Glass fiber modified polypropylene composite material as well as preparation method and application thereof

Abstract

The invention relates to a glass fiber modified polypropylene composite material as well as a preparation method and application thereof. The glass fiber modified polypropylene composite material is prepared from the following components in parts by weight: 60-80 parts of ternary co-polypropylene, 20-40 parts of modified glass fiber, 2-8 parts of a compatilizer and 1 part of other auxiliaries, wherein the modified glass fiber is obtained by jointly modifying glass fiber with a COFs material and a coupling agent. According to the glass fiber modified polypropylene composite material disclosed by the invention, under the action of the COFs material growing on the surface of the glass fiber in situ and the coupling agent, the compatibility between the polypropylene resin and the glass fiber is greatly improved, and the uniformity of a dispersed phase and a continuous phase is improved by improving the interfacial compatibility between the glass fiber and the polypropylene resin; the interface bonding strength is improved, the separation of the glass fiber and the resin is reduced, and the mechanical property of the glass fiber reinforced polypropylene composite material is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer composite materials, and in particular to a glass fiber modified polypropylene composite material and a preparation method and application thereof. Background Art

[0002] Polypropylene (PP) is one of the five most widely used general-purpose resins in the world. Compared with other thermoplastic resins, PP has the characteristics of low density, wide sources, low price, excellent mechanical properties, and good chemical stability. It has become an indispensable raw material for packaging, light industry, construction, electronic appliances, and automobile industries. However, pure polypropylene has limited its application due to its strength, dimensional stability and other defects. Therefore, it is usually filled and modified with mineral powder, fiber, etc. to achieve the purpose of enhancement and modification. Among them, glass fiber filling modification is the most commonly used enhancement and modification method. Therefore, it is of great value and significance to further improve the mechanical properties of glass fiber modified PP materials. Summary of the invention

[0003] Based on this, the purpose of the present invention is to provide a glass fiber modified polypropylene composite material and a preparation method and application thereof. The present invention can greatly improve the mechanical properties of the glass fiber reinforced polypropylene composite material.

[0004] To achieve the above object, the present invention adopts the following technical solutions: The present invention first provides a glass fiber modified polypropylene composite material, which is prepared from the following components in parts by weight: 60-80 parts of terpolymer polypropylene, 20-40 parts of modified glass fiber, 2-8 parts of a compatibilizer, and 1 part of other additives; wherein the modified glass fiber is obtained by modifying the glass fiber with a COFs material and a coupling agent.

[0005] The glass fiber modified polypropylene composite material of the present invention greatly improves the compatibility between polypropylene resin and glass fiber under the action of COFs material in situ grown on the surface of glass fiber and coupling agent, improves the interface compatibility between glass fiber and polypropylene resin, improves the uniformity of dispersed phase and continuous phase, increases the interface bonding strength, reduces the separation of glass fiber and resin, and greatly improves the mechanical properties of the glass fiber reinforced polypropylene composite material.

[0006] As a further improvement of the above scheme of the present invention, the preparation method of the modified glass fiber includes: mixing 2,5-dimethylterephthaloyl hydrazide, (4-formaldehyde phenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol evenly, adding acetic acid, glass fiber and coupling agent, and then vacuuming and heating for reaction; after the reaction is completed, cooling to room temperature and filtering to obtain the modified glass fiber.

[0007] As a further improvement of the above scheme of the present invention, the mass ratio of 2,5-dimethylterephthaloyl hydrazide, (4-formaldehyde phenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, glass fiber and coupling agent is 67:79:3:2:60:5000~10000:100~200; And / or, the vacuuming is to evacuate to a vacuum degree of -0.1MPa to -0.09MPa, and the heating reaction is carried out at 110-130°C for 70-80h.

[0008] As a further improvement of the above solution of the present invention, the coupling agent is one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a phosphate coupling agent.

[0009] As a further improvement of the above solution of the present invention, the melt flow rate of the terpolymer polypropylene is 30-150 g / 10 min.

[0010] As a further improvement of the above solution of the present invention, the compatibilizer is at least one of PP-g-MAH and POE-g-MAH.

[0011] As a further improvement of the above solution of the present invention, the other additives include at least one of an antioxidant, a lubricant, a light absorber, a light stabilizer, and a pigment.

[0012] The present invention also provides a method for preparing the glass fiber modified polypropylene composite material as described above, which comprises the following steps: mixing terpolymer polypropylene, a compatibilizer and other additives in proportion and adding the mixture into an extruder from a main feed port, adding modified glass fiber in proportion from a side feed port, melting, extruding, granulating, cooling and drying to obtain the glass fiber modified polypropylene composite material.

[0013] As a further improvement of the above scheme of the present invention, the temperatures of each zone of the extruder are: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in the die head; the screw speed of the extruder is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0014] The present invention also provides an application of the glass fiber modified polypropylene composite material as described above in the preparation of household appliances and automobile products.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses COFs material and a coupling agent to modify and coat glass fiber, and uses the COFs material to grow in situ on the surface of the glass fiber to improve the roughness of the glass fiber surface. The in situ grown COFs material has polarity and adsorption effects, providing a carrier for the coupling agent to be deposited on the surface of the glass fiber. At the same time, the coupling agent contains chemical functional groups, which can form covalent bonds with the silanol groups on the surface of the glass fiber or the molecules on the surface of other inorganic fillers, providing crosslinking points for the in situ growth of the COFs material on the glass fiber. The two complement each other and play a synergistic role, thereby greatly improving the surface activity of the glass fiber.

[0016] 2. The glass fiber modified polypropylene composite material of the present invention greatly improves the compatibility between polypropylene resin and glass fiber under the action of COFs material and coupling agent grown in situ on the surface of glass fiber, improves the uniformity of dispersed phase and continuous phase, increases the interfacial bonding strength, reduces the separation of glass fiber and resin, and greatly improves the mechanical properties of glass fiber reinforced polypropylene composite material. At the same time, the glass fiber exposure phenomenon is improved to form a glass fiber reinforced polypropylene composite material with low floating fiber and good appearance. Compared with the prior art, the composite material of the present invention has the characteristics of high strength, high modulus and high toughness, and can meet the application of extreme environments such as severe cold areas.

[0017] 3. Under the premise of ensuring the high mechanical strength of the glass fiber reinforced polypropylene material, the present invention selects high-fluidity and low-crystallinity ternary copolymer polypropylene as the resin matrix, which can better impregnate the glass fiber during the composite molding process with the glass fiber.

[0018] 4. The glass fiber modified polypropylene composite material prepared by the present invention can be recycled and reused, meeting the development needs of green and recycled materials for automobiles. DETAILED DESCRIPTION

[0019] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0021] The specific information of the raw materials used in the following examples and comparative examples is as follows: Terpolymer polypropylene: brand CB5230, manufacturer: Korea Petrochemical; modified glass fiber: homemade, homemade method: weigh 670g of 2,5-dimethylterephthaloyl hydrazide, 790g of (4-formaldehyde phenyl)-1,3,5-triazine, 30g of o-dichlorobenzene and 20g of n-butanol, mix evenly, add 60g of acetic acid (concentration of 6 mol / L), then add 20kg of glass fiber (fiber length of 15mm, manufacturer: Hebei Senade Nanomaterial Technology Co., Ltd.) and 1kg of coupling agent; put them into a rotary vacuum drying oven, evacuate to a vacuum degree below -0.09MPa, rotate and heat to 120℃, and react at 120℃ for 72h, then cool to room temperature to obtain modified glass fiber synergistically modified by COFs and coupling agent; (3) Silane coupling agent KH550: manufacturer: Shandong Yuanjin New Materials Co., Ltd.; (4) Compatibilizer PP-g-MAH: grafting rate is 1.5%, the manufacturer is Dongguan Xingyuan Chemical Co., Ltd.; (5) Other additives are mixed with lubricant, primary antioxidant, secondary antioxidant, light absorber and light stabilizer in a mass ratio of 1:1:1:1:1; wherein: the lubricant is silicone masterbatch with brand MB50-002, produced by Dow Corning of the United States; the primary antioxidant is Irganox 565, produced by BASF of Germany; the secondary antioxidant is AN 168, produced by Qingdao Deda Special Chemical Group; the light absorber is Chiguard 5050, produced by Qitai Co., Ltd.; the light stabilizer is LA-52, produced by Aidico (China) Investment Co., Ltd.; (6) Glass fiber: The fiber length is 15 mm. The manufacturer is Hebei Senade Nanomaterial Technology Co., Ltd.

[0022] The above raw materials are all conventional commercially available materials.

[0023] The above raw materials are only for illustrating the sources and components of the raw materials used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0024] Example 1 This embodiment provides a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 80 parts of terpolymer polypropylene, 20 parts of modified glass fiber, 2 parts of compatibilizer, and 1 part of other additives.

[0025] The preparation method of the glass fiber modified polypropylene composite material of the present embodiment comprises the following steps: placing terpolymer polypropylene, compatibilizer and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding modified glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling and drying to obtain a glass fiber modified polypropylene composite material with good appearance. Wherein, the temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0026] Example 2 This embodiment provides a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 80 parts of terpolymer polypropylene, 20 parts of modified glass fiber, 4 parts of compatibilizer, and 1 part of other additives.

[0027] The preparation method of the glass fiber modified polypropylene composite material of the present embodiment comprises the following steps: placing terpolymer polypropylene, compatibilizer and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding modified glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling and drying to obtain a glass fiber modified polypropylene composite material with good appearance. Wherein, the temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0028] Example 3 This embodiment provides a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 80 parts of terpolymer polypropylene, 20 parts of modified glass fiber, 8 parts of compatibilizer, and 1 part of other additives.

[0029] The preparation method of the glass fiber modified polypropylene composite material of the present embodiment comprises the following steps: placing terpolymer polypropylene, compatibilizer and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding modified glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling and drying to obtain a glass fiber modified polypropylene composite material with good appearance. Wherein, the temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0030] Example 4 This embodiment provides a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 70 parts of terpolymer polypropylene, 30 parts of modified glass fiber, 4 parts of compatibilizer, and 1 part of other additives.

[0031] The preparation method of the glass fiber modified polypropylene composite material of the present embodiment comprises the following steps: placing terpolymer polypropylene, compatibilizer and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding modified glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling and drying to obtain a glass fiber modified polypropylene composite material with good appearance. Wherein, the temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0032] Example 5 This embodiment provides a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 60 parts of terpolymer polypropylene, 40 parts of modified glass fiber, 4 parts of compatibilizer, and 1 part of other additives.

[0033] The preparation method of the glass fiber modified polypropylene composite material of the present embodiment comprises the following steps: placing terpolymer polypropylene, compatibilizer and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding modified glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling and drying to obtain a glass fiber modified polypropylene composite material with good appearance. Wherein, the temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0034] Comparative Example 1 This comparative example proposes a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 80 parts of terpolymer polypropylene, 20 parts of glass fiber, and 1 part of other additives.

[0035] The preparation method of the glass fiber modified polypropylene composite material of this comparative example comprises the following steps: placing terpolymer polypropylene and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling, and drying to obtain a glass fiber modified polypropylene composite material with good appearance. The temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0036] Comparative Example 2 This comparative example proposes a glass fiber modified polypropylene composite material, which includes the following component raw materials in parts by weight: 80 parts of terpolymer polypropylene, 20 parts of glass fiber, 2 parts of compatibilizer, and 1 part of other additives.

[0037] The preparation method of the glass fiber modified polypropylene composite material of this comparative example comprises the following steps: placing terpolymer polypropylene and other additives in a high mixer in proportion and mixing for 5 minutes, then adding them into a twin-screw extruder from the main feeding port, adding glass fiber in proportion from the side feeding port, melting, extruding, granulating, cooling, and drying to obtain a glass fiber modified polypropylene composite material with good appearance. The temperature of each zone of the twin-screw extruder is: 160°C in zone 1, 180°C in zone 2, 190°C in zone 3, 200°C in zone 4, 210°C in zone 5, 220°C in zone 6, and 210°C in die head, the screw speed is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0038] The amounts of the raw materials used in the above examples and comparative examples are shown in Table 1.

[0039] Table 1 Amount of each raw material used in the examples and comparative examples (parts by weight)

[0040] Test Case The glass fiber modified polypropylene composite materials in the above Examples 1-5 and Comparative Examples 1-2 were subjected to mechanical property tests and appearance evaluations. The test results are shown in Table 2.

[0041] Table 2 Performance test results

[0042] Note: The detection method of floating fiber grade is: take glass fiber reinforced polypropylene composite material and make a sample with a polishing mold, observe the surface with a secondary original phase instrument, and divide the number of glass fibers appearing on the surface of the sample in the designated area of ​​2mm*2mm into 5 grades. The lower the grade, the better the surface appearance, and vice versa. Among them, grade 1 means that the number of glass fibers is less than 30, grade 2 means that the number of glass fibers is between 30 and 60, grade 3 means that the number of glass fibers is between 60 and 100, grade 4 means that the number of glass fibers is between 100 and 200, and grade 5 means that the number of glass fibers is more than 200.

[0043] According to the results in Table 2, it can be seen that compared with Comparative Examples 1-2, Examples 1-5 use modified glass fibers in combination with a compatibilizer, which greatly improves the mechanical properties and impact strength of the composite materials and greatly improves the problem of surface floating fibers.

[0044] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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.

[0045] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A glass fiber modified polypropylene composite material, characterized in that: The invention is prepared from the following components in parts by weight: 60-80 parts of terpolymer polypropylene, 20-40 parts of modified glass fiber, 2-8 parts of compatibilizer and 1 part of other auxiliary agents; wherein the modified glass fiber is obtained by synergistically modifying the glass fiber with COFs material and coupling agent.

2. The glass fiber modified polypropylene composite material according to claim 1, characterized in that: The preparation method of the modified glass fiber comprises: uniformly mixing 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol, adding acetic acid, glass fiber and coupling agent, and then vacuuming and heating for reaction; cooling to room temperature after the reaction is completed, filtering, and obtaining the modified glass fiber.

3. The glass fiber modified polypropylene composite material according to claim 2, characterized in that: The mass ratio of 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, glass fiber and coupling agent is 67:79:3:2:6:2000-10000:100-200; And / or, the vacuuming is to evacuate to a vacuum degree of -0.1MPa to -0.09MPa, and the heating reaction is carried out at 110-130°C for 70-80h.

4. The glass fiber modified polypropylene composite material according to claim 1, characterized in that: The coupling agent is one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a phosphate coupling agent.

5. The glass fiber modified polypropylene composite material according to claim 1, characterized in that: The melt flow rate of the terpolymer polypropylene is 30-150 g / 10 min.

6. The glass fiber modified polypropylene composite material according to claim 1, characterized in that: The compatibilizer is at least one of PP-g-MAH and POE-g-MAH.

7. The glass fiber modified polypropylene composite material according to claim 1, characterized in that: The other additives include at least one of an antioxidant, a lubricant, a light absorber, a light stabilizer, and a pigment.

8. A method for preparing a glass fiber modified polypropylene composite material as claimed in any one of claims 1 to 7, characterized in that: It includes the following steps: The terpolymer polypropylene, compatibilizer and other additives are mixed in proportion and added into the extruder from the main feeding port, and the modified glass fiber is added in proportion from the side feeding port. After melting, extrusion, granulation, cooling and drying, the glass fiber modified polypropylene composite material is obtained.

9. The method for preparing the glass fiber modified polypropylene composite material according to claim 8, characterized in that: The temperatures of each zone of the extruder are: 160°C for zone 1, 180°C for zone 2, 190°C for zone 3, 200°C for zone 4, 210°C for zone 5, 220°C for zone 6, and 210°C for the die head; the screw speed of the extruder is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

10. Use of the glass fiber modified polypropylene composite material according to any one of claims 1 to 7 in the preparation of household appliances and automobile products.

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