CN113185769B - Preparation method of EVA white master batch with anti-aging function - Google Patents
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Abstract
The invention provides an EVA white master batch with an aging-resistant function and a preparation method thereof2@ carbon microspheres; dispersing the aluminum salt solution into an aluminum salt solution, performing ultrasonic treatment, filtering, washing, drying and calcining to obtain Al2O3@TiO2@ reduced carbon microspheres; dispersing the titanium oxide into a titanium salt solution, performing ultrasonic treatment, filtering, washing, drying and calcining to obtain TiO2@Al2O3@TiO2(ii) a Adding TiO into the mixture2@Al2O3@TiO2Adding zinc salt into oleylamine, stirring, introducing Ar gas, heating to make TiO2@Al2O3@TiO2Fully and uniformly mixing with zinc salt; injecting ethanol, stirring, heating, and dynamically drying to obtain TiO2@Al2O3@TiO2A ZnO nanosheet heterojunction powder; mixing ethylene-vinyl acetate copolymer, ethylene-octene copolymer, and TiO2@Al2O3@TiO2And mixing the/ZnO nanosheet heterojunction, the antioxidant, the coupling agent and the crosslinking agent, uniformly mixing, adding into a double-screw extruder, extruding, cooling, drawing strips, air-drying and granulating to obtain the white master batch with the EVA ageing-resistant function. The master batch 1mm sample piece can block ultraviolet rays, has an anti-aging function, and has an ultraviolet blocking rate of over 96 percent at a waveband of 400 nm.
Description
Technical Field
The invention relates to an EVA white master batch with an aging-resistant function and a preparation method thereof, belonging to the field of aging-resistant materials.
Background
EVA refers to an ethylene-vinyl acetate resin, which is a plastic resin that can be used as a hot melt adhesive, and is widely used in the fields of laminated glass, encapsulation of solar photovoltaic modules, adhesion of metal plates and plastic plates, and the like, particularly in the solar photovoltaic field.
Ethylene chain segments and vinyl acetate chain segments in the EVA molecular structure are linear aliphatic chain structures, and the molecular bonds are mainly formed by carbon-oxygen bonds and carbon-hydrogen bonds. These bonds are broken and recombined under the irradiation of short wavelength ultraviolet light to generate chromophoric groups, so that the EVA generates yellowing phenomenon. The current general solution is to add a crosslinking system with thermal initiation to make EVA form a spatial network molecular chain structure, increase the molecular stability, and add a stabilizer with an ultraviolet absorption function, a light stabilizer and the like. However, this method is because the crosslinking agent remaining in EVA reacts slowly with these auxiliary agents during long-term aging, and the ultraviolet stabilizer newly introduced reacts with the auxiliary agents such as the crosslinking agent and the antioxidant remaining therein under long-term ultraviolet irradiation to cause yellowing. The EVA master batch has the defects of poor aging resistance, overlarge thermal shrinkage and the like, and has great obstacles and limitations on subsequent production and use, so that an aging-resistant EVA material is required to be provided to solve the defect which cannot be overcome by the EVA.
Inorganic titanium dioxide is usually added into the EVA master batch, and the material can be endowed with the light-blocking effect through the color blocking of the inorganic titanium dioxide, so that the anti-aging effect is achieved. Chinese patent No. cn201110333804.x discloses that titanium dioxide and organic material are prepared into white master batch, and the light blocking effect of pure titanium dioxide is not ideal.
Therefore, the preparation method of the white master batch with the EVA anti-aging function is provided, and the ultraviolet barrier material with the complex structure of multiple cores is prepared by introducing the carbon microsphere seeds. The multi-core structure pair has a special active site closed structure, forms a unique closed microenvironment, protects the inner core from external chemical erosion, and further improves the strong absorption capacity of the composite material in an ultraviolet band; meanwhile, the heterojunction effectively separates photo-generated electron holes, and meanwhile, the larger specific surface area is also beneficial to enhancing the absorption capacity of an ultraviolet band, so that the blocking rate of ultraviolet rays is improved, and the problems that the traditional material is not too aged on the application surface and the like are solved.
Disclosure of Invention
The invention aims to provide an EVA white master batch with an aging-resistant function and a preparation method thereof2@Al2O3@TiO2and/ZnO nanosheet heterojunction, and carbon microsphere seeds are introduced to prepare the ultraviolet barrier material with a complex structure with multiple cores. The multi-core structure pair has a special active site closed structure, forms a unique closed microenvironment, protects the inner core from external chemical erosion, and further improves the strong absorption capacity of the composite material in an ultraviolet band; meanwhile, the heterojunction effectively separates photo-generated electron holes, and meanwhile, the larger specific surface area is also beneficial to enhancing the absorption capacity of an ultraviolet band, so that the blocking rate of ultraviolet rays is improved, and the problems that the traditional material is not too aged on the application surface and the like are solved.
In order to achieve the purpose, the invention provides the following technical scheme: an EVA white master batch with anti-aging function and a preparation method thereof, which comprises the following steps,
1) dispersing the carbon microsphere seeds into a titanium salt (2-4M) solution, wherein the molar ratio of the carbon microsphere seeds to the titanium salt is 1: 5, performing ultrasonic assistance at 30-50 ℃ for 6-8 hours, filtering, washing with deionized water for 2-3 times, and drying to obtain A;
2) calcining the A in air at a heating speed of 1-2 ℃/min at 500-600 ℃ for 2-3 h, and keeping the temperature for 30-60 min when the temperature is reduced to 300-400 ℃ to obtain TiO2TiO with shell and carbon microsphere seed as core2@ carbon microsphere seed, labeled B;
3) dispersing B in an aluminum salt (2-4M) solution to obtain an aluminum salt and TiO2In a molar ratio of 3: 1, repeating the step 1) and the step 2) to obtain aluminum oxide Al2O3Is the outermost shell, TiO2Is an intermediate shell, and the gradually reduced carbon microsphere seed is the innermost shell, namely Al2O3@TiO2@ reduced carbon microsphere seed, labeled C;
4) dispersing C into a titanium salt (2-4M) solutionIn (1), a titanium salt and Al are added2O3In a molar ratio of 3: 1, repeating the step 1) and the step 2), wherein the consumption of the carbon microsphere seeds is completely removed to obtain TiO2@Al2O3@TiO2；
5) Adding TiO into the mixture2@Al2O3@TiO2Adding zinc salt and the zinc salt into oleylamine, magnetically stirring, introducing inert gas Ar gas into the oleylamine for 20-60 min, gradually heating the solution to 120-150 ℃ to ensure that TiO is dissolved in water2@Al2O3@TiO2And the zinc salt is completely dissolved. Injecting ethanol into the solution at a rate of 1-15 mL/min for 1-20 min, magnetically stirring at the temperature for 30-60 min, and then heating to 220-250 ℃. Keeping the reaction mixture at the temperature for 20-30 min, and naturally cooling to room temperature to obtain the final product TiO2@Al2O3@TiO2a/ZnO nanosheet heterojunction;
6) 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-octene copolymer and TiO2@Al2O3@TiO235 parts of/ZnO nanosheet heterojunction, 1 part of antioxidant 2, 6-di-tert-butyl-4-ethylphenol, 3 parts of coupling agent aluminum-titanium composite coupling agent and 1 part of crosslinking agent tert-butyl peroxybenzoate are mixed, uniformly mixed and added into a double-screw extruder, the temperature is controlled at nine sections, and the white master batch with the EVA aging resistance function is prepared by extrusion, cooling, drawing, air drying and grain cutting.
Preferably, in the step 1), the titanium salt is one or a combination of tetrabutyl titanate, isopropyl titanate or ethyl titanate.
Preferably, in the step 3), the aluminum salt is one or a combination of aluminum acetate, aluminum citrate and aluminum chloride.
Preferably, in the step 5), the zinc salt is one or a combination of zinc acetate, zinc citrate and zinc chloride.
Preferably, in the step 6), the nine-stage temperature-controlled processing temperature of the twin-screw extruder is set as follows: the temperature in the first zone is 120 ℃, the temperature in the second zone is 128 ℃, the temperature in the third zone is 135 ℃, the temperature in the fourth zone is 142 ℃, the temperature in the fifth zone is 150 ℃, the temperature in the sixth zone is 142 ℃, the temperature in the seventh zone is 135 ℃, the temperature in the eighth zone is 128 ℃ and the temperature in the ninth zone is 120 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention aims to provide an EVA anti-aging white master batch and a preparation method thereof. The multi-core structure pair has a special active site closed structure, forms a unique closed microenvironment, protects the inner core from external chemical erosion, and further improves the strong absorption capacity of the composite material in an ultraviolet band; meanwhile, the heterojunction effectively separates photo-generated electron holes, and meanwhile, the larger specific surface area is also beneficial to enhancing the absorption capacity of an ultraviolet band, so that the blocking rate of ultraviolet rays is improved, and the problems that the traditional material is not too aged on the application surface and the like are solved.
Drawings
FIG. 1 shows TiO product of example 12@Al2O3@TiO2Particle size distribution diagram of/ZnO nanosheet heterojunction powder
FIG. 2 is TiO product of example 22@Al2O3@TiO2Particle size distribution diagram of/ZnO nanosheet heterojunction powder
FIG. 3 is a SEM image of the section of the white master batch with the aging resistance function of the EVA of the product of example 2
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
dispersing the carbon microsphere seeds into a tetrabutyl titanate (2M) solution to ensure that the molar ratio of the carbon microsphere seeds to the tetrabutyl titanate is 1: 5, performing ultrasonic assistance at 30 ℃ for 8 hours, filtering, washing with deionized water for 2 times, and drying to obtain A; placing A in the airCalcining at 500 deg.C for 3h at 1 deg.C/min in gas, and maintaining at 300 deg.C for 60min to obtain TiO2TiO with shell and carbon microsphere seed as core2@ carbon microsphere seed, labeled B; dispersing B into aluminum acetate (2M) solution to make aluminum acetate and TiO2In a molar ratio of 3: 1, repeating the step 1) and the step 2) to obtain aluminum oxide Al2O3Is the outermost shell, TiO2Is an intermediate shell, and the gradually reduced carbon microsphere seed is the innermost shell, namely Al2O3@TiO2@ reduced carbon microsphere seed, labeled C; dispersing C in tetrabutyl titanate (2M) solution to make tetrabutyl titanate and Al2O3In a molar ratio of 3: 1, repeating the step 1) and the step 2), wherein the consumption of the carbon microsphere seeds is completely removed to obtain TiO2@Al2O3@TiO2(ii) a Adding TiO into the mixture2@Al2O3@TiO2Adding zinc acetate into 10mL oleylamine, magnetically stirring, introducing inert gas Ar for 20min, gradually heating to 150 deg.C to obtain TiO2@Al2O3@TiO2And zinc acetate were all dissolved. The above solution was injected with 1mL/min of ethanol for 1min, magnetically stirred at that temperature for 30min, and then heated to 220 ℃. Keeping the reaction mixture at the temperature for 30min, and naturally cooling to room temperature to obtain the final product TiO2@Al2O3@TiO2a/ZnO nanosheet heterojunction; 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-octene copolymer and TiO2@Al2O3@TiO235 parts of/ZnO nanosheet heterojunction, 1 part of antioxidant 2, 6-di-tert-butyl-4-ethylphenol, 3 parts of coupling agent aluminum-titanium composite coupling agent and 1 part of crosslinking agent tert-butyl peroxybenzoate are mixed, uniformly mixed and added into a double-screw extruder, and the nine-section temperature control processing temperature of the double-screw extruder is set as follows: the temperature in the first zone is 120 ℃, the temperature in the second zone is 128 ℃, the temperature in the third zone is 135 ℃, the temperature in the fourth zone is 142 ℃, the temperature in the fifth zone is 150 ℃, the temperature in the sixth zone is 142 ℃, the temperature in the seventh zone is 135 ℃, the temperature in the eighth zone is 128 ℃ and the temperature in the ninth zone is 120 ℃. Extruding, cooling, drawing, air-drying and granulating to obtain the white master batch with the EVA ageing-resistant function.
Wherein FIG. 1 is TiO2@Al2O3@TiO2The particle size of the/ZnO nanosheet heterojunction is approximately about 200 nm.
Testing of the addition of TiO2@Al2O3@TiO2The ultraviolet blocking rate of the 1mm sheet of the/ZnO nanosheet heterojunction EVA anti-aging functional white master batch is shown in the table 1.
Example two:
dispersing the carbon microsphere seeds into a solution of isopropyl titanate (4M) so that the molar ratio of the carbon microsphere seeds to the isopropyl titanate is 1: 5, performing ultrasonic assistance at 50 ℃ for 6 hours, filtering, washing with deionized water for 3 times, and drying to obtain A; calcining the A in air at 600 deg.C for 2h at a heating rate of 2 deg.C/min, and maintaining the temperature for 60min when the temperature is reduced to 400 deg.C to obtain TiO2TiO with shell and carbon microsphere seed as core2@ carbon microsphere seed, labeled B; dispersing B into aluminum citrate (4M) solution to ensure that the aluminum citrate and TiO2In a molar ratio of 3: 1, repeating the step 1) and the step 2), wherein the consumption of the carbon microsphere seeds is completely removed to obtain the aluminum oxide Al2O3Is the outermost shell, TiO2Is an intermediate shell, and the gradually reduced carbon microsphere seed is the innermost shell, namely Al2O3@TiO2@ reduced carbon microsphere seed, labeled C; dispersing C into isopropyl titanate (4M) solution to obtain isopropyl titanate and Al2O3In a molar ratio of 3: 1, repeating the step 1) and the step 2) to obtain TiO2@Al2O3@TiO2(ii) a Adding TiO into the mixture2@Al2O3@TiO2Adding zinc citrate into 10mL oleylamine, magnetically stirring, introducing inert gas Ar for 30min, gradually heating to 150 deg.C to obtain TiO2@Al2O3@TiO2And zinc citrate were all dissolved. The above solution was injected with ethanol at 10mL/min for 10min, magnetically stirred at this temperature for 60min, and then heated to 220 ℃. Keeping the reaction mixture at the temperature for 30min, and naturally cooling to room temperature to obtain the final product TiO2@Al2O3@TiO2a/ZnO nanosheet heterojunction; 50 parts of ethylene-vinyl acetate copolymer and ethylene10 parts of-octene copolymer, TiO2@Al2O3@TiO235 parts of/ZnO nanosheet heterojunction, 1 part of antioxidant 2, 6-di-tert-butyl-4-ethylphenol, 3 parts of coupling agent aluminum-titanium composite coupling agent and 1 part of crosslinking agent tert-butyl peroxybenzoate are mixed, uniformly mixed and added into a double-screw extruder, and the nine-section temperature control processing temperature of the double-screw extruder is set as follows: the temperature in the first zone is 120 ℃, the temperature in the second zone is 128 ℃, the temperature in the third zone is 135 ℃, the temperature in the fourth zone is 142 ℃, the temperature in the fifth zone is 150 ℃, the temperature in the sixth zone is 142 ℃, the temperature in the seventh zone is 135 ℃, the temperature in the eighth zone is 128 ℃ and the temperature in the ninth zone is 120 ℃. Extruding, cooling, drawing, air-drying and granulating to obtain the white master batch with the EVA ageing-resistant function.
Wherein FIG. 2 is TiO2@Al2O3@TiO2The particle size of the/ZnO nanosheet heterojunction is approximately about 200 nm.
Testing of the addition of TiO2@Al2O3@TiO2The ultraviolet blocking rate of the 1mm sheet of the/ZnO nanosheet heterojunction EVA anti-aging functional white master batch is shown in the table 1.
Example 3
Dispersing the carbon microsphere seeds into an ethyl titanate (2M) solution to ensure that the molar ratio of the carbon microsphere seeds to the ethyl titanate is 1: 5, performing ultrasonic assistance at 50 ℃ for 8 hours, filtering, washing 3 times with deionized water, and drying to obtain A; calcining the A in air at 600 deg.C for 2h at a heating rate of 1 deg.C/min, and maintaining the temperature for 60min when the temperature is reduced to 400 deg.C to obtain TiO2TiO with shell and carbon microsphere seed as core2@ carbon microsphere seed, labeled B; dispersing B into aluminum chloride (2M) solution to obtain aluminum chloride and TiO2In a molar ratio of 3: 1, repeating the step 1) and the step 2) to obtain aluminum oxide Al2O3Is the outermost shell, TiO2Is an intermediate shell, and the gradually reduced carbon microsphere seed is the innermost shell, namely Al2O3@TiO2@ reduced carbon microsphere seed, labeled C; dispersing C in ethyl titanate (2M) solution to make ethyl titanate and Al2O3In a molar ratio of 3: 1, repeating the step 1) and the step 2), wherein the consumption of the carbon microsphere seeds is completely removed to obtain TiO2@Al2O3@TiO2(ii) a Adding TiO into the mixture2@Al2O3@TiO2Adding zinc salt and 15mL oleylamine, magnetically stirring, introducing inert gas Ar for 60min, gradually heating to 120 deg.C to obtain TiO2@Al2O3@TiO2And zinc chloride were all dissolved. The above solution was injected with 15mL/min of ethanol for 20min, magnetically stirred at this temperature for 30min, and then heated to 240 ℃. Keeping the reaction mixture at the temperature for 30min, and naturally cooling to room temperature to obtain the final product TiO2@Al2O3@TiO2a/ZnO nanosheet heterojunction; 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-octene copolymer and TiO2@Al2O3@TiO235 parts of/ZnO nanosheet heterojunction, 1 part of antioxidant 2, 6-di-tert-butyl-4-ethylphenol, 3 parts of coupling agent aluminum-titanium composite coupling agent and 1 part of crosslinking agent tert-butyl peroxybenzoate are mixed, uniformly mixed and added into a double-screw extruder, and the nine-section temperature control processing temperature of the double-screw extruder is set as follows: the temperature in the first zone is 120 ℃, the temperature in the second zone is 128 ℃, the temperature in the third zone is 135 ℃, the temperature in the fourth zone is 142 ℃, the temperature in the fifth zone is 150 ℃, the temperature in the sixth zone is 142 ℃, the temperature in the seventh zone is 135 ℃, the temperature in the eighth zone is 128 ℃ and the temperature in the ninth zone is 120 ℃. Extruding, cooling, drawing, air-drying and granulating to obtain the white master batch with the EVA ageing-resistant function.
Testing of the addition of TiO2@Al2O3@TiO2The ultraviolet blocking rate of the 1mm sheet of the/ZnO nanosheet heterojunction EVA anti-aging functional white master batch is shown in the table 1.
TABLE 1 addition of TiO2@Al2O3@TiO2Ultraviolet blocking rate of 1mm sheet of white master batch with ageing-resistant function of/ZnO nanosheet heterojunction EVA
| Sample (I) | 400nm wavelength violetExternal barrier | Ultraviolet barrier rate of 400nm wavelength after aging for 1 month |
| Example 1 | 96.2％ | 94.3％ |
| Example 2 | 96.9％ | 94.5％ |
| Example 3 | 97.6％ | 94.8％ |
Claims (2)
1. A preparation method of EVA white master batch with anti-aging function is characterized by comprising the following steps,
1) dispersing the carbon microsphere seeds into a titanium salt solution of 2-4M, wherein the molar ratio of the carbon microsphere seeds to the titanium salt is 1: 5, performing ultrasonic assistance at 30-50 ℃ for 6-8 hours, then filtering, washing with deionized water for 2-3 times, and drying to obtain A;
2) calcining the A in the air at a heating speed of 1-2 ℃/min at 500-600 ℃ for 2-3 h, and keeping the temperature for 30-60 min when the temperature is reduced to 300-400 ℃ to obtain TiO 2@ carbon microsphere seeds with TiO 2 as a shell and carbon microsphere seeds as a core, wherein the label is B;
3) dispersing B into 2-4M of aluminum salt solution, wherein the molar ratio of aluminum salt to TiO 2 is 3: 1), repeating the step 1) and the step 2) to obtain alumina Al 2O 3 serving as an outermost shell, TiO 2 serving as an intermediate shell and gradually reduced carbon microsphere seeds serving as an innermost shell, namely Al 2O 3@ TiO 2@ reduced carbon microsphere seeds, and marking the seeds as C;
4) dispersing C into a titanium salt 2-4M solution, wherein the molar ratio of the titanium salt to Al 2O 3 is 3: 1, repeating the step 1) and the step 2), wherein the consumption of the carbon microsphere seeds is almost completely finished, and obtaining TiO 2@ Al 2O 3@ TiO 2;
5) adding TiO 2@ Al 2O 3@ TiO 2 and a zinc salt into oleylamine, performing magnetic stirring, introducing an inert gas Ar gas for 20-60 min, gradually heating the solution to 120-150 ℃, uniformly mixing TiO 2@ Al 2O 3@ TiO 2 and the zinc salt, injecting ethanol into the solution at a rate of 1-15 mL/min for 1-20 min, performing magnetic stirring at the temperature for 30-60 min, then heating to 220-250 ℃, keeping the reaction mixture at the temperature for 20-30 min, and naturally cooling to room temperature to obtain a final product TiO 2@ Al 2O 3@ TiO 2/ZnO nanosheet heterojunction;
6) mixing 50 parts of ethylene-vinyl acetate copolymer, 10 parts of ethylene-octene copolymer, 35 parts of TiO 2@ Al 2O 3@ TiO 2/ZnO nanosheet heterojunction, 1 part of antioxidant 2, 6-di-tert-butyl-4-ethylphenol, 3 parts of coupling agent aluminum-titanium composite coupling agent and 1 part of crosslinking agent tert-butyl peroxybenzoate, uniformly mixing, adding into a double-screw extruder, controlling the temperature at nine sections, extruding, cooling, drawing strips, air-drying and granulating to obtain white master batches with the EVA anti-aging function;
in the step 1), the titanium salt is one or a combination of tetrabutyl titanate, isopropyl titanate or ethyl titanate;
the aluminum salt in the step 3) is one or the combination of aluminum citrate or aluminum chloride;
the zinc salt in the step 5) is one or the combination of zinc acetate, zinc citrate or zinc chloride.
2. The preparation method of the EVA white masterbatch with the aging resistance function of claim 1, wherein nine-stage temperature control processing temperature of the twin-screw extruder in the step 6) is set as follows: the temperature in the first zone is 120 ℃, the temperature in the second zone is 128 ℃, the temperature in the third zone is 135 ℃, the temperature in the fourth zone is 142 ℃, the temperature in the fifth zone is 150 ℃, the temperature in the sixth zone is 142 ℃, the temperature in the seventh zone is 135 ℃, the temperature in the eighth zone is 128 ℃ and the temperature in the ninth zone is 120 ℃.
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| CN109107562A (en) * | 2018-09-19 | 2019-01-01 | 安庆师范大学 | A kind of preparation method of Zinc oxide/titanium dioxide complex microsphere |
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| CN101066988A (en) * | 2007-05-10 | 2007-11-07 | 复旦大学 | Magnetic metal oxide microsphere in core-shell structure and its prepn process |
| CN103199299A (en) * | 2012-01-06 | 2013-07-10 | 王复民 | Lithium ion battery anode protection layer and its manufacturing method |
| CN103191721A (en) * | 2013-04-15 | 2013-07-10 | 天津大学 | Method for preparing tungsten trioxide/titanium dioxide nanocomposite with core-shell structure |
| CN109107562A (en) * | 2018-09-19 | 2019-01-01 | 安庆师范大学 | A kind of preparation method of Zinc oxide/titanium dioxide complex microsphere |
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