A color master batch, a polyaryletherketone dope colored fiber and a preparation method thereof

Abstract

This invention relates to the field of polyaryletherketone (PAEK) modification technology, specifically to a color masterbatch, PAEK solution-colored fibers, and their preparation methods. The color masterbatch comprises the following components by weight: 45-60 parts of low-melting-point PAEK, 20-35 parts of liquid crystal polymer, 10-20 parts of plant dye with a thermal decomposition temperature higher than 350℃, 0.5-1.5 parts of maleic anhydride, 1-3 parts of nano-silica, and 1-3 parts of amino-modified polysiloxane. The color masterbatch is then mixed with PAEK and melt-spun to obtain PAEK solution-colored fibers. This invention uses plant dyes to prepare a color masterbatch suitable for PAEK and can be used for coloring and spinning PAEK solutions. The fibers have strong spinnability, are not prone to breakage, and the resulting fibers have uniform coloring.

Description

Technical Field

[0001] This invention relates to the field of polyaryletherketone modification technology, specifically to a color masterbatch, polyaryletherketone solution-colored fibers, and their preparation methods. Background Technology

[0002] Polyaryletherketone (PAEK) is a high-performance thermoplastic engineering plastic with excellent high-temperature resistance, mechanical strength and chemical stability. It is widely used in aerospace, medical implants, automotive industry and electronic devices.

[0003] Traditional PAEK resin melt exhibits extremely high viscosity (significantly higher than PEEK, etc.) at conventional processing temperatures (350℃-400℃), making it impossible to achieve uniform dispersion of masterbatches or pigments in this viscous system. High viscosity severely limits the resin's ability to wet pigment particles, hindering the effective transmission of mechanical shear forces; pigments easily aggregate into large agglomerates, leading to color differences, color spots, or strength defects. Therefore, to ensure uniform dispersion, higher shear rates, longer processing times, or modified process parameters (temperature, pressure) are required, placing more stringent demands on equipment. High viscosity also results in poor drawability of the spinning melt, particularly hindering fine fiber spinning and limiting high-end applications.

[0004] Currently, PAEK products on the market are typically in their "original color" (beige to dark brown). While traditional post-dyeing can solve some color problems, it is energy-intensive, causes serious wastewater issues (heavy metal residues), and fails to meet environmental and medical safety standards. In existing technologies, PAEK solution coloring technology can address some of the pain points of post-dyeing processes, but it is still limited by pigment dispersibility and process adaptability. Therefore, there are relatively few color masterbatches suitable for PAEK. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a color masterbatch, polyaryletherketone (PAEK) solution-dyed fibers, and a method for preparing the same. The invention uses plant dyes to produce a color masterbatch suitable for PAEK, which can be used for coloring and spinning polyaryletherketone (PAEK) solutions. The resulting fibers have strong spinnability, are not prone to breakage, and exhibit uniform coloring.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] The first aspect of this invention provides a color masterbatch, comprising the following components in parts by weight:

[0008] Low melting point PAEK 45-60 parts,

[0009] 20-35 parts of liquid crystal polymer,

[0010] 10-20 parts of plant dyes with a thermal decomposition temperature above 350℃

[0011] Maleic anhydride 0.5-1.5 parts,

[0012] 1-3 parts of nano-silica

[0013] 1-3 parts of amino-modified polysiloxane.

[0014] Furthermore, the low-melting-point PAEK has a melting point in the range of 300-315°C (ISO 11357) and a viscosity of less than 300 Pa·s.

[0015] The liquid crystal polymer is a thermotropic liquid crystal polymer (TLCP) with a melting temperature in the range of 250-350℃. TLCP is suitable for the preparation of color masterbatches, while the melt mixing process of lyotropic liquid crystal polymers (LLCP) and color masterbatches is incompatible; both have low viscosity, and low viscosity materials are more conducive to the stability of the spinning process and the optimization of fiber properties.

[0016] The plant dye is plant-based indigo dye, and its thermal decomposition temperature is usually above 380℃.

[0017] Furthermore, the method for obtaining the amino-modified polysiloxane is as follows:

[0018] α,ω-dihydroxypolydimethylsiloxane, aminosiloxane compound, and tetrabutyl titanate were dissolved in benzene-based solvents and reacted at a temperature in the range of 100-140℃ for 2-5 hours under nitrogen protection. Then, the solvent was removed under reduced pressure to obtain amino-modified polysiloxane.

[0019] Preferably, the molecular weight of the α,ω-dihydroxypolydimethylsiloxane is in the range of 5000-12000 g / mol;

[0020] The aminosiloxane compound is selected from one or more of 3-aminopropyltriethoxysilane, (3-aminopropyl)diethoxyethylsilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane.

[0021] The mass ratio of the α,ω-dihydroxypolydimethylsiloxane, the aminosiloxane compound, and the tetrabutyl titanate is 100:5-10:0.5-1.

[0022] Furthermore, the preparation process of the color masterbatch is as follows: the components are premixed at at least 1000 rpm, and then melt-blended, extruded, and granulated to obtain the masterbatch.

[0023] Furthermore, the melt blending extrusion employs a twin-screw extruder, with the temperatures of each zone set as follows: Zone 1 335℃~345℃, Zone 2 335℃~345℃, Zone 3 335℃~345℃, Zone 4 335℃~345℃, Zone 5 335℃~345℃, Zone 6 335℃~345℃, Zone 7 330℃~340℃, Zone 8 330℃~340℃, Zone 9 330℃~340℃, and the die head 340℃~350℃.

[0024] The second aspect of the present invention provides a method for preparing polyaryletherketone solution-dyed fibers, comprising mixing the above-mentioned masterbatch with polyaryletherketone and then performing melt spinning to obtain polyaryletherketone solution-dyed fibers;

[0025] The amount of color masterbatch used is 0.01%-20% of the weight of the polyaryletherketone.

[0026] Further, the polyaryletherketone is selected from one or more of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketoneetherketoneketone (PEKEKK).

[0027] Furthermore, the melt spinning adopts a single-screw spinning machine, and the temperatures of each zone are set as follows: Zone 1 300℃~310℃, Zone 2 320℃~330℃, Zone 3 330℃~340℃, Zone 4 335℃~345℃, Zone 5 345℃~350℃, and Die Zone 345℃~350℃.

[0028] Furthermore, the preparation method of the polyaryletherketone solution-dyed fiber also includes heat-treating the dyed fiber at 150-200℃ for 1-3 hours to improve the crystallinity of the product, thereby enhancing mechanical properties, improving dimensional stability, and eliminating internal stress.

[0029] The final aspect of the present invention provides polyaryletherketone solution-dyed fibers obtained by the above preparation method.

[0030] Beneficial technical effects:

[0031] This invention utilizes low-melting-point PAEK, adding plant-derived indigo dye with a high thermal decomposition temperature and LCP with extremely low melt viscosity to the low-melting-point PAEK system. It also incorporates amino-modified polysiloxane to improve melt flowability, further reducing the problems of uneven dye dispersion and premature dye degradation leading to significant color differences in the colored materials caused by the high viscosity of polyaryletherketone itself during granulation and melt spinning. The masterbatch employs maleic anhydride as a chemical compatibilizer and nano-silica as a physical compatibilizer. Through a dual compatibilization mechanism of chemical grafting and physical anchoring, it solves the problem of weak interfacial bonding between LCP and PAEK, resulting in excellent melt flowability after the masterbatch is combined with the matrix resin. This reduces processing difficulty, increases the tensile strength of the material, and gives the material good spinnability and a high yield of fiber products. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0033] Unless otherwise specifically stated, the numerical values ​​set forth in these embodiments do not limit the scope of the invention. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that values ​​expressed, for example, as "within the range of ab" or "between the range of ab," do not include the endpoint values ​​a and b; values ​​expressed as "for ab," "is ab," or "ab" include the endpoint values ​​a and b.

[0034] Experimental methods not specified in the following examples are generally performed according to national standards; if there is no corresponding national standard, they are performed according to general standard requirements or general methods.

[0035] The low-melting-point PAEK used below is the commercially available Vigus product LMPAEK. TM Model 101PWD has a melting point of 305℃ (ISO 11357) and a viscosity of 141 Pa·s (ISO 11443); Model 103PWD has a melting point of 303℃ (ISO 11357) and a viscosity of 277 Pa·s (ISO 11443).

[0036] The liquid crystal polymers used below are commercially available products from Celanese Corporation, product brand name... A950, grade: injection molding grade, melt temperature 280℃.

[0037] The polyaryletherketones used in the following spinning process are exemplified by PEEK. When other similar fibers are required, other polyaryletherketones with similar structures to PEEK can be used as substitutes.

[0038] Preparation Example 1

[0039] This case study focuses on the preparation of amino-modified polysiloxanes:

[0040] 100 g of α,ω-dihydroxypolydimethylsiloxane (molecular weight 10000 g / mol), 8 g of 3-aminopropyltriethoxysilane, and 0.8 g of tetrabutyl titanate were dissolved in 80 mL of toluene and reacted at 120 °C for 4 h under nitrogen protection. The solution was then removed under reduced pressure to obtain amino-modified polysiloxane (amine value 1.2 mmol / g).

[0041] Example 1

[0042] A color masterbatch comprises the following components in parts by weight: 56 parts of low melting point PAEK (model 101PWD), 20 parts of LCP, 20 parts of plant indigo dye, 1.5 parts of maleic anhydride, 1.5 parts of nano silica (average particle size 20-100nm), and 1 part of amino-modified polysiloxane of Preparation Example 1.

[0043] The above components were premixed at 3000 rpm for 5 minutes, and then added to a twin-screw extruder for melt blending extrusion and granulation to obtain color masterbatch. The temperatures of each zone of the twin-screw extruder were set as follows: Zone 1 335℃~345℃, Zone 2 335℃~345℃, Zone 3 335℃~345℃, Zone 4 335℃~345℃, Zone 5 335℃~345℃, Zone 6 335℃~345℃, Zone 7 330℃~340℃, Zone 8 330℃~340℃, Zone 9 330℃~340℃, and the die head 340℃~350℃.

[0044] A method for preparing PEEK solution-dyed fiber includes mixing the prepared masterbatch with PEEK (brand name 5600G) at a mass ratio of 1:20, mixing them evenly, and then adding the mixture to a single-screw extruder to melt and form a melt before spinning. The temperatures of each zone of the single-screw extruder are set as follows: Zone 1 300℃~310℃, Zone 2 320℃~330℃, Zone 3 330℃~340℃, Zone 4 335℃~345℃, Zone 5 345℃~350℃, and Die Zone 345℃~350℃, to obtain PEEK solution-dyed fiber. The dyed fiber is then heat-treated at 190℃ for 2 hours.

[0045] Example 2

[0046] A color masterbatch comprises the following components in parts by weight: 45 parts of low melting point PAEK (model 103PWD), 30 parts of LCP, 20 parts of plant indigo dye, 1 part of maleic anhydride, 2 parts of nano silica (average particle size 20-100nm), and 2 parts of amino-modified polysiloxane of Preparation Example 1.

[0047] The above components were premixed at 3000 rpm for 5 minutes, and then added to a twin-screw extruder for melt blending extrusion and granulation to obtain color masterbatch. The temperatures of each zone of the twin-screw extruder were set as follows: Zone 1 335℃~345℃, Zone 2 335℃~345℃, Zone 3 335℃~345℃, Zone 4 335℃~345℃, Zone 5 335℃~345℃, Zone 6 335℃~345℃, Zone 7 330℃~340℃, Zone 8 330℃~340℃, Zone 9 330℃~340℃, and the die head 340℃~350℃.

[0048] A method for preparing PEEK solution-dyed fiber includes mixing the prepared masterbatch with PEEK (brand name 5600G) at a mass ratio of 1:20, mixing them evenly, and then adding the mixture to a single-screw extruder to melt and form a melt before spinning. The temperatures of each zone of the single-screw extruder are set as follows: Zone 1 300℃~310℃, Zone 2 320℃~330℃, Zone 3 330℃~340℃, Zone 4 335℃~345℃, Zone 5 345℃~350℃, and Die Zone 345℃~350℃, to obtain PEEK solution-dyed fiber. The dyed fiber is then heat-treated at 190℃ for 2 hours.

[0049] Example 3

[0050] A color masterbatch comprises the following components in parts by weight: 50 parts of low melting point PAEK (model 103PWD), 35 parts of LCP, 20 parts of plant indigo dye, 1.5 parts of maleic anhydride, 3 parts of nano silica (average particle size 20-100nm), and 3 parts of amino-modified polysiloxane of Preparation Example 1.

[0051] The above components were premixed at 3000 rpm for 5 minutes, and then added to a twin-screw extruder for melt blending extrusion and granulation to obtain color masterbatch. The temperatures of each zone of the twin-screw extruder were set as follows: Zone 1 335℃~345℃, Zone 2 335℃~345℃, Zone 3 335℃~345℃, Zone 4 335℃~345℃, Zone 5 335℃~345℃, Zone 6 335℃~345℃, Zone 7 330℃~340℃, Zone 8 330℃~340℃, Zone 9 330℃~340℃, and the die head 340℃~350℃.

[0052] A method for preparing PEEK solution-dyed fiber includes mixing the prepared masterbatch with PEEK (brand name 5600G) at a mass ratio of 1:20, mixing them evenly, and then adding the mixture to a single-screw extruder to melt and form a melt before spinning. The temperatures of each zone of the single-screw extruder are set as follows: Zone 1 300℃~310℃, Zone 2 320℃~330℃, Zone 3 330℃~340℃, Zone 4 335℃~345℃, Zone 5 345℃~350℃, and Die Zone 345℃~350℃, to obtain PEEK solution-dyed fiber. The dyed fiber is then heat-treated at 190℃ for 2 hours.

[0053] Comparative Example 1

[0054] PEEK and plant dye indigo were premixed at a mass ratio of 100:1 and then added to a single-screw extruder for melting to form a melt before spinning (the parameters of the twin-screw extruder, spinning parameters, and other parameters not shown are the same as in Example 1).

[0055] Comparative Example 2

[0056] The preparation of the color masterbatch in this case is the same as in Example 1, except that maleic anhydride and nano silica are not added; PEEK solution-dyed fibers are prepared using this color masterbatch according to the method in Example 1.

[0057] Comparative Example 3

[0058] The preparation of the masterbatch in this case is the same as in Example 1, except that maleic anhydride was not added; PEEK solution-dyed fibers were prepared using this masterbatch according to the method in Example 1.

[0059] Comparative Example 4

[0060] The preparation of the color masterbatch in this case is the same as in Example 1, except that no nano-silica is added; PEEK solution-dyed fibers are prepared using this color masterbatch according to the method in Example 1.

[0061] Comparative Example 5

[0062] The preparation of the color masterbatch in this case is the same as in Example 1, except that LCP is not added; PEEK solution-dyed fibers are prepared using this color masterbatch according to the method in Example 1.

[0063] Comparative Example 6

[0064] The preparation of the color masterbatch in this case is the same as in Example 1, except that amino-modified polysiloxane is not used, but α,ω-dihydroxypolydimethylsiloxane is used directly; PEEK solution-dyed fibers are prepared using this color masterbatch according to the method in Example 1.

[0065] Test case

[0066] The performance of the dyed fibers prepared above was tested, and the results are shown in Table 1.

[0067] Table 1 Properties of Colored Fibers

[0068]

[0069] As shown in Table 1, in Comparative Example 1, due to the poor flowability of PEEK, the dye could not be evenly dispersed in PEEK when directly blended with it, resulting in poor spinnability and a low yield. In Comparative Example 2, the masterbatch did not contain maleic anhydride or nano-silica, leading to poor fiber spinnability and low strength. In Comparative Example 3, the masterbatch lacked maleic anhydride, slightly affecting fiber spinnability and resulting in a slightly lower yield, but also lower strength. In Comparative Example 4, the masterbatch lacked nano-silica, resulting in acceptable fiber strength but reduced toughness, leading to filament breakage and a low yield. In Comparative Example 5, the masterbatch did not use liquid crystal polymers, resulting in poor fiber spinnability and a low yield. In Comparative Example 6, the masterbatch used unmodified polysiloxane, which, compared to Example 1, had slightly lower breaking strength, leading to slightly poorer fiber spinnability and a slightly lower yield.

[0070] This invention uses low-melting-point PAEK, and adds plant-based indigo dye with a high thermal decomposition temperature and LCP with extremely low melt viscosity to the low-melting-point PAEK system. It also combines amino-modified polysiloxane to improve melt flowability. It uses maleic anhydride as a chemical compatibilizer and nano-silica as a physical compatibilizer for grafting, so that the masterbatch and the matrix resin are combined to achieve excellent melt flowability, good spinnability, high breaking strength of the filament, and high yield of fiber products.

[0071] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A color masterbatch, characterized in that, Includes the following components by weight: Low melting point PAEK 45-60 parts, 20-35 parts of liquid crystal polymer, 10-20 parts of plant dyes with a thermal decomposition temperature above 350℃ Maleic anhydride 0.5-1.5 parts, 1-3 parts of nano-silica 1-3 parts of amino-modified polysiloxane; The low-melting-point PAEK has a melting point in the range of 300-315℃ and a viscosity of less than 300 Pa·s; the liquid crystal polymer is a thermotropic liquid crystal polymer with a melting temperature in the range of 250-350℃. The method for obtaining the amino-modified polysiloxane is as follows: α,ω-dihydroxypolydimethylsiloxane, aminosiloxane compound, and tetrabutyl titanate were dissolved in benzene-based solvents and reacted at a temperature in the range of 100-140℃ for 2-5 hours under nitrogen protection. Then, the solvent was removed under reduced pressure to obtain amino-modified polysiloxane.

2. The color masterbatch according to claim 1, characterized in that, The plant dye is an indigo dye with a thermal decomposition temperature above 380℃.

3. The color masterbatch according to claim 1, characterized in that, The molecular weight of the α,ω-dihydroxypolydimethylsiloxane is in the range of 5000-12000 g / mol; The aminosiloxane compound is selected from one or more of 3-aminopropyltriethoxysilane, (3-aminopropyl)diethoxyethylsilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane. The mass ratio of the α,ω-dihydroxy polydimethylsiloxane, the aminosiloxane compound, and the tetrabutyl titanate is 100: 5-10: 0.5-1.

4. A color masterbatch according to any one of claims 1-3, characterized in that, The preparation process of the color masterbatch is as follows: the components are premixed at at least 1000 rpm, and then melt-blended, extruded, and granulated.

5. A color masterbatch according to claim 4, characterized in that, The melt blending extrusion is performed using a twin-screw extruder, with the temperatures of each zone set as follows: Zone 1 335℃~345℃, Zone 2 335℃~345℃, Zone 3 335℃~345℃, Zone 4 335℃~345℃, Zone 5 335℃~345℃, Zone 6 335℃~345℃, Zone 7 330℃~340℃, Zone 8 330℃~340℃, Zone 9 330℃~340℃, and die head 340℃~350℃.

6. A method for preparing polyaryletherketone solution-dyed fibers, characterized in that, This includes mixing the color masterbatch described in any one of claims 1-5 with polyaryletherketone and then performing melt spinning to obtain polyaryletherketone solution-dyed fibers; The amount of color masterbatch used is 0.01%-20% of the weight of the polyaryletherketone.

7. The method for preparing polyaryletherketone solution-dyed fibers according to claim 6, characterized in that, The polyaryletherketone is selected from one or more of polyetheretherketone, polyetherketone, polyetherketoneketone, polyetheretherketoneketone, and polyetherketoneetherketoneketone; The melt spinning is performed using a single-screw spinning machine, with the temperatures of each zone set as follows: Zone 1 300℃~310℃, Zone 2 320℃~330℃, Zone 3 330℃~340℃, Zone 4 335℃~345℃, Zone 5 345℃~350℃, and Die Zone 345℃~350℃.

8. The method for preparing polyaryletherketone solution-dyed fibers according to claim 6, characterized in that, The preparation method further includes heat-treating the colored fibers at 150-200℃ for 1-3 hours.

9. Polyaryletherketone solution-dyed fiber, characterized in that, The fiber was prepared using the method described in any one of claims 6-8 for preparing polyaryletherketone solution-dyed fiber.

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