Low-color-difference color master batch and corresponding polyolefin product

Abstract

The invention relates to a low-color-difference color master batch and a corresponding polyolefin product. The color master batch is mainly suitable for coloring polyethylene and polypropylene films or injection molded parts. According to the invention, epoxidized poly-alpha-olefin with a determined chemical structure is selected as a dispersing agent, and the epoxidized poly-alpha-olefin has an epoxy group with relatively high polarity and a non-polar long carbon chain, and has dispersing and lubricating effects, so that the compatibility of the carrier resin and the polar coloring agent is improved, and the carrier resin and the polar coloring agent are melted and mixed more sufficiently; the color master batch has the advantages of lower color difference, more uniform coloring, more stable coloring performance, bright color and no flow lines in the application of coloring polyolefin products, and meanwhile, the yellowing of the polyolefin products at high temperature is avoided.

Description

Technical Field

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

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

[0003] Currently, the development direction of masterbatch technology has always been committed to the matching and compatibility of pigments, dispersants, and carriers to improve the dispersibility and concentration of pigments in the masterbatch composition. With the requirements of the plastic industry to reduce costs and improve production efficiency, masterbatch is increasingly developing towards high pigment concentration. However, the higher the pigment content in the masterbatch, the more difficult it is to achieve good pigment dispersibility, and the higher the requirements for the selection of masterbatch formulations and their raw materials.

[0004] Polyolefin resins in the plastic industry account for more than half of the market in extrusion, injection molding, blow molding, blown film, casting, calendering, drawing and other process applications. The masterbatch used in polyolefins accounts for about 2 / 3 of the masterbatch market. However, the market share of colored masterbatch in the current masterbatch market is very low, mostly special colors formulated by suppliers for specific customers.

[0005] Colored high-concentration single-color masterbatch has the characteristics of a high concentration of colorants (the colorant content is usually 40 - 70%). Reducing the content of carrier resin in the masterbatch formulation means that the addition amount of colored single-color masterbatch required to achieve the same color concentration is low. While the unit cost of coloring decreases, the cost performance is also improved. However, the problem is that it is difficult to disperse the high-content colorants evenly. Colorants are mostly polar organic substances, and carrier resins are mostly non-polar resins, and there are differences in their compatibility. Therefore, poor dispersibility of colorants leads to obvious color differences in the masterbatch, especially it is difficult to be used in scenarios with high requirements for the whiteness or surface gloss of polyolefin products. The current conventional method is to select oxidized polyethylene wax with a relatively high polarity as a dispersant, but the molecular structure of oxidized polyethylene wax is not uniform, and there are large performance differences between batches. At the same time, the prepared masterbatch has poor antioxidant properties. Summary of the Invention

[0006] Aiming at 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 corresponding polyolefin products.

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

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

[0009] Among them, the thermoplastic carrier resin includes at least one or a combination of homopolyethylene, homopolypropylene, homopolystyrene, homopolyvinyl 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, polyethersulfone, polysulfone, polyether ketone, polyamide, polycarbonate.

[0010] Preferably, the above-mentioned thermoplastic carrier resin includes: homopolyethylene, homopolypropylene, 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 can be used alone or in combination.

[0011] Among them, 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-based colorants, monoazo colorants, diazo colorants, azo condensation colorants, diazo condensation colorants, aminoketone colorants, etc. Among them, aromatic heterocyclic colorants include phthalocyanine, benzimidazolone, quinophthalone, quinacridone, violanthrone, dioxazine, isoindoline, and thioindigo, etc. At the same time, these colorants can be 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 composition of inorganic colorants and organic colorants. More preferably, the colorant is selected from a mixture of rutile titanium dioxide: phthalocyanine green in a mass ratio of 4:1.

[0013] Among them, the polymerization degree of the epoxidized α-olefin is 2-6. Preferably, the polymerization degree of the epoxidized α-olefin is 3-4;

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

[0015] Preferably, the epoxidized α-olefin is prepared by an epoxidation reaction of a poly-α-olefin oligomer. The structure of the poly-α-olefin oligomer includes: Among them, a, b, c, and d are independent of each other, and their values can be the same or different. The value ranges of a, b, c, and d are from 1 to 17. Preferably, the value ranges of a, b, c, and d are from 1 to 11.

[0016] Furthermore, the poly-α-olefin oligomer is obtained by coordination polymerization of a metallocene catalyst system and one or more linear α-olefins. The number of carbon atoms of the linear α-olefin ranges from 4 to 20. Among them, the metallocene catalyst system includes at least one metallocene catalyst, and the metallocene catalyst is an inorganic-organic complex containing at least one metallocycle or metallocycle 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 the poly-α-olefin oligomer, 88 wt% aqueous formic acid solution, 30 wt% aqueous hydrogen peroxide solution, 70 wt% aqueous sulfuric acid solution, and the solvent ethyl n-propyl ether at a mass ratio of 1:0.15:0.75:0.05:0.75 at a temperature of 60-80 °C for 3-6 h. After the reaction is completed, the solvent is first distilled off and then purified by column chromatography. Among them, the eluent used for column chromatography 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 and lubricants.

[0019] Preferably, the antioxidant is at least one of hindered phenol antioxidants and hindered amine antioxidants. More preferably, the antioxidant is a hindered phenol antioxidant, specifically including any one or a combination of several of: 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-hydroxy-3,5-di-tert-amylphenyl)ethyl]-4,6-di-tert-amylphenyl acrylate, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), alkylated bisphenol, tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0020] The lubricant functions to weaken the adhesion between the colorant powders and improve the dispersion effect on 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 several of: micronized wax, magnesium stearate, sodium stearate, zinc stearate or calcium stearate.

[0022] In some embodiments, the masterbatch further includes an inert filler. Among them, 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 inert filler can enhance the surface hardness of the masterbatch and at the same time reduce the production cost of the masterbatch.

[0023] Further, the masterbatch includes, by 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 poly-α-olefin, 0-10 wt% of other additives;

[0024] Further, the masterbatch includes, by 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 poly-α-olefin, 0-10 wt% of other additives, and 1-10 wt% of inert filler.

[0025] In a second aspect, the method for preparing the masterbatch described above includes: stirring or mixing all components of the masterbatch formulation, then subjecting them to melt blending to disperse them uniformly, and then pelletizing, drying, and packaging.

[0026] Among them, the stirring or mixing is carried out in a high-speed mixer. Preferably, the time for stirring or mixing is 15 - 60 min.

[0027] Further, a twin-screw extruder is used to carry out melt blending of the formulation components of the masterbatch. The temperature for melt blending is 150 - 300 °C; preferably, the temperature for melt blending is 180 - 250 °C; more preferably, the temperature for melt blending is 220 °C; the screw speed for melt blending is not less than 200 rpm; preferably, the screw speed for melt blending is 200 - 400 rpm; more preferably, the screw speed for 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 includes films or injection-molded parts of polyethylene and polypropylene.

[0030] The beneficial effects of the present invention are as follows: Epoxidized poly-α-olefin with a determined chemical structure is selected as a dispersant for the masterbatch, replacing conventional oxidized polyethylene wax in the masterbatch formulation. Epoxidized poly-α-olefin has a relatively high-polar epoxy group and a non-polar long carbon chain, and has both dispersing and lubricating effects. Thereby, the compatibility between the carrier resin and the polar colorant is improved, the melt mixing of the two is more sufficient, the color difference of the masterbatch in the application of coloring polyolefin products is lower, the coloring is more uniform, the coloring performance is more stable, the color is bright without flow marks, and at the same time, the yellowing of polyolefin products at high temperatures is avoided.

[0031] On the other hand, epoxidized poly-α-olefin is derived from light component by-products generated during the coordination polymerization of linear α-olefins, thereby expanding the application field of low-molecular-weight poly-α-olefins and increasing their market economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 1H NMR and 13C NMR spectra of epoxidized C6 tetramer.

[0033] Figure 2 1H NMR and 13C NMR spectra of epoxidized C8 trimer.

[0034] Figure 3 1H NMR and 13C NMR spectra of epoxidized C10 trimer.

[0035] Figure 4 1H NMR and 13C NMR spectra of epoxidized C12 trimer. Detailed Embodiments

[0036] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it 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 also fall within the scope defined by the appended claims of this 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 also intended to include the plural form. In addition, it should also be understood that when the terms "comprising" and / or "including" 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 embodiments, they are generally in accordance with the conventional conditions in the art or in accordance with the conditions recommended by the reagent company; the materials, reagents, etc. used in the embodiments, unless otherwise specified, can be obtained through commercial channels.

[0039] Preparation of Epoxidized Poly-α-olefin:

[0040] First, poly-α-olefin oligomers are obtained by the coordination polymerization of linear α-olefins. The polymerization reaction is carried out in a 2000 mL PARR high-pressure stirring reactor. First, the reactor is heated to above 100 °C and vacuum baked for 1 h, during which it is replaced with high-purity nitrogen multiple times to remove water / oxygen impurities in the reactor. Subsequently, the reactor temperature is adjusted to the reaction temperature of 70 °C through jacket cooling water circulation. 800 mL of α-olefin is added, the stirring rate is set to 500 rpm, and after stirring for 15 min, the main catalyst, the handle-type metal-organic compound silyloxysilicon-bridged bis(cyclopentadienyl)zirconium dichloride (Apexim Technology), dissolved in 350 mL of n-hexane is added to the reactor. The corresponding structural formula is: And co-catalyst modified methylaluminoxane (MMAO-12, with an Al content of 7 wt%, solvent is toluene, from Millipore Sigma), chain transfer agent triisobutylaluminum (TIBA, 0.1 mol / L dissolved in hexane solvent, from 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). Open the nitrogen valve to fill nitrogen until the pressure reaches 0.15 MPa. After reacting for 1 h, end the reaction. Open the vent pipe to relieve pressure, and discharge the crude product from the reaction kettle. Add 10 mL of acidified ethanol to the crude product to terminate the reaction, then add activated clay accounting for 3 wt% of the total amount of the crude product to adsorb and remove catalyst residues. Subsequently, perform pressure filtration to obtain the filtrate, and subject the filtrate to vacuum distillation separation to obtain poly-α-olefin oligomers with different carbon numbers.

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

[0042] Charge the poly-α-olefin oligomers, 88 wt% aqueous formic acid solution, 30 wt% aqueous hydrogen peroxide solution, 70 wt% aqueous sulfuric acid solution, and solvent ethyl n-propyl ether according to a mass ratio of 1:0.15:0.75:0.05:0.75, and stir and react at a temperature of 70 °C for 4 h. After the reaction is completed, rotate and evaporate the liquid in the reaction flask to remove the azeotrope of water and ethyl n-propyl ether, and then purify it by column chromatography. The eluent used in the chromatography column is a mixed solvent of petroleum ether / ethyl acetate with a volume ratio of 10:1. Finally, obtain purified epoxidized poly-α-olefin. The epoxidized poly-α-olefin specifically includes: epoxidized C6 tetramer, epoxidized C8 trimer, epoxidized C10 trimer, and epoxidized C12 trimer.

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

[0044] Example 1

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

[0046] Weigh the above formulation, then mix it in a high-speed mixer for 20 minutes, and carry out melt blending using a twin-screw extruder with the temperature controlled at 200 °C and the screw speed of 220 rpm. Through the shearing and kneading of the screw, the colorant is evenly dispersed in the carrier resin, and then granulation, drying, and packaging processes are carried out to obtain the masterbatch.

[0047] Example 2

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

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

[0050] Example 3

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

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

[0053] Example 4

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

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

[0056] Example 5

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

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

[0059] Example 6

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

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

[0062] Example 7

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

[0064] Example 8

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

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

[0067] Comparative Example 1

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

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

[0070] Comparative Example 2

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

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

[0073] Comparative Example 3

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

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

[0076] Performance Testing of Masterbatch: Add 5% of the masterbatches prepared in Examples 1-8 and Comparative Examples 1-3 to homopolypropylene plastic, and continuously inject 20 sample plates. Detect the coloring uniformity and flow marks of each color plate. Use a color difference meter to detect the color difference between the first and the last color plates, and then place them in an oven at 180°C for 30 minutes of aging to observe whether the sample plates turn yellow. The performance test results of the masterbatch are shown in Table 1.

[0077] As can be seen from the test results in Table 1, when the masterbatches prepared by adding epoxidized poly-α-olefin in Examples 1-8 are used for coloring polyolefin products, they can be uniformly colored, the color differences do not exceed 0.6, and the color of the color plates is bright without flow marks. In Comparative Example 1, conventional oxidized polyethylene wax is used, and it is difficult to maintain the effect of low color difference under the condition of high-concentration colorants, and the proportion of non-uniform color plates increases significantly. Moreover, the color plates turn yellow after aging at 180°C. The addition amount of epoxidized poly-α-olefin in Comparative Example 2 is lower (less than 5wt%), resulting in an increase in color difference and the proportion of non-uniform color plates. In Comparative Example 3, the proportion of the carrier resin is reduced and the amount of epoxidized poly-α-olefin is increased, resulting in flow marks on the color plates. This is because the masterbatch system requires a high-molecular-weight thermoplastic resin as the carrier resin, that is, the matrix of the masterbatch, which plays the role of coating, adhesion, and loading for the colorant. Although epoxidized poly-α-olefin has a higher polarity, its molecular weight is significantly lower and it can only be used as a dispersant, and it is difficult to be used as a carrier resin for the masterbatch to carry the colorant.

[0078] Table 1

[0079] specimen non-uniform color patch ratio / % flow mark color difference 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 severe 1.3 white, no yellowing

[0080] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of them. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Although the specific implementation manners of the present invention have been described above, it is not a limitation to the protection scope of the present invention. Those skilled in the art should understand that based on the technical solutions of the present invention, various modifications or deformations that can be made without creative labor by those skilled in the art are still within the protection scope of the present invention.

Claims

1. A masterbatch, characterized in that: Masterbatches include: Thermoplastic carrier resin, colorant, epoxidized polyalphaolefin, other additives; Wherein, 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, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyether sulfone, polysulfone, polyether ketone, polyamide, and polycarbonate, or a combination of multiple thereof; Wherein, the colorant is selected from at least one or a combination of inorganic colorants and organic colorants; at the same time, the colorant can be any form of dry powder, a single colorant dispersion prepared according to a conventional method, or a mixed dispersion of multiple colorants; Wherein, the degree of polymerization of the epoxidized alpha olefin is 3-4, and the structure of the epoxidized alpha olefin 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.

2. The masterbatch according to claim 1, characterized in that: The masterbatch also includes 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 alpha olefin is prepared by an epoxidation reaction of a polyalpha olefin oligomer, wherein the structure of the polyalpha olefin oligomer comprises: or Among them, a, b, c and d are independent of each other and can be the same or different in value. 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 of the linear alpha olefins ranges from 4 to 20. The metallocene catalyst system comprises 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; preferably, the central atom is selected from zirconium (Zr).

6. The masterbatch according to claim 1, characterized in that: The antioxidant is at least one of a hindered phenol antioxidant and a hindered amine 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-[ Any one or a combination of 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; Preferably, the lubricant is selected from any one or a combination of micronized wax, magnesium stearate, sodium stearate, zinc stearate or calcium stearate.

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

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

9. 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 8, and then performing melt blending to make them dispersed evenly, and then granulating, drying and packaging; Wherein, the stirring or mixing is carried out in a high-speed mixer, and preferably, the stirring or mixing time is 15-60 min; The formula components of the masterbatch 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 200 rpm.

10. A polyolefin product prepared from the masterbatch according to any one of claims 1 to 8; Preferably, the polyolefin product comprises a polyethylene or polypropylene film or an injection molded part.

Images