Antibacterial shading PET (polyethylene terephthalate) film for mobile phone and preparation method thereof
阅读说明：本技术 一种手机用抗菌遮光pet薄膜及其制备方法 (Antibacterial shading PET (polyethylene terephthalate) film for mobile phone and preparation method thereof ) 是由 朱致国 于 2021-08-12 设计创作，主要内容包括：本发明提出了一种手机用抗菌遮光PET薄膜及其制备方法,属于PET材料技术领域,由以下原料按重量份制备而成：二氧化钛载银纳米粉末改性PET树脂80-100份、聚苯胺包覆纳米二氧化硅/石墨复合物5-10份、噁唑环聚合物1-2份、增塑剂2-4份、增韧剂1-3份、润滑剂0.1-0.4份、抗氧剂0.2-0.8份；所述噁唑环聚合物的化学结构式如下：其中,n＝100-500；本发明提供的手机用抗菌遮光PET薄膜及其制备方法,工艺方法简单,加工成本较低,制备的PET薄膜具有优异的抗静电性能、抗菌、遮光和力学性能,可以用于手机屏幕的保护膜中,起到很好的保护隐私,卫生以及抗静电的效果。(The invention provides an antibacterial shading PET film for a mobile phone and a preparation method thereof, belonging to the technical field of PET materialsThe preparation method comprises the following steps: 80-100 parts of titanium dioxide silver-loaded nano powder modified PET resin, 5-10 parts of polyaniline-coated nano silicon dioxide/graphite compound, 1-2 parts of oxazole ring polymer, 2-4 parts of plasticizer, 1-3 parts of toughening agent, 0.1-0.4 part of lubricant and 0.2-0.8 part of antioxidant; the chemical structural formula of the oxazole ring polymer is as follows:)
1. An antibacterial shading PET film for a mobile phone is characterized by being prepared from the following raw materials in parts by weight: 80-100 parts of titanium dioxide silver-loaded nano powder modified PET resin, 5-10 parts of polyaniline-coated nano silicon dioxide/graphite compound, 1-2 parts of oxazole ring polymer, 2-4 parts of plasticizer, 1-3 parts of toughening agent, 0.1-0.4 part of lubricant and 0.2-0.8 part of antioxidant;
the chemical structural formula of the oxazole ring polymer is as follows:
wherein n is 100-;
the preparation method of the titanium dioxide silver-loaded nano powder modified PET resin comprises the following steps:
s1, dissolving tetrabutyl titanate and silver nitrate in an ethanol-water solution, mixing and stirring for 2-4h, adding an ammonia water solution, stirring for reaction for 5-10h, filtering, and washing with water to obtain titanium dioxide powder adsorbing silver-ammonia complex ions;
s2, adding the titanium dioxide powder adsorbing the silver ammino ions obtained in the step S1 into deionized water, performing ultrasonic dispersion, adding sodium borohydride, reacting for 0.5-1h, filtering the obtained suspension, washing with water, and drying to obtain titanium dioxide silver-loaded nano powder;
s3, dissolving PET resin in ethanol, aging for 5-7h at room temperature, adding 0.5-1 wt% of silane coupling agent, heating to 60-80 ℃, reacting for 0.5-1h, adding the titanium dioxide silver-loaded nano powder obtained in the step S2, ultrasonically stirring for 20-30min, uniformly stirring, adding into a Haake torque rheometer, and blending for 5-10min at 220-240 ℃ to obtain the titanium dioxide silver-loaded nano powder modified PET resin.
2. The antibacterial shading PET film for the mobile phone according to claim 1, wherein the mass ratio of the tetrabutyl titanate to the silver nitrate to the sodium borohydride is (15-25): (2-5): (0.5-1); the mass fraction of ethanol in the ethanol-water solution is 60-80%, and the balance is water; the silane coupling agent is a silane coupling agent with amino groups and is selected from at least one of KH550, KH602 and KH 792; the mass ratio of the PET resin to the titanium dioxide silver-loaded nano powder is 100: (10-17); the ultrasonic power is 1000-2000W, and the ultrasonic time is 10-20 min.
3. The antibacterial shading PET film for the mobile phone according to claim 1, characterized in that the preparation method of the oxazole ring polymer is as follows: dissolving polyacrylamide, p-toluenesulfonic acid monohydrate (PTSA) and acetylene alcohol in toluene, and reacting for 10-20h to obtain the oxazole ring polymer.
4. The antibacterial shading PET film for the mobile phone according to claim 1, wherein the polyaniline-coated nano silica/graphite composite is prepared by the following method:
mixing an aniline solution and an HCl solution, then adding graphite particles and alkyl orthosilicate, carrying out ultrasonic dispersion for 5-10min, and carrying out magnetic stirring for 10-20min to obtain a mixed solution;
and adding an initiator into the mixed solution, stirring and reacting for 4-7h, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, and drying at 80-90 ℃ for 4-6h to obtain the polyaniline-coated nano silicon dioxide/graphite compound.
5. The antibacterial and lightproof PET film for mobile phones according to claim 4, wherein the initiator is at least one selected from ammonium persulfate, potassium persulfate and sodium persulfate; the alkyl orthosilicate is ethyl orthosilicate or methyl orthosilicate.
6. The PET film for a mobile phone with antibacterial and light-shielding function according to claim 1, wherein the plasticizer is one or more selected from di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butylbenzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diisononyl phthalate, diisodecyl phthalate, or diethyl phthalate.
7. The antibacterial and lightproof PET film for mobile phones according to claim 1, wherein the toughening agent is at least one selected from the group consisting of Acoma AX8900, LG EM500, DuPont PTW and DuPont 1125 AC.
8. The antibacterial and lightproof PET film for mobile phones according to claim 1, wherein the antioxidant is selected from one or more of diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-t-butyl-4-methylphenol, bis (3, 5-t-butyl-4-hydroxyphenyl) sulfide, pentaerythrityl tetrakis [ beta- (3, 5-t-butyl-4-hydroxyphenyl) propionate ], bisdodecanol ester, bistetradecanol ester, dioctadecyl ester, trioctyl ester, tridecyl ester, tridodecanol ester or trihexadecyl ester.
9. The antibacterial and lightproof PET film for mobile phones according to claim 1, wherein the lubricant is one or more selected from oleic acid, stearic acid, PE wax, calcium stearate, montan wax, ethylene bis-stearamide, erucamide.
10. A method for preparing the antibacterial shading PET film for the mobile phone according to any one of claims 1 to 9, which comprises the following steps: drying the titanium dioxide silver-loaded nano powder modified PET resin and a vacuum drying oven at 120 ℃ for 5-10h, then adding the polyaniline-coated nano silicon dioxide/graphite compound, the oxazole ring polymer, the plasticizer, the toughening agent, the lubricant and the antioxidant into a side feed port of a double-screw extruder, adding the titanium dioxide silver-loaded nano powder modified PET resin through a main feed port, carrying out melt blending, carrying out wire drawing and grain cutting, carrying out melt extrusion to obtain a thick film, shaping after biaxial stretching, and cutting to obtain the antibacterial shading PET film for the mobile phone.
Technical Field
The invention relates to the technical field of PET materials, in particular to an antibacterial shading PET film for a mobile phone and a preparation method thereof.
Background
With the development of industry, electronic products such as mobile phones, tablets, computers and intelligent wearing are increasingly popularized, the production industry of electronic elements such as semiconductors is increasingly strong, and the integration level of electronic elements and electronic circuits is higher and higher.
The PET resin is polyethylene terephthalate plastic, commonly called polyester resin, which is a polycondensate of terephthalic acid and ethylene glycol, and is commonly called as thermoplastic polyester or saturated polyester together with PBT (polybutylene terephthalate), the molecular structure of the PET resin is highly symmetrical and has certain crystal orientation capability, so the PET resin has higher film forming property, has good weather resistance, and in addition, the PET resin has excellent wear and friction resistance, dimensional stability and electrical insulation property, and PET bottles made of the PET have the advantages of high strength, no toxicity, seepage resistance, light weight, high production efficiency and the like, so the PET resin is widely applied, but has poor antibacterial property, strong light transmittance, low crystallization speed, poor impact resistance and difficult processing.
Therefore, the development of an antibacterial and light-shielding PET film for mobile phones has become a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide an antibacterial shading PET film for a mobile phone and a preparation method thereof, the process method is simple, the processing cost is low, and the prepared PET film has excellent antistatic performance, antibacterial performance, shading performance and mechanical performance, can be used in a protective film of a mobile phone screen, and has good privacy, sanitation and antistatic effects.
The technical scheme of the invention is realized as follows:
the invention provides an antibacterial shading PET film for a mobile phone, which is prepared from the following raw materials in parts by weight: 80-100 parts of titanium dioxide silver-loaded nano powder modified PET resin, 5-10 parts of polyaniline-coated nano silicon dioxide/graphite compound, 1-2 parts of oxazole ring polymer, 2-4 parts of plasticizer, 1-3 parts of toughening agent, 0.1-0.4 part of lubricant and 0.2-0.8 part of antioxidant;
the chemical structural formula of the oxazole ring polymer is as follows:
wherein n is 100-;
the preparation method of the titanium dioxide silver-loaded nano powder modified PET resin comprises the following steps:
s1, dissolving tetrabutyl titanate and silver nitrate in an ethanol-water solution, mixing and stirring for 2-4h, adding an ammonia water solution, stirring for reaction for 5-10h, filtering, and washing with water to obtain titanium dioxide powder adsorbing silver-ammonia complex ions;
s2, adding the titanium dioxide powder adsorbing the silver ammino ions obtained in the step S1 into deionized water, performing ultrasonic dispersion, adding sodium borohydride, reacting for 0.5-1h, filtering the obtained suspension, washing with water, and drying to obtain titanium dioxide silver-loaded nano powder;
s3, dissolving PET resin in ethanol, aging for 5-7h at room temperature, adding 0.5-1 wt% of silane coupling agent, heating to 60-80 ℃, reacting for 0.5-1h, adding the titanium dioxide silver-loaded nano powder obtained in the step S2, ultrasonically stirring for 20-30min, uniformly stirring, adding into a Haake torque rheometer, and blending for 5-10min at 220-240 ℃ to obtain the titanium dioxide silver-loaded nano powder modified PET resin.
As a further improvement of the invention, the mass ratio of the tetrabutyl titanate to the silver nitrate to the sodium borohydride is (15-25): (2-5): (0.5-1); the mass fraction of ethanol in the ethanol-water solution is 60-80%, and the balance is water; the silane coupling agent is a silane coupling agent with amino groups and is selected from at least one of KH550, KH602 and KH 792; the mass ratio of the PET resin to the titanium dioxide silver-loaded nano powder is 100: (10-17); the ultrasonic power is 1000-2000W, and the ultrasonic time is 10-20 min.
As a further improvement of the invention, the preparation method of the oxazole ring polymer is as follows: dissolving polyacrylamide, p-toluenesulfonic acid monohydrate (PTSA) and acetylene alcohol in toluene, and reacting for 10-20h to obtain the oxazole ring polymer.
As a further improvement of the invention, the polyaniline-coated nano-silica/graphite composite is prepared by the following method:
mixing an aniline solution and an HCl solution, then adding graphite particles and alkyl orthosilicate, carrying out ultrasonic dispersion for 5-10min, and carrying out magnetic stirring for 10-20min to obtain a mixed solution;
and adding an initiator into the mixed solution, stirring and reacting for 4-7h, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, and drying at 80-90 ℃ for 4-6h to obtain the polyaniline-coated nano silicon dioxide/graphite compound.
As a further improvement of the invention, the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the alkyl orthosilicate is ethyl orthosilicate or methyl orthosilicate.
As a further improvement of the invention, the plasticizer is selected from one or more of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diisononyl phthalate, diisodecyl phthalate or diethyl phthalate.
As a further improvement of the invention, the toughening agent is selected from at least one of akoma AX8900, LG EM500, dupont PTW, dupont 1125 AC.
As a further improvement of the invention, the antioxidant is selected from one or more of diphenylamine, p-phenylenediamine, dihydroquinoline, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, didodecanol ester, ditetradecanol ester, dioctadecyl ester, trioctyl ester, tridecyl ester, tridodecyl ester or trihexadecyl ester.
As a further improvement of the invention, the lubricant is selected from one or more of oleic acid, stearic acid, PE wax, calcium stearate, montan wax, ethylene bisstearamide and erucamide.
The invention further provides a preparation method of the antibacterial shading PET film for the mobile phone, which comprises the following steps: drying the titanium dioxide silver-loaded nano powder modified PET resin and a vacuum drying oven at 120 ℃ for 5-10h, then adding the polyaniline-coated nano silicon dioxide/graphite compound, the oxazole ring polymer, the plasticizer, the toughening agent, the lubricant and the antioxidant into a side feed port of a double-screw extruder, adding the titanium dioxide silver-loaded nano powder modified PET resin through a main feed port, carrying out melt blending, carrying out wire drawing and grain cutting, carrying out melt extrusion to obtain a thick film, shaping after biaxial stretching, and cutting to obtain the antibacterial shading PET film for the mobile phone.
The invention has the following beneficial effects: the prepared titanium dioxide silver-loaded nano powder modified PET resin is prepared by hydrogen titanium dioxide gel prepared by a sol-gel method and silver ammino ions are adsorbed on the surface of the hydrogen titanium dioxide gel to obtain titanium dioxide powder with the silver ammino ions adsorbed by the titanium dioxide, the titanium dioxide powder is dispersed in water and then is reduced by sodium borohydride reaction to obtain simple substance silver nano particles, so that the titanium dioxide silver-loaded nano powder is obtained, carrier titanium dioxide in the nano powder has good photocatalytic effect, and meanwhile, due to the nano structure of the powder, electric charges and hydrogen can be generated under the sunlight, so that the antistatic property and the shading effect of the PET resin are improved, and due to the existence of the silver nano particles and the titanium dioxide, the PET resin has good antibacterial property and antistatic property, so that the resin has good shading, antistatic and antibacterial properties;
in the polyaniline-coated nano silicon dioxide/graphite compound prepared by the invention, the mechanical property of a PET film can be obviously improved by adding the nano silicon dioxide, the compressive strength and the elongation at break of the PET film are improved, the graphite particles have good conductivity, a large amount of conductive polyaniline is polymerized on the surface of the polyaniline-coated nano silicon dioxide/graphite compound, the antistatic property of a PET material is obviously improved, and meanwhile, polyaniline molecules and a matrix PET have good compatibility. In addition, polyaniline in the polyaniline-coated microspheres has a strong absorption effect on visible light, and meanwhile, due to the black color of graphite particles, the PET film has excellent shading performance;
the oxazole ring polymer prepared by the invention is mainly polypropylene long chain, is provided with a plurality of oxygen-containing azole heterocycles, and is easy to form and comprises the following components: hydrogen bonds, coordination bonds with metals, hydrophobic effect, pi-pi accumulation, electrostatic effect and the like, so that excellent broad-spectrum antibacterial, antifungal, antiviral, antistatic and other effects are shown, and the polypropylene long-chain structure enables the oxazole ring polymer to have good compatibility in PET resin, so that the effects of antibiosis, antistatic and mechanical property improvement of the oxazole ring polymer are improved.
Therefore, the antibacterial shading PET film for the mobile phone and the preparation method thereof provided by the invention have the advantages that the process method is simple, the processing cost is low, the prepared PET film has excellent antistatic performance, antibacterial performance, shading performance and mechanical performance, and can be used for a protective film of a mobile phone screen, so that the effects of protecting privacy, sanitation and resisting static electricity are good.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The embodiment provides an antibiotic shading PET film for cell-phone:
the raw materials comprise the following components in parts by weight: 80 parts of titanium dioxide silver-loaded nano powder modified PET resin, 5 parts of polyaniline-coated nano silicon dioxide/graphite compound, 1 part of oxazole ring polymer, 2 parts of diisononyl phthalate, 0.1 part of Acoma AX 89001 part, 0.2 part of PE wax and 0.2 part of p-phenylenediamine.
The preparation method of the oxazole ring polymer comprises the following steps:
the synthetic route is as follows:
the preparation method of the oxazole ring polymer comprises the following steps: 1mol of polyacrylamide (n ═ 100), 1mol of p-toluenesulfonic acid monohydrate (PTSA), and 1.5mol of acetylene alcohol were dissolved in toluene and reacted for 10 hours to obtain the oxazole ring polymer, with the yield of 90%.
The obtained oxazole ring polymer was analyzed by infrared spectroscopy as follows:
2924cm-1is a characteristic absorption peak of methylene antisymmetric stretching vibration, 2857cm-1Is a characteristic absorption peak of methylene symmetric stretching vibration, 1550cm-1、1475cm-1、1274cm-1And 958cm-1Characteristic absorption peak of oxazole ring; 1448cm-1The characteristic absorption peak of methylene deformation is obtained by an infrared spectrogram, and the oxazole ring polymer with the structure is successfully synthesized.
The preparation method of the titanium dioxide silver-loaded nano powder modified PET resin comprises the following steps:
s1, dissolving 15g of tetrabutyl titanate and 2g of silver nitrate in 100mL of 60 wt% ethanol aqueous solution, mixing and stirring for 2h, adding 50mL of 30 wt% ammonia aqueous solution, stirring for reaction for 5h, filtering, and washing with water to obtain titanium dioxide powder adsorbing silver-ammonia complex ions;
s2, adding the titanium dioxide powder adsorbing the silver ammino ions obtained in the step S1 into 100mL of deionized water, performing ultrasonic dispersion with ultrasonic power of 1000W and ultrasonic time of 10min, adding 0.5g of sodium borohydride, reacting for 0.5h, filtering the obtained suspension, washing with water, and drying to obtain titanium dioxide silver-loaded nano powder;
s3, dissolving 100g of PET resin in 200mL of ethanol, aging at room temperature for 5h, adding 0.5 wt% of silane coupling agent KH792, heating to 60 ℃, reacting for 0.5h, adding 10g of titanium dioxide silver-loaded nano powder obtained in the step S2, ultrasonically stirring for 20min, uniformly stirring, adding into a Haake torque rheometer, and blending at 220 ℃ for 5min to obtain the titanium dioxide silver-loaded nano powder modified PET resin.
The polyaniline-coated nano silicon dioxide/graphite compound is prepared by the following method:
mixing 0.1mol aniline solution and 50mL 5mol/L HCl solution, then adding 7g graphite particles and 15g ethyl orthosilicate, carrying out ultrasonic dispersion at 1000W for 5min, and carrying out magnetic stirring for 10min to obtain a mixed solution;
and adding 2.5g of ammonium persulfate into the mixed solution, stirring to react for 4 hours, filtering, washing the solid by using absolute ethyl alcohol and deionized water in sequence, and drying at 80 ℃ for 4 hours to obtain the polyaniline-coated nano silicon dioxide/graphite compound.
The preparation method of the antibacterial shading PET film for the mobile phone comprises the following steps: drying the titanium dioxide silver-loaded nano powder modified PET resin in a vacuum drying oven at 110 ℃ for 5 hours, then adding polyaniline-coated nano silicon dioxide/graphite compound, oxazole ring polymer, diisononyl phthalate, acoma AX8900, PE wax and p-phenylenediamine into a side feeding port of a double-screw extruder, adding the titanium dioxide silver-loaded nano powder modified PET resin through a main feeding port, carrying out melt blending, carrying out wire drawing and grain cutting, carrying out melt extrusion to obtain a thick film, shaping after biaxial stretching, cutting to obtain the antibacterial shading PET film for the mobile phone.
Example 2
The embodiment provides an antibiotic shading PET film for cell-phone:
the raw materials comprise the following components in parts by weight: 100 parts of titanium dioxide silver-loaded nano powder modified PET resin, 10 parts of polyaniline-coated nano silicon dioxide/graphite compound, 2 parts of oxazole ring polymer, 4 parts of butyl benzyl phthalate, 3 parts of DuPont PTW, 0.4 part of oleic acid and 0.8 part of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether.
The preparation method of the oxazole ring polymer comprises the following steps:
the preparation method of the oxazole ring polymer comprises the following steps: 1mol of polyacrylamide (n ═ 100), 1mol of p-toluenesulfonic acid monohydrate (PTSA), and 1.5mol of acetylene alcohol were dissolved in toluene and reacted for 20 hours to obtain the oxazole ring polymer in a yield of 92%.
The preparation method of the titanium dioxide silver-loaded nano powder modified PET resin comprises the following steps:
s1, dissolving 25g of tetrabutyl titanate and 5g of silver nitrate in 100mL of 80 wt% ethanol aqueous solution, mixing and stirring for 4h, adding 50mL of 35 wt% ammonia aqueous solution, stirring and reacting for 10h, filtering, and washing with water to obtain titanium dioxide powder adsorbing silver-ammonia complex ions;
s2, adding the titanium dioxide powder adsorbing the silver ammino ions obtained in the step S1 into 100mL of deionized water, performing ultrasonic dispersion with ultrasonic power of 2000W and ultrasonic time of 20min, adding 1g of sodium borohydride, reacting for 1h, filtering the obtained suspension, washing with water, and drying to obtain titanium dioxide silver-loaded nano powder;
s3, dissolving 100g of PET resin in 200mL of ethanol, aging at room temperature for 7h, adding 1 wt% of silane coupling agent KH602, heating to 80 ℃, reacting for 1h, adding 17g of the titanium dioxide silver-loaded nano powder obtained in the step S2, ultrasonically stirring for 30min at 1000W, uniformly stirring, adding into a Haake torque rheometer, and blending at 240 ℃ for 10min to obtain the titanium dioxide silver-loaded nano powder modified PET resin.
The polyaniline-coated nano silicon dioxide/graphite compound is prepared by the following method:
mixing 0.1mol aniline solution and 50mL 5mol/L HCl solution, then adding 7g graphite particles and 15g ethyl orthosilicate, performing ultrasonic dispersion at 1000W for 10min, and performing magnetic stirring for 20min to obtain a mixed solution;
and adding 2.5g of ammonium persulfate into the mixed solution, stirring to react for 7 hours, filtering, washing the solid by using absolute ethyl alcohol and deionized water in sequence, and drying at 90 ℃ for 6 hours to obtain the polyaniline-coated nano silicon dioxide/graphite compound.
The preparation method of the antibacterial shading PET film for the mobile phone comprises the following steps: drying the titanium dioxide silver-loaded nano powder modified PET resin in a vacuum drying oven at 120 ℃ for 10 hours, then adding polyaniline-coated nano silicon dioxide/graphite compound, oxazole ring polymer, butyl benzyl phthalate, DuPont PTW, oleic acid and bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether into a side feeding port of a double-screw extruder, adding the titanium dioxide silver-loaded nano powder modified PET resin through a main feeding port, carrying out melt blending, carrying out wire drawing and grain cutting, carrying out melt extrusion to obtain a thick film, carrying out shaping after biaxial stretching, and cutting to obtain the antibacterial shading PET film for the mobile phone.
Example 3
The embodiment provides an antibiotic shading PET film for cell-phone:
the raw materials comprise the following components in parts by weight: 90 parts of titanium dioxide silver-loaded nano powder modified PET resin, 7 parts of polyaniline-coated nano silicon dioxide/graphite compound, 1.5 parts of oxazole ring polymer, 3 parts of di (2-ethylhexyl) phthalate, 5002 parts of LG EM, 0.3 part of stearic acid and 0.5 part of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the oxazole ring polymer comprises the following steps:
the preparation method of the oxazole ring polymer comprises the following steps: 1mol of polyacrylamide (n ═ 100), 1mol of p-toluenesulfonic acid monohydrate (PTSA), and 1.5mol of acetylene alcohol were dissolved in toluene and reacted for 18 hours to obtain the oxazole ring polymer in a yield of 94%.
The preparation method of the titanium dioxide silver-loaded nano powder modified PET resin comprises the following steps:
s1, dissolving 20g of tetrabutyl titanate and 3.5g of silver nitrate in 100mL of 70 wt% ethanol aqueous solution, mixing and stirring for 3h, adding 50mL of 35 wt% ammonia aqueous solution, stirring and reacting for 7h, filtering, and washing with water to obtain titanium dioxide powder adsorbing silver-ammonia complex ions;
s2, adding the titanium dioxide powder adsorbing the silver ammino ions obtained in the step S1 into 100mL of deionized water, performing ultrasonic dispersion with ultrasonic power of 1500W and ultrasonic time of 15min, adding 0.75g of sodium borohydride, reacting for 1h, filtering the obtained suspension, washing with water, and drying to obtain titanium dioxide silver-loaded nano powder;
s3, dissolving 100g of PET resin in ethanol, aging at room temperature for 6h, adding 0.75 wt% of silane coupling agent KH550, heating to 70 ℃, reacting for 1h, adding 14g of titanium dioxide silver-loaded nano powder obtained in the step S2, ultrasonically stirring for 25min at 1000W, uniformly stirring, adding into a Haake torque rheometer, and blending for 7min at 230 ℃ to obtain the titanium dioxide silver-loaded nano powder modified PET resin.
The polyaniline-coated nano silicon dioxide/graphite compound is prepared by the following method:
mixing 0.1mol aniline solution and 50mL 5mol/L HCl solution, then adding 7g graphite particles and 15g ethyl orthosilicate, carrying out ultrasonic dispersion at 1000W for 7min, and carrying out magnetic stirring for 15min to obtain a mixed solution;
and adding 2.5g of ammonium persulfate into the mixed solution, stirring to react for 5 hours, filtering, washing the solid by using absolute ethyl alcohol and deionized water in sequence, and drying at 85 ℃ for 5 hours to obtain the polyaniline-coated nano silicon dioxide/graphite compound.
The preparation method of the antibacterial shading PET film for the mobile phone comprises the following steps: drying the titanium dioxide silver-loaded nano powder modified PET resin in a vacuum drying oven at 115 ℃ for 7 hours, then adding polyaniline-coated nano silicon dioxide/graphite compound, oxazole ring polymer, di (2-ethylhexyl) phthalate, LGEM 500, stearic acid and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester into a side feeding port of a double-screw extruder, adding the titanium dioxide silver-loaded nano powder modified PET resin through a main feeding port, carrying out melt blending, carrying out wire drawing and grain cutting, carrying out melt extrusion to obtain a thick film, carrying out shaping after biaxial stretching, and cutting to obtain the antibacterial shading PET film for the mobile phone.
Comparative example 1
Compared with the example 3, the titanium dioxide silver-loaded nano powder modified PET resin is modified by the titanium dioxide nano powder, and other conditions are not changed.
The preparation method of the titanium dioxide nano powder modified PET resin comprises the following steps:
dissolving 100g of PET resin in ethanol, aging at room temperature for 6h, adding 0.75 wt% of silane coupling agent KH550, heating to 70 ℃, reacting for 1h, adding 14g of titanium dioxide nanopowder obtained in step S2, ultrasonically stirring for 25min at 1000W, uniformly stirring, adding into a Haake torque rheometer, and blending for 7min at 230 ℃ to obtain the dioxide nanopowder modified PET resin.
Comparative example 2
Compared with the example 3, the titanium dioxide silver-loaded nano powder modified PET resin is modified by the silver nano powder, and other conditions are not changed.
The preparation method of the silver nano powder modified PET resin comprises the following steps:
dissolving 100g of PET resin in ethanol, aging at room temperature for 6h, adding 0.75 wt% of silane coupling agent KH550, heating to 70 ℃, reacting for 1h, adding 14g of the silver nanopowder obtained in the step S2, ultrasonically stirring for 25min at 1000W, uniformly stirring, adding into a Haake torque rheometer, and blending for 7min at 230 ℃ to obtain the silver nanopowder modified PET resin.
Comparative example 3
Compared with the embodiment 3, no graphite is added in the preparation of the polyaniline-coated nano silicon dioxide/graphite composite, and other conditions are not changed.
The polyaniline-coated nano silicon dioxide/graphite compound is prepared by the following method:
mixing 0.1mol aniline solution with 50mL 5mol/L HCl solution, then adding 22g ethyl orthosilicate, ultrasonically dispersing for 7min at 1000W, and magnetically stirring for 15min to obtain a mixed solution;
and adding 2.5g of ammonium persulfate into the mixed solution, stirring to react for 5 hours, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, and drying at 85 ℃ for 5 hours to obtain the polyaniline-coated graphite compound.
Comparative example 4
Compared with the embodiment 3, the preparation of the polyaniline-coated nano silicon dioxide/graphite compound is not added with tetraethoxysilane, and other conditions are not changed.
The polyaniline-coated nano silicon dioxide/graphite compound is prepared by the following method:
mixing 0.1mol aniline solution and 50mL 5mol/L HCl solution, then adding 22g graphite particles, carrying out 1000W ultrasonic dispersion for 7min, and carrying out magnetic stirring for 15min to obtain a mixed solution;
and adding 2.5g of ammonium persulfate into the mixed solution, stirring to react for 5 hours, filtering, washing the solid by using absolute ethyl alcohol and deionized water in sequence, and drying at 85 ℃ for 5 hours to obtain the polyaniline-coated nano-silica composite.
Comparative example 5
Compared with the example 3, the titanium dioxide silver-loaded nano powder modified PET resin is replaced by the PET resin, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 90 parts of PET resin, 7 parts of polyaniline-coated nano silicon dioxide/graphite compound, 3 parts of di (2-ethylhexyl) phthalate, 5002 parts of LG EM, 0.3 part of stearic acid and 0.5 part of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Comparative example 6
Compared with the embodiment 3, the polyaniline-coated nano silicon dioxide/graphite composite is not added, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 97 parts of titanium dioxide silver-loaded nano powder modified PET resin, 3 parts of di (2-ethylhexyl) phthalate, 5002 parts of LG EM, 0.3 part of stearic acid and 0.5 part of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Comparative example 7
Compared with example 3, no oxazole ring polymer was added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 91.5 parts of titanium dioxide silver-loaded nano powder modified PET resin, 7 parts of polyaniline-coated nano silicon dioxide/graphite compound, 3 parts of di (2-ethylhexyl) phthalate, 5002 parts of LG EM, 0.3 part of stearic acid and 0.5 part of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Test example 1 antibacterial property test
The films obtained in inventive examples 1 to 3 and comparative examples 1 to 6 were tested according to test method 1 of standard GB21551.2-2010, using a film application method, the results of which are shown in Table 1.
Detection bacteria: escherichia coli; staphylococcus aureus bacteria; candida albicans.
TABLE 1
Group of
Antibacterial ratio of Escherichia coli (%)
Staphylococcus aureus antibacterial ratio (%)
Candida albicans (%)
Example 1
98.4
99.2
95.7
Example 2
98.9
99.1
95.2
Example 3
99.4
99.7
96.5
Comparative example 1
90.5
91.4
88.5
Comparative example 2
92.1
92.9
87.2
Comparative example 3
96.2
96.7
93.4
Comparative example 4
96.0
95.9
92.5
Comparative example 5
64.5
65.2
59.3
Comparative example 6
94.7
95.2
93.2
Comparative example 7
92.5
94.7
91.0
As can be seen from the table, the antibacterial shading PET film for the mobile phone, which is prepared by the invention, has good antibacterial and bacteriostatic effects.
Test example 2
The films obtained in examples 1 to 3 of the present invention and comparative examples 1 to 6 were subjected to the performance test, and the results are shown in Table 2.
TABLE 2
As can be seen from the table, the antibacterial shading PET film for the mobile phone, which is prepared by the invention, has good antistatic property, mechanical property and shading effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.