Titanium dioxide/tocopherol compound composite material and preparation method thereof
阅读说明：本技术 一种二氧化钛/生育酚类化合物的复合材料及其制备方法 (Titanium dioxide/tocopherol compound composite material and preparation method thereof ) 是由 潘柯敏 马强 于 2020-12-10 设计创作，主要内容包括：本发明涉及纳米复合材料的表面改性技术领域,具体涉及一种二氧化钛/生育酚类化合物的复合材料及其制备方法。该复合材料是由ZnTiO-3膜和生育酚和/或生育酚衍生物包覆于纳米TiO-2表面而制得。该复合材料是先进行ZnTiO-3膜包覆于纳米TiO-2表面,再进行生育酚或者生育酚衍生物包覆于纳米TiO-2表面。本发明将ZnTiO-3膜(无机)和生育酚及其衍生物(有机)包覆于纳米TiO-2表面,可有效解决纳米TiO-2光照产生的活性氧自由基溢出的问题,极大地提高了纳米TiO-2在化妆品中的使用性能。(The invention relates to the technical field of surface modification of nano composite materials, in particular to a titanium dioxide/tocopherol compound composite material and a preparation method thereof. The composite material is made of ZnTiO 3 Coating film and tocopherol and/or tocopherol derivative on nano TiO 2 And (3) surface preparation. The composite material is firstly ZnTiO 3 Coating on the nano TiO 2 Coating the surface with tocopherol or tocopherol derivative on the nano TiO 2 A surface. The invention uses ZnTiO as a raw material 3 Film (inorganic) and tocopherol and derivatives thereof (organic) coatedNano TiO 2 2 The surface can effectively solve the problem of nano TiO 2 The overflow of active oxygen free radicals generated by illumination greatly improves the nano TiO 2 Can be used in cosmetics.)
1. A titanium dioxide/tocopherol compound composite material, characterized in that: the composite material is made of ZnTiO3The film and the tocopherol and/or the tocopherol derivative are coated on the nano TiO2And (3) surface preparation.
2. The titanium dioxide/tocopherol compound composite according to claim 1, characterized in that: the composite material is firstly ZnTiO3Coating on the nano TiO2Coating the surface with tocopherol and/or tocopherol derivative on the nano TiO2A surface.
3. The titanium dioxide/tocopherol compound composite according to claim 2, characterized in that: the ZnTiO compound3Coating on the nano TiO2The surface is prepared by the following steps: mixing rutile type nano TiO2Dispersing in deionized water, wherein the rutile type nanometer TiO2The mass ratio of the disodium ethylenediamine tetraacetate to the deionized water is 0.1-0.4: 1, the pH value of the system is adjusted to 2-3, and the disodium ethylenediamine tetraacetate is added while stirring, wherein the disodium ethylenediamine tetraacetate and the rutile type nano TiO are added2The mass ratio of (A) to (B) is 0.03-0.1: 1; and then dropwise adding a zinc salt solution with the molar concentration of 0.5-2.0 mol/L, wherein the molar mass ratio of zinc salt to disodium ethylene diamine tetraacetate is 0.5-1.0: 1, filtering and drying after dropwise adding, calcining the obtained filter cake for 2-5 hours in an air atmosphere at the temperature of 500-650 ℃, and crushing to obtain the zinc salt.
4. The titanium dioxide/tocopherol compound composite according to claim 3, characterized in that: the zinc salt solution is one of zinc nitrate solution, zinc sulfate solution or zinc chloride solution.
5. The titanium dioxide/tocopherol compound composite according to claim 2, characterized in that: the tocopherol and/or the tocopherol derivative are coated on the nano TiO2The surface comprises the following preparation steps:
1) sulfonic group grafted modified nano TiO2Preparation of the Complex
While stirring, ZnTiO is added3Coating on the nano TiO2Adding the surface compound into mercaptosilane coupling agent solution with the mass percentage concentration of 10-20%, wherein ZnTiO3Coating on the nano TiO2The mass ratio of the surface compound to the mercaptosilane coupling agent solution is 0.3-0.6: 1, the obtained paste is dried for 5-10 hours at the temperature of 80-100 ℃, and then is rapidly added into a hydrogen peroxide solution with the mass percentage concentration of 20-35%, wherein ZnTiO is3Coating on the nano TiO2The mass ratio of the surface compound to the hydrogen peroxide solution is 0.05-0.2: 1, stirring and reacting for 20-60 minutes, filtering, washing and drying to obtain the sulfonic group grafted modified nano TiO2The complex of (a);
2) preparation of titanium dioxide/tocopherol compound composite material
Stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 1)2Spraying 5-10% tocopherol ethanol solution in the mass percentage concentration into the compound, wherein the sulfonic group modifies the nano TiO2Composite (ZnTiO)3Film coated nano TiO2The mass of the composite) and the mass ratio of the ethanol solution of the tocopherol and/or the tocopherol derivative is 0.1-0.3: 1, and after spraying is finished, the obtained product is dried for 3-8 hours at the temperature of 80-100 ℃ to obtain the composite material of the nano titanium dioxide/the tocopherol compound.
6. The titanium dioxide/tocopherol compound composite according to claim 5, characterized in that: the mercaptosilane coupling in the step 1) is one of 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; the tocopherol compound in the step 2) comprises tocopherol and/or a tocopherol derivative.
7. The titanium dioxide/tocopherol compound composite according to claim 6, characterized in that: the tocopherol derivative is one of tocopherol acetate, tocopherol linoleate or tocopherol succinate.
8. A process for preparing the titanium dioxide/tocopherol compound composite according to any one of claims 1 to 7, characterized in that: the preparation method comprises the following steps:
1)ZnTiO3film coated nano TiO2Preparation of the Complex
Mixing rutile type nano TiO2Dispersing in deionized water, wherein the rutile type nanometer TiO2The mass ratio of the disodium ethylenediamine tetraacetate to the deionized water is 0.1-0.4: 1, the pH value of the system is adjusted to 2-3, and the disodium ethylenediamine tetraacetate is added while stirring, wherein the disodium ethylenediamine tetraacetate and the rutile type nano TiO are added2The mass ratio of (A) to (B) is 0.03-0.1: 1; then dropwise adding a zinc salt solution with the molar concentration of 0.5-2.0 mol/L, wherein the molar mass ratio of zinc salt to ethylene diamine tetraacetic acid is 0.5-1.0: 1, filtering and drying after dropwise adding, calcining the obtained filter cake for 2-5 hours in an air atmosphere at the temperature of 500-650 ℃, and crushing to obtain ZnTiO3Film coated nano TiO2The complex of (a);
2) sulfonic group grafted modified nano TiO2Preparation of the Complex
Adding the product obtained in the step 1) into a mercaptosilane coupling agent solution with the mass percentage concentration of 10-20% while stirring, wherein the mass ratio of the product obtained in the step 1) to the mercaptosilane coupling agent solution is 0.3-0.6: 1, drying the obtained paste at the temperature of 80-100 ℃ for 5-10 hours, quickly adding the dried paste into a hydrogen peroxide solution with the mass percentage concentration of 20-35%, wherein the mass ratio of the product obtained in the step 1) to the hydrogen peroxide solution is 0.05-0.2: 1, stirring and reacting for 20-60 minutes, filtering, washing and drying to obtain the sulfonic group grafted modified nano TiO2The complex of (a);
3) preparation of nano titanium dioxide/tocopherol compound composite material
Stirring while modifying the sulfonic acid group obtained in step 2)TiO rice2Spraying 5-10% ethanol solution of tocopherol compounds in mass percentage concentration into the compound, wherein the sulfonic group modifies the nano TiO2Composite (ZnTiO)3Film coated nano TiO2The mass of the composite) and the mass ratio of the ethanol solution of the tocopherol and/or the tocopherol derivative is 0.1-0.3: 1, and after spraying is finished, the obtained product is dried for 3-8 hours at the temperature of 80-100 ℃ to obtain the composite material of the nano titanium dioxide/the tocopherol compound.
9. The method for preparing titanium dioxide/tocopherol compound composite material according to claim 8, wherein: the zinc salt solution in the step 1) is one of a zinc nitrate solution, a zinc sulfate solution or a zinc chloride solution; the mercaptosilane coupling in the step 2) is one of 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; the tocopherol compound in the step 3) comprises tocopherol or a tocopherol derivative.
10. The method for preparing titanium dioxide/tocopherol compound composite material according to claim 9, wherein: the tocopherol derivative is one of tocopherol acetate, tocopherol linoleate or tocopherol succinate.
Technical Field
The invention relates to the technical field of surface modification of nano composite materials, in particular to a composite material of tocopherol and a derivative thereof modified rutile type titanium dioxide and a preparation method thereof.
Background
Rutile type nano titanium dioxide (TiO)2) Have been used in the field of sunscreen cosmetics for their excellent shielding properties against ultraviolet rays in sunlight. However, rutile type nano TiO2The sunscreen cosmetic has strong photoactivity, and when the sunscreen cosmetic is directly added into a sunscreen cosmetic formula, organic matters in the cosmetics are easily degraded, so that the problems of demulsification, deterioration, odor and the like of the formula are caused, and the service performance of the sunscreen cosmetic is seriously influenced. Currently, nano TiO is usually treated by a single inorganic coating method2To prevent the active oxygen free radicals generated by light from overflowing. However, in this method, the surface of the inorganic coating layer has certain pores, and part of the active oxygen radicals can still permeate and migrate to the surface of the inorganic coating layer and cannot be completely removed, so that the use performance of the cosmetic is greatly influenced. How to effectively eliminate nano TiO2Active oxygen free radical overflow generated by illumination is a key technical problem to be solved.
Tocopherol (also known as vitamin E) and derivatives thereof are the main antioxidants, and can eliminate active oxygen free radicals and inhibit nano TiO by interrupting chain reaction of free radicals2The purpose of photoactivity. However, the molecular structure of tocopherol and derivatives thereof has oxygen-containing active functional groups (such as hydroxyl or epoxy groups), and the molecular structure still receives nano TiO to a certain extent2The generated photogenerated electrons-holes are oxidized, thereby shortening the service life thereof.
In the prior art, although a lot of reports about the common use of the components of nano titanium dioxide and tocopherol or tocopherol acetate exist, the nano titanium dioxide and the tocopherol or tocopherol acetate are used as the conventional components in cosmetic compositions, and the fact that the tocopherol and derivatives thereof are still subjected to nano TiO is not realized2The generated photogenerated electrons-holes are oxidized, so that how to further improve the oxidation resistance of the tocopherol and the derivatives thereof and prolong the service life is another key technical problem to be solved by the invention.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a titanium dioxide/tocopherol compound composite material,aims to solve two problems: in one aspect, the nano TiO2The problem that active oxygen free radicals can not be eliminated during the use of the sunscreen cosmetic; on the other hand, the antioxidant performance of the tocopherol and the derivatives thereof is improved, and the service cycle of the tocopherol and the derivatives thereof is prolonged.
The invention also aims to provide a preparation method of the titanium dioxide/tocopherol compound composite material.
In order to realize one purpose of the invention, the invention adopts the technical scheme that: a composite material of titanium dioxide/tocopherol compound is prepared from ZnTiO3The film and the tocopherol and/or the tocopherol derivative are coated on the nano TiO2And (3) surface preparation.
Preferably, the composite material is firstly ZnTiO3Coating on the nano TiO2Coating the surface with tocopherol and/or tocopherol derivative on the nano TiO2A surface.
Further preferably, the ZnTiO compound of the invention3Coating on the nano TiO2The surface is prepared by the following steps: mixing rutile type nano TiO2Dispersing in deionized water, wherein the rutile type nanometer TiO2The mass ratio of the disodium ethylenediamine tetraacetate to the deionized water is 0.1-0.4: 1, the pH value of the system is adjusted to 2-3, and the disodium ethylenediamine tetraacetate is added while stirring, wherein the disodium ethylenediamine tetraacetate and the rutile type nano TiO are added2The mass ratio of (A) to (B) is 0.03-0.1: 1; and then dropwise adding a zinc salt solution with the molar concentration of 0.5-2.0 mol/L, wherein the molar mass ratio of zinc salt to disodium ethylene diamine tetraacetate is 0.5-1.0: 1, filtering and drying after dropwise adding, calcining the obtained filter cake for 2-5 hours in an air atmosphere at the temperature of 500-650 ℃, and crushing to obtain the zinc salt.
Further preferably, the zinc salt solution of the present invention is one of a zinc nitrate solution, a zinc sulfate solution or a zinc chloride solution.
Further preferably, the tocopherol and/or the tocopherol derivative are/is coated on the nano TiO2The surface comprises the following preparation steps:
1) sulfonic group grafted modified nano TiO2Preparation of the Complex
While stirring, ZnTiO is added3Coating on the nano TiO2Adding the surface compound into mercaptosilane coupling agent solution with the mass percentage concentration of 10-20%, wherein ZnTiO3Coating on the nano TiO2The mass ratio of the surface compound to the mercaptosilane coupling agent solution is 0.3-0.6: 1, the obtained paste is dried for 5-10 hours at the temperature of 80-100 ℃, and then is rapidly added into a hydrogen peroxide solution with the mass percentage concentration of 20-35%, wherein ZnTiO is3Coating on the nano TiO2The mass ratio of the surface compound to the hydrogen peroxide solution is 0.05-0.2: 1, stirring and reacting for 20-60 minutes, filtering, washing and drying to obtain the sulfonic group grafted modified nano TiO2The complex of (a);
2) preparation of titanium dioxide/tocopherol compound composite material
Stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 1)2Spraying 5-10% tocopherol ethanol solution in the mass percentage concentration into the compound, wherein the sulfonic group modifies the nano TiO2Composite (ZnTiO)3Film coated nano TiO2The mass of the composite) and the mass ratio of the ethanol solution of the tocopherol and/or the tocopherol derivative is 0.1-0.3: 1, and after spraying is finished, the obtained product is dried for 3-8 hours at the temperature of 80-100 ℃ to obtain the composite material of the nano titanium dioxide/the tocopherol compound.
Wherein, the mercaptosilane coupling in the step 1) is one of 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; the tocopherol compound in the step 2) comprises tocopherol and/or a tocopherol derivative.
More preferably, the tocopherol derivative is one of tocopherol acetate, tocopherol linoleate or tocopherol succinate.
In order to realize another purpose of the invention, the invention adopts the technical scheme that: a preparation method of a titanium dioxide/tocopherol compound composite material comprises the following preparation steps:
1)ZnTiO3film coated nano TiO2Preparation of the Complex
Mixing rutile type nano TiO2Dispersing in deionized water, wherein the rutile type nanometer TiO2The mass ratio of the disodium ethylenediamine tetraacetate to the deionized water is 0.1-0.4: 1, the pH value of the system is adjusted to 2-3, and the disodium ethylenediamine tetraacetate is added while stirring, wherein the disodium ethylenediamine tetraacetate and the rutile type nano TiO are added2The mass ratio of (A) to (B) is 0.03-0.1: 1; then dropwise adding a zinc salt solution with the molar concentration of 0.5-2.0 mol/L, wherein the molar mass ratio of zinc salt to ethylene diamine tetraacetic acid is 0.5-1.0: 1, filtering and drying after dropwise adding, calcining the obtained filter cake for 2-5 hours in an air atmosphere at the temperature of 500-650 ℃, and crushing to obtain ZnTiO3Film coated nano TiO2The complex of (a);
2) sulfonic group grafted modified nano TiO2Preparation of the Complex
Adding the product obtained in the step 1) into a mercaptosilane coupling agent solution with the mass percentage concentration of 10-20% while stirring, wherein the mass ratio of the product obtained in the step 1) to the mercaptosilane coupling agent solution is 0.3-0.6: 1, drying the obtained paste at the temperature of 80-100 ℃ for 5-10 hours, quickly adding the dried paste into a hydrogen peroxide solution with the mass percentage concentration of 20-35%, wherein the mass ratio of the product obtained in the step 1) to the hydrogen peroxide solution is 0.05-0.2: 1, stirring and reacting for 20-60 minutes, filtering, washing and drying to obtain the sulfonic group grafted modified nano TiO2The complex of (a);
3) preparation of nano titanium dioxide/tocopherol compound composite material
Stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 2)2Spraying 5-10% ethanol solution of tocopherol compounds in mass percentage concentration into the compound, wherein the sulfonic group modifies the nano TiO2Composite (ZnTiO)3Film coated nano TiO2Mass of the compound) and the ethanol solution of tocopherol and/or tocopherol derivatives in a ratio of 0.1-0.3: 1, and after spraying, the obtained mixture is sprayedAnd drying the product at the temperature of 80-100 ℃ for 3-8 hours to obtain the nano titanium dioxide/tocopherol compound composite material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention selects and adds Ethylene Diamine Tetraacetic Acid (EDTA), and has the advantages that: rutile type nano TiO2The EDTA with positive charge and negative charge on the particle surface can be quickly adsorbed to the nano TiO2A surface. When a zinc salt is added, zinc ion (Zn)2+) With nano TiO2The ethylene diamine tetraacetic acid on the surface generates complex reaction, so that the EDTA-Zn complex is evenly coated on the nano TiO2The surface of the particles. Under the conditions of air atmosphere and calcination, EDTA-Zn complex is decomposed, organic matters are burnt and removed, ZnO and nano TiO can be mixed2Solid-phase reaction to form ZnTiO3Thereby in the nano TiO2Efficient formation of ZnTiO on the surface3And (5) film layer.
2. The invention selects a mercapto silane coupling agent to ZnTiO3Film-coated nano TiO2The graft modification is carried out, and the advantages are that: the mercapto (-SH) in the mercaptosilane coupling agent is easily oxidized by hydrogen peroxide to form sulfonic acid (-SO)3H) The sulfonic group can generate hydrogen bond or chemical bonding with oxygen-containing active functional groups in the tocopherol and the derivatives thereof, and on one hand, the nano TiO is subjected to chemical reaction2Is connected with tocopherol and derivatives thereof in a chemical bond mode, and improves the nano TiO2The use stability of the/tocopherol composite; on the other hand, the purpose of stabilizing the oxygen-containing active functional groups in the tocopherol is achieved, the antioxidation of the tocopherol and the derivatives thereof is improved, and the service life of the tocopherol and the derivatives thereof is prolonged.
3. The invention uses ZnTiO as a raw material3Nano TiO coated with film (inorganic) and/or tocopherol and its derivative (organic)2The surface can effectively solve the problem of nano TiO2The overflow of active oxygen free radicals generated by illumination greatly improves the nano TiO2Can be used in cosmetics.
Drawings
FIG. 1 shows the results of step 1 in example 4The ZnTiO thus obtained3Film coated nano TiO2XRD spectrum of (1). In the figure, at 2 θ ═ 23.85 °, 32.82 °, 35.40 °, 40.50 °, 48.93 °, 53.70 °, 57.10 °, 62.04 ° and 63.65 °, there is hexagonal phase ZnTiO3The diffraction peaks of (1) and (2) respectively correspond to the crystal planes of (012), (104), (110), (113), (024), (116), (018), (214) and (300), confirming that ZnTiO3Is present.
Detailed Description
The present invention will be further described below with reference to examples and comparative examples, but the scope of the present invention is by no means limited.
Example 1
1. 1.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the pH of the system to 2, and adding 0.1 kg of disodium ethylene diamine tetraacetate while stirring; then 297.4 ml of zinc sulfate solution with the molar concentration of 0.5 mol/L is dripped, after the dripping is finished, the solution is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 500 ℃ and the calcination is carried out for 5 hours, and the powder is crushed to obtain ZnTiO3Film coated nano TiO2A complex;
2. adding 0.5 kg of the compound obtained in the step 1 into 1.67 kg of 3-mercaptopropyltrimethoxysilane solution with the mass percentage concentration of 10% while stirring, drying the paste at the temperature of 100 ℃ for 5 hours after finishing dripping, quickly adding the paste into 10.0 kg of hydrogen peroxide solution with the mass percentage concentration of 20%, stirring and reacting for 60 minutes, filtering, washing and drying to obtain the sulfonic acid group graft modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 225.0 kg of ethanol solution of 5% tocopheryl linoleate in percentage by mass is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 8 hours at the temperature of 80 ℃, so that the nano titanium dioxide/tocopheryl linoleate composite material is prepared.
Example 2
1. 4.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, and adjustingAdding 0.12 kg of disodium ethylene diamine tetraacetate while stirring, wherein the pH value of the system is 2.5; then 178.5 ml of zinc chloride solution with the molar concentration of 2.0 mol/L is dripped, after the dripping is finished, the mixture is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 650 ℃ and the mixture is calcined for 2 hours, and the mixture is crushed to obtain ZnTiO3Film coated nano TiO2A complex;
2. adding 0.5 kg of the compound obtained in the step 1 into 0.83 kg of 3-mercaptopropyltriethoxysilane solution with the mass percentage concentration of 20% while stirring, drying the obtained paste at the temperature of 80 ℃ for 10 hours after the dropwise addition is finished, quickly adding the paste into 2.5 kg of hydrogen peroxide solution with the mass percentage concentration of 35%, stirring and reacting for 20 minutes, filtering, washing and drying to obtain the sulfonic acid group graft modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And spraying 1.67 kg of ethanol solution of 10% tocopherol succinate by mass percent into the composite, and drying the obtained product for 3 hours at the temperature of 100 ℃ after the spraying is finished to obtain the nano titanium dioxide/tocopherol succinate composite material.
Example 3
1. 2.5 kg rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the pH value of the system to 3, and adding 0.16 kg of disodium ethylene diamine tetraacetate while stirring; then 362.5 ml of zinc nitrate solution with the molar concentration of 1.0 mol/L is dripped, after the dripping is finished, the solution is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 550 ℃, the calcination is carried out for 3 hours, and the crushing is carried out, thus obtaining ZnTiO3Film coated nano TiO2A complex;
2. while stirring, 0.5 kg of the compound obtained in the step 1 is added into 1.11 kg of a 15 mass percent 3-mercaptopropyltrimethoxysilane solution, after the dropwise addition is finished, the obtained paste is dried for 7.5 hours at the temperature of 90 ℃, then is rapidly added into 4.0 kg of a 25 mass percent hydrogen peroxide solution, and is stirred and reacted for 40 minutes,filtering, washing and drying to obtain the sulfonic group grafted modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And 2.5 kg of ethanol solution of tocopherol acetate with the mass percentage concentration of 7.5 percent is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 90 ℃, so that the nano titanium dioxide/tocopherol acetate composite material is prepared.
Example 4
1. 3.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the pH value of the system to 3, and adding 0.15 kg of disodium ethylene diamine tetraacetate while stirring; then 180.0 ml of zinc nitrate solution with the molar concentration of 1.5 mol/L is dripped, after the dripping is finished, the zinc nitrate solution is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 600 ℃ for calcining for 4 hours, and the ZnTiO is obtained after the crushing3Film coated nano TiO2A complex;
2. adding 0.5 kg of the compound obtained in the step 1 into 1.0 kg of 3-mercaptopropyltriethoxysilane solution with the mass percentage concentration of 18% while stirring, drying the obtained paste at the temperature of 95 ℃ for 6 hours after the dropwise addition is finished, quickly adding the paste into 5.0 kg of hydrogen peroxide solution with the mass percentage concentration of 30%, stirring and reacting for 30 minutes, filtering, washing and drying to obtain the sulfonic acid group graft modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And 2.0 kg of ethanol solution of 10% tocopherol by mass is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 95 ℃ to obtain the nano titanium dioxide/tocopherol composite material.
Comparative example 1
In comparative example 1, step 1 and step 2 in example 4 were omitted, and other process conditions were not changed, and the specific operation steps were as follows:
while stirring, add 0.5 kg rutile type nano TiO2Middle sprayAnd 2.0 kg of ethanol solution of 10% tocopherol by mass is sprayed, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 95 ℃ to obtain the nano titanium dioxide/tocopherol composite material.
Comparative example 2
In comparative example 2, the step 1 in example 4 was omitted, and other process conditions were not changed, and the specific operation steps were as follows:
1. while stirring, 0.5 kg of rutile type TiO nanoparticles was taken2Adding 1.0 kg of 3-mercaptopropyltriethoxysilane solution with the mass percentage concentration of 18%, drying the obtained paste for 6 hours at the temperature of 95 ℃ after the dropwise addition is finished, quickly adding the paste into 5.0 kg of hydrogen peroxide solution with the mass percentage concentration of 30%, stirring and reacting for 30 minutes, filtering, washing and drying to obtain the sulfonic acid group grafted modified nano TiO2A complex;
2. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And 2.0 kg of ethanol solution of 10% tocopherol by mass is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 95 ℃ to obtain the nano titanium dioxide/tocopherol composite material.
Comparative example 3
In comparative example 3, the step 2 of example 4 was omitted, and other process conditions were not changed, and the specific operation steps were as follows:
1. 3.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the pH value of the system to 3, and adding 0.15 kg of disodium ethylene diamine tetraacetate while stirring; then 180.0 ml of zinc nitrate solution with the molar concentration of 1.5 mol/L is dripped, after the dripping is finished, the zinc nitrate solution is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 600 ℃ for calcining for 4 hours, and the ZnTiO is obtained after the crushing3Film coated nano TiO2A complex;
2. while stirring, spraying 2.0 kg of ethanol solution of 10% tocopherol by mass into 0.5 kg of the compound obtained in the step 1, and drying the obtained product at the temperature of 95 ℃ for 5 hours to obtain the nano titanium dioxide/tocopherol composite material.
Comparative example 4
In comparative example 4, the disodium ethylene diamine tetraacetate in step 1 of example 4 was replaced by ethylenediamine, and other process conditions were not changed, and the specific operation steps were as follows:
1. 3.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the system pH to 3, and adding 0.15 kg of ethylenediamine while stirring; then 180.0 ml of zinc nitrate solution with the molar concentration of 1.5 mol/L is dripped, after the dripping is finished, the zinc nitrate solution is filtered and dried, the obtained filter cake is placed in the air atmosphere, the temperature is 600 ℃ for calcining for 4 hours, and the ZnTiO is obtained after the crushing3Coated nano TiO2A complex;
2. adding 0.5 kg of the compound obtained in the step 1 into 1.0 kg of 3-mercaptopropyltriethoxysilane solution with the mass percentage concentration of 18% while stirring, drying the obtained paste at the temperature of 95 ℃ for 6 hours after the dropwise addition is finished, quickly adding the paste into 5.0 kg of hydrogen peroxide solution with the mass percentage concentration of 30%, stirring and reacting for 30 minutes, filtering, washing and drying to obtain the sulfonic acid group graft modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And 2.0 kg of ethanol solution of 10% tocopherol by mass is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 95 ℃ to obtain the nano titanium dioxide/tocopherol composite material.
Comparative example 5
In comparative example 5, the hydrogen peroxide oxidation step in step 2 of example 4 was omitted, and other process conditions were not changed, and the specific operation steps were as follows:
1. 3.0 kg of rutile type nano TiO2Dispersing in 10.0 kg of deionized water, adjusting the pH value of the system to 3, and adding 0.15 kg of disodium ethylene diamine tetraacetate while stirring; then 180.0 ml of a solution with a molar concentration of 1.5 mol are added dropwiseAdding zinc nitrate solution in each liter, filtering, drying, calcining the obtained filter cake for 4 hours at the temperature of 600 ℃ in the air atmosphere, and crushing to obtain ZnTiO3Film coated nano TiO2A complex;
2. while stirring, 0.5 kg of the compound obtained in the step 1 is added into 1.0 kg of 3-mercaptopropyltriethoxysilane solution with the mass percentage concentration of 18 percent, and after the dropwise addition is finished, the obtained paste is dried for 6 hours at the temperature of 95 ℃ to obtain the mercaptosilane grafted and modified nano TiO2A complex;
3. stirring the solution while adding the sulfonic acid group-modified nano TiO obtained in the step 22And 2.0 kg of ethanol solution of 10% tocopherol by mass is sprayed into the composite, and after the spraying is finished, the obtained product is dried for 5 hours at the temperature of 95 ℃ to obtain the nano titanium dioxide/tocopherol composite material.
Evaluation of Performance
The light stability of the nano titanium dioxide/tocopherol composites prepared in the examples and comparative examples was evaluated by the following performance tests, and the test results are shown in table 1. As can be seen from Table 1, the nano titanium dioxide/tocopherol composite material prepared by the invention has excellent light stability.
Testing the light stability: the samples to be tested obtained in the examples and the comparative examples are uniformly mixed with 1, 3-butanediol according to the mass ratio of 1:1.2, then 3.0 g of the mixture is coated on a glass slide, a cover glass is covered, and the L, a and b values are measured by an SC-80C type (Beijing Kangguang optical instruments, Ltd.) full-automatic color difference instrument. The samples were then irradiated under a high pressure mercury lamp for 1 hour and then measured for L, a, b values using a color difference meter. The color difference value of the sample before and after the light irradiation was calculated by the following formula (ΔE)。ΔThe larger E, the poorer the photostability.
ΔE＝[(L-L*)2+(a-a*)2+(b-b*)2]1/2
TABLE 1
Name (R)
Color difference value (ΔE)
Example 1
4
Example 2
5
Example 3
3
Example 4
2
Comparative example 1
23
Comparative example 2
20
Comparative example 3
15
Comparative example 4
12
Comparative example 5
10
- 上一篇：一种医用注射器针头装配设备
- 下一篇：化妆料组合物、化妆品