Cationic dyeable polyester masterbatch for pp or pe and process for its preparation

Abstract

This invention discloses a cationic dyeable polyester masterbatch for PP or PE and its preparation method, belonging to the technical field of cationic dyeable masterbatch. It includes the following raw materials by weight: cationic dyeable modified polyester fiber, double-modified halloysite nanotubes, maleic anhydride-grafted polypropylene, chain extender, pentaerythritol stearate, and antioxidant. The above raw materials are mixed evenly in a high-speed mixer, then fed into a twin-screw extruder for melt blending and extrusion granulation to obtain the cationic dyeable polyester masterbatch. The double-modified halloysite nanotubes are prepared by successively modifying halloysite nanotubes with phytic acid and hydrophobizing them with oleic acid. Through this method, the final masterbatch and PP or PE products exhibit good nanofiller dispersibility, dyeing performance, and mechanical property retention.

Description

Technical Field

[0001] This invention relates to the field of cationic dyeable masterbatch technology, specifically to a cationic dyeable polyester masterbatch for PP or PE and its preparation method. Background Technology

[0002] Polypropylene (PP) and polyethylene (PE) are the most widely used varieties among the five major general-purpose plastics. They have advantages such as low density, chemical resistance, excellent processing performance and low price, and are widely used in automotive interiors, home appliances, packaging materials, medical and health care and fiber products.

[0003] However, both PP and PE have nonpolar molecular chains, lacking polar groups that can bind to dye molecules, resulting in extremely poor dyeing properties. Conventional disperse dyes, acid dyes, or cationic dyes are unable to effectively color them. Traditionally, coloring of PP or PE products mainly relies on adding pigments or masterbatches. However, pigment coloring suffers from problems such as insufficient color vibrancy, poor transparency, low color matching flexibility, and uneven pigment dispersion, making it difficult to meet the demands of high-end applications for color richness, dyeing uniformity, and personalized customization.

[0004] Existing technologies have made numerous improvements to cationic dyeable polyester masterbatches. For example, Chinese patent CN118166437A discloses a cationic dyeable matte polyester masterbatch and its preparation method, including the following steps: mixing and extruding a cationic dyeable polyester matrix, modified titanium dioxide, and auxiliaries to obtain a cationic dyeable polyester matte masterbatch; the preparation of the modified titanium dioxide includes: adding zinc salt to titanium dioxide slurry for an inorganic coating reaction to obtain zinc oxide-coated titanium dioxide; and then modifying the zinc oxide-coated titanium dioxide with a coupling agent to obtain modified titanium dioxide. The above invention utilizes zinc ions, which have a weak coordination effect with benzenesulfonate ions, to coat titanium dioxide. Simultaneously, chemically grafting coupling agents onto the titanium dioxide surface and adding appropriate amounts of surfactants and dispersants during masterbatch processing jointly improve the dispersibility of the matting agent titanium dioxide in the cationic dyeable polyester matrix, thereby preparing a masterbatch product suitable for subsequent production and processing.

[0005] However, the following shortcomings still exist in practical applications: The aforementioned comparative documents focus on the matting modification of cationic dyeable polyester fibers. The masterbatch is directly used for polyester fiber spinning with CDP as the matrix. It fails to solve the problem of blending CDP with non-polar matrices such as PP or PE. Its application scope is limited to the field of polyester fibers, and its flexibility and versatility are insufficient.

[0006] Based on this, the present invention designs a cationic dyeable polyester masterbatch for PP or PE and its preparation method to solve the above problems. Summary of the Invention

[0007] In view of the above-mentioned shortcomings of the existing technology, the present invention provides a cationic dyeable polyester masterbatch for PP or PE and a method for preparing the same.

[0008] To achieve the above objectives, the present invention provides the following technical solution: A cationic dyeable polyester masterbatch for PP or PE, comprising the following raw materials: Cationic dyeable modified polyester fiber 85-90 parts, double-modified halloysite nanotubes 5-10 parts, maleic anhydride grafted polypropylene 2-4 parts, chain extender 0.5-1.5 parts, pentaerythritol stearate 0.3-0.5 parts, antioxidant 0.3-0.5 parts; After the above raw materials are mixed evenly in a high-speed mixer, they are fed into a twin-screw extruder for melt blending and extrusion granulation to obtain cationic dyeable polyester masterbatch. The dual-modified halloysite nanotubes were prepared by successively modifying halloysite nanotubes with phytic acid and hydrophobizing them with oleic acid. The specific process is as follows: After pretreatment of halloysite nanotubes, activated halloysite nanotubes are obtained. The activated halloysite nanotubes are dispersed in deionized water and trisodium citrate is added for ultrasonic treatment. Then, phytic acid solution of aluminum chloride or ferric sulfate is added and reacted under acidic conditions. After the reaction is completed, the halloysite is obtained by centrifugation, washing and drying. Phytic acid-modified halloysite was dispersed in anhydrous ethanol, followed by the addition of oleic acid, γ-aminopropyltriethoxysilane and p-toluenesulfonic acid. After the reflux reaction was completed, the mixture was centrifuged, washed and dried to obtain double-modified halloysite nanotubes.

[0009] Furthermore, the antioxidants are antioxidant 1010 and antioxidant 168, and the chain extender is chain extender ADR-4468.

[0010] Furthermore, the amounts of antioxidants in the raw materials, by weight, are as follows: antioxidant 1010 0.2~0.3 parts, antioxidant 168 0.1~0.2 parts.

[0011] To better achieve the objectives of this invention, this invention also provides a method for preparing cationic dyeable polyester masterbatch for PP or PE, specifically including the following steps: I. Preparation of Double-Modified Halloysite Nanotubes (1) Activation of halloysite nanotubes Activated halloysite nanotubes were obtained by pretreatment of halloysite nanotubes. (2) Phytic acid modification treatment Activated halloysite nanotubes were dispersed in deionized water and subjected to ultrasonic treatment with the addition of trisodium citrate. Then, a phytic acid solution of aluminum chloride or ferric sulfate was added and reacted under acidic conditions. After the reaction was completed, the halloysite was obtained by centrifugation, washing and drying. The acidic conditions specifically involve adjusting the pH to 3.0-4.5 with glacial acetic acid, followed by a water bath reaction at 55-65°C for 4-8 hours after pH adjustment. (3) Oleic acid hydrophobication treatment Phytic acid-modified halloysite was dispersed in anhydrous ethanol, followed by the addition of oleic acid, γ-aminopropyltriethoxysilane and p-toluenesulfonic acid. After the reflux reaction was completed, the mixture was centrifuged, washed and dried to obtain double-modified halloysite nanotubes. The reaction conditions are: reflux reaction at 75~85℃ for 4~8 hours under nitrogen protection, and stirring speed of 300~500 r / min during the reaction process; II. Preparation of cationic dyeable polyester masterbatch for PP or PE (1) Weighing of raw materials Weigh the raw materials according to the following parts by weight: 85-90 parts of cationic dyeable modified polyester fiber, 5-10 parts of double-modified halloysite nanotubes, 2-4 parts of maleic anhydride grafted polypropylene, 0.5-1.5 parts of chain extender ADR-4468, 0.3-0.5 parts of pentaerythritol stearate, 0.2-0.3 parts of antioxidant 1010 and 0.1-0.2 parts of antioxidant 168; (2) Preparation of dyeable masterbatch After the above raw materials are mixed evenly in a high-speed mixer, they are fed into a twin-screw extruder for melt blending and extrusion granulation to obtain cationic dyeable polyester masterbatch.

[0012] Furthermore, in the preparation process of dual-modified halloysite nanotubes, the specific steps for activating the halloysite nanotubes are as follows: Halloysite nanotubes were vacuum dried at 80-90℃ for 10-12 hours to obtain dried HNTs; The dried HNTs were dispersed in a 0.3-0.8 mol / L hydrochloric acid solution at a solid-liquid ratio of 1:10-20. The solution was ultrasonically treated for 20-40 minutes at an ultrasonic power of 200-400 W and a frequency of 40-60 kHz. After ultrasonic treatment, the HNTs were repeatedly centrifuged and washed with deionized water until the pH reached 5-6. After washing, the HNTs were vacuum dried at 70-90℃ for 10-14 hours. After drying, the HNTs were ground and passed through a 150-250 mesh sieve to obtain activated HNTs.

[0013] Furthermore, in the preparation process of dual-modified halloysite nanotubes, the specific steps of phytic acid modification are as follows: Activated HNTs were dispersed in deionized water at a solid-liquid ratio of 1:15-25, and 1.5-2.5% of trisodium citrate by mass of HNTs was added. The mixture was then sonicated for 20-40 minutes at an ultrasonic power of 150-300 W and a frequency of 40-50 kHz. After sonication, add 25-35% phytic acid by mass of HNTs, and pre-add 1-5 mmol / L aluminum chloride or ferric sulfate to the phytic acid solution. Adjust the pH to 3.0-4.5 with glacial acetic acid. After pH adjustment, react in a water bath at 55-65℃ for 4-8 hours. Maintain mechanical stirring during the reaction at a speed of 300-500 r / min. After the reaction was completed, the mixture was centrifuged at a speed of 8000~12000 r / min. After centrifugation, the mixture was washed with deionized water until the pH reached 6.5~7.5, and then vacuum dried at 55~65℃ for 20~28 hours to obtain PA-HNTs.

[0014] Furthermore, in the preparation of dual-modified halloysite nanotubes, the specific steps of the oleic acid hydrophobication treatment are as follows: PA-HNTs were dispersed in anhydrous ethanol at a solid-liquid ratio of 1:10~20. Oleic acid (5~8% by mass of PA-HNTs), γ-aminopropyltriethoxysilane (1~2% by mass of PA-HNTs), and p-toluenesulfonic acid (0.8~1.5% by mass of oleic acid) were added. The mixture was refluxed at 75~85℃ for 4~8 hours under nitrogen protection, with a stirring speed of 300~500 r / min during the reaction. After the reaction was completed, the mixture was centrifuged at a speed of 8000~12000 r / min. After centrifugation, the mixture was washed 3~5 times with anhydrous ethanol. After washing, it was vacuum dried at 55~65℃ for 10~14 hours. After drying, it was ground through a 150~250 mesh sieve to obtain double-modified halloysite nanotubes.

[0015] Furthermore, in the preparation process of cationic dyeable polyester masterbatch for PP or PE, the specific parameters are as follows: Add the raw materials to a high-speed mixer and premix for 8 to 15 minutes at a temperature of 75 to 85°C and a speed of 1000 to 1500 r / min to obtain a premix. The premixed material is fed into a co-rotating twin-screw extruder with a screw speed of 180~280 r / min, a feeding frequency of 15~25Hz, and a vacuum degree of -0.06 to -0.09 MPa. The extruded melt is cooled, dried, granulated, and sieved to obtain cationic dyeable polyester masterbatch.

[0016] To better achieve the objectives of this invention, this invention also provides a cationic dyeable polyester masterbatch for PP or PE prepared by the above preparation method.

[0017] To better achieve the objectives of this invention, the present invention also provides an application of cationic dyeable polyester masterbatch for PP or PE, the specific process of which is as follows: Cationic dyeable polyester masterbatch is added to PP or PE blends at a ratio of 5-15 wt%, along with a compatibilizer. The materials are then fed into a high-speed mixer and mixed evenly. The mixture is then fed into a twin-screw extruder for melt blending, extrusion, and granulation to obtain cationic dyeable PP or PE products.

[0018] Compared with the prior art, the beneficial effects of this invention are as follows: 1. This invention achieves the cationic dyeability of PP or PE nonpolar matrix by adding specially modified cationic dyeable polyester masterbatch, which expands the application scope of cationic dyeable technology in the field of general plastics and has good matrix universality and process flexibility. 2. In the preparation of cationic dyeable polyester masterbatch, phytic acid and oleic acid are used to perform dual modification of halloysite nanotubes, so that the final masterbatch and PP or PE products have good nanofiller dispersibility, dyeing performance and mechanical property retention. 3. In the preparation of dual-modified halloysite nanotubes, the phytic acid modification process and the oleic acid hydrophobication process have a synergistic effect on the retention rate of tensile strength and the dispersion particle size D90 of HNTs in the masterbatch. That is, when the two work together, they have a synergistic effect on improving the dispersibility and mechanical properties of the filler. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. 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.

[0020] Example 1: A method for preparing a cationic dyeable polyester masterbatch, specifically including the following steps: I. Preparation of Double-Modified Halloysite Nanotubes (1) Activation of halloysite nanotubes Halloysite nanotubes (HNTs) were vacuum dried at 80°C for 12 hours to remove physically adsorbed water, thus obtaining dried HNTs. The dried HNTs were dispersed in a 0.8 mol / L hydrochloric acid solution at a solid-liquid ratio of 1:10. The solution was ultrasonically treated for 20 minutes at an ultrasonic power of 200 W and a frequency of 60 kHz. After ultrasonic treatment, the HNTs were repeatedly centrifuged and washed with deionized water until the pH reached 6. After washing, the HNTs were vacuum dried at 70°C for 14 hours. After drying, the HNTs were ground and passed through a 150-mesh sieve to obtain activated HNTs.

[0021] (2) Phytic acid modification treatment Activated HNTs were dispersed in deionized water at a solid-liquid ratio of 1:15, and 2.5% of the mass of activated HNTs in trisodium citrate was added. The mixture was then sonicated for 20 minutes at an ultrasonic power of 150 W and a frequency of 50 kHz. After sonication, phytic acid accounting for 25% of the mass of activated HNTs was added, and 5 mmol / L aluminum chloride was added to the phytic acid solution beforehand. The pH was adjusted to 3.0 with glacial acetic acid. After pH adjustment, the reaction was carried out in a water bath at 65°C for 4 hours. During the reaction, mechanical stirring was maintained at a stirring speed of 500 r / min. After the reaction was completed, the mixture was centrifuged at 8000 r / min. After centrifugation, the mixture was washed with deionized water until the pH reached 7.5. It was then vacuum dried at 55℃ for 28 hours to obtain phytic acid modified halloysite (PA-HNTs).

[0022] (3) Oleic acid hydrophobication treatment PA-HNTs were dispersed in anhydrous ethanol at a solid-liquid ratio of 1:10. Oleic acid (8% by mass of PA-HNTs), γ-aminopropyltriethoxysilane (APTES) (1% by mass of PA-HNTs), and p-toluenesulfonic acid (TsOH) (1.5% by mass of oleic acid) were added. The mixture was refluxed at 75°C for 8 hours under nitrogen protection, with a stirring speed of 300 r / min during the reaction. After the reaction was completed, the mixture was centrifuged at 8000 r / min. After centrifugation, the mixture was washed 5 times with anhydrous ethanol. After washing, it was vacuum dried at 55℃ for 14 hours. After drying, it was ground through a 150-mesh sieve to obtain double-modified halloysite nanotubes.

[0023] II. Preparation of cationic dyeable polyester masterbatch for PP or PE (1) Weighing of raw materials Weigh the raw materials according to the following parts by weight: 85 parts of cationic dyeable modified polyester fiber (CDP), 10 parts of double-modified halloysite nanotubes, 2 parts of maleic anhydride grafted polypropylene (MAH-g-PP), 1.5 parts of chain extender (BASF chain extender ADR-4468), 0.3 parts of pentaerythritol stearate (PETS), 0.3 parts of antioxidant 1010 and 0.1 parts of antioxidant 168; (2) Preparation of dyeable masterbatch The above raw materials were added to a high-speed mixer and premixed for 8 minutes at a temperature of 75°C and a speed of 1500 r / min to obtain a premix. The premixed material is fed into a co-rotating twin-screw extruder with a screw speed of 180 r / min, a feeding frequency of 25 Hz, and a vacuum degree of -0.06 MPa. The extruded melt is cooled, dried, granulated, and sieved to obtain cationic dyeable polyester masterbatch.

[0024] III. Application of Cationic Dyeable Polyester Masterbatch The above-mentioned cationic dyeable polyester masterbatch is added to PP at a ratio of 5 wt%, along with a compatibilizer. The materials are then fed into a high-speed mixer and mixed evenly. The mixture is then fed into a twin-screw extruder for melt blending, extrusion, and granulation to obtain cationic dyeable PP products.

[0025] Example 2: A method for preparing a cationic dyeable polyester masterbatch, specifically including the following steps: I. Preparation of Double-Modified Halloysite Nanotubes (1) Activation of halloysite nanotubes The HNTs were vacuum dried at 90°C for 10 hours to remove physically adsorbed water, thus obtaining dried HNTs. The dried HNTs were dispersed in a 0.3 mol / L hydrochloric acid solution at a solid-liquid ratio of 1:20. The solution was ultrasonically treated for 40 minutes at an ultrasonic power of 400 W and a frequency of 40 kHz. After ultrasonic treatment, the HNTs were repeatedly centrifuged and washed with deionized water until the pH reached 5. After washing, the HNTs were vacuum dried at 90°C for 10 hours. After drying, the HNTs were ground and passed through a 250-mesh sieve to obtain activated HNTs.

[0026] (2) Phytic acid modification treatment Activated HNTs were dispersed in deionized water at a solid-liquid ratio of 1:25, and 1.5% of the mass of activated HNTs trisodium citrate was added. The mixture was then sonicated for 40 minutes at an ultrasonic power of 300 W and a frequency of 40 kHz. After sonication, phytic acid accounting for 35% of the mass of activated HNTs was added, and 1 mmol / L of ferric sulfate was added to the phytic acid solution beforehand. The pH was adjusted to 4.5 with glacial acetic acid. After pH adjustment, the reaction was carried out in a water bath at 55°C for 8 hours. During the reaction, mechanical stirring was maintained at a stirring speed of 300 r / min. After the reaction was completed, the mixture was centrifuged at 12,000 r / min. After centrifugation, the mixture was washed with deionized water until the pH reached 6.5, and then vacuum dried at 65°C for 20 hours to obtain PA-HNTs.

[0027] (3) Oleic acid hydrophobication treatment PA-HNTs were dispersed in anhydrous ethanol at a solid-liquid ratio of 1:20. Oleic acid (5% by mass of PA-HNTs), APTES (2% by mass of PA-HNTs), and TsOH (0.8% by mass of oleic acid) were added. The mixture was refluxed at 85°C for 4 hours under nitrogen protection, with a stirring speed of 500 r / min during the reaction. After the reaction was completed, the mixture was centrifuged at 12,000 r / min. After centrifugation, the mixture was washed three times with anhydrous ethanol. After washing, it was vacuum dried at 65°C for 10 hours. After drying, it was ground through a 250-mesh sieve to obtain double-modified halloysite nanotubes.

[0028] II. Preparation of cationic dyeable polyester masterbatch for PP or PE (1) Weighing of raw materials Weigh the raw materials according to the following parts by weight: 90 parts CDP, 5 parts double-modified halloysite nanotubes, 4 parts MAH-g-PP, 0.5 parts chain extender ADR-4468, 0.5 parts PETS, 0.2 parts antioxidant 1010 and 0.2 parts antioxidant 168; (2) Preparation of dyeable masterbatch The above raw materials are added to a high-speed mixer and premixed for 15 minutes at a temperature of 85℃ and a speed of 1000 r / min to obtain a premix. The premixed material is fed into a co-rotating twin-screw extruder with a screw speed of 280 r / min, a feeding frequency of 15 Hz, and a vacuum degree of -0.09 MPa. The extruded melt is cooled, dried, granulated, and sieved to obtain cationic dyeable polyester masterbatch.

[0029] III. Application of Cationic Dyeable Polyester Masterbatch The above-mentioned cationic dyeable polyester masterbatch is added to PE at a ratio of 15wt%, along with a compatibilizer. The materials are then fed into a high-speed mixer and mixed evenly. The mixture is then fed into a twin-screw extruder for melt blending, extrusion, and granulation to obtain cationic dyeable PE products.

[0030] Example 3: A method for preparing a cationic dyeable polyester masterbatch, specifically including the following steps: I. Preparation of Double-Modified Halloysite Nanotubes (1) Activation of halloysite nanotubes HNTs were vacuum dried at 85°C for 10.5 hours to remove physically adsorbed water, resulting in dried HNTs. The dried HNTs were dispersed in a 0.5 mol / L hydrochloric acid solution at a solid-liquid ratio of 1:15. The solution was ultrasonically treated for 30 minutes at an ultrasonic power of 300 W and a frequency of 50 kHz. After ultrasonic treatment, the solution was repeatedly centrifuged and washed with deionized water until the pH reached 5.5. After washing, the solution was vacuum dried at 80°C for 12 hours. After drying, the solution was ground and passed through a 200-mesh sieve to obtain activated HNTs.

[0031] (2) Phytic acid modification treatment Activated HNTs were dispersed in deionized water at a solid-liquid ratio of 1:20, and trisodium citrate was added at a mass of 2% of the activated HNTs. The mixture was then sonicated for 30 minutes at an ultrasonic power of 200 W and a frequency of 45 kHz. After sonication, phytic acid accounting for 30% of the mass of activated HNTs was added, and 2.5 mmol / L aluminum chloride was added to the phytic acid solution beforehand. The pH was adjusted to 3.5 with glacial acetic acid. After pH adjustment, the reaction was carried out in a water bath at 60°C for 6 hours. During the reaction, mechanical stirring was maintained at a stirring speed of 400 r / min. After the reaction was completed, the mixture was centrifuged at 10,000 r / min. After centrifugation, the mixture was washed with deionized water until the pH reached 7.0, and then vacuum dried at 60°C for 24 hours to obtain PA-HNTs.

[0032] (3) Oleic acid hydrophobication treatment PA-HNTs were dispersed in anhydrous ethanol at a solid-liquid ratio of 1:15. Oleic acid (6.5% by mass of PA-HNTs), APTES (1.5% by mass of PA-HNTs), and TsOH (1.1% by mass of oleic acid) were added. The mixture was refluxed at 80°C for 6 hours under nitrogen protection, with a stirring speed of 350 r / min during the reaction. After the reaction was completed, the mixture was centrifuged at 9500 r / min. After centrifugation, the mixture was washed four times with anhydrous ethanol. After washing, it was vacuum dried at 60℃ for 12 hours. After drying, it was ground through a 200-mesh sieve to obtain double-modified halloysite nanotubes.

[0033] II. Preparation of cationic dyeable polyester masterbatch for PP or PE (1) Weighing of raw materials Weigh the raw materials according to the following weight proportions: 87 parts CDP, 8 parts double-modified halloysite nanotubes, 3 parts MAH-g-PP, 1 part chain extender ADR-4468, 0.4 parts PETS, 0.25 parts antioxidant 1010 and 0.15 parts antioxidant 168; (2) Preparation of dyeable masterbatch The above raw materials were added to a high-speed mixer and premixed for 12 minutes at a temperature of 80°C and a speed of 1300 r / min to obtain a premix. The premixed material is fed into a co-rotating twin-screw extruder with a screw speed of 245 r / min, a feeding frequency of 20 Hz, and a vacuum degree of -0.07 MPa. The extruded melt is cooled, dried, granulated, and sieved to obtain cationic dyeable polyester masterbatch.

[0034] III. Application of Cationic Dyeable Polyester Masterbatch The above-mentioned cationic dyeable polyester masterbatch is added to PP at a ratio of 9.5 wt%, along with a compatibilizer. The materials are then fed into a high-speed mixer and mixed evenly. The mixture is then fed into a twin-screw extruder for melt blending, extrusion, and granulation to obtain cationic dyeable PP products.

[0035] Comparative Example 1: Compared with Example 3, the difference is that trisodium citrate was not added in the phytic acid modification treatment, and the other steps were the same as in Example 3.

[0036] Comparative Example 2: Compared with Example 3, the difference is that TsOH was not added during the oleic acid hydrophobication treatment, and the other steps were the same as in Example 3.

[0037] Comparative Example 3: Compared with Example 3, the difference is that trisodium citrate was not added in the phytic acid modification treatment, and TsOH was not added in the oleic acid hydrophobication treatment. The other steps were the same as in Example 3.

[0038] Comparative Example 4: Compared with Example 3, the difference is that in the preparation process of the dual-modified halloysite nanotubes, oleic acid hydrophobication treatment was performed first, followed by phytic acid modification treatment.

[0039] Experimental example: The masterbatches and PP or PE products prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to the following performance tests, and the test results are shown in Table 1.

[0040] Dispersed particle size of HNTs in masterbatch D90 (dispersed particle size, μm): The particle size value corresponding to when the cumulative distribution percentage of HNTs particles in the masterbatch reaches 90%, that is, 90% of the particles have a particle size smaller than this value. Dyeing uniformity (grade): The reference standard is GB / T 250-2008; K / S value: The reference standard is GB / T 6688-2008; Tensile strength retention rate (%): Pure PP or PE and PP or PE with added masterbatch are injection molded into standard dumbbell-shaped specimens using the same process. The specimens are tested at a tensile speed of 50 mm / min until they break, and the tensile strength is recorded. Tensile strength retention rate refers to the percentage of tensile strength retained in PP or PE products with added masterbatch and molding compared with pure PP or PE products without added masterbatch. The reference standard is GB / T 1040.2-2022. Color fastness to washing (grade): The reference standard is GB / T 3921-2008.

[0041] Table 1. Performance test results of the masterbatches and PP or PE products prepared in Examples 1-3 and Comparative Examples 1-4

[0042] As can be seen from Examples 1-3, the dispersion particle size D90 of the double-modified halloysite nanotubes in the masterbatch is in the range of 1.5-2.2 μm, the dyeing uniformity is between grade 4.0 and 5.0, the K / S value is between 16.2 and 21.0, the tensile strength retention rate is between 88% and 96%, and the color fastness to washing is between grade 3.5 and 4.5. The above data show that the cationic dyeable polyester masterbatch prepared by the present invention has excellent nanofiller dispersibility, good dyeing performance and mechanical property retention rate, among which the performance indicators of Example 3 are the best.

[0043] As shown in Example 3 and Comparative Example 1, when no trisodium citrate was added during the phytic acid modification treatment, the dispersed particle size of HNTs in the prepared masterbatch increased from 1.5 μm to 3.2 μm, the K / S value decreased from 21.0 to 13.5, and the tensile strength retention rate decreased from 96% to 82%. This indicates that the addition of trisodium citrate helps the phytic acid to be uniformly grafted on the surface of halloysite nanotubes, improves the dispersibility of the filler, and thus enhances the dyeing depth and mechanical properties.

[0044] As shown in Example 3 and Comparative Example 2, when p-toluenesulfonic acid is not added during the hydrophobication treatment of oleic acid, the dispersed particle size of HNTs in the prepared masterbatch increases from 1.5 μm to 2.9 μm, the dyeing uniformity decreases from grade 5.0 to grade 3.5, and the color fastness to washing decreases from grade 4.5 to grade 3.0. This indicates that TsOH, as an esterification catalyst, can effectively promote the grafting reaction between oleic acid and halloysite surface, improve the hydrophobic modification effect, and thus improve the dispersion uniformity and color fastness of fillers in polyester matrix.

[0045] As can be seen from Example 3 and Comparative Example 3, the phytic acid modification process and the oleic acid hydrophobication process have a synergistic effect on the tensile strength retention rate and the HNTs dispersion particle size D90 in the masterbatch. That is, when the two work together, they have a synergistic effect on improving the dispersibility and mechanical properties of the filler.

[0046] As shown in Example 3 and Comparative Example 4, when oleic acid hydrophobication treatment is performed first, followed by phytic acid modification treatment, the dispersed particle size of HNTs in the prepared masterbatch increases from 1.5 μm to 4.8 μm, the dyeing uniformity decreases from grade 5.0 to grade 3.0, and the K / S value decreases from 21.0 to 11.0. This indicates that the modification order is crucial to the final effect. The order of phytic acid modification followed by oleic acid hydrophobication treatment is more conducive to the formation of a stable dual-modified structure. If the order is reversed, phytic acid is difficult to effectively graft onto the hydrophobic halloysite surface, resulting in a significant decrease in the modification effect.

[0047] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A cationic dyeable polyester masterbatch for PP or PE, characterized in that, Including the following raw materials: Cationic dyeable modified polyester fiber 85-90 parts, double-modified halloysite nanotubes 5-10 parts, maleic anhydride grafted polypropylene 2-4 parts, chain extender 0.5-1.5 parts, pentaerythritol stearate 0.3-0.5 parts, antioxidant 0.3-0.5 parts; After the above raw materials are mixed evenly in a high-speed mixer, they are fed into a twin-screw extruder for melt blending and extrusion granulation to obtain cationic dyeable polyester masterbatch. The dual-modified halloysite nanotubes were prepared by successively modifying halloysite nanotubes with phytic acid and hydrophobizing them with oleic acid. The specific process is as follows: After pretreatment of halloysite nanotubes, activated halloysite nanotubes are obtained. The activated halloysite nanotubes are dispersed in deionized water and trisodium citrate is added for ultrasonic treatment. Then, phytic acid solution of aluminum chloride or ferric sulfate is added and reacted under acidic conditions. After the reaction is completed, the halloysite is obtained by centrifugation, washing and drying. Phytic acid-modified halloysite was dispersed in anhydrous ethanol, followed by the addition of oleic acid, γ-aminopropyltriethoxysilane and p-toluenesulfonic acid. After the reflux reaction was completed, the mixture was centrifuged, washed and dried to obtain double-modified halloysite nanotubes.

2. The cationic dyeable polyester masterbatch for PP or PE according to claim 1, characterized in that, The antioxidants are antioxidant 1010 and antioxidant 168, and the chain extender is chain extender ADR-4468.

3. The cationic dyeable polyester masterbatch for PP or PE according to claim 2, characterized in that, The amounts of antioxidants in the raw materials, by weight, are as follows: Antioxidant 1010 0.2~0.3 parts, Antioxidant 168 0.1~0.2 parts.

4. A method for preparing cationic dyeable polyester masterbatch for PP or PE according to any one of claims 1 to 3, characterized in that, Specifically, the following steps are included: I. Preparation of Double-Modified Halloysite Nanotubes (1) Activation of halloysite nanotubes Activated halloysite nanotubes were obtained by pretreatment of halloysite nanotubes. (2) Phytic acid modification treatment Activated halloysite nanotubes were dispersed in deionized water and subjected to ultrasonic treatment with the addition of trisodium citrate. Then, a phytic acid solution of aluminum chloride or ferric sulfate was added and reacted under acidic conditions. After the reaction was completed, the halloysite was obtained by centrifugation, washing and drying. The acidic conditions specifically involve adjusting the pH to 3.0-4.5 with glacial acetic acid, followed by a water bath reaction at 55-65°C for 4-8 hours after pH adjustment. (3) Oleic acid hydrophobication treatment Phytic acid-modified halloysite was dispersed in anhydrous ethanol, followed by the addition of oleic acid, γ-aminopropyltriethoxysilane and p-toluenesulfonic acid. After the reflux reaction was completed, the mixture was centrifuged, washed and dried to obtain double-modified halloysite nanotubes. The reaction conditions are: reflux reaction at 75~85℃ for 4~8 hours under nitrogen protection, and stirring speed of 300~500 r / min during the reaction process; II. Preparation of cationic dyeable polyester masterbatch for PP or PE (1) Weighing of raw materials Weigh the raw materials according to the following parts by weight: 85-90 parts of cationic dyeable modified polyester fiber, 5-10 parts of double-modified halloysite nanotubes, 2-4 parts of maleic anhydride grafted polypropylene, 0.5-1.5 parts of chain extender ADR-4468, 0.3-0.5 parts of pentaerythritol stearate, 0.2-0.3 parts of antioxidant 1010 and 0.1-0.2 parts of antioxidant 168; (2) Preparation of dyeable masterbatch After the above raw materials are mixed evenly in a high-speed mixer, they are fed into a twin-screw extruder for melt blending and extrusion granulation to obtain cationic dyeable polyester masterbatch.

5. The method for preparing cationic dyeable polyester masterbatch for PP or PE according to claim 4, characterized in that, In the preparation of dual-modified halloysite nanotubes, the specific activation steps of the halloysite nanotubes are as follows: Halloysite nanotubes were vacuum dried at 80-90℃ for 10-12 hours to obtain dried HNTs; The dried HNTs were dispersed in a 0.3-0.8 mol / L hydrochloric acid solution at a solid-liquid ratio of 1:10-20. The solution was ultrasonically treated for 20-40 minutes at an ultrasonic power of 200-400 W and a frequency of 40-60 kHz. After ultrasonic treatment, the HNTs were repeatedly centrifuged and washed with deionized water until the pH reached 5-6. After washing, the HNTs were vacuum dried at 70-90℃ for 10-14 hours. After drying, the HNTs were ground and passed through a 150-250 mesh sieve to obtain activated HNTs.

6. The method for preparing cationic dyeable polyester masterbatch for PP or PE according to claim 4, characterized in that, In the preparation of dual-modified halloysite nanotubes, the specific steps of phytic acid modification are as follows: Activated HNTs were dispersed in deionized water at a solid-liquid ratio of 1:15-25, and 1.5-2.5% of trisodium citrate by mass of HNTs was added. The mixture was then sonicated for 20-40 minutes at an ultrasonic power of 150-300 W and a frequency of 40-50 kHz. After sonication, add 25-35% phytic acid by mass of HNTs, and pre-add 1-5 mmol / L aluminum chloride or ferric sulfate to the phytic acid solution. Adjust the pH to 3.0-4.5 with glacial acetic acid. After pH adjustment, react in a water bath at 55-65℃ for 4-8 hours. Maintain mechanical stirring during the reaction at a speed of 300-500 r / min. After the reaction was completed, the mixture was centrifuged at a speed of 8000~12000 r / min. After centrifugation, the mixture was washed with deionized water until the pH reached 6.5~7.5, and then vacuum dried at 55~65℃ for 20~28 hours to obtain PA-HNTs.

7. The method for preparing cationic dyeable polyester masterbatch for PP or PE according to claim 4, characterized in that, In the preparation of dual-modified halloysite nanotubes, the specific steps of oleic acid hydrophobication treatment are as follows: PA-HNTs were dispersed in anhydrous ethanol at a solid-liquid ratio of 1:10~20. Oleic acid (5~8% by mass of PA-HNTs), γ-aminopropyltriethoxysilane (1~2% by mass of PA-HNTs), and p-toluenesulfonic acid (0.8~1.5% by mass of oleic acid) were added. The mixture was refluxed at 75~85℃ for 4~8 hours under nitrogen protection, with a stirring speed of 300~500 r / min during the reaction. After the reaction was completed, the mixture was centrifuged at a speed of 8000~12000 r / min. After centrifugation, the mixture was washed 3~5 times with anhydrous ethanol. After washing, it was vacuum dried at 55~65℃ for 10~14 hours. After drying, it was ground through a 150~250 mesh sieve to obtain double-modified halloysite nanotubes.

8. The method for preparing cationic dyeable polyester masterbatch for PP or PE according to claim 4, characterized in that, In the preparation process of cationic dyeable polyester masterbatch for PP or PE, the specific parameters are as follows: Add the raw materials to a high-speed mixer and premix for 8 to 15 minutes at a temperature of 75 to 85°C and a speed of 1000 to 1500 r / min to obtain a premix. The premixed material is fed into a co-rotating twin-screw extruder with a screw speed of 180~280 r / min, a feeding frequency of 15~25 Hz, and a vacuum degree of -0.06 to -0.09 MPa. The extruded melt is cooled, dried, granulated, and sieved to obtain cationic dyeable polyester masterbatch.

9. A cationic dyeable polyester masterbatch for PP or PE prepared by the preparation method according to any one of claims 4 to 8.

10. An application of the cationic dyeable polyester masterbatch for PP or PE according to any one of claims 1 to 3, characterized in that, The specific process is as follows: Cationic dyeable polyester masterbatch is added to PP or PE blends at a ratio of 5-15 wt%, along with a compatibilizer. The materials are then fed into a high-speed mixer and mixed evenly. The mixture is then fed into a twin-screw extruder for melt blending, extrusion, and granulation to obtain cationic dyeable PP or PE products.

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