CN117820637A - Photo-curing water dispersion, preparation method and application thereof - Google Patents
Photo-curing water dispersion, preparation method and application thereof Download PDFInfo
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- CN117820637A CN117820637A CN202311872060.8A CN202311872060A CN117820637A CN 117820637 A CN117820637 A CN 117820637A CN 202311872060 A CN202311872060 A CN 202311872060A CN 117820637 A CN117820637 A CN 117820637A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 93
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 90
- 239000011737 fluorine Substances 0.000 claims abstract description 90
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 72
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 32
- -1 acrylic ester compounds Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- AOITVOSSTJRHSS-UHFFFAOYSA-N (c{60}-i{h})[5,6]fullerane-1,2,3,4,5,7,13,23,24,27,29,32,35,36,39,40,42,44,49,50,53,55,56,58-tetracosol Chemical compound OC12C3C4C(O)(C56O)C7(O)C1C(C18O)(O)C9C2(O)C2C(C%10C%11(C(C%12(C(O)(C%13%14)C%15%11O)O)(O)C%11%16)O)C3C%15C4C%14C5C3C%13C(C4C5(O)C%13%14)(O)C%12C5C%11C5C%13(O)C%11C%12(O)C%13(O)C5C%16C%10(O)C2C%13(O)C9(O)C%12C8C2(O)C(C58O)C1C7C6C8(O)C3(O)C4C5C%14C2%11 AOITVOSSTJRHSS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910003472 fullerene Inorganic materials 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 26
- 239000003973 paint Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 3
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 19
- 229910000831 Steel Inorganic materials 0.000 abstract description 16
- 239000010959 steel Substances 0.000 abstract description 16
- 210000002268 wool Anatomy 0.000 abstract description 16
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
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- 238000009835 boiling Methods 0.000 description 3
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- 229920001778 nylon Polymers 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to a photo-curing aqueous dispersion, a preparation method and application thereof. The photocuring aqueous dispersion is obtained by grafting reaction of raw materials comprising a fluorine-containing epoxy-polyurethane structure prepolymer, a hydroxyl fullerene monomer and a hydrophilic chain extender; the fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds; the fluorine-containing epoxy monomer is obtained by reacting raw materials comprising fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide. The invention can solve the defects of the existing photo-curing water dispersion in the aspects of durable stain resistance, steel wool resistance, rigidity and heat resistance, and the problem of resin stability of the self-emulsifying stain resistance and steel wool resistance photo-curing water dispersion.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a photo-curing aqueous dispersion, a preparation method and application thereof.
Background
At present, in the fields of consumer electronics products and plastic coating, the coating for resisting dirt and steel wool is mainly a traditional solvent type photo-curing coating, and the components comprise photo-curing resin, a photo-initiator, an oily diluent and an additive, so that the gloss of a paint film is difficult to reduce during preparation, and nearly half of solvents (such as toluene, xylene, ketone, ester and styrene) volatilize into the air during construction, so that the environment is polluted and the health of human beings is endangered. The stain-resistant and steel wool-resistant paint prepared by the solvent-based photo-curing paint in the market at present has the characteristic that the stain resistance and the steel wool resistance are rapidly deteriorated after the paint film is matted. Most water-based photocuring stain-resistant steel wool coating realizes the stain-resistant and steel wool-resistant effects by adding additives, the stability of the product is poor, the steel wool-resistant performance and the stain-resistant performance cannot reach the performance of solvent-based products, and after the water boiling resistance and the wear resistance test, the stain-resistant performance of a paint film also disappears completely, and the durability cannot reach the performance of the solvent-based products.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a photo-curing aqueous dispersion, a preparation method and application thereof, and aims to solve the defects of the existing photo-curing aqueous dispersion in the aspects of durable stain resistance, steel wool resistance, rigidity and heat resistance and the problem of resin stability of the self-emulsifying stain resistance and steel wool resistance photo-curing aqueous dispersion.
The invention provides a photocuring aqueous dispersion which is obtained by grafting reaction of raw materials comprising a fluorine-containing epoxy-polyurethane structure prepolymer, a hydroxyl fullerene monomer and a hydrophilic chain extender;
the fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds;
the fluorine-containing epoxy monomer is obtained by reacting raw materials comprising fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide.
Preferably, the mass ratio of the fluorine-containing monomer to the epichlorohydrin to the sodium hydroxide to the tetrabutylammonium hydroxide is 25-35: 53-78: 6-13: 7-18.
Preferably, the preparation method of the fluorine-containing epoxy monomer comprises the following steps:
a1 Stirring fluorine-containing monomer, epichlorohydrin and sodium hydroxide at 60-90 ℃ for reaction;
a2 Mixing the product solution obtained after the stirring reaction in the step a 1) with tetrabutylammonium hydroxide, and reacting at 60-90 ℃ to obtain the fluorine-containing epoxy monomer.
Preferably, the acid anhydride comprises at least one of tetrahydrophthalic anhydride, phthalic anhydride, and cis-1, 2,3, 6-tetrahydrophthalic anhydride;
the acrylic ester compound comprises at least one of pentaerythritol triacrylate, trimethylolpropane triacrylate and dipentaerythritol hexaacrylate;
the mass ratio of the fluorine-containing epoxy monomer to the anhydride to the acrylic ester compound is 32-44: 17-33: 45-68.
Preferably, the hydroxyl fullerene monomer is obtained by mixing and reacting raw materials comprising fullerene, toluene, sodium hydroxide, tetrabutyl ammonium hydroxide and hydrogen peroxide.
Preferably, the preparation method of the hydroxy fullerene monomer comprises the following steps:
b1 Dissolving fullerene in toluene solution to obtain fullerene solution;
b2 And (3) uniformly stirring the fullerene solution, sodium hydroxide and tetrabutylammonium hydroxide, then mixing with hydrogen peroxide, and stirring for reaction to obtain the hydroxy fullerene monomer.
Preferably, the method comprises the steps of,
in the step b 1) of the process,
the mass concentration of the toluene solution is 2% -16%;
the dosage ratio of the fullerene to the toluene solution is 1-8 mg: 1-50 mL;
the dissolution temperature is 60-80 ℃;
in the step b 2) of the process,
the mass ratio of the fullerene solution to the sodium hydroxide to the tetrabutyl ammonium hydroxide to the hydrogen peroxide is 1-10: 12-22: 7-16: 2 to 14. The mass concentration of the hydrogen peroxide is 7% -14%;
the step b 2) is carried out at 60 to 80 ℃.
Preferably, the mass ratio of the fluorine-containing epoxy-polyurethane structural prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender is 20-45 g: 3-12 mg: 3-10 g;
the hydrophilic chain extender comprises at least one of dimethylolpropionic acid, dimethylolbutyric acid, sodium ethylenediamine-based ethanesulfonate and N-methyldiethanolamine.
The invention also provides a process for preparing the above-described photocurable aqueous dispersion, comprising the steps of:
and (3) carrying out grafting reaction on the fluorine-containing epoxy-polyurethane structure prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender at 60-90 ℃ to obtain the photo-curing aqueous dispersion.
The invention also provides a photo-curing water dispersion paint which is prepared from the following raw materials in parts by weight:
the aqueous photocurable dispersion is the aqueous photocurable dispersion described above or the aqueous photocurable dispersion produced by the production process described above.
The invention provides a photocuring aqueous dispersion which is obtained by grafting reaction of raw materials comprising a fluorine-containing epoxy-polyurethane structure prepolymer, a hydroxyl fullerene monomer and a hydrophilic chain extender; the fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds; the fluorine-containing epoxy monomer is obtained by reacting raw materials comprising fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide.
According to the invention, fluorine-containing groups are accessed through epoxy, fluorine-containing monomers are introduced into a cross-linked network as a suspension chain, and the super yellowing resistance of an epoxy structure is utilized, so that the cured paint film can keep lasting stain resistance and can keep yellowing resistance. The fluorine-containing epoxy-polyurethane structural prepolymer is obtained by reacting fluorine-containing epoxy monomers, anhydride and acrylic ester compounds. Introducing a photo-curing group, and synthesizing an epoxy-polyurethane structure by adding an acrylic compound. The synthesis process adopts multi-functional synthesis to finally form a star-shaped structure, thereby reducing the winding of chain segments, reducing the viscosity of prepolymer, realizing the low viscosity characteristic, reducing the viscosity without adding solvent and having no solvation of experimental products. The fluorine-containing epoxy-polyurethane structure prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender are subjected to grafting reaction to form a fluorine-containing epoxy-polyurethane-fullerene ternary structure, so that the rigidity and wear resistance of the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocuring water dispersion coating can be greatly improved, the product has the durable super-steel wool resistance, and meanwhile, the durable dirt resistance is maintained.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a photo-curing water dispersion, which is prepared from raw materials comprising a fluorine-containing epoxy-polyurethane structure prepolymer, a hydroxyl fullerene monomer and a hydrophilic chain extender through a grafting reaction.
The fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds;
the fluorine-containing epoxy monomer is obtained by reacting raw materials comprising fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide.
The mass ratio of the fluorine-containing monomer to the epichlorohydrin to the sodium hydroxide to the tetrabutylammonium hydroxide is 25-35: 53-78: 6-13: 7 to 18, such as 26.5:58.9:6.6:8.
the epoxy value of the fluorine-containing epoxy monomer is 125-220 mol/g, such as 170-220 mol/g.
In some embodiments of the present invention, the method for preparing the fluorine-containing epoxy monomer includes the steps of:
a1 Stirring fluorine-containing monomer, epichlorohydrin and sodium hydroxide at 60-90 ℃ for reaction;
a2 Mixing the product solution obtained after the stirring reaction in the step a 1) with tetrabutylammonium hydroxide, and reacting at 60-90 ℃ to obtain the fluorine-containing epoxy monomer.
In step a 1):
the fluorine-containing monomer comprises at least one of diphenol hexafluoropropane diglycidyl ether, dihydroxyoctafluorobiphenyl diglycidyl ether, 1,3- (bishexafluorohydroxypropyl) benzene diglycidyl ether and 1,4- (bishexafluorohydroxypropyl) benzene diglycidyl ether.
The mass ratio of the fluorine-containing monomer to the epoxy chloropropane to the sodium hydroxide is 25-35: 53-78: 6 to 13.
The temperature of the stirring reaction is 70 ℃ and the time is 3-8 h.
In step a 2):
the mass ratio of the tetrabutylammonium hydroxide to the fluorine-containing monomer is 7-18: 25 to 35.
The temperature of the stirring reaction of the reaction is 70 ℃ and the time is 2-4 h.
After the reaction, the method further comprises: cooling and washing. The cooling is natural cooling to room temperature. The washing was performed with deionized water to remove residual solvent.
The fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds.
In some embodiments of the invention, the anhydride comprises at least one of tetrahydrophthalic anhydride, phthalic anhydride, and cis-1, 2,3, 6-tetrahydrophthalic anhydride.
In some embodiments of the invention, the acrylic compound includes at least one of pentaerythritol triacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate.
The mass ratio of the fluorine-containing epoxy monomer to the anhydride to the acrylic ester compound is 32-44: 17-33: 45-68, such as 33.5:18.9:47.6.
in some embodiments of the present invention, the method for preparing the fluorine-containing epoxy-polyurethane structural prepolymer comprises the steps of:
reacting fluorine-containing epoxy monomer, anhydride and acrylic ester compound at 60-90 ℃ to obtain fluorine-containing epoxy-polyurethane structural prepolymer.
The temperature of the reaction is 70 ℃; the time is 8 to 10 hours, such as 8.5 hours.
In the invention, the hydroxyl fullerene monomer is prepared by mixing and reacting raw materials comprising fullerene, toluene, sodium hydroxide, tetrabutyl ammonium hydroxide and hydrogen peroxide.
The fullerene is fullerene C60.
In some embodiments of the invention, the method for preparing a hydroxyfullerene monomer comprises the steps of:
b1 Dissolving fullerene in toluene solution to obtain fullerene solution;
b2 And (3) uniformly stirring the fullerene solution, sodium hydroxide and tetrabutylammonium hydroxide, then mixing with hydrogen peroxide, and stirring for reaction to obtain the hydroxy fullerene monomer.
In step b 1):
the mass concentration of the toluene solution is 2% -16%, such as 10%.
The dosage ratio of the fullerene to the toluene solution is 1-8 mg: 1-50 mL, such as 5mg:28mL.
The dissolution temperature is 60 to 80 ℃, such as 70 ℃.
In step b 2):
the mass ratio of the fullerene solution to the sodium hydroxide to the tetrabutyl ammonium hydroxide to the hydrogen peroxide is 1-10: 12-22: 7-16: 2 to 14, such as 4.3:14.7:12.3:8.7. the mass concentration of the hydrogen peroxide is 7% -14%, such as 7.5%.
The step b 2) is carried out at 60 to 80℃such as 70 ℃.
The stirring reaction time is 3-4 h.
After the stirring reaction, the method further comprises the following steps: separating liquid, dialyzing, removing water, washing and drying. The separating funnel is used for separating liquid. The method of water removal is rotary steaming.
In the invention, the photo-curing water dispersion is obtained by grafting reaction of raw materials comprising a fluorine-containing epoxy-polyurethane structure prepolymer, a hydroxyl fullerene monomer and a hydrophilic chain extender.
The mass ratio of the fluorine-containing epoxy-polyurethane structural prepolymer to the hydroxyl fullerene monomer to the hydrophilic chain extender is 20-45 g: 3-12 mg:3 to 10g, such as 35 to 45g: 6-9 mg:3 to 5g, specifically 38.5g:7.6mg:3.9g.
In some embodiments of the invention, the hydrophilic chain extender comprises at least one of dimethylolpropionic acid, dimethylolbutyric acid, sodium ethylenediamine-based ethane sulfonate, and N-methyldiethanolamine.
The invention also provides a process for preparing the above-described photocurable aqueous dispersion, comprising the steps of:
and (3) carrying out grafting reaction on the fluorine-containing epoxy-polyurethane structure prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender at 60-90 ℃ to obtain the photo-curing aqueous dispersion.
The grafting reaction time is 3-8 h.
After the grafting reaction, the method further comprises the following steps: mixing with water, emulsifying, and dispersing. And preparing the fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing aqueous dispersion.
The invention also provides a photo-curing water dispersion paint which is prepared from the following raw materials in parts by weight:
the aqueous photocurable dispersion is the aqueous photocurable dispersion described above or the aqueous photocurable dispersion produced by the production process described above.
The light-cured water dispersion coating is fluorine-containing epoxy-polyurethane-fullerene ternary structure light-cured water dispersion coating.
In some embodiments of the invention, the parts by weight of the photocurable aqueous dispersion is 80-95 parts, specifically 91 parts, 84.57 parts, 80.41 parts, 80 parts or 85.31 parts. The photoinitiator comprises one or more of TPO, 1173, 184, 819DW and BP; the weight portion of the photoinitiator is 2.5-3.5 portions, specifically 3 portions, 3.17 portions, 3.02 portions, 2.93 portions or 2.84 portions. The defoamer comprises one or more of polyoxypropylene polyoxyethylene glycerol ether, BYK024, BYK028 and Tego902W; the defoamer comprises, by weight, 0.3 part, 0.32 part, 6.03 parts, 5.85 parts and 5.69 parts. The leveling agent comprises one or more of polyether modified acrylic functional polydimethylsiloxane, BYK333 and Tego450; the leveling agent is 0.2-0.3 part by weight, specifically 0.2 part by weight, 0.21 part by weight, 0.3 part by weight, 0.29 part by weight or 0.28 part by weight. The wetting agent comprises one or more of Tego4100, tego270 and Tego245; the weight portion of the wetting agent is 0.1-0.5 portion, specifically 0.5 portion, 0.53 portion, 0.2 portion and 0.19 portion. The filler comprises at least one of matt powder E-1011, matt powder OK-520, nylon micro powder PA-12 and polymethyl methacrylate microspheres; the weight parts of the filler are 2-11 parts, specifically 5 parts, 10.57 parts, 10.05 parts, 5.85 parts and 2.84 parts. In certain embodiments, the water is present in an amount of 0.5 to 1 parts by weight, such as 0.63 parts; or 0.
The invention also provides a preparation method of the photo-curing water dispersion paint, which comprises the following steps:
and uniformly dispersing the photo-curing aqueous dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent, the filler and the water at room temperature to obtain the photo-curing aqueous dispersion coating.
The uniform dispersing time is 0.5-1.5 h.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to illustrate a photocurable aqueous dispersion, its preparation and application in detail, but are not to be construed as limiting the scope of the invention.
Synthesis example 1
a) Preparation of fluorine-containing epoxy monomer:
a-1) stirring and reacting fluorine-containing monomer diphenol hexafluoropropane diglycidyl ether, epoxy chloropropane and sodium hydroxide for 3 hours at 70 ℃;
a-2) mixing the product solution obtained after the stirring reaction in the step a-1) with tetrabutylammonium hydroxide, reacting for 4 hours at 70 ℃, naturally cooling to room temperature, and washing with deionized water to obtain a fluorine-containing epoxy monomer;
the mass ratio of the fluorine-containing monomer to the epichlorohydrin to the sodium hydroxide to the tetrabutylammonium hydroxide is 26.5:58.9:6.6:8.
the epoxy value of the fluorine-containing epoxy monomer is 170-220 mol/g measured by a hydrochloric acid-acetone method.
Synthesis example 2
Preparation of a fluorine-containing epoxy-polyurethane structural prepolymer:
reacting the fluorine-containing epoxy monomer obtained in synthesis example 1, phthalic anhydride and trimethylolpropane triacrylate at 70 ℃ for 8.5 hours to obtain a fluorine-containing epoxy-polyurethane structure prepolymer;
the mass ratio of the fluorine-containing epoxy monomer to the phthalic anhydride to the acrylic ester compound is 33.5:18.9:47.6.
synthesis example 3
Preparation of hydroxy fullerene monomer:
b-1) dissolving fullerene in toluene solution with the mass concentration of 10% at 70 ℃ to obtain fullerene solution; the dosage ratio of the fullerene to the toluene solution is 5mg:28mL;
b-2) uniformly stirring the fullerene solution, sodium hydroxide and tetrabutylammonium hydroxide at 70 ℃, then mixing with hydrogen peroxide with the mass concentration of 7.5%, stirring and reacting for 4 hours, separating the solution by using a separating funnel, dialyzing, rotationally evaporating water, washing and drying to obtain a hydroxyl fullerene monomer;
the mass ratio of the fullerene solution to the sodium hydroxide to the tetrabutyl ammonium hydroxide to the hydrogen peroxide is 4.3:14.7:12.3:8.7.
synthesis example 4
Preparation of a photo-curable aqueous dispersion:
the fluorine-containing epoxy-polyurethane structural prepolymer in synthesis example 2, the hydroxy fullerene monomer in synthesis example 3 and the hydrophilic chain extender dimethylolbutyric acid are subjected to grafting reaction for 4 hours at 70 ℃, and then are mixed with water for emulsification and dispersion to obtain a photocuring water dispersion;
the mass ratio of the fluorine-containing epoxy-polyurethane structural prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender is 38.5g:7.6mg:3.9g.
Application example 1
Preparation of fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion paint:
the preparation raw materials comprise:
the photo-curable aqueous dispersion was the photo-curable aqueous dispersion of example 1; the photoinitiator is TPO; the defoaming agent is polyoxypropylene polyoxyethylene glycerol ether; the leveling agent is BYK333; the wetting agent is Tego4100; the filler is polymethyl methacrylate microsphere.
The preparation method comprises the following steps:
and uniformly dispersing the photocuring water dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent and the filler for 1h at room temperature to obtain the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocuring water dispersion coating.
Application example 2
Preparation of fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion paint:
the preparation raw materials comprise:
the photo-curable aqueous dispersion was the photo-curable aqueous dispersion of example 1; the photoinitiator is 1173; the defoaming agent is BYK024; the leveling agent is BYK333; the wetting agent is Tego270; the filler is nylon micro powder PA-12.
The preparation method comprises the following steps:
and uniformly dispersing the photo-curing water dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent, the filler and water for 1h at room temperature to obtain the fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion coating.
Application example 3
Preparation of fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion paint:
the preparation raw materials comprise:
the photo-curable aqueous dispersion was the photo-curable aqueous dispersion of example 1; the photoinitiator was 184; the defoaming agent is BYK028; the leveling agent is Tego450; the wetting agent is Tego245; the filler is dumb powder E-1011;
the preparation method comprises the following steps:
and uniformly dispersing the photocuring water dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent and the filler for 1h at room temperature to obtain the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocuring water dispersion coating.
Application example 4
Preparation of fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion paint:
the preparation raw materials comprise:
the photo-curable aqueous dispersion was the photo-curable aqueous dispersion of example 1; the photoinitiator is 819DW; the defoamer is Tego902W; the leveling agent is BYK333; the wetting agent is Tego270; the filler is dumb powder OK520;
the preparation method comprises the following steps:
and uniformly dispersing the photocuring water dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent and the filler for 1h at room temperature to obtain the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocuring water dispersion coating.
Application example 5
Preparation of fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing water dispersion paint:
the preparation raw materials comprise:
the photo-curable aqueous dispersion was the photo-curable aqueous dispersion of example 1; the photoinitiator is BP; the defoaming agent is BYK024; the leveling agent is Tego450; the wetting agent is Tego4100; the filler is nylon micro powder PA-12;
the preparation method comprises the following steps:
and uniformly dispersing the photocuring water dispersion, the photoinitiator, the defoaming agent, the leveling agent, the wetting agent and the filler for 1h at room temperature to obtain the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocuring water dispersion coating.
Comparative example 1
The difference from application example 1 is that:
the photocurable aqueous dispersion was modified to a conventional aqueous polyurethane photocurable dispersion.
Preparation of the general aqueous polyurethane photo-curing dispersion:
the preparation method comprises the steps of (1) carrying out grafting reaction on polycarbonate dihydric alcohol, dicyclohexylmethane diisocyanate and a hydrophilic chain extender, namely dimethylolbutyric acid for 4 hours at 70 ℃, and then mixing the mixture with water for emulsification and dispersion to obtain a common aqueous polyurethane photo-curing aqueous dispersion;
the other raw material components and parameters are the same as those of application example 1, and the waterborne polyurethane photo-curing coating is obtained.
Comparative example 2
The difference from application example 2 is that:
the photocurable aqueous dispersion was modified to the ordinary aqueous polyurethane photocurable dispersion in comparative example 1. The other raw material components and parameters are the same as those of application example 2, and the waterborne polyurethane photo-curing coating is obtained.
Comparative example 3
The difference from application example 3 is that:
the photocurable aqueous dispersion was modified to the ordinary aqueous polyurethane photocurable dispersion in comparative example 1. The other raw material components and parameters are the same as those of application example 3, and the waterborne polyurethane photo-curing coating is obtained.
The properties of the aqueous photocurable coatings obtained in application examples 1 to 5 and comparative examples 1 to 3 were examined, and the results of the examination are shown in Table 1.
Table 1 results of Performance test of aqueous photocurable coatings obtained in examples 1 to 5 and comparative examples 1 to 3
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The data of application example 1 and comparative example 1, application example 2 and comparative example 2, application example 3 and comparative example 3 show that the fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing aqueous dispersion obviously improves the oil resistance pen and steel wool resistance compared with the common aqueous polyurethane photo-curing dispersion.
The method is characterized in that a paint film prepared from the fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing aqueous dispersion is tested, the difference of the paint film before and after boiling resistance and steel wool resistance test data is small, the good performance of the paint film is reserved, the ordinary water-based polyurethane photo-curing dispersion has cracking conditions in different degrees after boiling, and the fluorine-containing epoxy-polyurethane-fullerene ternary structure photo-curing aqueous dispersion paint film is good and has no cracking conditions.
The difference in filler content affects the actual steel wool resistant data, but all steel wool resistant data are better than common waterborne polyurethane photo-curing dispersions.
In the reference application examples and the comparative examples, the stain resistance was tested after 200 turns of steel wool, in which the stain resistance of the fluorine-containing epoxy-polyurethane-fullerene ternary structure photocurable aqueous dispersion remained. Analysis as the length of the side chain increases, hydrophobic and oleophobic interactions are enhanced due to the presence of the fluoromonomer and the fullerene monomer, and the polymer-rich region becomes thicker, so that the oil-resistant pen performance can be maintained even after the paint film is worn through the grinding head.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A photo-curing water dispersion is prepared from raw materials including fluorine-containing epoxy-polyurethane structure prepolymer, hydroxyl fullerene monomer and hydrophilic chain extender through grafting reaction;
the fluorine-containing epoxy-polyurethane structure prepolymer is prepared by reacting raw materials comprising fluorine-containing epoxy monomers, anhydride and acrylic ester compounds;
the fluorine-containing epoxy monomer is obtained by reacting raw materials comprising fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide.
2. The aqueous photocurable dispersion according to claim 1, characterized in that the mass ratio of the fluorine-containing monomer, epichlorohydrin, sodium hydroxide and tetrabutylammonium hydroxide is 25 to 35: 53-78: 6-13: 7-18.
3. The aqueous photocurable dispersion according to claim 1, characterized in that the process for the preparation of the fluorine-containing epoxy monomer comprises the following steps:
a1 Stirring fluorine-containing monomer, epichlorohydrin and sodium hydroxide at 60-90 ℃ for reaction;
a2 Mixing the product solution obtained after the stirring reaction in the step a 1) with tetrabutylammonium hydroxide, and reacting at 60-90 ℃ to obtain the fluorine-containing epoxy monomer.
4. The aqueous photocurable dispersion of claim 1, wherein said anhydride comprises at least one of tetrahydrophthalic anhydride, phthalic anhydride, and cis-1, 2,3, 6-tetrahydrophthalic anhydride;
the acrylic ester compound comprises at least one of pentaerythritol triacrylate, trimethylolpropane triacrylate and dipentaerythritol hexaacrylate;
the mass ratio of the fluorine-containing epoxy monomer to the anhydride to the acrylic ester compound is 32-44: 17-33: 45-68.
5. The aqueous photocurable dispersion of claim 1, wherein said hydroxyfullerene monomer is obtained by mixing and reacting raw materials comprising fullerene, toluene, sodium hydroxide, tetrabutylammonium hydroxide and hydrogen peroxide.
6. The aqueous photocurable dispersion according to claim 1, characterized in that the process for the preparation of the hydroxyfullerene monomer comprises the following steps:
b1 Dissolving fullerene in toluene solution to obtain fullerene solution;
b2 And (3) uniformly stirring the fullerene solution, sodium hydroxide and tetrabutylammonium hydroxide, then mixing with hydrogen peroxide, and stirring for reaction to obtain the hydroxy fullerene monomer.
7. The photocurable aqueous dispersion according to claim 6, characterized in that,
in the step b 1) of the process,
the mass concentration of the toluene solution is 2% -16%;
the dosage ratio of the fullerene to the toluene solution is 1-8 mg: 1-50 mL;
the dissolution temperature is 60-80 ℃;
in the step b 2) of the process,
the mass ratio of the fullerene solution to the sodium hydroxide to the tetrabutyl ammonium hydroxide to the hydrogen peroxide is 1-10: 12-22: 7-16: 2 to 14; the mass concentration of the hydrogen peroxide is 7% -14%;
the step b 2) is carried out at 60 to 80 ℃.
8. The photocurable aqueous dispersion according to claim 1, characterized in that the mass ratio of the fluorine-containing epoxy-polyurethane structural prepolymer, the hydroxy fullerene monomer and the hydrophilic chain extender is 20 to 45g: 3-12 mg: 3-10 g;
the hydrophilic chain extender comprises at least one of dimethylolpropionic acid, dimethylolbutyric acid, sodium ethylenediamine-based ethanesulfonate and N-methyldiethanolamine.
9. A process for preparing the aqueous photocurable dispersion according to any one of claims 1-8, comprising the steps of:
and (3) carrying out grafting reaction on the fluorine-containing epoxy-polyurethane structure prepolymer, the hydroxyl fullerene monomer and the hydrophilic chain extender at 60-90 ℃ to obtain the photo-curing aqueous dispersion.
10. The photo-curing water dispersion paint is prepared from the following raw materials in parts by weight:
the aqueous photocurable dispersion is an aqueous photocurable dispersion as recited in any one of claims 1-8 or an aqueous photocurable dispersion produced by the production process recited in claim 9.
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