CN116144161A - Polyphenylene ether composition capable of being formed by laser and preparation method thereof - Google Patents

Polyphenylene ether composition capable of being formed by laser and preparation method thereof Download PDF

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Publication number
CN116144161A
CN116144161A CN202111410125.8A CN202111410125A CN116144161A CN 116144161 A CN116144161 A CN 116144161A CN 202111410125 A CN202111410125 A CN 202111410125A CN 116144161 A CN116144161 A CN 116144161A
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metal oxide
groups
temperature
laser
hollow metal
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朱怀才
罗海威
刘羽玲
刘显勇
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Guangdong Sinoplast Advanced Material Co ltd
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Guangdong Sinoplast Advanced Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a polyphenyl ether composition capable of being formed by laser and a preparation method thereof. The polyphenyl ether composition capable of being formed by laser is prepared from the following raw materials in percentage by weight: 2-10% of hollow metal oxide, 0-2% of antioxidant and 100% of polyphenyl ether; the hollow metal oxide is obtained by coating the surface of POSS with metal oxide. The polyphenyl ether composition can be used for a laser direct molding technology, has good heat resistance and excellent mechanical property, is environment-friendly and nontoxic, and is low in price and simple in processing technology.

Description

Polyphenylene ether composition capable of being formed by laser and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to a polyphenyl ether composition for laser forming and a preparation method thereof.
Background
The three-dimensional molded interconnection device (3D-MID) is also called as a three-dimensional circuit or a three-dimensional circuit, and is characterized in that wires and patterns with electric functions are manufactured on an injection molded plastic shell, so that the functions of the electric interconnection function, the supporting component function, the supporting and protecting functions of the plastic shell and the like of a common circuit board are integrated into a whole, and a three-dimensional circuit carrier, namely the three-dimensional molded interconnection device, is formed. The three-dimensional molded interconnection device has the design advantages of being capable of selecting a shape, new in function and suitable for smaller and lighter development trends according to design requirements, and has the advantages of reducing installation levels, reducing the number of components, improving reliability, reducing the investment of the number and variety of materials, being beneficial to environmental protection treatment and the like. The 3D-MID has a considerable number of applications in the fields of automobiles, industry, computers, communication and the like, and is an important branch of the circuit board industry.
The 3D-MID mainly comprises two modes of 2ShotMID (double-mode injection molding) and Laser Direct Structure MID (LDS MID for short), and is mainly applied to LDS at present. LDS is the English abbreviation of Laser-Direct-Structuring, which means that a computer is used to control the movement of Laser according to the track of a conductive pattern, the Laser is irradiated onto a molded three-dimensional plastic device, and a circuit pattern is activated within a few seconds.
The plastics for laser direct structuring disclosed in patent CN101784607A, CN102066473A, CN102066122a and the like are added with a non-conductive organic metal compound (such as copper salt or copper chromium) with spinel structure as an LDS additive, and the organic metal compound is expensive and is unfavorable for popularization and use of the plastics for laser direct structuring.
Patent CN109694572a discloses a polyamide composition comprising polyamide and hollow metal oxide particles, a process for its preparation and its use; the hollow metal oxide particles comprise hollow microspheres and metal oxides coated on the surfaces of the hollow microspheres, wherein the metal oxides can be activated by laser to form metal cores. The polyamide composition is prepared by melt-extruding polyamide and hollow metal oxide particles by an extruder. However, when the hollow metal oxide is synthesized, high-temperature calcination is needed, and agglomeration of powder is easily caused, so that the dispersibility of the product is poor, and the quality stability of the product and the binding force of a metal coating are finally affected.
Disclosure of Invention
Based on this, the object of the present invention is to provide a polyphenylene ether composition which is inexpensive, has good mechanical properties, and can be directly molded by laser.
The specific technical scheme is as follows:
a polyphenyl ether composition capable of being formed by laser is prepared from the following raw materials in percentage by weight:
2-10% of hollow metal oxide;
0-2% of antioxidant;
polyphenylene ether was added to 100%;
the hollow metal oxide is obtained by coating the surface of POSS with metal oxide.
In some of these embodiments, the hollow metal oxide is 2.5-6% by weight.
In some of these embodiments, the hollow metal oxide is 2.5-4% by weight.
In some of these embodiments, the hollow metal oxide is 3-4% by weight.
In some of these embodiments, the hollow metal oxide is 3.5% by weight.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 35-70%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
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.
In some of these embodiments, the metal oxide is copper chrome black.
In some of these embodiments, the hollow metal oxide has a density of 1g/cm 3 -6g/cm 3 。
In some of these embodiments, the hollow metal oxide has a density of 1.2g/cm 3 -4g/cm 3 。
In some of these embodiments, the hollow metal oxide has a density of 1.5g/cm 3 -2.7g/cm 3 。
In some of these embodiments, the hollow metal oxide has a particle size of 0.1 μm to 100 μm.
In some of these embodiments, the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
In some embodiments, the hollow metal oxide is prepared from a metal salt corresponding to the metal oxide and an aminophenyl POSS by a sol-gel process or a hydrothermal process.
In some of these embodiments, the metal oxide corresponds to a mass ratio of metal salt to amine phenyl POSS of 1-5:1.
In some of these embodiments, the metal oxide corresponds to a mass ratio of metal salt to amine phenyl POSS of 3-4:1.
In some of these embodiments, the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate.
In some of these embodiments, the mass ratio of copper nitrate trihydrate to chromium nitrate nonahydrate is from 1:1.5 to 2.5.
In some of these embodiments, the method of preparing the hollow metal oxide includes the steps of:
(1) Mixing the aminophenyl POSS and the metal salt corresponding to the metal oxide, and adding water for dissolution;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after the dropwise adding is finished, continuing stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
In some of these embodiments, the ratio of the total mass of the aminophenyl POSS and the metal salt to water in step (1) is 1g:4mL-8mL.
In some of these embodiments, the heating temperature of step (2) is from 70 ℃ to 90 ℃.
In some embodiments, the stirring in step (2) is performed at a speed of 1000r/min to 1400r/min.
In some embodiments, the stirring in step (2) is performed at a speed of 1100r/min to 1300r/min.
In some embodiments, the concentration of the aqueous solution of citric acid is 0.07g/mL-0.10g/mL, and the amount of the aqueous solution of citric acid added dropwise is the same as the amount of water added in step (1).
In some of these embodiments, the sol stabilizer is ethylene glycol added in an amount of 0.1% -0.3% of the total volume of the aqueous citric acid solution and the water in step (1).
In some embodiments, the drying in the step (3) is constant temperature drying under the conditions that the vacuum degree is-0.5 Mpa to-0.7 Mpa and the temperature is 70 ℃ to 90 ℃.
In some of these embodiments, step (4) comprises: and (3) filling the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions of the pressure of 15-20 MPa and the temperature of 280-320 ℃, filtering, washing and drying the product to obtain the hollow metal oxide.
In some embodiments, the drying conditions in step (4) include: the temperature is 90-110 ℃ and the time is 6-10 hours.
In some embodiments, the antioxidant is present in an amount of 0.2 to 0.5 weight percent.
In some of these embodiments, the antioxidant consists of a hindered phenolic antioxidant and a phosphite antioxidant.
In some of these embodiments, the hindered phenolic antioxidant and the phosphite antioxidant are the same weight percent.
In some of these embodiments, the hindered phenolic antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
It is another object of the present invention to provide a method for producing the above-mentioned laser-formable polyphenylene ether composition.
The specific technical scheme is as follows:
the preparation method of the polyphenyl ether composition capable of being formed by laser comprises the following steps:
(a) Drying the polyphenyl ether, and mixing the polyphenyl ether with an antioxidant to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide in the lateral direction of the parallel double-screw extruder, and carrying out melt extrusion;
(c) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the polyphenyl ether composition capable of being formed by laser.
In some of these embodiments, the drying conditions of step (a) comprise: the temperature is 95-105 ℃ and the time is 3-5 h.
In some of these embodiments, the processing conditions of the parallel twin screw extruder include: the temperature of the first area is 240-260 ℃, the temperature of the second area is 260-275 ℃, the temperature of the third area is 270-285 ℃, the temperature of the fourth area is 270-285 ℃, the temperature of the fifth area is 270-285 ℃, the temperature of the sixth area is 270-285 ℃, the temperature of the seventh area is 270-285 ℃, the temperature of the eighth area is 270-285 ℃, the temperature of the ninth area is 260-270 ℃, the temperature of the die head is 270-285 ℃, and the residence time of the materials in the feed cylinder of the parallel double-screw extruder is controlled between 1 minute and 3 minutes.
The invention prepares a hollow metal oxide coated on the surface of POSS, and discovers that the hollow metal oxide coated on the surface of POSS can be used as an LDS additive by adding the hollow metal oxide coated on the surface of POSS in a polyphenyl ether composition, so that the polyphenyl ether composition can be used for laser direct molding and has good bonding force with a metal coating. Compared with the material directly taking metal oxide as an LDS additive, the LDS additive added by the polyphenyl ether composition provided by the invention is less, the metal coating adhesive force after laser etching is higher, the mechanical property is better, the cost is lower, when the addition amount of hollow metal oxide particles is 2.5wt%, the metal coating adhesive force can meet the requirement, and when the addition amount of hollow metal oxide particles is 3.5wt%, the metal coating adhesive force can reach the 5B level; and has the advantages of environmental protection, no toxicity, low price, simple processing technique and the like.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, 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 belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The raw materials used in the examples and comparative examples of the present invention are as follows:
polyphenylene oxide, blue star, brand LX035;
amine phenyl POSS, shanghai vast chemical industry limited;
copper nitrate trihydrate, san-foreign chemical trade company, tianjin;
chromium nitrate nonahydrate, division of kepler biotechnology, shandong;
citric acid monohydrate, kepler biotechnology limited, shandong;
ethylene glycol, tabacco Hengxin chemical technology Co., ltd;
copper chrome black, polymaleic acid 42-303B.
The following are specific examples.
The copper chromium black content in the hollow copper chromium black particles in the following examples was calculated by the following method: firstly, measuring the content of copper and chromium in the obtained hollow copper-chromium black particles, and then according to the content of copper and chromium and the molecular formula CuCr of the copper-chromium black 2 O 4 And calculating the quality of the corresponding copper-chromium black, and dividing the quality of the copper-chromium black by the quality of the obtained hollow copper-chromium black particles to obtain the content of the copper-chromium black in the hollow copper-chromium black particles.
EXAMPLE 1 preparation of hollow copper chromium Black particles
20g of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to be sufficiently dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain xerogel, and grinding the obtained xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, and after uniform stirring, the kettle is screwed upThe lid was set at 18MPa and crystallized at 300℃for 5 days. The obtained product is filtered, washed and dried in air at 100 ℃ for 8 hours to obtain the hollow copper-chromium black particles, the copper-chromium black content of which is 50 percent by weight, the particle size of which is 0.5 mu m-50 mu m and the density of which is 1.9g/cm 3 。
Preparation example 2 preparation of hollow copper chromium black particles
15g of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to make them sufficiently dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain xerogel, and grinding the obtained xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, after uniform stirring, the kettle cover is screwed, the pressure is set to 18MPa, and crystallization is carried out for 5 days at 300 ℃. The obtained product is filtered, washed and dried for 8 hours in the air at 100 ℃ to obtain the hollow copper-chromium black particles, the copper-chromium black content is 60 percent by weight, the particle size is 0.5 mu m-50 mu m, and the density is 2.2g/cm 3 。
Preparation example 3 preparation of hollow copper chromium black particles
40g of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to make them fully dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; stirring is continued until the sol is converted into gel, stirring is stopped, and the obtained wetPlacing the gel in a vacuum drying oven with vacuum degree of-0.6 Mpa, oven drying at 80deg.C to obtain xerogel, and grinding the xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, after uniform stirring, the kettle cover is screwed, the pressure is set to 18MPa, and crystallization is carried out for 5 days at 300 ℃. The obtained product is filtered, washed and dried in air at 100 ℃ for 8 hours to obtain the hollow copper-chromium black particles, wherein the content of the copper-chromium black is 35wt%, the particle size is 0.5 mu m-50 mu m, and the density is 1.6g/cm 3 。
Examples 4-8 preparation of laser-formable polyphenylene ether compositions
(a) Drying polyphenyl ether at 100 ℃ for 3-5 hours, and then placing the dried polyphenyl ether, pentaerythritol ester of an antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] and tri (2, 4-di-tert-butylphenyl) phosphite ester into a mixer for mixing for 20 minutes to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow copper chromium black particles prepared in the embodiment 2 into a sixth zone of the parallel double-screw extruder, and carrying out melt extrusion, wherein the processing technology of the parallel double-screw extruder is as follows: the temperature of the first area is 250 ℃, the temperature of the second area is 270 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 275 ℃, the temperature of the fifth area is 275 ℃, the temperature of the sixth area is 275 ℃, the temperature of the seventh area is 275 ℃, the temperature of the eighth area is 275 ℃, the temperature of the ninth area is 265 ℃, the temperature of the die head is 275 ℃, and the residence time of materials in a feed cylinder of a parallel double-screw extruder is controlled to be 1 min-3 min.
(c) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the polyphenyl ether composition capable of being formed by laser.
Wherein, the raw material components of each example are as follows:
Figure BDA0003365127010000081
Figure BDA0003365127010000091
EXAMPLE 9 preparation of laser-formable polyphenylene ether composition
This embodiment differs from embodiment 6 in that: the hollow copper chromium black particles provided in example 1 were replaced with hollow copper chromium black particles, and other raw materials and the amounts of raw materials and the preparation methods were the same as in example 6.
EXAMPLE 10 preparation of laser-formable polyphenylene ether composition
This embodiment differs from embodiment 6 in that: the hollow copper chromium black particles were replaced with the hollow copper chromium black particles provided in example 3, and other raw materials and the amounts of the raw materials and the preparation methods were the same as in example 6.
Comparative example 1 preparation of polyphenylene ether composition
The difference between this comparative example and example 6 is that: the hollow copper chromium black particles were replaced with copper chromium black powder, and other raw materials and the amounts of raw materials and the preparation method were the same as in example 6.
Comparative example 2 preparation of polyphenylene ether composition
The difference between this comparative example and example 7 is that: the hollow copper chromium black particles were replaced with copper chromium black powder, and other raw materials and the amounts of raw materials and the preparation method were the same as in example 7.
Comparative example 3 preparation of polyphenylene ether composition
The difference between this comparative example and example 5 is that: the hollow copper chrome black particles were replaced with hollow glass bead copper chrome black, and other raw materials and raw material amounts and preparation methods were the same as in example 5.
The preparation process of the hollow glass bead copper chrome black comprises the following steps:
(1) Adding 9g of hollow glass microspheres, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dispersing to form a mixed solution;
(2) Placing the mixed solution obtained in the step (1) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is completed, thus obtaining a hollow copper-chromium black precursor;
(3) Placing the hollow copper-chromium black precursor obtained in the step (2) into an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the copper-chromium black content is 60wt%, the particle size is 1-50 mu m, and the density is 2.0g/cm 3 。
Comparative example 4 preparation of polyphenylene ether composition
The difference between this comparative example and example 6 is that: the hollow copper chrome black particles were replaced with hollow glass bead copper chrome black, and other raw materials and raw material amounts and preparation methods were the same as in example 6. The preparation method of the hollow glass microsphere copper chrome black is the same as that of comparative example 3.
The polyphenylene ether compositions obtained in the examples and comparative examples were injection molded into plastic articles of a certain shape. According to conventional method, the wavelength is 900-1080nm, and the energy is 150-300mJ/cm 2 And (3) carrying out laser etching on the preset area of the plastic piece according to the set shape at the scanning speed of 0.1-1mm/s, carrying out chemical plating on the plastic piece subjected to laser etching, and forming a metal plating layer in the laser etching area of the plastic piece to obtain a plastic piece sample.
The plastic part samples prepared above were subjected to the following performance tests (the results are shown in Table 1):
tensile properties: the stretching rate is 50mm/min according to ASTM-D638;
impact properties: the thickness of the bars is 3.2mm according to ASTM-D256;
bending properties: bending rate of 10mm/min as tested according to ASTM-D790;
adhesion test (hundred test) of metal plating on plastic part surface: according to ASTM D3359 standard
Under the conditions of room temperature of 23+/-2 ℃ and relative humidity of 50+/-5%, scribing 10X 10 small grids of 1mm multiplied by 1mm on the surface of the test sample by using a sharp blade (the blade angle is 15 DEG to 30 DEG), wherein each scribing is deep and the coating bottom layer is coated; brushing the test area cleanly by using a hairbrush; firmly adhering the tested small grid by using a 3M600 adhesive tape, and forcefully wiping the adhesive tape by using an eraser to enlarge the contact area and the strength of the adhesive tape and a tested area; the end of the tape was grasped by hand and the tape was pulled off rapidly at an angle of 60 ° in the vertical direction and 2 identical tests were performed at the same position.
And (3) result judgment: and the adhesive force is qualified when the adhesive force is more than or equal to 4B.
5B, the scribing edge is smooth, and no metal coating is dropped off at the scribing edge and the crossing point;
4B-a small piece of metal-free coating is peeled off at the cross point of the scribing line, and the total peeled-off area is less than 5%;
3B-small pieces of metal-free plating layers are peeled off at the edges and the crossing points of the scribing lines, and the total peeled-off area is between 5 and 15 percent;
2B-a piece of metal-free coating is peeled off at the edge and the cross point of the scribing line, and the total peeled-off area is 15-35%;
1B-a piece of metal plating layer is peeled off at the edge and the cross point of the scribing line, and the total peeled-off area is between 35 and 65 percent;
0B-a piece of metal-free coating is peeled off at the edge and the crossing point of the scribing line, and the total peeled-off area is more than 65 percent.
TABLE 1 results of Performance test of examples 4-10 and comparative examples 1-4
Figure BDA0003365127010000111
As can be seen from the table, the polyphenyl ether composition capable of being formed by laser provided by the invention can be directly formed by laser and has good metal coating adhesion and mechanical properties.
As can be seen from comparison of examples 6-7 and comparative examples 1-2, the laser-formable polyphenyl ether composition provided by the invention has higher metal coating adhesive force and better impact property, and the metal coating adhesive force of the polyphenyl ether composition can reach the optimal effect of 5B by adding 3.5wt% of hollow copper chromium black particles; the adhesive force of the metal coating of the polyphenyl ether composition added with 3.5 weight percent of metal oxide powder can not meet the requirement, and when the addition amount of the metal oxide powder reaches 6 percent, the adhesive force of the metal coating can not meet the qualified requirement of 4B, and the impact performance of the polyphenyl ether composition can be greatly influenced; the polyphenylene oxide composition provided by the invention requires fewer hollow metal oxide particles than common metal oxide powder, and the obtained polyphenylene oxide composition has better impact performance.
As can be seen from comparison of examples 5-6 and comparative examples 3-4, the polyphenylene oxide composition provided by the invention has higher metal coating adhesive force and impact property, the adhesive force of the metal coating of the polyphenylene oxide composition can reach the qualification requirement of 4B by adding 2.5wt% of hollow copper chromium black particles, and the adhesive force of the metal coating of the polyphenylene oxide composition can reach the optimal effect of 5B by adding 3.5wt% of hollow copper chromium black particles; the adhesive force of the metal coating is only 2B, and the impact performance is poorer than that of the embodiment 5, and the adhesive force of the metal coating can reach the 4B qualification requirement only by adding 2.5 weight percent of hollow glass bead copper-chromium black, and the impact performance is much poorer than that of the embodiment 6; the method is characterized in that the powder is easy to agglomerate due to high-temperature calcination during the synthesis of the hollow metal oxide, so that the dispersion is poor, and meanwhile, the adhesion and impact performance of a metal coating of the polyphenyl ether composition are finally affected because the polyphenyl ether viscosity is large and is not beneficial to the dispersion of copper chrome black of the hollow glass beads.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The polyphenyl ether composition capable of being formed by laser is characterized by being prepared from the following raw materials in percentage by weight:
2-10% of hollow metal oxide;
0-2% of antioxidant;
polyphenylene ether was added to 100%;
the hollow metal oxide is obtained by coating the surface of POSS with metal oxide.
2. The laser-formable polyphenylene ether composition according to claim 1, wherein the hollow metal oxide is present in an amount of 2.5 to 6% by weight; and/or the number of the groups of groups,
the weight percentage of the antioxidant is 0.2-0.5%;
preferably, the hollow metal oxide is 2.5-4% by weight;
preferably, the hollow metal oxide is 3-4% by weight;
preferably, the hollow metal oxide is 3.5% by weight.
3. The laser-formable polyphenylene ether composition according to claim 1, wherein the weight percentage of the metal oxide in the hollow metal oxide is from 35 to 70%;
preferably, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%;
preferably, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
4. The laser formable polyphenylene ether composition according to claim 1, wherein 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 number of the groups of groups,
the antioxidant consists of hindered phenol antioxidants and phosphite antioxidants;
preferably, the metal oxide is copper chrome black;
preferably, the weight percentages of the hindered phenol antioxidant and the phosphite antioxidant are the same;
preferably, the hindered phenol antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
5. The laser-formable polyphenylene ether composition according to claim 1, wherein the hollow metal oxide has a density of 1g/cm 3 -6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the particle size of the hollow metal oxide is 0.1-100 mu m;
preferably, the hollow metal oxide has a density of 1.5g/cm 3 -2.7g/cm 3 ；
Preferably, the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
6. The laser formable polyphenylene ether composition according to any one of claims 1 to 5, wherein the hollow metal oxide is prepared from a metal salt corresponding to the metal oxide and an aminophenyl POSS by a sol-gel process or a hydrothermal process;
preferably, the mass ratio of the metal salt corresponding to the metal oxide to the aminophenyl POSS is 1-5:1;
preferably, the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate;
preferably, the mass ratio of the copper nitrate trihydrate to the chromium nitrate nonahydrate is 1:1.5-2.5.
7. The laser formable polyphenylene ether composition according to claim 6, wherein the method of preparing the hollow metal oxide comprises the steps of:
(1) Mixing the aminophenyl POSS and the metal salt corresponding to the metal oxide, and adding water for dissolution;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after the dropwise adding is finished, continuing stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
8. The laser-formable polyphenylene ether composition of claim 7, wherein,
the ratio of the total mass of the aminophenyl POSS and the metal salt to water in the step (1) is 1g:4mL-8mL; and/or the number of the groups of groups,
the heating temperature in the step (2) is 70-90 ℃; and/or the number of the groups of groups,
the stirring rotating speed in the step (2) is 1000r/min-1400r/min; and/or the number of the groups of groups,
the concentration of the aqueous solution of citric acid is 0.07g/mL-0.10g/mL, and the dripping amount of the aqueous solution of citric acid is the same as the water added in the step (1); and/or the number of the groups of groups,
the sol stabilizer is glycol, and the added volume of the sol stabilizer is 0.1% -0.3% of the total volume of the citric acid aqueous solution and the water in the step (1); and/or the number of the groups of groups,
the drying in the step (3) is constant temperature drying under the conditions that the vacuum degree is-0.5 Mpa to-0.7 Mpa and the temperature is 70 ℃ to 90 ℃; and/or the number of the groups of groups,
the step (4) comprises: and (3) filling the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions of the pressure of 15-20 MPa and the temperature of 280-320 ℃, filtering, washing and drying the product to obtain the hollow metal oxide.
9. A method for preparing the laser formable polyphenylene ether composition of any one of claims 1 to 8, comprising the steps of:
(a) Drying the polyphenyl ether, and mixing the polyphenyl ether with an antioxidant to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide in the lateral direction of the parallel double-screw extruder, and carrying out melt extrusion;
(c) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the polyphenyl ether composition capable of being formed by laser.
10. The method of preparing a laser-formable polyphenylene ether composition according to claim 9, wherein said drying conditions of step (a) comprise: the temperature is 95-105 ℃ and the time is 3-5 h; and/or the number of the groups of groups,
the processing conditions of the parallel double-screw extruder comprise: the temperature of the first area is 240-260 ℃, the temperature of the second area is 260-275 ℃, the temperature of the third area is 270-285 ℃, the temperature of the fourth area is 270-285 ℃, the temperature of the fifth area is 270-285 ℃, the temperature of the sixth area is 270-285 ℃, the temperature of the seventh area is 270-285 ℃, the temperature of the eighth area is 270-285 ℃, the temperature of the ninth area is 260-270 ℃, the temperature of the die head is 270-285 ℃, and the residence time of the materials in the feed cylinder of the parallel double-screw extruder is controlled between 1 minute and 3 minutes.
CN202111410125.8A 2021-11-19 2021-11-19 Polyphenylene ether composition capable of being formed by laser and preparation method thereof Pending CN116144161A (en)

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