CN109486165A - A kind of polyphenyl ether/styrene composition and its preparation method and application - Google Patents
A kind of polyphenyl ether/styrene composition and its preparation method and application Download PDFInfo
- Publication number
- CN109486165A CN109486165A CN201811626107.1A CN201811626107A CN109486165A CN 109486165 A CN109486165 A CN 109486165A CN 201811626107 A CN201811626107 A CN 201811626107A CN 109486165 A CN109486165 A CN 109486165A
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- temperature
- area
- polyphenyl ether
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- 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 present invention provides a kind of polyphenyl ether/styrene compositions and its preparation method and application.The polyphenyl ether/styrene composition includes polyphenylene oxide, polystyrene and hollow metal oxide particle；The hollow metal oxide particle includes cenosphere and the metal oxide for being coated on the cenosphere surface, and the metal oxide is the metal oxide that metal core can be formed by laser activation.The polyphenyl ether/styrene composition is by the way that polyphenylene oxide, polystyrene and hollow metal oxide particle to be prepared with the method for extruder melting extrusion.It is provided by the invention can laser direct forming, compared to directly using metal oxide as the material of LDS additive, the LDS additive of polyphenyl ether/styrene composition addition provided by the invention is less, coat of metal adhesive force is higher after laser ablation, mechanical property is more preferable, cost is lower, can be used as the material for preparing three dimensional mold interconnecting device.
Description
Technical field
The invention belongs to laser direct forming field of material technology, be related to a kind of polyphenyl ether/styrene composition and its
Preparation method and purposes.
Background technique
Three dimensional mold interconnecting device (3D-MID) is also known as three-dimensional circuit or stereo circuit, refers to the plastic housing in injection molding
Production has conducting wire, the figure of electric function on body, to realize the electric interconnection with common circuit board, bearing member
The functions such as support, the protection of device function and plastic casing are integrated in one, the stereo circuit carrier of formation.Three dimensional mold interconnecting
Device have can selected shape according to the design needs, function is new, is suitble to the design advantage of smaller, lighter development trend；Also
With reducing installation level, reducing component number, improving reliability and reducing the investment of material quantity and kind, it is conducive to ring
Advantage in terms of the economic environment such as guarantor's processing.3D-MID has in fields such as automobile, industry, computer, communications considerable at present
The application of quantity will become an important branch of circuit-board industry from now on.
The moulding process of 3D-MID mainly includes bimodulus injection molding (2Shot MID) and laser direct forming (Laser
Direct Structure) two kinds, at present based on LDS.LDS refers to the TRAJECTORY CONTROL laser with computer according to conductive pattern
Movement, by laser throwing shine on the molded three-dimensional plastic device of special material, electricity was activated within several seconds time
Road pattern.
CN 101784607A, CN 102066473A and the disclosed modeling for being used for laser direct forming of CN 102066122A
Have in material and is added to a kind of dielectric organometallic compounds (such as mantoquita or copper chromium object) work with spinel structure
For LDS additive, this organometallic compounds are expensive, and additive amount is more, are unfavorable in laser direct forming plastics
Popularization and use.
CN 101654564A discloses a kind of plastics composite and its surface selective metallization process, and this method uses
Photochemical catalyst is added in the plastic, and the plastics composite containing photochemical catalyst makes in plastics composite under laser irradiation condition
Part photocatalyst expose；Then the plastics composite after laser ablation is put into sacrificial containing metal cation salt, hole
In the aqueous solution of domestic animal agent, in the case where that can excite the light source irradiation condition of photochemical catalyst, the light for being exposed to plastics composite surface is urged
Agent can restore the metal ion in solution, obtain nanoscale metal particles；Finally carry out metal chemical plating.But the technique
It needs using special photochemical catalyst, to cooperate hole sacrifice agent also to improve photocatalysis efficiency, complex process；The light of use is urged
Agent additive amount is big, price；And obtained plastics machinery performance is poor.
Therefore, lower up for researching and developing a kind of cost in this field, preparation process is simpler, and mechanical performance preferably swashs
Light straight forming material, to promote the development and application of 3D-MID.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of polyphenyl ether/styrene composition
And its preparation method and application.The polyphenyl ether/styrene composition is added using hollow metal oxide particle as LDS
Agent, can laser direct forming, compared to directly using metal oxide as the material of LDS additive, polyphenyl provided by the invention
Ether/polyphenylacetylene combination addition LDS additive is less, and coat of metal adhesive force is higher after laser ablation, and mechanical property is more
Good, cost is lower.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of polyphenyl ether/styrene composition, including polyphenylene oxide, polystyrene and sky
Heart metal oxide particle；
The hollow metal oxide particle includes cenosphere and the metal oxidation for being coated on the cenosphere surface
Object, the metal oxide are the metal oxides that metal core can be formed by laser activation.
During laser irradiation three dimensional mold interconnecting device forms circuit pattern, the only LDS additive meeting on surface layer
It is activated out metal core, the LDS additive inside plastic device is then not involved in laser activation.The hollow metal oxygen that the present invention uses
Be hollow structure inside compound particle, density is lower, using its as LDS additive polyphenyl ether/styrene composition both
It can guarantee that circuit pattern is activated in material surface under laser irradiation, and the weight of the LDS additive of material internal can be reduced
Amount, reduces cost, and the influence of less additive amount polyphenylene ether/polystyrene substrate mechanical property is also smaller.
As the preferred technical solution of the present invention, the polyphenyl ether/styrene composition includes following weight percent
Component:
Polyphenylene oxide 35-94%；
Polystyrene 5-50%；
Hollow metal oxide particle 0.5-20%.
In the present invention, the weight percent of the polyphenylene oxide can be 35%, 38%, 40%, 45%, 50%, 55%,
58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92% or
94% etc..
The weight percent of the polystyrene can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%,
25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50% etc..
The weight percent of the hollow metal oxide particle 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% or
20% etc..
Preferably, the polyphenyl ether/styrene composition includes following weight percentage components:
Polyphenylene oxide 56-89%；
Polystyrene 10-40%；
Hollow metal oxide particle 1-4%.
As the preferred technical solution of the present invention, the metal oxide is selected from one of oxide or extremely of metal M
Few two kinds of combination, the metal M are selected from titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium
(Nb), one of rhodium (Rh), palladium (Pd), silver (Ag), cerium (Ce), iridium (Ir), platinum (Pt) or gold (Au) or at least two.
Preferably, the metal oxide is copper-chrome black.
Preferably, the metal oxide accounts for the 30-60% of the hollow metal oxide particle quality；Such as it can be
30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60% etc..
Preferably, the partial size of the hollow metal oxide particle be 0.1-100 μm, such as can be 0.1 μm, 0.5 μm,
1μm、2μm、5μm、8μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、60μm、70μm、80μm、
90 μm or 100 μm etc.；Further preferably 1-50 μm.
Preferably, the density of the hollow metal oxide particle is 1.5-3g/cm3；Such as it can be 1.5g/cm3、
1.8g/cm3、2g/cm3、2.2g/cm3、2.5g/cm3、2.8g/cm3Or 3g/cm3Deng.
As the preferred technical solution of the present invention, the preparation method of the hollow metal oxide particle includes following step
It is rapid:
(a) cenosphere and the corresponding dissolving metal salts of metal oxide are dispersed in water, form mixed liquor；
(b) mixed liquor for obtaining step (a) heats up, and catalyst is then added, and adjust pH to 6-7, is heated to moisture
It evaporates, obtains hollow metal oxide precursor；
(c) the hollow metal oxide precursor for obtaining step (b) is calcined, and obtains the hollow metal oxide
Grain；
It should be noted that " the corresponding metal salt of metal oxide " described in above-mentioned steps (a) refers to metal oxide
In metallic element salt, can be sulfate, nitrate, acetate or chloride etc..The present invention is to cenosphere and metal
The ratio of salt is not specifically limited, and those skilled in the art can be according to cenosphere and metal oxygen in hollow metal oxide particle
The ratio of compound is calculated in conjunction with general technology knowledge.
Preferably, heating described in step (b) is to be warming up to 40-100 DEG C；Such as it can be 40 DEG C, 45 DEG C, 50 DEG C, 55
DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc..
Preferably, catalyst described in step (b) is urea and/or dodecyl benzene sulfonic acid sodium salt.
Preferably, the method that catalyst is added described in step (b) is to be added dropwise.
Preferably, the temperature of calcining described in step (c) is 500-1200 DEG C, such as can be 500 DEG C, 520 DEG C, 550
℃、580℃、600℃、620℃、650℃、680℃、700℃、720℃、750℃、780℃、800℃、850℃、900℃、
950 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C or 1200 DEG C etc.；Further preferably 500-800 DEG C.
Preferably, the time of the calcining is 1-5h；Such as can be 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..
As the preferred technical solution of the present invention, the cenosphere is that hollow glass micropearl or hollow silicon dioxide are micro-
Pearl.
As the preferred technical solution of the present invention, the polyphenyl ether/styrene composition further includes 0.02-2wt% (example
As 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%,
0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt% or 2wt% etc.) antioxidant.
Preferably, the antioxidant is the compound of Hinered phenols antioxidant and phosphite ester antioxidant.
The Hinered phenols antioxidant and the mass ratio of phosphite ester antioxidant are preferably 1:1.
Second aspect, the present invention provides a kind of preparation method of above-mentioned polyphenyl ether/styrene composition, including walks as follows
It is rapid:
(1) by polyphenylene oxide, polystyrene and optionally antioxidant mixing, premix is formed；
(2) premix and hollow metal oxide particle melting extrusion obtained step (1), obtain the polyphenylene oxide/
Polyphenylacetylene combination.
It should be noted that " optionally " referring to described in above-mentioned steps (1) with and without when polyphenylene oxide/polyphenyl second
When adding antioxidant in ene compositions, then it is mixed with polyphenylene oxide, polystyrene；When in polyphenyl ether/styrene composition
When not adding antioxidant, then directly by polyphenylene oxide, polystyrene and hollow metal oxide particle melting extrusion.
As the preferred technical solution of the present invention, the preparation method further include: will be to the polyphenyl before step (1)
Ether and the polystyrene are dried.
The method of the drying process is preferably in 90-110 DEG C of drying 3-5h.
Preferably, mixing described in step (1) is carried out in mixing machine.
Preferably, the revolving speed of the mixing machine be 300-500r/min, such as can be 300r/min, 320r/min,
350r/min, 380r/min, 400r/min, 420r/min, 450r/min, 480r/min or 500r/min etc.；The mixing
Time is 10-20min, such as can be 10min, 12min, 13min, 15min, 16min, 18min or 20min etc..
Preferably, melting extrusion described in step (2) is carried out in parallel double-screw extruder.
Preferably, premix described in step (2) is added from the main spout of the parallel double-screw extruder, the sky
Heart metal oxide particle is added from the 6th area of the parallel double-screw extruder.
Preferably, area's temperature of the parallel double-screw extruder is 250-270 DEG C, such as can be 250 DEG C, 252
DEG C, 255 DEG C, 258 DEG C, 260 DEG C, 262 DEG C, 265 DEG C, 268 DEG C or 270 DEG C etc..
Two area's temperature are 270-290 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C or 290 DEG C etc.；
Three area's temperature are 270-290 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C or 290 DEG C etc.；
4th area are 270-290 DEG C of temperature, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C or 290 DEG C etc.；
Five area's temperature are 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc.；
Six area's temperature are 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc.；
Seven area's temperature are 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc.；
Eight area's temperature are 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc.；
Nine area's temperature are 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc.；
Die head temperature is 270-295 DEG C, such as can be 270 DEG C, 272 DEG C, 275 DEG C, 278 DEG C, 280 DEG C, 282 DEG C, 285
DEG C, 288 DEG C, 290 DEG C, 292 DEG C or 295 DEG C etc..
Preferably, residence time of the material in the parallel double-screw extruder is 1-3min；Such as can be 1min,
1.2min, 1.5min, 1.8min, 2min, 2.2min, 2.5min, 2.8min or 3min etc..
As the preferred technical solution of the present invention, the preparation method includes the following steps:
(1) polyphenylene ether and polystyrene are dried, and are then added to the mixer with antioxidant, in 300-
10-20min is mixed under the revolving speed of 500r/min, forms premix；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, hollow metal oxidation
Composition granule is added from the 6th area of the parallel double-screw extruder, and the area's temperature for controlling the parallel double-screw extruder is
250-270 DEG C, two area's temperature are 270-290 DEG C, and three area's temperature are 270-290 DEG C, and 4th area are 270-290 DEG C of temperature, five Qu Wen
Degree be 270-295 DEG C, six area's temperature be 270-295 DEG C, seven area's temperature be 270-295 DEG C, eight area's temperature be 270-295 DEG C, nine
Area's temperature is 270-295 DEG C, and die head temperature is 270-295 DEG C, residence time of the material in the parallel double-screw extruder
For 1-3min, the polyphenyl ether/styrene composition is obtained after melting extrusion.
The third aspect, the present invention provide a kind of purposes of above-mentioned polyphenyl ether/styrene composition, the polyphenylene oxide/poly-
S compositions are used for three dimensional mold interconnecting device.
Compared with prior art, the invention has the following advantages:
Polyphenyl ether/styrene composition provided by the invention using hollow metal oxide particle as LDS additive,
Can laser direct forming, compared to directly using metal oxide as the material of LDS additive, polyphenylene oxide provided by the invention/
The LDS additive of polyphenylacetylene combination addition is less, and coat of metal adhesive force is higher after laser ablation, hollow metal oxide
When particle additive amount reaches 3wt%, coat of metal adhesive force can reach 5B rank；Mechanical property is more preferable, and cost is lower.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
The source of the raw material used in the embodiment of the present invention is as follows:
Polyphenylene oxide: the LXR040 of China Blue Star Group Co., Ltd.；
Polystyrene: the 622P of China PetroChemical Corporation；
Hollow metal oxide particle: self-control, it is specific the preparation method is as follows:
Preparation example 1
The preparation of hollow copper-chrome black particle:
(a) 500mL distilled water is added in 14g hollow glass micropearl, 14g Gerhardite and 50g Chromium nitrate (Cr(NO3)3),nonahydrate
In, dissolution is uniformly dispersed, and forms mixed liquor；
(b) mixed liquor for obtaining step (a), which is placed in constant temperature blender with magnetic force, is stirred and heated to 60 DEG C, is then added dropwise
Urea adjusts the pH to 6-7 of mixed liquor under agitation, continues to be heated with stirring to moisture evaporating, obtains hollow copper chromium
Black presoma；
(c) the hollow copper-chrome black presoma for obtaining step (b) is placed in electric furnace, is calcined 2h at 550 DEG C, is obtained hollow
Copper-chrome black particle, copper-chrome black content are 50wt%, and partial size is 1-50 μm, density 1.8g/cm3。
Preparation example 2
(a) 500mL distilled water is added in 9g hollow glass micropearl, 14g Gerhardite and 50g Chromium nitrate (Cr(NO3)3),nonahydrate
In, dissolution is uniformly dispersed, and forms mixed liquor；
(b) mixed liquor for obtaining step (a), which is placed in constant temperature blender with magnetic force, is stirred and heated to 60 DEG C, is then added dropwise
Urea adjusts the pH to 6-7 of mixed liquor under agitation, continues to be heated with stirring to moisture evaporating, obtains hollow copper chromium
Black presoma；
(c) the hollow copper-chrome black presoma for obtaining step (b) is placed in electric furnace, is calcined 2h at 550 DEG C, is obtained hollow
Copper-chrome black particle, copper-chrome black content are 60wt%, and partial size is 1-50 μm, density 2.0g/cm3。
Preparation example 3
(a) 500mL distilled water is added in 32g hollow glass micropearl, 14g Gerhardite and 50g Chromium nitrate (Cr(NO3)3),nonahydrate
In, dissolution is uniformly dispersed, and forms mixed liquor；
(b) mixed liquor for obtaining step (a), which is placed in constant temperature blender with magnetic force, is stirred and heated to 60 DEG C, is then added dropwise
Urea adjusts the pH to 6-7 of mixed liquor under agitation, continues to be heated with stirring to moisture evaporating, obtains hollow copper chromium
Black presoma；
(c) the hollow copper-chrome black presoma for obtaining step (b) is placed in electric furnace, is calcined 2h at 550 DEG C, is obtained hollow
Copper-chrome black particle, copper-chrome black content are 30wt%, and partial size is 1-50 μm, density 1.6g/cm3。
Embodiment 1
The present embodiment provides a kind of polyphenyl ether/styrene compositions, including following weight percentage components:
Above-mentioned polyphenyl ether/styrene composition the preparation method is as follows:
(1) by polyphenylene oxide, polystyrene at 100 DEG C dry 4h, then with Hinered phenols antioxidant β-(4- hydroxy benzenes
Base -3,5- di-t-butyl) propionic acid octadecyl ester (antioxidant 1076) and (the 2,4- di-tert-butyl of phosphite ester antioxidant three
Base) phosphite ester (irgasfos 168) is added to the mixer together, and 20min is mixed under the revolving speed of 300r/min, form premix
Material；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, and preparation example 1 provides
Hollow copper-chrome black particle from the 6th area of parallel double-screw extruder be added, control a Qu Wendu of parallel double-screw extruder
It is 250 DEG C, two area's temperature are 270 DEG C, and three area's temperature are 270 DEG C, and 4th area are 270 DEG C of temperature, and five area's temperature are 275 DEG C, 6th area
Temperature is 275 DEG C, and seven area's temperature are 275 DEG C, and eight area's temperature are 275 DEG C, and nine area's temperature are 275 DEG C, and die head temperature is 275 DEG C,
Residence time of the material in parallel double-screw extruder is 1min, and polyphenyl ether/styrene composition is obtained after melting extrusion.
Embodiment 2
The present embodiment provides a kind of polyphenyl ether/styrene compositions, including following weight percentage components:
Above-mentioned polyphenyl ether/styrene composition the preparation method is as follows:
(1) by polyphenylene oxide, polystyrene at 90 DEG C dry 5h, then with Hinered phenols antioxidant β-(4- hydroxy phenyl-
3,5- di-t-butyl) propionic acid octadecyl ester (antioxidant 1076) and phosphite ester antioxidant three (2,4- di-tert-butyl-phenyl) be sub-
Phosphate (irgasfos 168) is added to the mixer together, and 10min is mixed under the revolving speed of 500r/min, forms premix；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, and preparation example 1 provides
Hollow copper-chrome black particle from the 6th area of parallel double-screw extruder be added, control a Qu Wendu of parallel double-screw extruder
It is 260 DEG C, two area's temperature are 280 DEG C, and three area's temperature are 280 DEG C, and 4th area are 280 DEG C of temperature, and five area's temperature are 285 DEG C, 6th area
Temperature is 285 DEG C, and seven area's temperature are 285 DEG C, and eight area's temperature are 285 DEG C, and nine area's temperature are 285 DEG C, and die head temperature is 285 DEG C,
Residence time of the material in parallel double-screw extruder is 2min, and polyphenyl ether/styrene composition is obtained after melting extrusion.
Embodiment 3
The present embodiment provides a kind of polyphenyl ether/styrene compositions, including following weight percentage components:
Above-mentioned polyphenyl ether/styrene composition the preparation method is as follows:
(1) by polyphenylene oxide, polystyrene at 110 DEG C dry 3h, then with Hinered phenols antioxidant β-(4- hydroxy benzenes
Base -3,5- di-t-butyl) propionic acid octadecyl ester (antioxidant 1076) and (the 2,4- di-tert-butyl of phosphite ester antioxidant three
Base) phosphite ester (irgasfos 168) is added to the mixer together, and 15min is mixed under the revolving speed of 400r/min, form premix
Material；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, and preparation example 1 provides
Hollow copper-chrome black particle from the 6th area of parallel double-screw extruder be added, control a Qu Wendu of parallel double-screw extruder
It is 270 DEG C, two area's temperature are 290 DEG C, and three area's temperature are 290 DEG C, and 4th area are 290 DEG C of temperature, and five area's temperature are 295 DEG C, 6th area
Temperature is 295 DEG C, and seven area's temperature are 295 DEG C, and eight area's temperature are 295 DEG C, and nine area's temperature are 295 DEG C, and die head temperature is 295 DEG C,
Residence time of the material in parallel double-screw extruder is 3min, and polyphenyl ether/styrene composition is obtained after melting extrusion.
Embodiment 4
The present embodiment provides a kind of polyphenyl ether/styrene compositions, including following weight percentage components:
Above-mentioned polyphenyl ether/styrene composition the preparation method is as follows:
(1) by polyphenylene oxide, polystyrene at 100 DEG C dry 4h, then with Hinered phenols antioxidant β-(4- hydroxy benzenes
Base -3,5- di-t-butyl) propionic acid octadecyl ester (antioxidant 1076) and (the 2,4- di-tert-butyl of phosphite ester antioxidant three
Base) phosphite ester (irgasfos 168) is added to the mixer together, and 20min is mixed under the revolving speed of 300r/min, form premix
Material；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, and preparation example 1 provides
Hollow copper-chrome black particle from the 6th area of parallel double-screw extruder be added, control a Qu Wendu of parallel double-screw extruder
It is 250 DEG C, two area's temperature are 280 DEG C, and three area's temperature are 280 DEG C, and 4th area are 285 DEG C of temperature, and five area's temperature are 290 DEG C, 6th area
Temperature is 290 DEG C, and seven area's temperature are 290 DEG C, and eight area's temperature are 290 DEG C, and nine area's temperature are 290 DEG C, and die head temperature is 290 DEG C,
Residence time of the material in parallel double-screw extruder is 2min, and polyphenyl ether/styrene composition is obtained after melting extrusion.
Embodiment 5
Difference with embodiment 3 is that the weight percent of polyphenylene oxide is 71.6%, the hollow copper-chrome black of preparation example 1
The weight percent of grain is 8%.
Embodiment 6
Difference with embodiment 3 is that the weight percent of polyphenylene oxide is 59.6%, the hollow copper-chrome black of preparation example 1
The weight percent of grain is 20%.
Embodiment 7
Difference with embodiment 3 is, the hollow copper-chrome black particle of preparation example 1 is replaced with to the hollow copper chromium of preparation example 2
Black particle.
Embodiment 8
Difference with embodiment 3 is, the hollow copper-chrome black particle of preparation example 1 is replaced with to the hollow copper chromium of preparation example 3
Black particle.
Comparative example 1
Difference with embodiment 3 is, hollow copper-chrome black particle is replaced with copper-chrome black powder, preparation step and embodiment
3 is identical.
Comparative example 2
Difference with embodiment 5 is, hollow copper-chrome black particle is replaced with copper-chrome black powder, preparation step and embodiment
5 is identical.
Above-described embodiment 1-8 and comparative example 1-2 the polyphenyl ether/styrene composition provided are injection molded into a setting
The plastic part of shape.Wavelength 900-1080nm, energy 150-300mJ/cm are used according to conventional methods2Laser 0.1-1mm/s's
Laser ablation is carried out according to setting pattern to the presumptive area of above-mentioned plastic part under sweep speed, by the plastic part of laser ablation
Electroless copper is carried out, forms copper coating in the laser ablation area of the plastic part.Then according to following standard and method to above-mentioned
The performance of plastic part after plastic part and electroless copper is tested:
Tensile strength: ASTM-D638 standard testing, rate of extension 50mm/min are pressed；
Notch impact strength: pressing ASTM-D256 standard testing, and batten is with a thickness of 3.2mm, and 23 DEG C of temperature, 50%RH；
Bending strength and bending modulus: pressing ASTM-D790 standard testing, is bent rate 10mm/min；
Copper coating adhesive force: pressing ASTM D3359 standard testing, specific as follows:
Under conditions of 23 ± 2 DEG C of room temperature, relative humidity 50 ± 5%, existed with sharp cutter (knife edge angle is 15 ° -30 °)
Test sample surface draws 10 × 10 1mm × 1mm small grids, each scribing line depth and coating bottom；With hairbrush by test zone
Clean down, firmly cling tested small grid with No. 600 adhesive tapes of 3M, and firmly wipe adhesive tape with erasing rubber, with increase adhesive tape with
The contact area and dynamics of tested region；Adhesive tape one end is held, shuts down gummed paper rapidly in vertical direction with 60 ° of angles, together
One position carries out 2 same tests；
Result judgement: it is required that being qualification when adhesive force >=4B；
5B- scribing edge is smooth, at the edge and intersection of scribing line without peeling paint；
4B- has the peeling paint of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
3B- has the peeling paint of small pieces at the edge and intersection of scribing line, and falls off the gross area between 5-15%；
2B- has sheet of peeling paint at the edge and intersection of scribing line, and falls off the gross area between 15-35%；
1B- has sheet of peeling paint at the edge and intersection of scribing line, and falls off the gross area between 35-65%；
0B- has sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Shown in the following Tables 1 and 2 of the result of above-mentioned performance test:
Table 1
Table 2
It can be seen from the data of table 1 and 2 polyphenyl ether/styrene composition provided by the invention can laser directly at
Type.Comparing embodiment 3 and comparative example 1 are it is found that polyphenyl ether/styrene composition provided by the invention has higher metal-plated
Layer adhesive force, the coat of metal adhesive force for adding the polyphenyl ether/styrene composition of 3wt% metal oxide powder then reach not
To requirement；Comparing embodiment 3 with comparative example 2 it is found that when the adhesive force of the coat of metal is identical, polyphenylene oxide provided by the invention/
Hollow metal oxide particle needed for polyphenylacetylene combination is less, and the power of obtained polyphenyl ether/styrene composition
It is also more preferable to learn performance.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of polyphenyl ether/styrene composition, which is characterized in that the polyphenyl ether/styrene composition includes polyphenyl
Ether, polystyrene and hollow metal oxide particle；
The hollow metal oxide particle includes cenosphere and the metal oxide for being coated on the cenosphere surface, institute
Stating metal oxide is the metal oxide that metal core can be formed by laser activation.
2. polyphenyl ether/styrene composition according to claim 1, which is characterized in that the polyphenyl ether/styrene
Composition includes following weight percentage components:
Polyphenylene oxide 35-94%；
Polystyrene 5-50%；
Hollow metal oxide particle 0.5-20%；
Preferably, the polyphenyl ether/styrene composition includes following weight percentage components:
Polyphenylene oxide 56-89%；
Polystyrene 10-40%；
Hollow metal oxide particle 1-4%.
3. polyphenyl ether/styrene composition according to claim 1 or 2, which is characterized in that the metal oxide choosing
One of oxide from metal M or at least two combination, the metal M be selected from titanium, chromium, manganese, iron, cobalt, nickel, copper, niobium,
One of rhodium, palladium, silver, cerium, iridium, platinum or gold or at least two；
Preferably, the metal oxide is copper-chrome black；
Preferably, the metal oxide accounts for the 30-60% of the hollow metal oxide particle quality；
Preferably, the partial size of the hollow metal oxide particle is 0.1-100 μm, further preferably 1-50 μm；
Preferably, the density of the hollow metal oxide particle is 1.5-3g/cm3。
4. polyphenyl ether/styrene composition according to claim 1-3, which is characterized in that the hollow gold
The preparation method for belonging to oxide particle includes the following steps:
(a) cenosphere and the corresponding dissolving metal salts of metal oxide are dispersed in water, form mixed liquor；
(b) mixed liquor for obtaining step (a) heats up, and catalyst is then added, and adjust pH to 6-7, is heated to moisture evaporation
It finishes, obtains hollow metal oxide precursor；
(c) the hollow metal oxide precursor for obtaining step (b) is calcined, and obtains the hollow metal oxide particle；
Preferably, heating described in step (b) is to be warming up to 40-100 DEG C；
Preferably, catalyst described in step (b) is urea and/or neopelex；
Preferably, the method that catalyst is added described in step (b) is to be added dropwise；
Preferably, the temperature of calcining described in step (c) is 500-1200 DEG C, further preferably 500-800 DEG C；
Preferably, the time of the calcining is 1-5h.
5. polyphenyl ether/styrene composition according to claim 1-4, which is characterized in that described hollow micro-
Pearl is hollow glass micropearl or hollow silicon dioxide microballon.
6. polyphenyl ether/styrene composition according to claim 1-5, which is characterized in that the polyphenylene oxide/
Polyphenylacetylene combination further includes the antioxidant of 0.02-2wt%；
Preferably, the antioxidant is the compound of Hinered phenols antioxidant and phosphite ester antioxidant.
7. a kind of preparation method of polyphenyl ether/styrene composition as claimed in any one of claims 1 to 6, feature exist
In the preparation method includes the following steps:
(1) by polyphenylene oxide, polystyrene and optionally antioxidant mixing, premix is formed；
(2) premix and hollow metal oxide particle melting extrusion obtained step (1), obtains the polyphenylene oxide/polyphenyl
Vinyl composition.
8. preparation method according to claim 7, which is characterized in that the preparation method further include: before step (1)
The polyphenylene oxide and the polystyrene will be dried；
Preferably, mixing described in step (1) is carried out in mixing machine；
Preferably, the revolving speed of the mixing machine is 300-500r/min, and the mixed time is 10-20min；
Preferably, melting extrusion described in step (2) is carried out in parallel double-screw extruder；
Preferably, premix described in step (2) is added from the main spout of the parallel double-screw extruder, the hollow gold
Belong to oxide particle to be added from the 6th area of the parallel double-screw extruder；
Preferably, area's temperature of the parallel double-screw extruder is 250-270 DEG C, and two area's temperature are 270-290 DEG C, 3rd area
Temperature is 270-290 DEG C, and 4th area are 270-290 DEG C of temperature, and five area's temperature are 270-295 DEG C, and six area's temperature are 270-295 DEG C,
Seven area's temperature are 270-295 DEG C, and eight area's temperature are 270-295 DEG C, and nine area's temperature are 270-295 DEG C, die head temperature 270-295
℃；
Preferably, residence time of the material in the parallel double-screw extruder is 1-3min.
9. preparation method according to claim 7 or 8, which is characterized in that the preparation method includes the following steps:
(1) polyphenylene ether and polystyrene are dried, and are then added to the mixer with antioxidant, in 300-500r/min
Revolving speed under mix 10-20min, form premix；
(2) premix for obtaining step (1) is added from the main spout of parallel double-screw extruder, hollow metal oxide
Grain is added from the 6th area of the parallel double-screw extruder, and the area's temperature for controlling the parallel double-screw extruder is 250-
270 DEG C, two area's temperature are 270-290 DEG C, and three area's temperature are 270-290 DEG C, and 4th area are 270-290 DEG C of temperature, and five area's temperature are
270-295 DEG C, six area's temperature are 270-295 DEG C, and seven area's temperature are 270-295 DEG C, and eight area's temperature are 270-295 DEG C, nine Qu Wen
Degree is 270-295 DEG C, and die head temperature is 270-295 DEG C, and residence time of the material in the parallel double-screw extruder is 1-
3min obtains the polyphenyl ether/styrene composition after melting extrusion.
10. a kind of purposes of polyphenyl ether/styrene composition as claimed in any one of claims 1 to 6, which is characterized in that institute
Polyphenyl ether/styrene composition is stated for three dimensional mold interconnecting device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811626107.1A CN109486165B (en) | 2018-12-28 | 2018-12-28 | Polyphenyl ether/polystyrene composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811626107.1A CN109486165B (en) | 2018-12-28 | 2018-12-28 | Polyphenyl ether/polystyrene composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109486165A true CN109486165A (en) | 2019-03-19 |
| CN109486165B CN109486165B (en) | 2021-03-05 |
Family
ID=65713060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811626107.1A Active CN109486165B (en) | 2018-12-28 | 2018-12-28 | Polyphenyl ether/polystyrene composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109486165B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655792A (en) * | 2019-10-29 | 2020-01-07 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN113956605A (en) * | 2021-12-03 | 2022-01-21 | 四川大学 | Application of oxide in preparation of resin composition capable of being selectively metallized through laser activation |
| CN116144145A (en) * | 2021-11-19 | 2023-05-23 | 广东中塑新材料有限公司 | Polyethylene terephthalate-1, 4-cyclohexanedimethanol ester composition and preparation method thereof |
| CN116162361A (en) * | 2021-11-25 | 2023-05-26 | 广东中塑新材料有限公司 | Low dielectric LCP resin material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2706092A1 (en) * | 2012-08-28 | 2014-03-12 | Ems-Patent Ag | Polyamide moulding material and its application |
-
2018
- 2018-12-28 CN CN201811626107.1A patent/CN109486165B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2706092A1 (en) * | 2012-08-28 | 2014-03-12 | Ems-Patent Ag | Polyamide moulding material and its application |
| CN103665831A (en) * | 2012-08-28 | 2014-03-26 | Ems专利股份公司 | Polyamide moulding material and its application |
Non-Patent Citations (2)
| Title |
|---|
| FISCHER A J, ET AL: "Effect of fillers on the metallization of laser-structured polymer parts", 《JOURNAL OF POLYMER ENGINEERING》 * |
| WANG HZ ET AL: "Preparation and characterization of TiO2-coated hollow glass microsphere and its flame-retardant property in thermoplastic polyurethane", 《JOURNAL OF THERMAL ANALYSIS AND CALOROMETRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655792A (en) * | 2019-10-29 | 2020-01-07 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN110655792B (en) * | 2019-10-29 | 2022-06-14 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN116144145A (en) * | 2021-11-19 | 2023-05-23 | 广东中塑新材料有限公司 | Polyethylene terephthalate-1, 4-cyclohexanedimethanol ester composition and preparation method thereof |
| CN116144145B (en) * | 2021-11-19 | 2024-06-04 | 广东中塑新材料有限公司 | Polyethylene terephthalate-1, 4-cyclohexanedimethanol ester composition and preparation method thereof |
| CN116162361A (en) * | 2021-11-25 | 2023-05-26 | 广东中塑新材料有限公司 | Low dielectric LCP resin material and preparation method thereof |
| CN116162361B (en) * | 2021-11-25 | 2024-04-09 | 广东中塑新材料有限公司 | Low dielectric LCP resin material and preparation method thereof |
| CN113956605A (en) * | 2021-12-03 | 2022-01-21 | 四川大学 | Application of oxide in preparation of resin composition capable of being selectively metallized through laser activation |
| CN113956605B (en) * | 2021-12-03 | 2023-10-24 | 四川大学 | Application of oxide in preparation of resin composition capable of being selectively metallized by laser activation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109486165B (en) | 2021-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109694572A (en) | A kind of daiamid composition and its preparation method and application | |
| CN109486165A (en) | A kind of polyphenyl ether/styrene composition and its preparation method and application | |
| TWI311162B (en) | Catalyst composition and deposition method | |
| CN106782757B (en) | A kind of printable compliant conductive slurry and its conducting wire and preparation method | |
| CN102747345B (en) | Method for chemically plating nickel on surface of copper circuit of PCB (printed circuit board) by dipping and activating nickel | |
| CN1049020C (en) | Polymeric resin for depositing catalytic palladium on a substrate | |
| CN108531045B (en) | Graphene-modified waterborne epoxy resin coating and preparation method and application thereof | |
| WO2020238144A1 (en) | Plastic electroplating method | |
| CN103774123B (en) | Selective metallization method for surface of polymer substrate, and polymer substrate with metallized patterns on surface obtained by same | |
| CN1981347A (en) | Conductive microparticle, process for producing the same and anisotropic conductive material | |
| CN103757615B (en) | Method for selectively metalizing surface of polymer base material and polymer base material prepared through method and provided with metalized pattern on surface | |
| CN109627712A (en) | A kind of PBT composition and its preparation method and application | |
| CN101684200B (en) | Plastic blending material, preparation method thereof and surface metalized plastic part | |
| CN114260450B (en) | Silver-plated micron-sized particles and preparation method and application thereof | |
| CN109694564A (en) | A kind of hollow metal oxide particle, preparation method, purposes and the polycarbonate compositions comprising it | |
| CN104575668B (en) | A kind of nanometer antiwear conductive silver paste | |
| JP3498184B2 (en) | Highly conductive composition | |
| CN103756370A (en) | Electro-conductive pearlescent pigment | |
| CN114369817A (en) | Preparation method and application of chemical black nickel plating solution | |
| JPH06215631A (en) | Fiber-like conductive substance and conductive resin composition containing it | |
| CN116178938B (en) | Flame-retardant polyamide 6 composite material and preparation method thereof | |
| CN115873382B (en) | Polybutylene terephthalate composition and preparation method thereof | |
| WO2007072912A1 (en) | Conductive fine particle and anisotropic conductive material | |
| CN116144102B (en) | High-toughness polypropylene material and preparation method thereof | |
| CN116144145B (en) | Polyethylene terephthalate-1, 4-cyclohexanedimethanol ester composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Huaicai Inventor after: Xie Ping Inventor after: Liang Zhenfeng Inventor after: Liu Yuling Inventor before: Zhu Huaicai |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 355, Bubugao Avenue, Wushajiangbei, Chang'an Town, Dongguan City, Guangdong Province, 523859 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: No.355, Bubugao Avenue, Wusha, Chang'an, Dongguan, Guangdong, 523859 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |
|
| CP03 | Change of name, title or address |