Preparation process of wear-resistant polypropylene composite material

Abstract

The invention relates to the technical field of high polymer materials, and discloses a preparation process of a wear-resistant polypropylene composite material, and the wear-resistant polypropylene composite material comprises the following raw materials: polypropylene, a wear-resistant impact-resistant auxiliary agent, a heat-resistant flame-retardant compound, a lubricant, an antioxidant and an ultraviolet light absorber. According to the invention, the wear-resistant and impact-resistant auxiliary agent and the heat-resistant and flame-retardant compound are prepared and added into the matrix of the polypropylene composite material, so that the prepared polypropylene composite material has excellent wear resistance, impact resistance, high temperature resistance and flame-retardant effect, can meet the use requirements in various environments, and is high in safety and low in cost. And the service life is long.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically relates to a preparation process of a wear-resistant polypropylene composite material. Background Art

[0002] As a general-purpose plastic, polypropylene has been widely used in many fields such as packaging, construction, automotive, and electronics due to its good processing performance and low cost. However, with the continuous improvement of the requirements for material properties in modern industry, ordinary polypropylene materials have poor wear resistance and impact resistance, are prone to wear during use, are prone to softening and deformation at high temperatures, and as a flammable material, they will produce a large amount of toxic gases when burned, posing serious safety hazards. Therefore, ordinary polypropylene materials are difficult to meet the usage requirements in various fields.

[0003] The patent with the publication number CN116462907B discloses a polypropylene composite plastic and its preparation method. This polypropylene composite plastic includes the following raw materials: polypropylene, ethylene-vinyl acetate copolymer, inorganic fiber, silane coupling agent, calcium sulfate whisker, stabilizer, antioxidant, and color powder. The polypropylene composite plastic prepared by this patent has excellent impact resistance and good wear resistance, but the plastic prepared by this patent does not consider the problem of flame retardancy and still has certain safety hazards during use. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation process of a wear-resistant polypropylene composite material, which solves the problems that ordinary polypropylene materials have poor impact resistance and wear resistance, and do not have high-temperature resistance and flame retardancy.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A preparation process of a wear-resistant polypropylene composite material includes the following preparation steps: Step 1: Put polypropylene, wear-resistant and impact-resistant additives, heat-resistant and flame-retardant composites, lubricants, antioxidants, and ultraviolet absorbers into a high-speed mixer, set the rotation speed to 500 - 600 r / min, and fully stir for 1 - 2 h to obtain a mixture. Step 2: Transfer the mixture to a twin-screw extruder, set the head temperature of the twin-screw extruder to 170 - 180 °C, and the screw rotation speed to 200 - 300 r / min. After melting and extrusion, granulate to obtain a wear-resistant polypropylene composite material.

[0006] Further, the wear-resistant polypropylene composite material includes the following raw materials in parts by weight: 70 - 90 parts of polypropylene, 8 - 12 parts of wear-resistant and impact-resistant additives, 10 - 15 parts of heat-resistant and flame-retardant composites, 3 - 5 parts of lubricants, 1 - 3 parts of antioxidants, and 1 - 2 parts of ultraviolet absorbers.

[0007] Furthermore, the lubricant is any one of stearic acid and white oil; the antioxidant is any one of antioxidant 1010, antioxidant 1135, and antioxidant 5057; the ultraviolet absorber is any one of ultraviolet absorber UV-120, ultraviolet absorber UV-531, and ultraviolet absorber UV-1300.

[0008] Furthermore, the preparation method of the wear-resistant and impact-resistant additive includes the following steps: S1: Place the hydroxyl-terminated liquid nitrile rubber and 1,8-naphthalic anhydride in toluene, fully mix and stir, then add a catalyst, heat up to 80 - 90 °C and react for 3 - 5 h, remove the low-boiling substances by vacuum distillation, and collect the product to obtain the modified nitrile rubber. S2: Place the sepiolite in deionized water, ultrasonically disperse for 10 - 15 min, then add the modified nitrile rubber, heat up to 80 - 85 °C, and stir fully at 200 - 250 r / min for 5 - 6 h. After filtration, washing, and drying, obtain the wear-resistant and impact-resistant additive.

[0009] In this solution, under the action of the catalyst, the hydroxyl group in the structure of the hydroxyl-terminated liquid nitrile rubber reacts with the anhydride group in the structure of 1,8-naphthalic anhydride to obtain the modified nitrile rubber with a carboxyl group in its structure. This kind of modified nitrile rubber uses nitrile rubber as the polymer chain segment, which can effectively improve the flexibility and impact resistance of the polypropylene composite material. At the same time, introducing the naphthalene ring into its molecular chain can enhance the heat resistance and wear resistance of the polypropylene composite material. And embedding the inorganic particle sepiolite into the polymer chain segment can further improve the wear resistance of the polypropylene composite material, enabling it to stably exist in a high-temperature environment, not easily wear, and adapt to the use requirements in various environments, and having a long service life.

[0010] Furthermore, in step S1, the catalyst is p-toluenesulfonic acid.

[0011] Furthermore, in step S2, the average particle size of the sepiolite is 1 μm.

[0012] Furthermore, the preparation method of the heat-resistant and flame-retardant composite includes the following steps: SS1: Place the polyetheramine and 4-maleimidobutyric acid in xylene, fully mix and stir, then add a composite catalyst, heat up to 80 - 85 °C and react for 3 - 5 h, remove the low-boiling substances by vacuum distillation, and collect the product to obtain the maleimide-modified polyetheramine. SS2: Place the maleimide-modified polyetheramine in N,N-dimethylformamide, fully mix and stir, add dimethyl vinyl phosphate and an initiator, heat up to 55 - 65 °C and react for 5 - 6 h, remove the low-boiling substances by vacuum distillation, and collect the product to obtain the heat-resistant and flame-retardant composite.

[0013] In this solution, under the action of a composite catalyst, the amino groups at both ends of the polyetheramine react with the carboxyl groups in the 4-maleimidobutyric acid structure to obtain maleimide-modified polyetheramine. Then, under the action of an initiator, the double bonds in the maleimide-modified polyetheramine structure react with the alkenyl groups in the dimethyl vinyl phosphate structure to undergo a radical polymerization reaction to obtain a heat-resistant and flame-retardant composite. This heat-resistant and flame-retardant composite uses polyetheramine as a polymer skeleton, and a large number of ether bonds in its structure can effectively improve the impact resistance of the composite material. By introducing maleimide groups into the polyetheramine molecular chain in a chemical bonding manner, the heat resistance of the composite material can be effectively enhanced. At the same time, by introducing phosphate ester groups into the polymer chain segment, the timeliness of the phosphate ester groups to play a role can be effectively enhanced, and a nitrogen-phosphorus synergistic flame-retardant system is formed, effectively enhancing the flame-retardant ability of the composite material and improving the use safety of the polypropylene composite material.

[0014] Further, in step SS1, the composite catalyst is 4-dimethylaminopyridine and dicyclohexylcarbodiimide with a mass ratio of 0.34 - 0.5:0.12 - 0.2.

[0015] Further, in step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

[0016] Advantages of the present invention: By preparing a wear-resistant and impact-resistant additive and a heat-resistant and flame-retardant composite and adding them to the matrix of the polypropylene composite material, the prepared polypropylene composite material has excellent wear resistance, impact resistance, high-temperature resistance, and flame-retardant effect, can meet the use requirements in various environments, and has high safety and a long service life.

[0017] Of course, it is not necessary for any product implementing the present invention to simultaneously achieve all the above-mentioned advantages. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0019] Figure 1 It is a process flow chart for preparing the wear-resistant polypropylene composite material of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] The preparation methods of the wear-resistant and impact-resistant additives and the heat-resistant and flame-retardant composites in the following embodiments and comparative examples of the present invention are as follows: 1. Preparation of wear-resistant and impact-resistant additives S1: 3 g of hydroxyl-terminated liquid nitrile rubber and 2.8 g of 1,8-naphthalene dicarboxylic anhydride were placed in 75 ml of toluene, and after thorough mixing and stirring, 0.05 g of p-toluenesulfonic acid was added, and the temperature was raised to 80°C for reaction for 3 h, and low-boiling substances were removed by vacuum distillation, and the product was collected to obtain modified nitrile rubber; S2: Place 3.5 g of sepiolite with an average particle size of 1 μm in 100 ml of deionized water, ultrasonically disperse for 10 minutes, add 3.6 g of modified nitrile rubber, heat to 80°C, stir at 200 r / min for 5 hours, filter, wash and dry to obtain a wear-resistant and impact-resistant additive.

[0022] 2. Preparation of heat-resistant flame-retardant composites SS1: 3.6 g of polyetheramine and 3.4 g of 4-maleimidebutyric acid were placed in 80 ml of xylene, and after thorough mixing and stirring, 0.34 g of 4-dimethylaminopyridine and 0.12 g of dicyclohexylcarbodiimide were added, and the temperature was raised to 80°C for reaction for 3 h. Low boiling materials were removed by vacuum distillation, and the product was collected to obtain maleimide-modified polyetheramine; SS2: Place 4.2 g of maleimide-modified polyetheramine in 100 ml of N,N-dimethylformamide, mix and stir thoroughly, add 4 g of dimethyl vinyl phosphate and 0.5 g of benzoyl peroxide, heat to 55°C and react for 5 h, remove low-boiling substances by vacuum distillation, and collect the product to obtain a heat-resistant flame-retardant composite.

[0023] Example 1

[0024] A wear-resistant polypropylene composite material comprises the following raw materials in parts by weight: 70 parts of polypropylene, 8 parts of wear-resistant and impact-resistant additives, 10 parts of heat-resistant and flame-retardant compounds, 3 parts of stearic acid, 1 part of antioxidant 1010, and 1 part of ultraviolet absorber UV-120; The preparation method of the wear-resistant polypropylene composite material comprises the following steps: Step 1: Put polypropylene, wear-resistant and impact-resistant additives, heat-resistant and flame-retardant composites, stearic acid, antioxidant 1010, and ultraviolet absorber UV-120 in parts by weight into a high-speed mixer. Set the rotation speed to 500 r / min and stir thoroughly for 1 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder. Set the head temperature of the twin-screw extruder to 170 °C and the screw rotation speed to 200 r / min. After melting and extruding, pelletize to obtain a polypropylene composite material.

[0025] Example 2

[0026] A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of wear-resistant and impact-resistant additives, 12 parts of heat-resistant and flame-retardant composites, 4 parts of white oil, 2 parts of antioxidant 1135, and 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Put polypropylene, wear-resistant and impact-resistant additives, heat-resistant and flame-retardant composites, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight into a high-speed mixer. Set the rotation speed to 550 r / min and stir thoroughly for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder. Set the head temperature of the twin-screw extruder to 175 °C and the screw rotation speed to 250 r / min. After melting and extruding, pelletize to obtain a polypropylene composite material.

[0027] Example 3

[0028] A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 90 parts of polypropylene, 12 parts of wear-resistant and impact-resistant additives, 15 parts of heat-resistant and flame-retardant composites, 5 parts of stearic acid, 3 parts of antioxidant 5057, and 2 parts of ultraviolet absorber UV-1300; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Put polypropylene, wear-resistant and impact-resistant additives, heat-resistant and flame-retardant composites, stearic acid, antioxidant 5057, and ultraviolet absorber UV-1300 in parts by weight into a high-speed mixer. Set the rotation speed to 600 r / min and stir thoroughly for 2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder. Set the head temperature of the twin-screw extruder to 180 °C and the screw rotation speed to 300 r / min. After melting and extruding, pelletize to obtain a polypropylene composite material.

[0029] Comparative Example 1 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 12 parts of heat-resistant flame retardant composite, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, heat-resistant flame retardant composite, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight in a high-speed mixer, set the rotation speed to 550 r / min, and fully stir for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 175 °C, the screw rotation speed to 250 r / min, melt and extrude, and then pelletize to obtain a polypropylene composite material.

[0030] Comparative Example 2 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of wear-resistant and impact-resistant additive, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, wear-resistant and impact-resistant additive, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight in a high-speed mixer, set the rotation speed to 550 r / min, and fully stir for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 175 °C, the screw rotation speed to 250 r / min, melt and extrude, and then pelletize to obtain a polypropylene composite material.

[0031] Comparative Example 3 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of modified nitrile rubber, 12 parts of heat-resistant flame retardant composite, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Place the polypropylene, modified nitrile rubber, heat-resistant flame retardant composite, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight in a high-speed mixer, set the rotation speed to 550 r / min, and fully stir for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 175 °C, the screw rotation speed to 250 r / min, melt and extrude, and then pelletize to obtain a polypropylene composite material.

[0032] Comparative Example 4 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of sepiolite, 12 parts of heat-resistant flame retardant composite, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Put the polypropylene, sepiolite, heat-resistant flame retardant composite, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight into a high-speed mixer, set the rotation speed to 550 r / min, and stir thoroughly for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 175 °C, the screw rotation speed to 250 r / min, melt and extrude, and then pelletize to obtain a polypropylene composite material.

[0033] Comparative Example 5 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of wear-resistant and impact-resistant additive, 12 parts of maleimide-modified polyetheramine, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Put the polypropylene, wear-resistant and impact-resistant additive, maleimide-modified polyetheramine, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight into a high-speed mixer, set the rotation speed to 550 r / min, and stir thoroughly for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 175 °C, the screw rotation speed to 250 r / min, melt and extrude, and then pelletize to obtain a polypropylene composite material.

[0034] Comparative Example 6 A wear-resistant polypropylene composite material, comprising the following raw materials in parts by weight: 80 parts of polypropylene, 10 parts of wear-resistant and impact-resistant additive, 12 parts of polyetheramine, 4 parts of white oil, 2 parts of antioxidant 1135, 1.5 parts of ultraviolet absorber UV-531; The preparation method of this wear-resistant polypropylene composite material comprises the following steps: Step 1: Put the polypropylene, wear-resistant and impact-resistant additive, polyetheramine, white oil, antioxidant 1135, and ultraviolet absorber UV-531 in parts by weight into a high-speed mixer, set the rotation speed to 550 r / min, and stir thoroughly for 1.5 h to obtain a mixed material; Step 2: Transfer the mixture to a twin-screw extruder. Set the head temperature of the twin-screw extruder at 175 °C and the screw speed at 250 r / min. After melting and extrusion, granulate to obtain the polypropylene composite material.

[0035] Performance testing Perform tablet pressing on the polypropylene composite materials prepared in Examples 1 - 3 and Comparative Examples 1 - 6 to make samples that meet the specifications. Refer to the standard GB / T 1633 - 2000 to test the Vicat softening temperature of the samples and detect the high-temperature resistance performance of the samples; refer to the standard GB / T 1043.1 - 2008 to test the impact strength of the samples to judge the impact resistance ability of the samples; refer to the UL-94 flame retardant rating standard to detect the flame retardant performance of the samples; use a Taber type abrasion tester to test the wear resistance of the samples. The specific operation is as follows: Place two grinding wheels on the sample, set the moving speed of the grinding wheels at 30 r / min to conduct a wear experiment on the sample, record the initial mass of the sample and the mass after 20,000 r of wear, and calculate according to the formula: Abrasion value = Initial mass - Mass after wear. The smaller the abrasion value, the stronger the wear resistance. The specific test results are shown in the following table:

[0036] As can be seen from the above table, the samples prepared in Examples 1 - 3 all have excellent high-temperature resistance, wear resistance, flame retardant performance, and impact resistance, while the performance of the samples prepared in Comparative Examples 1 - 6 is inferior to that of the samples prepared in the examples.

[0037] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0038] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A process for preparing a wear-resistant polypropylene composite material, characterized in that: The method comprises the following preparation steps: Step 1: Place polypropylene, wear-resistant and impact-resistant additives, heat-resistant and flame-retardant compounds, lubricants, antioxidants, and ultraviolet absorbers in a high-speed mixer, set the speed to 500-600 r / min, and stir thoroughly for 1-2 hours to obtain a mixture; Step 2: Transfer the mixed material to a twin-screw extruder, set the head temperature of the twin-screw extruder to 170-180° C., the screw speed to 200-300 r / min, and granulate after melt extrusion to obtain a wear-resistant polypropylene composite material.

2. The preparation process of a wear-resistant polypropylene composite material according to claim 1, characterized in that: The wear-resistant polypropylene composite material comprises the following raw materials in parts by weight: 70-90 parts of polypropylene, 8-12 parts of wear-resistant and impact-resistant additives, 10-15 parts of heat-resistant and flame-retardant compounds, 3-5 parts of lubricants, 1-3 parts of antioxidants, and 1-2 parts of ultraviolet absorbers.

3. The preparation process of a wear-resistant polypropylene composite material according to claim 2, characterized in that: The lubricant is any one of stearic acid and white oil; the antioxidant is any one of antioxidant 1010, antioxidant 1135, and antioxidant 5057; the ultraviolet absorber is any one of ultraviolet absorber UV-120, ultraviolet absorber UV-531, and ultraviolet absorber UV-1300.

4. The process for preparing a wear-resistant polypropylene composite material according to claim 1, characterized in that: The preparation method of the wear-resistant and impact-resistant additive comprises the following steps: S1: placing hydroxyl-terminated liquid nitrile rubber and 1,8-naphthalene dicarboxylic anhydride in toluene, mixing and stirring thoroughly, adding a catalyst, heating to 80-90°C for reaction for 3-5h, removing low-boiling substances by vacuum distillation, and collecting the product to obtain modified nitrile rubber; S2: Place sepiolite in deionized water, ultrasonically disperse for 10-15 minutes, add modified nitrile rubber, heat to 80-85°C, stir at 200-250r / min for 5-6 hours, filter, wash and dry to obtain a wear-resistant and impact-resistant additive.

5. The process for preparing a wear-resistant polypropylene composite material according to claim 4, characterized in that: In step S1, the catalyst is p-toluenesulfonic acid.

6. The process for preparing a wear-resistant polypropylene composite material according to claim 4, characterized in that: In step S2, the average particle size of the sepiolite is 1 μm.

7. The process for preparing a wear-resistant polypropylene composite material according to claim 1, characterized in that: The preparation method of the heat-resistant flame-retardant composite comprises the following steps: SS1: Put polyetheramine and 4-maleimidebutyric acid in xylene, mix and stir thoroughly, add composite catalyst, heat to 80-85°C and react for 3-5h, remove low boiling points by vacuum distillation, and collect the product to obtain maleimide-modified polyetheramine; SS2: Place maleimide-modified polyetheramine in N,N-dimethylformamide, mix and stir thoroughly, add dimethyl vinyl phosphate and initiator, raise the temperature to 55-65°C and react for 5-6 hours, remove low-boiling substances by vacuum distillation, and collect the product to obtain a heat-resistant flame-retardant composite.

8. The process for preparing a wear-resistant polypropylene composite material according to claim 7, characterized in that: In step SS1, the composite catalyst is 4-dimethylaminopyridine and dicyclohexylcarbodiimide in a mass ratio of 0.34-0.5:0.12-0.

2.

9. The process for preparing a wear-resistant polypropylene composite material according to claim 7, characterized in that: In step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

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