CN109486165B - Polyphenyl ether/polystyrene composition and preparation method and application thereof - Google Patents
Polyphenyl ether/polystyrene composition and preparation method and application thereof Download PDFInfo
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- CN109486165B CN109486165B CN201811626107.1A CN201811626107A CN109486165B CN 109486165 B CN109486165 B CN 109486165B CN 201811626107 A CN201811626107 A CN 201811626107A CN 109486165 B CN109486165 B CN 109486165B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Abstract
The invention provides a polyphenyl ether/polystyrene composition, a preparation method and application thereof. The polyphenylene ether/polystyrene composition comprises polyphenylene ether, polystyrene and hollow metal oxide particles; the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores. The polyphenyl ether/polystyrene composition is prepared by a method of melt extruding polyphenyl ether, polystyrene and hollow metal oxide particles by an extruder. Compared with a material directly taking metal oxide as an LDS additive, the polyphenylene oxide/polystyrene composition provided by the invention has the advantages that less LDS additive is added, the adhesion of a metal coating after laser etching is higher, the mechanical property is better, the cost is lower, and the polyphenylene oxide/polystyrene composition can be used as a material for preparing a three-dimensional molding interconnection device.
Description
Technical Field
The invention belongs to the technical field of laser direct forming materials, and relates to a polyphenyl ether/polystyrene composition, and a preparation method and application thereof.
Background
The three-dimensional molding interconnection device (3D-MID), also called a three-dimensional circuit or a three-dimensional circuit, is a three-dimensional circuit carrier formed by integrating the electrical interconnection function, the function of supporting components, the functions of supporting and protecting the plastic shell and the like of a common circuit board into a whole by manufacturing wires and patterns with electrical functions on the plastic shell which is formed by injection molding. The three-dimensional molding interconnection device has the design advantages that the shape can be selected according to the design requirement, the function is new, and the three-dimensional molding interconnection device is suitable for smaller and lighter development trends; the method also has the advantages of reducing installation levels, reducing the number of components, improving reliability, reducing the investment of material quantity and variety, being beneficial to economic environment aspects such as environment-friendly treatment and the like. 3D-MID has already had a considerable number of applications in fields such as car, industry, computer, communication at present, will certainly become an important branch of circuit board trade in the future.
The forming process of the 3D-MID mainly comprises two types, namely 2Shot MID (two-mold injection molding) and Laser Direct Structure (Laser Direct Structure), and currently, the LDS is mainly used. The LDS is a method in which a computer controls the movement of a laser according to the trace of a conductive pattern, the laser is projected onto a three-dimensional plastic device molded by a special material, and a circuit pattern is activated within a few seconds.
The plastics for laser direct structuring disclosed in CN 101784607A, CN 102066473a and CN 102066122A are both added with a non-conductive organic metal compound (such as copper salt or copper chromium compound) with a spinel structure as an LDS additive, and the organic metal compound is expensive and has a large amount of addition, which is not favorable for popularization and use in laser direct structuring plastics.
CN 101654564A discloses a plastic composition and a surface selective metallization process thereof, the method adopts the steps that a photocatalyst is added into plastic, and the plastic composition containing the photocatalyst exposes part of the photocatalyst in the plastic composition under the condition of laser irradiation; then, putting the plastic composition subjected to laser etching into an aqueous solution containing metal ion salts and a cavity sacrificial agent, and under the condition of light source irradiation capable of exciting the photocatalyst, reducing the metal ions in the solution by the photocatalyst exposed on the surface of the plastic composition to obtain nano-scale metal particles; and finally, carrying out metal chemical plating. However, the process needs to use a special photocatalyst and also needs to be matched with a hole sacrificial agent to improve the photocatalytic efficiency, and the process is complex; the adopted photocatalyst has large addition amount and high price; and the mechanical properties of the obtained plastic are poor.
Therefore, there is a need in the art to develop a laser direct structuring material with lower cost, simpler preparation process, and better mechanical properties to promote the development and application of 3D-MID.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polyphenyl ether/polystyrene composition, a preparation method and application thereof. The polyphenyl ether/polystyrene composition adopts hollow metal oxide particles as LDS additives, can be directly formed by laser, and has the advantages of less LDS additives, higher adhesion of a metal coating after laser etching, better mechanical property and lower cost compared with a material directly taking metal oxide as LDS additives.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyphenylene ether/polystyrene composition comprising polyphenylene ether, polystyrene and hollow metal oxide particles;
the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores.
During the process of forming circuit patterns by irradiating the three-dimensional molding interconnection device with laser, only the LDS additive on the surface layer can be activated to form the metal core, and the LDS additive inside the plastic device does not participate in laser activation. The hollow metal oxide particles adopted by the invention are hollow, the density is lower, the polyphenyl ether/polystyrene composition adopting the hollow metal oxide particles as the LDS additive can ensure that the surface of the material is activated to form a circuit pattern under laser irradiation, the weight of the LDS additive in the material can be reduced, the cost is reduced, and the influence of a small addition amount on the mechanical property of the polyphenyl ether/polystyrene substrate is smaller.
As a preferred technical scheme of the invention, the polyphenyl ether/polystyrene composition comprises the following components in percentage by weight:
35-94% of polyphenyl ether;
5-50% of polystyrene;
0.5-20% of hollow metal oxide particles.
In the present invention, the polyphenylene ether may be 35%, 38%, 40%, 45%, 50%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 94%, or the like in percentage by weight.
The polystyrene may be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, or the like, by weight.
The weight percentage of the hollow metal oxide particles can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 7%, 8%, 9%, 10%, 12%, 13%, 15%, 16%, 18%, 20%, or the like.
Preferably, the polyphenylene ether/polystyrene composition comprises the following components in percentage by weight:
56-89% of polyphenyl ether;
10-40% of polystyrene;
1-4% of hollow metal oxide particles.
As a preferred embodiment of the present invention, the metal oxide is one or a combination of at least two selected from oxides of metal M, and the metal M is one or at least two selected from titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), rhodium (Rh), palladium (Pd), silver (Ag), cerium (Ce), iridium (Ir), platinum (Pt), or gold (Au).
Preferably, the metal oxide is copper chromium black.
Preferably, the metal oxide comprises 30-60% by mass of the hollow metal oxide particles; for example, it may be 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, etc.
Preferably, the hollow metal oxide particles have a particle size of 0.1 to 100. mu.m, and may be, for example, 0.1. mu.m, 0.5. mu.m, 1. mu.m, 2. mu.m, 5. mu.m, 8. mu.m, 10. mu.m, 15. mu.m, 20. mu.m, 25. mu.m, 30. mu.m, 35. mu.m, 40. mu.m, 45. mu.m, 50. mu.m, 60. mu.m, 70. mu.m, 80. mu.m, 90. mu.m, 100. mu.m, or the like; more preferably 1 to 50 μm.
Preferably, the density of the hollow metal oxide particles is from 1.5 to 3g/cm3(ii) a For example, it may be 1.5g/cm3、1.8g/cm3、2g/cm3、2.2g/cm3、2.5g/cm3、2.8g/cm3Or 3g/cm3And the like.
As a preferred embodiment of the present invention, the method for preparing the hollow metal oxide particles comprises the steps of:
(a) dissolving and dispersing the hollow microspheres and metal salts corresponding to metal oxides in water to form a mixed solution;
(b) heating the mixed solution obtained in the step (a), adding a catalyst, adjusting the pH to 6-7, and heating until the water is evaporated to obtain a hollow metal oxide precursor;
(c) calcining the hollow metal oxide precursor obtained in step (b) to obtain the hollow metal oxide particles;
in the step (a), the "metal salt corresponding to the metal oxide" refers to a salt of a metal element in the metal oxide, and may be a sulfate, a nitrate, an acetate, a chloride, or the like. The ratio of the hollow microspheres to the metal salt is not particularly limited, and can be calculated by a person skilled in the art according to the ratio of the hollow microspheres to the metal oxide in the hollow metal oxide particles by combining general technical knowledge.
Preferably, the temperature rise in the step (b) is to 40-100 ℃; for example, the temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
Preferably, the catalyst in step (b) is urea and/or sodium dodecylbenzenesulfonate.
Preferably, the method for adding the catalyst in the step (b) is dropwise.
Preferably, the temperature of the calcination in step (c) is 500-; further preferably 500 ℃ and 800 ℃.
Preferably, the calcination time is 1-5 h; for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 4.8h, or 5h, etc. may be mentioned.
As a preferable technical scheme of the invention, the hollow microspheres are hollow glass microspheres or hollow silicon dioxide microspheres.
As a preferred embodiment of the present invention, the polyphenylene ether/polystyrene composition further comprises 0.02 to 2 wt% (e.g., 0.02 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, or 2 wt%) of an antioxidant.
Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant.
The mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is preferably 1: 1.
In a second aspect, the present invention provides a method for preparing the above polyphenylene ether/polystyrene composition, comprising the steps of:
(1) mixing polyphenylene ether, polystyrene and optionally an antioxidant to form a premix;
(2) and (2) carrying out melt extrusion on the premix obtained in the step (1) and the hollow metal oxide particles to obtain the polyphenyl ether/polystyrene composition.
It should be noted that the term "optionally" in the above step (1) means the presence or absence of an antioxidant which is mixed with polyphenylene ether and polystyrene when the antioxidant is added to the polyphenylene ether/polystyrene composition; when the antioxidant is not added to the polyphenylene ether/polystyrene composition, the polyphenylene ether, polystyrene and hollow metal oxide particles are directly melt extruded.
As a preferred embodiment of the present invention, the preparation method further comprises: the polyphenylene ether and the polystyrene are subjected to a drying treatment before step (1).
The drying treatment method is preferably drying at 90-110 ℃ for 3-5 h.
Preferably, the mixing in step (1) is carried out in a mixer.
Preferably, the rotation speed of the mixer is 300-500r/min, such as 300r/min, 320r/min, 350r/min, 380r/min, 400r/min, 420r/min, 450r/min, 480r/min or 500 r/min; the mixing time is 10-20min, such as 10min, 12min, 13min, 15min, 16min, 18min or 20 min.
Preferably, the melt extrusion in step (2) is carried out in a parallel twin-screw extruder.
Preferably, the premix in step (2) is fed from a main feeding port of the parallel twin-screw extruder, and the hollow metal oxide particles are fed from a sixth zone of the parallel twin-screw extruder.
Preferably, the temperature of one zone of the parallel twin-screw extruder is 250-270 ℃, and can be 250 ℃, 252 ℃, 255 ℃, 258 ℃, 260 ℃, 262 ℃, 265 ℃, 268 ℃ or 270 ℃ and the like.
The temperature of the second zone is 270 ℃ and 290 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃ or the like;
the temperature of the third zone is 270 ℃ and 290 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃ or the like;
the fourth zone is at a temperature of 270 ℃ and 290 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃ or the like;
the temperature of the fifth zone is 270 ℃ and 295 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃ and the like;
the temperature of the sixth zone is 270 ℃ and 295 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃ and the like;
the temperature of the seventh zone is 270 ℃ and 295 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃ and the like;
the temperature of the eight region is 270 ℃ and 295 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃ and the like;
the nine-zone temperature is 270 ℃ and 295 ℃, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃ and the like;
the die temperature is 270 ℃ and 295 ℃ and may be, for example, 270 ℃, 272 ℃, 275 ℃, 278 ℃, 280 ℃, 282 ℃, 285 ℃, 288 ℃, 290 ℃, 292 ℃ or 295 ℃.
Preferably, the residence time of the material in the parallel twin-screw extruder is 1-3 min; for example, it may be 1min, 1.2min, 1.5min, 1.8min, 2min, 2.2min, 2.5min, 2.8min or 3 min.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) drying the polyphenyl ether and the polystyrene, adding the polyphenyl ether and the polystyrene into a mixer together with an antioxidant, and mixing for 10-20min at the rotating speed of 300-500r/min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding hollow metal oxide particles from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 250-.
In a third aspect, the present invention provides the use of the above-described polyphenylene ether/polystyrene composition for three-dimensional molded interconnect devices.
Compared with the prior art, the invention has the following beneficial effects:
the polyphenyl ether/polystyrene composition provided by the invention adopts the hollow metal oxide particles as the LDS additive, can be directly formed by laser, and has less LDS additive, higher adhesion of a metal coating after laser etching and 5B grade of adhesion of the metal coating when the addition amount of the hollow metal oxide particles reaches 3 wt% compared with a material directly taking the metal oxide as the LDS additive; better mechanical property and lower cost.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the raw materials adopted in the embodiment of the invention are as follows:
polyphenylene ether: LXR040 from Bluestar (group) Inc., China;
polystyrene: 622P of the China petrochemical group corporation;
hollow metal oxide particles: the preparation method comprises the following steps:
preparation example 1
Preparing hollow copper-chromium black particles:
(a) adding 14g of hollow glass microspheres, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) 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 finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) in an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black is 50 wt%, the particle size is 1-50 mu m, and the density is 1.8g/cm3。
Preparation example 2
(a) Adding 9g of hollow glass beads, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) 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 finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) in an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black is 60 wt%, the particle size is 1-50 mu m, and the density is 2.0g/cm3。
Preparation example 3
(a) Adding 32g of hollow glass beads, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) 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 finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) in an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black is 30 wt%, the particle size is 1-50 mu m, and the density is 1.6g/cm3。
Example 1
This example provides a polyphenylene ether/polystyrene composition, comprising the following components in weight percent:
the preparation method of the polyphenyl ether/polystyrene composition comprises the following steps:
(1) drying polyphenyl ether and polystyrene at 100 ℃ for 4h, adding the dried polyphenyl ether and polystyrene together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 300r/min for 20min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of the first zone of the parallel double-screw extruder to be 250 ℃, the temperature of the second zone to be 270 ℃, the temperature of the third zone to be 270 ℃, the temperature of the fourth zone to be 270 ℃, the temperature of the fifth zone to be 275 ℃, the temperature of the sixth zone to be 275 ℃, the temperature of the seventh zone to be 275 ℃, the temperature of the eighth zone to be 275 ℃, the temperature of a die head to be 275 ℃, and keeping the material in the parallel double-screw extruder for 1min to obtain the polyphenylene ether/polystyrene composition after melt extrusion.
Example 2
This example provides a polyphenylene ether/polystyrene composition, comprising the following components in weight percent:
the preparation method of the polyphenyl ether/polystyrene composition comprises the following steps:
(1) drying polyphenyl ether and polystyrene at 90 ℃ for 5 hours, adding the dried polyphenyl ether and polystyrene together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 500r/min for 10min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 260 ℃, the temperature of a second zone to be 280 ℃, the temperature of a third zone to be 280 ℃, the temperature of a fourth zone to be 280 ℃, the temperature of a fifth zone to be 285 ℃, the temperature of a sixth zone to be 285 ℃, the temperature of a seventh zone to be 285 ℃, the temperature of an eighth zone to be 285 ℃, the temperature of a die head to be 285 ℃, and the residence time of the materials in the parallel double-screw extruder to be 2min, and obtaining the polyphenyl ether/polystyrene composition after melt extrusion.
Example 3
This example provides a polyphenylene ether/polystyrene composition, comprising the following components in weight percent:
the preparation method of the polyphenyl ether/polystyrene composition comprises the following steps:
(1) drying polyphenyl ether and polystyrene at 110 ℃ for 3h, adding the dried polyphenyl ether and polystyrene together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 400r/min for 15min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 270 ℃, the temperature of a second zone to be 290 ℃, the temperature of a third zone to be 290 ℃, the temperature of a fourth zone to be 290 ℃, the temperature of a fifth zone to be 295 ℃, the temperature of a sixth zone to be 295 ℃, the temperature of a seventh zone to be 295 ℃, the temperature of an eighth zone to be 295 ℃, the temperature of a ninth zone to be 295 ℃, the temperature of a die head to be 295 ℃, keeping time of the materials in the parallel double-screw extruder to be 3min, and obtaining the polyphenyl ether.
Example 4
This example provides a polyphenylene ether/polystyrene composition, comprising the following components in weight percent:
the preparation method of the polyphenyl ether/polystyrene composition comprises the following steps:
(1) drying polyphenyl ether and polystyrene at 100 ℃ for 4h, adding the dried polyphenyl ether and polystyrene together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 300r/min for 20min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of the first zone of the parallel double-screw extruder to be 250 ℃, the temperature of the second zone to be 280 ℃, the temperature of the third zone to be 280 ℃, the temperature of the fourth zone to be 285 ℃, the temperature of the fifth zone to be 290 ℃, the temperature of the sixth zone to be 290 ℃, the temperature of the seventh zone to be 290 ℃, the temperature of the eighth zone to be 290 ℃, the temperature of the die head to be 290 ℃, keeping the time of the materials in the parallel double-screw extruder to be 2min, and obtaining the polyphenyl ether/polystyrene composition after melt extrusion.
Example 5
The difference from example 3 is that polyphenylene ether was 71.6% by weight and the hollow copper chromium black pellets of preparation example 1 were 8% by weight.
Example 6
The difference from example 3 is that the polyphenylene ether was 59.6% by weight and the hollow copper chromium black pellets of preparation example 1 were 20% by weight.
Example 7
The difference from example 3 is that the hollow copper chromium black granules of preparation example 1 were replaced with the hollow copper chromium black granules of preparation example 2.
Example 8
The difference from example 3 is that the hollow copper chromium black granules of preparation example 1 were replaced with the hollow copper chromium black granules of preparation example 3.
Comparative example 1
The difference from example 3 is that the hollow copper chromium black particles were replaced with copper chromium black powder and the preparation procedure was the same as in example 3.
Comparative example 2
The difference from example 5 is that the hollow copper chromium black particles were replaced with copper chromium black powder and the preparation procedure was the same as in example 5.
The polyphenylene ether/polystyrene compositions provided in examples 1-8 and comparative examples 1-2 above were injection molded into shaped plastic parts. According to the conventional method, the wavelength is 900-1080nm, and the energy is 150-300mJ/cm2The laser carries out laser etching on the preset area of the plastic part according to a set pattern at the scanning speed of 0.1-1mm/s, the plastic part after laser etching is subjected to chemical copper plating, and a copper plating layer is formed in the laser etching area of the plastic part. The plastic parts and the electroless copper plated plastic parts were then tested for their performance according to the following criteria and methods:
tensile strength: the tensile rate is 50mm/min according to the test of ASTM-D638;
notched impact strength: the thickness of the sample strip is 3.2mm, the temperature is 23 ℃, and the RH is 50 percent according to the test of ASTM-D256 standard;
flexural strength and flexural modulus: the bending rate is 10mm/min according to the test of ASTM-D790;
and (3) adhesion of a copper plating layer: the test is carried out according to ASTM D3359 standard, which is as follows:
under the conditions of room temperature of 23 +/-2 ℃ and relative humidity of 50 +/-5%, 10 multiplied by 10 small grids of 1 multiplied by 1mm are scribed on the surface of a test sample by a sharp blade (the angle of the blade is 15-30 ℃), and each scribing line is deep and a plating bottom layer is formed; brushing the test area by using a brush, firmly sticking the tested small grid by using a 3M 600 adhesive tape, and forcibly wiping the adhesive tape by using an eraser to increase the contact area and force between the adhesive tape and the tested area; grasping one end of the adhesive tape by hand, rapidly pulling off the adhesive tape at an angle of 60 degrees in the vertical direction, and carrying out 2 times of same tests at the same position;
and (4) judging a result: the adhesive force is qualified when the adhesive force is required to be more than or equal to 4B;
5B-the scribing edge is smooth, and no paint falls off at the scribing edge and the intersection;
4B-there are small pieces of paint falling off at the cross point of the line, and the total area of falling off is less than 5%;
3B-small pieces of paint fall off at the edges and the cross points of the drawn lines, and the total area of the fall off is between 5 and 15 percent;
2B-pieces of paint fall off at the edges and the cross points of the lines, and the total area of the fall off is 15-35%;
1B-pieces of paint fall off at the edges and the intersections of the lines, and the total area of the fall off is 35-65%;
0B-there is a patch of paint falling off at the edge and intersection of the score line, and the total area of falling off is greater than 65%.
The results of the above performance tests are shown in tables 1 and 2 below:
TABLE 1
TABLE 2
As can be seen from the data in tables 1 and 2, the polyphenylene ether/polystyrene compositions provided by the present invention are laser directly moldable. Comparing example 3 with comparative example 1, it can be seen that the polyphenylene ether/polystyrene composition provided by the present invention has higher metal plating adhesion, and the metal plating adhesion of the polyphenylene ether/polystyrene composition with 3 wt% of metal oxide powder added does not meet the requirement; comparing example 3 with comparative example 2, it can be seen that when the adhesion of the metal plating layer is the same, the polyphenylene ether/polystyrene composition provided by the present invention requires less hollow metal oxide particles, and the mechanical properties of the resulting polyphenylene ether/polystyrene composition are also better.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (25)
1. A polyphenylene ether/polystyrene composition, wherein the polyphenylene ether/polystyrene composition comprises polyphenylene ether, polystyrene, and hollow metal oxide particles;
the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, and the metal oxide can be activated by laser to form metal cores;
the polyphenyl ether/polystyrene composition comprises the following components in percentage by weight:
56-89% of polyphenyl ether;
10-40% of polystyrene;
1-4% of hollow metal oxide particles;
the metal oxide accounts for 30-60% of the mass of the hollow metal oxide particles;
the preparation method of the hollow metal oxide particles comprises the following steps:
(a) dissolving and dispersing the hollow microspheres and metal salts corresponding to metal oxides in water to form a mixed solution;
(b) heating the mixed solution obtained in the step (a), adding a catalyst, adjusting the pH to 6-7, and heating until the water is evaporated to obtain a hollow metal oxide precursor;
(c) calcining the hollow metal oxide precursor obtained in step (b) to obtain the hollow metal oxide particles.
2. The polyphenylene ether/polystyrene composition of claim 1, wherein the metal oxide is selected from one or a combination of at least two of the oxides of metal M selected from one or at least two of titanium, chromium, manganese, iron, cobalt, nickel, copper, niobium, rhodium, palladium, silver, cerium, iridium, platinum, or gold.
3. The polyphenylene ether/polystyrene composition of claim 1, wherein the metal oxide is copper chromium black.
4. The polyphenylene ether/polystyrene composition of claim 1, wherein the hollow metal oxide particles have a particle size of 0.1 to 100 μm.
5. The polyphenylene ether/polystyrene composition of claim 4, wherein the hollow metal oxide particles have a particle size of 1 to 50 μm.
6. The polyphenylene ether/polystyrene composition of claim 1, wherein the hollow metal oxide particles have a density of 1.5 to 3g/cm3。
7. The polyphenylene ether/polystyrene composition of claim 1, wherein the temperature increase in step (b) is to 40-100 ℃.
8. The polyphenylene ether/polystyrene composition of claim 1, wherein in step (b) the catalyst is urea and/or sodium dodecylbenzenesulfonate.
9. The polyphenylene ether/polystyrene composition of claim 1, wherein the catalyst is added dropwise in step (b).
10. The polyphenylene ether/polystyrene composition of claim 1, wherein the temperature of the calcination in step (c) is 500-1200 ℃.
11. The polyphenylene ether/polystyrene composition of claim 10, wherein the temperature of the calcination in step (c) is 500-800 ℃.
12. The polyphenylene ether/polystyrene composition of claim 1, wherein the calcination time is 1-5 hours.
13. The polyphenylene ether/polystyrene composition of claim 1, wherein the cenospheres are cenospheres of hollow glass or hollow silica.
14. The polyphenylene ether/polystyrene composition of claim 1, further comprising 0.02 to 2 wt% of an antioxidant.
15. The polyphenylene ether/polystyrene composition of claim 14, wherein the antioxidant is a combination of hindered phenolic and phosphite antioxidants.
16. A method for preparing the polyphenylene ether/polystyrene composition of any of claims 1-15, comprising the steps of:
(1) mixing polyphenylene ether, polystyrene and optionally an antioxidant to form a premix;
(2) and (2) carrying out melt extrusion on the premix obtained in the step (1) and the hollow metal oxide particles to obtain the polyphenyl ether/polystyrene composition.
17. The method of manufacturing according to claim 16, further comprising: the polyphenylene ether and the polystyrene are subjected to a drying treatment before step (1).
18. The method of claim 16, wherein the mixing in step (1) is performed in a mixer.
19. The method as claimed in claim 16, wherein the rotation speed of the mixer is 300-500r/min, and the mixing time is 10-20 min.
20. The production method according to claim 16, wherein the melt extrusion in step (2) is carried out in a parallel twin-screw extruder.
21. The method of claim 20, wherein the premix in step (2) is fed from a main feeding port of the parallel twin-screw extruder, and the hollow metal oxide particles are fed from a sixth zone of the parallel twin-screw extruder.
22. The method as claimed in claim 20, wherein the temperature of the first zone of the parallel twin-screw extruder is 250-.
23. The method of claim 20, wherein the residence time of the material in the parallel twin screw extruder is 1-3 min.
24. The method of manufacturing according to claim 16, comprising the steps of:
(1) drying the polyphenyl ether and the polystyrene, adding the polyphenyl ether and the polystyrene into a mixer together with an antioxidant, and mixing for 10-20min at the rotating speed of 300-500r/min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding hollow metal oxide particles from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 250-.
25. Use of the polyphenylene ether/polystyrene composition according to any of claims 1 to 15, wherein the polyphenylene ether/polystyrene composition is used in a three-dimensional molded interconnect device.
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