Nano titanium dioxide composite material dispersant, preparation method and application thereof
Technical Field
The invention relates to the field of nano composite materials, in particular to a nano titanium dioxide composite material dispersant, a preparation method and application thereof.
Background
The current spectacle lenses on the market are mainly made of two materials, namely glass and resin. The glass spectacle lens is scratch-resistant compared with the resin lens, but has a relatively high refractive index, is much heavier than the resin lens, and is fragile and not durable. The resin spectacle lens is from conifer plants, is a polymer mixture consisting of a plurality of hydrocarbon secretions, is light in weight compared with a glass lens, but has a non-wear-resistant surface and is easy to scratch.
The surface of the lens made of glass or resin can generate static electricity, so that pollutants such as dust, particles and the like in the air are deposited on the surface of the lens, the lens needs to be frequently wiped when in use, and the surface of the lens is easily fogged in winter, so that the sight is blocked; some common spectacle lenses cannot filter out ultraviolet rays, cannot absorb the ultraviolet rays sufficiently, and damage eye health after being worn for a long time.
TiO2The film has super-hydrophilicity and super-permanence under illumination, so that the film has an antifogging function, and the nano TiO has the advantages of2Has strong super-hydrophilic property, is not easy to form water drops on the surface, and is nano TiO2Can react with hydrocarbon under the irradiation of visible lightThe organic pollutants adsorbed on the surface of the titanium dioxide can be decomposed into CO by the photocatalysis of the titanium oxide2And O2And a self-cleaning function is realized.
Disclosure of Invention
The invention aims to solve the problems that static electricity is easy to generate on the surface of a lens, fogging is easy to occur and ultraviolet rays cannot be absorbed in the prior art, and provides a preparation method of a nano titanium dioxide composite material dispersing agent suitable for spectacle lenses.
The invention also aims to provide a method for applying the nano titanium dioxide composite material dispersant to the preparation of the self-cleaning spectacle lens.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano titanium dioxide composite material dispersant comprises the following steps:
s1, tetrabutyl titanate and absolute ethyl alcohol are mixed according to a volume ratio of 1: (5-10) mixing to obtain a mixed solution A;
s2, mixing absolute ethyl alcohol and 2-4 mol/L hydrochloric acid according to a volume ratio of (10-18): (0.1-0.5) mixing to obtain a mixed solution B;
s3, dropwise adding the mixed solution B into the mixed solution A, wherein the volume of the added mixed solution B is the same as that of the mixed solution A; stirring at a rotating speed of 200-300 r/min in the dripping process; after the dropwise adding is finished, performing ultrasonic treatment at the temperature of 30-40 ℃ for 20-40 min; cooling for 2-4 h to obtain TiO2A dispersant;
s4, the TiO obtained in the step S32Putting the dispersing agent into a container at 200-250 ℃ for heat preservation for 1-3 h, then preserving heat at 500-550 ℃ for 1-2 h, cooling to room temperature, and grinding to obtain nano TiO2;
S5, the nano TiO obtained in the step S42Dissolving in deionized water to obtain nano TiO2Sol;
s6, adding Pr (NO) in step S53)3、Eu(NO3)3And Tb (NO)3)3Obtaining mixed gel, wherein Pr (NO)3)3Is the mass ofNano TiO in S420.01 to 0.03% of (1), Eu (NO)3)3Is nano TiO 4 in step S420.02-0.05% of (A), Tb (NO)3)3Is nano TiO 4 in step S420.02-0.04%;
s7, placing the mixed gel obtained in the step S6 into a container at 200-250 ℃ for heat preservation for 1-3 h, then preserving heat at 500-550 ℃ for 1-2 h, cooling to room temperature, and grinding to obtain Pr-Eu-Tb co-doped nano TiO2;
S8, doping the Pr-Eu-Tb co-doped nano TiO obtained in the step S72Dissolving the obtained product in absolute ethyl alcohol to obtain 0.01-0.03 g/mL Pr-Eu-Tb co-doped nano TiO2A dispersant.
Preferably, Pr (NO) in the step S63)3Is nano TiO 4 in step S420.01 to 0.02% of (1), Eu (NO)3)3Is nano TiO 4 in step S420.03 to 0.04% of (B), Tb (NO)3)3Is nano TiO 4 in step S420.03 to 0.04 percent of the total amount of the active carbon.
Preferably, the mixed gel in the step S7 is placed at 220-250 ℃ for heat preservation for 2.5h, and then at 520 ℃ for heat preservation for 1.5 h.
The invention provides a nano titanium dioxide composite material dispersing agent prepared by the preparation method.
Preferably, the nano titanium dioxide composite material dispersing agent is suitable for preparing self-cleaning spectacle lenses.
The invention also provides a method for preparing the self-cleaning spectacle lens by adopting the nano titanium dioxide composite material dispersing agent, which comprises the following steps:
s01, preparing a polycarbonate substrate;
s02, soaking the polycarbonate substrate obtained in the step S01 in deionized water for 1-3 h; soaking the mixture for 5 to 10 minutes by using 5 to 10 percent hydrogen peroxide;
s03, soaking the polycarbonate substrate processed in the step S02 into a dispersing agent containing the nano titanium dioxide composite material for 5-15S, and then drying in vacuum to obtain the nano titanium dioxide composite material.
Preferably, in the step S02, the polycarbonate substrate is soaked in deionized water for 1.2 to 2.2 hours.
Preferably, in the step S03, the time for immersing the polycarbonate substrate into the nano titanium dioxide composite material dispersing agent is 8-12S.
Preferably, the polycarbonate substrate comprises the following components in parts by weight: 90-120 parts of polycarbonate, 0.5-2.5 parts of phenyl salicylate, 1-1.5 parts of 2-ethylhexyl diphenyl phosphate, 20-40 parts of cellulose nitrate, 0.1-0.5 part of polyglycerol fatty acid ester, 10-30 parts of toluene, 2-4 parts of N-methyl pyrrolidone, 70-90 parts of plasticizer, 4-6 parts of calcium stearate, 0.2-0.4 part of barium perchlorate and 25-28 parts of coupling agent.
Preferably, the polycarbonate substrate comprises the following components in parts by weight: 100 parts of polycarbonate, 2 parts of phenyl salicylate, 1.2 parts of 2-ethylhexyl diphenyl phosphate, 30 parts of cellulose nitrate, 0.3 part of polyglycerol fatty acid ester, 23 parts of toluene, 3 parts of N-methyl pyrrolidone, 85 parts of plasticizer, 5 parts of calcium stearate, 0.3 part of barium perchlorate and 27 parts of coupling agent.
Preferably, the method for preparing the polycarbonate substrate comprises the following steps:
s11, mixing and stirring polycarbonate, phenyl salicylate, 2-ethylhexyl diphenyl phosphate, cellulose nitrate, polyglycerol fatty acid ester, toluene, N-methyl pyrrolidone and a plasticizer uniformly according to a proportion;
s12, putting the raw materials uniformly stirred in the step S11 into a kneader, and mixing for 70-120 min;
s13, melting and granulating the raw materials mixed in the step S12 by using a double-screw extruder, wherein the temperature of the extruder is set as follows: the first area is 165-175 ℃; the second zone is 185-205 ℃; a third zone is 210-215 ℃; the fourth zone is 225-230 ℃; and fifthly, molding at the temperature of 250-255 ℃, the head temperature of 270 ℃, the screw rotation speed of 90-100 r/min and the temperature of 280-300 ℃.
The invention forms a layer of Pr-Eu-Tb co-doped nano TiO on the surface of the polycarbonate glasses base material2Film, Pr-Eu-Tb co-doped nano TiO2Has better absorption function to ultraviolet light, and improves the filtering function of the spectacle lens to the ultraviolet light. Formed otherwise on the surface of the substrateThe composite nanometer film has strong mechanical performance and can avoid the abrasion of the spectacle lens. And the formed Pr-Eu-Tb co-doped nano TiO2The film has good antistatic ability, reduces the adsorption of dust, and the lens can keep a clean state for a long time.
Compared with the prior art, the invention has the following technical effects:
the invention provides a preparation method of a nano titanium dioxide composite material dispersing agent suitable for spectacle lenses, which adopts polycarbonate as a spectacle lens base material, and a layer of Pr-Eu-Tb co-doped nano TiO is coated on the base material in a calcining way2Film, Pr-Eu-Tb co-doped nano TiO2Has better absorption function to ultraviolet light, and improves the filtering function of the spectacle lens to the ultraviolet light. In addition, the composite nanometer film formed on the surface of the base material has stronger mechanical property, so that the abrasion of the spectacle lens can be avoided. And the formed Pr-Eu-Tb co-doped nano TiO2The film has good antistatic ability, reduces the adsorption of dust, and the lens can keep a clean state for a long time.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A preparation method of a nano titanium dioxide composite material dispersing agent suitable for spectacle lenses comprises the following steps:
s1, tetrabutyl titanate and absolute ethyl alcohol are mixed according to a volume ratio of 1: 5, mixing to obtain a mixed solution A;
s2, mixing absolute ethyl alcohol and 2mol/L hydrochloric acid according to a volume ratio of 10: 0.5, obtaining a mixed solution B;
s3, dropwise adding the mixed solution B into the mixed solution A, wherein the volume of the added mixed solution B is the same as that of the mixed solution A; stirring at the rotating speed of 200r/min in the dripping process; dripping deviceAfter the addition is finished, performing ultrasonic treatment for 20min at 40 ℃; cooling for 4h to obtain TiO2A dispersant;
s4, the TiO obtained in the step S32The dispersing agent is put into the room temperature environment and is insulated for 1h at 200 ℃, then is insulated for 2h at 550 ℃, and is cooled to room temperature to grind the nano TiO2;
S5, the nano TiO obtained in the step S42Dissolving in deionized water to obtain nano TiO2Sol;
s6, adding Pr (NO) in step S53)3、Eu(NO3)3And Tb (NO)3)3Obtaining mixed gel, wherein Pr (NO)3)3Is nano TiO 4 in step S420.01% of (1), Eu (NO)3)3Is nano TiO 4 in step S420.05% of (A), Tb (NO)3)3Is the nano TiO in the step S420.04% of;
s7, putting the mixed gel obtained in the step S6 into a container at 200 ℃ for heat preservation for 1h, then preserving heat at 550 ℃ for 2h, and grinding to obtain Pr-Eu-Tb co-doped nano TiO2;
S8, doping the Pr-Eu-Tb co-doped nano TiO obtained in the step S72Dissolving in absolute ethyl alcohol to obtain 0.03g/mL Pr-Eu-Tb co-doped nano TiO2A dispersant.
A method for preparing the self-cleaning spectacle lens by adopting the nano titanium dioxide composite material dispersant comprises the following steps:
s01, preparing a polycarbonate substrate;
s02, soaking the polycarbonate substrate obtained in the step S01 in deionized water for 1 h; soaking in 5% hydrogen peroxide for 5 min;
s03, the polycarbonate substrate processed in the step S02 is immersed in the dispersing agent containing the nano titanium dioxide composite material for 5S, and then dried under the vacuum condition.
The polycarbonate substrate comprises the following components in parts by weight: 120 parts of polycarbonate, 0.5 part of phenyl salicylate, 1.5 parts of 2-ethylhexyl diphenyl phosphate, 20 parts of cellulose nitrate, 0.5 part of polyglycerol fatty acid ester, 10 parts of toluene, 4 parts of N-methyl pyrrolidone, 70 parts of plasticizer, 4 parts of calcium stearate, 0.4 part of barium perchlorate and 25 parts of coupling agent.
The preparation method of the polycarbonate substrate comprises the following steps:
s11, mixing and stirring polycarbonate, phenyl salicylate, 2-ethylhexyl diphenyl phosphate, cellulose nitrate, polyglycerol fatty acid ester, toluene, N-methyl pyrrolidone and a plasticizer uniformly according to a proportion;
s12, putting the raw materials uniformly stirred in the step S11 into a kneader, and mixing for 120 min;
s13, melting and granulating the raw materials mixed in the step S12 by using a double-screw extruder, wherein the temperature of the extruder is set as follows: the first area is 165-175 ℃; the second zone is 185-205 ℃; a third zone is 210-215 ℃; the fourth zone is 225-230 ℃; and fifthly, molding at the temperature of 250-255 ℃, the head temperature of 270 ℃, the screw rotation speed of 90-100 r/min and the temperature of 280-300 ℃.
Example 2
A preparation method of a nano titanium dioxide composite material dispersing agent suitable for spectacle lenses comprises the following steps:
s1, tetrabutyl titanate and absolute ethyl alcohol are mixed according to a volume ratio of 1: 10, mixing to obtain a mixed solution A;
s2, mixing absolute ethyl alcohol and 4mol/L hydrochloric acid according to a volume ratio of 18: 0.5, obtaining a mixed solution B;
s3, dropwise adding the mixed solution B into the mixed solution A, wherein the volume of the added mixed solution B is the same as that of the mixed solution A; stirring at the rotating speed of 300r/min in the dripping process; after the dropwise addition is finished, performing ultrasonic treatment at 30 ℃ for 4 min; cooling for 2h to obtain TiO2A dispersant;
s4, the TiO obtained in the step S32The dispersing agent is placed at 250 ℃ for heat preservation for 1-3 h, then at 500 ℃ for heat preservation for 1-2 h, the mixture is cooled to room temperature, and the nano TiO is obtained by grinding2;
S5, the nano TiO obtained in the step S42Dissolving in deionized water to obtain nano TiO2Sol;
s6, adding Pr (NO) in step S53)3、Eu(NO3)3And Tb (NO)3)3Obtaining mixed gel, wherein Pr (NO)3)3Is nano TiO 4 in step S420.03% of (1), Eu (NO)3)3Is nano TiO 4 in step S420.02% of (1), Tb (NO)3)3Is the nano TiO in the step S420.02-0.04%;
s7, putting the mixed gel obtained in the step S6 into a container at 200-250 ℃ for heat preservation for 1-3 h, and then preserving heat at 500-550 ℃ for 1-2 h to obtain Pr-Eu-Tb co-doped nano TiO2;
S8, doping the Pr-Eu-Tb co-doped nano TiO obtained in the step S72Dissolving the obtained product in absolute ethyl alcohol to obtain 0.01-0.03 g/mL Pr-Eu-Tb co-doped nano TiO2A dispersant.
A method for preparing the self-cleaning spectacle lens by adopting the nano titanium dioxide composite material dispersant comprises the following steps:
s01, preparing a polycarbonate substrate;
s02, soaking the polycarbonate substrate obtained in the step S01 in deionized water for 3 hours; soaking in 10% hydrogen peroxide for 10 min;
s03, the polycarbonate substrate processed in the step S02 is immersed in the dispersing agent containing the nano titanium dioxide composite material for 15S, and then dried under the vacuum condition.
The polycarbonate substrate comprises the following components in parts by weight: 90 parts of polycarbonate, 2.5 parts of phenyl salicylate, 1 part of 2-ethylhexyl diphenyl phosphate, 40 parts of cellulose nitrate, 0.1 part of polyglycerol fatty acid ester, 30 parts of toluene, 2 parts of N-methyl pyrrolidone, 90 parts of plasticizer, 6 parts of calcium stearate, 0.2 part of barium perchlorate and 28 parts of coupling agent.
The preparation method of the polycarbonate substrate comprises the following steps:
s11, mixing and stirring polycarbonate, phenyl salicylate, 2-ethylhexyl diphenyl phosphate, cellulose nitrate, polyglycerol fatty acid ester, toluene, N-methyl pyrrolidone and a plasticizer uniformly according to a proportion;
s12, putting the raw materials uniformly stirred in the step S11 into a kneader, and mixing for 120 min;
s13, melting and granulating the raw materials mixed in the step S12 by using a double-screw extruder, wherein the temperature of the extruder is set as follows: the first area is 165-175 ℃; the second zone is 185-205 ℃; a third zone is 210-215 ℃; the fourth zone is 225-230 ℃; and fifthly, molding at the temperature of 250-255 ℃, the head temperature of 270 ℃, the screw rotation speed of 90-100 r/min and the temperature of 280-300 ℃.
Example 3
A preparation method of a nano titanium dioxide composite material dispersing agent suitable for spectacle lenses comprises the following steps:
s1, tetrabutyl titanate and absolute ethyl alcohol are mixed according to a volume ratio of 1: 8, mixing to obtain a mixed solution A;
s2, mixing absolute ethyl alcohol and concentrated hydrochloric acid according to a volume ratio of 14: 0.3, obtaining a mixed solution B;
s3, dropwise adding the mixed solution B into the mixed solution A, wherein the volume of the added mixed solution B is the same as that of the mixed solution A; stirring at a rotating speed of 250r/min in the dripping process; after the dropwise addition is finished, performing ultrasonic treatment at 30 ℃ for 4 min; cooling for 2h to obtain TiO2A dispersant;
s4, the TiO obtained in the step S32The dispersing agent is put into the room temperature at 250 ℃ for heat preservation for 1-3 h, then the heat preservation is carried out for 1-2 h at 500 ℃, and the mixture is cooled to room temperature2;
S5, the nano TiO obtained in the step S42Dissolving in deionized water to obtain nano TiO2Sol;
s6, adding Pr (NO) in step S53)3、Eu(NO3)3And Tb (NO)3)3Obtaining mixed gel, wherein Pr (NO)3)3Is nano TiO 4 in step S420.03% of (1), Eu (NO)3)3Is nano TiO 4 in step S420.02% of (1), Tb (NO)3)3Is the nano TiO in the step S420.03% of;
s7, putting the mixed gel obtained in the step S6 into a container at 200-250 ℃ for heat preservation for 2h, and then preserving heat at 520 ℃ for 1.5h to obtain Pr-Eu-Tb co-doped nano TiO2;
S8, doping the Pr-Eu-Tb co-doped nano TiO obtained in the step S72Dissolving in absolute ethyl alcohol to obtain 0.02g/mL Pr-Eu-Tb co-doped nano TiO2A dispersant.
A method for preparing the self-cleaning spectacle lens by adopting the nano titanium dioxide composite material dispersant comprises the following steps:
s01, preparing a polycarbonate substrate;
s02, soaking the polycarbonate substrate obtained in the step S01 in deionized water for 1.5 h; soaking in 8% hydrogen peroxide solution for 8 min;
s03, the polycarbonate substrate processed in the step S02 is immersed in the dispersing agent containing the nano titanium dioxide composite material for 10S, and then dried under the vacuum condition.
Preferably, the polycarbonate substrate comprises the following components in parts by weight: 90 parts of polycarbonate, 2.5 parts of phenyl salicylate, 1 part of 2-ethylhexyl diphenyl phosphate, 40 parts of cellulose nitrate, 0.1 part of polyglycerol fatty acid ester, 30 parts of toluene, 2 parts of N-methyl pyrrolidone, 90 parts of plasticizer, 6 parts of calcium stearate, 0.2 part of barium perchlorate and 28 parts of coupling agent.
The preparation method of the polycarbonate substrate comprises the following steps:
s11, mixing and stirring polycarbonate, phenyl salicylate, 2-ethylhexyl diphenyl phosphate, cellulose nitrate, polyglycerol fatty acid ester, toluene, N-methyl pyrrolidone and a plasticizer uniformly according to a proportion;
s12, putting the raw materials uniformly stirred in the step S11 into a kneader, and mixing for 120 min;
s13, melting and granulating the raw materials mixed in the step S12 by using a double-screw extruder, wherein the temperature of the extruder is set as follows: the first area is 165-175 ℃; the second zone is 185-205 ℃; a third zone is 210-215 ℃; the fourth zone is 225-230 ℃; and fifthly, molding at the temperature of 250-255 ℃, the head temperature of 270 ℃, the screw rotation speed of 90-100 r/min and the temperature of 280-300 ℃.
Comparative example 1
Compared with the example 3, the step S03 of the comparative example is that the nanometer TiO is codoped with Pr-Eu-Tb2Soaking in dispersant for 3 s. The rest is the same as in example 3.
Comparative example 2
Compared with the example 3, the step S03 of the comparative example is that the nanometer TiO is codoped with Pr-Eu-Tb2Soaking in dispersant for 20 s. The rest is the same as in example 3.
Comparative example 3
In comparison with example 3, this comparative example is performed in step S6 without adding Pr (NO)3)3. The rest is the same as in example 3.
Comparative example 4
In comparison with example 3, this comparative example is carried out in step S6 without adding Eu (NO)3)3. The rest is the same as in example 3.
Comparative example 5
In comparison with example 3, this comparative example was conducted without adding Tb (NO) in step S63)3. The rest is the same as in example 3.
Comparative example 6
In comparison with example 3, this comparative example is performed in step S6 without adding Pr (NO)3)3And Eu (NO)3)3. The rest is the same as in example 3.
Comparative example 7
In comparison with example 3, this comparative example is performed in step S6 without adding Pr (NO)3)3And Tb (NO)3)3. The rest is the same as in example 3.
Comparative example 8
In comparison with example 3, the step S6 of this comparative example is to add Eu (NO)3)3And Tb (NO)3)3. The rest is the same as in example 3.
Examples of the experiments
1. The hardness of each of the examples, comparative examples and polycarbonate substrates was measured using a MINILOAD model 2 microhardness tester from LEES, Germany. The indenter load of the microhardness tester was set to 5 g.
2. The examples, comparative examples and polycarbonate substrates were tested for uv transmission using a japanese model 2000 spectrometer. The wavelength range is 10-400 nm.
3. Transmittance of visible light for the examples, comparative examples, and polycarbonate substrates using a japanese model 2000 spectrometer. The test sample was then moved from the 5 ℃ environment to 25 ℃ and the visible light transmittance was immediately determined.
The measurement results are shown in table 1.
TABLE 1 measurement results
As can be seen from Table 1, the lenses obtained in the example group had higher strength, and low ultraviolet transmittance, high visible light transmittance, and the lenses were effective in preventing fogging when the temperature was changed. Comparative example 1 the composite nanoparticle film formed on the surface of the base material was relatively thin due to the short immersion time of the base material in the nano-dispersant, and thus the hardness was lower than that of the example group, and the ultraviolet and visible light transmittances were rather increased, but the anti-fogging effect was also deteriorated. Comparative example 2 has the effect that the hardness is increased, the ultraviolet transmittance is decreased, the visible light transmittance is decreased, and the anti-fogging effect is deteriorated, as compared with the case where the composite nanoparticle film extruded in the nano-dispersant is formed on the surface of the base material by soaking for a long time. Comparative examples 3 to 5 lack one rare earth element, the hardness of the obtained eye sheet decreases, the transmittance of violet light increases, the transmittance of visible light decreases on the contrary, and the antifogging effect becomes poor. Comparative examples 6 to 8 have lower hardness and higher ultraviolet transmittance, whereas visible light transmittance is smaller and antifogging effect is poor, compared to comparative examples 3 to 5, due to the lack of two rare earth elements. Therefore, the three rare earth elements of Pr, Eu and Tb have synergistic effect on improving the hardness of the spectacle lens, reducing the transmittance of ultraviolet light, improving the light transmittance of visible light and improving the antifogging effect.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.