Scratch-resistant polypropylene composite and method for producing same

Abstract

The application provides a scratch-resistant polypropylene composite material and a preparation method thereof, and relates to the technical field of polypropylene composite materials, and the scratch-resistant polypropylene composite material comprises the following components in parts by mass: 55-85 parts of polypropylene resin, 6-10 parts of polyethylene resin, 5-25 parts of a scratch-resistant agent, 3-10 parts of a toughening agent, and 1.0-1.5 parts of an auxiliary agent, and the scratch resistance of the polypropylene composite material is excellent.

Description

Technical Field

[0001] This invention relates to the field of polypropylene composite materials technology, specifically to scratch-resistant polypropylene composite materials and their preparation methods. Background Technology

[0002] Polypropylene (PP) materials are widely used due to their advantages such as low cost, high yield, excellent mechanical properties, and low density. However, PP materials have poor shear compression yield strength and low surface hardness, making PP products prone to whitening and changes in gloss when subjected to external shear stress, which seriously affects the appearance quality of the products. In particular, with the continuous development of new energy vehicles, interior products are trending towards more colorful and detailed textures, which poses a greater challenge to the scratch resistance of PP materials.

[0003] Currently, common methods to improve the scratch resistance of polypropylene materials include using highly crystalline polypropylene resin (CN114736458A) and adding external lubricants (CN115232353A). Although these existing methods can improve the scratch resistance of the product surface to a certain extent, their improvement effect is still difficult to meet the ever-increasing performance requirements. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a scratch-resistant polypropylene composite material and its preparation method, solving the technical problem that the improvement in the surface scratch resistance of existing polypropylene materials is limited.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] The first aspect of this invention provides a scratch-resistant polypropylene composite material, comprising the following components in parts by weight:

[0007] 55-85 parts of polypropylene resin

[0008] 6-10 parts of polyethylene resin

[0009] 5-25 parts of scratch-resistant agent

[0010] 3-10 parts toughening agent

[0011] Additives 1.0-1.5 parts.

[0012] Secondly, the present invention provides a method for preparing the scratch-resistant polypropylene composite material, comprising the following steps:

[0013] (1) Mix polypropylene resin, polyethylene resin, toughening agent, additives, and scratch-resistant agent evenly to obtain a premix;

[0014] (2) The premix is ​​prepared by melt co-extrusion process to obtain scratch-resistant polypropylene composite material.

[0015] Compared with existing technologies, it has the following beneficial effects:

[0016] This invention provides a scratch-resistant polypropylene composite material, comprising the following components in parts by weight: 55-85 parts polypropylene resin, 6-10 parts polyethylene resin, 5-25 parts scratch-resistant agent, 3-10 parts toughening agent, and 1.0-1.5 parts additives. The scratch-resistant agent is molybdenum disulfide intercalated modified talc, which includes molybdenum disulfide, talc, an intercalating agent, and a coupling agent, with a mass ratio of 1:2-5:0.1-0.2:1-3. This scratch-resistant agent improves the scratch resistance of the polypropylene composite material. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] This application provides a scratch-resistant polypropylene composite material and its preparation method, which solves the technical problem that the improvement of the surface scratch resistance of existing polypropylene materials is limited.

[0019] The technical solution in this application is to solve the above-mentioned technical problems, and the general idea is as follows:

[0020] This invention provides a scratch-resistant polypropylene composite material, comprising the following components in parts by weight:

[0021] 55-85 parts of polypropylene resin

[0022] 6-10 parts of polyethylene resin

[0023] 5-25 parts of scratch-resistant agent

[0024] 3-10 parts toughening agent

[0025] Additives 1.0-1.5 parts.

[0026] As a preferred embodiment, the scratch-resistant agent is molybdenum disulfide intercalated modified talc, comprising molybdenum disulfide, talc, intercalating agent, and coupling agent. The talc, coupling agent, and intercalating agent are reacted at 120-140℃ and 1400-2000 r / min for 30-50 minutes with a mass ratio of 1:2-5:0.1-0.2:1-3 to obtain the scratch-resistant agent.

[0027] The scratch-resistant agent prepared by the above method, under high-speed stirring conditions at 120-140℃, undergoes an exchange reaction between the intercalating agent and the interlayer material of talc, expanding the interlayer spacing and allowing molybdenum disulfide to enter the interlayer of talc. The coupling agent reacts with the hydroxyl groups (-OH) on the surface of talc to form chemical bonds, and then coats the surface of the molybdenum disulfide particles through physical adsorption and hydrogen bonding, thereby firmly connecting the molybdenum disulfide that has entered the interlayer with the talc to form molybdenum disulfide intercalated modified talc. Furthermore, during the blending of the molybdenum disulfide intercalated modified talc prepared by the above method with olefin resin, one end of the coupling agent forms a chemical bond with the surface of talc, and the other end reacts with the olefin resin, thereby uniformly dispersing the prepared molybdenum disulfide intercalated modified talc in the olefin resin material. Furthermore, under shear force, the uniformly dispersed molybdenum disulfide intercalated modified talc powder disrupts the talc powder's lamellar structure, releasing molybdenum disulfide which is then uniformly distributed within the olefin resin. This reduces the friction coefficient of the olefin resin material. Simultaneously, the uniformly dispersed talc powder lamellars increase the surface hardness of the olefin resin material. Consequently, the scratch resistance of the olefin resin material is improved through the synergistic regulation of surface hardness and friction coefficient. Therefore, the addition of a scratch-resistant agent in the preparation method of this application, along with the synergistic effect of the intercalating agent, coupling agent, molybdenum disulfide, and talc powder, results in a polypropylene composite material with excellent scratch resistance.

[0028] Preferably, the coupling agent is selected from any one of silane coupling agents and phthalate coupling agents.

[0029] Preferably, the intercalating agent is selected from any one of cationic surfactants, inorganic intercalating agents, and polyethylene glycol. The cationic surfactant is selected from any one of dodecyltrimethylammonium chloride, dodecylmethylbenzylammonium chloride, and bis(octadecyldimethylammonium chloride), the inorganic intercalating agent is selected from any one of zirconium chloride and aluminum chloride, and the polyethylene glycol has a molecular weight of 1000-7000.

[0030] Preferably, the talc powder has a mesh size of 1000-3000 mesh and a silicon content of 50%-70%.

[0031] Preferably, the polypropylene resin has a melt flow rate of 2-100 g / 10 min when tested at 230°C / 2.16 kg.

[0032] A second aspect of the present invention provides a method for preparing the scratch-resistant polypropylene composite material, comprising the following steps:

[0033] (1) Mix polypropylene resin, polyethylene resin, toughening agent, additives, and scratch-resistant agent evenly to obtain a premix;

[0034] (2) The premix is ​​prepared by melt co-extrusion process to obtain scratch-resistant polypropylene composite material.

[0035] Preferably, the melt co-extrusion process includes: an extrusion temperature of 80-200℃ and a vacuum degree of ≤-0.08MPa.

[0036] To better understand the above technical solution, the following will provide a detailed explanation of the technical solution in conjunction with specific implementation methods.

[0037] I. Preparation Method

[0038] The reagents or raw materials mentioned in the following examples and comparative examples are as follows:

[0039] Polypropylene resin:

[0040] Polypropylene resin 1 is copolymer PP BX3920 (Sino-Korean Petrochemical), polypropylene resin 2 is copolymer PP BX3800 (Sino-Korean Petrochemical), polypropylene resin 3 is copolymer PP K8009 (Wuhan Petrochemical), polypropylene resin 4 is copolymer PP M60RHC (Zhenhai Refining & Chemical), and polypropylene resin 5 is copolymer PP 2500HY (Ningxia Coal Chemical).

[0041] Polyethylene resin:

[0042] Polyethylene resin 1 is HDPE 7260 (Zhenhai Refining & Chemical), and polyethylene resin 2 is HDPE 2911 (Fushun Petrochemical).

[0043] Toughening agent:

[0044] Toughening agent 1 is POE LC565 (SK, South Korea), and toughening agent 2 is POE 8842 (Dow Chemical).

[0045] talcum powder:

[0046] Talc powder 1 is talc powder 9276 (Liaoning Xinda), talc powder 2 is talc powder HT-4C (Youkuangsu), talc powder 3 is talc powder AHCP250 (Liaoning Haicheng), and talc powder 4 is talc powder HYT-50 (Youkuangsu).

[0047] The coupling agent is silane coupling agent KH560 (Shanghai Yuanye Biotechnology), and the intercalating agent is cationic surfactant dodecyltrimethylammonium chloride 1231 (MCE China).

[0048] Molybdenum disulfide is Tribotecc MOS XF (Shanghai Puzhan Industrial Co., Ltd.).

[0049] Two-dimensional black phosphorus is CJ-DCLX001 (Shandong Supercrystal New Materials).

[0050] Additives:

[0051] Antioxidant 1010 (BASF AG), Antioxidant 168 (BASF AG), Light Stabilizer 3808PP5 (Cytec, Inc.), Lubricant Silicone Masterbatch HG-600S (Zhejiang Jiahua).

[0052] All materials are commercially available, commonly used products.

[0053] The reagents described above are only for illustrating the source and composition of the reagents used in the experiments of this invention, so as to provide full disclosure, and do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0054] Example 1

[0055] This embodiment provides a method for preparing a scratch-resistant polypropylene composite material, including the following steps:

[0056] (1) According to Table 1, weigh out polypropylene resin, polyethylene resin, toughening agent and additives respectively, and then put them into a high-speed mixer for 8 minutes to premix and obtain a premix.

[0057] (2) The above premix is ​​added to a co-rotating twin-screw extruder through a weighing scale from the main feed port and the scratch-resistant agent from the side feed port. After plasticizing, blending, distribution, cooling, drying and pelletizing, a scratch-resistant polypropylene composite material is finally obtained. The extrusion temperature is 80°C in the conveying section and 190°C in the melting and extrusion sections. The screw speed is 800 r / min and the vacuum degree is -0.08 MPa.

[0058] Table 1. Amounts of each raw material used in the preparation of scratch-resistant polypropylene composite material.

[0059]

[0060] The preparation method of the scratch-resistant agent includes the following steps:

[0061] (1) Add talc powder to the mixer and gradually increase the temperature from room temperature to 120°C during low-speed mixing;

[0062] (2) After the temperature rises to 120℃, add coupling agent and intercalating agent, and stir at 1400 r / min for 30 minutes;

[0063] (3) Add molybdenum disulfide and stir at high speed for 30 minutes;

[0064] (4) Stir at low speed and cool down. Once the temperature drops to room temperature, remove the product to obtain the scratch-resistant agent.

[0065] The usage of each of the above raw materials is shown in Table 2.

[0066] Table 2. Amounts of each raw material used in the preparation of the scratch-resistant agent

[0067]

[0068] Examples 2-4

[0069] The difference between this embodiment and Embodiment 1 is that the amounts of polypropylene resin, polyethylene resin, toughening agent, scratch-resistant agent, and additives are different, as detailed in Table 1, and the amounts of each raw material used to prepare the scratch-resistant agent are different, as detailed in Table 2. Other aspects are the same as in Embodiment 1.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 1 is that in the preparation method of the scratch-resistant agent, after the temperature is raised to 120°C in step (2), no coupling agent or intercalating agent is added, and the mixture is stirred at 1400 r / min for 30 minutes. The rest is the same as in Example 1.

[0072] Comparative Example 2

[0073] The difference between this comparative example and Example 1 is that talc powder is not added in the preparation method of the scratch-resistant agent, and the amount of molybdenum disulfide is 20 parts, while the rest is the same as in Example 1.

[0074] Comparative Example 3

[0075] The difference between this comparative example and Example 1 is that in the preparation method of the scratch-resistant agent, talc powder is 20 parts and molybdenum disulfide is not added, while the rest is the same as in Example 1.

[0076] Comparative Example 4

[0077] The difference between this comparative example and Example 1 is that, in the preparation method of the scratch-resistant agent, two-dimensional black phosphorus powder is used instead of talc powder; otherwise, it is the same as Example 1.

[0078] Comparative Example 5

[0079] The difference between this comparative example and Example 1 is that no scratch-resistant agent is added; otherwise, they are the same as in Example 1.

[0080] II. Testing Methods

[0081] The properties of the scratch-resistant polypropylene composite materials prepared in the examples and comparative examples were tested. The test items and methods are as follows:

[0082] 1. Material density: Tested according to ISO 1183-1 standard, at 23℃, using an alcohol density tester;

[0083] 2. Tensile strength: Tensile strength is tested according to ISO 527-2 standard, with dumbbell-shaped specimens and a test speed of 50 mm / min.

[0084] 3. Bending performance: Tested according to ISO 178 standard, with a test speed of 2 mm / min, a cuboid spline shape, and spline dimensions of 80 mm × 10 mm × 4 mm;

[0085] 4. Cantilever beam notched impact test: Tested according to ISO 180 standard, notch depth is 2mm, spline shape is cuboid spline, spline size is 80mm10mm4mm;

[0086] 5. Melt flow index: Tested according to ISO 1133-1 / 2 standard, test conditions are 230℃ and 2.16kg;

[0087] 6. Scratch resistance: Tested according to PV3952 standard, the test conditions are 10N load, 1mm scratch head, and the degree of whitening ΔL is tested. The larger the ΔL, the more obvious the whitening after scratching, and the worse the scratch resistance of the material.

[0088] The performance test results are shown in Table 3.

[0089] Table 3 Performance Test Results

[0090]

[0091] Table 3 shows that the whitening degree ΔL of the polypropylene composite materials prepared by adding scratch-resistant agents in Examples 1-4 was only about 0.5, while the whitening degree ΔL of the polypropylene composite material prepared by Comparative Example 5 without adding scratch-resistant agents was 3.03. This indicates that the scratch-resistant agent prepared in this application can significantly improve the scratch resistance of polypropylene materials. However, Comparative Examples 1-3 lacked any one of the coupling agent and intercalating agent, talc, or molybdenum disulfide in their preparation of scratch-resistant agents, and the improvement in the scratch resistance of the polypropylene composite materials could not reach the effect of Example 1. Therefore, the coupling agent and intercalating agent, talc, and molybdenum disulfide have a synergistic effect in improving the scratch resistance of polypropylene composite materials. As shown in Comparative Example 4, the polypropylene composite material prepared by replacing talc with two-dimensional black phosphorusene as a scratch-resistant agent could not achieve the scratch resistance effect of Example 1.

[0092] The polypropylene composite material prepared by the method of the present invention has excellent physical and mechanical properties, which can meet the performance requirements of polypropylene materials for automotive parts.

[0093] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0094] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0095] The present invention has been illustrated with the above embodiments to describe the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A scratch-resistant polypropylene composite material, characterized in that, The components include the following parts by weight: 55-85 parts of polypropylene resin 6-10 parts of polyethylene resin 5-25 parts of scratch-resistant agent 3-10 parts toughening agent Additives 1.0-1.5 parts.

2. The scratch-resistant polypropylene composite material as described in claim 1, characterized in that, The scratch-resistant agent is molybdenum disulfide intercalated modified talc powder.

3. The scratch-resistant polypropylene composite material as described in claim 2, characterized in that, The molybdenum disulfide intercalated modified talc powder includes molybdenum disulfide, talc powder, intercalating agent, and coupling agent, and the mass ratio of molybdenum disulfide, talc powder, intercalating agent, and coupling agent is 1:2-5:0.1-0.2:1-3.

4. The scratch-resistant polypropylene composite material as described in claim 3, characterized in that, The coupling agent is selected from any one of silane coupling agents and phthalate coupling agents.

5. The scratch-resistant polypropylene composite material as described in claim 3, characterized in that, The intercalating agent is selected from any one of cationic surfactants, inorganic intercalating agents, and polyethylene glycol; The cationic surfactant is selected from any one of dodecyltrimethylammonium chloride, dodecylmethylbenzylammonium chloride, and bis(octadecyl)dimethylammonium chloride; the inorganic intercalating agent is selected from any one of zirconium chloride and aluminum chloride; and the polyethylene glycol has a molecular weight of 1000-7000.

6. The scratch-resistant polypropylene composite material as described in claim 3, characterized in that, The talc powder has a mesh size of 1000-3000 and a silicon content of 50%-70%.

7. The scratch-resistant polypropylene composite material as described in claim 1, characterized in that, The polypropylene resin was tested at 230℃ / 2.16kg, and the melt flow rate was 2-100g / 10min.

8. A method for preparing the scratch-resistant polypropylene composite material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Mix polypropylene resin, polyethylene resin, toughening agent, additives, and scratch-resistant agent evenly to obtain a premix; (2) The premix is ​​prepared by melt co-extrusion process to obtain scratch-resistant polypropylene composite material.

9. The method for preparing the scratch-resistant polypropylene composite material as described in claim 8, characterized in that, The melt co-extrusion process includes: an extrusion temperature of 80-200℃ and a vacuum degree of ≤-0.08MPa.

10. The method for preparing the scratch-resistant polypropylene composite material as described in claim 8, characterized in that, The method for preparing the scratch-resistant agent includes: reacting talc powder with a coupling agent and an intercalating agent at 120-140℃ and 1400-2000r / min for 30-50 minutes, then adding molybdenum disulfide and reacting for another 30-50 minutes to obtain the scratch-resistant agent.

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