Glass fiber reinforced PA6 composite material and preparation method thereof

Abstract

The invention relates to the technical field of polyamide high polymer materials, in particular to a glass fiber reinforced PA6 composite material and a preparation method thereof. The glass fiber reinforced PA6 composite material comprises the following components in percentage by weight: 20-50% of PA6 resin; 50 wt%-80 wt% of flat glass fibers; 0 wt%-2 wt% of an antioxidant, which is not 0; 0 wt%-1 wt% of a lubricant, which is not 0; 0 wt%-2 wt% of black master batch, which is not 0; the sum of the dosages of the components is 100%. According to the glass fiber reinforced PA6 composite material provided by the invention, only three auxiliary agents are used, the components are simple, the components can be well matched in a specific ratio range, and the obtained glass fiber reinforced PA6 composite material has high glass fiber content, good melt processing characteristics, excellent comprehensive mechanical properties, good barrier property and apparent quality, and can be widely applied to the field of glass fiber reinforced plastic. And the forming processing method is simple.

Description

Technical Field

[0001] The present invention relates to the technical field of polyamide polymer materials, and particularly relates to a glass fiber reinforced PA6 composite material and a preparation method thereof. Background Art

[0002] Nylon 6 (PA6), as a general engineering plastic, has good mechanical properties, heat resistance, wear resistance, barrier properties, etc., and has currently been widely used in fields such as automotive parts, electronic products, and building materials. However, with the development of high-performance composite materials, pure PA6 has been difficult to meet the requirements. The most commonly used reinforcement method is to introduce glass fiber, which can improve the mechanical properties of PA6 and reduce the shrinkage rate. And as the content of glass fiber increases, the improvement effect will be more obvious. Usually, the mass content of glass fiber in PA6 is 5% - 70%.

[0003] However, adding a high content of glass fiber (mass content above 50%) to PA6 will greatly increase the processing viscosity of PA6, making the forming and processing of the composite material much more difficult. Moreover, the glass fiber is prone to agglomeration in the resin, weakening the reinforcement effect of the glass fiber. Severe agglomeration may even lead to a decline in the properties of the composite material. At the same time, a high content of glass fiber will also cause serious fiber floating on the surface of the product, thus reducing the appearance quality of the high-content glass fiber reinforced PA6 composite material product.

[0004] The patent application document CN115302653A discloses a high-content glass fiber reinforced polyamide composite material. By adding a shear element (shear screw block) from a conventional pure conveying element in the metering section, it realizes the improvement of glass fiber dispersion and solves problems such as broken strips. However, strong shearing will damage the glass fiber, resulting in a decrease in the retained fiber length. Although good dispersion of the glass fiber is achieved, the improvement of mechanical properties is very limited. The patent application document CN111978715A discloses a glass fiber reinforced nylon material, in which flat glass fiber is used to reinforce nylon to obtain a material with high hardness, good dimensional stability, and excellent mechanical properties, which can meet the manufacturing requirements of mobile phone camera skeletons. However, there are more than 10 kinds of additives used in the product, with a high use cost and increased processing difficulty.

[0005] Therefore, how to efficiently prepare a glass fiber reinforced composite material with a high glass fiber content, good processability, uniform dispersion of glass fiber, and excellent comprehensive mechanical properties is still an urgent problem to be solved in this field. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a glass fiber reinforced PA6 composite material and a preparation method thereof, so as to solve the problems of difficult processing, easy agglomeration of glass fiber, and low efficiency in improving mechanical properties of existing high-content glass fiber reinforced nylon materials.

[0007] The present invention provides a glass fiber reinforced PA6 composite material, comprising:

[0008]

[0009] The sum of the amounts of the respective components is 100%.

[0010] Preferably, the aspect ratio of the flat glass fiber is 2 to 5:1, the length is 3 to 6 mm, and the diameter is 5 to 30 μm.

[0011] Preferably, the aspect ratio of the flat glass fiber is 3:1 or 4:1.

[0012] Preferably, the flat glass fiber is flat glass fiber ECS301HP-3-M3 or flat glass fiber ECS301HP-3-M4.

[0013] Preferably, the content of the PA6 resin is 20 wt% to 35 wt%;

[0014] The content of the flat glass fiber is 65 wt% to 80 wt%.

[0015] Preferably, the antioxidant includes at least one of hindered phenols, amines, and phosphates;

[0016] The lubricant includes at least one of stearic acid amides, stearic acid alcohol esters, and stearates;

[0017] The black masterbatch includes a PA6 carrier carbon black masterbatch, a PET carrier carbon black masterbatch, or a PE carrier carbon black masterbatch.

[0018] Preferably, the antioxidant is 168 and 1010, and the mass ratio is 1.5 to 2.5:2.5 to 3.5;

[0019] The lubricant is ethylene bisstearamide;

[0020] The black masterbatch is a black masterbatch of model CABOT-PA3785.

[0021] Preferably, the content of the antioxidant is 0.2 wt% to 1 wt%;

[0022] The content of the lubricant is 0.3 wt% to 1 wt%;

[0023] The content of the black masterbatch is 0.3 wt% to 1 wt%.

[0024] The present invention also provides a method for preparing the above-mentioned glass fiber reinforced PA6 composite material, comprising the following steps:

[0025] A) Mix the PA6 resin, antioxidant, lubricant and black masterbatch evenly to obtain a premix;

[0026] B) After mixing the premix with flat glass fiber evenly, carry out extrusion and molding to obtain a glass fiber reinforced PA6 composite material.

[0027] Preferably, mixing the premix with flat glass fiber includes:

[0028] Add the premix to the main feeding port of a twin-screw extruder, add flat glass fiber to the side feeding port, and through the shearing of the screw, the premix and flat glass fiber are fully mixed;

[0029] The length-diameter ratio of the twin-screw extruder is 30 - 55:1;

[0030] The processing temperature of each section of the twin-screw extruder is controlled at 220 - 280 °C, and the vacuum degree is 0.08 - 0.12 MPa.

[0031] The present invention provides a glass fiber reinforced PA6 composite material, including: 20wt% - 50wt% of PA6 resin; 50wt% - 80wt% of flat glass fiber; 0wt% - 2wt% of antioxidant, and not zero; 0wt% - 1wt% of lubricant, and not zero; 0wt% - 2wt% of black masterbatch, and not zero; the sum of the amounts of each component is 100%. In the glass fiber reinforced PA6 composite material provided by the present invention, only three kinds of additives, namely antioxidant, lubricant and black masterbatch, are used. The components are simple. Each component can cooperate well within a specific ratio range. The obtained glass fiber reinforced PA6 composite material has a high glass fiber content, good melt processing characteristics, excellent comprehensive mechanical properties, good barrier properties and appearance quality, and a simple molding processing method. It can be used for simply and efficiently preparing PA6 products with high glass fiber content and high appearance quality, especially for preparing automotive parts and electronic devices with high performance and high appearance quality requirements. Detailed implementation manners

[0032] Next, the technical solutions of the present invention will be described clearly and completely in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0033] The present invention provides a glass fiber reinforced PA6 composite material, including:

[0034]

[0035] The sum of the amounts of each component is 100%.

[0036] In some embodiments of the present invention, the PA6 resin is low-viscosity nylon 6, with a relative viscosity of 1 to 3 mL / g, such as 2 mL / g; specifically, it can be BL3200. The content of the PA6 resin is preferably 20 wt% to 35 wt%; specifically, it can be 28.4 wt%, 43.4 wt%, 20 wt%.

[0037] In some embodiments of the present invention, the aspect ratio of the flat glass fiber is 2 to 5:1, preferably 3 to 5:1, more preferably 4 to 5:1, specifically it can be 3:1 or 4:1; the length is 3 to 6 mm, such as 3 mm; the diameter is 5 to 30 μm. For example, flat glass fiber ECS301HP-3-M3 or flat glass fiber ECS301HP-3-M4. The content of the flat glass fiber is preferably 65 wt% to 80 wt%; specifically, it can be 70 wt%, 55 wt%, 78 wt%.

[0038] In some embodiments of the present invention, the antioxidant is at least one of hindered phenols, amines, and phosphates. Such as 168 and 1010, with a mass ratio of 1.5 to 2.5:2.5 to 3.5, specifically 2:3. The content of the antioxidant is preferably 0.2 wt% to 1 wt%, such as 0.5 wt%, 0.7 wt%.

[0039] In some embodiments of the present invention, the lubricant is at least one of stearic acid amides, stearic acid alcohol esters, and stearates. Such as ethylene bisstearamide, specifically it can be lubricant - EBS HI-LUBE. The content of the lubricant is preferably 0.3 wt% to 1 wt%, such as 0.3 wt%, 0.8 wt%.

[0040] In some embodiments of the present invention, the masterbatch is PA6 carrier carbon black masterbatch, PET carrier carbon black masterbatch, or PE carrier carbon black masterbatch; specifically, it can be the masterbatch with the model number CABOT-PA3785. The content of the masterbatch is preferably 0.3 wt% to 1 wt%, such as 0.8 wt%, 0.5 wt%.

[0041] The present invention also provides a method for preparing the above-mentioned glass fiber reinforced PA6 composite material, comprising the following steps:

[0042] A) Mix the PA6 resin, antioxidant, lubricant, and masterbatch evenly to obtain a premix;

[0043] B) After mixing the premix with the flat glass fiber evenly, perform extrusion and molding to obtain the glass fiber reinforced PA6 composite material.

[0044] Regarding step A):

[0045] Mix the PA6 resin, antioxidant, lubricant and black masterbatch evenly to obtain a premix.

[0046] In some embodiments of the present invention, the even mixing is carried out in a mixer. After the even mixing, it further includes: drying.

[0047] Regarding step B):

[0048] After mixing the premix and flat glass fiber evenly, carry out extrusion and molding to obtain a glass fiber reinforced PA6 composite material.

[0049] In some embodiments of the present invention, mixing the premix and flat glass fiber evenly includes:

[0050] Add the premix to the main feeding port of a twin-screw extruder, add flat glass fiber to the side feeding port, and through the shearing of the screw, the premix and flat glass fiber are fully mixed.

[0051] The ratio of the length to the diameter of the twin-screw extruder is 30-55:1, such as 40:1.

[0052] The processing temperature of each section of the twin-screw extruder is controlled at 220-280°C, the vacuum degree is 0.08-0.12 MPa, such as 0.1 MPa. The temperature at the feeding end of the twin-screw extruder is 220-240°C, such as 220°C. Specifically, the temperatures of each section of the twin-screw extruder from the feeding end to the die are controlled at 220°C, 240°C, 250°C, 260°C, 270°C, 270°C, 280°C, 270°C, 260°C respectively.

[0053] The molding is cooling molding, specifically cooling and molding in a cooling water tank.

[0054] After the molding, it further includes: pelletizing.

[0055] The flat glass fiber is introduced into the glass fiber reinforced PA6 composite material provided by the present invention. Compared with traditional round glass fibers, it can reduce the problem of difficult molding and processing caused by the introduction of high-content glass fibers, and has good comprehensive performance. The specific advantages are as follows:

[0056] 1. After introducing high-content flat glass fibers, the mixture has good processing characteristics, can be used for extrusion molding and injection molding, and the appearance of the product is good without the phenomenon of floating glass fibers;

[0057] 2. After introducing high-content flat glass fibers, they are evenly dispersed in the matrix, reducing the agglomeration problem of traditional glass fibers and improving the dispersibility of glass fibers in the matrix;

[0058] 3. The introduction of high-content flat glass fibers improves the tensile, flexural, impact, and barrier properties of the composite material, and the composite material has excellent comprehensive properties.

[0059] 4. The introduction method of high-content flat glass fibers is simple and does not require a large amount of additives, and the preparation method of the composite material is simple and efficient.

[0060] 5. The present invention further defines the type of flat glass fiber, which is more conducive to improving the comprehensive properties of the glass fiber-reinforced PA6 composite material.

[0061] To further illustrate the present invention, the following provides a detailed description of a glass fiber-reinforced PA6 composite material and its preparation method according to the present invention in conjunction with examples, but it should not be construed as limiting the protection scope of the present invention.

[0062] In the examples,

[0063] PA6 resin: BL3200, Baling Petrochemical Company, Sinopec

[0064] Antioxidants: 168 and 1010, mass ratio of 2:3, Ciba Specialty Chemicals Switzerland

[0065] Lubricant: ethylene bisstearamide, lubricant - EBS HI-LUBE, Shinwon Korea

[0066] Black masterbatch, model CABOT-PA3785.

[0067] Example 1

[0068] The components and dosages of the glass fiber-reinforced PA6 composite material are shown in Table 1.

[0069] Table 1 Components and dosages of the glass fiber-reinforced PA6 composite material (unit: kg)

[0070] Component Dosage / kg PA6 resin 28.4 Flat glass fiber 70 Antioxidant 168 0.2 Antioxidant 1010 0.3 Lubricant 0.3 Black masterbatch 0.8

[0071] In Table 1, flat glass fiber: ECS301HP-3-M4, flatness ratio of 4:1, fiber length of 3 mm, Chongqing International Composite Co., Ltd.

[0072] Preparation of the glass fiber-reinforced PA6 composite material:

[0073] 1) Add PA6 resin, antioxidant, lubricant, and black masterbatch to a mixer and mix evenly. After drying, a premix is obtained.

[0074] 2) Add the premix to the main feeding port of a twin-screw extruder, add flat glass fiber to the side feeding port, and through the shearing of the screw, the premix and the flat glass fiber are fully mixed, extruded into strips through a die, then cooled and formed in a cooling water tank, and after pelletizing, a glass fiber reinforced PA6 composite material is obtained.

[0075] The length-diameter ratio of the twin-screw extruder is 40:1, and the temperatures of each section of the twin-screw extruder from the feeding end to the die are controlled at 220 °C, 240 °C, 250 °C, 260 °C, 270 °C, 270 °C, 280 °C, 270 °C, 260 °C respectively, and the vacuum degree is 0.1 MPa.

[0076] Example 2

[0077] The components and dosages of the glass fiber reinforced PA6 composite material are shown in Table 2.

[0078] Table 2 Components and dosages of the glass fiber reinforced PA6 composite material (unit: kg)

[0079]

[0080]

[0081] In Table 2, flat glass fiber: ECS301HP-3-M4, flatness ratio is 4:1, fiber length is 3 mm, Chongqing International Composite Co., Ltd.;

[0082] Preparation of the glass fiber reinforced PA6 composite material:

[0083] 1) Add PA6 resin, antioxidant, lubricant and black masterbatch to a mixer and mix evenly. After drying, a premix is obtained;

[0084] 2) Add the premix to the main feeding port of a twin-screw extruder, add flat glass fiber to the side feeding port, and through the shearing of the screw, the premix and the flat glass fiber are fully mixed, extruded into strips through a die, then cooled and formed in a cooling water tank, and after pelletizing, a glass fiber reinforced PA6 composite material is obtained.

[0085] The length-diameter ratio of the twin-screw extruder is 40:1, and the temperatures of each section of the twin-screw extruder from the feeding end to the die are controlled at 220 °C, 240 °C, 250 °C, 260 °C, 270 °C, 270 °C, 280 °C, 270 °C, 260 °C respectively, and the vacuum degree is 0.1 MPa.

[0086] Comparative Example 1

[0087] The difference from Example 1 is:

[0088] Replace the flat glass fiber with ordinary glass fiber: ECS301HP, Chongqing International Composite Materials Co., Ltd.;

[0089] The other components, dosages and steps are the same as those in Example 1, and a glass fiber reinforced PA6 composite material is prepared.

[0090] Comparative Example 2

[0091] The difference from Example 2 is that:

[0092] Replace the flat glass fiber with ordinary glass fiber: ECS301HP, Chongqing International Composite Materials Co., Ltd.;

[0093] The other components, dosages and steps are the same as those in Example 2, and a glass fiber reinforced PA6 composite material is prepared.

[0094] Example 3

[0095] The difference from Example 1 is that:

[0096] Replace the flat glass fiber ECS301HP-3-M4 in Example 1 with flat glass fiber ECS301HP-3-M3, with a flat ratio of 3:1 and a fiber length of 3 mm, Chongqing International Composite Materials Co., Ltd.;

[0097] The other components, dosages and steps are the same as those in Example 1, and a glass fiber reinforced PA6 composite material is prepared.

[0098] Example 4

[0099] The difference from Example 2 is that:

[0100] Replace the flat glass fiber ECS301HP-3-M4 in Example 2 with flat glass fiber ECS301HP-3-M3, with a flat ratio of 3:1 and a fiber length of 3 mm, Chongqing International Composite Materials Co., Ltd.;

[0101] The other components, dosages and steps are the same as those in Example 2, and a glass fiber reinforced PA6 composite material is prepared.

[0102] Example 5

[0103] The difference from Example 1 is that:

[0104] The component dosages of the glass fiber reinforced PA6 composite material are different, as shown in Table 3 specifically.

[0105] Table 3 Components and Dosages of Glass Fiber Reinforced PA6 Composite Material (Unit: kg)

[0106] Component Dosage / kg PA6 resin 20 Flat glass fiber 78 Antioxidant 168 0.3 Antioxidant 1010 0.4 Lubricant 0.8 Black masterbatch 0.5

[0107] The composite materials prepared in Examples 1-5 and Comparative Examples 1-2 were injection molded into standard specimens. Tensile specimens were prepared according to the dimensions of ISO 527 standard specimens; specimens for flexural strength and flexural modulus were prepared according to the dimensions of ISO 178 standard specimens; specimens for impact tests were prepared according to the dimensions of ISO 179 standard specimens; barrier tests were prepared according to ISO 15105-1:2007 standard.

[0108] The specific test standards are as follows:

[0109] Melt index test: Tested in accordance with ISO 1133-1:2011 standard, and the test conditions were 275 °C / 2.16 kg;

[0110] Tensile properties: Operated in accordance with the national standard of GB / T1040-2006 Determination of Tensile Properties of Plastics, ISO 527-1 / -2, and the speed was 20 mm / min;

[0111] Flexural properties: Operated in accordance with the national standard of GB / T9341-2008 Determination of Flexural Properties of Plastics, ISO 178:2010, and the speed was 20 mm / min;

[0112] Notched impact test: Operated in accordance with the national standard of GB / T1843-2008 Determination of Izod Impact Strength of Plastics, ISO179:2010 / 1Ea, and the speed was 3.5 m / s;

[0113] Unnotched impact test: Operated in accordance with the national standard of GB / T1843-2008 Determination of Izod Impact Strength of Plastics, ISO179:2010 / 1Eu, and the speed was 3.5 m / s;

[0114] Barrier property test: Tested according to ISO 15105-1:2007 standard, the temperature was 23 °C, and the relative humidity was 50%.

[0115] The test results are shown in Table 4.

[0116] Table 4 Performance test results of the composite materials prepared in Examples 1-5 and Comparative Examples 1-2

[0117]

[0118] As can be seen from Table 1, by introducing flat glass fibers, the glass fiber content in the PA6 matrix can be increased. On the premise of ensuring good processing characteristics, composite materials with good comprehensive mechanical properties, barrier properties and appearance quality can be prepared.

[0119] Comparing Example 1 and Comparative Example 1, it can be seen that at a glass fiber content of 70%, the melt index of the flat glass fiber system is 8.99 g / 10 min, while that of the traditional round glass fiber system is 2.50 g / 10 min. The introduction of flat glass fiber significantly improves its processing characteristics. The tensile strength of Example 1 can reach 231 MPa, the flexural strength reaches 387 MPa, and the impact strength reaches 79.1 KJ / m 2 , with excellent barrier properties, good appearance quality, and no floating fiber phenomenon. It is a high-content glass fiber-reinforced PA6 composite material that is simple to prepare and has excellent comprehensive properties.

[0120] In the comparative examples, as the content of round glass fiber increased, the mechanical properties of the composite material decreased. In the examples, the mechanical properties of the composite material increased with the increase in glass fiber content, showing excellent performance in the preparation of high-content glass fiber-reinforced PA6 composite materials. This is because a high content of flat glass fiber is more easily dispersed than traditional round glass fiber, which will reduce agglomeration in the matrix, making the processing characteristics and reinforcement effect of the glass fiber-reinforced composite material improve significantly.

[0121] Comparing Example 2 and Comparative Example 2, the melt index of the flat glass fiber system is 46.76 g / 10 min, while that of the round glass fiber system is 30.87 g / 10 min. Its processing characteristics are significantly improved, and the barrier and appearance characteristics are also improved. And this composite material can achieve good processing characteristics and comprehensive mechanical properties without too many additives, and can more efficiently and quickly prepare high-content glass fiber-reinforced PA6 composite materials.

[0122] The description of the above examples is only used to help understand the method and its core idea of the present invention. Various modifications to these examples will be obvious to those skilled in the art. The general principles defined herein can be implemented in other examples without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these examples shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A glass fiber reinforced PA6 composite material, comprising: The sum of the amounts of the respective components is 100%.

2. The glass fiber reinforced PA6 composite material according to claim 1, characterized in that, The aspect ratio of the flat glass fiber is 2 - 5:1, the length is 3 - 6 mm, and the diameter is 5 - 30 μm.

3. The glass fiber reinforced PA6 composite material according to claim 1, wherein The aspect ratio of the flat glass fiber is 3:1 or 4:

1.

4. The glass fiber reinforced PA6 composite material according to claim 1, wherein, The flat glass fiber is flat glass fiber ECS301HP - 3 - M3 or flat glass fiber ECS301HP - 3 - M4.

5. The glass fiber reinforced PA6 composite material according to claim 1, characterized in that, The content of the PA6 resin is 20wt% - 35wt%; The content of the flat glass fiber is 65wt% - 80wt%.

6. The glass fiber-reinforced PA6 composite material according to claim 1, characterized in that The antioxidant includes at least one of hindered phenols, amines, and phosphates; The lubricant includes at least one of stearic acid amides, stearic acid esters, and stearates; The black masterbatch includes a PA6 - based carbon black masterbatch, a PET - based carbon black masterbatch, or a PE - based carbon black masterbatch.

7. The glass fiber reinforced PA6 composite material according to claim 1, characterized in that, The antioxidant is 168 and 1010, and the mass ratio is 1.5 - 2.5:2.5 - 3.5; The lubricant is ethylene bisstearamide; The black masterbatch is the black masterbatch with the model number CABOT - PA3785.

8. The glass fiber reinforced PA6 composite material according to claim 1, characterized in that, The content of the antioxidant is 0.2wt% - 1wt%; The content of the lubricant is 0.3wt% - 1wt%; The content of the black masterbatch is 0.3wt% - 1wt%.

9. A method for preparing the glass fiber reinforced PA6 composite material according to any one of claims 1 - 8, comprising the following steps: A) Mix the PA6 resin, antioxidant, lubricant, and black masterbatch evenly to obtain a premix; B) After mixing the premix with the flat glass fiber evenly, perform extrusion and molding to obtain the glass fiber reinforced PA6 composite material.

10. The preparation method according to claim 9, characterized in that, Mixing the premix with the flat glass fiber evenly includes: Adding the premix to the main feeding port of a twin - screw extruder, adding the flat glass fiber to the side feeding port, and through the shearing of the screw, the premix and the flat glass fiber are fully mixed; The length - to - diameter ratio of the twin - screw extruder is 30 - 55:1; The processing temperature of each section of the twin - screw extruder is controlled at 220 - 280°C, and the vacuum degree is 0.08 - 0.12 MPa.

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