CN116948355A - PEEK color master batch and preparation method and application thereof - Google Patents
PEEK color master batch and preparation method and application thereof Download PDFInfo
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- CN116948355A CN116948355A CN202310732113.XA CN202310732113A CN116948355A CN 116948355 A CN116948355 A CN 116948355A CN 202310732113 A CN202310732113 A CN 202310732113A CN 116948355 A CN116948355 A CN 116948355A
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- peek
- inorganic pigment
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 55
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 55
- 239000004595 color masterbatch Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 title claims abstract 13
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000049 pigment Substances 0.000 abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 26
- 229920001721 polyimide Polymers 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 16
- 239000004408 titanium dioxide Substances 0.000 description 13
- 239000000155 melt Substances 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention discloses a PEEK color master batch, a preparation method and application thereof, wherein the PEEK color master batch 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 1-2wt% of the inorganic pigment; the particle size of the inorganic pigment is less than 2 mu m. The PI film layer is attached to the surface of the inorganic pigment in the PEEK color master batch, so that the surface energy of the inorganic pigment is reduced, the inorganic pigment is well dispersed in PEEK melt and is not easy to agglomerate, and the PEEK color master batch with good pigment dispersing effect is obtained.
Description
Technical Field
The invention belongs to the field of plastic masterbatch production, and particularly relates to a PEEK color masterbatch, a preparation method and application thereof.
Background
Polyether ether ketone (PEEK) is a high-performance special engineering plastic, has the characteristics of heat resistance, radiation resistance, chemical resistance, high impact strength, good wear resistance and fatigue resistance, flame retardance, excellent electrical property and the like, and is widely applied to the fields of aerospace, electronics, electricity, medical treatment, energy sources, electricity, machinery, automobiles, paint and the like. The color master batch is a new coloring product of plastics and fibers, and is a polymer compound prepared by uniformly loading pigment into resin. The color master batch has the following advantages: (1) better dispersion of the pigment in the article; (2) facilitate maintaining the chemical stability of the pigment; (3) ensuring the stability of the color of the product; (4) avoiding the influence of the powdery pigment on the health of operators.
The traditional inorganic pigment treatment method is to blend the inorganic pigment with a small molecule dispersant. However, these small molecular dispersants have poor temperature resistance, and although the temperature resistance requirements of common engineering plastics such as PA, PBT, PPO and other materials can be met, the temperature resistance requirements of high-melting-point materials can not be met. Therefore, a method of blending a small-molecule dispersant and an inorganic pigment cannot obtain a good dispersion effect in processing of high-melting-point material color master batches such as PEEK.
The PEEK (PEEK) masterbatch is a product obtained by taking PEEK as carrier resin, adding a certain amount of inorganic pigment and dispersing aid, and then extruding and granulating through a double screw. However, the PEEK color master batch produced by the conventional process has the defects that inorganic pigments are easy to agglomerate, the dispersion effect in the master batch is not ideal, and the use effect is affected. This is due to the fact that PEEK has a melting point as high as 343℃and a processing temperature of 360-400℃in general. At this temperature, the usual dispersing assistants volatilize or decompose. Because of the small particle size of the inorganic pigment and high surface energy, the inorganic pigment can generate obvious agglomeration effect without the effective action of a dispersing auxiliary. The pigment in the PEEK color master batch is agglomerated, the dispersion effect is not ideal, and the actual use effect of the color master batch is affected. Therefore, how to reduce the agglomeration of the pigment in the PEEK color master batch and improve the dispersion effect thereof becomes a problem to be solved.
Disclosure of Invention
The present invention aims to solve the technical problems in the prior art described above. Therefore, the invention provides PEEK color master batch, a preparation method and application thereof, and a novel surface treatment technology is carried out on inorganic pigment, so that the PEEK color master batch has good dispersibility in PEEK melt and is not easy to agglomerate.
According to a first aspect of the invention, a PEEK color master batch is provided, which 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 1-2wt% of the inorganic pigment; the particle size of the inorganic pigment is less than 2 mu m. The particle size of the inorganic pigment is the particle size of secondary particles after the inorganic pigment powder is agglomerated.
According to a second aspect of the present invention, there is provided a preparation method of the PEEK color master batch, comprising the steps of:
(1) Dispersing inorganic pigment powder into PI solution under the action of ultrasound, carrying out solid-liquid separation, and drying the solid to obtain coated inorganic pigment;
(2) And (3) blending and extruding the coated inorganic pigment and PEEK resin to obtain PEEK color master batch.
In some embodiments of the invention, in step (1), the particle size of the inorganic pigment powder is 0.1 to 0.5 μm.
In some embodiments of the invention, in step (1), the PI solution has a mass concentration of 0.1% to 0.5%. Too low a concentration of PI solution may result in incomplete coating of the inorganic pigment.
In some embodiments of the invention, in step (1), the solid-to-liquid ratio of the inorganic pigment powder to the PI solution is 1: (50-100).
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.
In some embodiments of the invention, in step (1), stirring is performed during the dispersing, the stirring speed being 1500-3500 rpm; and/or the frequency of the ultrasonic wave is 25-50 kHZ.
In some embodiments of the invention, in step (1), the time of the ultrasound is 5 to 25 minutes.
In some embodiments of the invention, in step (1), the temperature of the drying is 50-70 ℃.
In some embodiments of the invention, in step (2), the process parameters of the drying are as follows: the temperature is 120-150 ℃; and/or the drying medium is dehumidified air, and the dew point temperature of the dehumidified air is lower than-40 ℃; and/or the drying time is greater than 4 hours.
In some embodiments of the invention, in step (2), the means of blending extrusion is a twin screw extruder.
In some preferred embodiments of the invention, the temperatures of the zones of the twin screw extruder are as follows: 1 zone (280-300 ℃), 2 zone (300-340 ℃), 3 zone (320-360 ℃), 4 zone (340-380 ℃), 5 zone (360-380 ℃), 6 zone (360-380 ℃), 7 zone (360-390 ℃) and 8 zone (360-380 ℃).
In some embodiments of the invention, in step (2), during the blending extrusion, further comprising filtering the extruded melt, the filtered filter pores having a diameter of 30 to 50 μm. Filtering the extruded melt removes cross-linked particles and impurities from the melt.
In some preferred embodiments of the invention, after filtering the extruded melt, the melt enters a die at a temperature of 340-370 ℃ to be extruded into strands.
In some preferred embodiments of the invention, the strand is pelletized after cooling in a water bath having a temperature of 25 to 90 ℃.
In some preferred embodiments of the invention, the strand is cooled and then subjected to air blowing to remove surface moisture.
The invention also provides application of the preparation method in preparing PEEK plastic.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. according to the PEEK color master batch, a layer of polymer material polyimide is attached to the surface of the inorganic pigment, so that the surface energy of the inorganic pigment is reduced, the agglomeration among the inorganic pigments is effectively reduced, and a dispersing agent is not needed. Compared with components such as a micromolecular silane coupling agent, the coating of the macromolecule is adopted, so that the problems of migration and precipitation in the subsequent use process are avoided, and the comprehensive performance of the final product is ensured.
2. The polyimide is prepared into a dilute solution, and the inorganic pigment is put into the dilute solution to be effectively dispersed in the solution under the actions of high-speed stirring and high-frequency ultrasound. The filtered inorganic pigment is dried, and the polyimide polymer material is uniformly attached to the surface of the inorganic pigment after the solvent is evaporated.
3. Polyimide (PI) and polyether ether ketone (PEEK) have good compatibility, and polyimide has good temperature resistance, and has no obvious degradation or decomposition at the processing temperature required by PEEK. Therefore, when the inorganic pigment with PI attached to the surface is subjected to double-screw blending extrusion, the inorganic pigment can be ensured to have good dispersion in PEEK melt and is not easy to agglomerate, so that the polyether-ether-ketone (PEEK) color master batch with good pigment dispersion effect is obtained.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a graph showing the dispersion of pigments in the masterbatch produced in example 1 of the present invention;
FIG. 2 is a graph showing the dispersion of pigments in the masterbatch produced in comparative example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The PEEK color master batch comprises the following components in parts by weight: 80 parts of PEEK resin 5500 parts of titanium dioxide; wherein a polyimide film layer is attached to the surface of the titanium dioxide. The polyimide is TY005-1.
The preparation method of the PEEK color master batch comprises the following steps:
(1) Polyimide was dissolved in acetone to control the concentration thereof to be in the range of 0.1 to 0.5%. After the dissolution is completed, adding titanium dioxide with the particle size of 0.1-0.5 mu m, wherein the solid-liquid ratio of the titanium dioxide to the polyimide solution is 1:80, stirring speed is 2500rpm, carrying out ultrasonic treatment, and the ultrasonic frequency is 30KHz. After 20min of ultrasonic treatment, the suspension was filtered. And drying the filtered inorganic pigment at 60 ℃ to obtain the modified titanium dioxide.
(2) And mixing the dried titanium dioxide with PEEK resin according to a proportion. Wherein the PEEK resin accounts for 80 percent and the modified titanium dioxide accounts for 20 percent. The mixed raw materials are dried by adopting dehumidified air at 150 ℃ and the dew point temperature of the dehumidified air is minus 50 ℃ and the drying time is 5 hours. And (5) feeding the dried raw materials into a double-screw extruder for blending extrusion. The temperatures in the zones of the twin-screw are as follows: 1 (300 ℃), 2 (320 ℃), 3 (350 ℃), 4 (370 ℃), 5 (380 ℃), 6 (380 ℃), 7 (380 ℃) and 8 (380 ℃). And (5) extruding the melt by a double screw, and filtering the melt by a filtering device. The filter device is switchable, and is provided with a filter screen, wherein the filter accuracy of the filter screen is 40 mu m.
(3) The filtered melt was extruded into strands at a die temperature of 360 ℃. The melt strand is cooled by a water tank, the temperature of which is controlled at 50 ℃. And (3) cooling the solidified material strips through a water tank, blowing off superfluous surface moisture through blowing, and granulating to obtain PEEK color master batch products.
As shown in FIG. 1, the PEEK color master batch produced by the preparation method has a maximum particle size of less than 2 μm after inorganic powder aggregation and good dispersibility.
Comparative example 1
The PEEK color master batch comprises the following components in parts by weight: 80 parts of PEEK resin 5500 parts of titanium dioxide; wherein the titanium dioxide is subjected to surface treatment.
The preparation method of the PEEK color master batch comprises the following steps:
(1) Mixing titanium dioxide with the particle size of 0.1-0.5 mu m with a silane coupling agent, stirring at a high speed of 1500rpm for 15min, wherein the weight of the coupling agent is 1% of that of the titanium dioxide. And then the titanium dioxide is dried for 60min at 90 ℃.
(2) And mixing the dried titanium dioxide with PEEK resin according to a proportion. Wherein the PEEK resin accounts for 80 percent and the titanium dioxide accounts for 20 percent. The mixed raw materials are dried by adopting dehumidified air at 150 ℃ and the dew point temperature of the dehumidified air is minus 50 ℃ and the drying time is 5 hours. And (5) feeding the dried raw materials into a double-screw extruder for blending extrusion. The temperatures in the zones of the twin-screw are as follows: 1 (300 ℃), 2 (320 ℃), 3 (350 ℃), 4 (370 ℃), 5 (380 ℃), 6 (380 ℃), 7 (380 ℃) and 8 (380 ℃). And (5) extruding the melt by a double screw, and filtering the melt by a filtering device. The filter device is switchable, and is provided with a filter screen, wherein the filter accuracy of the filter screen is 40 mu m.
(3) The filtered melt was extruded into strands at a die temperature of 360 ℃. The melt strand is cooled by a water tank, the temperature of which is controlled at 50 ℃. And (3) cooling the solidified material strips through a water tank, blowing off superfluous surface moisture through blowing, and granulating to obtain PEEK color master batch products.
As shown in figure 2, the PEEK color master batch produced by the preparation method has the maximum particle size of more than 5 mu m after inorganic powder aggregation, and the aggregation phenomenon is serious.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The PEEK color master batch is characterized by 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 1-2wt% of the inorganic pigment; the particle size of the inorganic pigment is less than 2 mu m.
2. A method for preparing the PEEK color master batch according to claim 1, comprising the steps of:
(1) Dispersing inorganic pigment powder into PI solution under the action of ultrasound, carrying out solid-liquid separation, and drying the solid to obtain coated inorganic pigment;
(2) And (3) blending and extruding the coated inorganic pigment and PEEK resin to obtain PEEK color master batch.
3. The method according to claim 2, wherein in the step (1), the particle diameter of the inorganic pigment powder is 0.1 to 0.5. Mu.m.
4. The method according to claim 2, wherein in the step (1), the PI solution has a mass concentration of 0.1% to 0.5%.
5. The method according to claim 2, wherein in the step (1), a solid-to-liquid ratio of the inorganic pigment powder to the PI solution is 1: (50-100).
6. The method according to claim 2, wherein in the step (1), stirring is performed during the dispersion, and the stirring speed is 1500 to 3500rpm; and/or the frequency of the ultrasonic wave is 25-50 kHZ.
7. The method of claim 2, wherein in step (2), the means for blending extrusion is a twin screw extruder.
8. The process of claim 7, wherein the twin screw extruder zones are at the following temperatures: 1 zone (280-300 ℃), 2 zone (300-340 ℃), 3 zone (320-360 ℃), 4 zone (340-380 ℃), 5 zone (360-380 ℃), 6 zone (360-380 ℃), 7 zone (360-390 ℃) and 8 zone (360-380 ℃).
9. The method according to claim 2, wherein in the step (2), during the blending extrusion, the extruded melt is further filtered, and the diameter of the filter pores of the filtration is 30 to 50 μm.
10. Use of the preparation method according to any one of claims 2 to 9 for the preparation of PEEK plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310732113.XA CN116948355A (en) | 2023-06-19 | 2023-06-19 | PEEK color master batch and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310732113.XA CN116948355A (en) | 2023-06-19 | 2023-06-19 | PEEK color master batch and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN116948355A true CN116948355A (en) | 2023-10-27 |
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| CN202310732113.XA Pending CN116948355A (en) | 2023-06-19 | 2023-06-19 | PEEK color master batch and preparation method and application thereof |
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| Country | Link |
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