Orange enhanced color master batch and preparation method thereof

Abstract

The invention discloses an orange enhanced color master batch and a preparation method thereof, and belongs to the technical field of high polymer material coloring, the method comprises the following steps: mixing and ball-milling a pigment and a modified coupling agent, adding magnesium stearate, and sanding to obtain color paste; mixing and banburying the color paste, PP, an antioxidant, a plasticizer and a light stabilizer; extruding and granulating through a double-screw extruder to obtain pretreated color master batches; and finally, drying and screening to obtain the orange enhanced color master batch. Compared with the prior art, the color master batch is prepared through a specific synthesis process, the compatibility of the pigment and PP is enhanced, and the dispersity and aging resistance of the color master batch are improved. The color master batch provided by the invention has excellent color uniformity, stability and aging resistance, and is suitable for the field of high-performance plastic coloring.

Description

Technical Field

[0001] The invention relates to the technical field of polymer material coloring, in particular to an orange enhanced masterbatch and a preparation method thereof. Background Art

[0002] In the field of polymer coloring technology, masterbatch, as an efficient and convenient colorant, is widely used in the production of plastics, fibers, rubber and other products. Polypropylene (PP), as an important engineering plastic, is widely used due to its excellent mechanical properties, wear resistance and chemical stability. However, there are some technical difficulties in the preparation process of traditional PP masterbatch, which limits its development in high-performance application fields.

[0003] First, poor pigment dispersion in PP carriers is a long-standing problem. Pigment dispersion directly affects the color uniformity and stability of the final product. During high-temperature processing, pigment particles tend to agglomerate, resulting in uneven color distribution, affecting the appearance and quality of the product. In addition, pigment dispersion also affects the physical properties of the product, such as strength and toughness.

[0004] Secondly, the masterbatch of the prior art is not stable and aging resistant during processing. During the long-term use of plastic products, especially in outdoor applications, the masterbatch needs to have good light resistance, heat resistance and chemical corrosion resistance to maintain the color durability and product integrity.

[0005] In addition, the traditional masterbatch preparation method often involves complicated processes and high-cost raw materials, which limits its application in large-scale industrial production. Therefore, the development of a simple, efficient and cost-effective masterbatch preparation method is of great significance to promote the development of plastic coloring technology.

[0006] Chinese invention patent CN116426098A discloses a color masterbatch and its preparation method and application, which includes the following components by mass: 45-99 parts of polymer carrier, 1-45 parts of depolymerized pigment preformulation, 0.1-10 parts of antioxidant, the depolymerized pigment preformulation is a composite dispersant, organic pigment, coupling agent and deionized water, melt mixed and ground, filtered and dried to obtain a composition, which has good dispersibility for organic pigments and strong tinting power. However, the color masterbatch obtained by this preparation method still needs to be improved in terms of color uniformity and stability. Summary of the invention

[0007] In view of the above problems, the present invention provides an orange enhanced masterbatch and a preparation method thereof, aiming to improve the dispersibility of the pigment in the PP carrier, enhance the stability and aging resistance of the masterbatch through an innovative modified coupling agent and a specific preparation process, while simplifying the production process and reducing the production cost.

[0008] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions: A preparation method of an orange enhanced masterbatch is as follows, in parts by weight: Step 1, 25-35 parts of orange pigment and 2-4 parts of modified coupling agent are mixed evenly, ball-milled at 1-10°C for 30-60 minutes, mixed with 0.5-2 parts of dispersant, and cyclically ground by a sand mill for 2-4 hours to ensure high dispersibility of the pigment, thereby obtaining a color paste; Step 2, mixing the color paste obtained in step 1 with 60-70 parts of PP, adding 0.4-0.6 parts of antioxidant, 0.2-0.4 parts of plasticizer and 0.1-0.3 parts of light stabilizer, and mixing using an internal mixer to obtain an internal mixer product; Step 3, transferring the banburying product obtained in step 2 to a twin-screw extruder for extrusion granulation, cooling and pelletizing the extruded material to obtain a pre-treated masterbatch; Step 4: Dry the pretreated masterbatch obtained in step 3 to control the moisture content to less than 0.5% to 0.7% to ensure the stability and processing performance of the masterbatch. The dried masterbatch is sieved to control the particle size to 2 to 5 mm and the length to 3 to 5 mm to obtain an orange enhanced masterbatch.

[0009] The dispersant is at least one of magnesium stearate, zinc stearate, calcium stearate and polyethylene wax.

[0010] The antioxidant is at least one of antioxidant 1010, antioxidant TPP, and antioxidant CA.

[0011] The orange pigment is permanent orange.

[0012] The plasticizer is at least one of diisooctyl phthalate, diisooctyl phthalate, dibutyl phthalate and diisodecyl phthalate.

[0013] The light stabilizer is light stabilizer 770.

[0014] The mixing temperature is controlled at 190-220° C., and the mixing time is 30-60 minutes.

[0015] During the extrusion granulation process, the temperature of the front section of the extruder is 195-200°C, the temperature of the rear section is 225-230°C, the temperature of the die head is 220-230°C, and the melt temperature is maintained at 224-227°C for extrusion.

[0016] The preparation method of the modified coupling agent is as follows, in parts by weight: S1, adding 200-400 parts of 5-chloro-5H-dibenzophosphopentene, 100-150 parts of 1,7-octadiene-3-ol and 100-120 parts of triethylamine to 2500-3500 parts of N,N-dimethylformamide solvent, stirring was started at 15-25°C for 1-5 hours, then the temperature was raised to 35-45°C at a heating rate of 2-4°C / min, and stirring was continued for 1-4 hours, and then the solvent was removed by reduced pressure distillation to obtain a pretreated product, the pretreated product was added to 2000-3000 parts of chloroform, 1500-2500 parts of water were added, the mixture was shaken and a liquid separation operation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and reduced pressure distillation was performed again, and vacuum drying was performed at 1-5°C for 12-48 hours to obtain a purified product; S2, the purified product prepared in step S1 is mixed with 180-220 parts of 1,4-dithioerythritol and 4-6 parts of 1-hydroxycyclohexylphenyl ketone, added into 2500-3000 parts of chloroform, stirred, and placed under a UV lamp with a light intensity of 300-400 mJ / cm 2 , after irradiation for 5 to 15 minutes, let it stand and perform vacuum distillation to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 15-25 parts of citric acid, and 250-350 parts of 3-methacryloxypropyltri(isopropenyloxy)silane to 1500-2500 parts of 90-98wt% ethanol aqueous solution for 2-6 hours, then performing reduced pressure distillation, and performing vacuum drying at 1-5°C for 12-48 hours to obtain the modified coupling agent.

[0017] In the preparation method of the orange enhanced masterbatch of the present invention, the functions of the various substances are as follows: Permanent Orange is used as an orange pigment to provide the color required for masterbatch.

[0018] The modified coupling agent improves the compatibility between the pigment and polypropylene resin (PP), and enhances the dispersion and stability of the pigment.

[0019] Magnesium stearate acts as a dispersant, reducing friction during the grinding process and helping the pigment to disperse more evenly.

[0020] PP acts as a carrier resin, carrying the pigment and ensuring uniform distribution of the masterbatch during plastic processing.

[0021] Antioxidant 1010 prevents masterbatch from oxidative degradation during processing or long-term use, thus extending the product life.

[0022] Di(2-ethylhexyl) phthalate is used as a plasticizer to improve the processing properties of masterbatch and increase its flexibility.

[0023] Light stabilizer 770 is used as a light stabilizer to improve the light stability of masterbatch.

[0024] 5-Chloro-5H-dibenzophosphopentene is used as the starting material of the modified coupling agent to provide phosphorus element, which may be used to enhance the heat resistance and light resistance of the pigment.

[0025] 1,7-Octadien-3-ol is used as a synthetic raw material for the modified coupling agent, providing reaction sites and helping to form a stable coupling structure.

[0026] Triethylamine is used as a catalyst or auxiliary agent for synthesizing the modified coupling agent to promote the reaction.

[0027] N,N-dimethylformamide is used as a solvent in the synthesis process of the coupling agent to dissolve the reactants and provide a homogeneous reaction system.

[0028] As a component in the synthesis of modified coupling agents, 1,4-dithioerythritol may be used to introduce sulfur atoms and enhance the chemical bonding between pigment and resin.

[0029] 1-Hydroxycyclohexyl phenyl ketone is used as an auxiliary agent of the photoinitiator to improve the efficiency of the synthetic reaction of the modified coupling agent.

[0030] Citric acid, as a pH regulator, may be used to control pH during the synthesis of modified coupling agents and optimize reaction conditions.

[0031] 3-Methacryloxypropyltri(isopropenyloxy)silane is used as a synthetic raw material for the modified coupling agent, providing silane groups to enhance the coupling effect between the pigment and the resin.

[0032] Through the synergistic effect of these substances, the orange enhanced masterbatch of the present invention exhibits excellent dispersibility, stability and aging resistance during processing and application.

[0033] Compared with the prior art, it has the following beneficial effects: 1) The present invention can effectively improve the dispersibility of the permanent orange pigment in the polypropylene carrier by using a modified coupling agent and a specific grinding process (ball milling and sand milling), thereby obtaining an orange enhanced masterbatch. This high dispersibility helps to improve the color uniformity and stability of the final plastic product.

[0034] 2) The use of the modified coupling agent of the present invention enhances the compatibility between the pigment and the polypropylene resin, thereby improving the stability and processing performance of the masterbatch. During the extrusion granulation process, the modified coupling agent helps the pigment to better combine with the polypropylene resin, reduces pigment agglomeration and migration, and ensures the excellent performance of the masterbatch during processing and use.

[0035] 3) The antioxidant, light stabilizer and special modified coupling agent added in the present invention improve the aging resistance of the masterbatch. This allows the masterbatch to maintain good color stability and mechanical properties during long-term use, especially under conditions of exposure to aging factors such as light, heat, and oxygen, thereby extending the service life of the plastic product. DETAILED DESCRIPTION

[0036] Main sources of substances: Permanent Orange: Item No.: C77201315, Type: Disazo Pigment, Shandong Yousuo Chemical Technology Co., Ltd.

[0037] PP: Brand: YPJ-1215C, Yangzi Petrochemical.

[0038] 5-Chloro-5H-dibenzophosphopentene: CAS number: 33300-85-5.

[0039] 3-Methacryloyloxypropyltri(isopropenyloxy)silane: CAS number: 78051-94-2.

[0040] Methacryloyloxypropyltriethoxysilane: CAS number: 21142-29-0.

[0041] Vinyltriethoxysilane: CAS number: 78-08-0.

[0042] The remaining raw materials in the examples and comparative examples of the present invention are all commercially available products.

[0043] The design idea of ​​the present invention is to use a specific modified coupling agent to enhance the compatibility and bonding between the pigment and PP through a precisely controlled chemical modification process, thereby preparing a PP masterbatch with high dispersibility, low color difference and high aging resistance. This process involves the fine synthesis of the modified coupling agent, and its molecular structure is designed to improve the pigment dispersibility and ensure that the obtained masterbatch exhibits excellent uniform coloring and long-term stability in plastic products. Through this method, the quality and appearance of plastic products can be significantly improved to meet the needs of high-performance plastic coloring.

[0044] Example 1 A method for preparing an orange enhanced masterbatch is as follows: Step 1, 30 kg of permanent orange and 3 kg of modified coupling agent were mixed evenly, ball-milled at 5° C. for 50 minutes, mixed with 1 kg of magnesium stearate, and cyclically ground by a sand mill for 3 hours to ensure high dispersibility of the pigment, to obtain a color paste; Step 2: Mix the color paste obtained in step 1 with 65 kg of PP, add 0.5 kg of antioxidant 1010, 0.3 kg of diisooctyl phthalate and 0.2 kg of light stabilizer 770, and mix them using an internal mixer. The mixing temperature is controlled at 200 ° C. for 40 minutes to obtain a internal mixer product. Step 3, transferring the banburying product obtained in step 2 to a twin-screw extruder for extrusion granulation, the temperature of the front section of the extruder is 200°C, the temperature of the rear section is 225°C, the temperature of the die head is 230°C, and the melt temperature is maintained at 225°C for extrusion; the extruded material is cooled and pelletized to obtain a pretreated masterbatch; Step 4: Dry the pretreated masterbatch obtained in step 3 to control the moisture content to less than 0.5% to ensure the stability and processing performance of the masterbatch. The dried masterbatch is sieved to control the particle size to 2.7 mm and the length to 3.6 mm to obtain an orange enhanced masterbatch.

[0045] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0046] Example 2 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0047] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g hexene 5-1,2-diol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, and vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0048] Example 3 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0049] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,3-dimercaptopropane-2-ol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0050] Example 4 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0051] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 3-mercapto-1,2-propylene glycol and 5 g of 1-hydroxycyclohexyl phenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0052] Example 5 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0053] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1-mercapto-2-propanol and 5 g of 1-hydroxycyclohexyl phenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0054] Example 6 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0055] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of methacryloxypropyltriethoxysilane to 2000g of 95wt% ethanol aqueous solution for treatment for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0056] Comparative Example 1 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0057] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 5-hexene-1-ol and 110g triethylamine are added to 3000g N, in N-dimethylformamide solvent, stirring is started at 20 ℃, continues 3 hours, then the temperature is raised to 40 ℃, and the heating rate is 3 ℃ / min, and stirring is continued for 2 hours, then the solvent is removed by underpressure distillation to obtain a pre-treated material, the pre-treated material is added to 2500g chloroform, after adding 2000g water, it is shaken and a liquid separation operation is performed, and an organic phase is selected, anhydrous sodium sulfate is added thereto for drying, and the filtrate is collected after filtration, and underpressure distillation is performed again, and vacuum drying is performed at 2 ℃ for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0058] Comparative Example 2 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0059] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 6-mercaptohexan-1-ol and 5 g of 1-hydroxycyclohexyl phenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid, and 300g of 3-methacryloxypropyltri(isopropenyloxy)silane to 2000g of 95wt% ethanol aqueous solution for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0060] Comparative Example 3 The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, the only difference being that the preparation method of the modified coupling agent is different.

[0061] The preparation method of the modified coupling agent is as follows: S1, 300g 5-chloro-5H-dibenzophosphopentene, 120g 1,7-octadiene-3-ol and 110g triethylamine were added to 3000g N, N-dimethylformamide solvent, stirring was started at 20°C, continued for 3 hours, then the temperature was raised to 40°C, the heating rate was 3°C / min, and stirring was continued for 2 hours, then the solvent was removed by vacuum distillation to obtain a pre-treated product, the pre-treated product was added to 2500g chloroform, 2000g water was added and then shaken and liquid separation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and vacuum distillation was performed again, vacuum drying was performed at 2°C for 24 hours to obtain a purified product; S2, the purified product prepared in step S1 was mixed with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexylphenyl ketone, added to 2800 g of chloroform, stirred, and placed under a UV lamp with a light intensity of 350 mJ / cm 2 After irradiation for 10 min, the mixture was allowed to stand and distilled under reduced pressure to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 20g of citric acid and 300g of vinyltriethoxysilane into 2000g of 95wt% ethanol aqueous solution for treatment for 5 hours, then performing reduced pressure distillation, and performing vacuum drying at 2°C for 24 hours to obtain the modified coupling agent.

[0062] Comparative Example 4 A method for preparing an orange enhanced masterbatch is as follows: Step 1, ball-mill 30 kg of permanent orange at 5° C. for 50 minutes, mix with 1 kg of magnesium stearate, and circulate through a sand mill for 3 hours to ensure high dispersibility of the pigment to obtain a color paste; Step 2: Mix the color paste obtained in step 1 with 65 kg PP, add 0.5 kg antioxidant 1010, 0.3 kg diisooctyl phthalate and 0.2 kg light stabilizer 770, and mix them using an internal mixer. The mixing temperature is controlled at 200 ° C. for 40 minutes to obtain a internal mixer product. Step 3, transferring the banburying product obtained in step 2 to a twin-screw extruder for extrusion granulation, the temperature of the front section of the extruder is 200°C, the temperature of the rear section is 225°C, the temperature of the die head is 230°C, and the melt temperature is maintained at 225°C for extrusion; the extruded material is cooled and pelletized to obtain a pretreated masterbatch; Step 4: Dry the pretreated masterbatch obtained in step 3 to control the moisture content to less than 0.5% to ensure the stability and processing performance of the masterbatch. The dried masterbatch is sieved to control the particle size to 2.7 mm and the length to 3.6 mm to obtain an orange enhanced masterbatch.

[0063] Test Example 1 Color difference test In order to evaluate the difference in coloring performance between the orange enhanced masterbatch produced in the example and the control group, the orange enhanced masterbatch was added to the PP resin at a weight ratio of 9% and pressed into PP plastic samples. Subsequently, the color difference value ΔE of the same batch of dyed PP plastic samples was measured using a CM-5 spectrophotometer manufactured by Konica Minolta. Through this method, the effects of different masterbatch preparation methods on the color consistency of the final colored plastic can be compared.

[0064] The test results are shown in Table 1.

[0065] Table 1

[0066] Test Example 2 Aging test Test Example 1 was used to press a PP plastic sample. According to the national standard GB / T 3681.2-2021 "Plastic Solar Radiation Exposure Test Method Part 2: Direct Natural Weathering and Weathering After Exposure to Window Glass", the material was subjected to a one-year natural weathering test to evaluate its weather resistance. The test site was selected in Hainan, with the sample facing south and the inclination angle set to 45 degrees to simulate the exposure conditions in actual use. The PP plastic samples corresponding to the same batch were stored in a dark and sealed indoor room temperature as a control group. Through this long-term exposure test, the aging resistance and service life of plastic materials in the natural environment can be effectively evaluated.

[0067] The test results are shown in Table 2.

[0068] Table 2

[0069] It can be seen from the data in Tables 1 and 2 that the orange enhanced masterbatch prepared in Example 1 has small color difference and strong aging resistance.

[0070] In Example 1 of the present invention, the 1,7-octadiene-3-ol used has a longer carbon chain and more double bonds than the hexene 5-1,2-diol in Example 2 and the 5-hexene-1-ol in Comparative Example 1, which enables 1,7-octadiene-3-ol to provide more reaction sites and better steric hindrance. This structural difference helps to enhance the compatibility and binding force between the pigment and the polymer carrier, thereby improving the dispersibility and stability of the masterbatch. The longer carbon chain also helps to improve the entanglement between the modified coupling agent and the polymer chain, and enhances the thermal stability and aging resistance of the masterbatch during processing. Therefore, the masterbatch using 1,7-octadiene-3-ol performs better in color difference and aging resistance, which is related to the carbon chain length and the number of double bonds in the molecular structure, which work together to improve the overall performance of the masterbatch.

[0071] 1,4-dithioerythritol is a compound containing two thiol groups (-SH) located at the two ends of the molecule and connected by a butane chain. This structure makes 1,4-dithioerythritol highly reactive because it can form stable thioether bonds with a variety of substances. In the preparation of orange enhanced masterbatch, the use of 1,4-dithioerythritol as a component of the modified coupling agent can improve the dispersibility of the pigment and the stability of the masterbatch. Compared with other thiol compounds such as 1,3-dimercaptopropane-2-ol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol and 6-mercaptohexan-1-ol, the two thiol groups of 1,4-dithioerythritol provide more reaction sites, which helps to enhance the interaction between the pigment and the polymer, thereby improving the dispersibility and stability of the masterbatch. In addition, the longer carbon chain of 1,4-dithioerythritol may help to form a more uniform distribution in the polymer matrix, further enhancing the dispersibility of the pigment. In terms of aging resistance, the two thiol groups of 1,4-dithioerythritol can form a strong interaction, which enhances the binding force between the pigment and the polymer, thereby improving the aging resistance of the masterbatch. This structural advantage makes the masterbatch using 1,4-dithioerythritol perform better in color difference and aging resistance.

[0072] In Example 1 of the present invention, 3-methacryloxypropyl tri(isopropenyloxy)silane is used as a coupling agent, and its molecular structure contains two functional groups, methacryloxy and isopropenyloxy. This structure provides several key advantages: first, the methacryloxy group can form a covalent bond with the active group in the polymer matrix, thereby enhancing the interfacial bonding between the pigment and the polymer; second, the isopropenyloxy group provides steric hindrance, which helps to disperse the pigment in the polymer matrix and reduce pigment aggregation, thereby improving the dispersibility and stability of the masterbatch; this structure may also help to improve the thermal stability of the masterbatch during processing, thereby enhancing its aging resistance. In contrast, the methacryloxypropyl triethoxysilane used in Example 6 and the vinyl triethoxysilane used in Comparative Example 3, although they also provide a certain coupling effect, are not as effective as 3-methacryloxypropyl tri(isopropenyloxy)silane in improving the dispersibility and aging resistance of the masterbatch due to the lack of sufficient steric hindrance. Therefore, the modified coupling agent in Example 1 can more effectively improve the color difference consistency and aging resistance of the orange enhanced masterbatch due to its unique molecular structure.

Claims

1. A method for preparing an orange enhanced masterbatch, characterized in that: The method is as follows, in parts by weight: Step 1, 25-35 parts of orange pigment and 2-4 parts of modified coupling agent are mixed evenly, ball-milled at 1-10° C. for 30-60 minutes, mixed with 0.5-2 parts of dispersant, and cyclically ground by a sand mill for 2-4 hours to obtain a color paste; Step 2, mixing the color paste obtained in step 1 with 60-70 parts of PP, and then adding 0.4-0.6 parts of antioxidant, 0.2-0.4 parts of plasticizer and 0.1-0.3 parts of light stabilizer, mixing, and obtaining a banburying product; Step 3, extruding and granulating the banburying product obtained in step 2, cooling and pelletizing to obtain pre-treated masterbatch; Step 4: Dry the pretreated masterbatch obtained in step 3 to obtain the orange enhanced masterbatch.

2. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The dispersant is at least one of magnesium stearate, zinc stearate, calcium stearate and polyethylene wax.

3. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 1010, antioxidant TPP, and antioxidant CA.

4. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The orange pigment is permanent orange.

5. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The plasticizer is at least one of diisooctyl phthalate, diisooctyl phthalate, dibutyl phthalate and diisodecyl phthalate.

6. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The light stabilizer is light stabilizer 770.

7. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The mixing temperature is controlled at 190-220° C., and the mixing time is 30-60 minutes.

8. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: During the extrusion granulation process, the temperature of the front section of the extruder is 195-200°C, the temperature of the rear section is 225-230°C, the temperature of the die head is 220-230°C, and the melt temperature is maintained at 224-227°C for extrusion.

9. The method for preparing the orange enhanced masterbatch according to claim 1, characterized in that: The preparation method of the modified coupling agent is as follows, in parts by weight: S1, adding 200-400 parts of 5-chloro-5H-dibenzophosphopentene, 100-150 parts of 1,7-octadiene-3-ol and 100-120 parts of triethylamine to 2500-3500 parts of N,N-dimethylformamide solvent, stirring was started at 15-25°C for 1-5 hours, then the temperature was raised to 35-45°C at a heating rate of 2-4°C / min, and stirring was continued for 1-4 hours, and then the solvent was removed by reduced pressure distillation to obtain a pretreated product, the pretreated product was added to 2000-3000 parts of chloroform, 1500-2500 parts of water were added, the mixture was shaken and a liquid separation operation was performed, an organic phase was selected, anhydrous sodium sulfate was added thereto for drying, the filtrate was collected after filtration, and reduced pressure distillation was performed again, and vacuum drying was performed at 1-5°C for 12-48 hours to obtain a purified product; S2, the purified product prepared in step S1 is mixed with 180-220 parts of 1,4-dithioerythritol and 4-6 parts of 1-hydroxycyclohexylphenyl ketone, added into 2500-3000 parts of chloroform, stirred, and placed under a UV lamp with a light intensity of 300-400 mJ / cm 2 , after irradiation for 5 to 15 minutes, let it stand and perform vacuum distillation to obtain a post-processed product; S3, adding the post-treated product prepared in step S2, 15-25 parts of citric acid, and 250-350 parts of 3-methacryloxypropyltri(isopropenyloxy)silane to 1500-2500 parts of 90-98wt% ethanol aqueous solution for 2-6 hours, then performing reduced pressure distillation, and performing vacuum drying at 1-5°C for 12-48 hours to obtain the modified coupling agent.

10. An orange enhanced masterbatch, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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