A peel-resistant insulated wire cable and a method of making the same

Abstract

The present application relates to the technical field of cable manufacturing, in particular to a stripping-resistant insulated cable and a preparation method thereof, the present application adopts fluorine-containing polyaryletherketone resin PI-PAEK containing imide side chain as the adhesive layer outside the conductor, improves the adhesive strength between the polyaryletherketone outer cladding layer and the copper conductor, and can produce good compatibility with the polyaryletherketone outer cladding layer, so that the overall cladding layer outside the conductor forms a whole layer structure with good compatibility, the bending and torsion performance of the stripping-resistant insulated cable of the present application can meet the requirements, the dielectric constant is smaller, the electrical insulation performance is better, and the requirements of the vehicle cable can be met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cable manufacturing, in particular to a stripping-resistant insulated cable and a preparation method thereof. BACKGROUND

[0002] The cable for vehicles mainly serves the generator of the vehicle, the small vehicle-mounted motor and the motor and wiring harness of the new energy vehicle and other components. The polyether ether ketone (PEEK) material plays a key role in the early development stage of new products due to its excellent temperature difference resistance, good flexibility, stable chemical properties, excellent electrical properties, outstanding dielectric strength, radiation resistance, insulation characteristics and self-extinguishing function, etc., which fully meets the special needs of oil-cooled motors. However, the adhesion of pure PEEK material is poor, and its compatibility with impregnated paint is poor, which is difficult to adhere, which is an obstacle to its application in the field of wires and cables.

[0003] The prior art such as patent CN111554443B provides a processing technology of PEEK electromagnetic wire. The copper wire is coated with 220-grade polyamide-imide insulating paint or 240-grade polyamide-imide insulating paint for more than 18 times, and then baked until the paint film reaches the specified thickness, and then the polyether ether ketone enameled wire is coated. The process is relatively complex, and still needs expensive polyamide or polyamide-imide as an intermediate layer.

[0004] Therefore, it is a technical problem to be solved by the present application to develop a cable with simple process, low cost and good adhesion. SUMMARY

[0005] In order to solve the above technical problems, a stripping-resistant insulated cable and a preparation method thereof are provided. The present application uses fluorine-containing polyaryletherketone resin containing imide side chain as the bonding layer outside the conductor, improves the bonding strength between the polyaryletherketone outer coating layer and the copper conductor, and can produce good compatibility with the polyaryletherketone outer coating layer, so that the overall coating layer outside the conductor forms a whole layer structure with good compatibility. The stripping-resistant insulated cable of the present application can meet the requirements of bending and twisting performance, has good electrical insulation performance, and can meet the requirements of the cable for vehicles.

[0006] In order to achieve the above purposes, the present application realizes the following technical scheme:

[0007] A stripping-resistant insulated cable, comprising a conductor, and a bonding layer and an outer coating layer arranged outside the conductor;

[0008] The material of the bonding layer is fluorine-containing polyaryletherketone resin containing imide side chain, and the specific chemical structure is as follows:

[0009]

[0010] Further, the number average molecular weight M n between 15000 g / mol and 30000 g / mol, the weight average molecular weight M w between 35000 g / mol and 120000 g / mol, the molecular weight distribution index is between 1.8 and 2.6, and the melt viscosity at 400℃ is 90 Pa·s to 150 Pa·s. The synthesis method of the compound is referred to Example 1 of the patent CN202411516988.7 of the applicant, and the preparation of the corresponding compound according to the protection scope of the patent can obtain the compound in the above range.

[0011] Further, the material of the outer cladding layer is polyaryletherketone or a melt blend of polyaryletherketone and the fluorine-containing polyaryletherketone resin with imide side chains, and the proportion of polyetheretherketone in the melt blend is between 50wt% and 100wt%. Since the glass transition temperature of the fluorine-containing polyaryletherketone resin with imide side chains is relatively high, about 185℃, and the glass transition temperature of pure PEEK is 143℃, the blend of the two can obtain a blend with a higher glass transition temperature, so that the cable can be applied in higher temperature places.

[0012] The polyaryletherketone is selected from one or more of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketone ketone (PEKK), polyether ether ketone ketone (PEEKK) and polyether ketone ether ketone ketone (PEKEKK).

[0013] Further, the dielectric constant of the adhesive layer at 25℃ is below 3.0, and the dielectric constant of the outer cladding layer at 25℃ is below 3.5.

[0014] Further, the thickness of the adhesive layer is between 10μm and 100μm, the thickness of the outer cladding layer is between 100μm and 500μm, and the adhesive layer and the outer cladding layer can form a whole.

[0015] The preparation method of the above-mentioned peel-resistant insulated cable comprises the following steps:

[0016] The conductor is coated with an adhesive layer solution by multiple solution immersion method, and after drying, an adhesive layer is formed outside the conductor. The coating-drying operation is repeated or not repeated until the adhesive layer reaches the desired thickness, and an intermediate product is obtained.

[0017] Then, an outer cladding layer is extrusion-coated outside the intermediate product by extrusion coating method, and a peel-resistant insulated cable is obtained.

[0018] The adhesive layer solution contains fluorine-containing polyaryletherketone resin with imide side chains.

[0019] wherein the material of the outer cladding layer is a polyaryletherketone or a melt blend of a polyaryletherketone and the imide side chain containing fluorine-containing polyaryletherketone resin.

[0020] Further, the mass percentage of the adhesive layer solution is at least 5%, preferably 10%-50%, and the solvent for dissolving the imide side chain containing fluorine-containing polyaryletherketone resin is selected from one or more of DMF, DMAc, NMP, DMSO, CHCl3, and THF.

[0021] Further, the extrusion coating method uses a screw extruder to extrude the intermediate product, and the extrusion parameters are set as follows: the temperature of the feeding section of the screw extruder is 140-200℃ along the extrusion direction, the temperature of each zone of the melting section is increased in the range of 250-420℃, the temperature of the metering section is in the range of 350-400℃, and the temperature of the die head is 370-400℃.

[0022] Beneficial technical effects:

[0023] The imide side chain containing fluorine-containing polyaryletherketone resin PI-PAEK is used as the adhesive layer outside the conductor, the adhesion strength between the polyaryletherketone outer cladding layer and the copper conductor is improved, good compatibility with the polyaryletherketone outer cladding layer is achieved, the overall cladding layer outside the conductor forms a whole layer structure with good compatibility, the peel-resistant insulated cable of the present application can meet the requirements of bending and torsion, has a smaller dielectric constant, and has better electrical insulation, and can meet the requirements of vehicle cables. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The description of the at least one exemplary embodiment is actually only illustrative, but not as any limitation on the present application and its application or use. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0025] Unless otherwise specifically stated, the numerical values set forth in these examples are not limiting of the scope of the present application. Techniques, methods, and materials known to those of ordinary skill in the related art can not be discussed in detail herein. However, the techniques, methods, and materials are fully described in the literature that is incorporated by reference. In the examples shown and discussed herein, any specific values should be interpreted as illustrative only and not as a limitation. Thus, other examples of the exemplary embodiments can have different values.

[0026] The experimental methods in the following examples without specific conditions are generally determined according to the national standard; if there is no corresponding national standard, it is carried out according to the general standard requirement or general method.

[0027] The following polyaryletherketone is taken as polyether ether ketone as an example, PEEK is synthesized by Shandong Junhao High Performance Polymer Co., Ltd., the size is 200 mesh-3 mm, the melt index is 5-16 g / 10 min (400℃, 2.16 kg), the melt viscosity is 120-410 Pa.s (400℃), and the chemical structure is as follows:

[0028]

[0029] Preparation Example 1

[0030] The preparation method of the imide side group containing bisphenol AF type polyaryletherketone (PI-PAEK) used below is disclosed in the Chinese patent with application number 202411516988.7 of Shandong Junhao High Performance Polymer Co., Ltd., which details the preparation method of the polymer in Example 1, specifically by condensation polymerization of bisphenol AF containing two imide groups with 4,4'-difluorobenzophenone.

[0031] Specifically, bisphenol AF containing two imide groups is first synthesized, and the chemical reaction process and the structure of bisphenol AF containing two imide groups are as follows:

[0032]

[0033] Then, fluorine-containing polyaryletherketone containing imide side chain (PI-PAEK) is produced, and the chemical reaction process and the chemical structure of PI-PAEK are as follows:

[0034]

[0035] According to the condensation polymerization reaction temperature of 160-180℃ and the reaction time of 4-12h, the number average molecular weight M n of the prepared PI-PAEK is between 15000g / mol and 30000g / mol, the weight average molecular weight M w is between 35000g / mol and 120000g / mol, the molecular weight distribution index is between 1.8 and 2.6, and the melt viscosity at 400℃ is 90Pa·s-150Pa·s.

[0036] The PI-PAEK prepared by the condensation polymerization reaction temperature of 160℃ and the reaction time of 7h in Example 1 of the Chinese patent with application number 202411516988.7 has a number average molecular weight M n = 2.58 x 10 4 g / mol, a weight average molecular weight M w = 5.7 x 104 g / mol, PDI = 2.21; T g = 185°C, with a tensile strength of 87 MPa and an elongation at break of more than 30%; it can be heated and dissolved in DMF, DMAc, NMP, DMSO, and can be dissolved at room temperature in CHCl3, THF. The PI-PAEK with the above parameters is used in the following cases, and of course PI-PAEK with other parameters within the above range can also be used in other cases.

[0037] Example 1

[0038] A method for preparing a peel-resistant insulated cable, comprising the following steps:

[0039] S1, preliminary preparation

[0040] Material drying: PI-PAEK and PEEK are baked at a temperature of 120°C for 5 hours respectively;

[0041] Wire drawing step: an oxygen-free copper rod with a diameter of 2.5 mm is passed through a wire drawing device into a wire drawing box, and after multiple wire drawing, the specified product specification (diameter 1 mm) is reached, then the wire surface residual water spots are cleaned and dried, and then annealing treatment is performed; during annealing, the annealing furnace temperature is 500°C; the annealing temperature in the furnace is heated by an electric heating tube, and a thermocouple is used for real-time temperature control; water vapor is used in the annealing furnace to protect the copper rod, and after annealing, the copper wire cleaning process is performed again;

[0042] S2, preparation of adhesive layer

[0043] PI-PAEK is dissolved in N,N-dimethylformamide to prepare a 25wt% adhesive solution. The copper wire treated in S1 is immersed and coated in the adhesive solution, and then baked in an oven to remove the organic solvent, forming a PI-PAEK adhesive layer outside the copper wire conductor. The immersion-baking process is repeated until the coated adhesive layer reaches a thickness of 30μm, forming an intermediate product; then the intermediate product is wound on a spool by a winding device, and the core wire surface is free of lubricant before winding.

[0044] S3, preparation of outer coating layer

[0045] The extruder parameter settings are as follows: the feeding section temperature of the screw extruder is set to 160°C, the temperature of each zone of the melting section is increased from 280 to 380°C, the temperature of the metering section is 380-390°C, the temperature of the die head is 380-390°C, after waiting for each section to reach the temperature and keeping the temperature for 30 minutes, the PEEK resin is fed, at the same time, the intermediate product is unwound, and the PEEK is extruded and wrapped outside the intermediate product, since the temperature also reaches the melting temperature of the PI-PAEK adhesive layer, the PI-PAEK adhesive layer and the PEEK outer wrapping layer form an integral layer due to good compatibility during the extrusion and wrapping process, and the designed thickness of the peel-resistant insulated cable is obtained after cooling and winding.

[0046] Example 2

[0047] A method for preparing a peel-resistant insulated cable, comprising the following steps:

[0048] S1, the preliminary preparation is the same as that of Example 1.

[0049] S2, adhesive layer preparation

[0050] The PI-PAEK is dissolved with CHCl3 to prepare a 35wt% adhesive solution. The copper wire after S1 treatment is immersed and coated in the adhesive solution, and then baked in the oven to remove the organic solvent, thereby forming a PI-PAEK adhesive layer outside the copper wire conductor. The immersion-baking process is repeated until the wrapped adhesive layer reaches a thickness of 40μm, forming an intermediate product. Then the intermediate product is wound on a spool by a winding device, and the core wire surface is free of lubricant before winding.

[0051] S3, outer wrapping layer preparation

[0052] The extruder parameter settings are as follows: the feeding section temperature of the screw extruder is set to 160°C, the temperature of each zone of the melting section is increased from 280 to 380°C, the temperature of the metering section is 380-390°C, the temperature of the die head is 380-390°C, after waiting for each section to reach the temperature and keeping the temperature for 30 minutes, the PEEK resin is fed, at the same time, the intermediate product is unwound, and the PEEK is extruded and wrapped outside the intermediate product, since the temperature also reaches the melting temperature of the PI-PAEK adhesive layer, the PI-PAEK adhesive layer and the PEEK outer wrapping layer form an integral layer due to good compatibility during the extrusion and wrapping process, and the designed thickness of the peel-resistant insulated cable is obtained after cooling and winding.

[0053] Example 3

[0054] A method for preparing a peel-resistant insulated cable, comprising the following steps:

[0055] S1, the preliminary preparation is the same as that of Example 1.

[0056] S2, adhesive layer preparation

[0057] PI-PAEK was dissolved in CHCl3to prepare a 45wt% adhesive solution. The S1 treated copper wire was dip-coated in the adhesive solution and then baked in an oven to remove the organic solvent, forming a PI-PAEK adhesive layer outside the copper wire conductor. The dip-coating and baking process was repeated until the coated adhesive layer reached a thickness of 50μm, forming an intermediate product. The intermediate product was then wound onto a spool using a take-up device, and the core wire surface was free of lubricant before winding.

[0058] S3, outer coating layer preparation

[0059] The extruder parameters were set as follows: the temperature of the feeding section of the screw extruder was 180℃, the temperature of each zone of the melting section was increased from 260-380℃, the temperature of the metering section was 380-390℃, and the temperature of the die head was 390-400℃. After waiting for each section to reach the appropriate temperature and maintaining the temperature for 30 minutes, the PEEK resin was fed, and the intermediate product was unwound. The PEEK was extruded around the intermediate product, and since the temperature also reached the melting temperature of the PI-PAEK adhesive layer, the PI-PAEK adhesive layer and the PEEK outer coating layer formed a whole layer due to their good compatibility. After cooling and winding, the designed thickness of the peel-resistant insulated wire cable was obtained.

[0060] Example 4

[0061] The preparation of this example was the same as that of Example 2, except that the material of the outer coating layer was a melt-blended mixture of PEEK and PI-PAEK, and the mass ratio of PEEK to PI-PAEK was 8:2. After mixing the two materials uniformly, melt-blended extrusion and granulation were performed at 360-400℃, and then the melt-blended mixture was extruded around the intermediate product to form a whole layer.

[0062] Comparative Example 1

[0063] The preparation of this example was the same as that of Example 2, except that the material of the adhesive layer was hexafluoro bisphenol A type polyaryletherketone (PAEK-AF), and the specific chemical structure was as follows:

[0064]

[0065] The preparation of this compound was referred to: “Synthesis and characterization of polyaryletherketone containing trifluoromethyl groups”, Engineering Plastics and Applications [J], 2012, Vol. 40, No. 1, P73-76; the specific number average molecular weight M n of this compound was 34800g / mol, PDI = 2.56, and the melt viscosity at 400℃ was 144Pa·s.

[0066] Comparative Example 2

[0067] The case is prepared and implemented as the same as example 2, except that there is no S2 step, and the PEEK outer coating layer is directly extruded on the outer surface of the copper wire conductor.

[0068] The performance of the above examples and comparative examples is tested, and the results are shown in Table 1.

[0069] Table 1 Product performance of examples and comparative examples

[0070]

[0071] As shown in Table 1, the PI-PAEK adhesive layer with low dielectric constant is introduced between the PEEK outer coating layer and the copper wire conductor, which has good adhesion to the copper wire, and can have good compatibility with PEEK and form an integral whole when the PEEK outer coating layer is extruded subsequently, thereby improving the peeling force of the integral product, and the integral product has good peeling resistance, and the bending and twisting performance can meet the requirements, and the dielectric constant is smaller, and the electrical insulation is better, which can meet the requirements of the vehicle insulation cable; in addition, the PI-PAEK has a high glass transition temperature, and after being blended with PEEK as the outer coating layer material, the cable can be applied in a higher temperature use scenario, thereby improving the service life of the insulation cable under high temperature.

[0072] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacement or change according to the technical solution and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A peel resistant insulated wire cable characterized by, The conductor is provided with a bonding layer and an outer cladding layer outside the conductor; the thickness of the bonding layer is 30-50 μm; the bonding layer and the outer cladding layer can form an entirety; The thickness of the entirety product is 280-300 μm, which refers to the overall thickness of the conductor outer insulation layer, including the bonding layer and the outer cladding layer; The material of the bonding layer is a fluorine-containing polyarylene ether ketone resin containing imide side chains, and the chemical structure is as follows: ； The number average molecular weight Mn of the fluorine-containing polyarylene ether ketone resin containing imide side chains is 15,000-30,000 g / mol, the weight average molecular weight Mw is 35,000-120,000 g / mol, the molecular weight distribution index is 1.8-2.6, and the melt viscosity of the 400℃ molten liquid is 90-150 Pa·s; The preparation method comprises the following steps: The conductor is coated with the adhesive layer solution by multiple solution immersion method, and the adhesive layer is formed on the outer surface of the conductor after drying The operation of drying is performed until the adhesive layer reaches the desired thickness, and an intermediate product is obtained Then, an outer cladding layer is extruded on the intermediate product by an extrusion coating method to obtain a peel-resistant insulated cable; The bonding layer solution contains the fluorine-containing polyarylene ether ketone resin containing imide side chains, and the mass percentage of the bonding layer solution is 25-50%. The material of the outer cladding layer is a melt blend of polyether ether ketone and the fluorine-containing polyarylene ether ketone resin containing imide side chains, and the proportion of the polyether ether ketone in the melt blend is 50-100 wt%.

2. The stripable insulated cable of claim 1, wherein, The dielectric constant of the bonding layer at 25℃ is below 3.0, and the dielectric constant of the outer cladding layer at 25℃ is below 3.

5.

3. The stripable insulated cable of claim 1, wherein, The solvent for dissolving the fluorine-containing polyarylene ether ketone resin containing imide side chains is selected from one or more of DMF, DMAc, NMP, DMSO, CHCl3 and THF.

4. The abrasion-resistant, peel-away insulated cable of claim 1, wherein, The intermediate product is extruded by a screw extruder in the extrusion coating method, and the extrusion parameters are set as follows: the feeding section temperature of the screw extruder is 140-200℃ along the extrusion direction, the temperature of each zone of the melting section increases in the range of 250-420℃, and the metering section temperature is 350-400℃.

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