CN102816515A - Aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, preparation method and application thereof - Google Patents
Aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses an aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, a preparation method and an application thereof, and belongs to the technical field of polymer synthesis. The preparation method comprises: preparing a tetraethyl orthosilicate sol; dissolving polyether polyol in an N-methyl pyrrolidone solution of dimethylol propionic acid; adding hydroxyethyl methacrylate to carry out end capping; adding triethylamine to form a salt to prepare an aqueous polyurethane acrylate prepolymer emulsion; adding hexafluorobutyl acrylate and trimethylolpropane triacrylate to prepare an aqueous fluorinated acrylate polyurethane prepolymer emulsion; adding gamma-methacryloxy propyl trimethoxyl silane to the prepolymer emulsion, mixing, and adding the prepared tetraethyl orthosilicate sol; and finally adding 2-hydroxy-2-methyl-1-propiophenone to prepare the finished product. The coating of the present invention has advantages of rapid curing, excellent mechanical properties, low surface tension, aging resistance, yellowing resistance, good water resistance, and the like, and can be used as coatings for building and furniture.
Description
Technical field
The invention belongs to the macromolecule synthesising technology field, it is emulsion modified to relate to a kind of aqueous polyurethane acrylate, particularly a kind of water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating.
Background technology
Tradition aqueous polyurethane acrylate (WPUA) adopts the thermofixation moulding process mostly, has long, shortcoming such as energy consumption is big set time; The ultraviolet light polymerization moulding process has fast, the energy-saving and cost-reducing and production efficiency advantages of higher of solidification rate; And the UV-curable waterborne system can obtain coating (being applicable to general coating method) as thin as a wafer through the solid content of regulating prescription, has that equipment is easy to clean, accumulating is convenient, nonflammable, safe and plurality of advantages such as minimizing disaster hidden-trouble.Photo-cured coating is a kind of environment-friendly coating without solvent, at home and abroad, no matter be that theoretical investigation or practical application are all just in fast development.Ultraviolet-curing paint mainly comprises that by the required various auxiliary agents of photolytic activity oligomer, photoactive monomer, light trigger and photocuring skimmer, flow agent, mould inhibitor etc. form, and ultraviolet-curing paint is to utilize the energy of UV-light to cause low molecule performed polymer or the polymerization between oligomer and the reactive monomer in the coating, crosslinked and obtain cured paint film.
The inorganic-organic hybridization material is meant that inorganic particles is scattered among the macromolecular material and a kind of matrix material that forms with nanoscale; Through the synergy between organic and inorganic component; Material has the over-all properties of macromolecular material and inorganic functional material concurrently; The performance of material is more effectively improved, and the research about polymer/inorganic nano-hybrid functional composite material has at present become one of advanced composite material and the most active problem of paint field.Nano silicon is a kind of nontoxic, tasteless nonmetal functional materials, in fields such as rubber, plastics, tackiness agent and coating, is widely used.Handle nano-silicon dioxide particle with the silane coupling agent that contains unsaturated group; The effect of sealing particle surface activity hydroxy is not only arranged; Can also control resin property through molecular designing; Therefore, many-sided performances such as the snappiness of resin, hardness, tolerance can design control in advance.Because fluoroacrylic resin has advantages such as surface tension is little, physical strength is high, ageing-resistant, anti-xanthochromia, water-tolerant; Through further Nano sol/urethane acrylate hybrid material being carried out modification; Synthetic a kind of silicon-dioxide-fluorate acrylic acid polyurethane ultraviolet curing oligopolymer, this novel photo-cured coating has the advantage of fluoroacrylic resin, urethane, inorganic materials and ultraviolet light polymerization etc. four.Along with the mankind to the enlarging day by day and the enhancing day by day of environmental consciousness of material performance requirement, this new green environment protection product will obtain bigger development.Main achievement in research is at present:
（1）Synthesis?and?characterization?of?core-shell?SiO
2-fluorinated?polyacrylate?nanocomposite?latex?particles?containing?fluorine?in?the?shell。Colloids?and?Surfaces?A,?2010,?360:?41-46。Reported with SiO
2For nuclear, fluorine-containing are the SiO of shell
2-fluorine-containing urethane, the TEM microgram shows nanometer SiO
2Particle is enclosed in and has formed nuclear shell structure nano composite emulsion particle in the fluoropolymer shell.Have bigger water contact angle, but set time is long, energy consumption is bigger.
(2) preparation and the performance of ultraviolet light curing nano colloidal sol/urethane acrylate hybrid material, Beijing University of Chemical Technology's journal (natural science edition), 2011,38 (5): 47-50.Reported with the gamma-methyl allyl acyloxypropyl trimethoxysilane to be raw material, adopted sol-gel method to synthesize the Nano sol of ultraviolet light polymerization, utilized Nano sol and urethane acrylate to prepare ultraviolet light polymerization organic/inorganic nano hybrid material again.Mechanical property to nano-hybrid material is tested; The result shows; Along with the increase of Nano sol content, the mechanical property of hybrid material, sticking power etc. are improved, but the water tolerance and the erosion resistance of the performance of hybrid material such as sample thermostability, film are not all studied.
(3) UV-solidifies GMA-PUA-nanometer SiO
2The hybridization coating cure kinetics, coatings industry, 2011,41 (8): 39-42.Reported with methyl allyl acyloxypropyl trimethoxysilane (MAPTMS) modified manometer silicon dioxide; Be applied to SY-Monomer G/urethane acrylate system and carry out ultraviolet light polymerization, utilize DSC (DSC), dynamic mechanical spectrometer (DMA), Fourier infrared spectrograph (FT-IR) that this system is studied.The result shows that system has consistency preferably.As modified Nano SiO
2Massfraction is 10% o'clock, and second-order transition temperature reaches peak, has improved 7.3 ℃.The methyl allyl acyloxypropyl trimethoxysilane that this experiment is used is the meeting polymerization reaction take place under the effect of moisture and heat, and is relatively more difficult in the process of preserving medicine and interpolation medicine, and skin and eyes are had slight pungency.
Summary of the invention
To the deficiency that exists in the above-mentioned prior art, the invention provides a kind of employing sol-gel method and prepare SiO
2The method of-fluorate acrylic acid ester polyurethane photo-cured coating; Be earlier tetraethoxy and absolute ethyl alcohol to be mixed and made into tetraethoxy colloidal sol under acidic conditions, polyether glycol be dissolved in the N-Methyl pyrrolidone solution of dimethylol propionic acid, drip vulcabond; With the dibutyl tin dilaurate is catalyzer; Add Rocryl 400 and carry out end-blocking, make aqueous polyurethane acrylate performed polymer emulsion, add R 1216 acid butyl ester and Viscoat 295 then and make water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion to add deionized water behind the triethylamine salify; Then γ-methacryloxypropyl trimethoxy silane is added the performed polymer emulsion; Mix the back and add the above-mentioned tetraethoxy colloidal sol for preparing, make water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer, add 2-hydroxy-2-methyl-1-phenyl-acetone at last; Make water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating
Wherein, described polyether glycol is the three-functionality-degree polyether glycol of molecular weight 3000,
Described isocyanic ester is an isophorone diisocyanate;
Described tetraethoxy colloidal sol preparation process is following:
Steps A, with thorough mixing under tetraethoxy and the absolute ethyl alcohol room temperature;
Step B, drip the deionized water solution of nitric acid, after dropwising system temperature is risen to 70 ℃, insulated and stirred backflow 3h to mixing solutions;
Step C, add N after cooling, dinethylformamide continues to stir 30min and makes tetraethoxy colloidal sol as the dry chemistry additive,
Described tetraethoxy: absolute ethyl alcohol: deionized water: H
+Mol ratio be 1:6.4:3.8:0.085.
(1) according to the preparation method of described water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating, wherein, described aqueous polyurethane acrylate performed polymer emulsion preparation step is following:
Steps A, polyether glycol is dissolved in the N-Methyl pyrrolidone solution of dimethylol propionic acid, add the N-Methyl pyrrolidone solution of dimethylol propionic acid, wherein N-Methyl pyrrolidone: the polyether glycol mass ratio is 0.5 ~ 2:1, preferred 1.5:1;
Step B, be heated to 60 ℃, add vulcabond,
The ratio of the hydroxyl mole number summation of the isocyano mole number of vulcabond and polyether glycol and dimethylol propionic acid wherein, promptly-ratio of NCO:-OH is 1.5:1 ~ 2:1, preferred 1.7:1,
The quality of dimethylol propionic acid is 4% ~ 8%, preferred 6% of vulcabond, polyether glycol and a dimethylol propionic acid quality summation;
Step C, adding dibutyl tin dilaurate are catalyzer, and its quality is 0.15% ~ 0.35% of a step B reaction system total mass, and be preferred 0.2%, is warmed up to 70 ℃ and stirs 3 ~ 4h, is preferably 3h;
Step D, system is cooled to 60 ℃, add Rocryl 400 and carry out end-blocking, its mole number is identical with the mole number of vulcabond; After stirring 4h, be cooled to 40 ℃, add the triethylamine salify; The triethylamine mole number is identical with the dimethylol propionic acid mole number, reaction 30min;
Step e, constant temperature add deionized water down for 60 ℃, and stirring reaction 30min can make aqueous polyurethane acrylate performed polymer emulsion,
Wherein the deionized water quality is 2:1 ~ 6:1 with the ratio of polyether glycol, vulcabond, dimethylol propionic acid and Rocryl 400 total mass, preferred 4:1.
(2) according to the preparation method of described water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating, wherein, the preparation process of described water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion is following:
Steps A, the aqueous polyurethane acrylate performed polymer emulsion that makes to above-mentioned steps add reactive thinner R 1216 acid butyl ester and Viscoat 295,
Wherein the quality of R 1216 acid butyl ester is 1% ~ 10% of the above-mentioned aqueous polyurethane acrylate performed polymer quality of the emulsion that makes, and is preferred 5%,
The quality of Viscoat 295 is 1% ~ 10%, preferred 5% of a described aqueous polyurethane acrylate performed polymer quality of the emulsion;
Step B, with the described solution of steps A in 40 ~ 50 ℃ the reaction 4h, can make water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion.
(3) according to the preparation method of described water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating, wherein, the preparation process of described water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer is following:
Steps A, add the water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion that γ-methacryloxypropyl trimethoxy silane makes in above-mentioned steps as coupling agent, insulated and stirred 1h;
Step B, in the system of above-mentioned steps A, add the above-mentioned tetraethoxy colloidal sol for preparing, stir 12h, can make water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer,
Wherein the quality of tetraethoxy colloidal sol is 1% ~ 10% of the above-mentioned water-based fluorate acrylic acid ester polyurethane quality that makes, and is preferred 3%,
The mass ratio of γ-methacryloxypropyl trimethoxy silane and tetraethoxy colloidal sol is 1:1 ~ 1:10, preferred 1:2.
(4) according to the preparation method of described water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating; Wherein, Add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone in water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution that above-mentioned steps makes; Process after stirring 30min
Wherein the quality of 2-hydroxy-2-methyl-1-phenyl-acetone be described water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution quality 1% ~ 20%, preferred 10%.
(5) according to the preparation method of described water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating; Wherein, Add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone in water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution that above-mentioned steps makes; Process after stirring 30min
Wherein the quality of 2-hydroxy-2-methyl-1-phenyl-acetone be described water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution quality 1% ~ 20%, preferred 10%.
The present invention adopts sol-gel method to prepare WFPUA/SiO
2Photo-cured coating, the preparation process is simple, has selected silane coupling agent KH-570, can realize inorganic SiO
2The particulate homodisperse, and between polymkeric substance and inorganic materials, form a kind of bonding force, this bonding force can make polymkeric substance and inorganic substance on molecular level, combine, thereby can obtain the homodisperse polymer/inorganic nanometer matrix material of inorganic nano-particle.
Water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing the coating that utilizes method of the present invention to make; Combine the advantage of fluoroacrylic resin, urethane, inorganic nano material and ultraviolet light polymerization etc. four; Have advantages such as solidification rate is fast, energy-saving and cost-reducing, production efficiency is high, good little, ageing-resistant, the anti-xanthochromia of mechanical property, surface tension, water-tolerant, can be used as the coating use of building and furniture.
Embodiment:
Below in conjunction with embodiment the present invention is elaborated, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
In the container of whipping appts is housed, add the 29.44g absolute ethyl alcohol, after 20.8g tetraethoxy (TEOS) stirring at normal temperature is even; In container, slowly splash into the deionized water 68.4g that contains 0.5355g nitric acid; Temperature is risen to 70 ℃ of reaction 3h, treat that colloidal sol cooling back adds the N of 23.8351g, dinethylformamide (DMF); Continue to stir 30min, can obtain tetraethoxy (TEOS) colloidal sol.
In that being housed, whisking appliance, reflux condensing tube, temperature take into account in the 500mL four-hole bottle of feeding device; Add polyether glycol (NJ-330), the dimethylol propionic acid (DMPA) of 0.8864g and N-Methyl pyrrolidone (NMP) solvent of 15g of 12.03g, system is warming up to 60 ℃, add 5.55g isophorone diisocyanate (IPDI); Drip 0.05g catalyzer dibutyl tin dilaurate (T-12); After stirring 30min, system temperature is risen to 70 ℃, after continuing to react 3h; Be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 3.25g cools the temperature to 40 ℃ behind the reaction 4h; Add triethylamine 0.8776g, reaction 0.5h drips the 64.2695g deionized water and disperses; 0.5h after, in performed polymer, add 1.125g reactive thinner R 1216 acid butyl ester (FA) and 1.125g Viscoat 295 (TMPTA), behind the reaction 4h; Temperature is remained on 40 ~ 50 ℃; γ-the methacryloxypropyl trimethoxy silane (KH-570) that adds 1.58g stirs 1h, in system, adds the above-mentioned tetraethoxy for preparing (TEOS) colloidal sol 3.16g; Continue to stir 12h, can obtain water-based SiO
2-fluorate acrylic acid ester polyurethane photocuring performed polymer; In the performed polymer that makes, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 4.36g, stir 30min, make water-based SiO
2-fluorate acrylic acid ester polyurethane photo-cured coating (hby-1).
Embodiment 2
In the container of whipping appts is housed, add the 29.44g absolute ethyl alcohol, after 20.8g tetraethoxy (TEOS) stirring at normal temperature is even; In container, slowly splash into the deionized water 68.4g that contains 0.5355g nitric acid; Temperature is risen to 70 ℃ of reaction 3h, treat that colloidal sol cooling back adds the N of 23.8351g, dinethylformamide (DMF); Continue to stir 30min, can obtain tetraethoxy (TEOS) colloidal sol.
Take into account in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, add polyether glycol (NJ-330), the dimethylol propionic acid (DMPA) of 0.9907g and N-Methyl pyrrolidone (NMP) solvent of 15g of 9.975g, system is warming up to 60 ℃; Add 5.55g isophorone diisocyanate (IPDI), drip 0.05g catalyzer dibutyl tin dilaurate (T-12), behind the stirring 30min; System temperature is risen to 70 ℃, after continuing to react 3h, be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 3.25g cools the temperature to 40 ℃ behind the reaction 4h, adds triethylamine 0.9810g; Reaction 0.5h, Dropwise 5 8.3248g deionized water disperses, behind the 0.5h; In performed polymer, add 1.125g reactive thinner R 1216 acid butyl ester (FA) and 1.125g Viscoat 295 (TMPTA); Behind the reaction 4h, temperature is remained on 40 ~ 50 ℃, add γ-methacryloxypropyl trimethoxy silane (KH-570) of 0.79g; Stir 1h, in system, add the above-mentioned tetraethoxy for preparing (TEOS) colloidal sol 1.5805g; Continue to stir 12h, can obtain water-based SiO
2-fluorate acrylic acid ester polyurethane photocuring performed polymer; In the performed polymer that makes, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 4.36g, stir 30min, make water-based SiO
2-fluorate acrylic acid ester polyurethane photo-cured coating (hby-2).
Embodiment 3
In the container of whipping appts is housed; Add the 29.44g absolute ethyl alcohol, after 20.8g tetraethoxy (TEOS) stirring at normal temperature is even, in container, slowly splash into the deionized water 68.4g that contains 0.5355g nitric acid; Temperature is risen to 70 ℃ of reaction 3h; Treat that colloidal sol cooling back adds the N of 23.8351g, dinethylformamide (DMF) continues to stir 30min, can obtain tetraethoxy (TEOS) colloidal sol.
Take into account in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, add polyether glycol (NJ-330), the dimethylol propionic acid (DMPA) of 0.9907g and N-Methyl pyrrolidone (NMP) solvent of 15g of 9.975g, system is warming up to 60 ℃; Add 5.55g isophorone diisocyanate (IPDI), drip 0.05g catalyzer dibutyl tin dilaurate (T-12), behind the stirring 30min; System temperature is risen to 70 ℃, after continuing to react 3h, be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 3.25g cools the temperature to 40 ℃ behind the reaction 4h, adds triethylamine 0.9810g; Reaction 0.5h, Dropwise 5 8.3248g deionized water disperses, behind the 0.5h; In performed polymer, add 1.125g reactive thinner R 1216 acid butyl ester (FA) and 1.125g Viscoat 295 (TMPTA); Behind the reaction 4h, temperature is remained on 40 ~ 50 ℃, add γ-methacryloxypropyl trimethoxy silane (KH-570) of 3.95g; Stir 1h, in system, add the above-mentioned tetraethoxy for preparing (TEOS) colloidal sol 7.9g; Continue to stir 12h, can obtain water-based SiO
2-fluorate acrylic acid ester polyurethane photocuring performed polymer; In the performed polymer that makes, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 8.64g, stir 30min, make water-based SiO
2-fluorate acrylic acid ester polyurethane photo-cured coating (hby-3).
Embodiment 4
In the container of whipping appts is housed, add the 29.44g absolute ethyl alcohol, after 20.8g tetraethoxy (TEOS) stirring at normal temperature is even; In container, slowly splash into the deionized water 68.4g that contains 0.5355g nitric acid; Temperature is risen to 70 ℃ of reaction 3h, treat that colloidal sol cooling back adds the N of 23.8351g, dinethylformamide (DMF); Continue to stir 30min, can obtain tetraethoxy (TEOS) colloidal sol.
Take into account in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, add polyether glycol (NJ-330), the dimethylol propionic acid (DMPA) of 0.9907g and N-Methyl pyrrolidone (NMP) solvent of 15g of 9.975g, system is warming up to 60 ℃; Add 5.55g isophorone diisocyanate (IPDI), drip 0.05g catalyzer dibutyl tin dilaurate (T-12), behind the stirring 30min; System temperature is risen to 70 ℃, after continuing to react 3h, be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 3.25g cools the temperature to 40 ℃ behind the reaction 4h, adds triethylamine 0.9810g; Reaction 0.5h, Dropwise 5 8.3248g deionized water disperses, behind the 0.5h; In performed polymer, add 5.1845g reactive thinner R 1216 acid butyl ester (FA) and 5.1845g Viscoat 295 (TMPTA); Behind the reaction 4h, temperature is remained on 40 ~ 50 ℃, add γ-methacryloxypropyl trimethoxy silane (KH-570) of 1.58g; Stir 1h, in system, add the above-mentioned tetraethoxy for preparing (TEOS) colloidal sol 3.16g; Continue to stir 12h, can obtain water-based SiO
2-fluorate acrylic acid ester polyurethane photocuring performed polymer; In the performed polymer that makes, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 7.9g, stir 30min, make water-based SiO
2-fluorate acrylic acid ester polyurethane photo-cured coating (hby-4).
Embodiment 5
In the container of whipping appts is housed, add the 29.44g absolute ethyl alcohol, after 20.8g tetraethoxy (TEOS) stirring at normal temperature is even; In container, slowly splash into the deionized water 68.4g that contains 0.5355g nitric acid; Temperature is risen to 70 ℃ of reaction 3h, treat that colloidal sol cooling back adds the N of 23.8351g, dinethylformamide (DMF); Continue to stir 30min, can obtain tetraethoxy (TEOS) colloidal sol.
Take into account in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, add polyether glycol (NJ-330), the dimethylol propionic acid (DMPA) of 0.9907g and N-Methyl pyrrolidone (NMP) solvent of 15g of 9.975g, system is warming up to 60 ℃; Add 5.55g isophorone diisocyanate (IPDI), drip 0.05g catalyzer dibutyl tin dilaurate (T-12), behind the stirring 30min; System temperature is risen to 70 ℃, after continuing to react 3h, be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 3.25g cools the temperature to 40 ℃ behind the reaction 4h, adds triethylamine 0.9810g; Reaction 0.5h, Dropwise 5 8.3248g deionized water disperses, behind the 0.5h; In performed polymer, add 5.1845g reactive thinner R 1216 acid butyl ester (FA) and 5.1845g Viscoat 295 (TMPTA); Behind the reaction 4h, temperature is remained on 40 ~ 50 ℃, add γ-methacryloxypropyl trimethoxy silane (KH-570) of 1.58g; Stir 1h, in system, add the above-mentioned tetraethoxy for preparing (TEOS) colloidal sol 3.16g; Continue to stir 12h, can obtain water-based SiO
2-fluorate acrylic acid ester polyurethane photocuring performed polymer; In the performed polymer that makes, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 9.84g, stir 30min, make water-based SiO
2-fluorate acrylic acid ester polyurethane photo-cured coating (hby-5).
Experimental technique
Measure water-based SiO
2-fluorinated acrylic ester polyaminoester emulsion or the water-intake rate of filming, tensile strength, elongation at break and surface tension, shown in result such as the following table:
| Sample | hyb-1 | hyb-2 | hyb-3 | hyb-4 | hyb-5 |
| Water-intake rate % | 72.76 | 22.47 | 48.66 | 0.62 | 92.39 |
| Tensile strength (MPa) | 1.22 | 1.58 | 1.42 | 1.79 | 0.45 |
| Elongation at break (%) | 16.4 | 89.68 | 98.4 | 155.71 | 28.53 |
| Surface tension (mN/m) | 31.23 | 30.84 | 31.56 | 30.42 | 30.42 |
The resulting SiO of the present invention
2-fluorate acrylic acid polyaminoester emulsion; Advantage in conjunction with fluoroacrylic resin, urethane, inorganic nano material and ultraviolet light polymerization etc. four: little, ageing-resistant, the anti-xanthochromia of mechanical property, surface tension that solidification rate is fast, energy-saving and cost-reducing, production efficiency is high, good, water-tolerant etc., the coating that can be used as building and furniture uses.
Claims (7)
1. the preparation method of water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating; Be earlier tetraethoxy and absolute ethyl alcohol to be mixed and made into tetraethoxy colloidal sol under acidic conditions; Polyether glycol is dissolved in the N-Methyl pyrrolidone solution of dimethylol propionic acid; Dripping vulcabond, is catalyzer with the dibutyl tin dilaurate, adds Rocryl 400 and carries out end-blocking; Make aqueous polyurethane acrylate performed polymer emulsion to add deionized water behind the triethylamine salify; Add R 1216 acid butyl ester and Viscoat 295 then and make water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion, then γ-methacryloxypropyl trimethoxy silane is added the performed polymer emulsion, mix the back and add the above-mentioned tetraethoxy colloidal sol for preparing; Make water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer; Add 2-hydroxy-2-methyl-1-phenyl-acetone at last, make water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating
Wherein, described polyether glycol is the three-functionality-degree polyether glycol of molecular weight 3000,
Described isocyanic ester is an isophorone diisocyanate;
Described tetraethoxy colloidal sol preparation process is following:
Steps A, with thorough mixing under tetraethoxy and the absolute ethyl alcohol room temperature;
Step B, drip the deionized water solution of nitric acid, after dropwising system temperature is risen to 70 ℃, insulated and stirred backflow 3h to mixing solutions;
Step C, add N after cooling, dinethylformamide continues to stir 30min and makes tetraethoxy colloidal sol as the dry chemistry additive,
Described tetraethoxy: absolute ethyl alcohol: deionized water: H
+Mol ratio be 1:6.4:3.8:0.085.
2. the preparation method of water-based silicon-dioxide according to claim 1-fluorinated acrylic ester polyurethane ultraviolet curing coating is characterized in that, described aqueous polyurethane acrylate performed polymer emulsion preparation step is following:
Steps A, polyether glycol is dissolved in the N-Methyl pyrrolidone solution of dimethylol propionic acid, add the N-Methyl pyrrolidone solution of dimethylol propionic acid, wherein N-Methyl pyrrolidone: the polyether glycol mass ratio is 0.5 ~ 2:1, preferred 1.5:1;
Step B, be heated to 60 ℃, add vulcabond,
The ratio of the hydroxyl mole number summation of the isocyano mole number of vulcabond and polyether glycol and dimethylol propionic acid wherein, promptly-ratio of NCO:-OH is 1.5:1 ~ 2:1, preferred 1.7:1,
The quality of dimethylol propionic acid is 4% ~ 8%, preferred 6% of vulcabond, polyether glycol and a dimethylol propionic acid quality summation;
Step C, adding dibutyl tin dilaurate are catalyzer, and its quality is 0.15% ~ 0.35% of a step B reaction system total mass, and be preferred 0.2%, is warmed up to 70 ℃ and stirs 3 ~ 4h, is preferably 3h;
Step D, system is cooled to 60 ℃, add Rocryl 400 and carry out end-blocking, its mole number is identical with the mole number of vulcabond; After stirring 4h, be cooled to 40 ℃, add the triethylamine salify; The triethylamine mole number is identical with the dimethylol propionic acid mole number, reaction 30min;
Step e, constant temperature add deionized water down for 60 ℃, and stirring reaction 30min can make aqueous polyurethane acrylate performed polymer emulsion,
Wherein the deionized water quality is 2:1 ~ 6:1 with the ratio of polyether glycol, vulcabond, dimethylol propionic acid and Rocryl 400 total mass, preferred 4:1.
3. the preparation method of water-based silicon-dioxide according to claim 1-fluorinated acrylic ester polyurethane ultraviolet curing coating is characterized in that, the preparation process of described water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion is following:
Steps A, the aqueous polyurethane acrylate performed polymer emulsion that makes to step 2 add reactive thinner R 1216 acid butyl ester and Viscoat 295,
Wherein the quality of R 1216 acid butyl ester is 1% ~ 10% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes of step 2, and is preferred 5%,
The quality of Viscoat 295 is 1% ~ 10%, preferred 5% of a described aqueous polyurethane acrylate performed polymer quality of the emulsion;
Step B, with the described solution of steps A in 40 ~ 50 ℃ the reaction 4h, can make water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion.
4. the preparation method of water-based silicon-dioxide according to claim 1-fluorinated acrylic ester polyurethane ultraviolet curing coating is characterized in that, the preparation process of described water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer is following:
Steps A, add the water-based fluorinated acrylic ester base polyurethane prepolymer for use as emulsion that γ-methacryloxypropyl trimethoxy silane makes in step 3 as coupling agent, insulated and stirred 1h;
Step B, in the system of above-mentioned steps A, add the above-mentioned tetraethoxy colloidal sol for preparing, stir 12h, can make water-based silicon-dioxide-fluorate acrylic acid urethane photocuring performed polymer,
Wherein the quality of tetraethoxy colloidal sol is 1% ~ 10% of the water-based fluorate acrylic acid ester polyurethane quality that makes of step 3, and is preferred 3%,
The mass ratio of γ-methacryloxypropyl trimethoxy silane and tetraethoxy colloidal sol is 1:1 ~ 1:10, preferred 1:2.
5. the preparation method of water-based silicon-dioxide according to claim 1-fluorinated acrylic ester polyurethane ultraviolet curing coating; It is characterized in that; Add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone in water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution that step 4 makes; Process after stirring 30min
Wherein the quality of 2-hydroxy-2-methyl-1-phenyl-acetone be described water-based silicon-dioxide-fluorate acrylic acid urethane photocuring prepolymer solution quality 1% ~ 20%, preferred 10%.
6. water-based silicon-dioxide-fluorinated acrylic ester polyurethane ultraviolet curing coating of preparing of the said preparation method of claim 1.
7. the said water-based silicon-dioxide of claim 6-fluorinated acrylic ester polyurethane ultraviolet curing coating is as the application of ultraviolet-curing paint.
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| CN103184406A (en) * | 2013-03-19 | 2013-07-03 | 河海大学 | Hybrid material hole sealing agent for improving corrosion resistance of plasma spraying coating in acid environment |
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| CN105885673A (en) * | 2016-05-18 | 2016-08-24 | 兰州科天环保节能科技有限公司 | Water-based antifouling ultraviolet-curing metal paint |
| CN106349459A (en) * | 2016-08-24 | 2017-01-25 | 深圳市谛源光科有限公司 | Modified preparation method of high-adhesion UV (Ultraviolet) resin for surface of electronic glass |
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