Modified polyether ether ketone heat shrink composition and use thereof

Abstract

The application provides a modified polyether ether ketone heat shrinkage composition and application thereof. The composition comprises, by weight parts, 40-60 parts of polyether ether ketone resin, 40-60 parts of fusible polytetrafluoroethylene and 2-4 parts of carboxylated polyaryletherketone. The application can effectively improve the compatibility of polytetrafluoroethylene and polyether ether ketone by using carboxylated polyaryletherketone as an interface modifier and by means of the melt processing characteristics of fusible polytetrafluoroethylene, thereby further improving the flexibility and wear resistance of the prepared modified polyether ether ketone heat shrinkage pipe. Meanwhile, the fusible polytetrafluoroethylene can generate a crosslinked network after irradiation treatment, so that the prepared modified polyether ether ketone heat shrinkage pipe has excellent shrinkage performance. Research shows that the heat shrinkage ratio of the prepared modified polyether ether ketone heat shrinkage pipe can be up to 2:1, the recovery rate is 95.6%, the tensile strength and hardness are low, and the friction coefficient is small, which indicates that the pipe has excellent shrinkage performance, flexibility and wear resistance.

Description

TECHNICAL FIELD

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

[0002] Polyether ether ketone resin (abbreviation: PEEK resin) is a polymer composed of repeating units containing a ketone bond and two ether bonds in the main chain structure. As a special engineering plastic with excellent mechanical properties, radiation resistance and chemical corrosion resistance, it can be used in a wide temperature range and harsh chemical and physical environments. It is widely used in aerospace, medical devices, food industry and other fields as a heat-shrinkable material, high-temperature structural material and electrical insulating material.

[0003] However, the shrinkage ratio of the commercially available polyether ether ketone heat-shrinkable tube is only 1.4:1, and the rigidity of the polyether ether ketone heat-shrinkable tube after shrinkage is large, which cannot meet the use requirements of heat-shrinkable materials. Therefore, it is necessary to improve the shrinkage ratio and flexibility of the PEEK-based heat-shrinkable material to broaden the application of the polyether ether ketone heat-shrinkable tube. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a modified polyether ether ketone heat-shrinkable composition and application thereof. The heat-shrinkable material prepared by using the composition can significantly improve the flexibility and shrinkage performance of the material, and also improve the wear resistance of the material.

[0005] To achieve this purpose, the present application adopts the following technical solutions:

[0006] In a first aspect, the present application provides a modified polyether ether ketone heat-shrinkable composition, which comprises, by weight, 40-60 parts of polyether ether ketone resin, 40-60 parts of meltable polytetrafluoroethylene, and 2-4 parts of carboxylated polyaryletherketone.

[0007] Preferably, the melt index of the polyether ether ketone resin is (8-15) g / 10 min.

[0008] Preferably, the melt index of the meltable polytetrafluoroethylene is (5-10) g / 10 min.

[0009] Preferably, the modified polyether ether ketone heat-shrinkable composition further comprises 0.5-1 parts of a high-temperature-resistant lubricant and 0.5-1 parts of a high-temperature-resistant antioxidant.

[0010] Preferably, the high-temperature-resistant lubricant is selected from nano-silicon dioxide and / or nano-molybdenum disulfide.

[0011] Preferably, the high-temperature-resistant antioxidant is selected from tris[2.4-di-tert-butylphenyl] phosphite and / or triphenyl phosphite.

[0012] In a second aspect, the present application provides a modified polyether ether ketone heat-shrinkable tubing prepared from the modified polyether ether ketone heat-shrinkable composition.

[0013] In a third aspect, the present application provides a preparation method of the modified polyether ether ketone heat-shrinkable tubing, comprising the following steps:

[0014] S1: uniformly mixing polyether ether ketone resin, carboxylated polyaryletherketone, optional high-temperature-resistant lubricant, and optional high-temperature-resistant antioxidant according to proportions to obtain a mixture;

[0015] S3: extruding the mixture into a base pipe, performing electron irradiation treatment on the obtained base pipe, then performing heating and expansion treatment on the base pipe, and cooling and forming the base pipe to obtain the modified polyether ether ketone heat-shrinkable tubing.

[0016] Preferably, the carboxylated polyaryletherketone is obtained by acidizing a copolymer of 4,4'-difluorobenzophenone, hydroquinone and phenolphthalein monomer.

[0017] Preferably, the acidizing treatment is performed using an acidic solution, and the acidic solution is dilute hydrochloric acid with a concentration of 0.5-1 mol / L.

[0018] Preferably, the acidizing treatment is performed for 12-24 hours.

[0019] Preferably, the electron irradiation has a dose of 200-400 kGy.

[0020] Preferably, the expansion treatment has an expansion ratio of 1.6-2.

[0021] In a fourth aspect, the present application provides a use of the modified polyether ether ketone heat-shrinkable tubing in the protection of electronic and electrical components.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] The present application provides a modified polyether ether ketone heat-shrinkable composition. By using carboxylated polyaryletherketone as an interfacial modifier and taking advantage of the melt processing characteristics of meltable polytetrafluoroethylene, the compatibility of polytetrafluoroethylene and polyether ether ketone can be effectively improved, thereby further improving the flexibility and wear resistance of the prepared modified polyether ether ketone heat-shrinkable tubing. Meanwhile, the crosslinking network of meltable polytetrafluoroethylene can be generated after irradiation treatment, so that the prepared modified polyether ether ketone heat-shrinkable tubing has excellent shrinkage performance. According to research, the heat-shrinkable ratio of the prepared modified polyether ether ketone heat-shrinkable tubing can be as high as 2:1, the recovery rate is 95.6%, the tensile strength and hardness are low, and the friction coefficient is small, indicating that the prepared modified polyether ether ketone heat-shrinkable tubing has excellent shrinkage performance, flexibility and wear resistance. DETAILED DESCRIPTION

[0024] 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.

[0025] In view of the problem that the shrinkage of the polyether ether ketone heat shrinkable tube is low and the rigidity after shrinkage is large, resulting in poor flexibility in the prior art, the present application provides a modified polyether ether ketone heat shrinkable composition, which comprises, by weight, 40-60 parts of polyether ether ketone resin, 40-60 parts of meltable polytetrafluoroethylene, and 2-4 parts of carboxylated polyaryletherketone. The 40-60 parts can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, or 60 parts, etc., and the 2-4 parts can be 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, or 4 parts, etc. The present application does not have special restrictions on the source of the polyether ether ketone resin and the meltable polytetrafluoroethylene (also known as "tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer"), which can be a general commercially available product. 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 tube, and the plasticizing performance of the tube will be poor. If it is too high, the tube will not be able to be formed, so the present application preferably has a melt index of (8-15) g / 10 min, which 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. Similarly, the present application preferably has a melt index of (5-10) g / 10 min for the meltable polytetrafluoroethylene, which can be 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 8 g / 10 min, 9 g / 10 min, or 10 g / 10 min, etc. In order to facilitate subsequent processing, the present application preferably comprises, by weight, 40-60 parts of polyether ether ketone resin, 40-60 parts of meltable polytetrafluoroethylene, 2-4 parts of carboxylated polyaryletherketone, 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-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.

[0026] The application can effectively improve the compatibility of polytetrafluoroethylene and polyether ether ketone by using carboxylated polyaryletherketone as an interface modifier and by virtue of the melt processing characteristics of the meltable polytetrafluoroethylene, thereby further improving the flexibility and wear resistance of the prepared modified polyether ether ketone heat shrinkable tube. Meanwhile, the meltable polytetrafluoroethylene can generate a crosslinked network after irradiation treatment, so that the prepared modified polyether ether ketone heat shrinkable tube has excellent shrinkage performance.

[0027] Based on this, the application further provides a modified polyether ether ketone heat shrinkable tube prepared from the modified polyether ether ketone heat shrinkable composition involved in the above technical solutions.

[0028] The preparation method of the modified polyether ether ketone heat shrinkable tube is simple, and the polyether ether ketone heat shrinkable composition is weighed according to the proportion, mixed uniformly, and then the modified polyether ether ketone heat shrinkable tube can be obtained through extrusion and expansion processes. In some embodiments of the application, the modified polyether ether ketone heat shrinkable tube is prepared according to the following method:

[0029] S1: polyether ether ketone resin, carboxylated polyaryletherketone, optional high-temperature-resistant lubricant and optional high-temperature-resistant antioxidant are weighed according to the proportion and mixed uniformly to obtain a mixture;

[0030] S3: the mixture is extruded into a base tube, the obtained base tube is subjected to electron irradiation treatment, and then is subjected to heating, expansion treatment, cooling and molding to obtain the modified polyether ether ketone heat shrinkable tube.

[0031] The carboxylated polyaryletherketone is obtained by acid treatment of a copolymer of 4,4'-difluorobenzophenone, hydroquinone and phenolphthaline monomer, the acid treatment is performed by using an acid solution, preferably dilute hydrochloric acid, the concentration of the dilute hydrochloric acid is 0.5-1 mol / L, which can be 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1 mol / L, etc., the acid treatment time is 12-24 h, which can be 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 24 h, etc. In some embodiments of the present application, the carboxylated polyaryletherketone is prepared by the following method: first, 4,4'-difluorobenzophenone, hydroquinone, solvent and catalyst are mixed and subjected to a first reaction, the mixing is preferably performed in a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, the first reaction is performed by using gradient heating, preferably salification at 170-190℃ for 0.5-1 h, then heating to 210-230℃, 240-260℃ and 280-300℃ for 0.5-1 h each, then the obtained reaction product and phenolphthaline monomer are mixed in a three-necked flask and subjected to a second reaction, the second reaction is first performed at the last gradient temperature of the first reaction for 1-2 h, then heating to 280-320℃ for 3-6 h, thus obtaining the polyaryletherketone copolymer. In the present application, the solvent is preferably sulfolane and / or dimethyl sulfoxide; the catalyst is preferably alkali metal carbonate, including potassium carbonate and / or sodium carbonate. In the present application, the molar ratio of 4,4'-difluorobenzophenone to the sum of the molar numbers of the dihydroxy monomers (hydroquinone and phenolphthaline monomer) is preferably (0.99-1.01):1, which can be 0.99:1, 1:1 or 1.01:1, etc.; the molar ratio of hydroquinone to phenolphthaline monomer is preferably (0.8-0.9):(0.1-0.2), the (0.8-0.9) can be 0.8, 0.82, 0.85, 0.88 or 0.9, etc., the (0.1-0.2) can be 0.1, 0.12, 0.15, 0.18 or 0.2, etc.; the ratio of the mass of the solvent to the sum of the masses of 4,4'-difluorobenzophenone and phenolphthaline monomer is preferably (8-10):1, which can be 8:1, 8.2:1, 8.5:1, 8.8:1, 9:1, 9.2:1, 9.5:1, 9.8:1 or 10:1, etc.; the molar ratio of the catalyst to the sum of the molar numbers of the dihydroxy monomers (hydroquinone and phenolphthaline monomer) 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 application, after the second reaction is completed, the reaction product is discharged into cold water to exchange the solvent in the material, the obtained product is subjected to a pulverization treatment, preferably in a pulverizer, and then washed with acetone and distilled water respectively for 8-10 times to remove inorganic salts and residual organic solvents, to obtain a polyaryletherketone copolymer. After obtaining the polyaryletherketone copolymer, the present application preferably disperses the polyaryletherketone copolymer in 0.5-1 mol / L dilute hydrochloric acid, acidifies by refluxing for 12-24 h, washes with pure water until neutral, and dries at 120-150°C for 10-20 h, preferably at 130-140°C for 12-15 h to obtain a carboxylated polyaryletherketone in powder form.

[0032] According to the present application, the polyether ether ketone resin, the carboxylated polyaryletherketone, the optional high-temperature-resistant lubricant, and the optional high-temperature-resistant antioxidant are weighed in proportion and uniformly mixed to obtain a mixture. The mixing is preferably performed in a high-speed mixer, and the mixing speed is 500-1000 r / min, which can be 500 r / min, 600 r / min, 700 r / min, 800 r / min, 900 r / min, or 1000 r / min, etc., and the mixing time is 5-10 min, which can be 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min, etc. In some embodiments of the present application, in order to make the raw materials more uniformly mixed and facilitate subsequent processing, the product is subjected to extrusion and pelletization drying, and finally a mixture (also referred to as "polyether ether ketone heat shrinkage special material") is obtained. In the present application, the extrusion is performed in a high-temperature-resistant and corrosion-resistant plastic extruder, the temperature of the extruder is in the range of 360°C-380°C, preferably 365°C-370°C, the extrusion speed is controlled in the range of 80-120 r / min, preferably 90-110 r / min, and the main feeding speed is controlled in the range of 8-10 r / min. The pelletization drying can be performed using a conventional pelletization process.

[0033] After the mixture is obtained, the mixture is extruded to obtain a base pipe according to the present application, the obtained base pipe is subjected to electron irradiation treatment, and then is subjected to heating, expansion treatment, and cooling forming to obtain the modified polyether ether ketone heat-shrinkable pipe. The extrusion is preferably performed in an extruder of a high-temperature-resistant and corrosion-resistant plastic, the temperature of the extruder ranges from 360 DEG C to 380 DEG C, preferably ranges from 365 DEG C to 370 DEG C, the extrusion speed is controlled to range from 80 r / min to 120 r / min, preferably ranges from 90 r / min to 110 r / min, and the main feeding speed is controlled to range from 8 r / min to 10 r / min. In some embodiments of the present application, the extrusion needs to be performed through special die, mandrel, cooling forming and other auxiliary machines to extrude the mixture into the base pipe. After the base pipe is obtained, the obtained base pipe is preferably subjected to irradiation with a dose of 200 kGy to 400 kGy in a nitrogen atmosphere, which can be 200 kGy, 250 kGy, 300 kGy, 350 kGy or 400 kGy, etc. After the irradiation is completed, the base pipe is heated at 240 DEG C to 280 DEG C, preferably at 250 DEG C to 270 DEG C, and is expanded by means of vacuum pumping or compressed gas to generate negative pressure, so that the expansion ratio of the base pipe ranges from 1.6 to 2 (specifically can be 1.6, 1.7, 1.8, 1.9 or 2, etc.), and then is cooled and formed, so that the modified polyether ether ketone heat-shrinkable pipe is obtained.

[0034] 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. In order to avoid redundancy, they will not be described one by one.

[0035] Through research, the heat-shrinkable ratio of the prepared modified polyether ether ketone heat-shrinkable pipe can reach 2:1 at most, the recovery rate is 95.6%, and the tensile strength and hardness are low, and the friction coefficient is small, indicating that it has excellent shrinkage performance, flexibility and wear resistance.

[0036] Based on this, the present application also provides an application of the modified polyether ether ketone heat-shrinkable pipe involved in the above technical solution in the protection of electronic and electrical components.

[0037] In order to further illustrate the present application, the following examples are used to illustrate the present application in detail. The experimental materials used in the following examples of the present application can be purchased from the market or prepared according to the conventional preparation method known to those skilled in the art.

[0038] Example 1

[0039] The present embodiment provides a modified polyether ether ketone heat-shrinkable pipe, and a preparation method thereof is as follows:

[0040] (1) Synthesis of carboxylated polyaryletherketone

[0041] In a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 220.38 g of 4,4'-difluorobenzophenone and 88.08 g of hydroquinone were added, followed by 3725 g of dimethyl sulfoxide and 345.5 g of potassium carbonate, and then the mixture was stirred and heated to 190°C for 1 h, and then heated to 230°C, 260°C and 300°C for 1 h each time. Then 64.06 g of phenolphthaline monomer was added, and the reaction was continued for 2 h. Then the temperature was increased to 320°C for 3 h, and then the product was discharged into cold water. The crude product was crushed by a crusher, and then washed with acetone and distilled water for 10 times respectively to remove inorganic salts and residual organic solvents. Then the polyaryletherketone copolymer in salt form was dispersed in 1 mol / L dilute hydrochloric acid, and then acidified by refluxing for 24 h. Then the product was washed with pure water until neutral, and then dried at 150°C for 20 h to obtain carboxylated polyaryletherketone powder;

[0042] (2) Preparation of modified polyether ether ketone heat shrinkage special material

[0043] The dried polyether ether ketone resin (melt index 8 g / 10 min) 40 parts, fusible polytetrafluoroethylene (melt index 5 g / 10 min) 60 parts, carboxylated polyaryletherketone 4 parts, nano silicon dioxide 1 part, and tris[2.4-di-tert-butylphenyl] phosphite 1 part were uniformly mixed in a high-speed mixer. The mixing speed was 1000 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°C-380°C, the extrusion speed was controlled at 120 r / min, and the main feeding speed was controlled at 10 r / min. The final modified polyether ether ketone heat shrinkage special material was obtained by using conventional pelletizing process for pelletizing and drying.

[0044] (3) Preparation of modified polyether ether ketone heat shrinkage pipe material

[0045] The modified polyether ether ketone heat shrinkage special material was placed into a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360°C-380°C, the extrusion speed was controlled at 60 r / min, and the main feeding speed was controlled at 8 r / min. The base pipe was extruded by using specific die, mandrel, cooling and sizing auxiliary machines, and then was used.

[0046] Finally, the sample was irradiated by electron beam irradiation technology under nitrogen atmosphere at a dose of 400 kGy. The above obtained base pipe was heated at 280°C, and was expanded by vacuum pumping or compressed gas method. The expansion ratio was 2 times, and the pipe was cooled and sized to obtain the required modified polyether ether ketone heat shrinkage pipe material.

[0047] Example 2

[0048] The present example provides a modified polyether ether ketone heat shrinkage pipe material, and the preparation method is as follows:

[0049] (1) Synthesis of carboxylated polyaryletherketone

[0050] In a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 220.38 g of 4,4'-difluorobenzophenone and 88.08 g of hydroquinone were added, followed by 3725 g of dimethyl sulfoxide and 345.5 g of potassium carbonate, and then the mixture was stirred and heated to 190°C for 1 h, and then heated to 230°C, 260°C and 300°C for 1 h each time. Then 64.06 g of phenolphthalin monomer was added, and the reaction was continued for 2 h. Then the temperature was increased to 320°C for 3 h, and then the product was discharged into cold water. The crude product was crushed by a crusher, and then washed with acetone and distilled water for 10 times respectively to remove inorganic salts and residual organic solvents. Then the polyaryletherketone copolymer in salt form was dispersed in 1 mol / L dilute hydrochloric acid, and then acidified by refluxing for 24 h. Then the product was washed with pure water until neutral, and then dried at 150°C for 20 h to obtain carboxylated polyaryletherketone powder.

[0051] (2) Preparation of modified polyether ether ketone heat shrinkage special material

[0052] The dried polyether ether ketone resin (melt index 12 g / 10 min) 50 parts, fusible polytetrafluoroethylene (melt index 8 g / 10 min) 50 parts, carboxylated polyaryletherketone 3 parts, nano silicon dioxide 0.75 parts, and tris[2.4-di-tert-butylphenyl] phosphite 0.75 parts were uniformly mixed in a high-speed mixer. The mixing speed was 750 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°C-380°C, the extrusion speed was controlled at 100 r / min, and the main feeding speed was controlled at 9 r / min. The final antistatic polyether ether ketone heat shrinkage special material was obtained by using conventional pelletizing process for pelletizing and drying.

[0053] (3) Preparation of modified polyether ether ketone heat shrinkage pipe material

[0054] The modified polyether ether ketone heat shrinkage special material was used in a high-temperature and corrosion-resistant plastic extruder, and the extruder temperature range was 360°C-380°C, the extrusion speed was controlled at 45 r / min, and the main feeding speed was controlled at 6 r / min. The base pipe was extruded by using specific die, mandrel, cooling and sizing auxiliary machines.

[0055] Finally, the sample was irradiated at a dose of 300 kGy under a nitrogen atmosphere by using electron beam irradiation technology. The above obtained base pipe was heated at 260°C, and the base pipe was expanded by vacuum pumping or compressed gas method, and the expansion ratio was 1.8 times, and then the base pipe was cooled and sized to obtain the required modified polyether ether ketone heat shrinkage pipe material.

[0056] Example 3

[0057] The modified polyether ether ketone heat shrinkage pipe material is prepared by the following method:

[0058] (1) Synthesis of carboxylated polyaryletherketone

[0059] In a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 220.38 g of 4,4'-difluorobenzophenone and 88.08 g of hydroquinone were added, followed by 3725 g of dimethyl sulfoxide and 345.5 g of potassium carbonate. The mixture was stirred and heated to 190°C for 1 h for salification. The temperature was then raised to 230°C, 260°C and 300°C for 1 h each. Then 64.06 g of phenolphthalin monomer was added and the reaction was continued for 2 h. The temperature was then raised to 320°C for 3 h. The product was discharged into cold water. The crude product was ground by a grinder and washed with acetone and distilled water for 10 times respectively to remove inorganic salts and residual organic solvents. Then the polyaryletherketone copolymer in salt form was dispersed in 1 mol / L dilute hydrochloric acid. The acidification was carried out by refluxing for 24 h. The product was washed with pure water until neutral. The product was dried at 150°C for 20 h to obtain carboxylated polyaryletherketone powder.

[0060] (2) Preparation of modified polyether ether ketone heat shrinkage special material

[0061] The dried polyether ether ketone resin (melt index 15 g / 10 min) 60 parts, fusible polytetrafluoroethylene (melt index 10 g / 10 min) 40 parts, carboxylated polyaryletherketone 2 parts, nano-silicon dioxide 0.5 parts, and tris[2.4-di-tert-butylphenyl] phosphite 0.5 parts were uniformly mixed in a high-speed mixer. The mixing speed was 500 r / min and the mixing time was 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°C-380°C, the extrusion speed was controlled at 80 r / min, and the main feeding speed was controlled at 8 r / min. The granulation drying was carried out by conventional granulation process, and finally the modified polyether ether ketone heat shrinkage special material was obtained.

[0062] (3) Preparation of modified polyether ether ketone heat shrinkage pipe material

[0063] The modified polyether ether ketone heat shrinkage special material was used in a high-temperature and corrosion-resistant plastic extruder. The extruder temperature range was 360°C-380°C, the extrusion speed was controlled at 30 r / min, and the main feeding speed was controlled at 4 r / min. The base pipe was extruded by a specific die, a mandrel, and a cooling and shaping auxiliary machine.

[0064] Finally, the sample was irradiated with an electron beam irradiation technology under a nitrogen atmosphere at a dose of 200 kGy. The above obtained base pipe was heated at 240°C, and expanded by vacuum pumping or compressed gas injection method, with an expansion ratio of 1.6 times and cooling and shaping, to obtain the required modified polyether ether ketone heat shrinkage pipe material.

[0065] Example 4

[0066] The present embodiment provides a modified polyether ether ketone heat shrinkable tubing, and a preparation method thereof is as follows:

[0067] (1) Synthesis of carboxylated polyaryletherketone

[0068] In a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 216.02 g of 4,4'-difluorobenzophenone and 99.09 g of hydroquinone were added, followed by 2777.12 g of sulfolane and 304.04 g of potassium carbonate. After stirring and heating, the salt was formed at 170°C for 0.5 h. After heating to 210°C, 240°C and 280°C for 1 h each, 32.03 g of phenolphthalein monomer was added. After continuing to react at 280°C for 7 h, the product was discharged into cold water. The crude product was crushed by a crusher and washed with acetone and distilled water for 8 times respectively to remove inorganic salts and residual organic solvents. Then the polyaryletherketone copolymer in salt form was dispersed in 0.5 mol / L dilute hydrochloric acid, and after acidification by reflux for 12 h, it was washed with pure water until neutral. After drying at 120°C for 10 h, carboxylated polyaryletherketone powder was obtained.

[0069] (2) Preparation of modified polyether ether ketone heat shrinkable special material

[0070] The dried polyether ether ketone resin (melt index 8 g / 10 min) 40 parts, fusible polytetrafluoroethylene (melt index 5 g / 10 min) 60 parts, carboxylated polyaryletherketone 4 parts, nano-silicon dioxide 1 part, and triphenyl phosphite 1 part were uniformly mixed in a high-speed mixer. The mixing speed was 1000 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°C-380°C, the extrusion speed was controlled at 120 r / min, and the main feeding speed was controlled at 10 r / min. The granulation drying was carried out by conventional granulation process, and finally the modified polyether ether ketone heat shrinkable special material was obtained.

[0071] (3) Preparation of modified polyether ether ketone heat shrinkable tubing

[0072] The modified polyether ether ketone heat shrinkable special material was extruded by a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range was 360°C-380°C, the extrusion speed was controlled at 60 r / min, and the main feeding speed was controlled at 8 r / min. The base pipe was extruded by a specific die, a mandrel, a cooling and sizing auxiliary machine, and was ready for use.

[0073] Finally, the sample was irradiated by electron beam irradiation technology under nitrogen atmosphere at a dose of 400 kGy. The above obtained base pipe was heated at 280°C, and was expanded by vacuum pumping or compressed gas injection method, with an expansion ratio of 2 times, and was cooled and sized to obtain the required modified polyether ether ketone heat shrinkable tubing.

[0074] Example 5

[0075] The present embodiment provides a modified polyether ether ketone heat shrinkable tubing, and a preparation method thereof is as follows:

[0076] (1) Synthesis of carboxylated polyaryletherketone

[0077] In a three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 216.02 g of 4,4'-difluorobenzophenone and 99.09 g of hydroquinone were added, followed by 2777.12 g of sulfolane and 304.04 g of potassium carbonate. After stirring and heating, the salt was formed at 170°C for 0.5 h, and then the temperature was raised to 210°C, 240°C and 280°C for 1 h each. Then 32.03 g of phenolphthalein monomer was added, and the reaction was continued at 280°C for 7 h. After cooling, the product was discharged into cold water. The crude product was crushed by a crusher and washed with acetone and distilled water for 8 times respectively to remove inorganic salts and residual organic solvents. Then the polyaryletherketone copolymer in salt form was dispersed in 0.5 mol / L dilute hydrochloric acid, and acidified by refluxing for 12 h. After washing with pure water to neutral, the product was dried at 120°C for 10 h to obtain carboxylated polyaryletherketone powder.

[0078] (2) Preparation of modified polyether ether ketone heat shrinkable special material

[0079] The dried polyether ether ketone resin (melt index 15 g / 10 min) 60 parts, fusible polytetrafluoroethylene (melt index 10 g / 10 min) 40 parts, carboxylated polyaryletherketone 2 parts, nano-silicon dioxide 0.5 parts, and triphenyl phosphite 0.5 parts were uniformly mixed in a high-speed mixer. The mixing speed was 500 r / min, and the mixing time was 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°C-380°C, the extrusion speed was controlled at 80 r / min, and the main feeding speed was controlled at 8 r / min. The granulation drying was carried out by conventional granulation process, and finally the modified polyether ether ketone heat shrinkable special material was obtained.

[0080] (3) Preparation of modified polyether ether ketone heat shrinkable tubing

[0081] The modified polyether ether ketone heat shrinkable special material was extruded by a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range was 360°C-380°C, the extrusion speed was controlled at 30 r / min, and the main feeding speed was controlled at 4 r / min. The base pipe was extruded by a specific die, a mandrel, and a cooling and sizing auxiliary machine.

[0082] Finally, the sample was irradiated by electron beam irradiation technology under nitrogen atmosphere at a dose of 200 kGy. The above obtained base pipe was heated at 240°C, and expanded by vacuum pumping or compressed gas method, with an expansion ratio of 1.6 times, and then cooled and sized to obtain the required modified polyether ether ketone heat shrinkable tubing.

[0083] Comparative Example 1

[0084] The present comparative example provides a modified polyether ether ketone heat shrinkable tubing, which is prepared as follows:

[0085] (1) Preparation of modified polyether ether ketone heat shrinkable special material

[0086] The dried polyether ether ketone resin (melt index 8 g / 10 min) 40 parts, fusible polytetrafluoroethylene (melt index 5 g / 10 min) 60 parts, nano-silicon dioxide 1 part, tris [2.4-di-tert-butyl phenyl] phosphite 1 part, are uniformly mixed in a high-speed mixer. The mixing speed is 1000 r / min, and the mixing time is 10 min. 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 120 r / min, and the main feeding speed is controlled at 10 r / min. The conventional pelletizing process is used for pelletizing and drying, and finally the modified polyether ether ketone heat shrinkable special material is obtained;

[0087] (2) Preparation of modified polyether ether ketone heat shrinkable tubing

[0088] The modified polyether ether ketone heat shrinkable special material is used in a high-temperature and corrosion-resistant plastic extruder, the extruder temperature range is 360-380°C, the extrusion speed is controlled at 60 r / min, and the main feeding speed is controlled at 8 r / min. After passing through special dies, mandrels, cooling and sizing, etc. Auxiliary machines are used to extrude the base pipe for use.

[0089] Finally, the sample is irradiated with an electron beam irradiation technology under a nitrogen atmosphere at a dose of 400 kGy, and the above obtained base pipe is heated at 280°C, and expanded by vacuum pumping or compressed gas method, with an expansion ratio of 1.8 times and cooling and sizing, to obtain the required modified polyether ether ketone heat shrinkable tubing.

[0090] Comparative Example 2

[0091] The present comparative example provides a modified polyether ether ketone heat shrinkable tubing, which is prepared as follows:

[0092] (1) Preparation of modified polyether ether ketone heat shrinkable special material

[0093] The dried polyether ether ketone resin (melt index 8 g / 10 min) 100 parts, carboxylated polyaryletherketone (preparation method same as example 1) 4 parts, nano-silica 1 part, tris [2.4-di-tert-butylphenyl] phosphite 1 part, are uniformly mixed in a high-speed mixer. The mixing speed is 1000 r / min, and the mixing time is 10 min. 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. The conventional pelletizing process is used for pelletizing and drying, and finally the modified polyether ether ketone heat shrinkage special material is obtained;

[0094] (2) Preparation of modified polyether ether ketone heat shrinkage pipe

[0095] The modified 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. The base pipe is extruded through specific die, mandrel, cooling and shaping, etc. auxiliary machines.

[0096] Finally, the sample is irradiated at a dose of 400 kGy under a nitrogen atmosphere by using electron beam irradiation technology, the above obtained base pipe is heated at 280℃, and the base pipe is expanded by vacuum pumping or compressed gas method, the expansion ratio is 1.4 times, and the base pipe is cooled and shaped to obtain the required modified polyether ether ketone heat shrinkage pipe.

[0097] Performance test

[0098] The modified polyether ether ketone heat shrinkage pipe obtained in the above examples 1-5 and comparative examples 1-2 is tested accordingly, and the test method is as follows:

[0099] The shrinkage rate and recovery rate test refers to GB / T13519-2016; the hardness test is performed according to GB / T2411-2008; the tensile strength test is performed according to GB / T1040-2006; and the friction coefficient is performed according to GB / T3960-2016.

[0100] The test results are shown in Table 1 as follows:

[0101] Table 1

[0102]

[0103] As shown in Table 1, compared with comparative examples 1-2, the modified polyether ether ketone heat shrinkage pipe provided by the present application has higher recovery rate under the same shrinkage ratio, and the shrinkage ratio of the modified polyether ether ketone heat shrinkage pipe provided by the present application is as high as 2:1, and the hardness and tensile strength are lower, and the friction coefficient is small, which indicates that it has excellent shrinkage performance, flexibility and wear resistance.

[0104] The foregoing description of the disclosed embodiments enables one of ordinary skill 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 method for producing a modified polyether ether ketone heat-shrinkable tubing, characterized by, It comprises the following steps: S1: proportionally weigh polyether ether ketone resin, fusible polytetrafluoroethylene, carboxylated polyaryletherketone, high-temperature-resistant lubricant, high-temperature-resistant antioxidant, and mix uniformly to obtain a mixture; S2: extrude the mixture into a base pipe, perform electronic irradiation treatment on the obtained base pipe, then perform heating and expansion treatment, and cool to form a modified polyether ether ketone heat-shrinkable pipe material; The polyether ether ketone resin is 40-60 parts, the fusible polytetrafluoroethylene is 40-60 parts, the carboxylated polyaryletherketone is 2-4 parts, the high-temperature-resistant lubricant is 0.5-1 part, and the high-temperature-resistant antioxidant is 0.5-1 part; the melt index of the polyether ether ketone resin is (8-15) g / 10 min; the melt index of the fusible polytetrafluoroethylene is (5-10) g / 10 min; The high-temperature-resistant lubricant is selected from nano silicon dioxide and / or nano molybdenum disulfide; The carboxylated polyaryletherketone is obtained by acidizing the copolymerization product of 4,4'-difluorobenzophenone, hydroquinone and phenolphthalein monomer; The dose of the electronic irradiation is 200-400 kGy; The expansion ratio of the expansion treatment is 1.6-2.

2. The production method according to claim 1, characterized by, The high-temperature-resistant antioxidant is selected from tris[2.4-di-tert-butylphenyl] phosphite and / or triphenyl phosphite.

3. The production method according to claim 1 or 2, characterized by, The acidizing treatment is performed using an acid solution, the acid solution is dilute hydrochloric acid, and the concentration of the dilute hydrochloric acid is 0.5-1 mol / L; The acidizing treatment is performed for 12-24 h.

4. A modified polyether ether ketone heat shrinkable tubing characterized by, Prepared by the preparation method in any one of claims 1-3.

5. The application of the modified polyether ether ketone heat-shrinkable pipe material prepared by the preparation method in any one of claims 1-3 or the modified polyether ether ketone heat-shrinkable pipe material in claim 4 in the protection of electronic and electrical components.

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