A radiation-resistant modified PEEK material and preparation method thereof

Abstract

The present application provides a radiation-resistant modified PEEK material and a preparation method thereof, which belongs to the technical field of polymer modified materials. The modified PEEK material contains the following components in weight percentage: 30%-60% PEEK, 3%-5% toughening agent, 1%-3% compatibilizer, 10%-30% lead powder, 10%-30% glass fiber and 0.3%-0.5% other additives; other additives include antioxidants and lubricants. The preparation method includes mixing PEEK, lead powder, toughening agent, compatibilizer and other additives; placing the mixed material in a twin-screw extruder, adding glass fiber, and melt extruding; cooling the extruded material and sending it to a pelletizer for pelletizing; packaging the cut particles to obtain the modified PEEK material. Through the processing scheme of the present application, the radiation resistance of the PEEK material is improved.

Description

Technical Field

[0001] The present application relates to the technical field of polymer modified materials, and in particular to a radiation-resistant modified PEEK material and a preparation method thereof. Background Art

[0002] Conventional PEEK materials have excellent comprehensive properties, such as high temperature resistance of 260 degrees, excellent mechanical properties, good self-lubrication, chemical corrosion resistance, flame retardancy, peeling resistance, and good wear resistance, and can be used in high-end machinery, nuclear engineering, aviation and other technologies. However, its radiation resistance, metallic texture and density are relatively low. Summary of the invention

[0003] In view of this, the embodiments of the present application provide a radiation-resistant modified PEEK material and a preparation method thereof, which at least partially solve the problems of low radiation resistance, metallic texture and density of PEEK materials in the prior art.

[0004] In a first aspect, an embodiment of the present application provides a radiation-resistant modified PEEK material, wherein the modified PEEK material comprises the following components in percentage by weight:

[0005]

[0006] The other adjuvants include antioxidants and lubricants.

[0007] According to a specific implementation method of the embodiment of the present application, the lead powder has a mesh size of more than 500 meshes, a glass fiber diameter of 0.5 mm-1.2 mm, and a specific surface area of ​​1500 m 2 / kg-2000m 2 / kg.

[0008] According to a specific implementation of the embodiment of the present application, the lead powder is a flake structure.

[0009] According to a specific implementation of the embodiment of the present application, the length and width of the thin sheet structure are both more than 4 times the thickness.

[0010] According to a specific implementation of the embodiment of the present application, the lead powder is acid-washed lead powder.

[0011] According to a specific implementation method of an embodiment of the present application, the compatibilizer is a graft formed by maleic anhydride on PP, PE or POE, or a graft formed by glycidyl methacrylate on PP, PE or POE, or a block copolymer formed by maleic anhydride, or a block copolymer formed by glycidyl methacrylate; the toughening agent is an olefin elastomer, a butadiene rubber elastomer or a ethyl acetate elastomer.

[0012] In a second aspect, an embodiment of the present application further provides a method for preparing a radiation-resistant modified PEEK material as described in any embodiment of the first aspect above, the preparation method comprising:

[0013] Mix PEEK, lead powder, toughening agent, compatibilizer and other additives;

[0014] The mixed material is placed in a twin-screw extruder, and glass fiber is added for melt extrusion;

[0015] The extruded material is cooled and sent to a pelletizer for pelletizing;

[0016] The cut particles are packaged to obtain the modified PEEK material.

[0017] According to a specific implementation of the embodiment of the present application, before the mixing step, the method further includes: acid washing the lead powder.

[0018] According to a specific implementation of the embodiment of the present application, the pickling comprises the following steps:

[0019] Add 10%-30% concentration of dilute sulfuric acid to the lead powder, stir and heat to 60℃-100℃, continue stirring and react for 5min-30min, then filter, add an aqueous solution of baking soda to neutralize the surface, then wash with clean water, and dry for later use.

[0020] According to a specific implementation of the embodiment of the present application, the temperature ranges of the temperature zones of the twin-screw extruder are: the temperature range of the first temperature zone is 345°C-365°C, the temperature range of the second temperature zone is 355°C-385°C, the temperature range of the third temperature zone is 360°C-390°C, the temperature range of the fourth temperature zone is 360°C-390°C, the temperature range of the fifth temperature zone is 360°C-390°C, and the temperature range of the head is 360°C-390°C;

[0021] The main engine frequency of the twin-screw extruder is 30Hz-50Hz, and the feeding frequency is 10Hz-30Hz;

[0022] The rotation speed of the pelletizer is 300r / min-500r / min.

[0023] Beneficial Effects

[0024] The radiation-resistant modified PEEK material and its preparation method in the embodiment of the present application are prepared by introducing lead powder and corresponding compatibilizers, toughening agents, and glass fibers to prepare a PEEK special material with excellent comprehensive performance. Further adding flaky lead powder, which has a large specific surface area and strong covering power, is evenly distributed in the PEEK material matrix to better block high-energy rays and prevent radiation, effectively improving the radiation resistance of the PEEK material. DETAILED DESCRIPTION

[0025] The embodiments of the present application are described in detail below.

[0026] The following describes the implementation methods of the present application through specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the content disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific implementation methods, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present application.

[0027] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present application, it should be understood by those skilled in the art that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number of aspects described herein can be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein can be used to implement this device and / or practice this method.

[0028] Additionally, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects described may be practiced without these specific details.

[0029] PEEK itself has good radiation resistance and is relatively hard and wear-resistant, but in some special application fields, its radiation resistance and metal texture problems need to be further improved. This application is mainly used in the field of military identification plates. In the actual production process, it is found that the radiation resistance and metal texture of the common PEEK plus glass fiber materials on the market are insufficient. Therefore, it is hoped that by introducing special lead powder and corresponding compatibilizers, toughening agents and glass fibers, a special PEEK material with excellent comprehensive performance can be prepared.

[0030] In a first aspect, an embodiment of the present application provides a radiation-resistant modified PEEK material, wherein the modified PEEK material comprises the following components in percentage by weight:

[0031]

[0032] The other adjuvants include antioxidants and lubricants.

[0033] In order to better improve the radiation resistance, the effect of the particle size of the lead powder on the radiation performance was studied and an experiment was conducted. In this embodiment, the mesh size of the lead powder is above 500 meshes. The comparative experiment shows that the finer lead powder, i.e., the lead powder with a larger mesh size, has a higher specific surface area and better radiation resistance.

[0034] In one embodiment, the effect of the structural shape of the lead powder on the radiation resistance of the PEEK material is studied. In this embodiment, the lead powder is a flaky structure. By introducing the flaky lead powder and the corresponding compatibilizer, toughening agent and glass fiber, a modified PEEK material with excellent comprehensive performance is prepared. The flaky lead powder has a large specific surface area and strong covering power, and can be evenly distributed in the PEEK resin matrix, which can better block high-energy rays, prevent radiation, and achieve good radiation resistance.

[0035] Furthermore, the structural dimensions of the lead powder are further limited to further improve the radiation resistance. In this embodiment, the length and width of the thin sheet structure are more than 4 times the thickness, so that the lead powder forms a flat structure and can be evenly spread in the PEEK material matrix, so that the formed modified PEEK material has a better radiation shielding area.

[0036] In one embodiment, the particle size of the lead powder is above 500 mesh, the particle size is uniform, the particle size distribution is wide, and the lead powder with a diameter distribution of 40μm-60μm (the average diameter of the lead powder, which can represent the size of the lead powder) accounts for more than 50% of the cumulative diameter of the powder. The lead powder formed in this way has a good radiation shielding area and can be evenly distributed in the PEEK material to achieve good radiation resistance.

[0037] Furthermore, the glass fiber diameter is 0.5mm-1.2mm and the specific surface area is 1500m 2 / kg-2000m 2 / kg, the amount of lead powder added is 10% to 15%. In this embodiment, the experiment shows that the same technical effect as adding 30% of the lead powder can be achieved. This is because the glass fiber has a silicon-oxygen bond and a large specific surface area, which can absorb a certain amount of lead powder to form an inclusion around the glass fiber, and the unabsorbed lead powder is scattered in the PEEK matrix. When the ray enters the PEEK matrix, the lead powder in the outer layer of the inclusion absorbs the ray energy. The absorption principle is that the lead nucleus is relatively large and the number of electron layers is relatively large. Its compact atomic structure allows lead to absorb and block ray energy; the unabsorbed ray penetrates the outer layer of the lead powder, and is reflected and refracted in the inner layer of the glass fiber of the inclusion. The reflected or refracted ray is then absorbed twice or multiple times by the outer layer of the lead powder; a small part of the overflowed ray is further absorbed and reflected by the scattered lead powder, and the radiation energy is completely consumed inside the PEEK matrix, so that the PEEK matrix has a higher radiation resistance.

[0038] In one embodiment, after selecting a good type and particle size of lead powder, pre-treating the surface of the lead powder is also a good method to improve the radiation resistance and comprehensive mechanical properties of the composite material. In this embodiment, the lead powder is acid-washed lead powder. The treated lead powder is blended with PEEK resin, plasticized, extruded, granulated, etc., to obtain a PEEK radiation-resistant composite material with good performance.

[0039] The acid-washed lead powder can increase the bonding strength between the lead powder and the resin, making the distribution of the lead powder in the PEEK material more uniform, thereby improving the radiation resistance and stability of the PEEK composite material. At the same time, with the same amount of lead powder added, a PEEK composite material with good mechanical properties is obtained, which is more conducive to application in the field of signboards.

[0040] In one embodiment, the melt index of PEEK ranges from 10 g / 10 min to 100 g / 10 min. Preferably, the melt index of PEEK ranges from 25 g / 10 min to 40 g / 10 min.

[0041] In one embodiment, the compatibilizer is a graft of maleic anhydride on PP (Polypropylene), PE (polyethylene) or POE (Polyaltha Olfin), or a graft of glycidyl methacrylate on PP, PE or POE, or a block copolymer formed by maleic anhydride, or a block copolymer formed by glycidyl methacrylate, such as SMA, 4700, 8900, PTW, etc.

[0042] Preferably, the compatibilizer is PTW from DuPont of the United States.

[0043] In one embodiment, the toughening agent is an olefin elastomer POE, or a ethyl acetate elastomer, such as EVA (Ethylene Vinyl Acetate, ethylene-vinyl acetate copolymer); or a butadiene rubber elastomer, such as HR181, SBS, SEBS, etc.

[0044] Preferably, the model of the toughening agent is POEDF610 produced by Mitsui Chemicals.

[0045] In one embodiment, other additives include 0.1% by weight of antioxidant 1010, 0.1% by weight of antioxidant 168, and 0.3% by weight of lubricant silicone powder.

[0046] The modified PEEK material of the present application is analyzed and verified by a specific experimental scheme, and the implementation scheme and test results are shown in Table 1. It should be noted that the glass fiber, toughening agent, compatibilizer and other additives in the modified PEKK material of the present application are not key components, and are defaulted to the optimal ratio (obtained through previous experiments) in the experiment.

[0047] Table 1 Test results of the experimental scheme for modified PEEK materials

[0048]

[0049]

[0050] Table 1 is a screening of lead powder. By comparing the ordinary mesh number and the lead powder with a higher mesh number in Example 1 and Example 3, it can be concluded that the finer lead powder has a higher specific surface area and better radiation resistance; at this higher mesh number, it is discussed that the lead powder with a special flaky structure (the length and width are more than 4 times the thickness) has a better radiation resistance effect than the ordinary lead powder with the same mesh number structure, specifically referring to Example 3 and Example 4 in the table. At the same time, the effect of the lead powder with a special flaky structure at a lower mesh number on the radiation resistance performance is also studied. Referring to Example 1 and Example 2, from the results, even at a lower mesh number, the lead powder with a special flaky structure still has a positive effect on the radiation resistance performance. Therefore, the lead powder with a special flaky structure can improve the radiation resistance of the PEEK material. The main reason is that the lead powder with a flaky structure can be more easily and evenly spread in the PEEK material due to the flat structure of the lead particles, achieving a higher radiation shielding area, and thus achieving good radiation resistance.

[0051] On this basis, the selected lead powder is further pickled and corroded. Referring to Example 4 and Example 5, the experimental results show that the lead powder after pickling can improve the radiation resistance of PEEK material. The reason is that the lead powder after pickling increases the dispersion of the lead powder in the resin matrix and the bonding effect between the lead powder and the resin matrix, so that the mechanical properties of the matrix can be maintained on the basis of improving the radiation resistance of the composite material, and a radiation-resistant PEEK composite material with excellent comprehensive performance can be obtained. At the same time, further increasing the content of lead powder (from 15% to 20%), the radiation resistance of the matrix does not increase much, but it brings a significant decrease in the mechanical properties of the system. Therefore, the scheme of Example 5 is a preferred embodiment with the best comprehensive performance.

[0052] In a second aspect, an embodiment of the present application further provides a method for preparing a radiation-resistant modified PEEK material as described in any embodiment of the first aspect above, the preparation method comprising:

[0053] Step 1: Mix PEEK, lead powder, toughening agent, compatibilizer and other additives. The mixing is carried out in a high-speed batching mixer, and the high-speed mixing gear is selected for high-speed mixing for 3 minutes. The high-speed batching mixer used in the production of modified plastics generally has only two gears, high speed and low speed. Generally, high-speed gear is used for mixing. The speed varies according to different manufacturers, basically around 500r / min-1000r / min.

[0054] Step 2: Place the mixed material in a twin-screw extruder, add glass fiber, and perform melt extrusion. The temperature ranges of the various temperature zones of the twin-screw extruder are: the temperature range of the first temperature zone is 345°C-365°C, the temperature range of the second temperature zone is 355°C-385°C, the temperature range of the third temperature zone is 360°C-390°C, the temperature range of the fourth temperature zone is 360°C-390°C, the temperature range of the fifth temperature zone is 360°C-390°C, and the temperature range of the die is 360°C-390°C; the main engine frequency of the twin-screw extruder is 30Hz-50Hz, and the feeding frequency is 10Hz-30Hz.

[0055] Step 3: Cool the extruded material and send it to a pelletizer for pelletizing; the rotation speed of the pelletizer is 300r / min-500r / min.

[0056] Step 4: Packing the cut particles to obtain the modified PEEK material.

[0057] In one implementation, before the mixing step, the method further includes: acid washing the lead powder.

[0058] When implemented specifically, pickling includes the following steps:

[0059] Add 10%-30% concentration of dilute sulfuric acid to the lead powder, stir and heat to 60℃-100℃, continue stirring and react for 5min-30min, then filter, add an aqueous solution of baking soda to neutralize the surface, then wash with clean water, and dry for later use.

[0060] The treated lead powder is blended with PEEK resin, plasticized, extruded, granulated and the like to obtain a PEEK radiation-resistant composite material with good performance.

[0061] Preferably, the concentration of dilute sulfuric acid during the pickling process is 10%, the temperature is 80° C., and the reaction time is 10 min.

[0062] Preferably, the temperature of the first temperature zone is 365°C, the temperature of the second temperature zone is 375°C, the temperature of the third temperature zone is 380°C, the temperature of the fourth temperature zone is 380°C, the temperature of the fifth temperature zone is 380°C, and the head temperature is 385°C; the main engine frequency is 40Hz; the feeding frequency is 20Hz; and the pelletizer speed is 300r / min.

[0063] The embodiment provided by the present invention prepares a PEEK special material with excellent comprehensive performance by introducing special lead powder and corresponding compatibilizer, toughening agent and glass fiber. In the present invention, the main thing is to compare the effects of lead powders of different types, shapes and particle sizes on the radiation resistance of the system, and to select lead powders with special particle size distribution and special shapes in a targeted manner, which have good radiation resistance at a lower addition amount. At the same time, the added lead powder is pretreated (pickling) to increase the bonding strength between the lead powder and the resin, so that the distribution of the lead powder in the PEEK material is more uniform, and the radiation resistance and stability of the PEEK composite material are improved. At the same time, at the same amount of lead powder added, a PEEK composite material with good mechanical properties is obtained, which is more conducive to application in the field of signboards.

[0064] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A radiation-resistant modified PEEK material, characterized in that: The modified PEEK material comprises the following components in weight percentage: PEEK30%-60% Toughener 3%-5% Compatibilizer 1%-3% Lead powder 10%-30% Glass fiber 10%-30% Other additives 0.3%-0.5% The other additives include antioxidants and lubricants; The lead powder has a mesh size of more than 500 meshes, the glass fiber has a diameter of 0.5 mm to 1.2 mm, and a specific surface area of ​​1500 m 2 / kg-2000m 2 / kg; the lead powder is acid-washed lead powder, and the lead powder is a flaky structure, and the length and width of the flaky structure are both more than 4 times the thickness.

2. The radiation-resistant modified PEEK material according to claim 1, characterized in that: The compatibilizer is a graft of maleic anhydride to PP, PE or POE, or a graft of glycidyl methacrylate to PP, PE or POE, or a block copolymer formed by maleic anhydride, or a block copolymer formed by glycidyl methacrylate; the toughening agent is an olefin elastomer or a butadiene rubber elastomer.

3. A method for preparing a radiation-resistant modified PEEK material according to any one of claims 1 to 2, characterized in that: The preparation method comprises: Mix PEEK, lead powder, toughening agent, compatibilizer and other additives; The mixed material is placed in a twin-screw extruder, and glass fiber is added for melt extrusion; The extruded material is cooled and sent to a pelletizer for pelletizing; Packing the cut particles to obtain the modified PEEK material; Before the mixing step, the method further comprises: acid washing the lead powder.

4. The preparation method according to claim 3, characterized in that: The pickling comprises the following steps: Add 10%-30% concentration of dilute sulfuric acid to the lead powder, stir and heat to 60℃-100℃, continue stirring and react for 5min-30min, then filter, add an aqueous solution of baking soda to neutralize the surface, then wash with clean water, and dry for later use.

5. The preparation method according to claim 3, characterized in that: The temperature ranges of the temperature zones of the twin-screw extruder are as follows: the temperature range of the first temperature zone is 345°C-365°C, the temperature range of the second temperature zone is 355°C-385°C, the temperature range of the third temperature zone is 360°C-390°C, the temperature range of the fourth temperature zone is 360°C-390°C, the temperature range of the fifth temperature zone is 360°C-390°C and the temperature range of the die head is 360°C-390°C; The main engine frequency of the twin-screw extruder is 30Hz-50Hz, and the feeding frequency is 10Hz-30Hz; The rotation speed of the pelletizer is 300r / min-500r / min.

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