A low color difference masterbatch and corresponding polyolefin product

Abstract

The present invention relates to a low-color-difference masterbatch and corresponding polyolefin products. The masterbatch is primarily suitable for coloring polyethylene and polypropylene films or injection-molded parts. The present invention uses an epoxidized polyalphaolefin (PAO) with a defined chemical structure as a dispersant. The epoxidized PAO has highly polar epoxy groups and non-polar long carbon chains, providing both dispersing and lubricating properties. This improves the compatibility of the carrier resin and the polar colorant, allowing for more complete melt mixing of the two. This results in lower color difference, more uniform coloring, more stable coloring performance, and bright, streaky-free color when used to color polyolefin products. Furthermore, it prevents yellowing of the polyolefin products at high temperatures.

Description

Technical Field

[0001] The invention belongs to the technical field of masterbatch formulation, and particularly relates to a low-color-difference masterbatch and corresponding polyolefin products. The masterbatch is mainly suitable for coloring polyethylene and polypropylene films or injection molded parts. Background Art

[0002] In the plastics industry, the direct use of color powder for coloring has problems such as poor dispersibility, large dust, inaccurate measurement, serious color difference within and between batches, and poor color repeatability. Therefore, the use of masterbatch to replace color powder in the plastics industry is now very common. The development and production of new product masterbatch has become one of the most active areas in the plastics processing industry, especially in the building materials, general plastics, engineering plastics and plastic films industries, with huge market potential.

[0003] Currently, the development of masterbatch technology focuses on ensuring the matching and compatibility of pigments, dispersants, and carriers to improve the dispersion and concentration of pigments within the masterbatch composition. As the plastics industry strives to reduce costs and improve production efficiency, masterbatches are increasingly moving towards higher pigment concentrations. However, the higher the pigment content in the masterbatch, the more difficult it is to achieve proper pigment dispersion, placing higher demands on the masterbatch formulation and the selection of raw materials.

[0004] Polyolefin resins in the plastics industry occupy more than half of the market in process applications such as extrusion, injection molding, blow molding, film blowing, cast film, calendering, and wire drawing. Masterbatches used in polyolefins account for about 2 / 3 of the masterbatch market. However, the current market share of color masterbatches in the masterbatch market is very low, and most of them are special colors formulated by suppliers for specific customers.

[0005] Color high-concentration single-color masterbatches are characterized by high colorant concentration (usually 40-70%). The content of carrier resin is reduced in the masterbatch formula, which means that the amount of color single-color masterbatch required to achieve the same color concentration is low, reducing the unit cost of coloring while improving cost-effectiveness. However, the problem is that it is difficult to evenly disperse high-content colorants. Colorants are mostly polar organics, and carrier resins are mostly non-polar resins. There are differences in the compatibility of the two. Therefore, the poor dispersion of colorants leads to significant color differences in masterbatches, especially in scenarios where high whiteness or surface gloss of polyolefin products are required. The current conventional method is to select oxidized polyethylene wax with higher polarity as a dispersant, but the molecular structure of oxidized polyethylene wax is not uniform, and the performance gap between batches is large. At the same time, the prepared masterbatch has poor oxidation resistance. Summary of the Invention

[0006] In view of the defects of the prior art, the technical problem to be solved by the present invention is to provide a masterbatch with low color difference and a corresponding polyolefin product.

[0007] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are as follows:

[0008] In a first aspect, a masterbatch comprises: a thermoplastic carrier resin, a colorant, an epoxidized poly-alpha-olefin, and other additives.

[0009] The thermoplastic carrier resin includes at least one of homopolymer polyethylene, homopolymer polypropylene, homopolymer polystyrene, homopolymer polyvinyl chloride, polyethylene copolymer, polypropylene copolymer, polystyrene copolymer, polyvinyl chloride copolymer, linear low-density polyethylene, metallocene polyethylene, metallocene polypropylene, metallocene polyolefin elastomer, polyoxymethylene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyether sulfone, polysulfone, polyether ketone, polyamide, and polycarbonate, or a combination of multiple ones.

[0010] Preferably, the thermoplastic carrier resins mentioned above include: homopolymer polyethylene, homopolymer polypropylene, linear low-density polyethylene, metallocene polyethylene, metallocene polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-vinyl acetate copolymer and metallocene polyolefin elastomer, etc. The above thermoplastic carrier resins are used alone or in combination.

[0011] The colorant is selected from at least one or a combination of inorganic colorants and organic colorants. Inorganic colorants include, but are not limited to, iron oxide red, chrome red, iron oxide yellow, chrome yellow, zinc yellow, zinc sulfide, titanium dioxide, zinc white, cobalt blue, iron blue, manganese blue, cobalt green, chromium oxide, cobalt violet, manganese violet, iron oxide black, carbon black, etc. Organic colorants include, but are not limited to, aromatic heterocyclic colorants, perylene colorants, monoazo colorants, diazo colorants, azo condensation colorants, diazo condensation colorants, aminoketone colorants, etc., wherein aromatic heterocyclic colorants include phthalocyanine, benzimidazolinone, quinophthalone, quinacridone, peronone, dioxazine, isoindoline, and thioindigo. At the same time, these colorants can be in any form of dry powder, a single colorant dispersion prepared according to conventional methods, or a mixed dispersion of multiple colorants.

[0012] Preferably, the colorant is selected from a combination of an inorganic colorant and an organic colorant. More preferably, the colorant is selected from a mixture of rutile titanium dioxide and phthalocyanine green in a mass ratio of 4:1.

[0013] wherein the degree of polymerization of the epoxidized alpha olefin is 2-6, preferably, the degree of polymerization of the epoxidized alpha olefin is 3-4;

[0014] The structure of the epoxidized alpha olefin is selected from: Among them, a, b, c and d are independent of each other and can be the same or different. The value range of a, b, c and d is 1-17. Preferably, the value range of a, b, c and d is 1-11.

[0015] Preferably, the epoxidized alpha olefin is prepared by epoxidation of a polyalphaolefin oligomer. The structure of the polyalphaolefin oligomer includes: Among them, a, b, c and d are independent of each other and can be the same or different. The value range of a, b, c and d is 1-17. Preferably, the value range of a, b, c and d is 1-11.

[0016] Furthermore, the polyalphaolefin oligomer is obtained by coordination polymerization of a metallocene catalyst system and one or more linear alpha olefins, wherein the linear alpha olefins have a carbon atom count ranging from 4 to 20. The metallocene catalyst system includes at least one metallocene catalyst, which is an inorganic-organic complex containing at least one cyclopentadiene or cyclopentadiene derivative as a ligand and at least one Group IVB transition element as a central atom. Preferably, the central atom is selected from zirconium (Zr).

[0017] Furthermore, the epoxidation reaction specifically includes: reacting a polyalphaolefin oligomer, an 88 wt% formic acid aqueous solution, a 30 wt% hydrogen peroxide aqueous solution, a 70 wt% sulfuric acid aqueous solution and a solvent ethyl n-propyl ether in a mass ratio of 1:0.15:0.75:0.05:0.75 at a temperature of 60-80°C for 3-6 hours. After the reaction is completed, the solvent is first evaporated and then purified by column chromatography, wherein the eluent used for chromatography column purification is a petroleum ether / ethyl acetate mixed solvent with a volume ratio of 10:1.

[0018] Among them, other additives include any one or a combination of antioxidants or lubricants.

[0019] Preferably, the antioxidant is at least one of a hindered phenol antioxidant and a hindered amine antioxidant. More preferably, the antioxidant is a hindered phenol antioxidant, specifically including: 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-isopropylphenol, styrenated phenol, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylbenzene Any one or a combination of the following: 1,2-di-tert-pentylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), alkylated bisphenol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0020] The lubricant has the function of reducing the bonding between the colorant powders and improving the dispersion effect of the colorant; it also reduces the friction between the colorant and the thermoplastic carrier resin and reduces the possibility of thermal decomposition.

[0021] Preferably, the lubricant is selected from any one or a combination of micronized wax, magnesium stearate, sodium stearate, zinc stearate or calcium stearate.

[0022] In some embodiments, the masterbatch further comprises an inert filler, wherein the inert filler is a mixture of one or more of heavy calcium carbonate, light calcium carbonate, magnesium carbonate, clay, talc, barium sulfate, calcium sulfate, mica powder, aluminum hydroxide, calcium hydroxide, hydrotalcite, molecular sieve, kaolin or wollastonite. Adding the above-mentioned inert filler can enhance the surface hardness of the masterbatch while reducing the production cost of the masterbatch.

[0023] Furthermore, the masterbatch comprises, according to the mass percentage of each component in the composition: 15-30 wt% of thermoplastic carrier resin, 50-70 wt% of colorant, 5-15 wt% of epoxidized polyalphaolefin, and 0-10 wt% of other additives;

[0024] Furthermore, the masterbatch comprises, by weight percentage of each component in the composition: 15-30 wt% of thermoplastic carrier resin, 50-70 wt% of colorant, 5-15 wt% of epoxidized polyalphaolefin, 0-10 wt% of other additives, and 1-10 wt% of inert filler.

[0025] In a second aspect, the method for preparing the masterbatch mentioned above comprises: stirring or mixing all the components of the masterbatch formula, then melt-blending them to disperse them uniformly, and then granulating, drying, and packaging.

[0026] The stirring or mixing is carried out in a high-speed mixer, and preferably, the stirring or mixing time is 15-60 minutes.

[0027] Furthermore, a twin-screw extruder is used to melt-blend the formula components of the masterbatch, and the melt-blending temperature is 150-300°C; preferably, the melt-blending temperature is 180-250°C; more preferably, the melt-blending temperature is 220°C; the screw speed of the melt-blending is not less than 200 rpm; preferably, the screw speed of the melt-blending is 200-400 rpm; more preferably, the screw speed of the melt-blending is 220 rpm.

[0028] In a third aspect, a polyolefin product is prepared from the masterbatch described above.

[0029] Preferably, the polyolefin product comprises a polyethylene or polypropylene film or an injection molded part.

[0030] The beneficial effects of the present invention are as follows: epoxidized polyalphaolefin with a defined chemical structure is selected as a masterbatch dispersant, replacing conventional oxidized polyethylene wax in the masterbatch formulation; the epoxidized polyalphaolefin has a highly polar epoxy group and a non-polar long carbon chain, and has both dispersing and lubricating effects, thereby improving the compatibility of the carrier resin and the polar colorant, enabling more complete melt mixing of the two, resulting in lower color difference, more uniform coloring, more stable coloring performance, brighter color and no streaking in the application of the masterbatch for coloring polyolefin products, and preventing yellowing of the polyolefin products at high temperatures.

[0031] On the other hand, epoxidized polyalphaolefins are derived from light component by-products produced during the coordination polymerization of linear alpha olefins, thereby expanding the application areas of low molecular weight polyalphaolefins and increasing their market economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 These are the hydrogen and carbon nuclear magnetic resonance spectra of the epoxidized C6 tetramer.

[0033] Figure 2 These are the hydrogen and carbon nuclear magnetic resonance spectra of the epoxidized C8 trimer.

[0034] Figure 3 These are the H-NMR and C-NMR spectra of the epoxidized C10 trimer.

[0035] Figure 4 These are the hydrogen and carbon nuclear magnetic resonance spectra of the epoxidized C12 trimer. DETAILED DESCRIPTION

[0036] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0037] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0038] If the specific experimental conditions are not specified in the examples, they are usually based on conventional conditions in the field or conditions recommended by the reagent company; the materials, reagents, etc. used in the examples can be purchased through commercial channels unless otherwise specified.

[0039] Preparation of epoxidized polyalphaolefins:

[0040] First, polyalphaolefin oligomers were obtained by coordination polymerization of linear alpha olefins. The polymerization reaction was carried out in a 2000 mL PARR high-pressure stirred reactor. The reactor was first heated to above 100°C and vacuum-baked for 1 hour. During this period, the reactor was replaced with high-purity nitrogen several times to remove water and oxygen impurities in the reactor. The reactor temperature was then adjusted to 70°C by circulating cooling water in the jacket. 800 mL of alpha olefin was added and the stirring rate was increased to 500 rpm. After stirring for 15 minutes, the main catalyst, an organometallic compound siloxysilane-bridged zirconocene dichloride (Yapex Technology), dissolved in 350 mL of n-hexane, was added to the reactor. The corresponding structural formula is: The invention relates to a method for preparing a polymerization system comprising the following steps: preparing a co-catalyst modified methylaluminoxane (MMAO-12, 7 wt% Al content, toluene as solvent, Millipore Sigma) and a chain transfer agent triisobutylaluminum (TIBA, 0.1 mol / L dissolved in hexane solvent, Millipore Sigma); the concentration of the metallocene main catalyst in the polymerization reaction system is 0.3 mmol / L (calculated as Zr); the concentration of MMAO-12 in the polymerization reaction system is 30 mmol / L (calculated as Al); and the concentration of TIBA in the polymerization reaction system is 30 mmol / L (calculated as Al). The nitrogen valve is opened and the nitrogen pressure is increased to 0.15 MPa. The reaction is terminated after 1 hour. The vent pipe is opened to release the pressure, and the crude product is discharged from the reactor. 10 mL of acidified ethanol is added to the crude product to terminate the reaction. Activated clay accounting for 3 wt% of the total crude product is then added to remove catalyst residues by adsorption. The filtrate is then pressure filtered to obtain a filtrate, and the filtrate is subjected to vacuum distillation to separate polyalphaolefin oligomers with different carbon numbers.

[0041] Separation conditions of poly alpha olefin oligomers: when the alpha olefin is 1-hexene (C6), the fraction at 120-140°C is collected at a vacuum degree of 0.2 torr to separate the C6 tetramer; when the alpha olefin is 1-octene (C8), the fraction at 150-170°C is collected at a vacuum degree of 0.5 torr to separate the C8 trimer; when the alpha olefin is 1-decene (C10), the fraction at 140-160°C is collected at a vacuum degree of 0.2 torr to separate the C10 trimer; when the alpha olefin is 1-dodecene (C12), the fraction at 180-200°C is collected at a vacuum degree of 0.2 torr to separate the C12 trimer.

[0042] The polyalphaolefin oligomer, 88wt% formic acid aqueous solution, 30wt% hydrogen peroxide aqueous solution, 70wt% sulfuric acid aqueous solution and solvent ethyl n-propyl ether were added in a mass ratio of 1:0.15:0.75:0.05:0.75, and stirred at a temperature of 70°C for 4 hours. After the reaction was completed, the liquid in the reaction flask was rotary evaporated to remove the azeotrope of water and ethyl n-propyl ether, and then purified by column chromatography, wherein the eluent used in the chromatography column was a petroleum ether / ethyl acetate mixed solvent with a volume ratio of 10:1, and finally the purified epoxidized polyalphaolefin was obtained, and the epoxidized polyalphaolefin specifically included: epoxidized C6 tetramer, epoxidized C8 trimer, epoxidized C10 trimer and epoxidized C12 trimer.

[0043] Among them, the chemical structures of the purified epoxidized C6 tetramer, epoxidized C8 trimer, epoxidized C10 trimer and epoxidized C12 trimer were confirmed by nuclear magnetic resonance hydrogen spectrum 1H-NMR (solvent: CDCl3) and carbon spectrum 13C-NMR (solvent: CDCl3). The corresponding NMR spectra are listed in Figure 1-4 middle.

[0044] Example 1

[0045] Masterbatch formula: 18wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 10wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 5wt% epoxidized C6 tetramer, 3wt% micronized wax, 1wt% zinc stearate, 57wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 5wt% talc, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0046] The above formula was weighed and mixed in a high-speed mixer for 20 minutes. The mixture was melt-blended using a twin-screw extruder. The temperature was controlled at 200°C and the screw speed was 220 rpm. The colorant was evenly dispersed in the carrier resin through shearing and mixing of the screw. The mixture was then granulated, dried, and packaged to obtain a masterbatch.

[0047] Example 2

[0048] Masterbatch formula: 15wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 10wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 10wt% epoxidized C6 tetramer, 2.5wt% micronized wax, 0.5wt% zinc stearate, 56wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 5wt% barium sulfate, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0049] The preparation method of masterbatch is the same as that in Example 1.

[0050] Example 3

[0051] Masterbatch formula: 16wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 12wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 6wt% epoxidized C8 trimer, 4wt% micronized wax, 1wt% zinc stearate, 54wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 6wt% kaolin, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0052] The preparation method of masterbatch is the same as that in Example 1.

[0053] Example 4

[0054] Masterbatch formula: 15wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 9wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 10wt% epoxidized C8 trimer, 4wt% micronized wax, 1wt% zinc stearate, 56wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 4wt% kaolin, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0055] The preparation method of masterbatch is the same as that in Example 1.

[0056] Example 5

[0057] Masterbatch formula: 17wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 12wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 6wt% epoxidized C10 trimer, 3wt% micronized wax, 1wt% zinc stearate, 57wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 3wt% talc, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0058] The preparation method of masterbatch is the same as that in Example 1.

[0059] Example 6

[0060] Masterbatch formula: 16wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 10wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 12wt% epoxidized C10 trimer, 1wt% zinc stearate, 60wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0061] The preparation method of masterbatch is the same as that in Example 1.

[0062] Example 7

[0063] Masterbatch formulation: 17 wt% linear low-density polyethylene (LLDPE) with an MI of 50 g / 10 min, 11 wt% metallocene polyethylene (m-PE) with an MI of 30 g / 10 min, 7 wt% epoxidized C10 trimer, 1 wt% zinc stearate, 58 wt% colorant (rutile titanium dioxide: phthalocyanine green prepared in a mass ratio of 4:1), 5 wt% barium sulfate, and 1 wt% antioxidant 2,6-di-tert-butyl-4-methylphenol. The masterbatch preparation method is the same as that of Example 1.

[0064] Example 8

[0065] Masterbatch formula: 16wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 10wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 8wt% oxidized polyethylene wax, 1wt% zinc stearate, 56wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0066] The preparation method of masterbatch is the same as that in Example 1.

[0067] Comparative Example 1

[0068] Masterbatch formula: 16wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 10wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 8wt% oxidized polyethylene wax, 3wt% micronized wax, 1wt% zinc stearate, 56wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 5wt% kaolin, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0069] The preparation method of masterbatch is the same as that in Example 1.

[0070] Comparative Example 2

[0071] Masterbatch formula: 18wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 12wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 2wt% epoxidized C10 trimer, 3wt% micronized wax, 1wt% zinc stearate, 58wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 5wt% barium sulfate, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0072] The preparation method of masterbatch is the same as that in Example 1.

[0073] Comparative Example 3

[0074] Masterbatch formula: 8wt% linear low-density polyethylene (LLDPE) with an MI of 50g / 10min, 4wt% metallocene polyethylene (m-PE) with an MI of 30g / 10min, 20wt% epoxidized C10 trimer, 3wt% micronized wax, 1wt% zinc stearate, 58wt% colorant (rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1), 5wt% barium sulfate, and 1wt% antioxidant 2,6-di-tert-butyl-4-methylphenol.

[0075] The preparation method of masterbatch is the same as that in Example 1.

[0076] Performance test of masterbatch: The masterbatch prepared in Examples 1-8 and Comparative Examples 1-3 was added to homopolymer polypropylene plastic at 5%, and 20 samples were continuously injected. The color uniformity and flow pattern of each color plate were tested. The color difference between the first and last color plates was tested using a colorimeter. The samples were then placed in an oven at 180°C for aging for 30 minutes to observe whether the samples had yellowing. The performance test results of the masterbatch are shown in Table 1.

[0077] The test results in Table 1 show that the masterbatches prepared with epoxidized polyalphaolefins in Examples 1-8, when used to color polyolefin products, achieve uniform coloring with a color difference of no more than 0.6, resulting in bright, streaky colors. Comparative Example 1, using conventional oxidized polyethylene wax, struggles to maintain low color difference at high colorant concentrations, resulting in a significant increase in the proportion of uneven color patches. Furthermore, the color patches exhibit yellowing after aging at 180°C. Comparative Example 2 incorporates a lower epoxidized polyalphaolefin content (less than 5 wt%), leading to increased color difference and a higher proportion of uneven color patches. Comparative Example 3, which reduces the carrier resin content and increases the epoxidized polyalphaolefin content, exhibits streaking in the color patches. This is because the masterbatch system requires a high-molecular-weight thermoplastic resin as the carrier resin, the masterbatch matrix, to coat, bind, and support the colorant. While epoxidized polyalphaolefins have a higher polarity, their molecular weight is significantly lower, limiting their use to dispersants. This makes them difficult to use as a carrier resin in masterbatches to support the colorant.

[0078] Table 1

[0079] Sample Uneven color plate ratio / % Flow pattern Chromatic Aberration 180℃ aging test Example 1 5 none 0.6 White, no yellowing Example 2 0 none ＜0.5 White, no yellowing Example 3 0 none ＜0.5 White, no yellowing Example 4 0 none ＜0.5 White, no yellowing Example 5 5 none 0.6 White, no yellowing Example 6 0 none ＜0.5 White, no yellowing Example 7 0 none ＜0.5 White, no yellowing Example 8 0 none ＜0.5 White, no yellowing Comparative Example 1 35 a little 2.4 light yellow Comparative Example 2 10 a little 0.9 White, no yellowing Comparative Example 3 15 serious 1.3 White, no yellowing

[0080] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for parts thereof. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention. Although the above describes the specific embodiments of the present invention, it is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that, based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A masterbatch, characterized in that: Masterbatches include: Thermoplastic carrier resin, colorant, epoxidized polyalphaolefin, other additives; The thermoplastic carrier resin is selected from at least one of homopolymer polyethylene, homopolymer polypropylene, homopolymer polystyrene, homopolymer polyvinyl chloride, polyethylene copolymer, polypropylene copolymer, polystyrene copolymer, polyvinyl chloride copolymer, linear low-density polyethylene, metallocene polyethylene, metallocene polypropylene, metallocene polyolefin elastomer, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyethersulfone, polysulfone, polyetherketone, polyamide, and polycarbonate, or a combination thereof; The colorant is selected from at least one or a combination of inorganic colorants and organic colorants; and the colorant can be any form of dry powder, a single colorant dispersion, or a mixed dispersion of multiple colorants. Wherein, the degree of polymerization of the epoxidized poly-alpha olefin is 3-4, and the structure of the epoxidized alpha polyolefin is selected from: or ; Among them, a, b, c and d are independent of each other and can be the same or different. The value range of a, b, c and d is 1-17; Among them, other additives include any one or a combination of antioxidants or lubricants; The masterbatch comprises, by weight percentage of each component in the composition, 15-30 wt% of a thermoplastic carrier resin, 50-70 wt% of a colorant, 5-15 wt% of an epoxidized poly-alpha olefin, and 0-10 wt% of other additives.

2. The masterbatch according to claim 1, characterized in that: The masterbatch further comprises an inert filler, wherein the inert filler is a mixture of one or more of heavy calcium carbonate, light calcium carbonate, magnesium carbonate, clay, talc, barium sulfate, calcium sulfate, mica powder, aluminum hydroxide, calcium hydroxide, hydrotalcite, molecular sieve, kaolin or wollastonite.

3. The masterbatch according to claim 1, characterized in that: The thermoplastic carrier resin is selected from the group consisting of homopolymer polyethylene, homopolymer polypropylene, linear low-density polyethylene, metallocene polyethylene, metallocene polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-vinyl acetate copolymer and metallocene polyolefin elastomer, or a combination thereof.

4. The masterbatch according to claim 1, characterized in that: The epoxidized α-polyolefin is prepared by epoxidation of a polyα-olefin oligomer, wherein the structure of the polyα-olefin oligomer comprises: or ; Among them, a, b, c and d are independent of each other and can have the same or different values. The value range of a, b, c and d is 1-17.

5. The masterbatch according to claim 4, characterized in that: The polyalphaolefin oligomer is obtained by coordination polymerization of a metallocene catalyst system and one or more linear alpha olefins, wherein the number of carbon atoms in the linear alpha olefin is in the range of 4-20; The metallocene catalyst system includes at least one metallocene catalyst, which is an inorganic-organic complex containing at least one cyclopentadienyl or cyclopentadienyl derivative as a ligand and at least one Group IVB transition element as a central atom.

6. The masterbatch according to claim 5, characterized in that: The central atom is selected from zirconium (Zr).

7. The masterbatch according to claim 1, characterized in that: The antioxidant is a hindered phenol antioxidant, and the antioxidant is specifically selected from: 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-isopropylphenol, styrenated phenol, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2- Any one or a combination of the following: hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

8. The masterbatch according to claim 1, characterized in that: The lubricant is selected from any one or a combination of micronized wax, magnesium stearate, sodium stearate, zinc stearate or calcium stearate.

9. The masterbatch according to claim 1, characterized in that: The masterbatch comprises, by weight percentage of each component in the composition, 15-30 wt% of thermoplastic carrier resin, 50-70 wt% of colorant, 5-15 wt% of epoxidized poly-alpha olefin, 0-10 wt% of other additives, and 1-10 wt% of inert filler.

10. A method for preparing a masterbatch, characterized in that: The preparation method comprises: stirring or mixing all the components of the masterbatch according to any one of claims 1 to 9, then melt-blending them to make them uniformly dispersed, and then granulating, drying and packaging; Wherein, the stirring or mixing is carried out in a high-speed mixer; The masterbatch formula components are melt-blended using a twin-screw extruder, the melt-blending temperature is 150-300°C, and the screw speed of the melt-blending is not less than 200rpm.

11. The method for preparing a masterbatch according to claim 10, characterized in that: The stirring or mixing time is 15-60 minutes.

12. A polyolefin product prepared from the masterbatch according to any one of claims 1 to 9.

13. The polyolefin product according to claim 12, characterized in that Polyolefin products include polyethylene and polypropylene films or injection molded parts.

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