阅读说明：本技术 一种手机用防静电黑色pet薄膜及其制备方法 (Antistatic black PET 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防静电黑色PET薄膜及其制备方法,属于PET材料技术领域,由以下重量份的原料制备而成：二氧化锰载银纳米粉末5-12份、四唑聚合物0.5-1份、聚苯胺包覆纳米二氧化钛/苯并三唑复合物3-10份、PET树脂80-100份、偶联剂2-4份、润滑剂0.1-0.4份、增韧剂1-2份、抗氧剂0.1-0.3份,其中,所述四唑聚合物具有如下式Ⅰ所示结构：其中,n＝100-500；本发明提供的手机用防静电黑色PET薄膜及其制备方法,工艺方法简单,加工成本较低,制备的黑色PET薄膜具有优异的抗静电性能、抗菌性能和遮光性能,可以用于手机屏幕的保护膜中,具有广阔的应用前景。(The invention provides aAn anti-static black PET film for a mobile phone and a preparation method thereof belong to the technical field of PET materials, and are prepared from the following raw materials in parts by weight: 5-12 parts of manganese dioxide silver-loaded nano powder, 0.5-1 part of tetrazole polymer, 3-10 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 80-100 parts of PET resin, 2-4 parts of coupling agent, 0.1-0.4 part of lubricant, 1-2 parts of toughening agent and 0.1-0.3 part of antioxidant, wherein the tetrazole polymer has a structure shown as the following formula I:)

1. The antistatic black PET film for the mobile phone is characterized by being prepared from the following raw materials in parts by weight: 5-12 parts of manganese dioxide silver-loaded nano powder, 0.5-1 part of tetrazole polymer, 3-10 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 80-100 parts of PET resin, 2-4 parts of coupling agent, 0.1-0.4 part of lubricant, 1-2 parts of toughening agent and 0.1-0.3 part of antioxidant;

wherein the tetrazole polymer has a structure shown in the following formula I:

wherein n is 100-;

the preparation method of the manganese dioxide silver-loaded nano powder comprises the following steps:

s1, dissolving manganese chloride and silver nitrate in an ethanol-water solution, mixing and stirring for 2-4h, adding an ammonia water solution, stirring and reacting for 1-2h, filtering, washing with water, calcining, and grinding to obtain manganese dioxide powder adsorbing silver-ammonia complex ions;

s2, adding the manganese dioxide powder adsorbing the silver ammino ions obtained in the step S1 into deionized water, performing ultrasonic dispersion, dropwise adding a glucose solution, reacting for 0.5-1h, filtering the obtained suspension, washing with water, drying, and grinding to obtain the manganese dioxide silver-loaded nano powder.

2. The antistatic black PET film for the mobile phone of claim 1, wherein the mass ratio of the manganese chloride to the silver nitrate is (12-20): (3-7); the mass fraction of ethanol in the ethanol-water solution is 25-45%, and the balance is water; the mass fraction of the glucose solution is 15-30%; the calcination temperature is 150-200 ℃; the ultrasonic power is 1000-2000W, and the ultrasonic time is 10-20 min.

3. The antistatic black PET film for mobile phones according to claim 1, wherein the tetrazole polymer is prepared by the following method: in N₂Under protection, polyacrylamide, azodicarbonic acid diethyl ester and PCl are added₅Mixing, stirring for 1-2 hr, adding TMSN₃And continuing the reaction for 40-50h to obtain the tetrazole polymer.

4. The antistatic black PET film for the mobile phone of claim 1, wherein the coupling agent is a mixture of a silane coupling agent and a titanate coupling agent, and the mass ratio is (5-10): (2-5), wherein 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 titanate coupling agent is selected from at least one of TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-114, TMC-2, TMC-27, TMC-4 and TMC-401.

5. The antistatic black PET film for the mobile phone of claim 1, wherein the polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving tetrabutyl titanate, a titanate coupling agent and benzotriazole in a dichloromethane solution to obtain an oil phase;

(2) dissolving a surfactant in water to obtain a water phase;

(3) adding the oil phase into the water phase, emulsifying, adjusting the pH to 3-5 with HCl solution, reacting for 4-7h, and filtering to obtain titanium dioxide embedded benzotriazole nanoparticles;

(4) mixing an aniline solution and an HCl solution, then adding titanium dioxide embedded benzotriazole nanoparticles, performing ultrasonic dispersion for 5-10min, and magnetically stirring for 10-20min to obtain a suspension solution;

(5) and adding an initiator into the suspension liquid, magnetically stirring to react 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 titanium dioxide/benzotriazole compound.

6. The antistatic black PET film for mobile phones as claimed in claim 5, wherein the titanate coupling agent is at least one selected from TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-114, TMC-2, TMC-27, TMC-4, TMC-401; the mass ratio of the tetrabutyl titanate to the titanate coupling agent to the benzotriazole is (20-40): (0.5-1): (3-7); the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate and sodium stearate; the volume ratio of the oil phase to the water phase is (1-2): 10; the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the emulsification condition is 10000-.

7. The antistatic black PET film for mobile phone according to claim 1, wherein the lubricant is at least one selected from silicone oil, graphite, molybdenum disulfide, polytetrafluoroethylene, boron nitride and graphite fluoride.

8. The antistatic black PET film for mobile phones according to claim 1, wherein the antioxidant is at least one selected from 164, 168, 264, 1010, 1076, 1098, MB, DLTP.

9. The antistatic black PET film for mobile phones according to claim 1, wherein the toughening agent is at least one selected from styrene-butadiene thermoplastic elastomer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, polysulfide rubber and nitrile rubber.

10. A method for preparing the antistatic black PET film for the mobile phone according to any one of claims 1 to 9, comprising the steps of:

dissolving PET resin in acetone, heating to 40-70 ℃, adding a coupling agent, stirring for reaction for 1-2h, adding manganese dioxide silver-loaded nano powder, a tetrazole polymer, a polyaniline-coated nano titanium dioxide/benzotriazole compound, a lubricant, a toughening agent and an antioxidant, carrying out high-speed shearing, dispersing and emulsifying for 1h, continuing stirring for 2-4h, standing for defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a mold, and drying for 5-7h in an electric heating forced air drying oven at 50-70 ℃ to obtain the antistatic black PET film for the mobile phone.

Technical Field

The invention relates to the technical field of PET materials, in particular to an anti-static black 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. However, parts such as electronic semiconductor elements have poor antistatic capability, are easily affected by micro-current to cause failures, and are easily permanently damaged particularly when the electrostatic voltage is high.

Currently common metal oxide films, such as ITO (Sn doped In)₂O₃) IMO (Mo doped In)₂O₃) Etc., although having excellent overall photoelectric properties, In thereof₂O₃The price is expensive, the cost is high, and the indium with high toxicity has great harm to human bodies or materials.

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, 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 resistance 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 the PET resin has high transparency, poor antistatic effect, strong light transmittance, slow crystallization speed, poor impact resistance and difficult processing.

Therefore, the development of an antistatic black 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 anti-static black PET film for a mobile phone and a preparation method thereof, the process method is simple, the processing cost is low, and the prepared black PET film has excellent anti-static performance, antibacterial performance and shading performance, can be used for a protective film of a mobile phone screen, and has wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides an antistatic black PET film for a mobile phone, which is prepared from the following raw materials in parts by weight: 5-12 parts of manganese dioxide silver-loaded nano powder, 0.5-1 part of tetrazole polymer, 3-10 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 80-100 parts of PET resin, 2-4 parts of coupling agent, 0.1-0.4 part of lubricant, 1-2 parts of toughening agent and 0.1-0.3 part of antioxidant;

wherein the tetrazole polymer has a structure shown in the following formula I:

formula I;

wherein n is 100-;

the preparation method of the manganese dioxide silver-loaded nano powder comprises the following steps:

s1, dissolving manganese chloride and silver nitrate in an ethanol-water solution, mixing and stirring for 2-4h, adding an ammonia water solution, stirring and reacting for 1-2h, filtering, washing with water, calcining, and grinding to obtain manganese dioxide powder adsorbing silver-ammonia complex ions;

s2, adding the manganese dioxide powder adsorbing the silver ammino ions obtained in the step S1 into deionized water, performing ultrasonic dispersion, dropwise adding a glucose solution, reacting for 0.5-1h, filtering the obtained suspension, washing with water, drying, and grinding to obtain the manganese dioxide silver-loaded nano powder.

As a further improvement of the invention, the mass ratio of the manganese chloride to the silver nitrate is (12-20): (3-7); the mass fraction of ethanol in the ethanol-water solution is 25-45%, and the balance is water; the mass fraction of the glucose solution is 15-30%; the calcination temperature is 150-200 ℃; the ultrasonic power is 1000-2000W, and the ultrasonic time is 10-20 min.

As a further development of the invention, in N₂Under protection, polyacrylamide, azodicarbonic acid diethyl ester and PCl are added₅Mixing, stirring for 1-2 hr, adding TMSN₃And continuing the reaction for 40-50h to obtain the tetrazole polymer.

As a further improvement of the invention, the coupling agent is a mixture of a silane coupling agent and a titanate coupling agent, and the mass ratio of the silane coupling agent to the titanate coupling agent is (5-10): (2-5), wherein 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 titanate coupling agent is selected from at least one of TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-114, TMC-2, TMC-27, TMC-4 and TMC-401.

As a further improvement of the invention, the polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving tetrabutyl titanate, a titanate coupling agent and benzotriazole in a dichloromethane solution to obtain an oil phase;

(2) dissolving a surfactant in water to obtain a water phase;

(3) adding the oil phase into the water phase, emulsifying, adjusting the pH to 3-5 with HCl solution, reacting for 4-7h, and filtering to obtain titanium dioxide embedded benzotriazole nanoparticles;

(4) mixing an aniline solution and an HCl solution, then adding titanium dioxide embedded benzotriazole nanoparticles, performing ultrasonic dispersion for 5-10min, and magnetically stirring for 10-20min to obtain a suspension solution;

(5) and adding an initiator into the suspension liquid, magnetically stirring to react 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 titanium dioxide/benzotriazole compound.

As a further improvement of the invention, the titanate coupling agent is selected from at least one of TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-114, TMC-2, TMC-27, TMC-4 and TMC-401; the mass ratio of the tetrabutyl titanate to the titanate coupling agent to the benzotriazole is (20-40): (0.5-1): (3-7); the surfactant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate and sodium stearate; the volume ratio of the oil phase to the water phase is (1-2): 10; the initiator is selected from at least one of ammonium persulfate, potassium persulfate and sodium persulfate; the emulsification condition is 10000-.

As a further improvement of the present invention, the lubricant is selected from at least one of silicone oil, graphite, molybdenum disulfide, polytetrafluoroethylene, boron nitride, and graphite fluoride.

In a further improvement of the present invention, the antioxidant is at least one selected from 164, 168, 264, 1010, 1076, 1098, MB, and DLTP.

As a further improvement of the invention, the toughening agent is selected from at least one of styrene-butadiene thermoplastic elastomer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, polysulfide rubber and nitrile rubber.

The invention further provides a preparation method of the antistatic black PET film for the mobile phone, which comprises the following steps: dissolving PET resin in acetone, heating to 40-70 ℃, adding a coupling agent, stirring for reaction for 1-2h, adding manganese dioxide silver-loaded nano powder, a tetrazole polymer, a polyaniline-coated nano titanium dioxide/benzotriazole compound, a lubricant, a toughening agent and an antioxidant, carrying out high-speed shearing, dispersing and emulsifying for 1h, continuing stirring for 2-4h, standing for defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a mold, and drying for 5-7h in an electric heating forced air drying oven at 50-70 ℃ to obtain the antistatic black PET film for the mobile phone.

The invention has the following beneficial effects: according to the invention, benzotriazole is embedded in the nano titanium dioxide porous spheres and further coated in polyaniline, the nano titanium dioxide has broadband ultraviolet light scattering performance, has a strong ultraviolet absorption peak at the ultraviolet light wavelength of about 387nm, and is cooperated with benzotriazole with the ultraviolet absorption peak at about 340nm to absorb and shield a large amount of ultraviolet light in sunlight so as to reduce the ultraviolet light degradation degree of polyaniline, so that long-time ultraviolet light stability is endowed, and due to the existence of conductive polyaniline on the surface, polyaniline microspheres have a strong absorption effect on visible light, so that a PET film has excellent light shielding performance and antistatic performance;

manganese dioxide powder capable of adsorbing silver ammine complex ions is obtained after the manganese dioxide-loaded silver nano powder prepared by the invention is subjected to double decomposition reaction to generate manganese hydroxide and silver ammine ions, the manganese hydroxide and the silver ammine ions are mutually adsorbed and further calcined, the manganese dioxide powder capable of adsorbing silver ammine complex ions is obtained, the manganese dioxide powder is dispersed in water and reduced by glucose to obtain simple substance silver nano particles, and thus the manganese dioxide-loaded silver nano powder is obtained, the manganese dioxide powder is black, and the manganese dioxide-loaded silver nano powder is dispersed in PET resin to enable the PET film to be black;

the tetrazole polymer prepared by the invention has a plurality of tetrazole rings on a polymer chain, the ring skeleton of the tetrazole polymer is a planar structure of a multi-nitrogen electron-rich conjugated system, the tetrazole polymer can give electrons and receive electron characteristics, can generate a plurality of non-covalent bond interactions, and is easy to form hydrogen bonds, coordination with metal ions, pi-pi accumulation, electrostatic interaction and the like, so that electron transmission is easy to occur, and the tetrazole polymer has excellent antistatic performance.

Therefore, the antistatic black 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 black PET film has excellent antistatic performance, antibacterial performance and shading performance, can be used for a protective film of a mobile phone screen, and has wide application prospects.

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 invention provides an antistatic black PET film for a mobile phone, which comprises the following components in part by weight:

the raw materials comprise the following components in parts by weight: 5 parts of manganese dioxide silver-loaded nano powder, 0.5 part of tetrazole polymer, 3 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 80 parts of PET resin, 2 parts of coupling agent, 0.1 part of molybdenum disulfide, 1 part of polysulfide rubber and 10100.1 parts of antioxidant. The coupling agent is a mixture of a silane coupling agent KH602 and a titanate coupling agent TMC-2, and the mass ratio is 5: 2.

the tetrazole polymer is prepared as follows:

the synthetic route is as follows:

in N₂Under protection, 1mol of polyacrylamide (n is 100), 0.01mol of diethyl azodicarboxylate and 1.2mol of PCl₅After mixing, stirring and reacting for 1-2h, adding 1.05mol of TMSN₃And continuing the reaction for 40-50h to obtain the tetrazole polymer, and separating to obtain the yield of 57%.

The obtained tetrazole polymer was subjected to infrared spectroscopy as follows:

3340cm^-1is a characteristic absorption peak of the stretching vibration of N-H on the tetrazole ring; 2920cm^-1Is a characteristic absorption peak of methylene antisymmetric stretching vibration, 2855cm^-1 is a characteristic absorption peak of methylene symmetric stretching vibration, 1450cm-1 is a characteristic absorption peak of methylene deformation, 1200-1700cm^-1Absorption peaks generated by the torsion and stretching vibration of the tetrazole ring; 952cm^-1The characteristic absorption peak of the bending vibration of N-H on the tetrazole ring can be obtained by an infrared spectrogram, and the tetrazole polymer with the structure is successfully synthesized.

The preparation method of the manganese dioxide silver-loaded nano powder comprises the following steps:

s1, dissolving 12g of manganese chloride and 3g of silver nitrate in 100mL of 25 wt% ethanol aqueous solution, mixing and stirring for 2h, adding 50mL of 45 wt% ammonia aqueous solution, stirring and reacting for 1h, filtering, washing, calcining at 150 ℃ for 2h, and grinding to obtain manganese dioxide powder adsorbing silver-ammonia complex ions;

s2, adding the manganese 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, dropwise adding 50mL of 15 wt% glucose solution, reacting for 0.5h, filtering the obtained suspension, washing with water, drying, and grinding to obtain the manganese dioxide silver-loaded nano powder.

The polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving 20g of tetrabutyl titanate, 0.5g of titanate coupling agent TMC-401 and 3g of benzotriazole in 10mL of dichloromethane solution to obtain an oil phase;

(2) dissolving 1g of sodium dodecyl benzene sulfonate in 100mL of water to obtain a water phase;

(3) adding the oil phase into the water phase, emulsifying for 5min at the rotating speed of 10000r/min, adjusting the pH to 3 by using HCl solution, reacting for 4h, and filtering to obtain titanium dioxide embedded benzotriazole nano-particles;

(4) mixing 0.025mol aniline solution and 50mL 2mol/L HCl solution, then adding 5g titanium dioxide embedded benzotriazole nano particles, carrying out ultrasonic dispersion at 1000W for 5min, and carrying out magnetic stirring for 10min to obtain suspension liquid;

(5) and adding 3g of potassium persulfate into the suspension liquid, magnetically stirring to react for 4 hours, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, and drying at 80 ℃ for 4 hours to obtain the polyaniline-coated nano titanium dioxide/benzotriazole compound.

A preparation method of an antistatic black PET film for a mobile phone comprises the following steps:

dissolving PET resin in acetone, heating to 40 ℃, adding a coupling agent, stirring for reaction for 1h, adding manganese dioxide silver-loaded nano powder, a tetrazole polymer, a polyaniline-coated nano titanium dioxide/benzotriazole compound, molybdenum disulfide, polysulfide rubber and an antioxidant 1010, shearing, dispersing and emulsifying at the rotating speed of 10000r/min for 1h, continuing stirring for 2h, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a mold, and drying in an electrothermal forced air drying oven at 50 ℃ for 5h to obtain the antistatic black PET film for the mobile phone.

Example 2

The invention provides an antistatic black PET film for a mobile phone, which comprises the following components in part by weight:

the raw materials comprise the following components in parts by weight: 12 parts of manganese dioxide silver-loaded nano powder, 1 part of tetrazole polymer, 10 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 100 parts of PET resin, 4 parts of coupling agent, 0.4 part of boron nitride, 2 parts of ethylene-vinyl acetate copolymer and 0.3 part of antioxidant DLTP. The coupling agent is a mixture of a silane coupling agent KH792 and a titanate coupling agent TMC-3, and the mass ratio is 2: 1.

the tetrazole polymer is prepared as follows:

in N₂Under protection, 1mol of polyacrylamide (n is 100), 0.01mol of diethyl azodicarboxylate and 1.2mol of PCl₅After mixing, stirring and reacting for 2h, 1.05mol TMSN was added₃The reaction was continued for 50h to give the tetrazole polymer, which was isolated in 55% yield.

The preparation method of the manganese dioxide silver-loaded nano powder comprises the following steps:

s1, dissolving 12-20g of manganese chloride and 7g of silver nitrate in 100mL of 45 wt% ethanol aqueous solution, mixing and stirring for 4h, adding 50mL of 45 wt% ammonia aqueous solution, stirring and reacting for 1-2h, filtering, washing, calcining for 5h at 200 ℃, and grinding to obtain manganese dioxide powder adsorbing silver-ammonia complex ions;

s2, adding the manganese 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, dropwise adding 50mL of 30 wt% glucose solution, reacting for 1h, filtering the obtained suspension, washing with water, drying, and grinding to obtain the manganese dioxide silver-loaded nano powder.

The polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving 40g of tetrabutyl titanate, 1g of titanate coupling agent TMC-101 and 7g of benzotriazole in 20mL of dichloromethane solution to obtain an oil phase;

(2) dissolving 1g of sodium hexadecylbenzene sulfonate in 100mL of water to obtain a water phase;

(3) adding the oil phase into the water phase, emulsifying for 10min at the rotating speed of 20000r/min, adjusting the pH to 5 by using HCl solution, reacting for 7h, and filtering to obtain titanium dioxide embedded benzotriazole nanoparticles;

(4) mixing 0.025mol aniline solution and 50mL 2mol/L HCl solution, then adding 5g titanium dioxide embedded benzotriazole nano particles, carrying out ultrasonic dispersion at 1000W for 10min, and carrying out magnetic stirring for 20min to obtain suspension liquid;

(5) and adding 3g of potassium persulfate into the suspension liquid, magnetically stirring to react for 7 hours, filtering, washing the solid with absolute ethyl alcohol and deionized water in sequence, and drying at 90 ℃ for 6 hours to obtain the polyaniline-coated nano titanium dioxide/benzotriazole compound.

A preparation method of an antistatic black PET film for a mobile phone comprises the following steps:

dissolving PET resin in acetone, heating to 70 ℃, adding a coupling agent, stirring for reaction for 2 hours, adding manganese dioxide silver-loaded nano powder, a tetrazole polymer, a polyaniline-coated nano titanium dioxide/benzotriazole compound, boron nitride, an ethylene-vinyl acetate copolymer, an antioxidant DLTP, shearing, dispersing and emulsifying at the rotating speed of 10000r/min for 1 hour, continuing stirring for 4 hours, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a mold, and drying in an electric heating forced air drying oven at 70 ℃ for 5-7 hours to obtain the antistatic black PET film for the mobile phone.

Example 3

The invention provides an antistatic black PET film for a mobile phone, which comprises the following components in part by weight:

the raw materials comprise the following components in parts by weight: 7 parts of manganese dioxide silver-loaded nano powder, 0.7 part of tetrazole polymer, 6 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 90 parts of PET resin, 3 parts of coupling agent, 0.2 part of graphite, 1.5 parts of styrene-butadiene thermoplastic elastomer and 10760.2 parts of antioxidant. The coupling agent is a mixture of a silane coupling agent KH550 and a titanate coupling agent TMC-114, and the mass ratio is 7: 3.

the tetrazole polymer is prepared as follows:

in N₂Under protection, 1mol of polyacrylamide (n is 100), 0.01mol of diethyl azodicarboxylate and 1.2mol of PCl₅After mixing, the mixture was stirred and reacted for 1.5 hours, and 1.05mol of TMSN was added₃The reaction was continued for 48h to give the tetrazole polymer, which was isolated in 59% yield.

The preparation method of the manganese dioxide silver-loaded nano powder comprises the following steps:

s1, dissolving 16g of manganese chloride and 5g of silver nitrate in 100mL of 35 wt% ethanol aqueous solution, mixing and stirring for 3h, adding 50mL of 45 wt% ammonia aqueous solution, stirring and reacting for 1.5h, filtering, washing, calcining at 170 ℃ for 3.5h, and grinding to obtain manganese dioxide powder adsorbing silver-ammonia complex ions;

s2, adding the manganese 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, dropwise adding 50mL of 22 wt% glucose solution, reacting for 1h, filtering the obtained suspension, washing with water, drying, and grinding to obtain the manganese dioxide silver-loaded nano powder.

The polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving 30g of tetrabutyl titanate, 0.75g of titanate coupling agent TMC-3 and 5g of benzotriazole in 15mL of dichloromethane solution to obtain an oil phase;

(2) dissolving 1g of sodium octadecylbenzene sulfonate in 100mL of water to obtain a water phase;

(3) adding the oil phase into the water phase, emulsifying for 7min at the rotating speed of 15000r/min, adjusting the pH to 4 by using HCl solution, reacting for 5h, and filtering to obtain titanium dioxide embedded benzotriazole nano-particles;

(4) mixing 0.025mol aniline solution and 50mL 2mol/L HCl solution, then adding 5g titanium dioxide embedded benzotriazole nano particles, ultrasonically dispersing for 7min at 1000W, and magnetically stirring for 15min to obtain suspension liquid;

(5) and adding 3g of potassium persulfate into the suspension liquid, magnetically 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 nano titanium dioxide/benzotriazole compound.

A preparation method of an antistatic black PET film for a mobile phone comprises the following steps:

dissolving PET resin in acetone, heating to 55 ℃, adding a coupling agent, stirring for reaction for 1.5h, adding manganese dioxide silver-loaded nano powder, a tetrazole polymer, a polyaniline-coated nano titanium dioxide/benzotriazole compound, graphite, a styrene-butadiene thermoplastic elastomer and an antioxidant 1076, shearing, dispersing and emulsifying at the rotating speed of 10000r/min for 1h, continuing stirring for 3h, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a mold, and drying in an electrothermal blowing drying oven at 60 ℃ for 6h to obtain the antistatic black PET film for the mobile phone.

Comparative example 1

Compared with example 3, the manganese dioxide silver-loaded nanopowder is replaced by manganese dioxide nanopowder, and other conditions are not changed.

Comparative example 2

Compared with example 3, the manganese dioxide silver-loaded nanopowder is replaced by silver nanopowder, and other conditions are not changed.

Comparative example 3

Compared with the embodiment 3, the polyaniline-coated nano titanium dioxide/benzotriazole compound is replaced by the nano titanium dioxide/benzotriazole compound, and other conditions are not changed.

The polyaniline-coated nano titanium dioxide/benzotriazole compound is prepared by the following method:

(1) dissolving 30g of tetrabutyl titanate, 0.75g of titanate coupling agent TMC-3 and 5g of benzotriazole in 15mL of dichloromethane solution to obtain an oil phase;

(2) dissolving 1g of sodium octadecylbenzene sulfonate in 100mL of water to obtain a water phase;

(3) and adding the oil phase into the water phase, emulsifying for 7min at the rotating speed of 15000r/min, adjusting the pH to 4 by using HCl solution, reacting for 5h, and filtering to obtain the titanium dioxide embedded benzotriazole nano-particles.

Comparative example 4

Compared with example 3, the manganese dioxide-carried silver nanopowder is not added, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 13 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 0.7 part of tetrazole polymer, 90 parts of PET resin, 3 parts of coupling agent, 0.2 part of graphite, 1.5 parts of styrene-butadiene thermoplastic elastomer and 10760.2 parts of antioxidant.

Comparative example 5

Compared with the embodiment 3, the polyaniline-coated nano titanium dioxide/benzotriazole compound is not added, and other conditions are not changed.

The raw materials comprise the following components in parts by weight: 13 parts of manganese dioxide silver-loaded nano powder, 0.7 part of tetrazole polymer, 90 parts of PET resin, 3 parts of coupling agent, 0.2 part of graphite, 1.5 parts of styrene-butadiene thermoplastic elastomer and 10760.2 parts of antioxidant.

Comparative example 6

In comparison with example 3, no tetrazole polymer was added, and the other conditions were unchanged.

The raw materials comprise the following components in parts by weight: 7.7 parts of manganese dioxide silver-loaded nano powder, 6 parts of polyaniline-coated nano titanium dioxide/benzotriazole compound, 90 parts of PET resin, 3 parts of coupling agent, 0.2 part of graphite, 1.5 parts of styrene-butadiene thermoplastic elastomer and 10760.2 parts of antioxidant.

Test example 1

The antistatic black PET films for mobile phones prepared in examples 1 to 3 of the present invention and comparative examples 1 to 5 were subjected to performance tests, and the results are shown in Table 1.

TABLE 1

As can be seen from the above table, the antistatic black PET film for the mobile phone, prepared by the invention, has good antistatic performance, mechanical properties 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.