A high-efficiency polyester masterbatch and its preparation method

Abstract

This invention discloses a high-efficiency polyester masterbatch and its preparation method, relating to the field of polyester masterbatch technology. A high-efficiency polyester masterbatch is prepared from raw materials comprising the following parts by weight: 40-70 parts polyamide carrier, 20-50 parts colorant, 5-15 parts dispersant, 1-5 parts lubricant, and 0.5-3 parts antioxidant. This invention employs a special antioxidant designed specifically for polyamide carriers, improving compatibility with the carrier based on the principle of "like dissolves like," fundamentally solving the problem of uneven dispersion and "antioxidant blind spots" formed by traditional antioxidants. Simultaneously, the high thermal stability of the antioxidant molecular structure inhibits volatilization and migration during processing, resulting in a longer-lasting antioxidant protection effect on polyester products. This effectively reduces yellowing and color difference problems caused by oxidation during processing and use.

Description

Technical Field

[0001] This invention relates to the field of polyester masterbatch technology, specifically to a high-efficiency polyester masterbatch and its preparation method. Background Technology

[0002] Polyester, with its excellent mechanical strength, weather resistance, and molding processability, has become a core substrate in textiles, packaging, engineering plastics, and other fields. As a key material for coloring polyester, the performance of color masterbatch directly determines the appearance stability and service life of the final product. Oxidation resistance is one of the core indicators restricting the quality of color masterbatch. During extrusion and spinning processes at 200-250℃, and when finished products are used outdoors or in high-temperature environments, polyester is prone to react with oxygen, causing molecular chain oxidative degradation. This leads to yellowing, color depth reduction, and even a significant decrease in mechanical properties (such as tensile strength and elongation at break).

[0003] Currently, most polyester masterbatches use hindered phenolic and phosphite-based traditional antioxidants, which have significant technical shortcomings. On the one hand, these antioxidants have poor compatibility with the polyamide carriers commonly used in masterbatches, and are prone to uneven dispersion during high-speed mixing and melt extrusion, forming local "antioxidant blind spots." They are also prone to volatilization or migration to the product surface at high temperatures, causing the antioxidant protection effect to decay rapidly over time. On the other hand, the antioxidant efficiency is difficult to meet high-end requirements. For example, outdoor polyester fabrics need to withstand long-term UV-oxygen synergistic aging, and polyester for food packaging needs to maintain color stability after high-temperature sterilization. Traditional masterbatches often cause a significant drop in color after 3-6 months of use due to insufficient antioxidant resistance, which seriously affects the appearance of the product.

[0004] Furthermore, existing formulations often exhibit an antagonistic effect between colorants (such as phthalocyanine and quinacridone pigments) and traditional antioxidants. Some pigments can catalyze the oxidation process, further accelerating product degradation. As downstream industries demand higher weather resistance and durability from polyester products, the oxidation resistance deficiencies of traditional masterbatches have become a key bottleneck restricting the application of polyester materials in high-end fields (such as outdoor building materials and medical packaging). Therefore, there is an urgent need to develop polyester masterbatch technologies that are compatible with polyamide carriers, offer high antioxidant efficiency, and provide long-term stability. Summary of the Invention

[0005] The purpose of this invention is to address the problems of insufficient oxidation resistance of existing polyester masterbatches, poor compatibility between traditional antioxidants and polyamide carriers, easy volatility and migration, and antagonistic effects with colorants. This invention provides a high-efficiency polyester masterbatch that adapts the antioxidant to the carrier, disperses it evenly, provides long-lasting and stable antioxidant effects, avoids adverse effects with colorants, improves the processing stability of the masterbatch, extends the color retention life of polyester products, and meets the needs of high-end fields.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a high-efficiency polyester masterbatch, which is prepared from raw materials containing the following parts by weight: 40-70 parts of polyamide carrier, 20-50 parts of colorant, 5-15 parts of dispersant, 1-5 parts of lubricant, and 0.5-3 parts of antioxidant.

[0007] The antioxidant is a compound represented by Formula 1;

[0008] Equation 1 is as follows: ;

[0009] R1 in Formula 1 is a substituent;

[0010] R1 is selected from any one of the following: fluorine, trifluoromethyl, cyano, alkyl with 1-5 carbon atoms, and alkoxy with 1-5 carbon atoms.

[0011] Furthermore, the polyamide carrier is one or a mixture of several of polyamide 6 (PA6), polyamide 66 (PA66), and polyamide 1010 (PA1010).

[0012] Furthermore, the colorant is one or a mixture of several of the following: high-pigment carbon black, phthalocyanine blue, phthalocyanine green, permanent red, permanent yellow, quinacridone red, and isoindolinone yellow.

[0013] Furthermore, the dispersant is one or a mixture of several of the following: polyethylene wax, oxidized polyethylene wax, polypropylene wax, EVA wax, zinc stearate, and calcium stearate.

[0014] Furthermore, the lubricant is one or a mixture of several of stearic acid, stearamide, oleamide, and ethylene bis-stearamide.

[0015] Furthermore, the antioxidant is any one of the compounds described below:

[0016] ;

[0017] ;

[0018] ;

[0019] .

[0020] A method for preparing a high-efficiency polyester masterbatch includes the following steps:

[0021] (1) Premixing: The polyamide carrier, colorant, dispersant, lubricant and antioxidant are added to a mixer and mixed at a speed of 600-1200 r / min for 30-45 minutes to obtain a premix;

[0022] (2) Melt extrusion: The premixed material is fed into a twin-screw extruder for melt blending and extrusion granulation. The temperature of each section of the twin-screw extruder is set as follows: Zone 1 200-220℃, Zone 2 220-240℃, Zone 3 240-250℃, Zone 4 245-255℃, Die head 245-255℃, and the screw speed is 200-400r / min.

[0023] (3) Cooling, pelletizing and drying: The extruded strip material is cooled by a water tank, then pelletized by a pelletizer and dried to obtain the high-efficiency polyester masterbatch.

[0024] Furthermore, the mixing temperature of the mixer in step (1) is 40-60℃.

[0025] Furthermore, in step (1), the mixing is first carried out at 600 rpm for 15 minutes, and then at 1200 rpm for 15-30 minutes.

[0026] Furthermore, the length-to-diameter ratio of the twin-screw extruder in step (2) is 40:1-52:1.

[0027] Furthermore, the drying in step (3) is to dry the particles by blowing air at 80-100°C for 4-6 hours, so that the moisture content of the particles is less than 0.05%.

[0028] The imino group (-NH-) in the core structure of the antioxidant described in this invention can effectively capture and scavenge peroxide radicals (ROO·) and alkyl radicals (R·) generated during polymer processing and use. By providing a hydrogen atom, it reacts with free radicals to generate a stable, less reactive self-radical, thereby interrupting the auto-oxidation chain reaction that leads to polymer aging and delaying material degradation. The aryl group provides a large conjugated system and steric hindrance, which helps to disperse and stabilize the electron cloud of the free radical intermediate formed after the hydrogen atom provided by the imino group, preventing it from initiating new side reactions. The nitro group is a strong electron-withdrawing group, which can significantly enhance the stability of the entire molecular structure through the electron-withdrawing effect, especially stabilizing the carbon center connected to the imino group, reducing its reactivity, and making it less susceptible to further oxidative decomposition after exerting its antioxidant effect, thus maintaining long-term antioxidant capacity.

[0029] This invention utilizes a specialized antioxidant (compound of formula I) with an amide-bonded core and electron-withdrawing substituents, specifically designed for polyamides. Based on the principle of "like dissolves like," it achieves high compatibility with the polyamide carrier (PA6, PA66, or PA1010), fundamentally solving the problem of "antioxidant blind spots" caused by uneven dispersion. Simultaneously, its high thermal stability effectively inhibits volatilization and migration during processing, ensuring long-lasting antioxidant protection. By selecting high-performance colorants and leveraging the interfacial wetting effect of dispersants, the antioxidant and colorant achieve microscopic uniformity within the polyamide carrier. The uniform dispersion avoids the "antagonistic effect" between colorants and antioxidants and the problem of pigment catalytic oxidation caused by insufficient compatibility in traditional systems. Furthermore, the introduction of lubricants reduces melt viscosity and shear heat, reduces processing heat degradation and promotes dispersion. At the same time, through the segmented heating melt blending of a 40:1-52:1 high length-to-diameter ratio twin-screw extruder and the deep drying process at 80-100℃, the risk of polyamide hydrolysis and degradation is completely eliminated. Ultimately, the masterbatch synergistically ensures that while giving polyester products a bright color, it also provides excellent and long-lasting heat oxidation resistance and weather resistance, effectively preventing problems such as yellowing and color difference in products.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] 1. Superior Antioxidant Performance and Long-Lasting Effect: This invention uses a special antioxidant designed specifically for polyamide carriers. Based on the principle of "like dissolves like," it improves the compatibility with the carrier, fundamentally solving the problem of uneven dispersion of traditional antioxidants that creates "antioxidant blind spots." At the same time, thanks to the high thermal stability of the antioxidant molecular structure, it inhibits volatilization and migration during processing, making the oxidation protection effect of the masterbatch on polyester products longer-lasting. It can effectively reduce yellowing, color difference, and other issues caused by oxidation during processing and use.

[0032] 2. Eliminate the adverse effects of colorants and antioxidants: By selecting high-performance colorants and utilizing the interfacial wetting effect of dispersants, the antioxidants and colorants are microscopically and uniformly dispersed in the polyamide carrier. This avoids the "antagonistic effect" between colorants and antioxidants and the problem of pigment catalytic oxidation caused by insufficient compatibility in traditional systems, ensuring the color stability of polyester products and reducing product degradation caused by such adverse effects.

[0033] 3. Improved processing stability and product applicability: The introduction of lubricants reduces melt viscosity and shear heat, minimizing thermal degradation during processing and promoting the dispersion of components. Simultaneously, combined with the segmented heating melt blending and deep drying process of a high aspect ratio twin-screw extruder, the risk of polyamide hydrolysis and degradation is completely eliminated, comprehensively improving the processing stability of the masterbatch. Ultimately, the masterbatch imparts vibrant colors to polyester products while possessing superior heat oxidation resistance and weather resistance, better meeting the performance requirements of high-end fields (such as outdoor building materials and medical packaging) for polyester products. Attached Figure Description

[0034] Figure 1 This is the NMR spectrum of antioxidant 1 as described in this invention. Detailed Implementation

[0035] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Preparation Example 1

[0037] Preparation of Antioxidant 1:

[0038] .

[0039] Step 1: 10.00 g of compound 1 and 5.32 g of compound 2 were added to 130 ml of dichloromethane and stirred until evenly dispersed. Then, under a nitrogen atmosphere, 0.41 g of triphenylphosphine, 0.10 g of palladium on carbon and 1.90 g of sodium hydroxide were added sequentially, and the reaction was continued at 80 °C for 10 h. After the reaction was completed, the mixture was filtered with silica gel, the organic solvent was evaporated to dryness, and the mixture was purified by column chromatography (silica gel column chromatography, mobile phase: a mixed solution of petroleum ether and ethyl acetate). The purified compound 3 was obtained by evaporation to dryness.

[0040] Step 2: 10.05 g of compound 3, 4.95 g of compound 4, 13.27 g of potassium phosphate trihydrate, 0.15 g of pyridine-2-carboxylic acid, and 0.23 g of CuI were added to 150 ml of DMSO and heated to 85 °C for 14 h. After cooling, the reaction mixture was extracted with ammonia solution and methyl tert-butyl ether, the organic phase was retained, the organic solvent was evaporated to dryness, and the mixture was purified by column chromatography (silica gel column chromatography, mobile phase: a mixed solution of petroleum ether and ethyl acetate). The purified mixture was evaporated to dryness to obtain 11.23 g of antioxidant 1.

[0041] Structural assessment:

[0042] Mass spectrum of compound 3: 404, measured using ms+1;

[0043] Mass spectrometry of antioxidant 1: 564, measured using ms+1;

[0044] NMR of antioxidant 1: 1 HNMR ( Figure 1)δ8.34(m,2H),7.81-7.75(m,1H),7.74-7.62(m,2H),7.61-7.46(m,2H),7.25-7.13(m,3H),7.01(d,1H),6.61 -6.53(m,1H),6.46-6.38(m,2H),4.42(s,2H),3.86(s,3H),3.33-3.23(m,4H),3.04-2.94(m,4H),1.97(p,2H).

[0045] Preparation Example 2

[0046] In Preparation Example 2, antioxidant 2 was prepared by referring to the preparation method of Preparation Example 1, except that compound 2 was replaced with... The rest remained the same as in Preparation Example 1. The mass spectrometry of antioxidant 2 was 548, measured using ms+1.

[0047] The structure of antioxidant 2 is as follows: .

[0048] Preparation Example 3

[0049] In Preparation Example 3, antioxidant 4 was prepared by referring to the preparation method of Preparation Example 1, except that compound 2 was replaced with... The rest remained the same as in Preparation Example 1. The mass spectrometry of antioxidant 4 was 602, measured using ms+1.

[0050] The structure of antioxidant 4 is as follows: .

[0051] Preparation Example 4

[0052] In Preparation Example 4, antioxidant 5 was prepared by referring to the preparation method of Preparation Example 1, except that compound 2 was replaced with... The rest remained the same as in Preparation Example 1. The mass spectrometry of antioxidant 5 was 559, measured using ms+1.

[0053] The structure of antioxidant 5 is as follows: .

[0054] Preparation Example 5

[0055] In Preparation Example 5, antioxidant 7 was prepared by referring to the preparation method of Preparation Example 1, except that compound 2 was replaced with... The rest remained the same as in Preparation Example 1. The mass spectrometry of antioxidant 7 was 602, measured using ms+1.

[0056] The structure of antioxidant 7 is as follows: .

[0057] Example 1

[0058] Preparation of a high-efficiency polyester masterbatch:

[0059] 1. Raw material ratio:

[0060] Polyamide carrier, selected from: PA6, 55 parts, purchased from: Haiyang Technology Co., Ltd.;

[0061] Colorant, selected from: Phthalocyanine Blue, 30 parts, purchased from: Shuangle Pigment Co., Ltd.;

[0062] Dispersant, selected from: polyethylene wax, 8 parts, purchased from: Qingdao Bonnie Chemical Co., Ltd.;

[0063] Lubricant, selected from: stearamide, 2 parts, purchased from: Jiangxi Zhilian New Materials Co., Ltd.;

[0064] Antioxidant selected from: 1.5 parts of antioxidant 1 prepared by preparation example 1.

[0065] 2. Preparation method:

[0066] (1) Premixing: Add 55 parts of polyamide carrier PA6, 30 parts of phthalocyanine blue, 8 parts of polyethylene wax, 2 parts of stearamide and 1.5 parts of antioxidant 1 to a high-speed mixer, control the mixing temperature at 50℃, mix at 600 rpm for 15 min, and then mix at 1200 rpm for 20 min to obtain a uniformly mixed premix.

[0067] (2) Melt extrusion: The above premixed material is fed into a twin-screw extruder with a length-to-diameter ratio of 48:1 for melt blending and extrusion granulation. The temperature of each section of the twin-screw extruder is set as follows: Zone 1 210℃, Zone 2 230℃, Zone 3 245℃, Zone 4 250℃, and Die head 250℃. The screw speed is set to 300r / min.

[0068] (3) Cooling, pelletizing and drying: The extruded strip material is cooled to room temperature by a water tank, then pelletized by a pelletizer, and the resulting particles are placed in a forced-air drying oven and dried at 90°C for 5 hours to finally obtain a high-efficiency polyester masterbatch with a moisture content of less than 0.05%.

[0069] Examples 2-5

[0070] The preparation of a high-efficiency polyester masterbatch is carried out by referring to the preparation method of Example 1, except that the antioxidant is replaced in turn with the antioxidant prepared in Preparation Examples 2-5, and the rest is the same as in Example 1.

[0071] Comparative Example 1

[0072] The preparation of a high-efficiency polyester masterbatch is carried out by referring to the preparation method of Example 1, except that the antioxidant is replaced with antioxidant 1010, and the rest is the same as in Example 1.

[0073] Comparative Example 2

[0074] The preparation of a high-efficiency polyester masterbatch is carried out by referring to the preparation method of Example 1, except that the antioxidant is replaced with antioxidant CY, and the rest is the same as in Example 1.

[0075] Comparative Example 3

[0076] The preparation of a high-efficiency polyester masterbatch is the same as in Example 1, except that the antioxidant is not added.

[0077] Comparative Example 4

[0078] The preparation of a high-efficiency polyester masterbatch is carried out according to the preparation method of Example 1, except that the lubricant is not added and the rest is the same as in Example 1.

[0079] Performance testing:

[0080] 1. The method for measuring the melt index of the masterbatch is GB / T3682, with conditions of 230℃ / 2.16Kg, and the data are shown in Table 1;

[0081] 2. The measurement method for weather resistance color difference is GB / T16422.2-2014, and the data are shown in Table 1;

[0082] 3. The method for measuring surface resistivity is GB / T1410-2006, and the data are shown in Table 1.

[0083] Table 1.

[0084]

[0085] The melt index of the masterbatch in the example group (using the antioxidant specifically designed for this invention) was more stable overall with less fluctuation. In the comparative examples, the melt index of the groups using traditional antioxidants or without lubricants showed slight changes, indicating that the absence of lubricants leads to a decrease in stability. The example group exhibited significantly better weather resistance and color difference, meaning it had better weather resistance. In the comparative examples, the group without antioxidants had the worst weather resistance and color difference, and the group using traditional antioxidants also had a significantly greater color difference than the example group. Although the color difference of the group without lubricants was better than the first two comparative examples, it was still inferior to that of the example group. The surface resistivity of the example group was more concentrated overall, indicating better stability. In the comparative examples, the surface resistivity of the group without lubricants was relatively high, and the other comparative examples showed slightly larger fluctuations in surface resistivity compared to the example group.

[0086] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency polyester masterbatch, characterized in that, It is prepared from raw materials containing the following parts by weight: 40-70 parts polyamide carrier, 20-50 parts colorant, 5-15 parts dispersant, 1-5 parts lubricant, and 0.5-3 parts antioxidant; The antioxidant is a compound represented by Formula 1; Equation 1 is as follows: ; R1 in Formula 1 is a substituent; R1 is selected from any one of the following: fluorine, trifluoromethyl, cyano, alkyl with 1-5 carbon atoms, and alkoxy with 1-5 carbon atoms.

2. The high-efficiency polyester masterbatch according to claim 1, characterized in that, The polyamide carrier is one or a mixture of several of polyamide 6, polyamide 66, and polyamide 1010.

3. The high-efficiency polyester masterbatch according to claim 1, characterized in that, The colorant is one or a mixture of several of the following: high-pigment carbon black, phthalocyanine blue, phthalocyanine green, permanent red, permanent yellow, quinacridone red, and isoindolinone yellow.

4. The high-efficiency polyester masterbatch according to claim 1, characterized in that, The dispersant is one or a mixture of several of the following: polyethylene wax, oxidized polyethylene wax, polypropylene wax, EVA wax, zinc stearate, and calcium stearate.

5. The high-efficiency polyester masterbatch according to claim 1, characterized in that, The lubricant is one or a mixture of several of stearic acid, stearamide, oleamide, and ethylene bis-stearamide.

6. The high-efficiency polyester masterbatch according to claim 1, characterized in that, The antioxidant is any one of the compounds described below: ； ； ； 。 7. A method for preparing a high-efficiency polyester masterbatch as described in any one of claims 1-6, characterized in that, Includes the following steps: (1) Premixing: The polyamide carrier, colorant, dispersant, lubricant and antioxidant are added to a mixer and mixed at a speed of 600-1200 r / min for 30-45 minutes to obtain a premix; (2) Melt extrusion: The premixed material is fed into a twin-screw extruder for melt blending and extrusion granulation. The temperature of each section of the twin-screw extruder is set as follows: Zone 1 200-220℃, Zone 2 220-240℃, Zone 3 240-250℃, Zone 4 245-255℃, Die head 245-255℃, and the screw speed is 200-400r / min. (3) Cooling, pelletizing and drying: The extruded strip material is cooled by a water tank, then pelletized by a pelletizer and dried to obtain the high-efficiency polyester masterbatch.

8. The method for preparing a high-efficiency polyester masterbatch according to claim 7, characterized in that, The mixing temperature of the mixer in step (1) is 40-60℃; In step (1), the mixture is first mixed at 600 rpm for 15 minutes, and then mixed at 1200 rpm for 15-30 minutes.

9. The method for preparing a high-efficiency polyester masterbatch according to claim 7, characterized in that, The length-to-diameter ratio of the twin-screw extruder in step (2) is 40:1-52:

1.

10. The method for preparing a high-efficiency polyester masterbatch according to claim 7, characterized in that, The drying process described in step (3) involves drying the particles at 80-100°C with forced air for 4-6 hours to reduce the moisture content of the particles to less than 0.05%.

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