Glass fiber reinforced weather-resistant composite material and preparation method thereof

Abstract

The invention discloses a glass fiber reinforced weather-resistant composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The composite material is composed of 30%-60% of bio-based nylon 56, 10%-30% of polyadipyl m-xylylenediamine, 25%-35% of glass fibers, 1%-2% of a weather-resistant agent, 0.2%-1% of an antioxidant, 0.2%-1% of a compatilizer, 0.1%-0.5% of a heat stabilizer, 1%-3% of a lubricant and 1%-2% of black masterbatch. The composite material disclosed by the invention belongs to a low-carbon environment-friendly material, has good impact strength and weather resistance, and can be used for preparing a car roof trunk; according to the invention, the bio-based nylon 56, the polyadipyl m-xylylenediamine and the glass fibers are blended, so that the mechanical properties of the material are powerfully enhanced.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a glass fiber reinforced weather-resistant composite material and a preparation method thereof. Background Art

[0002] Since the advent of plastics in the 20th century, they have consumed vast quantities of fossil resources, generated significant carbon dioxide emissions, and subsequently created a vast amount of plastic pollution. The depletion of petrochemical resources and global warming have become major challenges facing human society today. Developing bio-based composites, leveraging the abundant and vast reserves of biomass resources, is of great significance for reducing carbon emissions.

[0003] Bio-based nylon 56 (PA56) is a new bio-based polyamide synthesized from the polymerization of bio-based pentamethylenediamine and petroleum-based adipic acid. It offers significant environmental advantages and broad application prospects. Its synthesis consumes biomass resources such as corn starch, making it a "carbon-negative" material from a carbon emissions perspective. Furthermore, the chemical structure of PA56 is similar to that of PA66, differing by only one carbon atom in the repeating unit of the molecular chain. The two fibers share similar densities, melting points, and mechanical properties in dry conditions. Bio-based PA56 fibers are currently widely used in textiles, engineering plastics, and other fields.

[0004] However, bio-based nylon 56 (PA56) has poor toughness and low notch impact strength, which will lead to reduced durability of the manufactured products and easy breakage under external impact loads. In order to extend the service life of the product and broaden its scope of use, the material must be specially modified. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a glass fiber reinforced weather-resistant composite material and a preparation method thereof, so as to solve the current problems of poor toughness and low notched impact strength of bio-based nylon 56.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The invention provides a glass fiber reinforced weather-resistant composite material. The composite material consists of 30%-60% of bio-based nylon 56, 10%-30% of poly(m-phenylenediamine adipamide), 25%-35% of glass fiber, 1%-2% of a weathering agent, 0.2%-1% of an antioxidant, 0.2%-1% of a compatibilizer, 0.1%-0.5% of a heat stabilizer, 1%-3% of a lubricant, and 1-2% of a black masterbatch.

[0008] Furthermore, the bio-based nylon 56 is produced by converting corn starch into 1,5-pentanediamine through a bio-fermentation process, and then polymerizing it with petroleum-based adipic acid, with the bio-based mass fraction accounting for about 45%.

[0009] Furthermore, the poly(m-xylylenediamine adipamide) is a crystalline polyamide resin, which is synthesized by condensation of m-xylylenediamine and adipic acid.

[0010] Furthermore, the weathering agent is a hindered amine light stabilizer, specifically di(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; the antioxidant is obtained by compounding pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite; the compatibilizer is prepared by grafting maleic anhydride onto polypropylene; the heat stabilizer is a composite antioxidant, prepared by one or more of a hindered phenol antioxidant, a phosphite antioxidant, an aromatic amine antioxidant, and a thioester antioxidant; and the lubricant is zinc stearate.

[0011] Furthermore, the condensation ratio of m-xylylenediamine and adipic acid is 1:1.

[0012] Furthermore, the glass fiber is an alkali-free glass fiber with a diameter of 10-15 μm.

[0013] Furthermore, the mass ratio of the pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate to tris(2,4-di-tert-butylphenyl) phosphite is 2:1.

[0014] Furthermore, a method for preparing a glass fiber reinforced weather-resistant composite material comprises the following steps:

[0015] S1. Weigh bio-based nylon 56, antioxidant, weathering agent, and lubricant, mix at 80-100°C for 10-15 minutes, and evenly disperse and stir the components to obtain a premix;

[0016] S2. First, poly(m-xylylene adipamide) is added to the main feed port of a twin-screw extruder, and glass fiber is added through the side feed port. At the same time, a compatibilizer, a heat stabilizer, and a black masterbatch are added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder is 280-300°C, and the screw speed is 200-300 r / min.

[0017] S3, mixing the premix and pellets, and extruding them twice to obtain composite pellets, and then performing injection molding on the composite pellets on an injection molding machine to obtain a glass fiber reinforced weather-resistant composite material.

[0018] Furthermore, in step S3, the extruder temperature during the secondary extrusion is 260-280°C, and the screw speed is 250-350r / min; during injection molding, the injection molding machine temperature is 250-270°C, the mold temperature is 40-60°C, the injection pressure is 80-120MPa, the holding pressure is 60-80MPa, the holding time is 10-15s, and the cooling time is 20-30s.

[0019] The beneficial effects of the present invention are:

[0020] 1. The composite material of the present invention is a low-carbon and environmentally friendly material with good impact strength and weather resistance, and can be used for the preparation of automobile roof luggage boxes.

[0021] 2. The present invention effectively enhances the mechanical properties of the material by blending bio-based nylon 56, poly(m-xylylene adipamide) and glass fiber.

[0022] 3. In the present invention, bio-based nylon 56 itself is a degradable material and is not resistant to UV aging. By adding some MXD6, the performance degradation problem of bio-based nylon 56 after UV aging is effectively improved.

[0023] 4. Among the raw materials of the present invention, bio-based nylon 56 has good biodegradability and provides certain matrix strength and toughness; poly(m-xylylenediamine adipamide) has excellent heat resistance, chemical resistance and mechanical properties; the alkali-free glass fiber selected as the reinforcing material significantly improves the strength and rigidity of the composite material; the weathering agent can effectively improve the weather resistance of the material and prevent aging and degradation caused by ultraviolet rays; the antioxidant can prevent oxidative degradation of the material during processing and use; the compatibilizer can enhance the interfacial bonding strength between bio-based nylon 56, poly(m-xylylenediamine adipamide) and glass fiber; the lubricant can improve the fluidity during processing and reduce the friction between the material and the equipment.

[0024] Other advantages, objectives and features of the present invention will be described in the following description and will be apparent to those skilled in the art to some extent, or those skilled in the art can be taught from the practice of the present invention. The objectives and other advantages of the present invention can be realized and obtained through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to make the purpose, technical solutions and beneficial effects of the invention clearer, the present invention is described with the following drawings:

[0026] Figure 1 is a process flow chart of the present invention;

[0027] Figure 2 This is a composite particle diagram of the finished product of the present invention. DETAILED DESCRIPTION

[0028] like Figure 1-2 As shown, the present invention provides a method for preparing a glass fiber reinforced weather-resistant composite material.

[0029] Example 1

[0030] S1. Weigh 35% of bio-based nylon 56, 0.2% of antioxidant, 1% of weathering agent, and 1% of lubricant, mix them at 80°C for 12 minutes, and evenly disperse and stir the components to obtain a premix;

[0031] S2. First, 10% of poly(m-xylylene adipamide) was added to the main feed port of a twin-screw extruder, and 25% of glass fiber was added through the side feed port. At the same time, 0.2% of a compatibilizer, 0.1% of a heat stabilizer, and 1.5% of a black masterbatch were added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder was 280° C., and the screw speed was 200 r / min.

[0032] S3. Mix the premix and pellets, set the extruder temperature to 260°C and the screw speed to 250 r / min for secondary extrusion to obtain composite pellets, place the composite pellets on an injection molding machine, set the injection molding machine temperature to 250°C, the mold temperature to 40°C, the injection pressure to 80 MPa, the holding pressure to 60 MPa, the holding time to 10 s, and the cooling time to 30 s, and perform injection molding to obtain a glass fiber reinforced weather-resistant composite material.

[0033] Example 2

[0034] S1. Weigh 60% of bio-based nylon 56, 0.2% of antioxidant, 1.5% of weathering agent, and 1% of lubricant, mix at 80°C for 12 minutes, and evenly disperse and stir the components to obtain a premix;

[0035] S2. First, 20% of poly(m-xylylene adipamide) was added to the main feed port of a twin-screw extruder, and 35% of glass fiber was added through the side feed port. At the same time, 0.2% of a compatibilizer, 0.1% of a heat stabilizer, and 1% of a black masterbatch were added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder was 280° C., and the screw speed was 200 r / min.

[0036] S3. Mix the premix and pellets, set the extruder temperature to 260°C and the screw speed to 250 r / min for secondary extrusion to obtain composite pellets, place the composite pellets on an injection molding machine, set the injection molding machine temperature to 250°C, the mold temperature to 40°C, the injection pressure to 80 MPa, the holding pressure to 60 MPa, the holding time to 10 s, and the cooling time to 30 s, and perform injection molding to obtain a glass fiber reinforced weather-resistant composite material.

[0037] The difference between Example 2 and Example 1 is that the ratios of the substances are different, but both are within the scope of protection of the present invention.

[0038] Example 3

[0039] S1. Weigh 47% of bio-based nylon 56, 1% of antioxidant, 1% of weathering agent, and 3% of lubricant, mix them at 80°C for 12 minutes, and evenly disperse and stir the components to obtain a premix;

[0040] S2. First, 30% of poly(m-xylylene adipamide) was added to the main feed port of a twin-screw extruder, and 30% of glass fiber was added through the side feed port. At the same time, 0.2% of a compatibilizer, 0.1% of a heat stabilizer, and 2% of a black masterbatch were added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder was 280° C., and the screw speed was 200 r / min.

[0041] S3, the premix and pellets are mixed, and the extruder temperature is set to 260 ° C, the screw speed is 250 r / min for secondary extrusion to obtain composite pellets, the composite pellets are placed on the injection molding machine, the injection molding machine temperature is set to 250 ° C, the mold temperature is 40 ° C, the injection pressure is 80 MPa, the holding pressure is 60 MPa, the holding time is 10 s, the cooling time is 30 s, and injection molding is performed to obtain a glass fiber reinforced weather-resistant composite material

[0042] The difference between Example 3 and Example 1 is that the ratios of the substances are different, but both are within the scope of protection of the present invention.

[0043] In order to demonstrate the superiority of the materials, proportions and methods of the present invention, comparative examples 1 to 3 are provided herein.

[0044] Comparative Example 1

[0045] S1. Weigh 70% of bio-based nylon 56, 0.2% of antioxidant, 1% of weathering agent, and 1% of lubricant, mix them at 80°C for 12 minutes, and evenly disperse and stir the components to obtain a premix;

[0046] S2. First, 10% of poly(m-xylylene adipamide) was added to the main feed port of a twin-screw extruder, and 10% of glass fiber was added through the side feed port. At the same time, 0.2% of a compatibilizer, 0.1% of a heat stabilizer, and 1.5% of a black masterbatch were added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder was 280° C., and the screw speed was 200 r / min.

[0047] S3. Mix the premix and pellets, set the extruder temperature to 260°C and the screw speed to 250 r / min for secondary extrusion to obtain composite pellets, place the composite pellets on an injection molding machine, set the injection molding machine temperature to 250°C, the mold temperature to 40°C, the injection pressure to 80 MPa, the holding pressure to 60 MPa, the holding time to 10 s, and the cooling time to 30 s, and perform injection molding to obtain a composite material.

[0048] The difference between Comparative Example 1 and Example 1 is that the ratio of bio-based nylon 56, poly(m-xylylene adipamide), and glass fiber is not within the scope of protection of the present invention, and the resulting material has poor performance.

[0049] Comparative Example 2

[0050] S1. Weigh 35% of bio-based nylon 56, 0.2% of antioxidant, 1% of weathering agent, and 1% of lubricant, mix them at 80°C for 12 minutes, and evenly disperse and stir the components to obtain a premix;

[0051] S2. First, 10% of poly(m-xylylene adipamide) was added to the main feed port of a twin-screw extruder and then added through the side feed port. At the same time, 0.2% of a compatibilizer, 0.1% of a heat stabilizer, and 1.5% of a black masterbatch were added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder was 280° C. and the screw speed was 200 r / min.

[0052] S3. Mix the premix and pellets, set the extruder temperature to 260°C and the screw speed to 250 r / min for secondary extrusion to obtain composite pellets, place the composite pellets on an injection molding machine, set the injection molding machine temperature to 250°C, the mold temperature to 40°C, the injection pressure to 80 MPa, the holding pressure to 60 MPa, the holding time to 10 s, and the cooling time to 30 s, and perform injection molding to obtain a composite material.

[0053] The difference between Comparative Example 2 and Example 1 is that no glass fiber is added, and the performance of the obtained material is poor.

[0054] Comparative Example 3

[0055] S1. Weigh 35% of bio-based nylon 56, 0.2% of antioxidant, 1% of weathering agent, 1% of lubricant, 10% of poly(m-phenylenediamine adipamide), 25% of glass fiber, add 0.2% of compatibilizer, 0.1% of heat stabilizer, and 1.5% of black masterbatch through the side feed port, add to the end of the twin-screw extruder, and mix evenly to obtain the material;

[0056] S2. Extrude the material from the twin-screw extruder and tract and pelletize it.

[0057] The difference between Comparative Example 3 and Example 1 is that all the materials are directly added and mixed at once, and each material is given sufficient reaction time, resulting in poor performance of the obtained material.

[0058] The materials obtained in Examples 1-3 and Comparative Examples 1-3 were tested using the following test methods: Tensile strength: ISO 527-2; Flexural strength / flexural modulus: ISO 178; Charpy notched impact strength: ISO 179 / 1eA, Condition 2J, 23°C; and UV aging test methods: Testing equipment: Xenon lamp aging chamber with continuous illumination, irradiation intensity: 50±5 W / m2 @ 300-400 nm; Black mark temperature: 90°C, chamber temperature: (70±10)°C, relative humidity: 15±10%. The results are shown in Table 1:

[0059]

[0060]

[0061] As can be seen from the table above, the glass fiber reinforced weather-resistant composite materials prepared in Examples 1-3 of this application exhibit significantly improved mechanical properties compared to the composite materials prepared in Comparative Examples 1-3. In terms of weather resistance, Examples 1-3 also exhibit excellent results. After UV aging testing, the impact resistance remains above 90%, fully meeting the requirements for outdoor use. However, due to changes in raw materials, formulations, and methods, the composite materials obtained in Comparative Examples 1-3 exhibit significantly lower performance than those of Examples 1-3 of the present invention. Therefore, the materials prepared using the method of the present invention achieve a balanced overall performance across all aspects.

[0062] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A glass fiber reinforced weather-resistant composite material, characterized by: The composite material consists of 30%-60% of bio-based nylon 56, 10%-30% of poly(m-phenylenediamine adipamide), 25%-35% of glass fiber, 1%-2% of a weathering agent, 0.2%-1% of an antioxidant, 0.2%-1% of a compatibilizer, 0.1%-0.5% of a heat stabilizer, 1%-3% of a lubricant, and 1-2% of a black masterbatch.

2. The glass fiber reinforced weather-resistant composite material according to claim 1, characterized in that: The bio-based nylon 56 is produced by converting corn starch into 1,5-pentanediamine through a bio-fermentation process and then polymerizing it with petroleum-based adipic acid. The bio-based mass fraction of the nylon 56 is approximately 45%.

3. The glass fiber reinforced weather-resistant composite material according to claim 2, characterized in that: The poly(m-xylylenediamine adipamide) is a crystalline polyamide resin, which is synthesized by polycondensation of m-xylylenediamine and adipic acid.

4. The glass fiber reinforced weather-resistant composite material according to claim 3, characterized in that: The weathering agent is a hindered amine light stabilizer, specifically di(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; the antioxidant is obtained by compounding pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite; the compatibilizer is prepared by grafting maleic anhydride onto polypropylene; the heat stabilizer is a composite antioxidant, prepared by one or more of a hindered phenol antioxidant, a phosphite antioxidant, an aromatic amine antioxidant, and a thioester antioxidant; and the lubricant is zinc stearate.

5. The glass fiber reinforced weather-resistant composite material according to claim 4, characterized in that: The ratio of the meta-xylylenediamine and adipic acid in the polycondensation is 1:

1.

6. The glass fiber reinforced weather-resistant composite material according to claim 2, characterized in that: The glass fiber is an alkali-free glass fiber with a diameter of 10-15 μm.

7. The glass fiber reinforced weather-resistant composite material according to claim 5, characterized in that: The mass ratio of the pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl) phosphite is 2:

1.

8. The method for preparing a glass fiber reinforced weather-resistant composite material according to any one of claims 1 to 7, characterized in that: The following steps are included: S1. Weigh bio-based nylon 56, antioxidant, weathering agent, and lubricant, mix at 80-100°C for 10-15 minutes, and evenly disperse and stir the components to obtain a premix; S2. First, poly(m-xylylene adipamide) is added to the main feed port of a twin-screw extruder, and glass fiber is added through the side feed port. At the same time, a compatibilizer, a heat stabilizer, and a black masterbatch are added to a hopper and mixed to obtain pellets. The temperature of the twin-screw extruder is 280-300°C, and the screw speed is 200-300 r / min. S3. Evenly mix the premix and the pellets, extrude them twice to obtain composite pellets, and perform injection molding on the composite pellets on an injection molding machine to obtain a glass fiber reinforced weather-resistant composite material.

9. The method for preparing a glass fiber reinforced weather-resistant composite material according to claim 8, characterized in that: In step S3, during the secondary extrusion, the extruder temperature is 260-280° C., and the screw speed is 250-350 r / min; during the injection molding, the injection molding machine temperature is 250-270° C., the mold temperature is 40-60° C., the injection pressure is 80-120 MPa, the holding pressure is 60-80 MPa, the holding time is 10-15 s, and the cooling time is 20-30 s.

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