PEEK color master batch, its preparation method and application

Abstract

The application discloses PEEK color master batch, a preparation method and application thereof, and belongs to the technical field of color master batch.The PEEK color master batch comprises the following components in parts by weight: PEEK resin 60-90 parts, and inorganic pigment 10-40 parts; wherein, the inorganic pigment is attached with a PI layer on the surface, the coating amount of the PI is 1-2 wt% of the inorganic pigment; and the particle size of the inorganic pigment is less than 2 mu m.The PEEK color master batch is attached with a PI film layer on the surface of the inorganic pigment, the surface energy of the inorganic pigment is reduced, the inorganic pigment has good dispersion in the PEEK melt, and is not prone to agglomeration, so that the polyether ether ketone (PEEK) color master batch with good pigment dispersion effect is obtained.

Description

Technical Field

[0001] This invention belongs to the field of plastic masterbatch production, and specifically relates to a PEEK color masterbatch, its preparation method, and its application. Background Technology

[0002] Polyetheretherketone (PEEK) is a high-performance special engineering plastic with characteristics such as heat resistance, radiation resistance, chemical resistance, high impact strength, good wear resistance and fatigue resistance, flame retardancy, and excellent electrical properties. It is widely used in aerospace, electronics, medical, energy, power, machinery, automobiles, coatings and other fields. Masterbatch is a new coloring product for plastics and fibers. It is a polymer composite obtained by uniformly loading pigments into resin. Masterbatch has the following advantages: (1) it makes the pigments more dispersed in the product; (2) it helps maintain the chemical stability of the pigments; (3) it ensures the stability of the product color; and (4) it avoids the health risks of powdered pigments to operators.

[0003] Traditional methods for processing inorganic pigments involve blending them with small-molecule dispersants. However, these small-molecule dispersants have poor temperature resistance. While they may meet the temperature requirements of common engineering plastics such as PA, PBT, and PPO, they cannot meet the temperature requirements of high-melting-point materials. Therefore, blending small-molecule dispersants with inorganic pigments does not achieve good dispersion results in the processing of masterbatches for high-melting-point materials such as PEEK.

[0004] Polyetheretherketone (PEEK) masterbatch refers to a product obtained by using PEEK as a carrier resin, adding a certain amount of inorganic pigments and dispersing agents, and then granulating it through twin-screw extrusion. However, in PEEK masterbatches produced using conventional processes, the inorganic pigments are prone to agglomeration, resulting in unsatisfactory dispersion within the masterbatch and affecting its performance. This is because PEEK has a high melting point of 343℃, and its processing temperature is generally between 360 and 400℃. At this temperature, common dispersing agents will volatilize or decompose. Due to the small particle size and high surface energy of inorganic pigments, significant agglomeration will occur without the effective action of dispersing agents. This leads to pigment agglomeration in the PEEK masterbatch, resulting in unsatisfactory dispersion and affecting the actual performance of the masterbatch. Therefore, how to reduce pigment agglomeration in PEEK masterbatches and improve its dispersion effect has become an urgent problem to be solved. Summary of the Invention

[0005] The present invention aims to solve the technical problems existing in the prior art. To this end, the present invention provides a PEEK masterbatch, its preparation method and application, and employs a novel surface treatment technology for inorganic pigments, enabling them to have good dispersibility in PEEK melt and to resist agglomeration.

[0006] According to a first aspect of the present invention, a PEEK masterbatch is provided, comprising the following components in parts by weight: 60-90 parts of PEEK resin and 10-40 parts of inorganic pigment; wherein, a layer of PI is attached to the surface of the inorganic pigment, and the coating amount of the PI is 1-2 wt% of the inorganic pigment; the particle size of the inorganic pigment is less than 2 μm. The particle size of the inorganic pigment is the secondary particle size after the inorganic pigment powder agglomerates.

[0007] According to a second aspect of the present invention, a method for preparing the PEEK masterbatch is provided, comprising the following steps:

[0008] (1) The inorganic pigment powder is dispersed in the PI solution under ultrasonic action, the solid and liquid are separated, the solid is dried to obtain the coated inorganic pigment.

[0009] (2) The coated inorganic pigment is blended and extruded with PEEK resin to obtain PEEK masterbatch.

[0010] In some embodiments of the present invention, in step (1), the particle size of the inorganic pigment powder is 0.1 to 0.5 μm.

[0011] In some embodiments of the present invention, in step (1), the mass concentration of the PI solution is 0.1% to 0.5%. Too low a concentration of the PI solution will result in incomplete coating of the inorganic pigment.

[0012] In some embodiments of the present invention, in step (1), the solid-liquid ratio of the inorganic pigment powder to the PI solution is 1:(50-100).

[0013] In some embodiments of the present invention, in step (1), the inorganic pigment includes, but is not limited to, at least one of titanium dioxide, iron oxide, chromium oxide or carbon black.

[0014] In some embodiments of the present invention, in step (1), stirring is performed during the dispersion process, the stirring speed is 1500 to 3500 rpm; and / or, the frequency of the ultrasound is 25 to 50 kHz.

[0015] In some embodiments of the present invention, in step (1), the ultrasound time is 5 to 25 minutes.

[0016] In some embodiments of the present invention, in step (1), the drying temperature is 50 to 70°C.

[0017] In some embodiments of the present invention, in step (2), the drying process parameters are as follows: the temperature is 120-150°C; and / or the drying medium is dehumidified air, the dew point temperature of the dehumidified air is below -40°C; and / or the drying time is greater than 4 hours.

[0018] In some embodiments of the present invention, in step (2), the apparatus for blending extrusion is a twin-screw extruder.

[0019] In some preferred embodiments of the present invention, the temperatures of each zone of the twin-screw extruder are as follows: Zone 1 (280-300°C), Zone 2 (300-340°C), Zone 3 (320-360°C), Zone 4 (340-380°C), Zone 5 (360-380°C), Zone 6 (360-380°C), Zone 7 (360-390°C), and Zone 8 (360-380°C).

[0020] In some embodiments of the present invention, step (2) further includes filtering the extruded melt during the blending extrusion process, wherein the filter pore diameter is 30–50 μm. Filtering the extruded melt removes crosslinked particles and impurities from the melt.

[0021] In some preferred embodiments of the present invention, after the extruded melt is filtered, the melt enters a die head and is extruded into a strip, the temperature of which is 340-370°C.

[0022] In some preferred embodiments of the present invention, the material strip is granulated after being cooled in a water tank, the temperature of which is 25-90°C.

[0023] In some preferred embodiments of the present invention, the material strip is further cooled and then blown to remove surface moisture.

[0024] The present invention also provides the application of the above preparation method in the preparation of PEEK plastics.

[0025] According to a preferred embodiment of the present invention, at least the following beneficial effects are achieved:

[0026] 1. In the PEEK masterbatch of this invention, the inorganic pigment surface is coated with a layer of high-molecular-weight polyimide, which reduces the surface energy of the inorganic pigment and effectively reduces the aggregation between inorganic pigments, eliminating the need for dispersants. Furthermore, compared to small-molecule silane coupling agents and other components, the use of macromolecular coating eliminates migration and precipitation issues during subsequent use, ensuring the overall performance of the final product.

[0027] 2. In this invention, polyimide is prepared into a dilute solution. Inorganic pigments are added to the dilute solution and effectively dispersed in the solution through high-speed stirring and high-frequency ultrasound. The filtered inorganic pigments are dried, and after the solvent evaporates, the polyimide polymer material is uniformly adhered to the surface of the inorganic pigments.

[0028] 3. Polyimide (PI) and polyetheretherketone (PEEK) have good compatibility, and polyimide has good temperature resistance, showing no significant degradation or decomposition at the processing temperatures required for PEEK. Therefore, when inorganic pigments with PI adhering to their surface are co-extruded in a twin-screw extruder, the inorganic pigments can be well dispersed in the PEEK melt, preventing agglomeration and resulting in a PEEK masterbatch with excellent pigment dispersion. Attached Figure Description

[0029] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0030] Figure 1 This is a diagram showing the pigment dispersion in the masterbatch produced in Example 1 of the present invention;

[0031] Figure 2 This is a diagram showing the pigment dispersion in the masterbatch produced in Comparative Example 1 of this invention. Detailed Implementation

[0032] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0033] Example 1

[0034] A PEEK masterbatch comprises the following components in parts by weight: 80 parts of 550g PEEK resin and 20 parts of titanium dioxide; wherein, a polyimide film layer is deposited on the surface of the titanium dioxide. The polyimide is TY005-1.

[0035] A method for preparing PEEK masterbatch as described above includes the following steps:

[0036] (1) Polyimide was dissolved in acetone at a concentration controlled within the range of 0.1–0.5%. After dissolution, titanium dioxide with a particle size of 0.1–0.5 μm was added, with a solid-liquid ratio of 1:80 between the titanium dioxide and the polyimide solution. The mixture was stirred at 2500 rpm and subjected to ultrasonic treatment at a frequency of 30 kHz. After ultrasonic treatment for 20 min, the suspension was filtered. The filtered inorganic pigment was dried at 60 °C to obtain modified titanium dioxide.

[0037] (2) The dried titanium dioxide was blended with PEEK resin in a specific ratio. The PEEK resin comprised 80% of the mixture, and the modified titanium dioxide comprised 20%. The blended raw material was dried at 150°C using dehumidified air with a dew point of -50°C for 5 hours. The dried raw material was then fed into a twin-screw extruder for co-extrusion. The temperatures of each zone of the twin-screw extruder were as follows: Zone 1 (300°C), Zone 2 (320°C), Zone 3 (350°C), Zone 4 (370°C), Zone 5 (380°C), Zone 6 (380°C), Zone 7 (380°C), and Zone 8 (380°C). After twin-screw extrusion, the melt was filtered. This filtration device was switchable and equipped with a filter screen with a filtration accuracy of 40 μm.

[0038] (3) The filtered melt enters the die and is extruded into thin strips at a temperature of 360°C. The melt strips are cooled in a water bath at a temperature of 50°C. After the strips have been cooled and solidified in the water bath, excess moisture is blown off by an air blower before pelletizing to obtain PEEK masterbatch products.

[0039] The PEEK masterbatch produced by the above preparation method, such as Figure 1 As shown, the maximum particle size of the inorganic powder after aggregation is less than 2 μm, and the dispersibility is good.

[0040] Comparative Example 1

[0041] A PEEK masterbatch comprises the following components in parts by weight: 80 parts of 550g PEEK resin and 20 parts of titanium dioxide; wherein the titanium dioxide has been surface-treated.

[0042] A method for preparing PEEK masterbatch as described above includes the following steps:

[0043] (1) Mix titanium dioxide with a particle size of 0.1-0.5 μm with a silane coupling agent, the weight of the coupling agent being 1% of the weight of the titanium dioxide. Stir at high speed (1500 rpm) for 15 min. Then dry the titanium dioxide at 90℃ for 60 min.

[0044] (2) The dried titanium dioxide was blended with PEEK resin in a specific ratio. The proportion of PEEK resin was 80%, and the proportion of titanium dioxide was 20%. The mixed raw material was dried at 150℃ using dehumidified air with a dew point temperature of -50℃ for 5 hours. The dried raw material was then fed into a twin-screw extruder for blending and extrusion. The temperatures of each zone of the twin-screw extruder were as follows: Zone 1 (300℃), Zone 2 (320℃), Zone 3 (350℃), Zone 4 (370℃), Zone 5 (380℃), Zone 6 (380℃), Zone 7 (380℃), and Zone 8 (380℃). After twin-screw extrusion, the melt was filtered by a filter device. This filter device was switchable and equipped with a filter screen with a filtration accuracy of 40μm.

[0045] (3) The filtered melt enters the die and is extruded into thin strips at a temperature of 360°C. The melt strips are cooled in a water bath at a temperature of 50°C. After the strips have been cooled and solidified in the water bath, excess moisture is blown off by an air blower before pelletizing to obtain PEEK masterbatch products.

[0046] The PEEK masterbatch produced by the above preparation method, such as Figure 2 As shown, the maximum particle size of the inorganic powder after aggregation is greater than 5 μm, and the agglomeration phenomenon is quite serious.

[0047] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. A PEEK masterbatch, characterized in that, The product comprises the following components in parts by weight: 60-90 parts of PEEK resin and 10-40 parts of inorganic pigment; wherein, a layer of PI is attached to the surface of the inorganic pigment, and the coating amount of the PI is 1-2 wt% of the inorganic pigment; the particle size of the inorganic pigment is less than 2 μm. The inorganic pigment includes at least one of titanium dioxide, iron oxide, chromium oxide, or carbon black. The PI is TY005 1.

2. A method for preparing PEEK masterbatch as described in claim 1, characterized in that, Includes the following steps: (1) The inorganic pigment powder is dispersed in the PI solution under ultrasonic action, the solid and liquid are separated, the solid is dried to obtain the coated inorganic pigment; (2) The coated inorganic pigment is blended with PEEK resin and extruded to obtain PEEK masterbatch; In step (1), the mass concentration of the PI solution is 0.1% to 0.5%, the solid-liquid ratio of the inorganic pigment powder to the PI solution is 1:(50 to 100), and the solvent of the PI solution is acetone.

3. The preparation method according to claim 2, characterized in that, In step (1), the particle size of the inorganic pigment powder is 0.1 to 0.5 μm.

4. The preparation method according to claim 2, characterized in that, In step (1), stirring is performed during the dispersion process, and the stirring speed is 1500-3500 rpm; and / or, the frequency of the ultrasound is 25-50 kHz.

5. The preparation method according to claim 2, characterized in that, In step (2), the apparatus for blending extrusion is a twin-screw extruder.

6. The preparation method according to claim 5, characterized in that, The temperatures of each zone of the twin-screw extruder are as follows: Zone 1 280-300℃, Zone 2 300-340℃, Zone 3 320-360℃, Zone 4 340-380℃, Zone 5 360-380℃, Zone 6 360-380℃, Zone 7 360-390℃, Zone 8 360-380℃.

7. The preparation method according to claim 2, characterized in that, In step (2), the extruded melt is filtered during the blending extrusion process, and the filter pore diameter is 30-50 μm.

8. The application of the preparation method according to any one of claims 2-7 in the preparation of PEEK plastics.

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