Laser-formable polyphenylene ether composition and method for preparing same

Abstract

The present invention discloses a laser-formable polyphenylene ether composition and a preparation method thereof. The laser-formable polyphenylene ether composition is prepared from raw materials in the following weight percentages: 2-10% of hollow metal oxide, 0-2% of antioxidant, and polyphenylene ether is added up to 100%; the hollow metal oxide is obtained by coating a metal oxide on the surface of POSS. The polyphenylene ether composition of the present invention can be used in laser direct forming technology, has good heat resistance and excellent mechanical properties, and is environmentally friendly, non-toxic, inexpensive, and has a simple processing process.

Description

Technical Field

[0001] The present invention relates to the field of materials, and particularly to a polyphenylene ether composition for laser forming and a preparation method thereof. Background Art

[0002] Three-dimensional molded interconnect device (3D-MID), also known as three-dimensional circuit or stereoscopic circuit, refers to a plastic housing formed by injection molding, on which electrical function wires and patterns are fabricated, so as to integrate the electrical interconnection function, the function of supporting components, and the functions of supporting and protecting the plastic housing of a common circuit board, forming a three-dimensional circuit carrier, namely, a three-dimensional molded interconnect device. The three-dimensional molded interconnect device has design advantages such as being able to select shapes according to design requirements, having new functions, and being suitable for the development trend of being smaller and lighter. It also has economic and environmental advantages such as reducing the installation level, reducing the number of components, improving reliability, reducing the input of the quantity and variety of materials, and being conducive to environmental protection treatment. 3D-MID has been applied in a considerable number in fields such as automobiles, industry, computers, and communications, and will surely become an important branch of the circuit board industry in the future.

[0003] 3D-MID mainly includes two methods: 2ShotMID (two-shot injection molding) and Laser Direct Structure MID (abbreviated as LDS MID, laser laser forming). Currently, LDS is mainly applied. LDS is the English abbreviation of Laser-Direct-Structuring, which means that a computer controls the movement of a laser according to the trajectory of a conductive pattern, projects the laser onto a three-dimensional plastic device formed by molding, and activates a circuit pattern within a few seconds.

[0004] Patents such as CN101784607A, CN102066473A, and CN102066122A disclose that a non-conductive organometallic complex with a spinel structure (such as copper salt or copper chromate) is added to the plastic for laser direct forming as an LDS additive. This kind of organometallic complex is expensive and not conducive to the popularization and use of plastics for laser direct forming.

[0005] Patent CN109694572A discloses a polyamide composition, its preparation method and uses. The polyamide composition includes polyamide and hollow metal oxide particles. The hollow metal oxide particles include hollow microspheres and metal oxides coated on the surfaces of the hollow microspheres, and the metal oxides are metal oxides that can be laser-activated to form metal nuclei. The polyamide composition is prepared by the method of melt-extruding polyamide and hollow metal oxide particles with an extruder. However, when synthesizing the hollow metal oxide, high-temperature calcination is required, which easily causes the powder to agglomerate, resulting in poor dispersibility of the product and ultimately affecting the quality stability of the product and the bonding strength of the metal coating. Summary of the Invention

[0006] Based on this, the purpose of the present invention is to provide a polyphenylene ether composition that is inexpensive, has good mechanical properties, and can be directly laser-molded.

[0007] The specific technical solutions are as follows:

[0008] A laser-moldable polyphenylene ether composition is prepared from the following raw materials by weight percentage:

[0009] Hollow metal oxide 2-10%;

[0010] Antioxidant 0-2%;

[0011] Polyphenylene ether added to 100%;

[0012] The hollow metal oxide is obtained by coating metal oxides on the surface of POSS.

[0013] In some embodiments, the weight percentage of the hollow metal oxide is 2.5-6%.

[0014] In some embodiments, the weight percentage of the hollow metal oxide is 2.5-4%.

[0015] In some embodiments, the weight percentage of the hollow metal oxide is 3-4%.

[0016] In some embodiments, the weight percentage of the hollow metal oxide is 3.5%.

[0017] In some embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 35-70%.

[0018] In some embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%.

[0019] In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.

[0020] In some of these embodiments, the metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium, and iron.

[0021] In some of these embodiments, the metal oxide is copper chromite black.

[0022] In some of these embodiments, the density of the hollow metal oxide is 1 g / cm 3 -6 g / cm 3 。

[0023] In some of these embodiments, the density of the hollow metal oxide is 1.2 g / cm 3 -4 g / cm 3 。

[0024] In some of these embodiments, the density of the hollow metal oxide is 1.5 g / cm 3 -2.7 g / cm 3 。

[0025] In some of these embodiments, the particle size of the hollow metal oxide is 0.1 μm - 100 μm.

[0026] In some of these embodiments, the particle size of the hollow metal oxide is 0.5 μm - 50 μm.

[0027] In some of these embodiments, the hollow metal oxide is prepared by a sol-gel method or a hydrothermal method from a metal salt corresponding to the metal oxide and amine phenyl POSS.

[0028] In some of these embodiments, the mass ratio of the metal salt corresponding to the metal oxide and amine phenyl POSS is 1-5:1.

[0029] In some of these embodiments, the mass ratio of the metal salt corresponding to the metal oxide and amine phenyl POSS is 3-4:1.

[0030] In some of these embodiments, the metal salt corresponding to the metal oxide is copper nitrate trihydrate and chromium nitrate nonahydrate.

[0031] In some of these embodiments, the mass ratio of copper nitrate trihydrate and chromium nitrate nonahydrate is 1:1.5-2.5.

[0032] In some of these embodiments, the method for preparing the hollow metal oxide comprises the following steps:

[0033] (1) Mix the amine phenyl POSS and the metal salt corresponding to the metal oxide, and dissolve them in water;

[0034] (2) Heat the mixed solution prepared in step (1), and dropwise add an aqueous citric acid solution under stirring. After the addition is completed, add a sol stabilizer, and continue stirring until the sol is converted into a gel, then stop stirring;

[0035] (3) Dry the wet gel prepared in step (2), and then grind it into powder to obtain a precursor powder;

[0036] (4) Crystallize the precursor powder with water to obtain the hollow metal oxide.

[0037] In some embodiments, the ratio of the total mass of the amine phenyl POSS and the metal salt to water in step (1) is 1 g: 4 mL - 8 mL.

[0038] In some embodiments, the heating temperature in step (2) is 70 °C - 90 °C.

[0039] In some embodiments, the stirring speed in step (2) is 1000 r / min - 1400 r / min.

[0040] In some embodiments, the stirring speed in step (2) is 1100 r / min - 1300 r / min.

[0041] In some embodiments, the concentration of the aqueous citric acid solution is 0.07 g / mL - 0.10 g / mL, and the dropping amount of the aqueous citric acid solution is the same as the amount of water added in step (1).

[0042] In some embodiments, the sol stabilizer is ethylene glycol, and its added volume is 0.1% - 0.3% of the total volume of the aqueous citric acid solution and the water in step (1).

[0043] In some embodiments, the drying in step (3) is carried out under a constant temperature at a vacuum degree of -0.5 Mpa to -0.7 Mpa and a temperature of 70 °C - 90 °C.

[0044] In some embodiments, step (4) includes: loading the precursor powder into a reaction kettle, adding water, stirring evenly, then tightening the kettle lid, and crystallizing for 2 days - 7 days under the conditions of a pressure of 15 MPa - 20 MPa and a temperature of 280 °C - 320 °C. Filter, wash, and dry the product to obtain the hollow metal oxide.

[0045] In some embodiments, the drying conditions in step (4) include: a temperature of 90 °C - 110 °C and a time of 6 - 10 hours.

[0046] In some of these embodiments, the weight percentage of the antioxidant is 0.2 - 0.5%.

[0047] In some of these embodiments, the antioxidant consists of a hindered phenol antioxidant and a phosphite antioxidant.

[0048] In some of these embodiments, the weight percentages of the hindered phenol antioxidant and the phosphite antioxidant are the same.

[0049] In some of these embodiments, the hindered phenol antioxidant is pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite.

[0050] Another object of the present invention is to provide a method for preparing the above-mentioned laser-formable polyphenylene ether composition.

[0051] The specific technical solution is as follows:

[0052] A method for preparing the above-mentioned laser-formable polyphenylene ether composition, comprising the following steps:

[0053] (a) After drying the polyphenylene ether, it is mixed with an antioxidant to obtain a premix;

[0054] (b) The premix obtained in step (a) is added into a parallel twin-screw extruder through a main feeder, and the hollow metal oxide is added laterally to the parallel twin-screw extruder, and melt extrusion is carried out;

[0055] (c) The extruded material obtained in step (b) is subjected to strand drawing, cooling, and pelletizing to obtain the laser-formable polyphenylene ether composition.

[0056] In some of these embodiments, the drying conditions in step (a) include: the temperature is 95°C - 105°C, and the time is 3h - 5h.

[0057] In some of these embodiments, the processing process conditions of the parallel twin-screw extruder include: the temperature of the first zone is 240°C - 260°C, the temperature of the second zone is 260°C - 275°C, the temperature of the third zone is 270°C - 285°C, the temperature of the fourth zone is 270°C - 285°C, the temperature of the fifth zone is 270°C - 285°C, the temperature of the sixth zone is 270°C - 285°C, the temperature of the seventh zone is 270°C - 285°C, the temperature of the eighth zone is 270°C - 285°C, the temperature of the ninth zone is 260°C - 270°C, the die head temperature is 270°C - 285°C, and the residence time of the material in the barrel of the parallel twin-screw extruder is controlled within 1 minute - 3 minutes.

[0058] The present invention prepares a hollow metal oxide obtained by coating a metal oxide on the surface of POSS, and it is found that by adding the hollow metal oxide obtained by coating a metal oxide on the surface of POSS as an LDS additive to a polyphenylene ether composition, the resulting polyphenylene ether composition can be used for laser direct molding and has good adhesion to a metal coating. Compared with materials directly using metal oxides as LDS additives, the polyphenylene ether composition provided by the present invention adds less LDS additive, has higher adhesion of the metal coating after laser etching, better mechanical properties, lower cost. When the addition amount of the hollow metal oxide particles is 2.5 wt%, the adhesion of the metal coating can meet the requirements. When the addition amount of the hollow metal oxide particles is 3.5 wt%, the adhesion of the metal coating can reach level 5B; and it has the advantages of being environmentally friendly, non-toxic, inexpensive, and having a simple processing process. Detailed Embodiments

[0059] The technical solutions of the present invention will be further described below through specific examples. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0060] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention are only for the purpose of describing specific embodiments and are not used to limit the present invention.

[0061] The terms "comprising" and "having" and any variations thereof in the present invention are intended to cover non-exclusive inclusion. For example, a process, method, device, product or equipment that includes a series of steps is not limited to the listed steps or modules, but optionally further includes steps not listed, or optionally further includes other steps inherent to these processes, methods, products or equipment.

[0062] "Plurality" mentioned in the present invention refers to two or more. "And / or" describes the association relationship of associated objects and indicates that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. The character " / " generally represents an "or" relationship between the associated objects before and after.

[0063] The raw materials used in the examples and comparative examples of the present invention are as follows:

[0064] Polyphenylene ether, Bluestar, grade is LX035;

[0065] Aminophenyl POSS, Shanghai Hansi Chemical Co., Ltd.;

[0066] Copper nitrate trihydrate, Tianjin Sheng Sanyang Chemical Trading Co., Ltd.;

[0067] Chromium(III) nitrate nonahydrate, Shandong Kepler Biotechnology Co., Ltd.;

[0068] Citric acid monohydrate, Shandong Kepler Biotechnology Co., Ltd.;

[0069] Ethylene glycol, Yantai Hengxin Chemical Technology Co., Ltd.;

[0070] Copper chromite black, Domaid 42 - 303B.

[0071] The following are specific examples.

[0072] In the following examples, the content of copper chromite black in the hollow copper chromite black particles was calculated by the following method: First, the contents of copper and chromium in the obtained hollow copper chromite black particles were measured, and then the mass of the corresponding copper chromite black was calculated according to the contents of copper and chromium and the molecular formula CuCr₂O₄ of copper chromite black. Then, the mass of copper chromite black was divided by the mass of the obtained hollow copper chromite black particles to obtain the content of copper chromite black in the hollow copper chromite black particles.

[0073] Example 1 Preparation of Hollow Copper Chromite Black Particles

[0074] Mix 20 g of amine - phenyl POSS, 20 g of copper nitrate trihydrate, and 40 g of chromium(III) nitrate nonahydrate, add 500 ml of distilled water to dissolve them fully, and transfer them to a flask; weigh 45 g of citric acid monohydrate and prepare a 500 - mL aqueous citric acid solution; place the flask in a constant - temperature water bath, set the stirring device, the water - bath temperature is 80 °C, and under strong stirring (rotation speed is 1200 r / min), slowly drip the aqueous citric acid solution into the flask through a dropping funnel. After the dropping is completed, add 2 ml of ethylene glycol to stabilize the sol; continue stirring until the sol is converted into a gel, then stop stirring. Place the obtained wet gel in a vacuum drying oven with a vacuum degree of - 0.6 Mpa and dry it at 80 °C to obtain a dry gel. Then grind the obtained dry gel into powder to obtain a precursor powder; then put the precursor powder into a stainless - steel autoclave with a polytetrafluoroethylene liner, add deionized water, stir evenly, tighten the autoclave lid, set the pressure to 18 MPa, and crystallize at 300 °C for 5 days. The obtained product was filtered, washed, and then dried in air at 100 °C for 8 hours to obtain hollow copper chromite black particles, with a copper chromite black content of 50 wt%, a particle size of 0.5 μm - 50 μm, and a density of 1.9 g / cm 3 .

[0075] Preparation Example 2 Preparation of Hollow Copper Chromite Black Particles

[0076] Mix 15 g of amine-phenyl POSS, 20 g of copper nitrate trihydrate, and 40 g of chromium nitrate nonahydrate, add 500 ml of distilled water to dissolve them fully, and transfer the solution to a flask; weigh 45 g of citric acid monohydrate and prepare a 500 mL aqueous solution of citric acid; place the flask in a constant-temperature water bath, set up a stirring device, with the water bath temperature at 80 °C, and slowly drip the aqueous solution of citric acid into the flask through a dropping funnel under strong stirring (rotation speed of 1200 r / min). After the dripping is completed, add 2 ml of ethylene glycol to stabilize the sol; continue stirring until the sol is converted into a gel, then stop stirring. Place the obtained wet gel in a vacuum drying oven with a vacuum degree of -0.6 Mpa and dry it at a constant temperature of 80 °C to obtain a dry gel. Then grind the obtained dry gel into powder to prepare a precursor powder; then put the precursor powder into a stainless-steel autoclave with a polytetrafluoroethylene liner, add deionized water, stir evenly, tighten the autoclave lid, set the pressure to 18 MPa, and crystallize at 300 °C for 5 days. The obtained product is filtered, washed, and then dried in air at 100 °C for 8 hours to obtain hollow copper chromite black particles with a copper chromite black content of 60 wt%, a particle size of 0.5 μm - 50 μm, and a density of 2.2 g / cm 3 。

[0077] Preparation Example 3 Preparation of Hollow Copper Chromite Black Particles

[0078] Mix 40 g of amine-phenyl POSS, 20 g of copper nitrate trihydrate, and 40 g of chromium nitrate nonahydrate, add 500 ml of distilled water to dissolve them fully, and transfer the solution to a flask; weigh 45 g of citric acid monohydrate and prepare a 500 mL aqueous solution of citric acid; place the flask in a constant-temperature water bath, set up a stirring device, with the water bath temperature at 80 °C, and slowly drip the aqueous solution of citric acid into the flask through a dropping funnel under strong stirring (rotation speed of 1200 r / min). After the dripping is completed, add 2 ml of ethylene glycol to stabilize the sol; continue stirring until the sol is converted into a gel, then stop stirring. Place the obtained wet gel in a vacuum drying oven with a vacuum degree of -0.6 Mpa and dry it at a constant temperature of 80 °C to obtain a dry gel. Then grind the obtained dry gel into powder to prepare a precursor powder; then put the precursor powder into a stainless-steel autoclave with a polytetrafluoroethylene liner, add deionized water, stir evenly, tighten the autoclave lid, set the pressure to 18 MPa, and crystallize at 300 °C for 5 days. The obtained product is filtered, washed, and then dried in air at 100 °C for 8 hours to obtain hollow copper chromite black particles with a copper chromite black content of 35 wt%, a particle size of 0.5 μm - 50 μm, and a density of 1.6 g / cm 3 。

[0079] Preparation of Laser-Sinterable Polyphenylene Ether Compositions in Examples 4 - 8

[0080] (a) Dry the polyphenylene ether at 100 °C for 3 - 5 h, and then place the dried polyphenylene ether, pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as antioxidant, and tris(2,4-di-tert-butylphenyl) phosphite in a mixer and mix for 20 minutes to obtain a premix;

[0081] (b) Add the premix obtained in step (a) to a parallel twin-screw extruder through a main feeder, and add the hollow copper chromite black particles prepared in Example 2 in the sixth zone of the parallel twin-screw extruder, and melt and extrude. The processing process of the parallel twin-screw extruder is as follows: the temperature of the first zone is 250 °C, the temperature of the second zone is 270 °C, the temperature of the third zone is 275 °C, the temperature of the fourth zone is 275 °C, the temperature of the fifth zone is 275 °C, the temperature of the sixth zone is 275 °C, the temperature of the seventh zone is 275 °C, the temperature of the eighth zone is 275 °C, the temperature of the ninth zone is 265 °C, and the die temperature is 275 °C. The residence time of the material in the barrel of the parallel twin-screw extruder is controlled within 1 minute - 3 minutes.

[0082] (c) Subject the extruded material obtained in step (b) to strand pelletizing, cooling, and cutting to obtain the laser-formable polyphenylene ether composition.

[0083] Among them, the dosages of the raw material components in each example are as follows:

[0084]

[0085]

[0086] Preparation of the laser-formable polyphenylene ether composition of Example 9

[0087] The difference between this example and Example 6 is that: the hollow copper chromite black particles are replaced with the hollow copper chromite black particles provided in Example 1, and other raw materials, raw material dosages, and preparation methods are the same as those in Example 6.

[0088] Preparation of the laser-formable polyphenylene ether composition of Example 10

[0089] The difference between this example and Example 6 is that: the hollow copper chromite black particles are replaced with the hollow copper chromite black particles provided in Example 3, and other raw materials, raw material dosages, and preparation methods are the same as those in Example 6.

[0090] Preparation of the polyphenylene ether composition of Comparative Example 1

[0091] The difference between this comparative example and Example 6 is that: the hollow copper chromite black particles are replaced with copper chromite black powder, and other raw materials, raw material dosages, and preparation methods are the same as those in Example 6.

[0092] Preparation of the polyphenylene ether composition of Comparative Example 2

[0093] The difference between this comparative example and Example 7 is that the hollow copper chromite black particles are replaced with copper chromite black powder, and other raw materials, the amounts of raw materials, and the preparation method are the same as those in Example 7.

[0094] Preparation of Polyphenylene Oxide Composition in Comparative Example 3

[0095] The difference between this comparative example and Example 5 is that the hollow copper chromite black particles are replaced with hollow glass bead copper chromite black, and other raw materials, the amounts of raw materials, and the preparation method are the same as those in Example 5.

[0096] The preparation process of the hollow glass bead copper chromite black is as follows:

[0097] (1) Add 9 g of hollow glass beads, 14 g of copper nitrate trihydrate, and 50 g of chromium nitrate nonahydrate to 500 mL of distilled water, disperse evenly to form a mixed solution;

[0098] (2) Place the mixed solution obtained in step (1) on a thermostatic magnetic stirrer, stir and heat to 60 °C, then dropwise add urea, adjust the pH of the mixed solution to 6 - 7 under stirring conditions, and continue stirring and heating until the water evaporates completely to obtain a hollow copper chromite black precursor;

[0099] (3) Place the hollow copper chromite black precursor obtained in step (2) in an electric furnace, calcine at 550 °C for 2 h to obtain hollow copper chromite black particles, with a copper chromite black content of 60 wt%, a particle size of 1 - 50 μm, and a density of 2.0 g / cm 3 .

[0100] Preparation of Polyphenylene Oxide Composition in Comparative Example 4

[0101] The difference between this comparative example and Example 6 is that the hollow copper chromite black particles are replaced with hollow glass bead copper chromite black, and other raw materials, the amounts of raw materials, and the preparation method are the same as those in Example 6. Among them, the preparation method of the hollow glass bead copper chromite black is the same as that in Comparative Example 3.

[0102] Inject the polyphenylene oxide compositions obtained in the above examples and comparative examples into plastic parts of a certain shape. According to the conventional method, use a laser with a wavelength of 900 - 1080 nm and an energy of 150 - 300 mJ / cm 2 to laser-etch the predetermined area of the above plastic parts in accordance with the set shape at a scanning rate of 0.1 - 1 mm / s. The laser-etched plastic parts are chemically plated to form a metal coating in the laser-etched area of the plastic parts to obtain plastic part specimens.

[0103] Perform the following performance tests on the above-prepared plastic part specimens (the results are shown in Table 1):

[0104] Tensile properties: Test according to ASTM-D638 standard, with a tensile rate of 50 mm / min;

[0105] Impact performance: tested according to ASTM-D256 standard, the specimen thickness is 3.2mm;

[0106] Bending performance: tested according to ASTM-D790 standard, bending rate 10mm / min;

[0107] Adhesion test of metal coating on plastic parts (100-grid test): Tested according to ASTM D3359 standard

[0108] At room temperature of 23±2℃ and relative humidity of 50±5%, use a sharp blade (blade angle of 15°-30°) to draw 10×10 1mm×1mm small grids on the surface of the test sample, and each line should be as deep as the bottom layer of the coating; use a brush to clean the test area; use 3M600 tape to firmly stick to the small grid to be tested, and use an eraser to wipe the tape vigorously to increase the contact area and strength between the tape and the tested area; grab one end of the tape with your hand, and quickly tear off the tape at an angle of 60° in the vertical direction, and perform the same test twice at the same position.

[0109] Result determination: Adhesion ≥ 4B is qualified.

[0110] 5B - The edges of the lines are smooth, and there is no metal coating falling off at the edges and intersections of the lines;

[0111] 4B - There are small pieces of metal coating falling off at the intersection of the scribe lines, and the total area of ​​the falling off is less than 5%;

[0112] 3B - There are small pieces of metal coating falling off at the edges and intersections of the scribe lines, and the total area of ​​the falling off is between 5% and 15%;

[0113] 2B - There are patches of metal coating falling off at the edges and intersections of the scribe lines, and the total area of ​​the falling off is between 15% and 35%;

[0114] 1B - There are pieces of metal coating falling off at the edges and intersections of the scribe lines, and the total area of ​​the falling off is between 35% and 65%;

[0115] 0B - There are patches of metal-free coating falling off at the edges and intersections of the scribe lines, and the total area of ​​the falling off is greater than 65%.

[0116] Table 1 Performance test results of Examples 4-10 and Comparative Examples 1-4

[0117]

[0118] It can be seen from the above table that the laser formable polyphenylene ether composition provided by the present invention can be directly laser formed and has good metal coating adhesion and mechanical properties.

[0119] Comparing Examples 6 - 7 with Comparative Examples 1 - 2, it can be seen that the laser - formable polyphenylene ether composition provided by the present invention has higher metal plating adhesion and better impact properties. Adding 3.5 wt% of hollow copper chromite black particles can achieve the optimal effect of 5B for the metal plating adhesion of the polyphenylene ether composition; while for the polyphenylene ether composition added with 3.5 wt% of metal oxide powder, the metal plating adhesion fails to meet the requirements. When the addition amount of metal oxide powder reaches 6%, the metal plating adhesion still cannot reach the qualified requirement of 4B, and its impact properties will be greatly affected; the hollow metal oxide particles required for the polyphenylene ether composition provided by the present invention are less than ordinary metal oxide powders, and the impact properties of the obtained polyphenylene ether composition are also better.

[0120] Comparing Examples 5 - 6 with Comparative Examples 3 - 4, it can be seen that the polyphenylene ether composition provided by the present invention has higher metal plating adhesion and impact properties. Adding 2.5 wt% of hollow copper chromite black particles can make the metal plating adhesion of the polyphenylene ether composition meet the qualified requirement of 4B, and adding 3.5 wt% of hollow copper chromite black particles can achieve the optimal effect of 5B for the metal plating adhesion of the polyphenylene ether composition; while adding 2.5 wt% of hollow glass bead copper chromite black, the metal plating adhesion is only 2B, and its impact properties are also worse than those of Example 5. Adding 3.5 wt% of hollow glass bead copper chromite black can make its metal plating adhesion reach the qualified requirement of 4B, and at the same time its impact properties are much worse than those of Example 6; this is because high - temperature calcination is required during the synthesis of hollow metal oxides, which easily causes powder agglomeration, resulting in poor dispersion. At the same time, due to the high viscosity of polyphenylene ether, it is not conducive to the dispersion of hollow glass bead copper chromite black, ultimately affecting the metal plating adhesion and impact properties of the polyphenylene ether composition.

[0121] The technical features of the above - described embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above - described embodiments are described. However, as long as the combinations of these technical features do not conflict, they should be considered as the scope recorded in this specification.

[0122] The above - described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be subject to the appended claims.

Claims

1. A laser - formable polyphenylene ether composition, characterized in that, It is prepared from the following raw materials by weight percentage: Hollow metal oxide 2 - 10%; Antioxidant 0 - 2%; Polyphenylene ether added to 100%; The hollow metal oxide is obtained by coating a metal oxide on the surface of POSS; the weight percentage of the metal oxide in the hollow metal oxide is 35 - 70%; The hollow metal oxide is prepared by a sol - gel method from a metal salt corresponding to the metal oxide and amino - phenyl POSS; The preparation method of the hollow metal oxide comprises the following steps: (1) Mix the amino - phenyl POSS and the metal salt corresponding to the metal oxide, and dissolve in water; (2) Heat the mixed solution obtained in step (1), and drop - wise add an aqueous citric acid solution under stirring. After the dropping is completed, add a sol stabilizer, and continue stirring until the sol is converted into a gel and then stop stirring; (3) Dry the wet gel obtained in step (2), and then grind it into powder to obtain a precursor powder; (4) Crystallize the precursor powder with water to obtain the hollow metal oxide.

2. The laser - formable polyphenylene ether composition according to claim 1, characterized in that, The weight percentage of the hollow metal oxide is 2.5 - 6%; and / or, The weight percentage of the antioxidant is 0.2 - 0.5%.

3. The laser - formable polyphenylene ether composition according to claim 2, characterized in that, The weight percentage of the hollow metal oxide is 2.5 - 4%.

4. The laser - formable polyphenylene ether composition according to claim 3, characterized in that, The weight percentage of the hollow metal oxide is 3 - 4%.

5. The laser - formable polyphenylene ether composition according to claim 4, characterized in that, The weight percentage of the hollow metal oxide is 3.5%.

6. The laser - formable polyphenylene ether composition according to claim 1, characterized in that, The weight percentage of the metal oxide in the hollow metal oxide is 45 - 65%.

7. The laser - formable polyphenylene ether composition according to claim 6, characterized in that, The weight percentage of the metal oxide in the hollow metal oxide is 50 - 60%.

8. The laser - formable polyphenylene ether composition according to claim 1, characterized in that, The metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium, and iron; and / or, The antioxidant is composed of a hindered phenol antioxidant and a phosphite antioxidant.

9. The laser - formable polyphenylene ether composition according to claim 8, characterized in that, The metal oxide is copper chromite black.

10. The laser - formable polyphenylene ether composition according to claim 8, characterized in that, The weight percentages of the hindered phenol antioxidant and the phosphite antioxidant are the same.

11. The laser - formable polyphenylene ether composition according to claim 8, characterized in that, The hindered phenol antioxidant is pentaerythritol tetra[β - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate], and the phosphite antioxidant is tris(2,4 - di - tert - butylphenyl) phosphite.

12. The laser - formable polyphenylene ether composition according to claim 1, characterized in that, The density of the hollow metal oxide is 1 g / cm 3 -6g / cm 3 and / or, The particle size of the hollow metal oxide is 0.1μm - 100μm.

13. The laser-moldable polyphenylene ether composition according to claim 12, wherein, The density of the hollow metal oxide is 1.5 g / cm 3 - 2.7 g / cm 3 .

14. The laser-moldable polyphenylene ether composition according to claim 12, wherein, The particle size of the hollow metal oxide is 0.5μm - 50μm.

15. The laser-moldable polyphenylene ether composition according to any one of claims 1-14, wherein, The mass ratio of the metal salt corresponding to the metal oxide and amino - phenyl POSS is 1 - 5:

1.

16. The laser-moldable polyphenylene ether composition according to any one of claims 1-14, wherein, The metal salt corresponding to the metal oxide is copper nitrate trihydrate and chromium nitrate nonahydrate.

17. The laser-moldable polyphenylene ether composition according to claim 16, wherein, The mass ratio of copper nitrate trihydrate and chromium nitrate nonahydrate is 1:1.5 - 2.

5.

18. The laser-moldable polyphenylene ether composition according to any one of claims 1-14, wherein, In step (1), the ratio of the total mass of the amino - phenyl POSS and the metal salt to water is 1g:4mL - 8mL; and / or, The heating temperature in step (2) is 70°C - 90°C; and / or, The stirring speed in step (2) is 1000r / min - 1400r / min; and / or, The concentration of the citric acid aqueous solution is 0.07 g / mL - 0.10 g / mL, and the dropping amount of the citric acid aqueous solution is the same as the amount of water added in step (1); and / or, The sol stabilizer is ethylene glycol, and its added volume is 0.1% - 0.3% of the total volume of the citric acid aqueous solution and the water in step (1); and / or, Step (4) includes: loading the precursor powder into a reaction kettle, adding water, stirring evenly, tightening the kettle lid, crystallizing for 2 days - 7 days under the conditions of a pressure of 15 MPa - 20 MPa and a temperature of 280 °C - 320 °C, filtering, washing, and drying the product to obtain the hollow metal oxide.

19. A method for preparing the laser-moldable polyphenylene ether composition according to any one of claims 1-18, wherein, It includes the following steps: (a) Mixing the dried polyphenylene ether with an antioxidant to obtain a premixed material; (b) Adding the premixed material obtained in step (a) into a parallel twin-screw extruder through a main feeder, and laterally adding the hollow metal oxide into the parallel twin-screw extruder, and melt-extruding; (c) Subjecting the extruded material obtained in step (b) to strand drawing, cooling, and pelletizing to obtain the laser-formable polyphenylene ether composition.

20. The method for preparing the laser-moldable polyphenylene ether composition according to claim 19, wherein, The drying conditions in step (a) include: a temperature of 95 °C - 105 °C and a time of 3 h - 5 h; and / or, The processing process conditions of the parallel twin-screw extruder include: the temperature of zone 1 is 240 °C - 260 °C, the temperature of zone 2 is 260 °C - 275 °C, the temperature of zone 3 is 270 °C - 285 °C, the temperature of zone 4 is 270 °C - 285 °C, the temperature of zone 5 is 270 °C - 285 °C, the temperature of zone 6 is 270 °C - 285 °C, the temperature of zone 7 is 270 °C - 285 °C, the temperature of zone 8 is 270 °C - 285 °C, the temperature of zone 9 is 260 °C - 270 °C, the die head temperature is 270 °C - 285 °C, and the residence time of the material in the barrel of the parallel twin-screw extruder is controlled within 1 minute - 3 minutes.

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