CN112266457B - Photocuring hydrophilic polyurea nano particle and preparation method and application thereof - Google Patents
Photocuring hydrophilic polyurea nano particle and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention discloses a photocuring hydrophilic polyurea nano particle and a preparation method and application thereof, wherein the photocuring hydrophilic polyurea nano particle comprises the following components: 10-43 parts of diamine, 13-40 parts of isocyanate, 50-150 parts of solvent, 2-15 parts of acrylate with hydroxyl, 2-15 parts of hydrophilic agent, 0.02-0.5 part of catalyst and 0.02-0.5 part of polymerization inhibitor. The invention prepares the polyurea nano particles with the photocuring function by reacting diamine and isocyanate to form polyurea and adding the hydroxyl acrylate end-capping and hydrophilic agent, overcomes the influence of organic microspheres and inorganic nano particles which are widely applied at present on the optical performance of the coating, and the coating prepared from the photocuring hydrophilic polyurea nano particles not only has better optical performance, but also can provide better wear-resistant scratch-resistant, hydrophilic and antifogging functions for the coating.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to photocuring hydrophilic polyurea nanoparticles and a preparation method and application thereof.
Background
The antifogging material is more and more widely applied to medical equipment, electronic products, automobile glass and the like, and the requirement is higher and higher. Has strict requirements on the performances of the antifogging material such as abrasion resistance, scratch resistance, solvent resistance, water resistance and the like. At present, organic microspheres are more and more popular in the application aspect of coatings, can provide functions of abrasion resistance, scratch resistance and the like for the coatings, but the particle size of the microspheres at the micron level is easy to cause extinction of the coatings, seriously influences the transparency of the coatings and has great influence on the optical performance of the coatings. Inorganic nanoparticles widely applied in the market, such as nano silicon oxide, nano aluminum oxide and the like, generally have higher refractive index, and have larger difference with the refractive index of organic components of the coating, so that the optical transmittance of the coating is seriously influenced, and meanwhile, the inorganic nanoparticles are poor in compatibility with the organic components and are easy to precipitate.
However, organic nanoparticles are very rare in the market, organic nanoparticles with photocuring function are more rare, and photocuring materials are more and more widely applied to coatings due to the advantages of environmental protection, high performance and the like, so that the research on hydrophilic antifogging organic nanoparticles with photocuring function is very important.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the photocuring hydrophilic polyurea nano particles, and the polyurea nano particles not only can provide good optical performance and wear-resisting and scratch-resisting performance for the coating, but also can provide the functions of super-hydrophilicity, fog prevention and the like.
The invention also aims to provide a preparation method of the photocuring hydrophilic polyurea nano particles.
The invention is realized by the following technical scheme:
the photocuring hydrophilic polyurea nano particle comprises the following components in parts by weight:
10-43 parts of diamine
13-40 parts of isocyanate
50-150 parts of solvent
2-15 parts of acrylate with hydroxyl
2-15 parts of hydrophilic agent
0.02-0.5 part of catalyst
0.02-0.5 part of polymerization inhibitor.
Preferably, the diamine is one or a mixture of several of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, p-phenylenediamine, 4-diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophoronediamine or dodecyldiamine, and preferably one or a mixture of several of 4, 4-diaminodicyclohexylmethane, 3-dimethyl-4, 4-diaminodicyclohexylmethane or isophoronediamine.
Preferably, the isocyanate is diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, p-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, one or more of m-xylylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, naphthalene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and hexamethylene diisocyanate biuret.
Preferably, the solvent is one or a mixture of several of toluene, xylene, cyclohexane, methylcyclohexane, ethyl acetate, butyl acetate, butanone and diformate.
Preferably, the hydroxyl-bearing acrylate is one or a mixture of caprolactone acrylate, caprolactone methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate, and preferably is hydroxyethyl acrylate or hydroxypropyl acrylate.
Preferably, the hydrophilic agent is one or a mixture of more of hydroxyl sulfonate, amino sulfonate, carboxylate with hydroxyl, carboxylate with amino, hydroxyl or amino sulfonic acid and carboxyl with hydroxyl or amino, preferably one or a mixture of more of 3-hydroxypropanesulfonic acid, hydroxyethyl sodium sulfonate, 4-hydroxybutyl sulfonic acid, 4-hydroxybutyl sodium sulfonate, cyclohexyl sodium sulfamate, ethylene diamine ethyl sodium sulfonate, hexamethylene diamine sodium already carboxylate, aminocyclohexanecarboxylic acid or 3-hydroxypropionic acid.
Preferably, the catalyst is one or a mixture of several of an organic tin catalyst and an organic bismuth catalyst; the polymerization inhibitor is one or a mixture of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
The particle size of the polyurea particles can be adjusted by controlling the molar ratio of diamine to isocyanate, preferably, the molar ratio of diamine to isocyanate is 1: 2-9: 10, respectively.
Preferably, the particle size of the photocuring hydrophilic polyurea nano particles is less than 400nm, the particle size is controlled to be less than 400nm, and the coating prepared from the photocuring hydrophilic polyurea nano particles is high in transparency.
The invention also provides a preparation method of the photocuring hydrophilic polyurea nano particle, which comprises the following steps:
(1) adding a solvent into a reaction device according to the proportion, adding isocyanate, uniformly stirring, simultaneously cooling to-10-20 ℃, dropwise adding diamine, controlling the temperature to be less than 30 ℃, preserving heat after dropwise adding is finished, and dispersing at a high speed for 1-2 hours;
(2) adding a catalyst, a polymerization inhibitor and acrylate with hydroxyl, heating to 60-100 ℃, and preserving heat for 1-2 hours;
(3) adding a hydrophilic agent, and keeping the temperature for 1-2 hours at 60-100 ℃;
(4) cooling, filtering to obtain a filter cake, cleaning the filter cake, filtering again, drying and crushing to obtain the photocuring hydrophilic polyurea nano particles.
The invention also provides application of the photocuring hydrophilic polyurea nano particles in optical coatings.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares hydrophilic polyurea nano particles with photocuring function by reacting diamine and isocyanate to form polyurea and adding hydroxyl acrylate end capping and hydrophilic agent, overcomes the influence of organic microspheres and inorganic nano particles which are widely applied at present on the optical performance of a coating, and the particle size of the photocuring hydrophilic polyurea nano particles is less than 400 nm.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials adopted by the invention can be obtained commercially.
Example 1:
adding 100 parts of toluene/butanone (in a weight ratio of 1: 2) into a reactor, adding 30 parts of isophorone diisocyanate, stirring and dispersing while cooling to-10 ℃, dropwise adding 18.2 parts of isophorone diamine, controlling the temperature to be less than 10 ℃, preserving heat after dropwise adding, and dispersing at a high speed for 2 hours; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 3 parts of hydroxyethyl acrylate, heating to 70 ℃, and keeping the temperature for 2 hours; adding 3.2 parts of 4-hydroxybutyl sulfonic acid, heating to 90 ℃, and preserving heat for 2 hours; cooling to room temperature, filtering, adding 50 parts of toluene/butanone (weight ratio 1: 2) into the filter cake, performing ultrasonic dispersion, filtering, and drying to obtain the photocuring hydrophilic polyurea nanoparticles SUA-1.
Example 2:
adding 100 parts of methylcyclohexane/butyl acetate (weight ratio is 1: 1) into a reactor, adding 36 parts of dicyclohexyl methane diisocyanate, stirring and dispersing while cooling to-10 ℃, dropwise adding 16.1 parts of isophorone diamine, controlling the temperature to be less than 10 ℃, keeping the temperature and dispersing at high speed for 2 hours after dropwise adding is finished; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 3.5 parts of hydroxybutyl acrylate, heating to 70 ℃, and preserving heat for 2 hours; adding 5 parts of sodium cyclamate, and keeping the temperature at 70 ℃ for 2 hours; cooling to room temperature, filtering, adding 50 parts of methylcyclohexane/butyl acetate (the total weight ratio is 1: 2) into the filter cake, performing ultrasonic dispersion, filtering and drying to obtain the photocuring hydrophilic polyurea nano particles SUA-2.
Example 3:
adding 125 parts of toluene/butyl acetate (mass ratio is 1: 2) into a reactor, adding 25 parts of hexamethylene diisocyanate, stirring and dispersing while cooling to 0 ℃, dropwise adding 26.8 parts of dodecanediamine, controlling the temperature to be less than 15 ℃, preserving heat after dropwise adding, and dispersing at high speed for 1.5 hours; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 4 parts of caprolactone acrylate, heating to 80 ℃, and preserving heat for 2 hours; adding 5 parts of sodium hexamethylene dicarboxylate, and keeping the temperature at 80 ℃ for 2 hours; cooling to room temperature, filtering, adding 50 parts of toluene/butyl acetate (mass ratio of 1: 2) into the filter cake, performing ultrasonic dispersion, filtering and drying to obtain the photocuring hydrophilic polyurea nano particles SUA-3.
Example 4:
adding 135 parts of cyclohexane/butyl acetate (mass ratio is 1: 1) into a reactor, adding 30 parts of 2, 4-toluene diisocyanate, stirring and dispersing while cooling to 10 ℃, dropwise adding 16 parts of hexamethylenediamine, controlling the temperature to be less than 20 ℃, preserving heat, and dispersing at a high speed for 2 hours; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 2.9 parts of hydroxypropyl acrylate, heating to 90 ℃, and preserving heat for 1.5 hours; adding 6.8 parts of ethylenediamine ethyl sodium sulfonate, and keeping the temperature at 75 ℃ for 2 hours; cooling to room temperature, filtering, adding 50 parts of cyclohexane/butyl acetate (mass ratio of 1: 1) into the filter cake, performing ultrasonic dispersion, filtering and drying to obtain the photocuring hydrophilic polyurea nano particles SUA-4.
Example 5:
adding 150 parts of toluene/diformate (mass ratio is 1: 2) into a reactor, adding 22 parts of p-phenylene diisocyanate, stirring and dispersing, simultaneously cooling to-10 ℃, dropwise adding 28.6 parts of 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, controlling the temperature to be less than 30 ℃, keeping the temperature, and dispersing at high speed for 1 hour; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 4 parts of hydroxyethyl acrylate, heating to 70 ℃, and keeping the temperature for 2 hours; adding 5 parts of sodium cyclamate, and keeping the temperature at 85 ℃ for 1.5 hours; cooling to room temperature, filtering, adding 50 parts of toluene/diformate (mass ratio is 1: 2) into the filter cake, performing ultrasonic dispersion, filtering and drying to obtain the photocuring hydrophilic polyurea nano particles SUA-5.
Comparative example 1:
100 parts of toluene/butanone (mass ratio is 1: 2) are added into a reactor, 32.7 parts of isophorone diisocyanate are added, the temperature is reduced to-10 ℃ while stirring and dispersing, 20 parts of isophorone diamine is dripped, the temperature is controlled to be less than 10 ℃, heat preservation is carried out after the dripping is finished, and high-speed dispersion is carried out for 2 hours; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 6.8 parts of hydroxyethyl acrylate, heating to 70 ℃, and preserving heat for 2 hours; cooling to room temperature, filtering, adding 50 parts of toluene/butanone (mass ratio 1: 2) into the filter cake, performing ultrasonic dispersion, filtering, and drying to obtain the photocuring polyurea nanoparticles UA-1.
Comparative example 2:
100 parts of toluene/butanone (mass ratio is 1: 2) are added into a reactor, 32.7 parts of isophorone diisocyanate are added, the temperature is reduced to-10 ℃ while stirring and dispersing, 20 parts of isophorone diamine is dripped, the temperature is controlled to be less than 10 ℃, heat preservation is carried out after the dripping is finished, and high-speed dispersion is carried out for 2 hours; adding 0.1 part of organic tin catalyst, heating to 70 ℃, and keeping the temperature for 2 hours; cooling to room temperature, filtering, adding 50 parts of toluene/butanone (1: 2) into the filter cake, performing ultrasonic dispersion, filtering, and drying to obtain polyurea microsphere particles UA-2.
Comparative example 3:
adding 100 parts of toluene/butanone (the total amount ratio is 1: 2) into a reactor, adding 30 parts of isophorone diisocyanate, stirring and dispersing, simultaneously cooling to-10 ℃, dropwise adding 22.8 parts of isophorone diamine, controlling the temperature to be less than 10 ℃, preserving heat, and dispersing at high speed for 2 hours after dropwise adding; adding 0.2 part of p-hydroxyanisole, 0.1 part of organic tin catalyst and 1 part of hydroxyethyl acrylate, heating to 70 ℃, and keeping the temperature for 2 hours; adding 1.8 parts of 4-hydroxybutyl sulfonic acid, heating to 90 ℃, and preserving heat for 2 hours; cooling to room temperature, filtering, adding 50 parts of toluene/butanone (the total amount is 1: 2) into the filter cake, performing ultrasonic dispersion, filtering and drying to obtain the photocuring hydrophilic polyurea nanoparticles SUA-6.
The polyurea nanoparticles prepared in examples 1-5 and comparative examples 1-3 were prepared into a coating according to the formulation in table 1, and the coating was roll-coated on a PET film, baked at 80 ℃ for 5 minutes, cured by 365nm uv light, with energy of 600mj, and a dry film thickness of 12 um. The coatings were tested for performance and the results are shown in table 2.
TABLE 1 coating composition (mass ratio)
Table 2 test results of the coatings of examples and comparative examples
As can be seen from the results of the examples and comparative examples in Table 2, the hydrophilic photo-curable polyurea nanoparticles prepared by the invention through the reaction of diamine and isocyanate to form polyurea and the addition of the hydroxyl-containing acrylate end-capping agent and the hydrophilic agent have small particle size and high transparency, and can provide better wear-resistant and scratch-resistant functions for the coating. In comparative example 1, where an acrylate group was introduced, but no hydrophilic agent was introduced, the water contact angle of the coating was significantly higher than that of the examples. In comparative example 2, no acrylate group and no hydrophilic agent were introduced, and the water contact angle and the weight loss after abrasion of the coating were significantly higher than those of the examples. In comparative example 3, although an acrylate group and a hydrophilic agent were introduced, the polyurea particles had a large particle size and the light transmittance was significantly lower than in the examples.
Each performance test method or standard:
weight loss rate of the coating after grinding: national standard GBT 1768-;
light transmittance: national standard G B/T2410-2008.
Claims (11)
1. The photocuring hydrophilic polyurea nano particle is characterized by comprising the following components in parts by weight:
10-43 parts of diamine
13-40 parts of isocyanate
50-150 parts of solvent
2-15 parts of acrylate with hydroxyl
2-15 parts of hydrophilic agent
0.02-0.5 part of catalyst
0.02-0.5 part of polymerization inhibitor
The molar ratio of diamine to isocyanate is 1: 2-9: 10 is between;
the particle size of the photocuring hydrophilic polyurea nano particles is less than 400 nm.
2. The photo-curable hydrophilic polyurea nanoparticles of claim 1, wherein: the diamine is one or more of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, p-phenylenediamine, 4' -diaminodicyclohexylmethane, 3' -dimethyl-4, 4' -diaminodicyclohexylmethane, isophoronediamine or dodecanediamine.
3. The photo-curable hydrophilic polyurea nanoparticles of claim 2, wherein: the diamine is one or more of 4, 4' -diaminodicyclohexyl methane, 3' -dimethyl-4, 4' -diaminodicyclohexyl methane or isophorone diamine.
4. The photo-curable hydrophilic polyurea nanoparticles of claim 1, wherein: the isocyanate is diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, tetramethyl m-phenylene diisocyanate, one or a mixture of more of m-xylylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene diisocyanate, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer or hexamethylene diisocyanate biuret.
5. The photo-curable hydrophilic polyurea nanoparticles of claim 1, wherein: the acrylate with hydroxyl group is one or a mixture of caprolactone acrylate, caprolactone methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate.
6. The photo-curable hydrophilic polyurea nanoparticles of claim 5, wherein: the hydroxyl-bearing acrylate is hydroxyethyl acrylate or hydroxypropyl acrylate.
7. The photo-curable hydrophilic polyurea nanoparticles of claim 1, wherein: the hydrophilic agent is one or a mixture of more of hydroxyl sulfonate, amidosulfonate, carboxylate with hydroxyl, carboxylate with amidoamine, hydroxyl or amidosulfonic acid and hydroxyl or amidocarboxylic acid.
8. The photo-curable hydrophilic polyurea nanoparticles of claim 7, wherein: the hydrophilic agent is one or a mixture of more of 3-hydroxypropanesulfonic acid, sodium isethionate, 4-hydroxybutyl sulfonic acid, 4-hydroxybutyl sodium sulfonate, sodium cyclohexylsulfamate, ethylene diamine ethyl sulfonate, sodium hexamethylene dicarboxylate, aminocyclohexanecarboxylic acid or 3-hydroxypropionic acid.
9. The photo-curable hydrophilic polyurea nanoparticles of claim 1, wherein: the solvent is one or a mixture of more of toluene, xylene, cyclohexane, methylcyclohexane, ethyl acetate, butyl acetate, butanone or diformate; the catalyst is one or a mixture of more of an organic tin catalyst and an organic bismuth catalyst; the polymerization inhibitor is one or a mixture of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
10. The method for preparing photo-curing hydrophilic polyurea nanoparticles according to any one of claims 1 to 9, wherein: the method comprises the following steps:
(1) adding a solvent into a reaction device according to the proportion, adding isocyanate, uniformly stirring, simultaneously cooling to-10-20 ℃, dropwise adding diamine, controlling the temperature to be less than 30 ℃, preserving heat after dropwise adding is finished, and dispersing at a high speed for 1-2 hours;
(2) adding a catalyst, a polymerization inhibitor and acrylate with hydroxyl, heating to 60-100 ℃, and preserving heat for 1-2 hours;
(3) adding a hydrophilic agent, and keeping the temperature for 1-2 hours at 60-100 ℃;
(4) cooling, filtering to obtain a filter cake, cleaning the filter cake, filtering again, drying and crushing to obtain the photocuring hydrophilic polyurea nano particles.
11. Use of the photo-curable hydrophilic polyurea nanoparticles according to any one of claims 1 to 9 in optical coatings.
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