A pps / lcp composition and a method for producing the same

Abstract

The application discloses a PPS / LCP composition and a preparation method thereof, which is prepared from the following components according to weight parts: PPS resin 43-64 parts, LCP resin 5-15 parts, special glass fiber 15-25 parts, laser sensitizer A 5-10 parts, laser sensitizer B 1-5 parts, compatible agent 2-5 parts, coupling agent 1-3 parts, and antioxidant 0.2-0.6 parts; wherein the laser sensitizer A is functionalized multi-walled carbon nanotube, and the laser sensitizer B is any one of basic copper phosphate, copper chromium black, zinc hydroxystannate and tin oxide. The application provides a low-dielectric PPS / LCP composition with excellent mechanical properties, flame-retardant properties and laser direct forming property, the dielectric constant of the composition is reduced by adopting PPS and LCP, the toughness and crystallization rate of PPS are improved, and the strength and rigidity of LCP are improved, so that the PPS / LCP composition has excellent comprehensive performance. The laser direct forming property of the PPS / LCP composition is improved by compounding basic copper phosphate and functionalized multi-walled carbon nanotube.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically a PPS / LCP composition and its preparation method. Background Technology

[0002] LDS (Laser Direct Structuring) is a specialized 3D-MID (Three-Dimensional Moulded Interconnect Device) manufacturing technology that combines laser processing, injection molding, and electroplating. It primarily utilizes a CNC laser to directly transfer circuit patterns onto the surface of a molded plastic component, forming a circuit interconnect structure using the three-dimensional surface of the workpiece. This process typically includes injection molding, laser activation, electroplating, spraying / assembly, and RF testing. It has found widespread application in fields such as mobile phone antennas, three-dimensional circuits, and smart sensing, including wearable devices, smart medical devices, autonomous vehicles, smart homes, and drones, and is one of the key technologies for achieving lightweight, thin, and miniaturized smart terminals.

[0003] Polyphenylene sulfide (PPS) possesses advantages such as high temperature resistance, corrosion resistance, radiation resistance, non-staining properties, non-toxicity, excellent mechanical and electrical properties, and good dimensional stability of finished products. The linear, rigid structure formed by the direct connection of sulfur atoms to the para-position of the benzene ring in the PPS molecular chain results in high crystallinity and excellent dimensional stability and rigidity. It is hailed as the sixth major general-purpose engineering plastic after the five major general-purpose engineering plastics. However, the structure of PPS determines its hardness and brittleness. Liquid crystal polymers (LCPs) are crystalline materials in the molten state, possessing excellent flowability, chemical stability, mechanical strength, electrical insulation properties, and thermal stability. However, when used alone, LCPs suffer from poor strength, rigidity, and heat resistance.

[0004] Currently, some research has been conducted on laser-formed PPS compositions in existing technologies. For example, Chinese patent CN109852051A discloses a nylon / polyphenylene sulfide alloy material and its preparation method, comprising: 35-80 parts nylon, 1-10 parts polyphenylene sulfide, and 20-50 parts glass fiber. It can be seen that current existing technologies mainly involve ordinary glass fiber reinforced PPS-based LDS materials, and the LDS additives used are spinel oxides containing copper and chromium. These oxides contain the heavy metal chromium, which can cause environmental pollution. Furthermore, copper-chromium oxides can only provide black, limiting the application of LDS technology in many fields, especially in areas with high color requirements. Summary of the Invention

[0005] In view of this, the present invention provides a PPS / LCP composition and its preparation method. The composition has excellent mechanical properties, flame retardant properties, laser direct formability and low dielectric properties, and can be widely used in 5G devices, electronic and electrical components, etc.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] In a first aspect, the present invention discloses a PPS / LCP composition prepared from the following components in parts by weight:

[0008]

[0009] Among them, laser sensitizer A is a functionalized multi-walled carbon nanotube, and laser sensitizer B is any one of basic copper phosphate, copper chromate black, zinc hydroxystannate, and tin oxide.

[0010] As a further aspect of the present invention, the number-average relative molecular mass of the PPS resin is 15,000 to 25,000.

[0011] As a further aspect of the present invention: the LCP resin is a thermotropic liquid crystal polymer.

[0012] As a further aspect of the present invention: the special glass fiber has a dielectric constant of 3.5 to 4.0, a cross-sectional length of 26 to 30 μm, a width of 6.5 to 7.5 μm, and an aspect ratio of 4:1.

[0013] As a further aspect of the present invention: the compatibilizer is double-grafted SEBS; the double-grafted SEBS is hydrogenated styrene-butadiene-styrene copolymer double-grafted with glycidyl methacrylate and maleic anhydride.

[0014] As a further aspect of the present invention: the coupling agent is γ-aminopropyltriethoxysilane; the antioxidant is bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0015] As a further aspect of the present invention, the preparation method of the functionalized multi-walled carbon nanotubes is as follows:

[0016] (1) Multi-walled carbon nanotubes and nano zinc oxide were uniformly dispersed in anhydrous ethanol at a mass ratio of 100:10-20, and the intermediate product was obtained after filtration.

[0017] (2) The intermediate product is mixed with acrylic acid solution, tetrabutyl titanate and ammonium persulfate aqueous solution, vacuumed and reacted at 90-100℃ in a nitrogen atmosphere for 2-4 hours. After cooling to room temperature, the reaction product is washed, filtered and dried to obtain functionalized multi-walled carbon nanotubes.

[0018] As a further aspect of the present invention: in the acrylic acid solution, the volume ratio of acrylic acid, deionized water, and anhydrous ethanol is 1:(0.3-0.5):(0.2-0.4); the mass concentration of the ammonium persulfate aqueous solution is 4-6 wt%.

[0019] As a further aspect of the present invention: in step (2), the mass ratio of the intermediate product, acrylic acid solution, tetrabutyl titanate, and ammonium persulfate aqueous solution is 100:(450-500):(1-3):(2-5).

[0020] On the other hand, the present invention discloses a method for preparing the PPS / LCP composition as described above, comprising the following steps:

[0021] (1) PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl) pentaerythritol diphosphite are mixed evenly to obtain the first mixture;

[0022] (2) Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane are mixed evenly to obtain a second mixture;

[0023] (3) The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to the side of the extruder, and special glass fiber is added to the other side. The mixture is melt-extruded and granulated to obtain a PPS / LCP composition.

[0024] The temperatures are as follows: Zone 1: 300–310℃; Zone 2: 300–310℃; Zone 3: 305–315℃; Zone 4: 305–315℃; Zone 5: 310–320℃; Zone 6: 310–320℃; Zone 7: 315–325℃; Zone 8: 315–325℃; Die head temperature: 310–320℃; Screw speed: 400–600 rpm.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] 1. This invention provides a low-dielectric PPS / LCP composition with excellent mechanical properties, flame retardant properties, and laser-moldable characteristics. It innovatively proposes using PPS combined with LCP to reduce the dielectric constant of the composition. Furthermore, the polyphenylene sulfide and liquid crystal polymer complement each other, improving both the toughness and crystallization rate of PPS and the strength and rigidity of LCP, thus resulting in excellent overall performance. The addition of basic copper phosphate and functionalized multi-walled carbon nanotubes further enhances the laser-moldability of the PPS / LCP composition.

[0027] 2. This invention creatively proposes a preparation process for surface-modified multi-walled carbon nanotubes using nano-zinc oxide, which not only improves the compatibility of multi-walled carbon nanotubes in the resin matrix, but also significantly enhances the laser direct forming properties of the PPS / LCP composition when added to the PPS / LCP resin matrix.

[0028] 3. Synergistic effect of laser sensitizer A and laser sensitizer B. This invention utilizes the excellent absorption performance of Cu / Zn / Sn formed after laser sensitizer B is excited for lasers of different wavelengths, which is beneficial for LDS forming. After being compounded with functionalized multi-walled carbon nanotubes, on the one hand, the Zn formed on the surface of the functionalized multi-walled carbon nanotubes by laser irradiation also has excellent laser absorption performance. In addition, the multi-walled carbon nanotubes themselves have a certain degree of conductivity, which can promote the formation of conductive networks and further promote the formation of conductive patterns, thereby giving the composite material a better laser forming function. Detailed Implementation

[0029] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0031] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0032] Polyphenylene sulfide resin with a number-average relative molecular mass of 20,000 and carboxyl-terminated groups was purchased from Zhejiang Xinhecheng Special Materials Co., Ltd.

[0033] Special glass fiber with a dielectric constant of 3.8 (1GHz), a cross-sectional length of 28μm, a width of 7μm, and an aspect ratio of 4:1, was purchased from Chongqing International Composite Materials Co., Ltd.

[0034] Ordinary reinforced glass fiber with a dielectric constant of 7.0 (1 GHz) and a fiber diameter of 14 μm was purchased from Chongqing International Composite Materials Co., Ltd.

[0035] Double-grafted SEBS, with a grafting rate of 1.2 wt% of glycidyl methacrylate and 1.2 wt% of maleic anhydride, was purchased from Shenyang Ketong Plastics Co., Ltd.

[0036] Basic copper phosphate, with a particle size of 0.2 μm, was purchased from Merck Chemical Technology (Shanghai) Co., Ltd.

[0037] Copper Chromium Black, Black 28, purchased from Hubei Jingcheng New Materials Co., Ltd.;

[0038] Zinc hydroxystannate was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0039] Tin oxide with a particle size of 50 nm was purchased from Nanjing Kelston Chemical Technology Co., Ltd.

[0040] γ-aminopropyltriethoxysilane was purchased from Nanjing Nengde New Material Technology Co., Ltd.

[0041] Multi-walled carbon nanotubes, purchased from LG, South Korea;

[0042] Butyl titanate, purchased from Shandong Huian Chemical Co., Ltd.;

[0043] Ammonium persulfate was purchased from Jinan Yiliuba Chemical Co., Ltd.

[0044] Bis(2,4-dicumylphenyl)pentaerythritol diphosphite was purchased from Hubei Zhonglong Kangcheng Fine Chemical Co., Ltd.

[0045] All materials are commercially available, commonly used products.

[0046] It is understood that the above-mentioned raw materials and reagents are merely examples of some specific embodiments of the present invention, making the technical solution of the present invention clearer, and do not mean that the present invention can only use the above-mentioned reagents. The specific scope shall be determined by the claims. In addition, unless otherwise specified, "parts" in the examples and comparative examples refer to parts by weight.

[0047] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0048] In the examples and comparative examples, the preparation methods of the functionalized carbon nanotubes used are as follows:

[0049] (1) Add 100g of multi-walled carbon nanotubes and 15g of nano zinc oxide to a flask, and add anhydrous ethanol to ultrasonically disperse for 1-3 hours. Filter to obtain a mixture.

[0050] (2) Add 500 ml of an aqueous solution of acrylic acid to the reactor. The volume ratio of acrylic acid, deionized water and anhydrous ethanol in the aqueous solution is 1:0.4:0.3. Then add 100 g of the mixture from step (1), 2 g of tetrabutyl titanate and 3 ml of 5 wt% ammonium persulfate aqueous solution. Vacuum the reactor and purge with nitrogen to control the system pressure inside the reactor to 0.3 MPa.

[0051] (3) Stir the reaction vessel and heat it to 95°C for 3 hours. Cool it to room temperature and wash, filter and dry it to obtain nano-oxide surface modified multi-walled carbon nanotubes.

[0052] Example 1

[0053] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 3 parts double-grafted SEBS, 3 parts functionalized multi-walled carbon nanotubes, 8 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0054] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed to obtain the first mixture.

[0055] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0056] The first mixture is fed into the main feed port of a parallel twin-screw extruder via a feeder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0057] Process parameters for the parallel twin-screw extruder: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die temperature 315℃, Screw speed 500rpm.

[0058] Example 2

[0059] Weigh out the following components for later use: 43 parts PPS resin, 15 parts LCP resin, 25 parts special glass fiber, 5 parts double-grafted SEBS, 5 parts functionalized multi-walled carbon nanotubes, 5 parts copper chromium black, 2 parts γ-aminopropyltriethoxysilane, and 0.2 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0060] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0061] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0062] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0063] Parallel twin-screw extruder process parameters: Zone 1 temperature 310℃, Zone 2 temperature 310℃, Zone 3 temperature 315℃, Zone 4 temperature 315℃, Zone 5 temperature 320℃, Zone 6 temperature 320℃, Zone 7 temperature 325℃, Zone 8 temperature 325℃, Die head temperature 320℃, Screw speed 500rpm.

[0064] Example 3

[0065] Weigh the following components for later use: 64 parts PPS resin, 5 parts LCP resin, 15 parts special glass fiber, 2 parts double-grafted SEBS, 1 part functionalized multi-walled carbon nanotubes, 10 parts zinc hydroxystannate, 3 parts γ-aminopropyltriethoxysilane, and 0.3 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0066] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0067] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0068] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0069] Parallel twin-screw extruder process parameters: Zone 1 temperature 295℃, Zone 2 temperature 295℃, Zone 3 temperature 300℃, Zone 4 temperature 300℃, Zone 5 temperature 310℃, Zone 6 temperature 310℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die head temperature 320℃, Screw speed 400rpm.

[0070] Example 4

[0071] Weigh out the following components for later use: 59 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 2 parts double-grafted SEBS, 2 parts functionalized multi-walled carbon nanotubes, 6 parts tin oxide, 1 part γ-aminopropyltriethoxysilane, and 0.3 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0072] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0073] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0074] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0075] Parallel twin-screw extruder process parameters: Zone 1 temperature 300℃, Zone 2 temperature 300℃, Zone 3 temperature 305℃, Zone 4 temperature 305℃, Zone 5 temperature 310℃, Zone 6 temperature 310℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die head temperature 320℃, Screw speed 600rpm.

[0076] Example 5

[0077] Weigh out the following components for later use: 50 parts PPS resin, 15 parts LCP resin, 20 parts special glass fiber, 4 parts double-grafted SEBS, 2 parts functionalized multi-walled carbon nanotubes, 7 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.3 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0078] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0079] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0080] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0081] The process parameters for the parallel twin-screw extruder include: zone 1 temperature 300℃, zone 2 temperature 300℃, zone 3 temperature 305℃, zone 4 temperature 305℃, zone 5 temperature 310℃, zone 6 temperature 310℃, zone 7 temperature 320℃, zone 8 temperature 320℃, die temperature 320℃, and screw speed 600rpm.

[0082] Comparative Example 1

[0083] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts ordinary reinforced glass fiber, 3 parts double-grafted SEBS, 3 parts functionalized multi-walled carbon nanotubes, 8 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0084] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0085] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0086] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to the side of the extruder, while ordinary glass fiber is added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0087] Parallel twin-screw extruder process parameters: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die head temperature 315℃, Screw speed 500rpm.

[0088] Comparative Example 2

[0089] Weigh out the following components for later use: 64 parts PPS resin, 20 parts special glass fiber, 3 parts double-grafted SEBS, 3 parts functionalized multi-walled carbon nanotubes, 8 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0090] PPS resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0091] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0092] The first mixture is added to the main feed port of a parallel twin-screw extruder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0093] The process parameters for the parallel twin-screw extruder include: zone 1 temperature 305℃, zone 2 temperature 305℃, zone 3 temperature 310℃, zone 4 temperature 310℃, zone 5 temperature 315℃, zone 6 temperature 315℃, zone 7 temperature 320℃, zone 8 temperature 320℃, die temperature 315℃, and screw speed 500rpm.

[0094] Comparative Example 3

[0095] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 3 parts functionalized multi-walled carbon nanotubes, 8 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0096] PPS resin, LCP resin and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0097] Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed thoroughly to obtain a second mixture.

[0098] The first mixture is fed into the main feed port of a parallel twin-screw extruder via a feeder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0099] Parallel twin-screw extruder process parameters: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die head temperature 315℃, Screw speed 500rpm.

[0100] Comparative Example 4

[0101] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 3 parts double-grafted SEBS, 3 parts multi-walled carbon nanotubes, 8 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0102] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed evenly to obtain the first mixture.

[0103] Multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture.

[0104] The first mixture is fed into the main feed port of a parallel twin-screw extruder via a feeder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0105] Parallel twin-screw extruder process parameters: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die head temperature 315℃, Screw speed 500rpm.

[0106] Comparative Example 5

[0107] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 3 parts double-grafted SEBS, 11 parts functionalized multi-walled carbon nanotubes, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0108] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed to obtain the first mixture.

[0109] Functionalized multi-walled carbon nanotubes and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture;

[0110] The first mixture is fed into the main feed port of a parallel twin-screw extruder via a feeder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0111] Process parameters for the parallel twin-screw extruder: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die temperature 315℃, Screw speed 500rpm.

[0112] Comparative Example 6

[0113] Weigh out the following components for later use: 54 parts PPS resin, 10 parts LCP resin, 20 parts special glass fiber, 3 parts double-grafted SEBS, 11 parts basic copper phosphate, 2 parts γ-aminopropyltriethoxysilane, and 0.6 parts bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0114] PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl)pentaerythritol diphosphite were added to a mixer and mixed to obtain the first mixture.

[0115] Basic copper phosphate and γ-aminopropyltriethoxysilane were added to another mixer and mixed evenly to obtain a second mixture;

[0116] The first mixture is fed into the main feed port of a parallel twin-screw extruder via a feeder, and the second mixture is added to one side of the extruder, while special glass fibers are added to the other side for melt extrusion and granulation to obtain the PPS / LCP composition.

[0117] Process parameters for the parallel twin-screw extruder: Zone 1 temperature 305℃, Zone 2 temperature 305℃, Zone 3 temperature 310℃, Zone 4 temperature 310℃, Zone 5 temperature 315℃, Zone 6 temperature 315℃, Zone 7 temperature 320℃, Zone 8 temperature 320℃, Die temperature 315℃, Screw speed 500rpm.

[0118] The laser-direct-forming PPS compositions prepared in the above examples and comparative examples were subjected to the following performance tests:

[0119] Tensile strength: Tested according to GB / T 1040-2006 standard, with a tensile rate of 50 mm / min.

[0120] Notched impact strength: Tested according to GB / T 1843-2008 standard.

[0121] Dielectric constant: Tested according to GB / T 5597-1999 standard, test frequency 5GHz.

[0122] Laser direct formability: Adhere to the plastic part surface metal coating adhesion test (also known as the cross hatch test), and test according to the ASTM D3359 standard. The specific method is as follows. Under the conditions of room temperature 23±2°C and relative humidity 50±5%, use a sharp blade (blade angle is 15°-30°) to draw 10×10 small grids of 1mm×1mm on the surface of the test sample, and each scratch reaches the bottom layer of the coating; use a brush to clean the test area; firmly stick the 3M No. 600 tape to the tested small grid, and use an eraser to wipe the tape forcefully to increase the contact area and force between the tape and the tested area; hold one end of the tape by hand and quickly tear off the transparent tape at a 60° angle in the vertical direction, and conduct 2 identical tests at the same position. Result judgment: The adhesion is required to be ≥4B to be qualified; 5B - The edges of the scratches are smooth, and there is no paint peeling off at the edges and intersection points of the scratches; 4B - There are small pieces of paint peeling off at the intersection points of the scratches, and the total peeling area is less than 5%; 3B - There are small pieces of paint peeling off at the edges and intersection points of the scratches, and the total peeling area is between 5% and 15%; 2B - There are成片 of paint peeling off at the edges and intersection points of the scratches, and the total peeling area is between 15% and 35%; 1B - There are成片 of paint peeling off at the edges and intersection points of the scratches, and the total peeling area is between 35% and 65%; 0B - There are成片 of paint peeling off at the edges and intersection points of the scratches, and the total peeling area is greater than 65%.

[0123] The performance test results are shown in Table 1.

[0124] Table 1

[0125]

[0126] As can be seen from Table 1, with the decrease of the addition amount of special glass fiber, the tensile strength and notch impact strength of the PPS-based LDS composition decrease. This is mainly because the connection on the interface between the glass fiber and the resin necessarily conducts the force acting on the molded part to the glass fiber, and the glass fiber bears most of the acting force, thus achieving the purpose of enhancing the resin. At the same time, when subjected to external impact, the glass fiber can not only absorb the impact energy, but also trigger the generation of crazes-shear bands, thereby absorbing a large amount of impact energy.

[0127] Furthermore, as can be seen from Examples 1 to 5, using any one of the following functionalized multi-walled carbon nanotubes—basic copper phosphate, copper chromium black, zinc hydroxystannate, and tin oxide—can synergistically improve the laser-direct formability of the PPS / LCP composition. The key to achieving laser-direct formability technology is the addition of one or more laser-sensitive substances to the resin matrix. These laser-direct formability functional additives are generally metal compounds that can decompose into metal particles and other ligands after high-energy laser irradiation. On the one hand, the metal particles exposed on the material surface provide catalytic activation centers for subsequent electroless plating, promoting the metal in the electroless plating solution... Ions are deposited onto the laser-irradiated area to form conductive patterns. Furthermore, the metal particles also increase the adhesion strength between the coating and the resin matrix. Cu / Zn / Sn formed after the excitation of basic copper phosphate, copper chromate black, zinc hydroxystannate, and tin oxide exhibits excellent absorption properties for lasers of different wavelengths, which is beneficial for LDS molding. When combined with functionalized multi-walled carbon nanotubes, the Zn formed by laser irradiation on the surface of the functionalized multi-walled carbon nanotubes also has excellent laser absorption properties. In addition, the multi-walled carbon nanotubes themselves have a certain degree of conductivity, thus promoting the formation of a conductive network and further facilitating the formation of conductive patterns. Examples 1-5 show that the adhesion of the metal coating on the surface of the plastic parts reaches 5B. As can be seen from Example 1 and Comparative Example 1, when the special glass fiber is replaced with ordinary glass fiber, its dielectric constant increases significantly. As can be seen from Example 1 and Comparative Example 2, when LCP resin is removed from the system, the mechanical properties of the material decrease, the dielectric constant increases, and the laser direct formability decreases slightly. This is because in the composite material, polyphenylene sulfide and liquid crystal polymer complement each other, improving both the toughness and crystallization rate of PPS and the strength and rigidity of LCP, thus exhibiting excellent comprehensive performance. As can be seen from Example 1 and Comparative Example 3, due to the grafting rate of glycidyl methacrylate of the double-grafted SEBS being 1–1.4 wt% and the grafting rate of maleic anhydride being 1–1.4 wt%, the material exhibits superior overall performance. The hydrogenated styrene-butadiene-styrene structural unit has excellent compatibility with polyphenylene sulfide resin. The epoxy groups of the grafted glycidyl methacrylate and the maleic anhydride groups of the grafted maleic anhydride can provide good interfacial compatibility between PPS resin and LCP resin, as well as compatibility and dispersibility with γ-aminopropyltriethoxysilane, functionalized multi-walled carbon nanotubes, and basic copper phosphate, thereby improving the overall performance of the composite material. As can be seen from Example 1 and Comparative Example 4, when the surface of multi-walled carbon nanotubes is not functionalized, it lacks good compatibility with the resin on the one hand, and lacks Zn, an element with high absorption rate for near-infrared lasers, on the surface of the conductive pathway of multi-walled carbon nanotubes, thus affecting the laser-forming properties of the composite material.

[0128] Although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0129] Therefore, the above description is only a preferred embodiment of this application and is not intended to limit the scope of this application; that is, all equivalent modifications made in accordance with the scope of the claims of this application shall be within the protection scope of the claims of this application.

Claims

1. A PPS / LCP composition, characterized in that, It is prepared from the following components in parts by weight: 43-64 parts of PPS resin, 5-15 parts of LCP resin 15-25 parts of special glass fiber, Laser sensitizer A: 5-10 parts Laser sensitizer B1 ~ 5 parts, 2-5 parts compatibilizer 1-3 parts coupling agent, Antioxidant 0.2~0.6 parts; Among them, laser sensitizer A is a functionalized multi-walled carbon nanotube, and laser sensitizer B is any one of basic copper phosphate, copper chromate black, zinc hydroxystannate, and tin oxide; The LCP resin is a thermotropic liquid crystal polymer; the special glass fiber has a dielectric constant of 3.5–4.0, a cross-sectional length of 26–30 μm, a width of 6.5–7.5 μm, and an aspect ratio of 4:1; the compatibilizer is double-grafted SEBS; the double-grafted SEBS is a hydrogenated styrene-butadiene-styrene copolymer double-grafted with glycidyl methacrylate and maleic anhydride; the preparation method of the functionalized multi-walled carbon nanotubes is as follows: (1) Multi-walled carbon nanotubes and nano zinc oxide were uniformly dispersed in anhydrous ethanol at a mass ratio of 100:10~20, and the intermediate product was obtained after filtration. (2) The intermediate product is mixed with acrylic acid solution, tetrabutyl titanate and ammonium persulfate aqueous solution, vacuumed and reacted at 90~100℃ in nitrogen atmosphere for 2-4h. After cooling to room temperature, the reaction product is washed, filtered and dried to obtain functionalized multi-walled carbon nanotubes.

2. The PPS / LCP composition according to claim 1, characterized in that, The number-average relative molecular mass of the PPS resin is 15,000 to 25,000.

3. The PPS / LCP composition according to claim 1, characterized in that, The coupling agent is γ-aminopropyltriethoxysilane; the antioxidant is bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

4. The PPS / LCP composition according to claim 1, characterized in that, In the acrylic acid solution, the volume ratio of acrylic acid, deionized water, and anhydrous ethanol is 1:(0.3-0.5):(0.2-0.4); the mass concentration of the ammonium persulfate aqueous solution is 4-6 wt%.

5. The PPS / LCP composition according to claim 1, characterized in that, In step (2), the mass ratio of the intermediate product, acrylic acid solution, tetrabutyl titanate, and ammonium persulfate aqueous solution is 100:(450~500):(1~3):(2~5).

6. The method for preparing the PPS / LCP composition according to any one of claims 1-5, characterized in that, Includes the following steps: (1) PPS resin, LCP resin, double-grafted SEBS and bis(2,4-dicumylphenyl) pentaerythritol diphosphite are mixed evenly to obtain the first mixture; (2) Functionalized multi-walled carbon nanotubes, basic copper phosphate, and γ-aminopropyltriethoxysilane are mixed evenly to obtain a second mixture; (3) The first mixture is added to the main feed port of the parallel twin-screw extruder, and the second mixture is added to the side of the extruder, and special glass fiber is added to the other side. The mixture is melt-extruded and granulated to obtain a PPS / LCP composition. The temperatures are as follows: Zone 1: 300–310℃; Zone 2: 300–310℃; Zone 3: 305–315℃; Zone 4: 305–315℃; Zone 5: 310–320℃; Zone 6: 310–320℃; Zone 7: 315–325℃; Zone 8: 315–325℃; Die head temperature: 310–320℃; Screw speed: 400–600 rpm.

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