Nanoparticle-modified transparent nylon composition and method of making the same

Abstract

This invention discloses a nanoparticle-modified transparent nylon composition and its preparation method, which is prepared from the following components in parts by weight: 100 parts transparent nylon, 2-5 parts nano titanium dioxide, 0.1-2 parts antioxidant, and 0.1-0.5 parts coupling agent. By simultaneously adding the aluminate coupling agent DL-411 and nano titanium dioxide with an average particle size of 5-15 nm to the transparent nylon, the tensile strength and impact strength of the transparent nylon are significantly improved, while the light transmittance remains at a high level without affecting transparency.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a nanoparticle-modified transparent nylon composition and its preparation method. Background Technology

[0002] Most nylons, such as nylon 6, nylon 66, and nylon 1010, have high crystallinity and large crystal particles, with light transmittance ranging from only 30% to 80%. Transparent nylon, on the other hand, is a special type of nylon that hardly crystallizes, has very imperfect crystallization, or has very small crystal particles. As a result, it has extremely high transparency, and this transparency is not lost due to post-processing or post-crystallization of the material.

[0003] In 1960, Nobel Explosives pioneered the development of transparent nylon, achieving a light transmittance of up to 90%. Evonik acquired Nobel Explosives' chemicals division in 1988, thus gaining access to the transparent nylon technology, which was later developed into the Trogamid series. Subsequently, Japan, the United States, Switzerland, and other countries also began development. Today, a wide variety of transparent nylon products are available.

[0004] Transparent nylon can generally be divided into three main categories: semi-aromatic transparent nylon, aromatic transparent nylon, and aliphatic transparent nylon. Semi-aromatic transparent nylon is produced by copolymerizing aromatic diacids with aliphatic diamines or vice versa. Aromatic transparent nylon is produced by copolymerizing aromatic diacids with aromatic diamines. Aliphatic transparent nylon is produced by copolymerizing aliphatic diacids and aliphatic diamines or by producing transparent nylon from long-chain lactams. The aromatic compounds themselves, the raw materials for semi-aromatic and aromatic transparent nylon, are highly toxic; polymerization of these compounds significantly increases the melting point of the material, making molding and processing difficult.

[0005] Aliphatic transparent nylon has seen rapid development and widespread application due to its simple processing technology and easy reaction. However, while aliphatic transparent nylon has good light transmittance, its mechanical properties are relatively low. Modification with ordinary fillers and glass fibers can turn the material into a semi-transparent state, significantly reducing its transparency. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a nanoparticle-modified transparent nylon composition and its preparation method. The transparent nylon composition obtained by the present invention has excellent transparency and mechanical properties.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A nanoparticle-modified transparent nylon composition, comprising the following components in parts by weight:

[0009]

[0010] As a preferred technical solution, the transparent nylon is aliphatic transparent nylon.

[0011] As a preferred technical solution, the aliphatic transparent nylon is transparent nylon 12.

[0012] As a preferred technical solution, the nano-titanium dioxide is anatase with an average particle size of 5-15 nm.

[0013] As a preferred technical solution, the antioxidant is a mixture of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and antioxidant 168.

[0014] The coupling agent is an aluminate coupling agent DL-411.

[0015] Another object of the present invention is to provide a method for preparing the above-described nanoparticle-modified transparent nylon composition, comprising the following steps:

[0016] (1) Add 100 parts of transparent nylon, 2-5 parts of nano titanium dioxide, and 0.1-2 parts of antioxidant, or 100 parts of transparent nylon, 2-5 parts of nano titanium dioxide, 0.1-2 parts of antioxidant, and 0.1-0.5 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0017] (2) Add the mixture into a twin-screw extruder, and after extrusion and pelletizing, the final product is obtained.

[0018] Furthermore, the temperature of the twin-screw extruder is 120-150℃ in zone one, 180-210℃ in zone two, 210-230℃ in zone three, 230-250℃ in zone four, 250-260℃ in zone five, and 255-260℃ in zone six.

[0019] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0020] Adding nano-titanium dioxide to transparent nylon can significantly improve its tensile strength, but it reduces its impact strength and light transmittance. Therefore, in this application, by simultaneously adding the aluminate coupling agent DL-411 and nano-titanium dioxide with an average particle size of 5-15 nm, the tensile strength and impact strength of the transparent nylon are significantly improved, while the light transmittance remains at a high level without affecting its transparency.

[0021] The compositions prepared by this invention can be used in high-end eyeglass frames, lenses, housings and transparent covers for daily necessities, as well as housings for high-voltage switches, relays, terminals, automotive interiors, dashboards, console components, and other products. Detailed Implementation

[0022] The present invention will be further described below with reference to embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0023] The reagents used in the following examples and comparative examples, along with their suppliers, are as follows:

[0024] Transparent nylon 12 is Swiss EMS PA12 TR55LY, with a tensile strength of 55 MPa and an impact strength of 12 kJ / m. 2 The light transmittance at 23℃ is 91.6%.

[0025] In Examples 1-5 and Comparative Examples 6-7, the nano-titanium dioxide was anatase with an average particle size of 10 nm. The nano-titanium dioxide in all examples and comparative examples was manufactured by Ningbo Jiwei Nanomaterials Co., Ltd.

[0026] The manufacturer of aluminate coupling agent DL-411 and silane coupling agent KH550 is Jinan Baite New Materials Co., Ltd.

[0027] The manufacturer of the aluminate coupling agent LS-821 is Kunshan Shengan Biotechnology Co., Ltd.

[0028] The antioxidant of this invention is a mixture of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and antioxidant 168, with a mixing mass ratio of 1:1. Both antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and antioxidant 168 are manufactured by BASF, Germany.

[0029] It should be noted that the above-mentioned products are for the purpose of illustrating the source and composition of the reagents used in the experiments of this invention, so as to fully disclose them, and do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0030] Example 1

[0031] (1) Add 100 parts of transparent nylon, 4 parts of nano titanium dioxide (anatase type, average particle size 10nm), 0.5 parts of antioxidant, and 0.3 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0032] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 120°C in zone one, 180°C in zone two, 210°C in zone three, 230°C in zone four, 250°C in zone five, and 255°C in zone six.

[0033] Comparative Example 1

[0034] (1) Add 100 parts of transparent nylon, 4 parts of nano titanium dioxide (anatase type, average particle size 10nm) and 0.5 parts of antioxidant to a mixer and mix evenly to obtain a mixture.

[0035] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 120°C in zone one, 180°C in zone two, 210°C in zone three, 230°C in zone four, 250°C in zone five, and 255°C in zone six.

[0036] Example 2

[0037] (1) Add 100 parts of transparent nylon, 2 parts of nano titanium dioxide (anatase type, average particle size 10nm), 0.1 parts of antioxidant, and 0.1 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0038] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 130°C in zone one, 190°C in zone two, 220°C in zone three, 240°C in zone four, 260°C in zone five, and 260°C in zone six.

[0039] Example 3

[0040] (1) Add 100 parts of transparent nylon, 5 parts of nano titanium dioxide (anatase type, average particle size 10nm), 1 part of antioxidant, and 0.4 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0041] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 150°C in zone one, 210°C in zone two, 230°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0042] Example 4

[0043] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 10nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0044] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0045] Comparative Example 2 (compared to Example 4)

[0046] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 3nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0047] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0048] Comparative Example 3 (compared to Example 4)

[0049] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 20nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0050] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0051] Comparative Example 4 (compared to Example 4)

[0052] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 50nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0053] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0054] Comparative Example 5 (compared to Example 4)

[0055] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (rutile type, average particle size 10nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0056] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0057] Comparative Example 6 (compared to Example 4)

[0058] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (rutile type, average particle size 20nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent DL-411 to a mixer and mix evenly to obtain a mixture.

[0059] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0060] Comparative Example 7 (compared to Example 4)

[0061] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 10nm), 0.8 parts of antioxidant, and 0.2 parts of silane coupling agent KH550 to a mixer and mix evenly to obtain a mixture.

[0062] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0063] Comparative Example 8 (compared to Example 4)

[0064] (1) Add 100 parts of transparent nylon, 3 parts of nano titanium dioxide (anatase type, average particle size 10nm), 0.8 parts of antioxidant, and 0.2 parts of aluminate coupling agent LS-821 to a mixer and mix evenly to obtain a mixture.

[0065] (2) The mixture is added to a twin-screw extruder, and the final product is obtained by extrusion and pelletizing. Further, the temperature of the twin-screw extruder is 140°C in zone one, 180°C in zone two, 220°C in zone three, 250°C in zone four, 260°C in zone five, and 260°C in zone six.

[0066] The performance test results of the products obtained in Examples 1-4 and Comparative Examples 1-8 are shown in Table 1. The test conditions for each product are as follows:

[0067] The tensile specimen has the dimensions of (170.0±5.0)mm*(13.0±0.5)mm*(3.2±0.2)mm, a tensile rate of 5mm / min, and a test standard of GB / T 1040.

[0068] The cantilever beam impact strength specimen used is of the following type: (125.0±5.0)mm*(13.0±0.5)mm*

[0069] (3.2±0.2)mm, test standard GB / T 1843.

[0070] The standard for light transmittance testing is GB / T 2680-94.

[0071] Table 1. Performance test results of the products prepared in each embodiment and comparative example.

[0072]

[0073] According to the test results, it can be seen that adding nano-titanium dioxide to Comparative Example 1 can significantly improve the tensile strength of transparent nylon 12, but the impact strength and light transmittance are reduced. In Example 1, after simultaneously adding aluminate coupling agent DL-411 and nano-titanium dioxide with an average particle size of 10nm, the tensile strength and impact strength of transparent nylon are significantly improved, the light transmittance can be maintained at a high level, and the transparency is not affected.

[0074] Compared with Example 4, Comparative Example 2 showed a significant decrease in tensile strength, impact strength, and light transmittance. This may be because the average particle size of the nanoparticles was too small. Although the manufacturer treated the dispersibility of the nanoparticles, obvious agglomeration occurred in the transparent nylon 12 matrix, leading to a decline in various properties.

[0075] Comparative examples 3 and 4 show that when the average particle size of the added nano-titanium dioxide is too large, the mechanical properties will gradually decrease and the transparency will be significantly affected.

[0076] The nano-titanium dioxide added in Comparative Example 5 is rutile type. Compared with anatase nano-titanium dioxide, the particle size is the same, and the mechanical properties of the transparent nylon composition are basically the same, but the light transmittance is significantly reduced.

[0077] Comparative Example 7 uses silane coupling agent KH550, and Comparative Example 8 uses aluminate coupling agent LS-821. Although the mechanical properties and transparency of the material are slightly improved when these two commonly used coupling agents are added to transparent nylon, they are still much inferior to those of Example 5 of this application.

[0078] The composition prepared by this invention has a light transmittance of 87.2-89.2%, and can be used in high-end eyeglass frames and lenses, housings and transparent covers for daily necessities, housings for high-voltage switches, housings for relays, terminals, automotive interiors, dashboards, console components, and other products.

[0079] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent modifications made using the present invention are within the patent protection scope of the present invention.

Claims

1. A nanoparticle-modified transparent nylon composition, characterized in that: It is prepared from the following components in parts by weight: 100 portions of transparent nylon 2-5 parts of nano titanium dioxide Antioxidant 0.1-2 parts, 0.1 to 0.5 parts of coupling agent; The nano-titanium dioxide is anatase type with an average particle size of 5-15 nm; the coupling agent is aluminate coupling agent DL-411; and the transparent nylon is aliphatic transparent nylon.

2. The nanoparticle-modified transparent nylon composition according to claim 1, characterized in that: The aliphatic transparent nylon is transparent nylon 12.

3. The nanoparticle-modified transparent nylon composition according to claim 1, characterized in that: The antioxidant is a mixture of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and antioxidant 168.

4. A method for preparing a nanoparticle-modified transparent nylon composition according to any one of claims 1-3, characterized in that: Includes the following steps: (1) Add 100 parts of transparent nylon, 2 to 5 parts of nano titanium dioxide, 0.1 to 2 parts of antioxidant, and 0.1 to 0.5 parts of coupling agent to a mixer and mix evenly to obtain a mixture. (2) Add the mixture into a twin-screw extruder, and after extrusion and pelletizing, the final product is obtained.

5. The preparation method according to claim 4, characterized in that: The temperature of the twin-screw extruder is 120-150℃ in zone one, 180-210℃ in zone two, 210-230℃ in zone three, 230-250℃ in zone four, 250-260℃ in zone five, and 255-260℃ in zone six.

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