Orange enhanced color masterbatch and its preparation method

Abstract

The present invention discloses an orange enhanced masterbatch and a preparation method thereof, belonging to the technical field of polymer material coloring. The method includes mixing and ball-milling a pigment with a modified coupling agent, adding magnesium stearate and then sand-milling to obtain a color paste; mixing the color paste with PP, antioxidant, plasticizer and light stabilizer and carrying out intensive mixing; then extruding and pelletizing through a twin-screw extruder to obtain a pretreated masterbatch; finally drying and screening to obtain the orange enhanced masterbatch. Compared with the prior art, the present invention is prepared by a specific synthesis process, enhancing the compatibility between the pigment and PP, and improving the dispersibility and aging resistance of the masterbatch. The masterbatch of the present invention has excellent color uniformity, stability and aging resistance, and is applicable to the field of high-performance plastic coloring.

Description

Technical Field

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

[0002] In the technical field of polymer material coloring, masterbatch, as an efficient and convenient colorant, is widely used in the production of products such as plastics, fibers, and rubbers. 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 problems in the preparation process of traditional PP masterbatch, which limit its development in high-performance application fields.

[0003] Firstly, the poor dispersion of pigments in the PP carrier is a long-existing problem. The dispersion of pigments directly affects the color uniformity and stability of the final product. During high-temperature processing, pigment particles are prone to agglomeration, resulting in uneven color distribution and affecting the appearance and quality of the product. In addition, the dispersion of pigments also affects the physical properties of the product, such as strength and toughness.

[0004] Secondly, the existing masterbatch has insufficient stability and aging resistance during the 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 persistence and product integrity.

[0005] In addition, traditional masterbatch preparation methods often involve complex processes and high-cost raw materials, which limit their application in large-scale industrial production. Therefore, developing a simple, efficient, and cost-effective masterbatch preparation method is of great significance for promoting the development of plastic coloring technology.

[0006] Chinese invention patent CN116426098A discloses a coloring masterbatch, a preparation method thereof, and an application, including components in the following parts by mass: 45-99 parts of a polymer carrier, 1-45 parts of a depolymerized pigment pre-formulation, and 0.1-10 parts of an antioxidant. The depolymerized pigment pre-formulation is a composition obtained by melt mixing, grinding, filtering, and drying a composite dispersant, an organic pigment, a coupling agent, and deionized water, and has good dispersion and strong coloring power for the organic pigment. However, the coloring 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 dispersion of pigments in the PP carrier, enhance the stability and aging resistance of the masterbatch, and simplify the production process and reduce the production cost through innovative modification coupling agents and specific preparation processes.

[0008] To achieve the above-mentioned invention object, the present invention adopts the following technical solutions:

[0009] The preparation method of an orange-enhanced masterbatch is as follows, by weight:

[0010] Step 1: Mix 25 - 35 parts of orange pigment with 2 - 4 parts of modified coupling agent evenly, ball mill at 1 - 10°C for 30 - 60 minutes, mix with 0.5 - 2 parts of dispersant, and perform cyclic grinding through a sand mill for 2 - 4 hours to ensure high dispersion of the pigment, obtaining a color paste;

[0011] Step 2: Mix the color paste obtained in Step 1 with 60 - 70 parts of PP, then add 0.4 - 0.6 parts of antioxidant, 0.2 - 0.4 parts of plasticizer, and 0.1 - 0.3 parts of light stabilizer, and use a mixer to knead, obtaining a kneaded product;

[0012] Step 3: Transfer the kneaded product obtained in Step 2 to a twin-screw extruder for extrusion granulation, cool and pelletize the extruded material, obtaining a pretreated masterbatch;

[0013] Step 4: Perform drying treatment on the pretreated masterbatch obtained in Step 3 to control the moisture content below 0.5% - 0.7% to ensure the stability and processing performance of the masterbatch. Screen the dried masterbatch to control the particle size at 2 - 5 mm and the length at 3 - 5 mm, obtaining an orange-enhanced masterbatch.

[0014] The dispersant is at least one of magnesium stearate, zinc stearate, calcium stearate, and polyethylene wax.

[0015] The antioxidant is at least one of antioxidant 1010, antioxidant TPP, and antioxidant CA.

[0016] The orange pigment is permanent orange.

[0017] The plasticizer is at least one of diisooctyl phthalate, diisooctyl phthalate, dibutyl phthalate, and diisodecyl phthalate.

[0018] The light stabilizer is light stabilizer 770.

[0019] The kneading temperature is controlled at 190 - 220°C, and the time is 30 - 60 minutes.

[0020] 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 die head temperature is 220 - 230°C, and the melt temperature is maintained at 224 - 227°C for extrusion.

[0021] The preparation method of the modified coupling agent is as follows, by weight:

[0022] S1. Add 200 - 400 parts of 5-chloro-5H-dibenzophosphole, 100 - 150 parts of 1,7-octadiene-3-ol, and 100 - 120 parts of triethylamine into 2500 - 3500 parts of N,N-dimethylformamide solvent. Start stirring at 15 - 25°C for 1 - 5 hours, then raise the temperature to 35 - 45°C at a heating rate of 2 - 4°C / min and continue stirring for 1 - 4 hours. Then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product into 2000 - 3000 parts of chloroform, add 1500 - 2500 parts of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter to collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 1 - 5°C for 12 - 48 hours to obtain a purified product;

[0023] S2. Mix the purified product prepared in step S1 with 180 - 220 parts of 1,4-dithiothreitol and 4 - 6 parts of 1-hydroxycyclohexyl phenyl ketone, add them into 2500 - 3000 parts of chloroform, stir, place under a UV lamp with a light intensity of 300 - 400 mJ / cm 2 , irradiate for 5 - 15 min, then let it stand and perform vacuum distillation to obtain a post-treatment product;

[0024] S3. Add the post-treatment product prepared in step S2, 15 - 25 parts of citric acid, and 250 - 350 parts of 3-methacryloxypropyl tris(isopropenyloxy)silane into 1500 - 2500 parts of 90 - 98 wt% ethanol aqueous solution for treatment for 2 - 6 hours, then perform vacuum distillation. Perform vacuum drying at 1 - 5°C for 12 - 48 hours to obtain the modified coupling agent.

[0025] In the preparation method of the orange enhanced masterbatch of the present invention, the functions of each substance are as follows:

[0026] Permanent Orange, as an orange pigment, provides the color required for the masterbatch.

[0027] The modified coupling agent improves the compatibility between the pigment and polypropylene resin (PP), and enhances the dispersibility and stability of the pigment.

[0028] Magnesium stearate, as a dispersant, reduces the friction during the grinding process and helps the pigment to be more evenly dispersed.

[0029] PP, as a carrier resin, carries the pigment and ensures the uniform distribution of the masterbatch during the plastic processing.

[0030] Antioxidant 1010 prevents the color masterbatch from oxidative degradation during processing or long-term use, and extends the product life.

[0031] Diisooctyl phthalate, as a plasticizer, improves the processing performance of the color masterbatch and increases its flexibility.

[0032] Light stabilizer 770, as a light stabilizer, improves the light stability of the color masterbatch.

[0033] 5-Chloro-5H-dibenzophosphole, as the starting material of the modified coupling agent, provides phosphorus element and may be used to enhance the heat resistance and light resistance of pigments.

[0034] 1,7-Octadien-3-ol, as the synthesis raw material of the modified coupling agent, provides reaction sites and helps to form a stable coupling structure.

[0035] Triethylamine, as a catalyst or assistant for synthesizing the modified coupling agent, promotes the reaction.

[0036] N,N-Dimethylformamide, as a solvent, is used in the synthesis process of the coupling agent to dissolve the reactants and provide a homogeneous reaction system.

[0037] 1,4-Dithiothreitol, as a component in the synthesis of the modified coupling agent, may be used to introduce sulfur atoms and enhance the chemical bonding between pigments and resins.

[0038] 1-Hydroxycyclohexyl phenyl ketone, as an assistant of the photoinitiator, improves the efficiency of the synthesis reaction of the modified coupling agent.

[0039] Citric acid, as a pH regulator, may be used for pH control in the synthesis process of the modified coupling agent to optimize the reaction conditions.

[0040] 3-Methacryloxypropyl tris(isopropenyloxy)silane, as the synthesis raw material of the modified coupling agent, provides a silyl group and enhances the coupling effect between pigments and resins.

[0041] Through the synergistic effect of these substances, the orange enhanced color masterbatch of the present invention exhibits excellent dispersibility, stability and anti-aging performance during processing and application.

[0042] Compared with the prior art, it has the following beneficial effects:

[0043] 1) By using the modified coupling agent and specific grinding processes (ball milling and sand milling), the present invention can effectively improve the dispersibility of the permanent orange pigment in the polypropylene carrier, thereby obtaining an orange enhanced color masterbatch. This high dispersibility helps to improve the color uniformity and stability of the final plastic product.

[0044] 2) The use of the modified coupling agent in 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, this modified coupling agent helps the pigment better combine with the polypropylene resin, reducing pigment agglomeration and migration, and ensuring excellent performance of the masterbatch during processing and use.

[0045] 3) The addition of antioxidants, light stabilizers, and special modified coupling agents in the present invention improves the aging resistance of the masterbatch. This enables the masterbatch to maintain good color stability and mechanical properties during long-term use, especially under conditions exposed to aging factors such as light, heat, and oxygen, and extends the service life of plastic products. Detailed implementation mode

[0046] Main sources of substances:

[0047] Permanent Orange: Product number: C77201315, type: bisazo pigment, Shandong Yousuo Chemical Technology Co., Ltd.

[0048] PP: Grade: YPJ-1215C, Yangzi Petrochemical.

[0049] 5-chloro-5H-dibenzophosphole: CAS number: 33300-85-5.

[0050] 3-methacryloxypropyltris(isopropenyloxy)silane: CAS number: 78051-94-2.

[0051] Methacryloxypropyltriethoxysilane: CAS number: 21142-29-0.

[0052] Vinyltriethoxysilane: CAS number: 78-08-0.

[0053] The remaining raw materials in the examples and comparative examples of the present invention are all commercially available products.

[0054] The design concept of the present invention is to use a specific modified coupling agent to enhance the compatibility and binding force 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 design aims to improve pigment dispersion, ensuring that the resulting masterbatch exhibits excellent uniform coloring and long-term stability in plastic products. By this method, the quality and appearance of plastic products can be significantly improved to meet the requirements of high-performance plastic coloring.

[0055] Example 1

[0056] A preparation method of an orange enhanced masterbatch is as follows:

[0057] Step 1: Mix 30 kg of permanent orange and 3 kg of modified coupling agent evenly, ball mill at 5°C for 50 minutes, mix with 1 kg of magnesium stearate, and perform cyclic grinding through a sand mill for 3 hours to ensure high dispersion of the pigment, obtaining a color paste;

[0058] 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 use a Banbury mixer for mixing. Control the mixing temperature at 200°C and the time at 40 minutes to obtain a mixed product;

[0059] Step 3: Transfer the mixed 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 die head temperature 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;

[0060] Step 4: Perform drying treatment on the pretreated masterbatch obtained in Step 3 to control the moisture content below 0.5% to ensure the stability and processing performance of the masterbatch. The dried masterbatch is sieved to control the particle size at 2.7 mm and the length at 3.6 mm to obtain an orange enhanced masterbatch.

[0061] The preparation method of the modified coupling agent is as follows:

[0062] S1: Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadiene-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent, start stirring at 20°C, continue for 3 hours, then raise the temperature to 40°C at a heating rate of 3°C / min, and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pretreated product. Add the pretreated product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying treatment, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying treatment at 2°C for 24 hours to obtain a purified product;

[0063] S2: Mix the purified product prepared in Step S1 with 200 g of 1,4-dithiothreitol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , irradiate for 10 minutes, let stand, and perform vacuum distillation to obtain a post-treated product;

[0064] S3. Add the post-treated product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyltris(isopropenyloxy)silane to 2000 g of a 95 wt% ethanol aqueous solution, treat for 5 hours, then perform vacuum distillation, and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0065] Example 2

[0066] The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, and the only difference lies in the different preparation methods of the modified coupling agent.

[0067] The preparation method of the modified coupling agent is as follows:

[0068] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 5-hexene-1,2-diol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent, start stirring at 20 °C, continue for 3 hours, then raise the temperature to 40 °C at a heating rate of 3 °C / min, and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pre-treated product. Add the pre-treated product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying treatment, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying treatment at 2 °C for 24 hours to obtain a purified product;

[0069] S2. Mix the purified product prepared in step S1 with 200 g of 1,4-dithiothreitol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , irradiate for 10 min, then let stand and perform vacuum distillation to obtain a post-treated product;

[0070] S3. Add the post-treated product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyltris(isopropenyloxy)silane to 2000 g of a 95 wt% ethanol aqueous solution, treat for 5 hours, then perform vacuum distillation, and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0071] Example 3

[0072] The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, and the only difference lies in the different preparation methods of the modified coupling agent.

[0073] The preparation method of the modified coupling agent is as follows:

[0074] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadien-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent. Start stirring at 20 °C for 3 hours. Then raise the temperature to 40 °C at a rate of 3 °C / min and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 2 °C for 24 hours to obtain a purified product;

[0075] S2. Mix the purified product prepared in step S1 with 200 g of 1,3-dimercaptopropan-2-ol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , irradiate for 10 min, then let stand and perform vacuum distillation to obtain a post-treatment product;

[0076] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyl tris(isopropenyloxy)silane to 2000 g of 95 wt% ethanol aqueous solution and treat for 5 hours. Then perform vacuum distillation and perform vacuum drying at 2 °C for 24 hours to obtain the modified coupling agent.

[0077] Example 4

[0078] The preparation method of an orange enhanced color masterbatch is basically the same as that of Example 1, and the only difference is the preparation method of the modified coupling agent.

[0079] The preparation method of the modified coupling agent is as follows:

[0080] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadien-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent. Start stirring at 20 °C for 3 hours. Then raise the temperature to 40 °C at a rate of 3 °C / min and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 2 °C for 24 hours to obtain a purified product;

[0081] S2. Mix the purified product prepared in step S1 with 200 g of 3-mercapto-1,2-propanediol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add them to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , after irradiating for 10 min, let it stand, and perform vacuum distillation to obtain a post-treatment product;

[0082] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyl tris(isopropenyloxy)silane to 2000 g of 95 wt% ethanol aqueous solution and process for 5 hours, then perform vacuum distillation and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0083] Example 5

[0084] The preparation method of an orange enhanced color masterbatch is basically the same as that of Example 1, and the only difference is the different preparation method of the modified coupling agent.

[0085] The preparation method of the modified coupling agent is as follows:

[0086] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadiene-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent, start stirring at 20 °C for 3 hours, then raise the temperature to 40 °C at a heating rate of 3 °C / min and continue stirring for 2 hours, then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product to 2500 g of chloroform, add 2000 g of water, shake and perform liquid separation operation, select the organic phase, add anhydrous sodium sulfate for drying treatment, filter and collect the filtrate, and perform vacuum distillation again and perform vacuum drying treatment at 2 °C for 24 hours to obtain a purified product;

[0087] S2. Mix the purified product prepared in step S1 with 200 g of 1-mercapto-2-propanol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add them to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , after irradiating for 10 min, let it stand, and perform vacuum distillation to obtain a post-treatment product;

[0088] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyl tris(isopropenyloxy)silane to 2000 g of 95 wt% ethanol aqueous solution and process for 5 hours, then perform vacuum distillation and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0089] Example 6

[0090] The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, and the only difference is the different preparation method of the modified coupling agent.

[0091] The preparation method of the modified coupling agent is as follows:

[0092] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadiene-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent. Start stirring at 20 °C and continue for 3 hours. Then raise the temperature to 40 °C at a heating rate of 3 °C / min and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter to collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 2 °C for 24 hours to obtain a purified product;

[0093] S2. Mix the purified product prepared in step S1 with 200 g of 1,4-dithioerythritol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add them to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , irradiate for 10 min, then let it stand and perform vacuum distillation to obtain a post-treatment product;

[0094] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of methacryloxypropyltriethoxysilane to 2000 g of 95 wt% ethanol aqueous solution and treat for 5 hours. Then perform vacuum distillation and perform vacuum drying at 2 °C for 24 hours to obtain the modified coupling agent.

[0095] Comparative Example 1

[0096] The preparation method of an orange enhanced masterbatch is basically the same as that of Example 1, and the only difference is the different preparation method of the modified coupling agent.

[0097] The preparation method of the modified coupling agent is as follows:

[0098] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 5-hexen-1-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent. Start stirring at 20 °C and continue for 3 hours. Then raise the temperature to 40 °C at a rate of 3 °C / min and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pretreated product. Add the pretreated product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 2 °C for 24 hours to obtain a purified product;

[0099] S2. Mix the purified product prepared in step S1 with 200 g of 1,4-dithiothreitol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , after irradiating for 10 min, let stand, and perform vacuum distillation to obtain a post-treated product;

[0100] S3. Add the post-treated product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyl tris(isopropenyloxy)silane to 2000 g of 95 wt% ethanol aqueous solution and treat for 5 hours. Then perform vacuum distillation and perform vacuum drying at 2 °C for 24 hours to obtain the modified coupling agent.

[0101] Comparative Example 2

[0102] The preparation method of an orange enhanced color masterbatch is basically the same as that of Example 1, and the only difference is the preparation method of the modified coupling agent.

[0103] The preparation method of the modified coupling agent is as follows:

[0104] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadien-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent. Start stirring at 20 °C and continue for 3 hours. Then raise the temperature to 40 °C at a rate of 3 °C / min and continue stirring for 2 hours. Then remove the solvent by vacuum distillation to obtain a pretreated product. Add the pretreated product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation. Select the organic phase, add anhydrous sodium sulfate for drying, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying at 2 °C for 24 hours to obtain a purified product;

[0105] S2. Mix the purified product prepared in step S1 with 200 g of 6-mercaptohexan-1-ol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add them to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , after irradiating for 10 min, let it stand, and perform vacuum distillation to obtain a post-treatment product;

[0106] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of 3-methacryloxypropyl tris(isopropenyloxy)silane to 2000 g of 95 wt% ethanol aqueous solution and treat for 5 hours, then perform vacuum distillation and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0107] Comparative Example 3

[0108] A preparation method of an orange-enhanced color masterbatch is basically the same as that of Example 1, and the only difference is that the preparation method of the modified coupling agent is different.

[0109] The preparation method of the modified coupling agent is as follows:

[0110] S1. Add 300 g of 5-chloro-5H-dibenzophosphole, 120 g of 1,7-octadiene-3-ol, and 110 g of triethylamine to 3000 g of N,N-dimethylformamide solvent, start stirring at 20 °C, continue for 3 hours, then raise the temperature to 40 °C at a heating rate of 3 °C / min and continue stirring for 2 hours, then remove the solvent by vacuum distillation to obtain a pre-treatment product. Add the pre-treatment product to 2500 g of chloroform, add 2000 g of water, shake, and perform liquid separation operation. Select the organic phase, add anhydrous sodium sulfate for drying treatment, filter, collect the filtrate, and perform vacuum distillation again. Perform vacuum drying treatment at 2 °C for 24 hours to obtain a purified product;

[0111] S2. Mix the purified product prepared in step S1 with 200 g of 1,4-dithiothreitol and 5 g of 1-hydroxycyclohexyl phenyl ketone, add them to 2800 g of chloroform, stir, place under a UV lamp with a light intensity of 350 mJ / cm 2 , after irradiating for 10 min, let it stand, and perform vacuum distillation to obtain a post-treatment product;

[0112] S3. Add the post-treatment product prepared in step S2, 20 g of citric acid, and 300 g of vinyltriethoxysilane to 2000 g of 95 wt% ethanol aqueous solution and treat for 5 hours, then perform vacuum distillation and perform vacuum drying treatment at 2 °C for 24 hours to obtain the modified coupling agent.

[0113] Comparative Example 4

[0114] The preparation method of an orange enhanced masterbatch is as follows:

[0115] Step 1: Ball mill 30 kg of permanent orange at 5 °C for 50 minutes, mix it with 1 kg of magnesium stearate, and perform cyclic grinding through a sand mill for 3 hours to ensure high dispersion of the pigment, obtaining a color paste;

[0116] Step 2: Mix the color paste obtained in Step 1 with 65 kg of PP, then add 0.5 kg of antioxidant 1010, 0.3 kg of diisooctyl phthalate, and 0.2 kg of light stabilizer 770, and use a Banbury mixer for mixing. The mixing temperature is controlled at 200 °C and the time is 40 minutes, obtaining a mixed product;

[0117] Step 3: Transfer the mixed 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 die head temperature 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;

[0118] Step 4: Perform a drying treatment on the pretreated masterbatch obtained in Step 3 to control the moisture content below 0.5% to ensure the stability and processing performance of the masterbatch. The dried masterbatch is screened to control the particle size at 2.7 mm and the length at 3.6 mm, obtaining an orange enhanced masterbatch.

[0119] Test Example 1

[0120] Color difference test

[0121] To evaluate the difference in the coloring performance of the orange enhanced masterbatch produced in the examples and the control group, the orange enhanced masterbatch was respectively incorporated into the PP resin at a weight ratio of 9%, and pressed into PP plastic templates. Subsequently, using a CM-5 type spectrophotometer manufactured by Konica Minolta, the color difference value ΔE of the same batch of dyed PP plastic templates was measured. Through this method, the influence of different masterbatch preparation methods on the color consistency of the final colored plastic can be compared.

[0122] The test results are shown in Table 1.

[0123] Table 1

[0124]

[0125] Test Example 2

[0126] Aging resistance test

[0127] The test example 1 was used to press a PP plastic sample. According to the national standard GB / T 3681.2-2021 Plastics - Methods of exposure to solar radiation - Part 2: Direct natural weathering and weathering in a chamber behind window glass, the material was subjected to a one-year natural weathering test to evaluate its weather resistance. The test location was selected in Hainan, the sample faced south, and the inclination angle was set at 45 degrees to simulate the exposure conditions in actual use. The PP plastic samples of the same batch were stored indoors at room temperature in the dark and airtight as a control group. Through this long-term exposure test, the aging resistance ability and service life of plastic materials in the natural environment can be effectively evaluated.

[0128] The test results are shown in Table 2.

[0129] Table 2

[0130]

[0131] From the data in Tables 1 and 2, it can be seen that the orange enhanced masterbatch prepared in Example 1 has a small color difference and strong aging resistance ability.

[0132] In Example 1 of the present invention, 1,7-octadien-3-ol used has a longer carbon chain and more double bonds compared with hexene-5-1,2-diol in Example 2 and 5-hexen-1-ol in Comparative Example 1. This enables 1,7-octadien-3-ol to provide more reaction sites and a better steric hindrance effect. 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, enhancing the thermal stability and aging resistance of the masterbatch during processing. Therefore, the masterbatch using 1,7-octadien-3-ol shows better performance in terms of color difference and aging resistance, which is related to the carbon chain length and the number of double bonds in the molecular structure, and they jointly improve the overall performance of the masterbatch.

[0133] 1,4-Dithiothreitol is a compound containing two mercapto groups (-SH), which are located at both ends of the molecule and connected by a butane chain. This structure makes 1,4-dithiothreitol have strong reactivity because it can form stable thioether bonds with various substances. In the preparation of orange enhanced masterbatch, using 1,4-dithiothreitol as a component of the modified coupling agent can improve the dispersibility of pigments and the stability of masterbatch. Compared with other mercapto compounds, such as 1,3-dimercaptopropan-2-ol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol and 6-mercaptohexan-1-ol, the two mercapto groups of 1,4-dithiothreitol provide more reactive sites, which helps to enhance the interaction between pigments and polymers, thus improving the dispersibility and stability of masterbatch. In addition, the longer carbon chain of 1,4-dithiothreitol may help to form a more uniform distribution in the polymer matrix, further enhancing the dispersibility of pigments. In terms of anti-aging performance, the two mercapto groups of 1,4-dithiothreitol can form strong interactions, enhancing the binding force between pigments and polymers, thus improving the anti-aging performance of masterbatch. This structural advantage makes the masterbatch using 1,4-dithiothreitol perform better in terms of color difference and anti-aging performance.

[0134] In Example 1 of the present invention, 3-methacryloxypropyl tris(isopropenyloxy)silane used as a coupling agent has two functional groups, methacryloxy and isopropenyloxy, in its molecular structure. This structure provides several key advantages: First, methacryloxy can form covalent bonds with active groups in the polymer matrix, enhancing the interfacial binding force between pigments and polymers; Second, isopropenyloxy provides steric hindrance, which helps to disperse pigments in the polymer matrix and reduce pigment aggregation, thus improving the dispersibility and stability of masterbatch; This structure may also help to improve the thermal stability of masterbatch during processing, thus enhancing its anti-aging performance. In contrast, although methacryloxypropyl triethoxysilane used in Example 6 and vinyltriethoxysilane used in Comparative Example 3 also provide certain coupling effects, they are not as effective as 3-methacryloxypropyl tris(isopropenyloxy)silane in improving the dispersibility and anti-aging performance of 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 anti-aging ability of orange enhanced masterbatch due to its unique molecular structure.

Claims

1. A preparation method of an orange enhancing masterbatch, characterized in that, The method is as follows, by weight parts: Step 1: Mix 25 - 35 parts of orange pigment and 2 - 4 parts of modified coupling agent evenly, ball mill at 1 - 10 °C for 30 - 60 minutes, mix it with 0.5 - 2 parts of dispersant, and perform cyclic grinding through a sand mill for 2 - 4 hours to obtain a color paste; Step 2: Mix the color paste obtained in Step 1 with 60 - 70 parts of PP, then add 0.4 - 0.6 parts of antioxidant, 0.2 - 0.4 parts of plasticizer, and 0.1 - 0.3 parts of light stabilizer, and knead to obtain a kneaded product; Step 3: Extrude and pelletize the kneaded product obtained in Step 2, cool and cut into pellets to obtain a pretreated masterbatch; Step 4: Dry the pretreated masterbatch obtained in Step 3 to obtain the orange enhanced masterbatch; The preparation method of the modified coupling agent is as follows, by weight parts: S1: Add 200 - 400 parts of 5 - chloro - 5H - dibenzophosphole, 100 - 150 parts of 1,7 - octadiene - 3 - ol, and 100 - 120 parts of triethylamine to 2500 - 3500 parts of N,N - dimethylformamide solvent, start stirring at 15 - 25 °C for 1 - 5 hours, then raise the temperature to 35 - 45 °C, with a heating rate of 2 - 4 °C / min, and continue stirring for 1 - 4 hours. Then remove the solvent by vacuum distillation to obtain a pretreated product. Add the pretreated product to 2000 - 3000 parts of chloroform, add 1500 - 2500 parts of water, shake and perform liquid - separation operation. Select the organic phase, add anhydrous sodium sulfate for drying treatment, filter and collect the filtrate, and perform vacuum distillation again. Perform vacuum drying treatment at 1 - 5 °C for 12 - 48 hours to obtain a purified product; S2. Mix the purified product prepared in step S1 with 180 - 220 parts of 1,4 - dithiothreitol and 4 - 6 parts of 1 - hydroxycyclohexyl phenyl ketone, add them to 2500 - 3000 parts of chloroform, stir, place under a UV lamp with a light intensity of 300 - 400 mJ / cm 2 . After irradiating for 5 - 15 min, let it stand, and perform vacuum distillation to obtain a post - treatment product; S3: Add the post - treated product prepared in Step S2, 15 - 25 parts of citric acid, and 250 - 350 parts of 3 - methacryloxypropyl tris(isopropenyloxy)silane to 1500 - 2500 parts of 90 - 98wt% ethanol aqueous solution for treatment for 2 - 6 hours, then perform vacuum distillation, and perform vacuum drying treatment at 1 - 5 °C for 12 - 48 hours to obtain the modified coupling agent.

2. The preparation method of the orange-enhanced color 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 preparation method of the orange enhanced color masterbatch according to claim 1, characterized in that, The antioxidant is at least one of antioxidant 1010, antioxidant TPP, and antioxidant CA.

4. The preparation method of the orange enhanced color masterbatch according to claim 1, characterized in that The orange pigment is permanent orange.

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

6. The preparation method of the orange enhanced color masterbatch according to claim 1, characterized in that The light stabilizer is light stabilizer 770.

7. The preparation method of the orange enhanced color masterbatch according to claim 1, characterized in that, The kneading temperature is controlled at 190 - 220 °C, and the time is 30 - 60 minutes.

8. The preparation method of the orange-enhanced color masterbatch according to claim 1, characterized in that, During the extrusion and pelletizing 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 die head temperature is 220 - 230 °C, and the melt temperature is maintained at 224 - 227 °C for extrusion.

9. An orange enhanced masterbatch, characterized in that, Prepared by the preparation method according to any one of claims 1 - 8.

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