High-strength and high-toughness glass fiber modified polypropylene composite material, preparation method and application thereof

Abstract

The application discloses a kind of high-strength high-toughness glass fiber modified polypropylene composite material and its preparation method and application, the composite material is prepared from the following components by mass parts: 41.4-83.1 polypropylene, 10-40 glass fiber, 3.5-10 hexadecyl trimethoxysilane modified nano Al2O3 material, 3-7 maleic anhydride grafted polypropylene, 0.2-1 antioxidant and 0.2-0.6 lubricant.The application utilizes hexadecyl trimethoxysilane modified nano Al2O3 surface, can reduce the agglomeration of nano Al2O3 in polypropylene, while it can improve the bonding strength between nano Al2O3 and matrix polypropylene, nano Al2O3 and glass fiber, so as to achieve the effect of strengthening and toughening, the modified polypropylene material prepared simultaneously has very high toughness and rigidity, can be applied in automotive interior and exterior goods, electronic and electrical appliances shell, household appliance shell and the like.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a high-strength, high-toughness glass fiber modified polypropylene composite material, its preparation method, and its application. Background Technology

[0002] Polypropylene (PP) is widely used due to its low density, good mechanical strength, heat resistance, and chemical corrosion resistance. PP is reinforced with glass fiber and can currently be divided into two categories: one using short glass fibers as reinforcement and the other using continuous long glass fibers. These two types have found extensive applications in fields such as home appliance manufacturing and automobile manufacturing. Because of its high strength, impact resistance, and excellent long-term fatigue and creep properties, it is often used to replace traditional reinforced engineering plastics and even steel, and has broad application value.

[0003] Glass fiber reinforced polypropylene materials have high strength, but generally poor toughness and low notched impact resistance. Traditional methods of filling polypropylene with elastomers are not suitable for modifying glass fiber reinforced polypropylene materials. Adding a small amount of elastomer has little effect on toughness, while adding a large amount of elastomer will affect the strength of the glass fiber material. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a high-strength, high-toughness glass fiber modified polypropylene composite material, which is achieved through the following technical solution:

[0005] A high-strength, high-toughness glass fiber modified polypropylene composite material is prepared from the following components in parts by weight: 41.4-83.1 parts polypropylene, 10-40 parts glass fiber, 3.5-10 parts hexadecyltrimethoxysilane modified nano-Al2O3 material, 3-7 parts maleic anhydride grafted polypropylene, 0.2-1 parts antioxidant and 0.2-0.6 parts lubricant.

[0006] As a preferred technical solution, the hexadecyltrimethoxysilane-modified nano-Al2O3 material is prepared by the following method: dispersing hexadecyltrimethoxysilane in a mixed reagent composed of anhydrous ethanol and water to obtain a dispersion; adding nano-Al2O3 to the above dispersion, mixing and stirring at 105-115℃ for 3-10 min, and then drying in an oven at 30℃ for 2-4 hours to obtain the hexadecyltrimethoxysilane-modified nano-Al2O3 material. More preferably, the mass ratio of hexadecyltrimethoxysilane, anhydrous ethanol, and water is 1:0.8-1.5:2-4; and the mass ratio of nano-Al2O3 to hexadecyltrimethoxysilane is 1:0.6-1.2.

[0007] As a preferred technical solution, the polypropylene is at least one of copolymer polypropylene and homopolymer polypropylene. The glass fiber is chopped glass fiber or continuous glass fiber. The functional group content in the maleic anhydride-grafted polypropylene is 0.4-1 wt%. The antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris[2,4-di-tert-butylphenyl]phosphite. The lubricant is at least one of ethylene bis-stearamide, pentaerythritol stearate, and silicone powder.

[0008] Another object of the present invention is to provide a method for preparing the high-strength, high-toughness glass fiber modified polypropylene composite material described above, comprising the following steps: thoroughly mixing polypropylene, hexadecyltrimethoxysilane-modified nano-Al2O3 material, maleic anhydride-grafted polypropylene, antioxidant, and lubricant according to a specified ratio, and then feeding the mixture into a twin-screw extruder through the main feed port, while simultaneously adding glass fiber through the side feed port. After melt extrusion, granulation, and drying, the high-strength, high-toughness glass fiber modified polypropylene composite material is obtained. Preferably, the main motor speed of the twin-screw extruder is 280-400 rpm, and the barrel temperature is 180-230°C.

[0009] A third objective of this invention is to provide applications of the aforementioned high-strength, high-toughness glass fiber modified polypropylene composite material, which is used to manufacture automotive interior and exterior trim, electronic and electrical housings, and household appliance housings.

[0010] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0011] The hexadecyltrimethoxysilane-modified nano-Al2O3 material used in this invention is produced by modifying nano-Al2O3 with hexadecyltrimethoxysilane, allowing the hexadecyltrimethoxysilane to be uniformly adsorbed on the outer surface of the nano-Al2O3. Because hexadecyltrimethoxysilane has a long-chain structure with one polar end and one non-polar end, it has strong adhesion to the surface of non-polar materials, achieving the following effects: i) reducing the agglomeration of nano-Al2O3 within polypropylene; ii) improving the bonding strength between nano-Al2O3 and the matrix polypropylene, and between nano-Al2O3 and glass fibers; iii) the hexadecyltrimethoxysilane-modified nano-Al2O3 material has a spherical structure, and its linear one-dimensional structure with glass fibers can form a secondary distribution in the polypropylene material. The two interact and mutually improve their dispersion uniformity.

[0012] The principle of glass fiber reinforced polypropylene is that the linear structure of glass fibers allows force to be transmitted to the glass fibers when the material is under stress, with the stronger glass fibers sharing the stress on the matrix material. When spherical hexadecyltrimethoxysilane-modified nano-Al2O3 is added, due to the spatial effect, the spherical hexadecyltrimethoxysilane-modified nano-Al2O3 is mainly concentrated at the tips of the clustered glass fibers. This distribution of the three material forms can, on the one hand, reduce the internal stress of the polypropylene matrix itself and improve the bonding strength with the glass fibers; on the other hand, when the material is under stress, the stress is transmitted through the glass fibers to the tips of the glass fibers, and the spherical hexadecyltrimethoxysilane-modified nano-Al2O3 distributed in the polypropylene matrix at the tips of the glass fibers effectively transfers the stress from the one-dimensional linear structure to the three-dimensional spatial structure, which is conducive to stress release; at the same time, when cracks occur in the polypropylene matrix at the tips of the glass fibers under stress, the spherical hexadecyltrimethoxysilane-modified nano-Al2O3 can effectively prevent the further propagation of the cracks.

[0013] In summary, the modified polypropylene material prepared by this invention has both high toughness and rigidity, and can be used in automotive interior and exterior trim, electronic and electrical housings, and home appliance housings. Detailed Implementation

[0014] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0016] For polypropylene, the preferred options are SK Group's PP BX3800, LyondellBasell Industries' PP EA5076, and Sinopec Group's PP T30S.

[0017] The fiberglass used is Chongqing International Composite Materials Co., Ltd.'s Fiberglass-305K-3.0 and Owens Corning's Fiberglass-248A.

[0018] Nano-Al2O3 is a commercially available industrial product, purchased from Nanjing Tianxing New Materials Co., Ltd.

[0019] For PP-G polypropylene grafted with maleic anhydride, GPM200A and GPM200B (Ningbo Nengzhiguang) are preferred.

[0020] The preferred antioxidants are BASF's antioxidants 1010 and 168;

[0021] The preferred lubricants are ethylene bis-hard amide and silicone E525.

[0022] 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 fully disclose them. They do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers. Other raw materials not listed are from manufacturers or models commonly used in the field and are commercially available.

[0023] Example 1

[0024] Weigh out 71 parts by weight of polypropylene (PP) T30S, 5 parts by weight of hexadecyltrimethoxysilane modified Al2O3 material, 3 parts by weight of polypropylene grafted maleic anhydride (GPM200A), 0.3 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.4 parts by weight of lubricant silicone E525. Mix them evenly and add them into the twin-screw extruder through the main feed port. At the same time, add 20 parts by weight of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 170℃, 195℃, 195℃, 200℃, 200℃, 200℃, 195℃, 195℃, 195℃, 200℃.

[0025] The preparation method of the hexadecyltrimethoxysilane modified Al2O3 material in this embodiment is as follows: (1) Weigh 1g of hexadecyltrimethoxysilane, add it to a mixture of 1g of anhydrous ethanol and 2g of deionized water, stir at 35°C for 20min to obtain an aqueous solution of hexadecyltrimethoxysilane; (2) Add 0.8g of nano Al2O3 and the above aqueous solution of hexadecyltrimethoxysilane to a high-temperature mixer and heat to 110°C. After mixing for 5min, dry in an oven at 30°C for 3 hours to obtain the nano Al2O3 material modified by hexadecyltrimethoxysilane.

[0026] Example 2

[0027] Weigh out 57.3 parts by weight of polypropylene PP EA5076, 7 parts by weight of hexadecyltrimethoxysilane modified Al2O3 material, 5 parts by weight of polypropylene grafted maleic anhydride GPM200A, 0.2 parts by weight of antioxidant 1010, 0.2 parts by weight of antioxidant 168 and 0.3 parts by weight of lubricant silicone E525, mix them evenly and add them into the twin-screw extruder through the main feed port. At the same time, add 30 parts by weight of glass fiber-248A through the side feed port. Control the main speed of the twin-screw extruder to be 360 ​​rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 180℃, 195℃, 195℃, 195℃, 200℃, 200℃, 210℃, 210℃, 210℃, 220℃.

[0028] The preparation method of the hexadecyltrimethoxysilane modified Al2O3 material in this embodiment is as follows: (1) Weigh 1g of hexadecyltrimethoxysilane, add it to a mixture of 1.2g of anhydrous ethanol and 3g of deionized water, stir at 32°C for 25min to obtain an aqueous solution of hexadecyltrimethoxysilane; (2) Add 1g of nano Al2O3 and the above aqueous solution of hexadecyltrimethoxysilane to a high-temperature mixer and heat to 110°C. After mixing for 8min, dry in an oven at 30°C for 2.5 hours to obtain the nano Al2O3 material modified by hexadecyltrimethoxysilane.

[0029] Example 3

[0030] Weigh out 71 parts by weight of polypropylene (PP) EA5076, 6.5 parts by weight of hexadecyltrimethoxysilane modified Al2O3 material, 6 parts by weight of polypropylene grafted maleic anhydride GPM200B, 0.2 parts by weight of antioxidant 1010, 0.6 parts by weight of antioxidant 168, and 0.5 parts by weight of lubricant ethylene bis-hard amide. Mix them evenly and add them into the twin-screw extruder through the main feed port. At the same time, add 25 parts by weight of glass fiber-248A through the side feed port. Control the main speed of the twin-screw extruder to be 300 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 190℃, 195℃, 200℃, 210℃, 210℃, 220℃, 220℃, 225℃, and 220℃ respectively.

[0031] The preparation method of the hexadecyltrimethoxysilane modified Al2O3 material in this embodiment is as follows: (1) Weigh 1g of hexadecyltrimethoxysilane, add an appropriate amount of 0.9g of anhydrous ethanol and 2.5g of deionized water to a mixture, stir at 38°C for 15min to obtain an aqueous solution of hexadecyltrimethoxysilane; (2) Add 0.7g of nano Al2O3 and the above aqueous solution of hexadecyltrimethoxysilane to a high-temperature mixer and heat to 110°C. After mixing for 6min, dry in an oven at 30°C for 3.5 hours to obtain the nano Al2O3 material modified by hexadecyltrimethoxysilane.

[0032] Example 4

[0033] Weigh out 83.1 parts by weight of polypropylene PP T30S, 3.5 parts of hexadecyltrimethoxysilane modified Al2O3 material, 3 parts of polypropylene grafted maleic anhydride GPM200A, 0.2 parts of antioxidant 168 and 0.2 parts of lubricant ethylene bis-hard amide, mix them evenly, and add them into the twin-screw extruder through the main feed port. At the same time, add 10 parts of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 190℃, 195℃, 200℃, 210℃, 210℃, 220℃, 220℃, 225℃ and 220℃ respectively.

[0034] The preparation method of the hexadecyltrimethoxysilane modified Al2O3 material in this embodiment is as follows: (1) Weigh 1g of hexadecyltrimethoxysilane, add it to a mixture of 0.8g of anhydrous ethanol and 2g of deionized water, stir at 30°C for 10min to obtain an aqueous solution of hexadecyltrimethoxysilane; (2) Add nano-Al2O3 and the above aqueous solution of hexadecyltrimethoxysilane to a high-temperature mixer and heat to 110°C. After mixing for 3min, dry in an oven at 30°C for 2 hours to obtain the nano-Al2O3 material modified by hexadecyltrimethoxysilane.

[0035] Example 5

[0036] Weigh out 41.4 parts by weight of polypropylene (PP) BX3800, 10 parts of hexadecyltrimethoxysilane modified Al2O3 material, 7 parts of polypropylene grafted maleic anhydride (GPM200B), 1 part of antioxidant 1010, and 0.6 parts of lubricant silicone E525, mix them evenly, and add them into the twin-screw extruder through the main feed port. At the same time, add 40 parts of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 190℃, 195℃, 200℃, 200℃, 200℃, 210℃, 220℃, 220℃, and 230℃ respectively.

[0037] The preparation method of the hexadecyltrimethoxysilane modified Al2O3 material in this embodiment is as follows: (1) Weigh 1g of a specified mass of hexadecyltrimethoxysilane, add an appropriate amount of 1.5g of anhydrous ethanol and 4g of deionized water to a mixture, stir at 40°C for 30min to obtain a hexadecyltrimethoxysilane aqueous solution; (2) Add 1.2g of nano Al2O3 and the above hexadecyltrimethoxysilane aqueous solution to a high-temperature mixer and heat to 110°C. After mixing for 10min, dry in a 30°C oven for 4 hours to obtain the hexadecyltrimethoxysilane modified nano Al2O3 material.

[0038] Comparative Example 1

[0039] Weigh out 76 parts by weight of polypropylene (PP) T30S, 3 parts by weight of polypropylene grafted maleic anhydride (GPM200A), 0.3 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.4 parts by weight of lubricant silicone E525. Mix them evenly and add them into the twin-screw extruder through the main feed port. At the same time, add 20 parts by weight of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 170℃, 195℃, 195℃, 200℃, 200℃, 200℃, 195℃, 195℃, 195℃, 200℃.

[0040] Comparative Example 2

[0041] Weigh out 71 parts by weight of polypropylene (PP) T30S, 5 parts of Al2O3 nanomaterials, 3 parts of polypropylene grafted maleic anhydride (GPM200A), 0.3 parts of antioxidant 1010, 0.3 parts of antioxidant 168, and 0.4 parts of lubricant silicone E525, mix them evenly, and add them to the twin-screw extruder through the main feed port. At the same time, add 20 parts of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 170℃, 195℃, 195℃, 200℃, 200℃, 200℃, 195℃, 195℃, 195℃, 200℃.

[0042] Comparative Example 3:

[0043] Weigh out 72 parts by weight of polypropylene (PP) T30S, 2 parts of Al2O3 nanomaterials, 3 parts of polypropylene grafted maleic anhydride (GPM200A), 0.3 parts of antioxidant 1010, 0.3 parts of antioxidant 168, and 0.4 parts of lubricant silicone E525, mix them evenly, and add them to the twin-screw extruder through the main feed port. At the same time, add 20 parts of glass fiber-305K-3.0 through the side feed port. Control the main speed of the twin-screw extruder to be 320 rpm. The temperature of the twin-screw extruder from the feeding section to the die head is 170℃, 195℃, 195℃, 200℃, 200℃, 200℃, 195℃, 195℃, 195℃, 200℃.

[0044] The high-strength, high-toughness glass fiber modified polypropylene materials prepared in Examples 1-5 and Comparative Examples 1-3 were tested for relevant properties. Tensile strength was tested according to ISO 527 standard, with a test specimen size of 150*10*4mm and a tensile speed of 50mm / min. Flexural strength and flexural modulus were tested according to ISO 178 standard, with a test specimen size of 80*10*4mm and a bending speed of 2mm / min. Cantilever beam notched impact strength was tested according to ISO 180 standard, with a test specimen size of 80*10*4mm, molded, type 1A. The results are shown in Table 1.

[0045] Table 1. Performance test results of high-strength, high-toughness glass fiber modified polypropylene materials in the examples and comparative examples.

[0046]

[0047] As can be seen from the test results in Table 1, the polypropylene modified material prepared by this invention can significantly improve the strength and impact resistance of the material due to the addition of hexadecyltrimethoxysilane-modified Al2O3.

[0048] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0049] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A high-strength, high-toughness glass fiber modified polypropylene composite material, characterized in that: It is prepared from the following components in parts by weight: 41.4-83.1 parts polypropylene, 10-40 parts glass fiber, 5-10 parts hexadecyltrimethoxysilane modified nano-Al2O3 material, 3-7 parts maleic anhydride grafted polypropylene, 0.2-1 parts antioxidant and 0.2-0.6 parts lubricant; The hexadecyltrimethoxysilane-modified nano-Al2O3 material was prepared by the following method: A dispersion was obtained by dispersing hexadecyltrimethoxysilane in a mixed reagent consisting of anhydrous ethanol and water; nano-Al2O3 was added to the above dispersion and mixed and stirred at a temperature of 105-115℃; finally, the mixture was dried to obtain hexadecyltrimethoxysilane modified nano-Al2O3 material. The mass ratio of nano-Al2O3 to hexadecyltrimethoxysilane is 1:0.6-1.2; The hexadecyltrimethoxysilane modified nano-Al2O3 material has a spherical structure.

2. The high-strength, high-toughness glass fiber modified polypropylene composite material according to claim 1, characterized in that: The mass ratio of hexadecyltrimethoxysilane, anhydrous ethanol, and water is 1:0.8-1.5:2-4.

3. The high-strength, high-toughness glass fiber modified polypropylene composite material according to claim 1, characterized in that: The polypropylene is at least one of copolymer polypropylene and homopolymer polypropylene.

4. The high-strength, high-toughness glass fiber modified polypropylene composite material according to claim 1, characterized in that: The glass fiber is either chopped glass fiber or continuous glass fiber.

5. The high-strength, high-toughness glass fiber modified polypropylene composite material according to claim 1, characterized in that: The antioxidant is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris[2,4-di-tert-butylphenyl]phosphite.

6. The high-strength, high-toughness glass fiber modified polypropylene composite material according to claim 1, characterized in that: The lubricant is at least one of ethylene bis-stearamide, pentaerythritol stearate, and silicone powder.

7. The method for preparing the high-strength, high-toughness glass fiber modified polypropylene composite material according to any one of claims 1-6, characterized in that: Includes the following steps: According to the formula, the polypropylene, hexadecyltrimethoxysilane modified nano-Al2O3 material, maleic anhydride grafted polypropylene, antioxidant and lubricant are thoroughly mixed and fed into the twin-screw extruder through the main feed port, while glass fiber is fed into the side feed port. After melt extrusion, granulation and drying, a high-strength and high-toughness glass fiber modified polypropylene composite material is obtained.

8. The application of the high-strength, high-toughness glass fiber modified polypropylene composite material as described in any one of claims 1-6, characterized in that: The high-strength, high-toughness glass fiber modified polypropylene composite material is used to manufacture automotive interior and exterior trim products and electronic appliance housings.

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