A wear-resistant spray-free PP material

Abstract

The present invention relates to a wear-resistant, spray-free PP material, belonging to the technical field of spray-free plastics. The present invention combines a modified surfactant with a masterbatch, thereby imparting antioxidant properties to the masterbatch while simultaneously improving dispersion and bonding within the polymer. The addition of plant nanofibers renders the material more wear-resistant, and the plant nanocarbon fibers are treated with ionic liquids to enhance their dispersibility and compatibility within the polymer. The PP material of the present invention has excellent wear resistance and good surface aesthetics, requiring no additional spraying treatment. Through refined material proportioning and process optimization, it achieves excellent mechanical properties and environmental friendliness, while also exhibiting good processing performance and stable color distribution.

Description

Technical Field

[0001] The invention belongs to the technical field of spray-free plastics and relates to a wear-resistant spray-free PP material. Background Art

[0002] Polypropylene (PP) materials occupy an important position in numerous industrial applications due to their excellent overall performance and economic efficiency. PP materials have excellent mechanical properties, including high impact resistance and good toughness. At the same time, their low density makes them excellent in lightweight applications. In addition, PP materials have excellent chemical corrosion resistance and can resist the erosion of various acids, alkalis and organic solvents, which makes them widely used in chemical, packaging and other fields. PP also has excellent processing performance and can be formed through various processes such as injection molding, extrusion, and blow molding, with strong adaptability. Its good thermal stability and electrical insulation properties further broaden its scope of application, especially in the field of electronics and electrical appliances. Due to the recyclability and low environmental impact of PP materials themselves, it is also considered a relatively environmentally friendly plastic material.

[0003] Despite the numerous advantages of traditional PP materials, their surface decorative properties are relatively limited, often requiring a spray coating process to enhance their appearance. However, this process not only increases production costs but also introduces environmental pollution and health risks. Therefore, the development of spray-free PP materials has become a key direction for industry development. By directly incorporating color and surface gloss modifiers into the material formula, spray-free PP materials achieve an excellent appearance immediately after molding, eliminating the need for an additional spray coating step. This material has broad application potential in areas such as automotive interiors and appliance housings, reducing production costs while minimizing negative environmental impacts. Furthermore, spray-free PP materials offer improved scratch and abrasion resistance, extending the product's service life and enhancing its overall market competitiveness.

[0004] However, despite the significant advantages of spray-free PP materials, existing technologies still face some challenges and problems. The first is the issue of color and gloss uniformity. Due to the complexity of the material formula, how to achieve the ideal appearance effect without affecting the mechanical properties of the material still requires in-depth research. Secondly, the weather resistance and long-term stability of spray-free PP materials also need to be further improved to meet the needs of outdoor applications. In addition, existing spray-free technology may not be able to completely replace traditional spraying processes in some cases, especially in the high-end market where higher requirements are placed on color and texture. Therefore, continuously improving material formulas and processing technologies to enhance the performance and application range of spray-free PP materials remains the key to future technological development. Summary of the Invention

[0005] The present invention relates to a wear-resistant, spray-free PP material, belonging to the technical field of spray-free plastics. The present invention combines a modified surfactant with a masterbatch, thereby imparting antioxidant properties to the masterbatch while simultaneously improving dispersion and bonding within the polymer. The addition of plant nanofibers renders the material more wear-resistant, and the plant nanocarbon fibers are treated with ionic liquids to enhance their dispersibility and compatibility within the polymer. The PP material of the present invention has excellent wear resistance and good surface aesthetics, requiring no additional spraying treatment. Through refined material proportioning and process optimization, it achieves excellent mechanical properties and environmental friendliness, while also exhibiting good processing performance and stable color distribution.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A wear-resistant spray-free PP material, characterized in that the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.3-0.8 parts by weight of masterbatch, 0.5-2 parts by weight of antioxidant surfactant, 1-5 parts by weight of filler, 0.1-1 parts by weight of lubricant, and 0.1-1 parts by weight of dispersant.

[0008] As a preferred technical solution of the present invention, the PP is a random copolymer polypropylene, and the MFI of the PP is 5-10 g / 10 min.

[0009] As a preferred technical solution of the present invention, the preparation method of the antioxidant surfactant is as follows: surfactant alkyl glycoside and antioxidant compound ferulic acid are added to solvent toluene and stirred evenly, catalyst sulfuric acid is added, and stirred at 50-80°C for 4-12 hours. After the reaction is completed, dilute hydrochloric acid is added to terminate the reaction, the solvent is removed by distillation, and the antioxidant surfactant is obtained by extraction-washing-drying.

[0010] As a preferred technical solution of the present invention, the filler is plant nanofiber.

[0011] As a preferred technical solution of the present invention, the plant nanofibers need to be pretreated. The specific operation steps are: dissolving the ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding the plant nanofibers, stirring at 60-100°C for 2-6 hours, and obtaining the pretreated plant nanofibers by filtering, washing, and drying.

[0012] As a preferred technical solution of the present invention, the lubricant is any one or more of zinc stearate, polyethylene wax, and oxidized polyethylene wax.

[0013] As a preferred technical solution of the present invention, the dispersant is any one of polypropylene grafted maleic anhydride and silicone dispersants.

[0014] As a preferred technical solution of the present invention, the preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0015] (1) Stir the masterbatch and antioxidant surfactant at 80-120°C for 10-30 minutes to fully mix;

[0016] (2) Adding the mixed masterbatch, antioxidant surfactant and PP into a twin-screw extruder, and adding lubricant, dispersant and filler at the same time;

[0017] (3) Set the temperature of each section of the extruder to 160-250°C, the screw speed to 200-400 rpm, and mix for 2-5 minutes;

[0018] (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0019] Beneficial effects of the present invention:

[0020] (1) The present invention obtains a surfactant with antioxidant properties by esterifying a surfactant alkyl glycoside with an antioxidant compound ferulic acid, and then mixing the masterbatch with the antioxidant surfactant to make the masterbatch better dispersed and compatible in PP, the masterbatch displayed on the surface of the product is more uniform, and no flow lines are formed on the surface of the product, thereby improving the texture of the material. The introduction of the antioxidant makes the material have a stable color.

[0021] (2) The present invention uses plant nanofibers as fillers to increase the wear resistance of the material, and pretreats the plant nanofibers with the ionic liquid 1-butyl-3-methylimidazole chloride. The ionic liquid can reduce the hydrogen bonding between the fibers, thereby reducing the agglomeration phenomenon and effectively improving the dispersibility of the plant nanofibers in the polymer matrix. Through the ionic liquid treatment, the chemical properties of the plant nanofiber surface are changed, thereby improving the compatibility of the polymer matrix and better improving the wear resistance of the material. DETAILED DESCRIPTION

[0022] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0023] In the following examples and comparative examples, the PP was purchased from LyondellBasell Industries, Inc. with the product number RP348RX B; the masterbatch was purchased from Tengcai Plastic Pigments Co., Ltd. with the product number tc-2-15; the alkyl polyglycoside was purchased from Yusheng Environmental Protection Technology Co., Ltd. with the product number 003; the plant nanofiber was purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd. with the model number llb75354; 1-butyl-3-methylimidazole chloride was purchased from Chengfeng Chemical Co., Ltd.; zinc stearate was purchased from Xingyuan Chemical Co., Ltd. with the product model XY-1100; polyethylene wax was purchased from Shanyi Plastics Co., Ltd.; oxidized polyethylene wax was purchased from Yiba Chemical Raw Materials Co., Ltd. with the product model CARDIS 325; polypropylene grafted maleic anhydride was purchased from Shanyi Plastics Co., Ltd.; and the silicone dispersant was purchased from Corning New Materials Co., Ltd. with the model number KMT-7001.

[0024] Example 1

[0025] A wear-resistant spray-free PP material, characterized in that: the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.5 parts by weight of masterbatch, 1 part by weight of antioxidant surfactant, 2 parts by weight of filler, 0.5 parts by weight of lubricant, and 0.5 parts by weight of dispersant.

[0026] The preparation method of the antioxidant surfactant comprises the following steps: adding a surfactant alkyl glycoside and an antioxidant compound ferulic acid into a solvent toluene and stirring evenly; adding a catalyst concentrated sulfuric acid; stirring at 60° C. for 8 hours; adding a 10% dilute hydrochloric acid solution to neutralize to a pH of 7.0 after the reaction is completed to terminate the reaction; removing the solvent by distillation; and then extracting, washing, and drying to obtain the antioxidant surfactant.

[0027] The mass ratio of the surfactant alkyl glycoside, the antioxidant ferulic acid, and toluene is 1:2:10. The concentration of the catalyst concentrated sulfuric acid is 98%, and the added amount is 1% of the reaction system. The extraction is water-ethyl acetate extraction.

[0028] The filler is plant nanofiber.

[0029] The plant nanofibers need to be pretreated, and the specific operation steps are: dissolving the ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding the plant nanofibers, stirring at 80°C for 4 hours, and obtaining the pretreated plant nanofibers by filtering, washing, and drying.

[0030] The mass ratio of the plant nanofiber, the ionic liquid and the dimethyl sulfoxide is 1:1:5.

[0031] The lubricant is polyethylene wax.

[0032] The dispersant is polypropylene grafted with maleic anhydride.

[0033] The preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0034] (1) The masterbatch and the antioxidant surfactant were stirred and thoroughly mixed at 100°C for 20 minutes;

[0035] (2) Adding the mixed masterbatch, antioxidant surfactant and PP into a twin-screw extruder, and adding lubricant, dispersant and filler at the same time;

[0036] (3) The extruder feed zone temperature was set to 180°C, the melting zone temperature was set to 200°C, and the homogenization zone temperature was set to 220°C; the screw speed was 300 rpm, and mixing was performed for 5 minutes;

[0037] (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0038] Example 2

[0039] A wear-resistant spray-free PP material, characterized in that: the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.5 parts by weight of masterbatch, 1 part by weight of antioxidant surfactant, 2 parts by weight of filler, 0.5 parts by weight of lubricant, and 0.5 parts by weight of dispersant.

[0040] The preparation method of the antioxidant surfactant comprises the following steps: adding a surfactant alkyl glycoside and an antioxidant compound ferulic acid into a solvent toluene and stirring evenly; adding a catalyst concentrated sulfuric acid; stirring at 60° C. for 8 hours; adding a 10% dilute hydrochloric acid solution to neutralize to a pH of 7.0 after the reaction is completed to terminate the reaction; removing the solvent by distillation; and then extracting, washing, and drying to obtain the antioxidant surfactant.

[0041] The mass ratio of the surfactant alkyl glycoside, the antioxidant ferulic acid, and toluene is 1:2:10. The concentration of the catalyst concentrated sulfuric acid is 98%, and the added amount is 1% of the reaction system. The extraction is water-ethyl acetate extraction.

[0042] The filler is plant nanofiber.

[0043] The plant nanofibers need to be pretreated. The specific operation steps are: dissolving ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding plant nanofibers, stirring at 100°C for 2 hours, and obtaining pretreated plant nanofibers by filtering, washing, and drying.

[0044] The mass ratio of the plant nanofiber, the ionic liquid and the dimethyl sulfoxide is 1:2:5.

[0045] The lubricant is zinc stearate and oxidized polyethylene wax, and the mass ratio of the zinc stearate to the oxidized polyethylene wax is 1:1.

[0046] The dispersant is an organosilicon dispersant.

[0047] The preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0048] (1) The masterbatch and the antioxidant surfactant were stirred and thoroughly mixed at 120°C for 20 minutes;

[0049] (2) Adding the mixed masterbatch, antioxidant surfactant and PP into a twin-screw extruder, and adding lubricant, dispersant and filler at the same time;

[0050] (3) The extruder feed zone temperature was set to 180°C, the melting zone temperature was set to 200°C, and the homogenization zone temperature was set to 220°C; the screw speed was 300 rpm, and mixing was performed for 2 minutes;

[0051] (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0052] Comparative Example 1

[0053] A wear-resistant spray-free PP material, characterized in that: the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.5 parts by weight of masterbatch, 1 part by weight of surfactant, 2 parts by weight of filler, 0.5 parts by weight of lubricant, and 0.5 parts by weight of dispersant.

[0054] The surfactant is an alkyl glycoside.

[0055] The filler is plant nanofiber.

[0056] The plant nanofibers need to be pretreated, and the specific operation steps are: dissolving the ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding the plant nanofibers, stirring at 80°C for 4 hours, and obtaining the pretreated plant nanofibers by filtering, washing, and drying.

[0057] The mass ratio of the plant nanofiber, the ionic liquid and the dimethyl sulfoxide is 1:1:5.

[0058] The lubricant is polyethylene wax.

[0059] The dispersant is polypropylene grafted with maleic anhydride.

[0060] The preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0061] (1) Stir the masterbatch and surfactant at 100°C for 20 minutes to fully mix;

[0062] (2) Add the mixed masterbatch, surfactant and PP into a twin-screw extruder, and add lubricant, dispersant and filler at the same time;

[0063] (3) The extruder feed zone temperature was set to 180°C, the melting zone temperature was set to 200°C, and the homogenization zone temperature was set to 220°C; the screw speed was 300 rpm, and mixing was performed for 5 minutes;

[0064] (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0065] Comparative Example 2

[0066] A wear-resistant spray-free PP material is characterized in that the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.8 parts by weight of masterbatch, 3 parts by weight of filler, 1 part by weight of lubricant, and 1 part by weight of dispersant.

[0067] The filler is plant nanofiber.

[0068] The plant nanofibers need to be pretreated, and the specific operation steps are: dissolving the ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding the plant nanofibers, stirring at 80°C for 4 hours, and obtaining the pretreated plant nanofibers by filtering, washing, and drying.

[0069] The mass ratio of the plant nanofiber, the ionic liquid and the dimethyl sulfoxide is 1:1:5.

[0070] The lubricant is polyethylene wax.

[0071] The dispersant is polypropylene grafted with maleic anhydride.

[0072] The preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0073] (1) Add the masterbatch and PP into a twin-screw extruder, and add lubricant, dispersant and filler at the same time;

[0074] (2) The extruder feed zone temperature was set to 180°C, the melting zone temperature was set to 200°C, and the homogenization zone temperature was set to 220°C; the screw speed was 300 rpm, and mixing was performed for 5 minutes;

[0075] (3) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0076] Comparative Example 3

[0077] A wear-resistant spray-free PP material, characterized in that: the wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.5 parts by weight of masterbatch, 1 part by weight of antioxidant surfactant, 2 parts by weight of filler, 0.5 parts by weight of lubricant, and 0.5 parts by weight of dispersant.

[0078] The preparation method of the antioxidant surfactant comprises the following steps: adding a surfactant alkyl glycoside and an antioxidant compound ferulic acid into a solvent toluene and stirring evenly; adding a catalyst concentrated sulfuric acid; stirring at 60° C. for 8 hours; adding a 10% dilute hydrochloric acid solution to neutralize to a pH of 7.0 after the reaction is completed to terminate the reaction; removing the solvent by distillation; and then extracting, washing, and drying to obtain the antioxidant surfactant.

[0079] The mass ratio of the surfactant alkyl glycoside, the antioxidant ferulic acid, and toluene is 1:2:10. The concentration of the catalyst concentrated sulfuric acid is 98%, and the added amount is 1% of the reaction system. The extraction is water-ethyl acetate extraction.

[0080] The filler is plant nanofiber.

[0081] The lubricant is polyethylene wax.

[0082] The dispersant is polypropylene grafted with maleic anhydride.

[0083] The preparation method of the wear-resistant spray-free PP material comprises the following steps:

[0084] (1) The masterbatch and the antioxidant surfactant were stirred and thoroughly mixed at 100°C for 20 minutes;

[0085] (2) Adding the mixed masterbatch, antioxidant surfactant and PP into a twin-screw extruder, and adding lubricant, dispersant and filler at the same time;

[0086] (3) The extruder feed zone temperature was set to 180°C, the melting zone temperature was set to 200°C, and the homogenization zone temperature was set to 220°C; the screw speed was 300 rpm, and mixing was performed for 5 minutes;

[0087] (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.

[0088] Performance Testing

[0089] Gloss test: Use a surface gloss tester, the test method is based on GB88072-1988, the test angle is 60°, and an area larger than 40cm 2 Wipe the surface of the sample clean, place it on the gloss tester, press it tightly and test it;

[0090] Color difference test: Use a spectrophotometer to measure the changes in the color space coordinates L, a, b and the color difference ΔE of the material before and after the test under D65 light source;

[0091] Wear resistance test: The wear resistance test of the examples and comparative examples was carried out according to GBT18102-2007 standard;

[0092] Antioxidation test: The glossiness of the samples of the materials of the examples and comparative examples after aging at 200°C for 7 days and the color difference of the comparative materials before and after aging at 200°C for 7 days were tested.

[0093] The test results are as follows:

[0094] Chromatic Aberration luster Wear resistance (rotation) Gloss after aging Color difference before and after aging Example 1 0.058 86 6400 84 0.081 Example 2 0.059 85 6200 82 0.079 Comparative Example 1 0.154 80 6000 70 0.387 Comparative Example 2 0.243 75 5800 68 0.401 Comparative Example 3 0.092 76 4200 74 0.124

[0095] The test results show that the present invention esterifies the surfactant alkyl glycoside with the antioxidant compound ferulic acid, and then mixes the masterbatch with the antioxidant surfactant to make the masterbatch better dispersed and compatible in PP, with smaller color difference and better gloss. In addition, by introducing ferulic acid, the material obtains antioxidant properties. After seven days of aging at 200°C, the gloss does not change significantly, and the color difference before and after aging is small. The plant nanofibers are pretreated with the ionic liquid 1-butyl-3-methylimidazolium chloride to effectively improve the dispersibility of the plant nanofibers in the polymer matrix and enhance the compatibility of the polymer matrix. The wear resistance of the material is further improved.

[0096] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any indirect modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A wear-resistant spray-free PP material, characterized by: The wear-resistant spray-free PP material is composed of the following raw materials in parts by weight: 100 parts by weight of PP, 0.3-0.8 parts by weight of masterbatch, 0.5-2 parts by weight of antioxidant surfactant, 1-5 parts by weight of filler, 0.1-1 parts by weight of lubricant, and 0.1-1 parts by weight of dispersant; The preparation method of the antioxidant surfactant comprises: adding a surfactant alkyl glycoside and an antioxidant compound ferulic acid to a solvent toluene and stirring evenly, adding a catalyst sulfuric acid, stirring at 50-80°C for 4-12 hours, adding dilute hydrochloric acid to terminate the reaction after the reaction is completed, removing the solvent by distillation, and then extracting, washing, and drying to obtain the antioxidant surfactant; The filler is plant nanofiber, which needs to be pretreated. The specific operation steps are: dissolving ionic liquid 1-butyl-3-methylimidazolium chloride in dimethyl sulfoxide and stirring evenly, adding plant nanofiber, stirring at 60-100°C for 2-6 hours, and obtaining pretreated plant nanofiber by filtering, washing and drying.

2. The wear-resistant spray-free PP material according to claim 1, characterized in that: The PP is random copolymer polypropylene, and the MFI of the PP is 5-10 g / 10 min.

3. The wear-resistant spray-free PP material according to claim 1, characterized in that: The lubricant is any one or more of zinc stearate, polyethylene wax, and oxidized polyethylene wax.

4. The wear-resistant spray-free PP material according to claim 1, characterized in that: The dispersant is any one of polypropylene grafted maleic anhydride and organosilicon dispersants.

5. The wear-resistant spray-free PP material according to claim 1, characterized in that: The preparation method comprises the following steps: (1) Stir the masterbatch and antioxidant surfactant at 80-120°C for 10-30 minutes to fully mix; (2) Adding the mixed masterbatch, antioxidant surfactant and PP into a twin-screw extruder, and adding lubricant, dispersant and filler at the same time; (3) Set the temperature of each section of the extruder to 160-250°C, the screw speed to 200-400 rpm, and mix for 2-5 minutes; (4) The molten material coming out of the extruder is cooled by a cooling water tank and then enters a pelletizer for pelletizing.