Polyether ether ketone heat shrink composition and use thereof

Abstract

The application provides a polyether ether ketone heat shrinkage composition and application thereof. The composition comprises 100 parts of polyether ether ketone resin and 30-50 parts of carbon conductive filler composite material by weight. The carbon conductive filler composite material is obtained by in-situ polymerization of carbon conductive filler and polyether ether ketone resin, the carbon conductive filler is obtained by zero-dimensional C 60 The synergistic addition of zero-dimensional C 60 , one-dimensional single-walled carbon nanotubes and two-dimensional reduced graphene oxide improves the filling efficiency of the carbon conductive filler. Research shows that when the heat shrinkage rate of the prepared polyether ether ketone heat shrinkage pipe material is 1.6:1, the recovery rate can be as high as 92.1%, the tensile strength is high, the original volume resistance, the volume resistance after immersion in aviation kerosene for 168 hours and the volume resistance after irradiation at a dose of 1000 kGy are all small. It is shown that the prepared heat shrinkage pipe material has excellent radiation resistance, aviation kerosene resistance, antistatic function, shrinkage performance and mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of heat-shrinkable materials technology, specifically relating to a polyetheretherketone heat-shrinkable composition and its application. Background Technology

[0002] The main characteristic of heat-shrinkable polymer tubing is that it shrinks under heat and wraps around the outer surface of the object being protected, providing insulation, moisture protection, sealing, protection, and splicing functions. Heat-shrinkable tubing is widely used in fields such as insulation and heat protection of electronic components, insulation protection of joints in communication cables and power cables, shielding connections of electrical components, insulation sealing, and sealing and corrosion protection of chemical and oil pipelines.

[0003] Polyetheretherketone (PEEK) resin is a special engineering plastic with excellent mechanical properties, radiation resistance, and chemical corrosion resistance. It can be used over a wide temperature range and in harsh chemical and physical environments, and is widely used in the manufacture of heat-shrinkable polymer tubing. However, insulating PEEK materials generate static electricity when subjected to friction during use. When applied in the petroleum, explosives, and chemical industries, the accumulation of static electricity can cause fires or even explosions.

[0004] To address this issue, most existing technologies use PEEK material as the matrix and add various conductive materials, such as graphite and carbon nanotubes, to create a composite material with antistatic properties through mixing and dispersion. This composite material can then be extruded and expanded to produce antistatic PEEK heat-shrinkable tubing, which can be wrapped around the outer surface of the object being protected to dissipate static electricity.

[0005] Currently, in the preparation of antistatic PEEK heat-shrinkable tubing, high aspect ratio conductive fillers offer high filling efficiency and achieve antistatic effects with low addition amounts, while also exhibiting excellent mechanical properties. However, high aspect ratio conductive fillers are prone to orientation disruption during the molding and processing of heat-shrinkable tubing, leading to the destruction of the conductive network and the loss of the composite material's original antistatic properties. Therefore, it is essential to impart antistatic properties to PEEK heat-shrinkable tubing while simultaneously forming a stable conductive network to expand the application areas of PEEK. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide a polyetheretherketone (PEEK) heat-shrinkable composition and its application. The PEEK heat-shrinkable composition is used to prepare PEEK heat-shrinkable tubing, which exhibits excellent antistatic properties, mechanical properties, resistance to aviation kerosene, and radiation resistance.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a polyetheretherketone heat-shrinkable composition comprising, by weight, 100 parts of polyetheretherketone resin and 30-50 parts of carbon conductive filler composite material.

[0009] Preferably, the carbon conductive filler composite material is obtained by in-situ polymerization of carbon conductive filler and polyetheretherketone resin.

[0010] Preferably, the carbon conductive filler comprises C 60 Single-walled carbon nanotubes and reduced graphene oxide.

[0011] Preferably, the C 60 The mass ratio of single-walled carbon nanotubes to reduced graphene oxide is 1:(5-7):(2-4).

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

[0013] Preferably, the polyetheretherketone heat-shrinkable composition further includes 0.5 to 1 part of a high-temperature resistant lubricant and 0.5 to 1 part of a high-temperature resistant antioxidant.

[0014] Preferably, the high-temperature resistant lubricant is selected from nano-silica 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] Secondly, the present invention provides a polyetheretherketone heat-shrinkable tubing, which is prepared from the polyetheretherketone heat-shrinkable composition involved in the above technical solution.

[0017] Thirdly, the present invention also provides a method for preparing the above-mentioned polyetheretherketone heat-shrinkable tubing, comprising the following steps:

[0018] S1: Carbon conductive filler, 4,4'-difluorobenzophenone, hydroquinone, solvent and catalyst are mixed and heated in an inert atmosphere to obtain carbon conductive filler composite material;

[0019] S2: Weigh out polyetheretherketone resin, carbon conductive filler composite material, optional high-temperature resistant lubricant, and optional high-temperature resistant antioxidant according to the proportion and mix them evenly to obtain a mixture.

[0020] S3: The mixture is extruded to obtain a base tube, which is then heated, expanded, and cooled to form a polyetheretherketone heat shrinkable tube.

[0021] Preferably, the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is (1.01 to 1.05):1.

[0022] Preferably, the mass ratio of the carbon conductive filler to the total mass of the 4,4'-difluorobenzophenone and hydroquinone is (0.1-0.2):1.

[0023] Preferably, the mass ratio of the solvent to the total mass of the 4,4'-difluorobenzophenone and hydroquinone is (10-15):1.

[0024] Preferably, the molar ratio of the catalyst to hydroquinone is (2.2-2.5):1.

[0025] Preferably, the heating reaction is specifically carried out at 170–190°C for 0.5–1 h, then at 210–230°C for 0.5–2 h, at 240–260°C for 0.5–2 h, and finally at 280–320°C for 6–8 h.

[0026] Fourthly, the present invention provides an application of the polyetheretherketone heat shrinkable tubing involved in the above technical solution in electrostatic protection in the fields of electronic and electrical components, nuclear industry, and petrochemical industry.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0028] This invention provides a polyetheretherketone (PEEK) heat-shrinkable composition comprising PEEK resin and a carbon conductive filler composite material. The carbon conductive filler composite material is obtained by in-situ polymerization of carbon conductive filler and PEEK resin, wherein the carbon conductive filler is obtained through zero-dimensional C... 60 The synergistic addition of one-dimensional single-walled carbon nanotubes and two-dimensional reduced graphene oxide can improve the filling efficiency of carbon conductive fillers. Even with low addition amounts, heat-shrinkable tubing exhibits excellent high-temperature resistance and antistatic properties while maintaining superior mechanical properties and ease of processing. Furthermore, because the polyetheretherketone (PEEK) heat-shrinkable composition retains a certain degree of crystallinity, the supporting effect of the crystalline molecules allows the material to maintain good shrinkage performance. Studies have shown that when the heat shrinkage ratio of the prepared PEEK heat-shrinkable tubing is 1.6:1, the recovery rate can reach up to 92.1%, indicating excellent shrinkage performance. Simultaneously, its original volume resistivity, the volume resistivity after immersion in aviation kerosene for 168 hours, and the volume resistivity at an irradiation dose of 1000 kGy are all low, indicating excellent antistatic properties, aviation kerosene resistance, and radiation resistance. In addition, the high tensile strength of the PEEK heat-shrinkable tubing indicates excellent mechanical properties. Detailed Implementation

[0029] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] To address the problem of unstable conductive structure in existing PEEK heat-shrinkable tubing, this invention provides a polyetheretherketone (PEEK) heat-shrinkable composition, comprising 100 parts by weight of PEEK resin and 30-50 parts by weight of carbon conductive filler composite material. The 30-50 parts can be 30, 32, 35, 38, 40, 42, 45, 48, or 50 parts, etc. This invention does not impose any particular restriction on the source of the PEEK resin; any commercially available product is acceptable. If the melt index of the polyetheretherketone resin is too low, it will be difficult to extrude during the preparation of heat-shrinkable pipes, and the plasticizing properties of the pipes will be poor. If it is too high, the pipes will not be able to be formed. Therefore, the preferred melt index of this invention is (8-15) g / 10min, specifically 8 g / 10min, 9 g / 10min, 10 g / 10min, 11 g / 10min, 12 g / 10min, 13 g / 10min, 14 g / 10min, or 15 g / 10min, etc. The carbon conductive filler composite material is obtained by in-situ polymerization of carbon conductive filler and polyetheretherketone resin. In some embodiments of this invention, the carbon conductive filler composite material is obtained by in-situ polymerization of carbon conductive filler and monomers for preparing polyetheretherketone resin (i.e., 4,4'-difluorobenzophenone, hydroquinone) in the presence of solvent and catalyst. In this invention, the carbon conductive filler includes C 60 Single-walled carbon nanotubes and reduced graphene oxide, of which C 60 Single-walled carbon nanotubes are zero-dimensional conductive nanomaterials, while one-dimensional conductive nanomaterials have a high aspect ratio. Reduced graphene oxide is a two-dimensional conductive nanomaterial with abundant active groups on its surface, such as carboxyl and hydroxyl groups. In some embodiments of the present invention, the C... 60 The mass ratio of single-walled carbon nanotubes to reduced graphene oxide is 1:(5-7):(2-4), wherein (5-7) can be 5, 5.2, 5.5, 5.8, 6, 6.2, 6.5, 6.8 or 7, etc., and (2-4) can be 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8 or 4, etc.

[0031] In some embodiments of the present invention, the polyetheretherketone heat-shrinkable composition comprises, by weight, 100 parts of polyetheretherketone resin, 30-50 parts of carbon conductive filler composite material, and further comprises 0.5-1 parts of high-temperature resistant lubricant and 0.5-1 parts of high-temperature resistant antioxidant. The 0.5-1 parts can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part, etc. The high-temperature resistant lubricant is selected from nano-silica 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.

[0032] This invention uses zero-dimensional C 60 The synergistic addition of one-dimensional single-walled carbon nanotubes and two-dimensional reduced graphene oxide, along with in-situ polymerization of carbon conductive fillers with polyetheretherketone (PEEK) resin composites, improves the filling efficiency of the carbon conductive filler. Even with low addition amounts, the prepared heat-shrinkable tubing exhibits excellent high-temperature resistance and antistatic properties while maintaining superior mechanical properties and ease of processing. Furthermore, because the PEEK heat-shrinkable composition retains a certain degree of crystallinity, the supporting effect of the crystalline molecules ensures the material maintains good shrinkage performance.

[0033] Based on this, the present invention also provides a polyetheretherketone heat shrinkable tubing, which is prepared from the polyetheretherketone heat shrinkable composition involved in the above technical solution.

[0034] The preparation method of the above-mentioned polyetheretherketone (PEEK) heat-shrinkable tubing is simple and convenient. First, carbon conductive filler and monomers for preparing PEEK resin (i.e., 4,4'-difluorobenzophenone and hydroquinone) are polymerized in situ in the presence of a solvent and catalyst to obtain a carbon conductive filler composite material. Then, a PEEK heat-shrinkable composition is prepared, and after uniform mixing, the PEEK heat-shrinkable tubing is obtained through extrusion and expansion processes. In some embodiments of the present invention, the PEEK heat-shrinkable tubing is prepared according to the following method:

[0035] S1: Carbon conductive filler, 4,4'-difluorobenzophenone, hydroquinone, solvent and catalyst are mixed and heated in an inert atmosphere to obtain carbon conductive filler composite material;

[0036] S2: Weigh out polyetheretherketone resin, carbon conductive filler composite material, optional high-temperature resistant lubricant, and optional high-temperature resistant antioxidant according to the proportion and mix them evenly to obtain a mixture.

[0037] S3: The mixture is extruded to obtain a base tube, which is then heated, expanded, and cooled to form a polyetheretherketone heat shrinkable tube.

[0038] According to this invention, carbon conductive filler, 4,4'-difluorobenzophenone, hydroquinone, solvent, and catalyst are first mixed and then heated in an inert atmosphere to obtain a carbon conductive filler composite material. The inert atmosphere can be any atmosphere known to those skilled in the art; nitrogen is preferred in this invention. In this invention, the carbon conductive filler comprises C in a mass ratio of 1:(5-7):(2-4). 60The components are single-walled carbon nanotubes and reduced graphene oxide; 4,4'-difluorobenzophenone and hydroquinone are commercially available products; the solvent is selected from sulfolane and / or dimethyl sulfoxide; the catalyst is an alkali metal carbonate, including potassium carbonate and / or sodium carbonate. In some embodiments of the present invention, the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is (1.01-1.05):1, which can be 1.01:1, 1.02:1, 1.03:1, 1.04:1, or 1.05:1, preferably (1.01-1.02):1; the mass ratio of the carbon conductive filler to the total mass of the 4,4'-difluorobenzophenone and hydroquinone is (0.1-0.2):1, which can be 0.1:1, 0. The ratio of the solvent to the total mass of 4,4'-difluorobenzophenone and hydroquinone is (10-15):1, which can be 10:1, 11:1, 12:1, 13:1, 14:1, or 15:1, etc.; the molar ratio of the catalyst to hydroquinone is (2.2-2.5):1, which can be 2.2:1, 2.3:1, 2.4:1, or 2.5:1, etc. In some embodiments of the present invention, it is preferred to mix the carbon conductive filler, 4,4'-difluorobenzophenone, and hydroquinone, preferably in a high-speed stirrer at a speed of 5000-8000 rpm for 5-8 min. The resulting mixture is then added to a three-necked flask equipped with a mechanical stirrer, a thermometer, and nitrogen gas, and then the solvent and catalyst are added for heating and reaction. In this invention, the heating reaction is a gradient heating process. The initial reaction temperature should be low to avoid loss of hydroquinone and reduce side reactions. The temperature is then slowly increased until the reaction is complete, specifically: reacting at 170–190°C for 0.5–1 h, then at 210–230°C for 0.5–2 h, then at 240–260°C for 0.5–2 h, and finally at 280–320°C for 6–8 h. In some embodiments of this invention, the heating reaction involves salt formation at 190°C for 1 h, followed by reacting at 230°C for 1 h, reacting at 260°C for 1 h, and then increasing the temperature to 320°C for 8 h. In other embodiments of this invention, the heating reaction involves salt formation at 170°C for 0.5 h, followed by reacting at 210°C for 1 h, reacting at 240°C for 1 h, and then increasing the temperature to 280°C for 6 h. After the above heating reaction is completed, a carbon conductive filler composite material is obtained. Preferably, the material is discharged in cold water to exchange the solvent in the material.As a more preferred technical solution, after the cold water discharge is completed, the crude product obtained is pulverized. The pulverization is preferably carried out in a pulverizer. Then, it is washed with acetone and distilled water for a total of 8 to 10 times to remove inorganic salts and residual organic solvents. Finally, the product is dried at 120 to 150°C for 10 to 20 hours, preferably at 130 to 140°C for 12 to 15 hours, to obtain a carbon conductive filler composite material, which is a black powder in appearance.

[0039] According to this invention, after obtaining the carbon conductive filler composite material, polyetheretherketone resin, the carbon conductive filler composite material, an optional high-temperature resistant lubricant, and an optional high-temperature resistant antioxidant are weighed in proportion and mixed evenly to obtain a mixture. The mixing is carried out in a high-speed mixer at a speed of 3000–5000 r / min, which can be 3000 r / min, 3500 r / min, 4000 r / min, or 4500 r / min, etc., and for a mixing time of 5–10 min, which can be 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min, etc. In some embodiments of this invention, it is preferable to extrude, pelletize, and dry the product after mixing to facilitate subsequent processing, ultimately obtaining the mixture (also known as "polyetheretherketone heat-shrinkable special material"). The extrusion is carried out in a high-temperature and corrosion-resistant plastic extruder. The temperature range of the extruder is 360℃~380℃, preferably 365℃~370℃. The extrusion speed is controlled at 80~120 r / min, preferably 90~110 r / min, and the main feed speed is controlled at 8~10 r / min. The pelleting and drying can be carried out using conventional pelleting processes.

[0040] After obtaining the mixture, the mixture is extruded to obtain a base tube according to the present invention. The base tube is then heated, expanded, and cooled to form a polyetheretherketone (PEEK) heat-shrinkable tube. The extrusion is preferably carried out in a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range is 360℃~380℃, preferably 365℃~370℃, the extrusion speed is controlled at 80~120 r / min, preferably 90~110 r / min, and the main feed speed is controlled at 8~10 r / min. In some embodiments of the present invention, the extrusion requires auxiliary equipment such as a specific die, mandrel, and cooling / shaping machine to extrude the mixture into a base tube. After obtaining the base tube, it is preferably heated to 280℃~310℃, and a negative pressure is generated by vacuuming or introducing compressed gas to expand the base tube. The expansion ratio is 1.4~1.6 times (specifically, it can be 1.4 times, 1.5 times, or 1.6 times, etc.). Then, it is cooled and shaped to obtain the PEEK heat-shrinkable tube.

[0041] The point values ​​listed above are merely for illustrative purposes and are not limited to these. Other point values ​​within the same range are also applicable, but to avoid redundancy, they will not be elaborated upon one by one.

[0042] Studies have shown that when the heat shrinkage ratio of the prepared polyetheretherketone (PEEK) heat shrinkable tubing is 1.6:1, the recovery rate can reach up to 92.1%, indicating its excellent shrinkage performance. Furthermore, its original volume resistivity, the volume resistivity after immersion in aviation kerosene for 168 hours, and the volume resistivity after irradiation at a dose of 1000 kGy are all low, indicating excellent antistatic properties, resistance to aviation kerosene, and radiation resistance. In addition, the PEEK heat shrinkable tubing exhibits high tensile strength, indicating its excellent mechanical properties.

[0043] Based on this, the present invention also provides the application of the polyetheretherketone heat shrinkable tubing involved in the above technical solution in electrostatic protection in electronic and electrical components, nuclear industry, and petrochemical fields.

[0044] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention can all be purchased commercially or prepared according to conventional preparation methods well known to those skilled in the art. Wherein, C 60 Purchased from Nanjing Xianfeng Co., Ltd., model XFC00-23; single-walled carbon nanotubes purchased from Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences, model TNSR; reduced graphene oxide purchased from Shanxi Coal Chemistry Institute, Chinese Academy of Sciences, model TG1000.

[0045] Example 1

[0046] This embodiment provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0047] (1) Synthesis of carbon conductive filler composite materials:

[0048] 66.53g of composite carbon conductive filler (C 60 A composition of single-walled carbon nanotubes and reduced graphene oxide (mass ratio 1:7:2) was prepared. 222.56 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a high-speed mixer at 8000 rpm for 8 min. The mixture was then added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas, along with 4989.9 g of dimethyl sulfoxide and 275.25 g of potassium carbonate. The mixture was stirred and heated, forming a salt at 190℃ for 1 h, then reacting at 230℃ for 1 h, then at 260℃ for 1 h, and finally at 320℃ for 8 h. The product was then discharged in cold water. The crude product was pulverized and washed 10 times with acetone and distilled water to remove inorganic salts and residual organic solvents. The final product was dried at 150℃ for 20 h to obtain a black polymer powder sample, i.e., a carbon conductive filler composite material.

[0049] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0050] 100 parts of dried polyetheretherketone resin (melt index 15 g / 10 min), 50 parts of composite carbon conductive filler / polyetheretherketone resin, 1 part of nano silica, and 1 part of tris[2,4-di-tert-butylphenyl]phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 5000 r / min, and the mixing time was 10 min. The mixed raw materials were added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 120 r / min, and the main feed speed was controlled at 10 r / min. The material was pelletized and dried using a conventional pelletizing process to finally obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0051] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0052] Antistatic polyether ether ketone (PEEK) heat-shrinkable material is placed into a high-temperature, corrosion-resistant plastic extruder. The extruder temperature range is 360℃~380℃, the extrusion speed is controlled at 60r / min, and the main feed speed is controlled at 8r / min. After being extruded into a base tube by auxiliary equipment such as a specific die, mandrel, and cooling and shaping, it is ready for use.

[0053] The base tube obtained above is heated to 310°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.6 times and then cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0054] Example 2

[0055] This embodiment provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0056] (1) Synthesis of carbon conductive filler composite materials:

[0057] 66.53g of composite carbon conductive filler (C 60A composition of single-walled carbon nanotubes and reduced graphene oxide (mass ratio 1:7:2) was prepared. 222.56 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a high-speed mixer at 8000 rpm for 8 min. The mixture was then added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas, along with 4989.9 g of dimethyl sulfoxide and 275.25 g of potassium carbonate. The mixture was stirred and heated, forming a salt at 190℃ for 1 h, then reacting at 230℃ for 1 h, then at 260℃ for 1 h, and finally at 320℃ for 8 h. The product was then discharged in cold water. The crude product was pulverized and washed 10 times with acetone and distilled water to remove inorganic salts and residual organic solvents. The final product was dried at 150℃ for 20 h to obtain a black polymer powder sample, i.e., a carbon conductive filler composite material.

[0058] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0059] 100 parts of dried polyetheretherketone resin (melt index 12 g / 10 min), 40 parts of composite carbon conductive filler / polyetheretherketone resin, 0.75 parts of nano-silica, and 0.75 parts of tris[2,4-di-tert-butylphenyl]phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 4000 r / min, and the mixing time was 7.5 min. The mixed raw materials were added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 100 r / min, and the main feed speed was controlled at 9 r / min. The material was pelletized and dried using a conventional pelletizing process to obtain antistatic polyetheretherketone heat-shrinkable special material.

[0060] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0061] Antistatic polyether ether ketone (PEEK) heat-shrinkable material is placed into a high-temperature, corrosion-resistant plastic extruder. The extruder temperature range is 360℃~380℃, the extrusion speed is controlled at 45r / min, and the main feed speed is controlled at 6r / min. After being extruded into a base tube by auxiliary equipment such as a specific die, mandrel, and cooling and shaping, it is ready for use.

[0062] The base tube obtained above is heated to 295°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.5 times and then cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0063] Example 3

[0064] This embodiment provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0065] (1) Synthesis of carbon conductive filler composite materials:

[0066] 66.53g of composite carbon conductive filler (C 60 A composition of single-walled carbon nanotubes and reduced graphene oxide (mass ratio 1:7:2) was prepared. 222.56 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a high-speed mixer at 8000 rpm for 8 min. The mixture was then added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas, along with 4989.9 g of dimethyl sulfoxide and 275.25 g of potassium carbonate. The mixture was stirred and heated, forming a salt at 190℃ for 1 h, then reacting at 230℃ for 1 h, then at 260℃ for 1 h, and finally at 320℃ for 8 h. The product was then discharged in cold water. The crude product was pulverized and washed 10 times with acetone and distilled water to remove inorganic salts and residual organic solvents. The final product was dried at 150℃ for 20 h to obtain a black polymer powder sample, i.e., a carbon conductive filler composite material.

[0067] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0068] 100 parts of dried polyetheretherketone resin (melt index 8 g / 10 min), 30 parts of composite carbon conductive filler / polyetheretherketone resin, 0.5 parts of nano silica, and 0.5 parts of tris[2,4-di-tert-butylphenyl]phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 3000 r / min, and the mixing time was 5 min. The mixed raw materials were then added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 80 r / min, and the main feed speed was controlled at 8 r / min. The material was pelletized and dried using a conventional pelletizing process to obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0069] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0070] Antistatic polyether ether ketone (PEEK) heat-shrinkable material is placed into a high-temperature, corrosion-resistant plastic extruder. The extruder temperature range is 360℃~380℃, the extrusion speed is controlled at 30r / min, and the main feed speed is controlled at 4r / min. After being extruded into a base tube by auxiliary equipment such as a specific die, mandrel, and cooling and shaping, it is ready for use.

[0071] The base tube obtained above is heated to 280°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.4 times, and the tube is cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0072] Example 4

[0073] This embodiment provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0074] (1) Synthesis of carbon conductive filler composite materials:

[0075] 33.05g of composite carbon conductive filler (C 60 A composition of single-walled carbon nanotubes and reduced graphene oxide (preferably in a mass ratio of 1:5:4) was prepared. 220.38 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a high-speed mixer at 5000 rpm for 5 minutes. The mixture was then added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas, along with 3305 g of sulfolane and 242.22 g of sodium carbonate. The mixture was stirred and heated, forming a salt at 170°C for 0.5 hours, then reacting at 210°C for 1 hour and 240°C for 1 hour. Finally, the temperature was increased to 280°C for 6 hours, and the mixture was discharged in cold water. The crude product was pulverized and washed eight times with acetone and distilled water to remove inorganic salts and organic solvents. The final product was dried at 120°C for 10 hours to obtain a black polymer powder sample, i.e., a carbon conductive filler composite material.

[0076] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0077] 100 parts of dried polyetheretherketone resin (melt index 15 g / 10 min), 50 parts of composite carbon conductive filler / polyetheretherketone resin, 1 part of nano molybdenum disulfide, and 1 part of triphenyl phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 5000 r / min, and the mixing time was 10 min. The mixed raw materials were then added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 120 r / min, and the main feed speed was controlled at 10 r / min. The material was pelletized and dried using a conventional pelletizing process to obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0078] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0079] The antistatic polyether ether ketone (PEEK) heat-shrinkable material is extruded into a high-temperature, corrosion-resistant plastic extruder. The extruder temperature range is 360℃~380℃, the extrusion speed is controlled at 60r / min, and the main feed speed is controlled at 8r / min. After being extruded into base tubes through specific dies, mandrels, cooling and shaping auxiliary equipment, it is ready for use.

[0080] The base tube obtained above is heated to 310°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.6 times and then cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0081] Example 5

[0082] This embodiment provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0083] (1) Synthesis of carbon conductive filler composite materials:

[0084] 33.05g of composite carbon conductive filler (C 60 A composition of single-walled carbon nanotubes and reduced graphene oxide (preferably in a mass ratio of 1:5:4) was prepared. 220.38 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a high-speed mixer at 5000 rpm for 5 min. The mixture was then added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen gas, along with 3305 g of sulfolane and 242.22 g of sodium carbonate. The mixture was stirred and heated, forming a salt at 170℃ for 0.5 h, then reacting at 210℃ for 1 h, and then at 240℃ for 1 h. Finally, the temperature was increased to 280℃ for 6 h, and the mixture was discharged in cold water. The crude product was pulverized and washed eight times with acetone and distilled water to remove inorganic salts and organic solvents. The final product was dried at 120℃ for 10 h to obtain a black polymer powder sample.

[0085] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0086] 100 parts of dried polyetheretherketone resin (melt index 8 g / 10 min), 30 parts of composite carbon conductive filler / polyetheretherketone resin, 0.5 parts of nano molybdenum disulfide, and 0.5 parts of triphenyl phosphite were uniformly mixed in a high-speed mixer at a speed of 3000 rpm for 5 min. The mixed raw materials were then added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 80 rpm, and the main feed speed was controlled at 8 rpm. The material was pelletized and dried using a conventional pelletizing process to obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0087] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0088] The antistatic polyether ether ketone (PEEK) heat-shrinkable material is extruded into 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 feed speed is controlled at 4r / min. After being extruded into a base tube by auxiliary equipment such as a specific die, mandrel, and cooling and shaping, it is ready for use.

[0089] The base tube obtained above is heated to 280°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.4 times, and the tube is cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0090] Comparative Example 1

[0091] This comparative example provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0092] (1) Synthesis of carbon conductive filler composite materials:

[0093] 222.56 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen purging. Simultaneously, 4989.9 g of dimethyl sulfoxide and 275.25 g of potassium carbonate were added. The mixture was stirred and heated, reacting at 190 °C for 1 hour to form a salt, then at 230 °C for 1 hour, and then at 260 °C for 1 hour. Finally, the temperature was increased to 320 °C and reacted for 8 hours. The product was then discharged in cold water. The crude product was pulverized and washed 10 times with acetone and distilled water to remove inorganic salts and organic solvents. The final product was dried at 150 °C for 20 hours to obtain a polymer powder sample.

[0094] The polymer powder was mixed with 66.53g of composite carbon conductive filler (C). 60 A composition of single-walled carbon nanotubes and reduced graphene oxide (in a mass ratio of 1:7:2) was added to a high-speed mixer and stirred at 8000 rpm for 8 minutes to obtain a carbon conductive filler composite material.

[0095] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0096] 100 parts of dried polyetheretherketone resin (melt index 15 g / 10 min), 50 parts of carbon conductive filler / polyetheretherketone resin, 1 part of nano silica, and 1 part of tris[2,4-di-tert-butylphenyl]phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 5000 r / min, and the mixing time was 10 min. The mixed raw materials were then added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 120 r / min, and the main feed speed was controlled at 10 r / min. The material was pelletized and dried using a conventional pelletizing process to obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0097] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0098] The antistatic polyether ether ketone (PEEK) heat-shrinkable material is extruded into a high-temperature and corrosion-resistant plastic extruder with an extruder temperature range of 360℃ to 380℃, an extrusion speed of 60 r / min, and a main feed speed of 8 r / min. After passing through specific dies, mandrels, cooling, and other auxiliary equipment, it is extruded into a base tube for later use.

[0099] The base tube obtained above is heated to 310°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.6 times and then cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0100] Comparative Example 2

[0101] This comparative example provides an antistatic polyetheretherketone (PEEK) heat-shrinkable tubing, the preparation method of which is as follows:

[0102] 222.56 g of 4,4'-difluorobenzophenone and 110.1 g of hydroquinone were added to a three-necked flask equipped with a mechanical stirrer, thermometer, and nitrogen purging. Simultaneously, 4989.9 g of dimethyl sulfoxide and 275.25 g of potassium carbonate were added. The mixture was stirred and heated, reacting at 190 °C for 1 hour to form a salt, then at 230 °C for 1 hour, and then at 260 °C for 1 hour. Finally, the temperature was increased to 320 °C and reacted for 8 hours. The product was then discharged in cold water. The crude product was pulverized and washed 10 times with acetone and distilled water to remove inorganic salts and organic solvents. The final product was dried at 150 °C for 20 hours to obtain a polymer powder sample.

[0103] The polymer powder and 66.53g of single-walled carbon nanotubes were added to a high-speed mixer and stirred at 8000rpm for 8min to obtain a carbon conductive filler composite material.

[0104] (2) Preparation of antistatic polyetheretherketone heat-shrinkable material:

[0105] 100 parts of dried polyetheretherketone resin (melt index 15 g / 10 min), 50 parts of carbon conductive filler / polyetheretherketone resin, 1 part of nano silica, and 1 part of tris[2,4-di-tert-butylphenyl]phosphite were uniformly mixed in a high-speed mixer. The mixing speed was 5000 r / min, and the mixing time was 10 min. The mixed raw materials were then added to the barrel of a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360℃~380℃, the extrusion speed was controlled at 120 r / min, and the main feed speed was controlled at 10 r / min. The material was pelletized and dried using a conventional pelletizing process to obtain an antistatic polyetheretherketone heat-shrinkable special material.

[0106] (3) Preparation of antistatic polyetheretherketone heat shrinkable tubing:

[0107] The antistatic polyether ether ketone (PEEK) heat-shrinkable material is extruded into a high-temperature and corrosion-resistant plastic extruder with an extruder temperature range of 360℃ to 380℃, an extrusion speed of 60 r / min, and a main feed speed of 8 r / min. After passing through specific dies, mandrels, cooling, and other auxiliary equipment, it is extruded into a base tube for later use.

[0108] The base tube obtained above is heated to 310°C and expanded by vacuuming or introducing compressed gas. The expansion ratio is 1.6 times and then cooled and shaped to obtain the desired antistatic polyether ether ketone heat shrinkable tube.

[0109] Performance testing

[0110] The antistatic polyetheretherketone heat shrinkable tubing obtained in Examples 1-5 and Comparative Examples 1-2 was subjected to corresponding tests, and the test methods are as follows:

[0111] Shrinkage and recovery rate tests shall be performed in accordance with GB / T13519-2016; volume resistivity tests shall be performed in accordance with GB / T31838.2-2019; tensile strength tests shall be performed in accordance with GB / T1040-2006.

[0112] The test results are shown in Table 1 below:

[0113] Table 1

[0114]

[0115]

[0116] As shown in Table 1, the antistatic polyetheretherketone (PEEK) heat-shrinkable tubing provided by this invention has a high shrinkage ratio of 1.6:1 and high tensile strength. Furthermore, its original volume resistivity, the volume resistivity after immersion in aviation kerosene for 168 hours, and the volume resistivity at an irradiation dose of 1000 kGy are all low, indicating excellent antistatic properties, aviation kerosene resistance, and radiation resistance. Compared with Comparative Examples 1 and 2, under the same compression ratio, the antistatic PEEK heat-shrinkable tubing provided by this invention exhibits a higher recovery rate, indicating superior shrinkage performance. In summary, the tubing prepared using the PEEK heat-shrinkable tubing provided by this invention has superior overall performance.

[0117] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not 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, 30-50 parts of carbon conductive filler composite material, 0.5-1 part of high-temperature-resistant lubricant, and 0.5-1 part of high-temperature-resistant antioxidant; the polyether ether ketone resin has a melt index of (8-15) g / 10 min; The carbon conductive filler composite material is obtained by in-situ polymerization of a carbon conductive filler and polyether ether ketone resin; The carbon conductive filler includes C 60 single-walled carbon nanotubes, and reduced graphene oxide; The C 60 The mass ratio of single-walled carbon nanotubes and reduced graphene oxide is 1 : (5-7) : (2-4); The preparation method of the polyether ether ketone heat shrinkage pipe material comprises the following steps: S1: mixing carbon conductive filler, 4,4'-difluorobenzophenone, hydroquinone, solvent and catalyst, and then performing a heating reaction in an inert atmosphere to obtain a carbon conductive filler composite material; S2: weighing polyether ether ketone resin, carbon conductive filler composite material, high-temperature-resistant lubricant and high-temperature-resistant antioxidant according to a proportion, and mixing them uniformly to obtain a mixture; S3: extruding the mixture to obtain a base pipe, heating the base pipe at 280-310℃, introducing compressed gas to expand the base pipe, and then cooling and forming the base pipe to obtain a polyether ether ketone heat shrinkage pipe material.

2. The polyether ether ketone heat shrinkable tubing of claim 1, 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.

3. The method of producing a polyether ether ketone heat-shrinkable tubing according to claim 1 or 2, characterized in that, The preparation method comprises the following steps: S1: mixing carbon conductive filler, 4,4'-difluorobenzophenone, hydroquinone, solvent and catalyst, and then performing a heating reaction in an inert atmosphere to obtain a carbon conductive filler composite material; S2: weighing polyether ether ketone resin, carbon conductive filler composite material, high-temperature-resistant lubricant and high-temperature-resistant antioxidant according to a proportion, and mixing them uniformly to obtain a mixture; S3: extruding the mixture to obtain a base pipe, heating the base pipe at 280-310℃, introducing compressed gas to expand the base pipe, and then cooling and forming the base pipe to obtain a polyether ether ketone heat shrinkage pipe material.

4. The production method according to claim 3, characterized by, The molar ratio of 4,4'-difluorobenzophenone to hydroquinone is (1.01-1.05):1; The mass ratio of the carbon conductive filler to the total mass of 4,4'-difluorobenzophenone and hydroquinone is (0.1-0.2):1; The mass ratio of the solvent to the total mass of 4,4'-difluorobenzophenone and hydroquinone is (10-15):1; The molar ratio of the catalyst to hydroquinone is (2.2-2.5):

1.

5. The preparation method according to claim 3, characterized in that, The heating reaction specifically comprises: reacting at 170-190℃ for 0.5-1 h, then reacting at 210-230℃ for 0.5-2 h, reacting at 240-260℃ for 0.5-2 h, and finally reacting at 280-320℃ for 6-8 h.

6. Application of the polyether ether ketone heat shrinkage pipe material of claim 1 or 2 or prepared by the preparation method of any one of claims 3-5 in electrostatic protection in the fields of electronic and electrical components, nuclear industry and petroleum and chemical industry.

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