Polyether ether ketone heat shrink composition and use thereof

Abstract

The application provides a polyether ether ketone heat shrinkage composition and application thereof.The polyether ether ketone heat shrinkage composition comprises, by weight parts, 100 parts of polyether ether ketone resin, 20-30 parts of meltable polytetrafluoroethylene and 8-15 parts of a composite antistatic agent.The composite antistatic agent is used to modify the interface of phenolphthalein polyaryletherketone, graphite and carbon fiber, so that the dispersion between the two is more uniform, the filling efficiency of the composite antistatic agent is improved, the conductive path is better built, and excellent antistatic function of the heat shrinkable pipe is realized.The addition of the meltable polytetrafluoroethylene produces a crosslinked network after irradiation treatment, so that the heat shrinkable pipe has excellent shrinkage performance and wear resistance performance.According to research, when the shrinkage ratio of the heat shrinkable pipe provided by the application is 1.8:1, the recovery rate can still reach 93.6%, the volume resistance and friction coefficient are small, the tensile strength is high, and it is indicated that the heat shrinkable pipe has excellent shrinkage, antistatic property, wear resistance and mechanical property.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of heat-shrinkable materials, and particularly relates to a polyether ether ketone heat-shrinkable composition and application thereof. BACKGROUND

[0002] Polyether ether ketone resin (abbreviation: PEEK resin) is a special engineering plastic with excellent mechanical properties, radiation resistance and chemical corrosion resistance, and can be used in a wide temperature range and harsh chemical and physical environments. Once the insulating PEEK material is subjected to friction during use, static electricity will be generated. In the fields of petroleum, explosives and chemical industry, the static electricity accumulation phenomenon will cause fire or even explosion.

[0003] To solve this problem, the existing technology mostly uses PEEK material as a matrix, adds various conductive materials such as graphite and carbon nanotubes, and then mixes and disperses to obtain a composite material with antistatic properties. The antistatic PEEK heat-shrinkable pipe material can be prepared by extrusion and expansion processes, and can be wrapped on the outer surface of the protected object to dissipate static electricity.

[0004] However, the existing antistatic PEEK heat-shrinkable pipe material has a low shrinkage ratio, which limits its application. Therefore, it is necessary to endow the PEEK heat-shrinkable pipe material with excellent antistatic properties and high shrinkage ratio to expand the application of PEEK. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a polyether ether ketone heat-shrinkable composition and application thereof. The heat-shrinkable pipe material prepared from the polyether ether ketone heat-shrinkable composition has high shrinkage ratio and excellent antistatic properties.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a polyether ether ketone heat-shrinkable composition, which comprises 100 parts by weight of polyether ether ketone resin, 20-30 parts by weight of meltable polytetrafluoroethylene, and 8-15 parts by weight of a composite antistatic agent.

[0008] Preferably, the composite antistatic agent comprises graphite, carbon fibers and phenolphthalein polyaryletherketone.

[0009] Preferably, the mass ratio of the graphite, carbon fibers and phenolphthalein polyaryletherketone is (4-6):1:(0.5-1).

[0010] Preferably, the particle size of the graphite is 2-5 μm.

[0011] Preferably, the length of the carbon fibers is 30-50 μm.

[0012] Preferably, the polyether ether ketone resin has a melt index of (8-15) g / 10 min.

[0013] Preferably, the polyether ether ketone heat shrinkage composition further comprises 0.5-1 part of a high-temperature-resistant lubricant and 0.5-1 part of a high-temperature-resistant antioxidant.

[0014] Preferably, the high-temperature-resistant lubricant is selected from nano-silicon dioxide and / or nano-molybdenum disulfide.

[0015] Preferably, the high-temperature-resistant antioxidant is selected from tris[2.4-di-tert-butylphenyl] phosphite and / or triphenyl phosphite.

[0016] In a second aspect, the present application provides a polyether ether ketone heat shrinkable pipe prepared from the polyether ether ketone heat shrinkage composition described in the above technical solution.

[0017] In a third aspect, the present application provides a preparation method of the polyether ether ketone heat shrinkable pipe described above, comprising the following steps:

[0018] The polyether ether ketone heat shrinkage composition is extruded, the obtained base pipe is subjected to electron irradiation treatment, and then the treated base pipe is subjected to heating, expansion treatment, and cooling forming to obtain the polyether ether ketone heat shrinkable pipe.

[0019] Preferably, the expansion ratio of the expansion treatment is 1.5-1.8.

[0020] In a fourth aspect, the present application provides an application of the polyether ether ketone heat shrinkable pipe described above in the electrostatic protection in the field of electronic and electrical components or petrochemical industry.

[0021] Compared with the prior art, the present application has the following beneficial effects:

[0022] The present application provides a polyether ether ketone heat shrinkage composition, which comprises a base polyether ether ketone resin, a meltable polytetrafluoroethylene, and a composite antistatic agent. The composite antistatic agent is obtained by the synergistic addition of two-dimensional graphite and one-dimensional carbon fibers, and the interface of the two is modified by phenolphthalein polyaryletherketone. The dispersion between the two is more uniform, the filling efficiency of the composite antistatic agent is improved, the conductive path is better built, the excellent antistatic function of the heat shrinkable pipe is realized, the excellent mechanical properties are maintained, and the heat shrinkable pipe is easy to process and form. The addition of the meltable polytetrafluoroethylene can produce a crosslinked network after irradiation treatment, so that the heat shrinkable pipe has excellent shrinkage and wear resistance. After research, when the shrinkage ratio of the heat shrinkable pipe provided by the present application is 1.8:1, the recovery rate can still reach 93.6%, the volume resistance and the friction coefficient are small, and the tensile strength is high, which indicates that the heat shrinkable pipe has excellent shrinkage, antistatic property, wear resistance, and mechanical properties, and excellent comprehensive performance. DETAILED DESCRIPTION

[0023] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0024] In view of the low shrinkage of the anti-static PEEK heat shrinkable pipe in the prior art, the present application provides a polyether ether ketone heat shrinkable composition, which comprises, by weight, 100 parts of polyether ether ketone resin, 20-30 parts of meltable polytetrafluoroethylene, and 8-15 parts of composite antistatic agent. The 20-30 parts can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, or 30 parts, etc.; and the 8-15 parts can be 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, or 15 parts, etc. In the present application, the source of the polyether ether ketone resin and the meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) is not particularly limited, and they can be general commercially available products. If the melt index of the polyether ether ketone resin is too low, it will be difficult to extrude during the preparation of the heat shrinkable pipe, and the pipe will have poor plasticizing performance. If the melt index is too high, the pipe will not be able to be formed, so the melt index of the polyether ether ketone resin is preferably (8-15) g / 10 min, and can be 8 g / 10 min, 9 g / 10 min, 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 13 g / 10 min, 14 g / 10 min, or 15 g / 10 min, etc.

[0025] The composite antistatic agent comprises graphite, carbon fibers, and phenolphthalein polyaryletherketone. The two-dimensional graphite and one-dimensional carbon fibers serve as conductive substances, and the phenolphthalein polyaryletherketone, which is compatible with the base resin (i.e., the polyether ether ketone resin), serves as an interfacial modifier. The phenolphthalein polyaryletherketone can be physically attached to the surfaces of the graphite and carbon fibers, ensuring that the graphite and carbon fibers can be uniformly dispersed and not easily agglomerated, thereby better establishing a conductive path. The source of the graphite, carbon fibers, and phenolphthalein polyaryletherketone is not particularly limited in the present application, and they can be general commercially available products. In the present application, the particle size of the graphite is 2-5 μm, and can be 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm, etc.; and the length of the carbon fibers is 30-50 μm, and can be 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, or 50 μm, etc.

[0026] In some embodiments of the present application, the mass ratio of the graphite, carbon fiber and phenolphthalein polyaryletherketone is (4-6):1:(0.5-1), wherein the (4-6) can be specifically 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8 or 6, and the (0.5-1) can be specifically 0.5, 0.6, 0.7, 0.8, 0.9 or 1. According to the range of the mass ratio, the anti-static PEEK heat shrinkable tube prepared by using the above composition has excellent shrinkability, anti-static property, wear resistance and mechanical property.

[0027] In some embodiments of the present application, the polyether ether ketone heat shrinkable composition comprises, by weight, 100 parts of polyether ether ketone resin, 20-30 parts of meltable polytetrafluoroethylene, 8-15 parts of composite antistatic agent, 0.5-1 part of high-temperature-resistant lubricant and 0.5-1 part of high-temperature-resistant antioxidant. The 0.5-1 part can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part. The high-temperature-resistant lubricant is selected from nano silicon dioxide and / or nano molybdenum disulfide, and the high-temperature-resistant antioxidant is selected from tris[2.4-di-tert-butylphenyl] phosphite and / or triphenyl phosphite.

[0028] The polyether ether ketone heat shrinkable composition provided by the present application comprises base polyether ether ketone resin, meltable polytetrafluoroethylene and composite antistatic agent. The base polyether ether ketone resin has excellent mechanical property, radiation resistance and chemical corrosion resistance. The meltable polytetrafluoroethylene can form a crosslinked network after irradiation treatment, so that the heat shrinkable tube prepared from the composition has excellent shrinkability and wear resistance. The composite antistatic agent is obtained by the synergistic addition of two-dimensional graphite and one-dimensional carbon fiber, and the interface between the two is modified by phenolphthalein polyaryletherketone. The dispersion between the two is more uniform, the filling efficiency of the composite antistatic agent is improved, the conductive path is better built, the heat shrinkable tube prepared has excellent anti-static function, excellent mechanical property and is easy to process.

[0029] Based on this, the present application provides a polyether ether ketone heat shrinkable tube prepared from the polyether ether ketone heat shrinkable composition involved in the above technical solution.

[0030] The preparation method of the polyether ether ketone heat shrinkable tube is simple and can be completed by the processes of extrusion, irradiation and expansion. In some embodiments of the present application, the preparation method comprises the following steps:

[0031] The polyether ether ketone heat shrinkable composition is extruded, the obtained base pipe is subjected to electron irradiation treatment, then the treated base pipe is heated and expanded, and the polyether ether ketone heat shrinkable tube is obtained by cooling and molding.

[0032] According to the present application, firstly, the polyether ether ketone heat shrinkage composition is prepared, the polyether ether ketone resin, the meltable polytetrafluoroethylene, the optional high-temperature-resistant lubricant, the optional high-temperature-resistant antioxidant and the composite antistatic agent are weighed according to the proportion and mixed to obtain the mixed material of the polyether ether ketone heat shrinkage composition. The mixing is ball milling mixing, which is preferably carried out in a horizontal ball mill, the speed of the ball milling mixing is 200-400 r / min, preferably 250-350 r / min, and the ball milling mixing time is 3-5 h, preferably 3.5-4 h. Then the mixed material is added into the barrel of an extruder of high-temperature-resistant and corrosion-resistant plastic, the temperature range of the extruder is 360-380 ℃, preferably 365-370 ℃, the extrusion speed is controlled to be 80-120 r / min, preferably 90-110 r / min, and the main feeding speed is controlled to be 8-10 r / min. Then, the pelletizing drying is carried out by using the conventional pelletizing process, and the polyether ether ketone heat shrinkage special material is obtained. In some embodiments of the present application, the composite antistatic agent is prepared by the following method: a certain amount of phenolphthalein polyaryletherketone is mixed with a solvent to form a 0.2-0.5 wt% (which can be 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4, 0.45 wt% or 0.5 wt%) polymer solution, then graphite and carbon fiber are mixed with the polymer solution, the mixing is carried out under ultrasonic and stirring conditions, the stirring speed is controlled to be 200-400 rpm, preferably 300-350 rpm, the stirring time is controlled to be 4-8 h, preferably 5-6 h, then filtration is carried out, and drying is carried out at 80-120 ℃, preferably at 90-110 ℃, to obtain the composite antistatic agent. The solvent is preferably N,N-dimethylformamide and / or N,N-dimethylacetamide; the size of the graphite is preferably 2-5 μm; the length of the carbon fiber is preferably 30-50 μm; and the mass ratio of the graphite to the carbon fiber is preferably (4-6):1. The mass ratio of the polymer solution to the total amount of graphite and carbon fiber powder is (30-50):1, which can be 30:1, 35:1, 40:1, 45:1 or 50:1, etc.

[0033] According to the present application, the polyether ether ketone heat shrinkage special material is extruded by using a high-temperature-resistant and corrosion-resistant plastic extruder, the temperature range of the extruder is 360-380 ℃, preferably 365-370 ℃, the extrusion speed is controlled to be 30-60 r / min, preferably 40-50 r / min, and the main feeding speed is controlled to be 4-8 r / min. Then, the base pipe is extruded by using specific die, mandrel, cooling and shaping auxiliary machines, etc.

[0034] According to the present application, after the base pipe is obtained, the obtained base pipe is subjected to electron irradiation treatment to ensure that the meltable polytetrafluoroethylene generates a crosslinked network. The dose of the electron irradiation treatment is 200-400 kGy, preferably 240-350 kGy, and more preferably 280-320 kGy. After the electron irradiation treatment is completed, the obtained base pipe is preferably heated at 280-310 DEG C, and more preferably at 290-300 DEG C, and is subjected to vacuumization and the introduction of compressed gas to generate negative pressure, so that the base pipe is expanded at an expansion ratio of 1.5-1.8 (specifically, 1.5, 1.6, 1.7 or 1.8, etc.), and is cooled and shaped to obtain a polyether ether ketone heat-shrinkable pipe.

[0035] The above-mentioned point values are only listed for illustration and are not limited thereto, and other point values within the numerical range are also applicable. To avoid redundancy, they will not be described one by one.

[0036] Through research, the polyether ether ketone heat-shrinkable pipe provided by the present application still has a recovery rate of 93.6% when the shrinkage ratio is 1.8:1, has small volume resistance and friction coefficient, and has high tensile strength, indicating that it has excellent shrinkage, antistatic property, wear resistance and mechanical properties, and excellent comprehensive performance.

[0037] Based on this, the present application also provides the application of the above-mentioned polyether ether ketone heat-shrinkable pipe in the electrostatic protection of electronic and electrical components or petrochemical industry.

[0038] In order to further illustrate the present application, the following examples are used for detailed description. The experimental raw materials used in the following examples of the present application can be purchased from the market or prepared according to the conventional preparation method well known to those skilled in the art. The meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) is purchased from Zhejiang Juhua Co., Ltd., and the model number is FJY-A15.

[0039] Example 1

[0040] The present embodiment provides an antistatic polyether ether ketone heat-shrinkable pipe, and the preparation method is as follows:

[0041] (1) Preparation of a composite antistatic agent:

[0042] 2g of phenolphthalein polyaryletherketone is dissolved in 1000g of N,N-dimethylformamide to form a polymer solution, then 17.14g of graphite (with a size of 5μm) and 2.86g of carbon fiber powder (with a length of 50μm) are added to the polymer solution, and ultrasonic stirring is performed at a stirring speed of 400rpm for 8h, and then filtration and drying at 120 DEG C are performed to obtain a composite antistatic agent.

[0043] (2) Preparation of an antistatic polyether ether ketone heat-shrinkable special material:

[0044] The dried polyether ether ketone resin (melt index 15 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 30 parts, nano-silica 1 part, tris [2.4-di-tert-butylphenyl] phosphite 1 part, and a composite antistatic agent 15 parts are uniformly mixed in a horizontal ball mill. The ball milling speed is 400 r / min, and the ball milling time is 5 h. The mixed raw materials are added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 120 r / min, and the main feeding speed is controlled at 10 r / min. Then, the product of the extruder is granulated and dried by a conventional granulation process, and finally an antistatic polyether ether ketone heat shrinkage special material is obtained;

[0045] (3) Preparation of antistatic polyether ether ketone heat shrinkage pipe material:

[0046] The antistatic polyether ether ketone heat shrinkage special material is extruded into a base pipe by using a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 60 r / min, and the main feeding speed is controlled at 8 r / min. After passing through specific die, mandrel, cooling and shaping, etc. Auxiliary machines, the base pipe is extruded for use;

[0047] After the base pipe is irradiated by electron beam irradiation technology at a dose of 400 kGy, the base pipe is heated at 310℃, and the base pipe is expanded by vacuum pumping or compressed gas, the expansion ratio is 1.8 times, and the base pipe is cooled and shaped, to obtain an antistatic polyether ether ketone heat shrinkage pipe material.

[0048] Example 2

[0049] This embodiment provides an antistatic polyether ether ketone heat shrinkage pipe material, and the preparation method is as follows:

[0050] (1) Preparation of composite antistatic agent:

[0051] 2g of phenolphthalein polyaryletherketone is dissolved in 1000g of N,N-dimethylformamide to form a polymer solution, then 17.14g of graphite (size 5μm) and 2.86g of carbon fiber powder (length 50μm) are added to the solution, ultrasonic stirring is carried out, the stirring speed is controlled at 400rpm, the stirring time is controlled at 8h, filtration is carried out, and drying is carried out at 120℃ to obtain a composite antistatic agent;

[0052] (2) Preparation of antistatic polyether ether ketone heat shrinkage special material:

[0053] The dried polyether ether ketone resin (melt index 12 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 25 parts, nano-silica 0.75 parts, tris [2.4-di-tert-butyl phenyl] phosphite 0.75 parts, and composite antistatic agent 12 parts are uniformly mixed in a horizontal ball mill. The ball milling speed is 300 r / min, and the ball milling time is 4 h. The mixed raw materials are added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360-380°C, the extrusion speed is controlled at 100 r / min, and the main feeding speed is controlled at 9 r / min. Then, the product of the extruder is granulated and dried by a conventional granulation process to obtain an antistatic polyether ether ketone heat shrinkage special material;

[0054] (3) Preparation of antistatic polyether ether ketone heat shrinkage pipe material:

[0055] The antistatic polyether ether ketone heat shrinkage special material is extruded into a base pipe by using a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range is 360-380°C, the extrusion speed is controlled at 45 r / min, and the main feeding speed is controlled at 6 r / min. The base pipe is extruded into a pipe by using specific die, mandrel, cooling and shaping, etc. auxiliary machines;

[0056] Finally, the sample is irradiated by electron beam irradiation technology at a dose of 300 kGy, and the above obtained base pipe is heated at 295°C, and expanded by vacuum pumping or compressed gas method, the expansion ratio is 1.7 times, and cooled and shaped to obtain the required antistatic polyether ether ketone heat shrinkage pipe material.

[0057] Example 3

[0058] This embodiment provides an antistatic polyether ether ketone heat shrinkage pipe material, and the preparation method is as follows:

[0059] (1) Preparation of composite antistatic agent:

[0060] 2 g of phenolphthalein polyaryletherketone is dissolved in 1000 g of N,N-dimethylformamide to form a polymer solution, then 17.14 g of graphite (size 5 μm) and 2.86 g of carbon fiber powder (length 50 μm) are added to the solution, ultrasonic stirring is carried out, the stirring speed is controlled at 400 rpm, the stirring time is controlled at 8 h, filtration is carried out, and drying is carried out at 120°C to obtain a composite antistatic agent;

[0061] (2) Preparation of antistatic polyether ether ketone heat shrinkage special material:

[0062] The dried polyether ether ketone resin (melt index 8 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 20 parts, nano-silica 0.5 parts, tris [2.4-di-tert-butyl phenyl] phosphite 0.5 parts, and a composite antistatic agent 8 parts are uniformly mixed in a horizontal ball mill. The ball milling speed is 200 r / min, and the ball milling time is 3 h. The mixed raw materials are added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360-380°C, the extrusion speed is controlled at 80 r / min, and the main feeding speed is controlled at 8 r / min. Then, the product of the extruder is granulated and dried by a conventional granulation process to obtain an antistatic polyether ether ketone heat-shrinkable special material;

[0063] (3) Preparation of antistatic polyether ether ketone heat-shrinkable pipe material:

[0064] The antistatic polyether ether ketone heat-shrinkable special material is extruded into a base pipe by using a high-temperature and corrosion-resistant plastic extruder with a temperature range of 360-380°C, an extrusion speed of 30 r / min, and a main feeding speed of 4 r / min. The base pipe is extruded into a pipe by using specific dies, mandrels, and cooling and sizing auxiliary machines;

[0065] Finally, the sample is irradiated by electron beam irradiation technology at a dose of 200 kGy. The obtained base pipe is heated at 280°C, expanded by vacuum pumping or compressed gas, and cooled and sized to obtain the required antistatic polyether ether ketone heat-shrinkable pipe material.

[0066] Example 4

[0067] This example provides an antistatic polyether ether ketone heat-shrinkable pipe material, and the preparation method is as follows:

[0068] (1) Preparation of a composite antistatic agent:

[0069] 5 g of phenolphthalein polyaryletherketone is dissolved in 1000 g of N,N-dimethylacetamide to form a polymer solution, then 17.14 g of graphite (size 2 μm) and 2.86 g of carbon fiber powder (length 30 μm) are added to the solution, and the solution is stirred and ultrasonicated at a speed of 200 rpm for 4 h. The solution is filtered and dried at 80°C to obtain a composite antistatic agent.

[0070] (2) Preparation of an antistatic polyether ether ketone heat-shrinkable special material:

[0071] Take the dried polyether ether ketone resin (melt index is 15 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 30 parts, nano-molybdenum disulfide 1 part, triphenyl phosphite 1 part, and composite antistatic agent 15 parts, and uniformly mix them in a horizontal ball mill. The ball milling speed is 400 r / min, and the ball milling time is 5 h. The mixed raw materials are added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 120 r / min, and the main feeding speed is controlled at 10 r / min. Then, the product of the extruder is granulated and dried by using the conventional granulation process, and finally the antistatic polyether ether ketone heat shrinkage special material is obtained;

[0072] (3) Preparation of antistatic polyether ether ketone heat shrinkage pipe material:

[0073] The antistatic polyether ether ketone heat shrinkage special material is extruded into a base pipe by using a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 60 r / min, and the main feeding speed is controlled at 8 r / min. After passing through specific die, mandrel, cooling and shaping, etc. Auxiliary machines, the base pipe is extruded for use.

[0074] Finally, the sample is irradiated by electron beam irradiation technology with a dose of 400 kGy, and the above obtained base pipe is heated at 310℃, and expanded by vacuum pumping or compressed gas method, the expansion ratio is 1.8 times, and cooled and shaped, to obtain the required antistatic polyether ether ketone heat shrinkage pipe material.

[0075] Example 5

[0076] This embodiment provides an antistatic polyether ether ketone heat shrinkage pipe material, and the preparation method is as follows:

[0077] (1) Preparation of composite antistatic agent:

[0078] 5g of phenolphthalein polyaryletherketone is dissolved in 1000g of N,N-dimethylacetamide to form a polymer solution, then 17.14g of graphite (size 2μm) and 2.86g of carbon fiber powder (length 30μm) are added to the solution, ultrasonic stirring is carried out, the stirring speed is controlled at 200rpm, the stirring time is controlled at 4h, filtration is carried out, and drying is carried out at 80℃ to obtain a composite antistatic agent;

[0079] (2) Preparation of antistatic polyether ether ketone heat shrinkage special material:

[0080] Take the dried polyether ether ketone resin (melt index is 8 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 20 parts, nano molybdenum disulfide 0.5 parts, triphenyl phosphite 0.5 parts, composite antistatic agent 8 parts, uniformly mixed in a horizontal ball mill. The ball milling speed is 200 r / min, and the ball milling time is 3h. The mixed raw materials are added to the barrel of the high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 80r / min, and the main feeding speed is controlled at 8r / min. Then, the product of the extruder is granulated and dried by using the conventional granulation process, and finally the antistatic polyether ether ketone heat shrinkage special material is obtained;

[0081] (3) Preparation of antistatic polyether ether ketone heat shrinkage pipe material:

[0082] The antistatic polyether ether ketone heat shrinkage special material is extruded by using a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 30r / min, and the main feeding speed is controlled at 4r / min. After extrusion through a specific die, a mandrel, and a cooling and shaping auxiliary machine, a base pipe is obtained.

[0083] Finally, the sample is irradiated by electron beam irradiation technology at a dose of 200kGy, and then the above obtained base pipe is heated at 280℃, and expanded by vacuum pumping or compressed gas, with an expansion ratio of 1.6 times and cooling and shaping, to obtain the required antistatic polyether ether ketone heat shrinkage pipe material.

[0084] Comparative Example 1

[0085] This comparative example provides an antistatic polyether ether ketone heat shrinkage pipe material, which is prepared by the following method:

[0086] (1) Preparation of antistatic polyether ether ketone heat shrinkage special material:

[0087] Take the dried polyether ether ketone resin (melt index is 15 g / 10 min) 100 parts, meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 30 parts, nano silicon dioxide 1 part, tri[2.4-di-tert-butylphenyl] phosphite 1 part, and graphite (size 5μm) 15 parts, uniformly mixed in a horizontal ball mill. The ball milling speed is 400 r / min, and the ball milling time is 5h. The mixed raw materials are added to the barrel of the high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360℃-380℃, the extrusion speed is controlled at 120r / min, and the main feeding speed is controlled at 10r / min. The granulation and drying are carried out by using the conventional granulation process, and finally the antistatic polyether ether ketone heat shrinkage special material is obtained;

[0088] (2) Preparation of antistatic polyether ether ketone heat shrinkage pipe material:

[0089] The anti-static polyether ether ketone heat-shrinkable special material is extruded by using a high-temperature-resistant and corrosion-resistant plastic extruder, the temperature range of the extruder is 360-380°C, the extrusion speed is controlled at 60 r / min, and the main feeding speed is controlled at 8 r / min. The base pipe is extruded by using specific die, mandrel, cooling and other auxiliary machines for use.

[0090] Finally, the sample is irradiated by electron beam irradiation technology at a dose of 400 kGy, the above obtained base pipe is heated at 310°C, and the base pipe is expanded by vacuum pumping or compressed gas method, the expansion ratio is 1.8 times, and the base pipe is cooled and shaped to obtain the required anti-static polyether ether ketone heat-shrinkable pipe material.

[0091] Comparative Example 2

[0092] The present comparative example provides an anti-static polyether ether ketone heat-shrinkable pipe material, and the preparation method is as follows:

[0093] (1) Preparation of composite antistatic agent:

[0094] Into 1000 g of N,N-dimethylformamide, 17.14 g of graphite (size 5 μm) and 2.86 g of carbon fiber powder (length 50 μm) are added, and the stirring is carried out under ultrasonic, the stirring speed is controlled at 400 rpm, the stirring time is controlled at 8 h, and then filtration and drying at 120°C are carried out to obtain the composite antistatic agent.

[0095] (2) Preparation of anti-static polyether ether ketone heat-shrinkable special material:

[0096] The dried polyether ether ketone resin (melt index 15 g / 10 min) 100 parts, the meltable polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer) 30 parts, the nano-silicon dioxide 1 part, the tris [2.4-di-tert-butyl phenyl] phosphite 1 part, and the composite antistatic agent 15 parts are uniformly mixed in a horizontal ball mill. The ball milling speed is 400 r / min, and the ball milling time is 5 h. The mixed raw materials are added into the barrel of a high-temperature-resistant and corrosion-resistant plastic extruder. The temperature range of the extruder is 360-380°C, the extrusion speed is controlled at 120 r / min, and the main feeding speed is controlled at 10 r / min. Then, the product of the extruder is granulated and dried by using the conventional granulation process to obtain the anti-static polyether ether ketone heat-shrinkable special material.

[0097] (3) Preparation of anti-static polyether ether ketone heat-shrinkable pipe material:

[0098] The anti-static polyether ether ketone heat-shrinkable special material is extruded by using a high-temperature-resistant and corrosion-resistant plastic extruder, the temperature range of the extruder is 360-380°C, the extrusion speed is controlled at 60 r / min, and the main feeding speed is controlled at 8 r / min. The base pipe is extruded by using specific die, mandrel, cooling and other auxiliary machines for use.

[0099] Finally, the sample is irradiated by electron beam irradiation technology at a dose of 400 kGy, and then the above obtained base pipe is heated at 310 DEG C, and expanded by vacuum pumping or compressed gas, the expansion ratio is 1.8 times, and cooled and shaped to obtain the required antistatic polyether ether ketone heat shrinkable tube.

[0100] Performance test

[0101] The antistatic polyether ether ketone heat shrinkable tube obtained in the above examples 1-5 and comparative examples 1-2 is tested accordingly, and the test method is as follows:

[0102] The shrinkage and recovery rate test refers to GB / T13519-2016; the volume resistance test is performed according to GB / T31838.2-2019; the tensile strength test is performed according to GB / T1040-2006; and the friction coefficient is performed according to GB / T3960-2016.

[0103] The test results are shown in Table 1 as follows:

[0104] Table 1

[0105]

[0106] As shown in Table 1, the antistatic polyether ether ketone heat shrinkable tube provided by the present application has a shrinkage ratio of 1.8:1, high tensile strength, small volume resistance and friction coefficient. Compared with comparative examples 1-2, the recovery rate of the antistatic polyether ether ketone heat shrinkable tube provided by the present application is higher under the same compression ratio, which indicates that the shrinkage performance of the antistatic polyether ether ketone heat shrinkable tube provided by the present application is more excellent.

[0107] The above description of the disclosed embodiments enables one skilled in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A polyether ether ketone heat shrinkable tubing characterized by, Prepared from a polyether ether ketone heat shrinkage composition; The polyether ether ketone heat shrinkage composition comprises, by weight parts, 100 parts of polyether ether ketone resin, 20-30 parts of meltable polytetrafluoroethylene, and 8-15 parts of a composite antistatic agent; The composite antistatic agent comprises graphite, carbon fiber, and phenolphthalein polyaryletherketone; The mass ratio of the graphite, carbon fiber, and phenolphthalein polyaryletherketone is (4-6):1:(0.5-1); The particle size of the graphite is 2-5 μm; The length of the carbon fiber is 30-50 μm; The polyether ether ketone heat shrinkage pipe is prepared by the following method: The polyether ether ketone heat shrinkage composition is extruded, the obtained base pipe is subjected to electron irradiation treatment, then the treated base pipe is subjected to heating and expansion treatment, and is cooled to form a polyether ether ketone heat shrinkage pipe; The expansion ratio of the expansion treatment is 1.5-1.

8.

2. The polyether ether ketone heat shrinkable tubing of claim 1, wherein, The melt index of the polyether ether ketone resin is (8-15) g / 10 min.

3. The polyether ether ketone heat shrinkable tubing of claim 1, wherein, The polyether ether ketone heat shrinkage composition further comprises 0.5-1 parts of a high-temperature-resistant lubricant and 0.5-1 parts of a high-temperature-resistant antioxidant.

4. The polyether ether ketone heat shrinkable tubing of claim 3, wherein, The high-temperature-resistant lubricant is selected from nano-silicon dioxide and / or nano-molybdenum disulfide; The high-temperature-resistant antioxidant is selected from tris[2.4-di-tert-butylphenyl] phosphite and / or triphenyl phosphite.

5. The method of producing a polyether ether ketone heat-shrinkable tubing according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: The polyether ether ketone heat shrinkage composition is extruded, the obtained base pipe is subjected to electron irradiation treatment, then the treated base pipe is subjected to heating and expansion treatment, and is cooled to form a polyether ether ketone heat shrinkage pipe.

6. Application of the polyether ether ketone heat shrinkage pipe according to any one of claims 1-4 or prepared by the preparation method of claim 5 in electrostatic protection in the field of electronic and electrical components or petrochemical industry.

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