CN118221982A - High-flame-retardance PET (polyethylene terephthalate) base film and preparation method thereof - Google Patents

High-flame-retardance PET (polyethylene terephthalate) base film and preparation method thereof Download PDF

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CN118221982A
CN118221982A CN202410411333.7A CN202410411333A CN118221982A CN 118221982 A CN118221982 A CN 118221982A CN 202410411333 A CN202410411333 A CN 202410411333A CN 118221982 A CN118221982 A CN 118221982A
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base film
carbon fiber
flame
retardance
silver
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CN118221982B (en
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於冬雷
王润霄
王勇军
胡昊
华斌
姜禹
高明辉
王�锋
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Yangzhou Boheng New Energy Material Technology Co ltd
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Abstract

The invention relates to the technical field of PET (polyethylene terephthalate) films, in particular to a high-flame-retardance PET base film and a preparation method thereof. According to the scheme, PET resin, silane coupling agent, compound filler, antioxidant, flame retardant and other materials are mixed, the mixture is extruded to form a film, the film is stretched through a biaxial stretching process, wherein the transverse stretching multiplying power is 3-5, the longitudinal stretching multiplying power is 2-4, the stretching temperature is 105-110 ℃, the stretching rate is 110mm/s, the PET base film prepared through the scheme is high in comprehensive mechanical property, the PET base film is high in flame retardance, the ultraviolet ageing resistance is improved, the PET base film can be widely applied to processing in the field of composite current collectors or batteries, and the practicability is high.

Description

High-flame-retardance PET (polyethylene terephthalate) base film and preparation method thereof
Technical Field
The invention relates to the technical field of PET (polyethylene terephthalate) films, in particular to a high-flame-retardance PET base film and a preparation method thereof.
Background
The current collector is one of indispensable component parts in the lithium ion battery, different current collector materials are carried on the positive electrode and the negative electrode of the lithium ion battery, the positive electrode is aluminum foil, the negative electrode is copper foil, the composite current collector gradually becomes a preferred scheme because of the limitation of the traditional current collector, the composite current collector replaces metal with partial organic matters, the composite current collector is designed to be similar to a sandwich structure, the middle layer is a polymer film, metal plating layers on two sides of the polymer film are generally selected, and materials such as PET, PP, PI are generally selected for the polymer film due to the rapid development of the composite current collector, so that the performance requirement on the polymer film is higher and higher.
The PET base film is one of the most commonly used base films in the market at present, but has poor flame retardant property, and the PET base film is used as an intermediate layer, so that the bonding property of the PET base film and metal layers on two sides is ensured, which is a urgent concern of the existing research personnel, and is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-flame-retardance PET (polyethylene terephthalate) base film and a preparation method thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
The preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing phosphorus oxychloride and pentaerythritol, heating to 80-85 ℃ in a nitrogen atmosphere, reacting for 0.5-1 h, continuously heating to 110-115 ℃, continuously reacting for 6-7 h, cooling after the reaction is finished, collecting a product, and vacuum drying to obtain chlorinated spiro phosphate;
maintaining nitrogen atmosphere, mixing chlorinated spiro phosphate and formic acid, stirring for 0.5-1 h at 30-40 ℃, collecting a product, washing and drying, dissolving in N, N-dimethylformamide, heating to 60-65 ℃, adding 4-propenoxy-2-hydroxybenzophenone, reacting for 1-2 h at a temperature, adding 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 24-28 h, and centrifugally collecting the product to obtain a flame retardant;
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler;
Mixing PET resin, a silane coupling agent, a compound filler, an antioxidant, a lubricant and a flame retardant, extruding, casting to form a film, and biaxially stretching to obtain the PET base film.
In a more optimized scheme, in the step 2, the consumption of each component is as follows: the flame retardant comprises, by mass, 100 parts of PET resin, 4-6 parts of a silane coupling agent, 6-8 parts of a compound filler, 1-1.5 parts of an antioxidant, 0.3-0.5 part of a lubricant and 5-10 parts of a flame retardant.
In a more optimized scheme, in the step 2, the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1, a step of; the antioxidant is antioxidant 168, and the lubricant is ethylene bis stearamide.
In a more optimized scheme, in the step 1, the molar ratio of the pentaerythritol to the phosphorus oxychloride is 1: (4.5 to 5.5); the mole ratio of the chlorinated spiro phosphate to the formic acid is 1: (2-2.2); the mole ratio of the chlorinated spiro phosphate to the 4-propylene oxy-2-hydroxybenzophenone to the 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane is (1.5-2): 1:1.
In the more optimized scheme, in the step 2, the extrusion temperature is 275-285 ℃, the transverse stretching multiplying power is 3-5 during biaxial stretching, the longitudinal stretching multiplying power is 2-4, the stretching temperature is 105-110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220-230 ℃.
According to a more optimized scheme, the preparation steps of the copper-plated carbon fiber are as follows: and (3) taking the carbon fiber, placing the carbon fiber in a heating furnace to burn for 50-60 min, placing the carbon fiber in an acetone solution to soak for 50-60 min, washing and drying the carbon fiber, and placing the carbon fiber in an electroplating solution to electroplate copper on the surface after the carbon fiber is dried, so as to obtain the copper-plated carbon fiber.
More optimized scheme, the electroplating solution comprises the following components: 40-50 g/L of copper sulfate, 10-12 g/L of sodium tartrate, 85-90 g/L of sodium citrate, 12-13 g/L of sodium nitrate and the balance of deionized water; the pH value of the electroplating solution is 9-10, and the technological parameters of copper electroplating are as follows: the electroplating temperature is 40-45 ℃, the time is 30-40 min, and the current density is 1-2A/dm 2.
According to a more optimized scheme, the preparation steps of the silver-plated polystyrene microsphere are as follows:
Dissolving polyvinylpyrrolidone in ethanol, stirring for 30-40 min under nitrogen atmosphere at the temperature of 70-75 ℃, adding styrene and azodiisobutyronitrile, reacting at the temperature of 70-75 ℃ for 10-11 h under heat preservation, washing and drying to obtain polystyrene microspheres;
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 10-20 min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring to silver ammonia solution, stirring for 3-5 min at 30-35 ℃, adding formaldehyde solution, continuing stirring for 20-30 min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres.
In a more optimized scheme, the dosage of polyvinylpyrrolidone is 3-4wt% of styrene; the use amount of the azodiisobutyronitrile is 1-1.5wt% of the styrene; the concentration of potassium dichromate is 0.1-0.2 mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01-0.02 mol/L, and the concentration of concentrated sulfuric acid is 60-65 mL/L; the concentration of stannous chloride is 0.1-0.2 mol/L, the concentration of palladium chloride is 0.2-0.3 g/L, the dosage of formaldehyde solution is 10-12 mL/L, the dosage of ammonia water in silver-ammonia solution is 60-65 mL/L, and the mass ratio of silver nitrate to styrene microspheres in silver-ammonia solution is 1: (2-2.5).
More optimized scheme, the PET base film with high flame retardance is prepared according to any one of the preparation methods.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a high-flame-retardance PET (polyethylene terephthalate) base film and a preparation method thereof.
In the scheme, phosphorus oxychloride and pentaerythritol are used as raw materials to generate chlorinated spiro phosphate, the chlorinated spiro phosphate, 4-propenyloxy-2-hydroxybenzophenone and 2, 4-divinyl-2,4,6,6,8,8-hexamethylcyclotetrasiloxane are used for grafting, C=C and P-H in a system are subjected to addition reaction, so that the silicon phosphorus flame retardant is prepared, the flame retardant performance of the PET base film can be effectively improved by adding the silicon phosphorus flame retardant, and the ultraviolet ageing resistance of the PET base film can be improved by introducing the 4-propenyloxy-2-hydroxybenzophenone. In addition, in order to avoid the influence of the introduction of the flame retardant on the tensile strength of the base film, the scheme selects 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane as a raw material, and ensures the tensile strength of the product while ensuring the flame retardant property of the product.
Meanwhile, the scheme is that a compound filler is added, the compound filler is compounded by carbon fibers, copper-plated carbon fibers and silver-plated polystyrene microspheres, on one hand, the tensile strength of a base film can be effectively improved due to the introduction of the compound filler, on the other hand, the scheme is characterized in that part of the filler is subjected to surface metallization treatment, copper-plated carbon fibers are formed on the surfaces of the carbon fibers in an electroplating manner, the polystyrene microspheres are used as cores, silver-plated polystyrene microspheres are formed on the surfaces of the carbon fibers in an electroplating manner, the carbon fibers, the copper-plated carbon fibers and the silver-plated polystyrene microspheres are compounded to serve as conductive fillers, and the metallized filler is introduced into the base film, so that the surface bonding performance of the base film and metal can be effectively improved, and the bonding performance is excellent when a composite current collector is prepared subsequently.
The application discloses a preparation method of a high-flame-retardance PET (polyethylene terephthalate) base film, which is prepared by the scheme, has high flame retardance and high ultraviolet ageing resistance, can be widely applied to processing in the field of composite current collectors or batteries, and has high practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the embodiment, the silane coupling agent is KH-550, the antioxidant is antioxidant 168, and the lubricant is ethylene bis stearamide. The length of the carbon fiber is 1-2 mm, and the diameter is 3 mu m; PET resin is PETCZ-333.
Example 1: the preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing 0.5mol of phosphorus oxychloride and 0.1mol of pentaerythritol, heating to 80 ℃ under nitrogen atmosphere, reacting for 1h, continuously heating to 110 ℃, continuously reacting for 7h, cooling after the reaction is finished, collecting a product, and vacuum drying to obtain the chlorinated spiro phosphate.
Maintaining nitrogen atmosphere, mixing 0.2mol of chlorinated spiro phosphate and 0.4mol of formic acid, stirring for 1h at 30 ℃, collecting the product, washing and drying, dissolving in N, N-dimethylformamide, heating to 60 ℃, adding 0.1mol of 4-propenoxy-2-hydroxybenzophenone, reacting for 2h under heat preservation, adding 0.1mol of 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 24h, centrifuging and collecting the product, and obtaining the flame retardant.
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler; the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1.
100 Parts of PET resin, 5 parts of silane coupling agent, 6 parts of compound filler, 1.5 parts of antioxidant, 0.5 part of lubricant and 8 parts of flame retardant are mixed by mass, and the PET base film is obtained by extrusion casting film forming, wherein the extrusion temperature is 275 ℃, the biaxial stretching is performed, the transverse stretching multiplying power is 3, the longitudinal stretching multiplying power is 4, the stretching temperature is 110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220 ℃.
The preparation method of the copper-plated carbon fiber comprises the following steps: and (3) firing the carbon fiber in a heating furnace for 60min at 480 ℃, soaking in an acetone solution for 50min, washing and drying, and then, electroplating copper on the surface of the electroplating solution after drying to obtain the copper-plated carbon fiber. The electroplating solution comprises the following components: 45g/L of copper sulfate, 12g/L of sodium tartrate, 85g/L of sodium citrate, 12g/L of sodium nitrate and the balance of deionized water; the technological parameters of the electroplated copper are as follows: the plating temperature was 45℃for 30 minutes and the current density was 2A/dm 2.
The preparation method of the silver-plated polystyrene microsphere comprises the following steps: 1.26g of polyvinylpyrrolidone is dissolved in 100mL of ethanol, stirred for 30min under nitrogen atmosphere, the temperature is 75 ℃, 36g of styrene and 0.54g of azodiisobutyronitrile are added, the reaction is carried out for 11h at 70 ℃, and the polystyrene microsphere is obtained after washing and drying.
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 10min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring into silver ammonia solution, stirring for 5min at 30 ℃, adding formaldehyde solution, continuing stirring for 30min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres. The concentration of potassium dichromate is 0.1mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01mol/L, and the concentration of concentrated sulfuric acid is 60mL/L; the concentration of stannous chloride is 0.1mol/L, the concentration of palladium chloride is 0.2g/L, the dosage of formaldehyde solution is 10mL/L, the dosage of ammonia water in silver ammonia solution is 60mL/L, and the mass ratio of silver nitrate to styrene microsphere in silver ammonia solution is 1:2.
Example 2: the preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing 0.5mol of phosphorus oxychloride and 0.1mol of pentaerythritol, heating to 85 ℃ under nitrogen atmosphere, reacting for 1h, continuously heating to 115 ℃, continuously reacting for 6.5h, cooling after the reaction is finished, collecting a product, and vacuum drying to obtain the chlorinated spiro phosphate.
Maintaining nitrogen atmosphere, mixing 0.2mol of chlorinated spiro phosphate and 0.4mol of formic acid, stirring for 1h at 35 ℃, collecting a product, washing and drying, dissolving in N, N-dimethylformamide, heating to 65 ℃, adding 0.1mol of 4-propenoxy-2-hydroxybenzophenone, reacting for 1.5h under heat preservation, adding 0.1mol of 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 26h, centrifuging and collecting the product, and obtaining the flame retardant.
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler; the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1.
100 Parts of PET resin, 5 parts of silane coupling agent, 7 parts of compound filler, 1.5 parts of antioxidant, 0.5 part of lubricant and 9 parts of flame retardant are mixed by mass, and the PET base film is obtained by extrusion casting film forming, wherein the extrusion temperature is 275 ℃, the biaxial stretching is performed, the transverse stretching multiplying power is 3, the longitudinal stretching multiplying power is 4, the stretching temperature is 110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220 ℃.
The preparation method of the copper-plated carbon fiber comprises the following steps: and (3) firing the carbon fiber in a heating furnace for 60min at 480 ℃, soaking in an acetone solution for 55min, washing and drying, and then, electroplating copper on the surface of the electroplating solution after drying to obtain the copper-plated carbon fiber. The electroplating solution comprises the following components: 45g/L of copper sulfate, 12g/L of sodium tartrate, 85g/L of sodium citrate, 12g/L of sodium nitrate and the balance of deionized water; the technological parameters of the electroplated copper are as follows: the plating temperature was 45℃for 30 minutes and the current density was 2A/dm 2.
The preparation method of the silver-plated polystyrene microsphere comprises the following steps: 1.26g of polyvinylpyrrolidone is dissolved in 100mL of ethanol, stirred for 35min under nitrogen atmosphere, the temperature is 75 ℃, 36g of styrene and 0.54g of azodiisobutyronitrile are added, the reaction is carried out for 10h at 75 ℃, and the polystyrene microsphere is obtained after washing and drying.
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 15min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring into silver ammonia solution, stirring for 4min at 35 ℃, adding formaldehyde solution, continuing stirring for 30min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres. The concentration of potassium dichromate is 0.1mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01mol/L, and the concentration of concentrated sulfuric acid is 60mL/L; the concentration of stannous chloride is 0.1mol/L, the concentration of palladium chloride is 0.2g/L, the dosage of formaldehyde solution is 10mL/L, the dosage of ammonia water in silver ammonia solution is 60mL/L, and the mass ratio of silver nitrate to styrene microsphere in silver ammonia solution is 1:2.
Example 3: the preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing 0.5mol of phosphorus oxychloride and 0.1mol of pentaerythritol, heating to 85 ℃ under nitrogen atmosphere, reacting for 0.5h, continuously heating to 115 ℃, continuously reacting for 6h, cooling after the reaction is finished, collecting a product, and drying in vacuum to obtain the chlorinated spiro phosphate.
Maintaining nitrogen atmosphere, mixing 0.2mol of chlorinated spiro phosphate and 0.4mol of formic acid, stirring for 0.5h at 40 ℃, collecting a product, washing and drying, dissolving in N, N-dimethylformamide, heating to 65 ℃, adding 0.1mol of 4-propenoxy-2-hydroxybenzophenone, carrying out heat preservation reaction for 1h, adding 0.1mol of 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 28h, and centrifugally collecting the product to obtain the flame retardant.
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler; the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1.
100 Parts of PET resin, 5 parts of silane coupling agent, 7 parts of compound filler, 1.5 parts of antioxidant, 0.5 part of lubricant and 10 parts of flame retardant are mixed by mass, and the PET base film is obtained by extrusion casting film forming, wherein the extrusion temperature is 275 ℃, the biaxial stretching is performed, the transverse stretching multiplying power is 3, the longitudinal stretching multiplying power is 4, the stretching temperature is 110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220 ℃.
The preparation method of the copper-plated carbon fiber comprises the following steps: and (3) firing the carbon fiber in a heating furnace for 60min at 480 ℃, soaking in an acetone solution for 60min, washing and drying, and then, electroplating copper on the surface of the electroplating solution after drying to obtain the copper-plated carbon fiber. The electroplating solution comprises the following components: 45g/L of copper sulfate, 12g/L of sodium tartrate, 85g/L of sodium citrate, 12g/L of sodium nitrate and the balance of deionized water; the technological parameters of the electroplated copper are as follows: the plating temperature was 45℃for 30 minutes and the current density was 2A/dm 2.
The preparation method of the silver-plated polystyrene microsphere comprises the following steps: 1.26g of polyvinylpyrrolidone is dissolved in 100mL of ethanol, stirred for 40min under nitrogen atmosphere, the temperature is 75 ℃, 36g of styrene and 0.54g of azodiisobutyronitrile are added, the reaction is carried out for 10h at 75 ℃, and the polystyrene microsphere is obtained after washing and drying.
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 20min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring into silver ammonia solution, stirring for 5min at 35 ℃, adding formaldehyde solution, continuing stirring for 30min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres. The concentration of potassium dichromate is 0.1mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01mol/L, and the concentration of concentrated sulfuric acid is 60mL/L; the concentration of stannous chloride is 0.1mol/L, the concentration of palladium chloride is 0.2g/L, the dosage of formaldehyde solution is 10mL/L, the dosage of ammonia water in silver ammonia solution is 60mL/L, and the mass ratio of silver nitrate to styrene microsphere in silver ammonia solution is 1:2.
Comparative example 1: using example 3 as a control group, the amount of the flame retardant was adjusted to 15 parts in comparative example 1, and the remaining steps were unchanged.
The preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing 0.5mol of phosphorus oxychloride and 0.1mol of pentaerythritol, heating to 85 ℃ under nitrogen atmosphere, reacting for 0.5h, continuously heating to 115 ℃, continuously reacting for 6h, cooling after the reaction is finished, collecting a product, and drying in vacuum to obtain the chlorinated spiro phosphate.
Maintaining nitrogen atmosphere, mixing 0.2mol of chlorinated spiro phosphate and 0.4mol of formic acid, stirring for 0.5h at 40 ℃, collecting a product, washing and drying, dissolving in N, N-dimethylformamide, heating to 65 ℃, adding 0.1mol of 4-propenoxy-2-hydroxybenzophenone, carrying out heat preservation reaction for 1h, adding 0.1mol of 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 28h, and centrifugally collecting the product to obtain the flame retardant.
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler; the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1.
100 Parts of PET resin, 5 parts of silane coupling agent, 7 parts of compound filler, 1.5 parts of antioxidant, 0.5 part of lubricant and 15 parts of flame retardant are mixed by mass, and the PET base film is obtained by extrusion casting film forming, wherein the extrusion temperature is 275 ℃, the biaxial stretching is performed, the transverse stretching multiplying power is 3, the longitudinal stretching multiplying power is 4, the stretching temperature is 110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220 ℃.
The preparation method of the copper-plated carbon fiber comprises the following steps: and (3) firing the carbon fiber in a heating furnace for 60min at 480 ℃, soaking in an acetone solution for 60min, washing and drying, and then, electroplating copper on the surface of the electroplating solution after drying to obtain the copper-plated carbon fiber. The electroplating solution comprises the following components: 45g/L of copper sulfate, 12g/L of sodium tartrate, 85g/L of sodium citrate, 12g/L of sodium nitrate and the balance of deionized water; the technological parameters of the electroplated copper are as follows: the plating temperature was 45℃for 30 minutes and the current density was 2A/dm 2.
The preparation method of the silver-plated polystyrene microsphere comprises the following steps: 1.26g of polyvinylpyrrolidone is dissolved in 100mL of ethanol, stirred for 40min under nitrogen atmosphere, the temperature is 75 ℃, 36g of styrene and 0.54g of azodiisobutyronitrile are added, the reaction is carried out for 10h at 75 ℃, and the polystyrene microsphere is obtained after washing and drying.
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 20min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring into silver ammonia solution, stirring for 5min at 35 ℃, adding formaldehyde solution, continuing stirring for 30min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres. The concentration of potassium dichromate is 0.1mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01mol/L, and the concentration of concentrated sulfuric acid is 60mL/L; the concentration of stannous chloride is 0.1mol/L, the concentration of palladium chloride is 0.2g/L, the dosage of formaldehyde solution is 10mL/L, the dosage of ammonia water in silver ammonia solution is 60mL/L, and the mass ratio of silver nitrate to styrene microsphere in silver ammonia solution is 1:2.
Comparative example 2: with example 3 as a control group, comparative example 2 was prepared by adjusting the process for preparing the flame retardant, and the remaining steps were unchanged.
The preparation method of the high-flame-retardance PET base film comprises the following steps:
Step 1: mixing 0.5mol of phosphorus oxychloride and 0.1mol of pentaerythritol, heating to 85 ℃ under nitrogen atmosphere, reacting for 0.5h, continuously heating to 115 ℃, continuously reacting for 6h, cooling after the reaction is finished, collecting a product, and drying in vacuum to obtain the chlorinated spiro phosphate.
Maintaining nitrogen atmosphere, mixing 0.2mol of chlorinated spiro phosphate with 0.4mol of formic acid, stirring for 0.5h at 40 ℃, collecting the product, washing and drying, dissolving in N, N-dimethylformamide, heating to 65 ℃, preserving heat for reaction for 1h, adding 0.1mol of 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 28h, and centrifugally collecting the product to obtain the flame retardant.
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler; the mass ratio of the carbon fiber to the copper-plated carbon fiber to the silver-plated polystyrene microsphere is 2:3:1.
100 Parts of PET resin, 5 parts of silane coupling agent, 7 parts of compound filler, 1.5 parts of antioxidant, 0.5 part of lubricant and 10 parts of flame retardant are mixed by mass, and the PET base film is obtained by extrusion casting film forming, wherein the extrusion temperature is 275 ℃, the biaxial stretching is performed, the transverse stretching multiplying power is 3, the longitudinal stretching multiplying power is 4, the stretching temperature is 110 ℃, the stretching rate is 110mm/s, and the heat setting temperature is 220 ℃.
The preparation method of the copper-plated carbon fiber comprises the following steps: and (3) firing the carbon fiber in a heating furnace for 60min at 480 ℃, soaking in an acetone solution for 60min, washing and drying, and then, electroplating copper on the surface of the electroplating solution after drying to obtain the copper-plated carbon fiber. The electroplating solution comprises the following components: 45g/L of copper sulfate, 12g/L of sodium tartrate, 85g/L of sodium citrate, 12g/L of sodium nitrate and the balance of deionized water; the technological parameters of the electroplated copper are as follows: the plating temperature was 45℃for 30 minutes and the current density was 2A/dm 2.
The preparation method of the silver-plated polystyrene microsphere comprises the following steps: 1.26g of polyvinylpyrrolidone is dissolved in 100mL of ethanol, stirred for 40min under nitrogen atmosphere, the temperature is 75 ℃, 36g of styrene and 0.54g of azodiisobutyronitrile are added, the reaction is carried out for 10h at 75 ℃, and the polystyrene microsphere is obtained after washing and drying.
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 20min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring into silver ammonia solution, stirring for 5min at 35 ℃, adding formaldehyde solution, continuing stirring for 30min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres. The concentration of potassium dichromate is 0.1mol/L, the concentration of sodium dodecyl benzene sulfonate is 0.01mol/L, and the concentration of concentrated sulfuric acid is 60mL/L; the concentration of stannous chloride is 0.1mol/L, the concentration of palladium chloride is 0.2g/L, the dosage of formaldehyde solution is 10mL/L, the dosage of ammonia water in silver ammonia solution is 60mL/L, and the mass ratio of silver nitrate to styrene microsphere in silver ammonia solution is 1:2.
Detection experiment:
The PET base films (thickness: 3 μm) prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for tensile strength by referring to the method disclosed in GB/T1040.1, and the samples were 15mm wide and 200mm long at a tensile rate of 100mm/min. The limiting oxygen index of the PET base film was tested with reference to the method disclosed in GB/T2046. And (3) placing the PET base film into an ultraviolet aging box for irradiation, wherein the total irradiation energy is 60kWh/m 2, the light source is UVB (280-320 nm), the irradiance of a lamp tube is 180W/m 2, and the tensile strength is retested after ultraviolet aging, and the retention rate is recorded.
Conclusion: the application discloses a preparation method of a high-flame-retardance PET (polyethylene terephthalate) base film, which is prepared by the scheme, has high flame retardance and high ultraviolet ageing resistance, can be widely applied to processing in the field of composite current collectors or batteries, and has high practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a high-flame-retardance PET (polyethylene terephthalate) base film is characterized by comprising the following steps of: the method comprises the following steps:
Step 1: mixing phosphorus oxychloride and pentaerythritol, heating to 80-85 ℃ in a nitrogen atmosphere, reacting for 0.5-1 h, continuously heating to 110-115 ℃, continuously reacting for 6-7 h, cooling after the reaction is finished, collecting a product, and vacuum drying to obtain chlorinated spiro phosphate;
maintaining nitrogen atmosphere, mixing chlorinated spiro phosphate and formic acid, stirring for 0.5-1 h at 30-40 ℃, collecting a product, washing and drying, dissolving in N, N-dimethylformamide, heating to 60-65 ℃, adding 4-propenoxy-2-hydroxybenzophenone, reacting for 1-2 h at a temperature, adding 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane, continuing to react for 24-28 h, and centrifugally collecting the product to obtain a flame retardant;
Step 2: mixing carbon fiber, copper-plated carbon fiber and silver-plated polystyrene microsphere to obtain a compound filler;
Mixing PET resin, a silane coupling agent, a compound filler, an antioxidant, a lubricant and a flame retardant, extruding, casting to form a film, and biaxially stretching to obtain the PET base film.
2. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: in the step 2, the dosages of each component are as follows: the flame retardant comprises, by mass, 100 parts of PET resin, 4-6 parts of a silane coupling agent, 6-8 parts of a compound filler, 1-1.5 parts of an antioxidant, 0.3-0.5 part of a lubricant and 5-10 parts of a flame retardant.
3. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: in the step 2, the mass ratio of the carbon fiber, the copper-plated carbon fiber and the silver-plated polystyrene microsphere is 2:3:1, a step of; the antioxidant is antioxidant 168, and the lubricant is ethylene bis stearamide.
4. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: in the step 1, the mole ratio of the pentaerythritol to the phosphorus oxychloride is 1: (4.5 to 5.5); the mole ratio of the chlorinated spiro phosphate to the formic acid is 1: (2-2.2); the mole ratio of the chlorinated spiro phosphate to the 4-propylene oxy-2-hydroxybenzophenone to the 2, 4-divinyl-2,4,6,6,8,8-hexamethyl cyclotetrasiloxane is (1.5-2): 1:1.
5. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: in the step 2, the extrusion temperature is 275-285 ℃, the transverse stretching multiplying power is 3-5, the longitudinal stretching multiplying power is 2-4, the stretching temperature is 105-110 ℃, the stretching speed is 110mm/s, and the heat setting temperature is 220-230 ℃.
6. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: the preparation method of the copper-plated carbon fiber comprises the following steps: and (3) taking the carbon fiber, placing the carbon fiber in a heating furnace to burn for 50-60 min, placing the carbon fiber in an acetone solution to soak for 50-60 min, washing and drying the carbon fiber, and placing the carbon fiber in an electroplating solution to electroplate copper on the surface after the carbon fiber is dried, so as to obtain the copper-plated carbon fiber.
7. The method for preparing the high-flame-retardance PET base film of claim 6, wherein the method comprises the following steps: the electroplating solution comprises the following components: 40-50 g/L of copper sulfate, 10-12 g/L of sodium tartrate, 85-90 g/L of sodium citrate, 12-13 g/L of sodium nitrate and the balance of deionized water; the pH value of the electroplating solution is 9-10, and the technological parameters of copper electroplating are as follows: the electroplating temperature is 40-45 ℃, the time is 30-40 min, and the current density is 1-2A/dm 2.
8. The method for preparing the high-flame-retardance PET base film of claim 1, wherein the method comprises the following steps: the preparation method of the silver-plated polystyrene microsphere comprises the following steps:
Dissolving polyvinylpyrrolidone in ethanol, stirring for 30-40 min under nitrogen atmosphere at the temperature of 70-75 ℃, adding styrene and azodiisobutyronitrile, reacting at the temperature of 70-75 ℃ for 10-11 h under heat preservation, washing and drying to obtain polystyrene microspheres;
Mixing potassium dichromate, sodium dodecyl benzene sulfonate and concentrated sulfuric acid, adding polystyrene microspheres, performing ultrasonic dispersion for 10-20 min, taking out, sensitizing by stannous chloride solution, activating palladium chloride solution, transferring to silver ammonia solution, stirring for 3-5 min at 30-35 ℃, adding formaldehyde solution, continuing stirring for 20-30 min, filtering, washing, and performing vacuum drying to obtain silver-plated polystyrene microspheres.
9. The method for preparing the high-flame-retardance PET base film of claim 8, wherein the method comprises the following steps: the dosage of the polyvinylpyrrolidone is 3-4wt% of that of styrene; the use amount of the azodiisobutyronitrile is 1-1.5wt% of the styrene; the concentration of stannous chloride is 0.1-0.2 mol/L, the concentration of palladium chloride is 0.2-0.3 g/L, the dosage of formaldehyde solution is 10-12 mL/L, the dosage of ammonia water in silver-ammonia solution is 60-65 mL/L, and the mass ratio of silver nitrate to styrene microspheres in silver-ammonia solution is 1: (2-2.5).
10. The high flame retardant PET base film prepared by the preparation method according to any one of claims 1 to 9.
CN202410411333.7A 2024-04-08 2024-04-08 High-flame-retardance PET (polyethylene terephthalate) base film and preparation method thereof Active CN118221982B (en)

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