of hydroxyl value in the HG/T 2709-1995 polyester polyol ";
Sticking power detects and is undertaken by GB/T1720-79 paint film adhesion assay method;
Hardness detects is undertaken by GB/T1730-2007 hardness of film assay method-pendulum dampingtest;
Weathering resistance detects by the artificial weathering of GB/T1865-1997 paint and varnish and man-made radiation's exposure (filterable xenon arc radiation) is undertaken;
Wear resistance detects by the GB/T1768-79 wear resistance assay method of filming is undertaken;
Thermotolerance detects is undertaken by GB/T1735-79 paint film thermotolerance assay method;
Oil-proofness detects is undertaken by HG2-T1611-85 paint film oil-proofness assay method;
Solvent resistance detects is undertaken by the anti-solvent wiping assay method of GB/T23989-2009 coating;
Levelling property detects and is undertaken by GB/T1750-89 paint flow levelling assay method.
Hydroxyl nanometer SiO
2The preparation of modified acrylic ester resin
Embodiment 1
1) 5.5g senecioate hydroxyl ethyl ester, 1.5g vinylformic acid and 0.5g methacrylic acid are mixed, add 2.0g nanometer SiO again
2Powder stirs into the wetting slurry of nanometer;
2) in the high-speed stirring still, add 30g vinyl acetic monomer and 1g macromolecule dispersing agent EFKA4010, the back that stirs adds the wetting slurry of nanometer, 2000rpm high speed dispersion 1 hour, makes nano dispersion fluid;
3) in the high-speed stirring still, add 20g vinyl acetic monomer and 0.5g macromolecule dispersing agent EFKA4010, the back that stirs adds 1.5g fluorine wax powder, 2000rpm high speed dispersion 1 hour, makes fluorine wax powder dispersion liquid;
4) in reactor, add 35g vinyl acetic monomer and 0.2g Diisopropyl azodicarboxylate, stir and add nano dispersion fluid down, be warming up to 50～60 ℃ after mixing, the mixed solution that dropping is made up of 144g acrylate mixing monomer (methyl methacrylate 100g, butyl acrylate 20g, Isooctyl acrylate monomer 5g, butyl methacrylate 19g) and 0.4g Diisopropyl azodicarboxylate, the control dropping time is 3 hours, and dropping temperature is 60～80 ℃;
5) drip after, 75～85 ℃ of reactions 1.5 hours, 80～90 ℃ of reactions 1.5 hours added the 0.09g lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid, stir cooling discharge.
The 242g solid content be 65%, viscosity is 3500mpa.s(25 ℃), hydroxyl value is 10.3mgKOH/g's
Nano modified acrylic ester resin, outward appearance is light yellow transparent liquid.
Embodiment 2
1) 8g senecioate hydroxyl ethyl ester, 3 gram methacrylic acid-β hydroxyl ethyl esters and 1g methacrylic acid are mixed, add 3.0g nanometer SiO again
2Powder stirs into the wetting slurry of nanometer;
2) in the high-speed stirring still, add 50g vinyl acetic monomer and 1g polymer and disperse EFKA6220, the back that stirs adds the wetting slurry of nanometer, 2000rpm high speed dispersion 1.5 hours, makes nano dispersion fluid;
3) in the high-speed stirring still, add 30g vinyl acetic monomer and 0.5g macromolecule dispersing agent EFKA4010, the back that stirs adds 2.5g fluorine wax powder, 2000rpm high speed dispersion 1 hour, makes fluorine wax powder dispersion liquid;
4) in reactor, add 50g vinyl acetic monomer and 0.2g dibenzoyl peroxide, stir and add nano dispersion fluid down, be warming up to 70～80 ℃ after mixing, drip the mixed solution that 139g acrylate mixing monomer (methyl methacrylate 100g, butyl acrylate 34g, Isooctyl acrylate monomer 5g) and 0.5g dibenzoyl peroxide are formed, the control dropping time is 3 hours, and dropping temperature is 75～85 ℃;
5) drip after, 75～85 ℃ of reactions 2 hours, 85～95 ℃ of reactions 2 hours added the 0.12g lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid and 29g vinyl acetic monomer, stir cooling discharge.
The 318g solid content be 50%, viscosity is 650mpa.s(25 ℃), hydroxyl value is 16.0mgKOH/g's
Nano modified acrylic ester resin, outward appearance is light yellow transparent liquid.
Embodiment 3
1) 15g methacrylic acid-β hydroxyl ethyl ester and 1g methacrylic acid are mixed, add 1.0g nanometer SiO again
2Powder stirs into the wetting slurry of nanometer;
2) in the high-speed stirring still, add 20g vinyl acetic monomer and 0.5g macromolecule dispersing agent EFKA6220, the back that stirs adds the wetting slurry of nanometer, 2000rpm high speed dispersion 1 hour, makes nano dispersion fluid;
3) in the high-speed stirring still, add 20g vinyl acetic monomer and 0.5g macromolecule dispersing agent EFKA6220, the back that stirs adds 2.0g fluorine wax powder, 2000rpm high speed dispersion 1 hour, makes fluorine wax powder dispersion liquid;
4) in reactor, add 28g vinyl acetic monomer and 0.1g Diisopropyl azodicarboxylate, stir and add nano dispersion fluid down, be warming up to 50～60 ℃ after mixing, drip the mixed solution that 136g acrylate mixing monomer (methyl methacrylate 100g, butyl acrylate 21g, butyl methacrylate 15g) and 0.2g Diisopropyl azodicarboxylate are formed, the control dropping time is 4 hours, and dropping temperature is 60～80 ℃;
5) drip after, 70～80 ℃ of reactions 3 hours, 80～90 ℃ of reactions 1.5 hours added the 0.15g lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid, stir cooling discharge.
The 224g solid content be 70%, viscosity is 4800mpa.s(25 ℃), hydroxyl value is the nano modified acrylic ester resin of 27.5mgKOH/g, outward appearance is light yellow transparent liquid.
Embodiment 4
1) 5g methacrylic acid-β hydroxyl ethyl ester, 14g methacrylic acid-β hydroxypropyl acrylate and 2g methacrylic acid are mixed, add 5.5g nanometer SiO again
2Powder stirs into the wetting slurry of nanometer;
2) in the high-speed stirring still, add 70g vinyl acetic monomer and macromolecule dispersing agent 0.5g Dispers630S and 1gDisperes610S, the back that stirs adds the wetting slurry of nanometer, 2000rpm high speed dispersion 2.5 hours, makes nano dispersion fluid;
3) in the high-speed stirring still, add 40g vinyl acetic monomer and 1.0g Dispers630S, the back that stirs adds 4.0g fluorine wax powder, 2000rpm high speed dispersion 1.5 hours, makes fluorine wax powder dispersion liquid;
4) in reactor, add 30g vinyl acetic monomer and 0.4g dibenzoyl peroxide, stir and add nano dispersion fluid down, be warming up to 70～80 ℃ ℃ after mixing, drip the mixed solution that 137g acrylate mixing monomer (methyl methacrylate 100g, butyl acrylate 12g, Isooctyl acrylate monomer 15g, butyl methacrylate 10g) and 0.8g dibenzoyl peroxide are formed, the control dropping time is 5 hours, and dropping temperature is 75～90 ℃;
5) drip after, 80～85 ℃ of reactions 3.5 hours, 85～100 ℃ of reactions 1.5 hours added the 0.23g lauryl mercaptan, continue reaction 1～2 hour;
6) add fluorine wax powder dispersion liquid, 10g N-BUTYL ACETATE and 21g butanone, stir cooling discharge.
The 342g solid content be 50%, viscosity is 760mpa.s(25 ℃) nano modified acrylic ester resin, outward appearance is light yellow transparent liquid.
The preparation of the HDI prepolymer cures agent of band isocyano
Embodiment 5
1) in reactor, adds 300gHDI and 100g vinyl acetic monomer, stir, add the linear hydroxyl-terminated polysiloxane of the 153g (trade mark: Tegomer H-Si 2311, functionality 2, hydroxyl value 130mg KOH/g, molecular weight 860), at room temperature cold stirring 0.5 hour, be warmed up to 60～70 ℃ of reactions 1 hour, 80～90 ℃ were reacted 3 hours;
2) be cooled to 50 ℃～60 ℃, drip the mixed solution that 63g TriMethylolPropane(TMP) and 72g vinyl acetic monomer are formed, 60～80 ℃ of dropping temperatures dripped off in 2 hours, insulation reaction 2 hours;
3) be warming up to 80～90 ℃ of reactions 4 hours, 90～100 ℃ were reacted 2～3 hours, cooling, discharging.
The 688g solid content be 75%, viscosity is 2300mpa.s(25 ℃), NCO content is 10.8% HDI prepolymer cures agent.
Embodiment 6
1) add 300gHDI and 90g vinyl acetic monomer in reactor, stir, add the linear hydroxyl-terminated polysiloxane of 115g (molecular weight 860), at room temperature cold stirring 0.5 hour is warmed up to 60～70 ℃ of reactions 1 hour, and 80～100 ℃ were reacted 2 hours;
2) be cooled to 50～60 ℃, drip the mixed solution that 67g TriMethylolPropane(TMP) and 71g vinyl acetic monomer are formed,
60～70 ℃ of dropping temperatures dripped off in 3 hours, insulation reaction 2 hours;
3) be warming up to 80～90 ℃ of reactions 3 hours, 90～100 ℃ were reacted 2 hours, cooling, discharging.
The 643g solid content be 75%, viscosity is 2100mpa.s(25 ℃), NCO content is 11.6% HDI prepolymer cures agent.
Embodiment 7
1) add 300gHDI and 140g vinyl acetic monomer in reactor, stir, add the linear hydroxyl-terminated polysiloxane of 250g (molecular weight 1000), at room temperature cold stirring 0.5 hour is warmed up to 60～70 ℃ of reactions 3 hours, and 80～90 ℃ were reacted 3 hours;
2) be cooled to 60～70 ℃, the mixed solution that Dropwise 5 7g TriMethylolPropane(TMP) and 62g vinyl acetic monomer are formed, 60～80 ℃ of dropping temperatures dripped off in 3 hours, insulation reaction 1 hour;
3) be warming up to 80～90 ℃ of reactions 5 hours, 90～100 ℃ were reacted 3～4 hours, cooling, discharging.
The 809g solid content be 75%, viscosity is 3800mpa.s(25 ℃), NCO content is 9.1% HDI prepolymer cures agent.
Embodiment 8
With the HDI prepolymer cures agent of the band isocyano of the hydroxyl nano modified acrylic ester resin of embodiment 1 preparation and embodiment 7 preparations by equivalence ratio OH: NCO=1: 1.2 mix, make a kind of high weather-proof high abrasion acroleic acid polyurethane coating mixed solution of the present invention, with the coating transfer method coating is transferred on the PVC film, homogeneity, levelling property are all very good, at room temperature deposit curing, the performance of prepared PVC decorative coveringn sees Table 1.
Embodiment 9
With the HDI prepolymer cures agent of the band isocyano of the hydroxyl nano modified acrylic ester resin of embodiment 2 preparation and embodiment 5 preparations by equivalence ratio OH: NCO=1: 1.6 mix, make a kind of high weather-proof high abrasion acroleic acid polyurethane coating mixed solution of the present invention, with coating machine it is coated onto on the PET film, coating homogeneity, good leveling property, the liquid that comes out through drying tunnel is surface drying, curing is at room temperature deposited in rolling at once, and the performance of prepared PET decorative coveringn sees Table 1.
Embodiment 10
With the HDI prepolymer cures agent of the band isocyano of the hydroxyl nano modified acrylic ester resin of embodiment 3 preparation and embodiment 6 preparations by equivalence ratio OH: NCO=1: 1.4 mix, make a kind of high weather-proof high abrasion acroleic acid polyurethane coating mixed solution of the present invention, with coating machine it is coated onto on the woodgrained paper, coating performance is good, coming out through drying tunnel can rolling, at room temperature deposit curing, the performance of prepared woodgrained paper decorative coveringn sees Table 1.
Certainly, the nanometer SiO that also can use other to make
2The HDI prepolymer cures agent of modified acrylic ester resin and band isocyano is combined, and obtains coating of the present invention.
The performance test table of table 1, acroleic acid polyurethane coating
By data in the table as can be known, good weatherability of the present invention, wear resistance is good, superior performance.
Claims (6)
1. one kind high weather-proof high abrasion acroleic acid polyurethane coating is by hydroxyl nanometer SiO
2Modified acrylic ester resin mixes with the hexamethylene-diisocyanate prepolymer cures agent of band isocyano.
2. the preparation method of the described a kind of high weather-proof high abrasion acroleic acid polyurethane coating of claim 1,
It is characterized in that: prepare hydroxyl nanometer SiO
2Modified acrylic ester resin may further comprise the steps:
With nanometer SiO
2Become the nanometer slurry with the vinylformic acid of band difunctionality base and acrylate monomer are wetting;
In the nanometer slurry, add organic solvent and dispersion agent, be uniformly dispersed, obtain nanometer SiO
2Dispersion liquid;
Ptfe micropowder wax and organic solvent and dispersant is even, obtain fluorine wax powder dispersion liquid;
The nanometer SiO that in reactor, adds organic solvent and initiator and make
2Dispersion liquid mixes, and is warming up to 50～80 ℃, drips the acrylate mixing monomer that contains initiator, and the control dropping time is 3～5 hours, and dropping temperature is 60～90 ℃;
After dropwising,, add lauryl mercaptan, continue reaction 1～2 hour 70～100 ℃ of reactions 3～5 hours;
Add fluorine wax powder dispersion liquid, stir, cooling discharge obtains hydroxyl nanometer SiO
2Modified acrylic ester resin;
The hexamethylene-diisocyanate prepolymer cures agent of preparation band isocyano may further comprise the steps:
1) in reactor, adds HDI and organic solvent, stir;
2) add linear hydroxyl-terminated polysiloxane, stir, be warming up to 60～100 ℃ of reactions 3～6 hours;
3) be cooled to 50～70 ℃, drip the mixed solution that TriMethylolPropane(TMP) and organic solvent are formed, 60～80 ℃ of dropping temperatures dripped off in 2～3 hours, insulation reaction 1～2 hour;
4) be warming up to 80～100 ℃ of reactions 5～9 hours;
5) cooling adds organic solvent, stirs, and discharging must be with the HDI prepolymer cures agent of NCO base.
3. a kind of high weather-proof high abrasion acroleic acid polyurethane coating according to claim 1 is characterized in that: hydroxyl nanometer SiO
2Modified acrylic ester resin is by nanometer SiO
2Dispersion liquid makes by radical polymerization in acrylate mixing monomer, and the proportioning of reactant is:
Methyl methacrylate 100 mass parts
Hydroxy acryl acid ester 5.5～19 mass parts
Butyl acrylate 12～34 mass parts
Isooctyl acrylate monomer 0～15 mass parts
Butyl methacrylate 1～19 mass parts
Methacrylic acid 0～2 mass parts
Vinylformic acid 0～1.5 mass parts
Nanometer SiO
21～5.5 mass parts;
The HDI prepolymer cures agent of band isocyano is formed by linear hydroxyl-terminated polysiloxane, TriMethylolPropane(TMP) and HDI pre-polymerization, and the proportioning of reactant is:
Linear hydroxyl-terminated polysiloxane 115～250 mass parts
TriMethylolPropane(TMP) 57～67 mass parts
HDI 300 mass parts.
4. a kind of high weather-proof high abrasion acroleic acid polyurethane coating according to claim 3 is characterized in that: hydroxyl nanometer SiO
2Modified acrylic ester resin also is added with the initiators for polymerization of reactant gross weight 0.1～1% in preparation process, 0.06～0.14% molecular weight regulator lauryl mercaptan, 0.6～1% dispersion agent, 1～2.5% product performance conditioning agent ptfe micropowder wax.
5. a kind of high weather-proof high abrasion acroleic acid polyurethane coating according to claim 4 is characterized in that: dispersion agent is at least a among polymer molecule dispersion agent Disperbyk163, Disperebyk2000, Disperes610S, Dispers630S, EFKA4010, the EKA6220.
6. a kind of high weather-proof high abrasion acroleic acid polyurethane coating according to claim 4, it is characterized in that: initiator of polyreaction is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
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| CN102533180A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Ultra-low viscosity pressure-sensitive adhesive |
| CN103614067A (en) * | 2013-11-22 | 2014-03-05 | 东莞市纳利光学材料有限公司 | Preparation methods of high-hardness scratch-resistant coating and protection film and high-hardness scratch-resistant protection film |
| CN104017480A (en) * | 2014-06-24 | 2014-09-03 | 博罗县石湾美源涂料有限公司 | Acrylic polyurethane silicofluoride coating as well as preparation method and application method thereof |
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| CN111849341A (en) * | 2020-07-22 | 2020-10-30 | 绵阳麦思威尔科技有限公司 | Organic-inorganic nano hybrid water-based high-temperature-resistant anticorrosive paint and preparation method thereof |
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| CN102533180A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Ultra-low viscosity pressure-sensitive adhesive |
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| CN104017480A (en) * | 2014-06-24 | 2014-09-03 | 博罗县石湾美源涂料有限公司 | Acrylic polyurethane silicofluoride coating as well as preparation method and application method thereof |
| CN104017480B (en) * | 2014-06-24 | 2016-06-15 | 博罗县石湾美源涂料有限公司 | A kind of fluorine silication acroleic acid polyurethane coating and preparation, application process |
| CN107075068A (en) * | 2014-09-10 | 2017-08-18 | Ppg工业俄亥俄公司 | Curable film-forming compositions and the method for reducing the dirt accumulation on base material |
| CN107075068B (en) * | 2014-09-10 | 2019-10-01 | Ppg工业俄亥俄公司 | Curable film-forming compositions and the method for reducing the dirt accumulation on substrate |
| CN111849341A (en) * | 2020-07-22 | 2020-10-30 | 绵阳麦思威尔科技有限公司 | Organic-inorganic nano hybrid water-based high-temperature-resistant anticorrosive paint and preparation method thereof |
| CN114834112A (en) * | 2022-05-19 | 2022-08-02 | 青岛炯晟新材料科技有限公司 | Puncture-resistant high-heat-insulation vacuum heat-insulation plate and preparation method thereof |
| CN114834112B (en) * | 2022-05-19 | 2024-03-29 | 青岛新材料科技工业园发展有限公司 | Puncture-resistant high-heat-insulation vacuum insulation panel and preparation method thereof |
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