PEEK composite insulation wire and preparation method thereof

Abstract

The application relates to the technical field of electromagnetic wires, and particularly discloses a PEEK composite insulating wire and a preparation method thereof. The PEEK composite insulating wire comprises an electric core and a resin layer wrapped outside the electric core, and the resin layer comprises the following raw materials in parts by weight: 100 parts of polyether ether ketone; and 10-20 parts of fillers. The fillers comprise carbon fibers and glass fibers, the fillers are modified fillers which are modified by a modifier, and the modifier comprises polyimide and nanotubes. The preparation method comprises the following steps: S1, raw material preparation of the resin layer: PEEK powder is dried at 120 DEG C for 24 hours, the fillers are mixed with the PEEK powder, and then melting is carried out to obtain the raw material of the resin layer; and S2, preparation of the composite insulating wire. The composite insulating wire can be used in electrical equipment such as automobiles, and has the advantages of high temperature resistance, high strength and the like.

Description

Technical Field

[0001] The present application relates to the technical field of electromagnetic wires, and more specifically, to a PEEK composite insulated wire and a preparation method thereof. Background Art

[0002] Polyetheretherketone (PEEK) is an excellent thermoplastic engineering plastic with high heat resistance, excellent mechanical properties, and easy processing. It has broad application prospects in the field of magnet wire insulation. However, the insulation performance and reliability of a single PEEK insulation layer in harsh environments such as high voltage and high temperature still need to be improved.

[0003] When insulated wire is used, the heat generated by the flow of current through it increases its temperature. As electrical equipment used in automobiles and other applications continues to become smaller and more powerful, temperatures within the devices rise. High temperatures can cause the resin coating of the insulated wire used in these devices to degrade and shrink. Therefore, further improvements in the high-temperature resistance and mechanical strength of PEEK insulated wire are needed. Summary of the Invention

[0004] In order to improve the defects of PEEK insulated wire in high temperature resistance and poor mechanical strength, the present application provides a PEEK composite insulated wire and a preparation method thereof, which adopts the following technical solutions:

[0005] In a first aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials in parts by weight:

[0006] 100 parts of polyetheretherketone;

[0007] 10-20 parts of filler;

[0008] The filler comprises carbon fiber and glass fiber, and the filler is a modified filler modified by a modifier, and the modifier comprises polyimide and nanotube.

[0009] By adopting the above technical solution, carbon fiber and glass fiber are preferably used as fillers. Carbon fiber and glass fiber can introduce an interlaced network structure into PEEK, effectively improving the strength of PEEK. In addition, both carbon fiber and glass fiber have good high temperature resistance and can introduce a heat-resistant network skeleton structure into PEEK, thereby improving the high temperature resistance of PEEK.

[0010] The filler is preferably modified using a combination of polyimide and nanotubes. Polyimide has high rigidity, excellent mechanical properties, and high heat resistance. It can also increase the surface energy of the filler, improve the compatibility between the filler and PEEK, and improve the uniformity of the filler's dispersion in PEEK, thereby forming a uniform and dense network structure. The combination of polyimide and nanotubes allows the nanotubes to adhere to the filler surface under the action of the polyimide, forming a composite structure of long linear structures and short linear structures with the filler, which can form a more complex interlaced network structure. The nanotubes can serve as anchor points to enhance the bonding between the filler and PEEK, further improving the mechanical strength of PEEK.

[0011] Optionally, the polyimide is a polyimide containing an etherketone structure.

[0012] By adopting the above technical solution, preferably using polyimide with an ether ketone structure as a modifier, the similar compatibility characteristics of the ether ketone structure are utilized to improve the compatibility and dispersion effect of the filler in PEEK.

[0013] Optionally, the nanotubes include any one of titanium dioxide nanotubes, silicon dioxide nanotubes, and carbon nitride nanotubes.

[0014] By adopting the above technical solution, preferably titanium dioxide nanotubes, silicon dioxide nanotubes or carbon nitride nanotubes are used, which can be loaded on the filler surface through polyimide, serve as anchor points of the filler, build a complex cross-linked network structure in PEEK, and stably improve the mechanical strength of PEEK.

[0015] Optionally, the silica nanotubes are amino-treated silica nanotubes.

[0016] By adopting the above technical solution, the silica nanotubes are subjected to an amination treatment, and amino groups are grafted on the surface of the silica nanotubes. The strong hydrogen bond interaction between the amino groups and the polyimide molecules is utilized to improve the connection strength between the silica nanotubes and the filler, so that the silica nanotubes can be stably used as anchor points. At the same time, the packing density between the polyimide molecular chains can be effectively enhanced, thereby improving the wear resistance of PEEK and further improving the mechanical strength of the resin layer.

[0017] Optionally, the preparation of the modifier is as follows:

[0018] Preparation of polyamic acid: APBP and PMDA were dried for 12 h, and then APBP was dissolved in an appropriate amount of DMAc solution under nitrogen. The mixture was stirred evenly, and PMDA was added. The polyamic acid (PAA) solution was stirred for 24 h and diluted with DMAc to a 0.25% precursor solution.

[0019] Preparation of the modifier: The nanotubes are crushed and dispersed in a DMAc solution to obtain a dispersion, and the dispersion is mixed with a precursor solution to obtain a modifier.

[0020] Optionally, the polyetheretherketone is a modified polyetheretherketone grafted with a rigid group, and the rigid group includes any one or more of a carbonyl group, a polyphenyl ether group or a biphenyl group.

[0021] By adopting the above technical solution, rigid groups are grafted on the polyetheretherketone molecular chain. The carbonyl group, polyphenyl ether group and biphenyl group have different rigidity strengths. Grafting on the polyetheretherketone molecular chain can adjust the flexibility between the polyetheretherketone molecular chains, so that the polyetheretherketone obtains excellent shape memory properties. The resin layer is composed of a fiber skeleton and polyetheretherketone with shape memory properties. The resin layer is not easily damaged and can provide long-term protection for the battery cell.

[0022] Optionally, the modified polyetheretherketone is prepared as follows: under the protection of an argon atmosphere, diphenylsulfone is heated and melted in a diphenylsulfone container, and then 4,4'-difluorobenzophenone, hydroquinone, biphenol, 4,4'-dihydroxydiphenyl ether, and a mixed salt of sodium carbonate and potassium carbonate are added to the system, and uniform stirring is maintained. The system is kept at 220°C for 2 hours, 250°C and 290°C for 1 hour each, and finally polymerized at 310°C for 2 hours. The product is discharged into water, crushed, washed 10 times with ethanol and water respectively, and then dried in an oven to obtain the modified polyetheretherketone.

[0023] By adopting the above technical solution, the preparation of modified polyetheretherketone was optimized. The more rigid biphenyl groups were combined with polyphenyl ether segments to make the molecular structure more like the structure of shape memory polymer, further improving the shape memory performance of the polymer and enabling the resin layer to protect the battery cell for a long time.

[0024] Optionally, the mass ratio of the 4,4'-dihydroxydiphenyl ether to biphenyl diphenol is 1-3:7-9.

[0025] By adopting the above technical solution, the addition amount of polyphenyl ether groups is optimized. At an appropriate addition amount, the modified polyetheretherketone can obtain a better shape memory effect, and can cooperate with the filler network to protect the battery cell for a long time.

[0026] Optionally, the glass fiber is bioactive glass fiber.

[0027] By adopting the above technical solution, the bioactive glass fiber is composed of chemical components such as CaO, P2O5, SiO2, and Na2O. The bioactive glass fiber has better compatibility with polyetheretherketone, thereby improving the reinforcing effect of the filler on polyetheretherketone.

[0028] Optionally, the surface of the glass fiber is wrapped with a polyethersulfone-sodium polystyrene sulfonate composite layer.

[0029] By adopting the above technical solution, polyethersulfone can be decomposed to produce large molecular free radicals, which undergo free radical polymerization reaction with sodium 4-styrenesulfonate to form a polyethersulfone-sodium polystyrenesulfonate composite material. The polyethersulfone-sodium polystyrenesulfonate composite material has excellent high-temperature resistance and can cover the surface of the glass fiber in the form of a thin layer and microspheres, introducing active groups into the glass fiber, and further promoting the bonding strength between the glass fiber and polyetheretherketone.

[0030] In a second aspect, the present application provides a method for preparing a PEEK composite insulated wire, which adopts the following technical solution:

[0031] A method for preparing a PEEK composite insulated wire comprises the following steps:

[0032] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0033] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0034] In summary, this application has the following beneficial effects:

[0035] 1. Because this application uses a combination of polyimide and nanotubes as modifiers to modify the filler, polyimide has high rigidity, excellent mechanical properties, and high heat resistance. It can also increase the surface energy of the filler, improve the compatibility between the filler and PEEK, and improve the uniformity of the filler's dispersion in PEEK, thereby forming a uniform and dense network structure. With the combination of polyimide and nanotubes, the nanotubes can adhere to the filler surface under the action of polyimide, forming a long linear structure-short linear structure composite structure with the filler, which can form a more complex interlaced network structure. The nanotubes can serve as anchor points to enhance the bonding effect between the filler and PEEK, further improving the mechanical strength of PEEK.

[0036] 2. In the present application, it is preferred to perform an amination treatment on the silica nanotubes, graft amino groups on the surface of the silica nanotubes, and utilize the strong hydrogen bond interaction between the amino groups and the polyimide molecules to improve the connection strength between the silica nanotubes and the filler, so that the silica nanotubes can be stably used as anchor points. At the same time, it can effectively enhance the packing density between the polyimide molecular chains, thereby improving the wear resistance of PEEK and further improving the mechanical strength of the resin layer.

[0037] 3. The present application adopts the method of grafting rigid groups on the polyetheretherketone molecular chain. The carbonyl group, polyphenyl ether group and biphenyl group have different rigidity strengths. Grafting on the polyetheretherketone molecular chain can adjust the flexibility between the polyetheretherketone molecular chains, so that the polyetheretherketone obtains excellent shape memory properties. The resin layer is composed of a fiber skeleton and polyetheretherketone with shape memory properties. The resin layer is not easily damaged and can provide long-term protection for the battery cell. DETAILED DESCRIPTION

[0038] The present application is further described in detail below with reference to the embodiments.

[0039] Preparation Example

[0040] Modifier Preparation Example

[0041] Preparation Example 1

[0042] The preparation of the modifier is as follows:

[0043] Preparation of polyamic acid: 0.05 mol APBP (pyromellitic dianhydride) and 0.05 mol PMDA (4,4′-bis(3-aminophenoxy)benzophenone) were taken separately and dried at 80°C for 12 h. APBP was dissolved in a solution containing an appropriate amount of DMAc (N,N-dimethylacetamide) under nitrogen and stirred evenly. PMDA was added and stirred for 24 h to form a polyamic acid (PAA) solution, which was then diluted with DMAc to a 0.25% precursor solution.

[0044] Preparation of the modifier: Silica nanotubes were crushed and dispersed in a DMAc solution to obtain a 1 mg / mL dispersion, which was then mixed with a precursor solution to obtain a modifier containing 0.1% of the nanotubes.

[0045] Preparation Example 2

[0046] The preparation of the modifier is as follows:

[0047] Preparation of polyamic acid: 0.05 mol APBP and 0.05 mol PMDA were dried at 80 °C for 12 h, and then APBP was dissolved in an appropriate amount of DMAc solution under nitrogen. The mixture was stirred evenly, and PMDA was added. The polyamic acid (PAA) solution was stirred for 24 h and diluted with DMAc to a 0.25% precursor solution.

[0048] Preparation of the modifier: CNTs were crushed and dispersed in a DMAc solution to obtain a 1 mg / mL dispersion, which was then mixed with a precursor solution to obtain a modifier containing 0.1% of the nanotubes.

[0049] Preparation Example 3

[0050] The preparation of the modifier is as follows:

[0051] Preparation of polyamic acid: 0.05 mol APBP and 0.05 mol PMDA were dried at 80 °C for 12 h, and then APBP was dissolved in an appropriate amount of DMAc solution under nitrogen. The mixture was stirred evenly, and PMDA was added. The polyamic acid (PAA) solution was stirred for 24 h and diluted with DMAc to a 0.25% precursor solution.

[0052] Preparation of the modifier: Aminated silica nanotubes were crushed and dispersed in a DMAc solution to obtain a 1 mg / mL dispersion. The dispersion was mixed with a precursor solution to obtain a modifier with a nanotube content of 0.1%.

[0053] Preparation example of modified polyetheretherketone

[0054] Preparation Example 4

[0055] The preparation of modified polyetheretherketone is as follows: argon is introduced into a three-necked flask equipped with an argon port and a mechanical stirring device. After the flask is filled with argon, diphenyl sulfone (133.5 g) is added to the flask and heated to 130°C. After the diphenyl sulfone is completely melted, 4,4'-difluorobenzophenone (33.39 g, 0.153 mol), hydroquinone (11.56 g, 0.105 mol), 4,4'-dihydroxybenzophenone (9.94 g, 0.045 mol), sodium carbonate (19.08 g, 0.18 mol) and potassium carbonate (0.21 g, 0.0015 mol) are added to the system. The mixture was then stirred evenly under an argon atmosphere and slowly heated. Water began to form after reaching 220°C. After 2 hours of dwelling, the system was completely dehydrated. The temperature was then continued to rise, dwelling at 250°C and 290°C for 1 hour each. The mixture was then heated to 310°C for polymerization. When the system in the bottle became highly viscous, the product was poured into 3 L of deionized water to obtain a white fibrous crude product. The crude product was then pulverized in a high-speed blender and washed ten times with ethanol and deionized water, respectively. The product was then dried in a vacuum oven at 120°C for 12 hours, ultimately yielding a white product, the modified polyetheretherketone.

[0056] Preparation Example 5

[0057] The preparation of modified polyetheretherketone is as follows: argon is introduced into a three-necked flask equipped with an argon port and a mechanical stirring device. After the flask is filled with argon, diphenyl sulfone (133.5 g) is added to the flask and heated to 130°C. After the diphenyl sulfone is completely melted, 4,4'-difluorobenzophenone (33.39 g, 0.153 mol), hydroquinone (14.86 g, 0.135 mol), biphenol (2.79 g, 0.015 mol), sodium carbonate (19.08 g, 0.18 mol) and potassium carbonate (0.21 g, 0.0015 mol) are added to the system. The mixture was then stirred evenly under an argon atmosphere and slowly heated. Water began to form after reaching 220°C. After 2 hours of dwelling, the system was completely dehydrated. The temperature was then continued to rise, dwelling at 250°C and 290°C for 1 hour each. The mixture was then heated to 310°C for polymerization. When the system in the bottle became highly viscous, the product was poured into 3 L of deionized water to obtain a white fibrous crude product. The crude product was then pulverized in a high-speed blender and washed ten times with ethanol and deionized water, respectively. The product was then dried in a vacuum oven at 120°C for 12 hours, ultimately yielding a white product, the modified polyetheretherketone.

[0058] Preparation Example 6

[0059] The modified polyetheretherketone is prepared as follows: argon is introduced into a three-necked flask equipped with an argon vent and a mechanical stirring device. After the argon fills the flask, diphenyl sulfone (133.5 g) is added to the flask, and the flask is heated to 130° C. After the diphenyl sulfone is completely melted, 4,4'-difluorobenzophenone (33.39 g, 0.153 mol), 4,4'-dihydroxydiphenyl ether (9.10 g, 0.045 mol), biphenyl diphenol (19.55 g, 0.105 mol), sodium carbonate (19.08 g, 0.18 mol) and potassium carbonate (0.21 g, 0.0015 mol) are added to the system. The mixture was then stirred evenly under an argon atmosphere and slowly heated. Water began to form after reaching 220°C. After 2 hours of dwelling, the system completely absorbed water. The temperature was then continued to rise, dwelling at 250°C and 290°C for 1 hour each. The system was then heated to 310°C for polymerization. When the system in the bottle became highly viscous, the product was poured into 3 L of deionized water to obtain a white fibrous crude product. The crude product was then pulverized in a high-speed blender and washed ten times with ethanol and deionized water, respectively. The product was then dried in a vacuum oven at 120°C for 12 hours to obtain a white product, the modified polyetheretherketone.

[0060] Preparation Example 7

[0061] PES (polyethersulfone) and NaSS (sodium styrene sulfonate) were dried in a vacuum oven at 120°C for 24 h. NaSS (6 wt%) and PES (2 wt%) were then completely dissolved in DMF. The mixed solution was added to an internally illuminated glass reaction bottle and degassed with N2 for 30 min. The reaction was then conducted using a mercury lamp (254 nm, 28 W, with a radiation intensity of 0.6 mW / cm 2 The mixed solution was irradiated at room temperature. During irradiation, the solution was magnetically stirred (500 rpm) and nitrogen gas was introduced. The irradiation time was 30 minutes to obtain PES-NaPSS. 0.9 g of PES-NaPSS was added to a mixture of 2 g of DMSO and 15.1 g of dichloromethane and magnetically stirred until completely dissolved. 97.1 g of deionized water was then added, and the mixture was placed in an ice bath. Ultrasonication was then performed for 30 minutes using an ultrasonic cell disruptor (1800 W power, 20 kHz frequency) to form a PES-NaPSS emulsion. The dichloromethane in the emulsion was recovered using a rotary evaporator to obtain a coating. The coating was then applied to the surface of glass fiber and dried to obtain the modified glass fiber.

[0062] Example

[0063] Examples 1-3

[0064] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0065] The filler includes carbon fibers and glass fibers of equal mass. The filler is a modified filler modified by a modifier, and the modifier is the modifier prepared in Preparation Example 1.

[0066] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0067] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0068] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0069] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0070] Table 1 Composition of Examples 1-3

[0071]

[0072] Example 4

[0073] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: 100 kg of polyetheretherketone and 20 kg of filler;

[0074] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation 2.

[0075] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0076] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0077] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0078] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0079] Example 5

[0080] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0081] The filler includes carbon fibers and glass fibers of equal mass. The filler is a modified filler modified by a modifier, and the modifier is the modifier prepared in Preparation Example 3.

[0082] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0083] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0084] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0085] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0086] Example 6

[0087] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0088] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation Example 3, and the polyetheretherketone is the modified polyetheretherketone prepared in Preparation Example 4.

[0089] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0090] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0091] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0092] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0093] Example 7

[0094] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0095] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation Example 3, and the polyetheretherketone is the modified polyetheretherketone prepared in Preparation Example 5.

[0096] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0097] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0098] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0099] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0100] Example 8

[0101] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0102] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation Example 3, and the polyetheretherketone is the modified polyetheretherketone prepared in Preparation Example 6.

[0103] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0104] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0105] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0106] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0107] Example 9

[0108] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0109] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation Example 3, the polyetheretherketone is the modified polyetheretherketone prepared in Preparation Example 5, and the glass fiber is bioactive glass fiber.

[0110] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0111] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0112] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0113] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0114] Example 10

[0115] In one aspect, the present application provides a PEEK composite insulated wire, comprising a battery core and a resin layer wrapped around the battery core, wherein the resin layer comprises the following raw materials: polyetheretherketone and filler;

[0116] The filler includes carbon fiber and glass fiber of equal mass. The filler is a modified filler modified by a modifier. The modifier is the modifier prepared in Preparation Example 3, the polyetheretherketone is the modified polyetheretherketone prepared in Preparation Example 5, and the glass fiber is the glass fiber prepared in Preparation Example 7.

[0117] Preparation of modified filler: The filler was immersed in the modifier for 2 hours, removed, dried at 80°C, heated to 200°C and kept warm for 1 hour, and then heated to 300°C and kept warm for 1 hour to obtain the modified filler.

[0118] On the other hand, the present application provides a method for preparing a PEEK composite insulated wire, comprising the following steps:

[0119] S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials;

[0120] S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

[0121] Comparative Example

[0122] Comparative Example 1

[0123] The difference between this comparative example and Example 3 is that the filler in this comparative example is not modified by a modifier.

[0124] Comparative Example 2

[0125] The difference between this comparative example and Example 3 is that the modifier in this comparative example only includes polyimide.

[0126] Performance testing

[0127] (1) Mechanical property test: The tensile strength of the resin layer was tested using an EZ-LX HS universal material testing machine (Shimadzu, Japan) at a tensile rate of 0.5 mm / min.

[0128] (2) Thermal stability test: The thermal stability of the resin layer was tested under the conditions of air flow rate: 50 mL / min, temperature range: 100-800 ℃, and heating rate: 10 ℃ / min.

[0129] Table 2 Performance test

[0130]

[0131] Combining the performance test comparison in Table 2, we can find that:

[0132] 1. By comparing Examples 1-3 with Comparative Examples 1-2, it can be found that the high-temperature resistance and mechanical properties of the insulated wires prepared in Examples 1-3 are improved. This shows that in the present application, polyimide and nanotubes are used as modifiers to modify the filler. Polyimide has high rigidity, excellent mechanical properties, and high temperature resistance. It can also increase the surface energy of the filler, improve the compatibility between the filler and PEEK, and improve the dispersion uniformity of the filler in PEEK to form a uniform and dense network structure. With the combination of polyimide and nanotubes, the nanotubes can adhere to the filler surface under the action of polyimide, and form a composite structure of long linear structure-short linear structure with the filler, which can form a more complex interlaced network structure. The nanotubes can serve as anchor points to improve the bonding effect between the filler and PEEK, that is, further improve the mechanical strength of PEEK.

[0133] 2. By comparing Examples 4-5 with Example 3, it can be found that the mechanical strength and high temperature resistance of the insulated wires prepared in Examples 4-5 are improved. This shows that in this application, the silica nanotubes are subjected to amino treatment, and amino groups are grafted on the surface of the silica nanotubes. The strong hydrogen bond interaction between the amino groups and the polyimide molecules is utilized to improve the connection strength between the silica nanotubes and the filler, so that the silica nanotubes are stabilized as anchor points. At the same time, the packing density between the polyimide molecular chains can be effectively enhanced, thereby improving the wear resistance of PEEK and further improving the mechanical strength of the resin layer.

[0134] 3. By comparing Examples 6-8 with Example 3, it can be found that the mechanical strength and high temperature resistance of the insulated wires prepared in Examples 6-8 are improved. This shows that in the present application, rigid groups are grafted on the polyetheretherketone molecular chain. The carbonyl group, polyphenyl ether group and biphenyl group have different rigid strengths. Grafting on the polyetheretherketone molecular chain can adjust the flexibility between the polyetheretherketone molecular chains, so that the polyetheretherketone obtains excellent shape memory properties. The resin layer is composed of a fiber skeleton and shape memory polyetheretherketone. The resin layer is not easily damaged and can protect the battery cell for a long time.

[0135] 4. By comparing Examples 9-10 with Example 3, it can be found that the mechanical strength and high temperature resistance of the insulated wires prepared in Examples 9-10 are improved. This shows that in the present application, polyethersulfone can be decomposed to produce macromolecular free radicals, which react with sodium 4-styrenesulfonate to form a polyethersulfone-sodium polystyrenesulfonate composite material. The polyethersulfone-sodium polystyrenesulfonate composite material has better high temperature resistance and can cover the surface of the glass fiber in the form of a thin layer and microspheres, introduce active groups into the glass fiber, and further promote the bonding strength between the glass fiber and polyetheretherketone.

[0136] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A PEEK composite insulated wire, characterized in that: It includes a battery core and a resin layer wrapped around the battery core, and the resin layer includes the following raw materials in parts by weight: 100 parts of polyetheretherketone; 10-20 parts of filler; The filler includes carbon fiber and glass fiber, and the filler is a modified filler modified by a modifier, and the modifier includes polyimide and nanotubes; The filler modification method includes: dipping the filler in a modifier for 2 hours, removing the filler, drying at 80°C, heating to 200°C and keeping the temperature for 1 hour, heating to 300°C and keeping the temperature for 1 hour to obtain a modified filler; The nanotubes adhere to the surface of the filler under the action of polyimide and construct a composite structure of long linear structure-short linear structure with the filler.

2. The PEEK composite insulated wire according to claim 1, characterized in that: The polyimide is a polyimide containing an etherketone structure.

3. The PEEK composite insulated wire according to claim 2, characterized in that: The nanotubes include any one of titanium dioxide nanotubes, silicon dioxide nanotubes and carbon nitride nanotubes.

4. The PEEK composite insulated wire according to claim 3, characterized in that: The silica nanotubes are amino-treated silica nanotubes.

5. The PEEK composite insulated wire according to claim 2, characterized in that: The preparation of the modifier is as follows: Preparation of polyamic acid: APBP and PMDA were dried for 12 h, and then APBP was dissolved in an appropriate amount of DMAc solution under nitrogen. The mixture was stirred evenly, and PMDA was added. The polyamic acid (PAA) solution was stirred for 24 h and diluted with DMAc to a 0.25% precursor solution. Preparation of the modifier: The nanotubes are crushed and dispersed in a DMAc solution to obtain a dispersion, and the dispersion is mixed with a precursor solution to obtain a modifier.

6. The PEEK composite insulated wire according to claim 1, characterized in that: The polyetheretherketone is a modified polyetheretherketone grafted with a rigid group, and the rigid group includes any one or more of a carbonyl group, a polyphenyl ether group or a biphenyl group.

7. The PEEK composite insulated wire according to claim 6, characterized in that: The modified polyetheretherketone is prepared as follows: under the protection of an argon atmosphere, diphenyl sulfone is placed in a container, and after heating to melt the diphenyl sulfone, 4,4'-difluorobenzophenone, hydroquinone, biphenol, 4,4'-dihydroxydiphenyl ether, and a mixed salt of sodium carbonate and potassium carbonate are added into the system, and uniform stirring is maintained. The system is kept at 220°C for 2 hours, 250°C and 290°C for 1 hour each, and finally polymerized at 310°C for 2 hours. The product is discharged into water, crushed, washed with ethanol and water 10 times each, and then dried in an oven to obtain the modified polyetheretherketone.

8. The PEEK composite insulated wire according to claim 7, characterized in that: The mass ratio of the 4,4'-dihydroxydiphenyl ether to biphenyl diphenol is 1-3:7-9.

9. The PEEK composite insulated wire according to claim 1, characterized in that: The surface of the glass fiber is wrapped with a polyethersulfone-sodium polystyrene sulfonate composite layer.

10. The method for preparing a PEEK composite insulated wire according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Preparation of resin layer raw materials: PEEK powder was dried at 120°C for 24 hours, and the filler and PEEK powder were mixed and melted to obtain the resin layer raw materials; S2. Preparation of composite insulated wire: Extruding the resin layer raw material outside the battery core to obtain a composite insulated wire.

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