Laser-weldable reinforced long-carbon-chain nylon material and preparation method therefor

Abstract

Disclosed in the present invention are a laser-weldable reinforced long-carbon-chain nylon material and a preparation method therefor. The nylon material comprises the following components in parts by mass: 40-90 parts of long-carbon-chain nylon, 5-40 parts of fiberglass, 0.01-0.09 parts of a high-performance laser welding pigment powder, and 0.1-5 parts of other auxiliaries. The high-performance laser welding pigment powder system has excellent color development and light transmittance and can meet black appearance and laser welding performance requirements when added at an amount of 0.04 wt%, and the extremely low addition amount does not affect the performance of the material itself and can significantly reduce the cost. The laser-weldable reinforced long-carbon-chain nylon material prepared by the present invention has a laser transmittance of 83.3%, a tensile strength of 113.05 MPa, and an equilibrium water absorption of 0.2%, meets the application requirements of a transmissive material, and can be applied to the manufacturing of automobile parts and components.

Description

Laser weldable reinforced long carbon chain nylon material and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to a laser weldable reinforced long carbon chain nylon material and a preparation method thereof, and belongs to the field of engineering plastics. BACKGROUND

[0002] Polyamide, also known as nylon, contains repeating amide groups in its molecular backbone. Nylon with a methylene length of more than 10 between two amide groups is called long carbon chain nylon. In addition to the lubricity, wear resistance and easy processing of most nylons, it also has good flexibility, low water absorption, high dimensional stability and excellent dielectric properties, and is widely used in the field of automobile manufacturing, such as automobile clutch hose, brake pipe and oil pipe, etc.

[0003] Laser transmission welding technology, as a new type of plastic welding process, has the advantages of high efficiency, high quality, flexibility and low cost, and has broad application prospects in the field of plastic manufacturing. The process of laser transmission welding technology mainly consists of three steps: when laser irradiates the welding parts, it first passes through the upper layer of the material with transmission property, which is partially absorbed and scattered in the process; the laser that is not absorbed and scattered enters the lower layer of the material with absorption property, continuously accumulates and converts into heat, and then returns to the upper layer area, finally causing the adjacent materials to melt; the adjacent materials are welded together by external force or material free expansion. Therefore, the light transmission of the transmission material is the primary condition for determining whether the welding is successful.

[0004] At present, the demand for black plastic in the automotive field is huge, and the commonly used black colorant is carbon black, which shows high absorption rate to laser and is difficult to be directly used for preparing the upper layer transmission material. CN106317864A discloses a black glass fiber reinforced nylon 6 material and a preparation method thereof, which is prepared by using aniline black as a colorant. However, this technology still needs to add 1-20% of transparent modifier, which increases the complexity of preparation and the cost of preparation. CN109929241A discloses a laser weldable nylon material combination, a preparation method and application thereof, which includes a light transmission layer nylon and a light absorption layer nylon, wherein the addition amount of organic color powder in the light transmission layer is 0.2-0.6%, the addition amount is large and the light transmission rate is below 80%, and the preparation process is complex. Based on the above problems, it is necessary to provide a preparation scheme of transmission material with small addition amount and small influence on the material, good light transmission performance, simple preparation process and low cost. TECHNICAL SOLUTION

[0005] The application discloses a laser-weldable reinforced long-carbon-chain nylon material and a preparation method thereof, which comprises the following components in parts by mass: long-carbon-chain nylon, glass fiber, high-performance laser-welding color powder and other additives.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted is:

[0007] A laser-weldable reinforced long-carbon-chain nylon material, which comprises the following components in parts by mass:

[0008] Long-carbon-chain nylon 40-90 parts;

[0009] Glass fiber 5-40 parts;

[0010] High-performance laser-welding color powder 0.01-0.09 parts;

[0011] Other additives 0.1-5 parts.

[0012] Further, the long-carbon-chain nylon is one or more of PA11, PA12, PA610, PA612, PA1010, PA1012 and PA1212.

[0013] Further, the glass fiber is a chopped glass fiber, the diameter of which is 9-13 mu m, and the length of which is 3-6 mm.

[0014] Further, the high-performance laser-welding color powder comprises, in percentage by mass, solvent blue 10-60%, pigment yellow 5-30%, oil-soluble violet 20-70% and anthraquinone 4-30%.

[0015] Further, the other additives comprise one or more of an antioxidant and a lubricant, wherein the mixing ratio of the antioxidant to the lubricant is 1-2:1-2.

[0016] Further, the antioxidant comprises but is not limited to one or more of a hindered amine, a hindered phenol, a phosphite and a thio.

[0017] Further, the lubricant comprises but is not limited to one or more of stearic acid and a salt thereof, butyl stearate, oleamide and ethylene bis-stearamide.

[0018] Preferably, the laser-weldable reinforced long carbon chain nylon material comprises the following components by mass fraction:

[0019] long carbon chain nylon 69.56 parts;

[0020] glass fiber 30 parts;

[0021] high-performance laser welding toner 0.04 parts;

[0022] other additives 0.4 parts.

[0023] Preferably, the high-performance laser welding toner comprises, by mass percentage: solvent blue 30%, pigment yellow 10%, oil-soluble purple 50%, and anthraquinone 10%.

[0024] The application also provides a preparation method of the laser-weldable reinforced long carbon chain nylon material, comprising the following steps:

[0025] The long carbon chain nylon, high-performance laser welding toner, and other additives are respectively mixed in a high-speed mixer to obtain a premix, and the premix and side-fed 5-40 parts of chopped glass fiber are sent into a double-screw extruder for mixing, melting, and homogenization, and then extruded and granulated, wherein the extrusion and granulation temperature is 180-230 DEG C, and the screw rotation speed is 400-600 rpm, to obtain the laser-weldable reinforced long carbon chain nylon material.

[0026] The application also provides an application of the laser-weldable reinforced long carbon chain nylon material in automobile parts, especially in the preparation of brake pipes and cooling water pipes. Advantages

[0027] The application optimizes the composition formula of the laser-weldable reinforced long carbon chain nylon, on the one hand, designs a high-performance laser welding toner system with excellent color development and light transmission, and when the addition amount is 0.04 wt%, it meets the requirements of black appearance and laser welding performance, and the extremely low addition amount does not affect the performance of the material itself, and can significantly reduce the cost; on the other hand, the chopped glass fiber is used, so that the nylon material has a certain hardness, thereby meeting the actual production needs of welding. The laser-weldable reinforced long carbon chain nylon material prepared by the application has a laser transmission rate of 83.3%, a tensile strength of 113.05 MPa, and an equilibrium water absorption rate of 0.2%, which can meet the application requirements of the transmission material, and has a wider practical application prospect. Embodiments of the application

[0028] In order for the person skilled in the art to better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be specifically described below in combination with the embodiments of the present application. The described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the person skilled in the art without creative labor should belong to the scope of protection of the present application.

[0029] The same commercially available products were used in the examples and comparative examples, and the sources of the raw materials used were as follows:

[0030] The long carbon chain nylon was PA1012 from Shandong Dongchen Ruisen New Material Technology Co., Ltd.; the glass fiber 1 was T435TM with a diameter of 10 μm and a length of 3 mm, purchased from Taishan Glass Fiber Co., Ltd.; the glass fiber 2 was CC-14-2400-003 with a diameter of 10 μm and a length of 3 mm, purchased from Shandong Chuxi New Material Co., Ltd.; the carbon black was purchased from Suzhou Baohua Carbon Black Co., Ltd.; the solvent blue 104 was purchased from Hubei Fangxing New Material Co., Ltd.; the pigment yellow 184 was purchased from BASF (China) Co., Ltd.; the oil-soluble violet 401 and 1,4-di-p-tolylamino anthraquinone were purchased from Hubei Xinhongli Chemical Co., Ltd.; the multi-hindered phenolic antioxidant was purchased from Tianjin Li'anlong New Material Co., Ltd.; and the ethylene-acrylic acid copolymer lubricant was purchased from Honeywell.

[0031] The high-performance laser welding toner ratio was as follows:

[0032] The high-performance laser welding toner 1 ratio was: solvent blue 50%, pigment yellow 10%, oil-soluble violet 35%, and anthraquinone 5%;

[0033] The high-performance laser welding toner 2 ratio was: solvent blue 30%, pigment yellow 10%, oil-soluble violet 50%, and anthraquinone 10%;

[0034] The high-performance laser welding toner 3 ratio was: solvent blue 20%, pigment yellow 20%, oil-soluble violet 50%, and anthraquinone 10%;

[0035] The high-performance laser welding toner 4 ratio was: solvent blue 30%, pigment yellow 10%, oil-soluble violet 35%, and anthraquinone 25%;

[0036] The high-performance laser welding toner 5 ratio was: solvent blue 20%, pigment yellow 15%, oil-soluble violet 60%, and anthraquinone 5%;

[0037] The high-performance laser welding toner 6 ratio was: solvent blue 100%.

[0038] Examples

[0039] The formulations of examples 1-8 are shown in Table 1

[0040] Formulation of Examples 1-8 of Table 1

[0041] Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Long carbon chain nylon 10 69.56 69.56 69.52 89.56 69.56 69.56 69.56 69.56 Glass fiber 1 30 30 30 30 30 Glass fiber 2 30 Polyhydric hindered phenol type antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Ethylene-acrylic acid copolymer type lubricant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 High performance laser welding toner 1 0.04 0.04 0.08 0.04 High performance laser welding toner 2 0.04 High performance laser welding toner 3 0.04 High performance laser welding toner 4 0.04 High performance laser welding toner 5 0.04

[0042] Preparation method: according to the mass fraction of Table 1 Examples 1-8, the long carbon chain nylon, high performance laser welding toner, other additives are fully mixed in a high mixer to obtain a premix, and the glass fiber is fed into a double screw extruder for mixing, melting and homogenization, and then extrusion granulation, the extrusion granulation temperature is 180-230℃, the screw rotation speed is 500 rpm, and different long carbon chain nylon materials are obtained.

[0043] Comparative examples

[0044] Formulation of Comparative Examples 1-5 as shown in Table 2

[0045] Formulation of Comparative Examples 1-5 of Table 2

[0046] Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Long carbon chain nylon 10 69.60 69.56 69.50 69.50 66.60 Glass fiber 1 30 30 30 30 Glass fiber 2 Polyhydric hindered phenol type antioxidant 0.2 0.2 0.2 0.2 0.2 Ethylene-acrylic acid copolymer type lubricant 0.2 0.2 0.2 0.2 0.2 High performance laser welding toner 1 0.13 High performance laser welding toner 6 0.04 Carbon black 0.1

[0047] Preparation method: according to the mass fraction of Table 2 Comparative Examples 1-5, the components are fully mixed in a high mixer to obtain a premix, and the glass fiber is fed into a double screw extruder for mixing, melting and homogenization, and then extrusion granulation, the extrusion granulation temperature is 180-230℃, the screw rotation speed is 500 rpm, and different long carbon chain nylon materials are obtained.

[0048] Performance test and evaluation of experimental examples

[0049] The long carbon chain nylon material obtained in the above examples and comparative examples was subjected to performance testing, and the specific testing methods were as follows:

[0050] Laser transmittance testing method: the long carbon chain nylon material obtained in the above examples and comparative examples was set as a test plate with a size of 60 mm x 60 mm x 1.2 mm, and was determined by an ultraviolet-visible spectrophotometer with a wavelength of 980 nm.

[0051] Mechanical property testing method:

[0052] Tensile property was tested in accordance with GB / T 1040-2006 “Determination of tensile properties of plastics”, the testing temperature was 23°C, and the tensile rate was 50 mm / min;

[0053] Bending strength was tested in accordance with GB / T 9341-2008 “Determination of bending properties of plastics”, the testing temperature was 23°C, and the bending rate was 2 mm / min;

[0054] Charpy notched impact strength was tested in accordance with GB / T 1043-2008 “Determination of Charpy impact properties of plastics”, V-shaped notched samples were used, the testing temperature was 23°C, and the pendulum energy was 5.5 J.

[0055] Water absorption testing method: the long carbon chain nylon material obtained above was set as a round piece with a diameter of 50 mm and a thickness of 3 mm, the sample was saturated with water for 72 h, and then was tested and evaluated in accordance with GB / T 1034-2008 “Determination of water absorption of plastics”.

[0056] The performance testing results of the long carbon chain nylon material obtained in the examples and comparative examples are shown in Table 3:

[0057] Table 3 Performance testing results of long carbon chain nylon material

[0058] Laser transmittance (%) 82.6 82.1 79.6 85.7 83.3 81.0 80.6 80.1 88.2 73.6 73.1 65.5 Tensile strength (MPa) 110.0 103.3 112.0 287.6 113.0 109.8 110.3 108.3 110.6 111.0 113.9 111.7 113.4 Bending strength (MPa) 146.2 139.8 146.0 164.6 147.1 139.5 140.3 144.3 146.6 144.3 147.2 148.0 147.5 Bending modulus (MPa) 5211.3 133.2 205.1 602.3 316.8 553.3 310.0 329.1 153.2 515.2 216.8 555.2 291.4 Notched impact (KJ / m2) 23.0 24.1 23.2 25.7 23.1 23.2 23.1 23.0 23.1 22.7 23.3 22.9 23.4 Water absorption (%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Color appearance Black Black Black Black Black Black Black Black Natural color Dark blue Black Black Black

[0059] From Table 3, it can be seen that by Examples 1, 5-8 and Comparative Example 1, when the content of the high-performance laser welding colorant 1-5 is 0.04 wt%, the long carbon chain nylon material can exhibit good black appearance, and the laser transmittance is greater than 80%, wherein the high-performance laser welding colorant 2 used in Example 5 exhibits more excellent laser transmittance performance, with a laser transmittance of 83.3%, without significantly changing the mechanical properties and water absorption of the nylon material (tensile strength is greater than 108 MPa, and water absorption is 0.2%).

[0060] From Comparative Examples 1 and 4, it can be seen that when the content of glass fiber decreases, the laser transmittance of the nylon material will further increase, but the mechanical properties will decrease accordingly.

[0061] From Comparative Examples 1-3 and Comparative Examples 4 and 5, it can be seen that when the content of the high-performance laser welding colorant of the present application is too high, the laser transmittance of the nylon material will decrease, thereby affecting the laser welding effect. From Comparative Example 2, it can be seen that when only one kind of dye colorant is added, the appearance color of the nylon transmission material is significantly different from that of the light-absorbing material of Comparative Example 3, which affects the actual use.

[0062] In conclusion, the laser-weldable reinforced long carbon chain nylon prepared by the application has good mechanical properties, water absorption and excellent laser transmission performance, the high-performance laser welding toner has a very small amount of addition, which indicates that the toner prepared by the application has excellent color development and light transmission, and does not affect the performance of the material itself, can significantly reduce the cost, and has a broad application prospect. The laser-weldable reinforced long carbon chain nylon obtained by the application can be applied in the preparation of automobile pipelines, such as brake pipes and cooling water pipes.

Claims

1. A laser weldable reinforced long carbon chain nylon material characterized by, By mass parts include the following components: Long carbon chain nylon 40~90 parts; Glass fiber 5~40 parts; High-performance laser welding toner 0.01~0.09 parts; Other additives 0.1~5 parts.

2. The laser weldable reinforced long carbon chain nylon material of claim 1, characterized by, The long carbon chain nylon is one or several of PA11, PA12, PA610, PA612, PA1010, PA1012, PA1212.

3. The laser weldable reinforced long carbon chain nylon material of claim 1, characterized by, The glass fiber is short glass fiber, the diameter is 9-13 μm, and the length is 3-6 mm.

4. The laser weldable reinforced long carbon chain nylon material of claim 1, characterized by, The high-performance laser welding toner includes solvent blue 10-60%, pigment yellow 5-30%, oil-soluble purple 20-70%, and anthraquinone 4-30% by mass percentage.

5. The laser weldable reinforced long chain carbon nylon material of claim 1, characterized by, The other additives include one or several of antioxidants and lubricants, wherein the mixing ratio of antioxidant to lubricant is 1-2:1-2.

6. The laser weldable reinforced long chain carbon nylon material of claim 5, characterized by, The antioxidant includes but is not limited to one or several of hindered amine, hindered phenol, phosphite, and thio.

7. The laser weldable reinforced long chain carbon nylon material of claim 5, characterized by, The lubricant includes but is not limited to one or several of stearic acid and its salt, butyl stearate, oleamide, and ethylene bis-stearamide.

8. The method of making a laser weldable reinforced long carbon chain nylon material of claim 1, wherein, According to claim 1, the long carbon chain nylon, high-performance laser welding toner, and other additives are taken by mass parts, added to a high mixer, and fully mixed to obtain a premix, which is sent into a double screw extruder with side feeding short glass fiber for mixing, melting, and homogenization, and then extruded and granulated, the extrusion and granulation temperature is 180-230℃, the screw rotation speed is 400-600 rpm, and the laser-weldable reinforced long carbon chain nylon material is obtained.

9. The application of the laser-weldable reinforced long carbon chain nylon material prepared by the preparation method of any one of claims 1-8 in automobile parts.