CN106928688B - A kind of modified polyphenyl ether material and preparation method thereof of low-dielectric loss high thermal conductivity - Google Patents
A kind of modified polyphenyl ether material and preparation method thereof of low-dielectric loss high thermal conductivity Download PDFInfo
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- 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
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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Abstract
The present invention relates to a kind of modified polyphenyl ether materials and preparation method thereof of low-dielectric loss high thermal conductivity, the polyphenyl ether material includes the component of following parts by weight: 20~55 parts of polyphenylene oxide, 5~25 parts of polystyrene, 5~10 parts of toughener, 35~65 parts of filler, 1~3 part of lubricant, 0.2~0.5 part of antioxidant；Above-mentioned polyphenyl ether material is prepared by the following method: (1) weighing filler and lubricant, and be pre-mixed the heat filling in filler to obtain premix heat filling with lubricant；(2) polyphenylene oxide, polystyrene, toughener, antioxidant are weighed again, are mixed together uniformly with premix heat filling, are obtained mixture；(3) it adds mixture into screw extruder, and low dielectric filler is added from side spout simultaneously, melting extrusion tie rod pelletizing is to get purpose product.Compared with prior art, the present invention has many advantages, such as that processing performance is good, the high and low dielectric loss of heating conduction.
Description
Technical field
The present invention relates to a kind of polyphenyl ether materials and preparation method thereof, more particularly, to a kind of low-dielectric loss high thermal conductivity
Modified polyphenyl ether material and preparation method thereof.
Background technique
With the continuous development of industrial production and science and technology, requirement of the people to Heat Conduction Material comprehensive performance is increasingly
Height, traditional metal material can no longer meet the requirement of certain special occasions.Heat as electronic equipment generates is rapid
Accumulation and increase will lead to device cisco unity malfunction, therefore heat dissipation has become an important factor for influencing its service life in time.So anxious
Need to develop high reliability, high-cooling property excellent combination property heat-conducting insulation material replace traditional material.Heat-conducting polymer material
Material especially heat-conducting plastic is since with lightweight, the molding of resistant to chemical etching, easy processing, electrical insulation capability be excellent, mechanics and resists tired
It the features such as labor function admirable, is increasingly valued by people, is increasingly becoming the new role in thermally conductive field, it is international and domestic in recent years
The hot spot of research and development.
Polyphenylene oxide has good electric property, is that the engineering plastics dielectric loss factor is the smallest, and by frequency and temperature
The influence of degree is smaller.In addition to this, polyphenylene oxide has good heat resistance, dimensional stability and the superiority such as water absorption rate is low
Energy.
Chinese patent 201110435098.X discloses a kind of low-density PPO/PS blend alloy material, by
It contains the following parts by weight and is made: 25-55 parts of polyphenylene oxide, 15-42 parts of polystyrene, 15-30 parts of glass microballoon, toughener
5-15 parts, 0.2-0.7 parts of lubricant, 0.2-0.5 parts of antioxidant.The patent due to own material itself heating conduction relatively
Difference, and without carrying out corresponding thermally conductive modification, the electrical communications components required for high thermal conductivity are unable to satisfy so as to cause product.
Summary of the invention
It is high that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of low-dielectric loss
Thermally conductive modified polyphenyl ether material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of modified polyphenyl ether material of low-dielectric loss high thermal conductivity, the component including following parts by weight:
The polystyrene is high impact polystyrene.
The toughener is selected from block copolymer (SBS), the hydrogenated styrene/butadiene/benzene of styrene and butadiene
Ethylene block copolymer (SEBS) or maleic anhydride graft phenylethene-ethylene-butadiene-styrene block copolymer elastomer
One or more of (SEBS-g-MAH).
The filler includes 1:(4~9 in mass ratio) the low dielectric filler and heat filling of addition, wherein it is described
Low dielectric filler is hollow glass micropearl, and the heat filling is selected from one of aluminium nitride, boron nitride or aluminum oxide
Or it is several.
The lubricant be selected from one of OP wax, silicone, PE wax, silicone oil or pentaerythritol stearate (PETS) or
It is several.
The antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxygens
Agent 1010), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (antioxidant 1076) or three [bis- uncles of 2,4-
One or more of butyl phenyl] phosphite ester (irgasfos 168).
A kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity, comprising the following steps:
(1) it is 1:(4~9 by the mass ratio of low dielectric filler and heat filling) weigh 35~65 parts of filler, lubricant 1~
3 parts, heat filling and lubricant are stirred, obtain pretreatment heat filling；
(2) 20~55 parts of polyphenylene oxide, 5~25 parts of polystyrene, 5~10 parts of toughener and 0.2~0.5 part of antioxygen are weighed again
Agent, the pretreated filler obtained with step (1) are mixed together uniformly, obtain mixture；
(3) mixture obtained step (2) is added in screw extruder, and simultaneously by low dielectric filler from side spout
Be added screw extruder in, the pelletizing of melting extrusion tie rod to get arrive purpose product.
Heat filling is, the process conditions that are stirred uniform in high-speed mixer and mixing with lubricant in step (1) are as follows:
With 800~1000rpm revolving speed stirring 5~20 minutes at 100~130 DEG C.
The process conditions mixed in step (2) are as follows: in 30~60 DEG C of temperature of high mixer, with 800~1000rpm revolving speed
It is mixed into 3~10min.
Extrusion temperature in step (3) in screw extruder is 240~290 DEG C, and screw speed is 200~300rpm.
Compared with prior art, the invention has the following advantages that
(1) present invention is base-material by using the polyphenylene oxide with good dielectric properties and heat resistance, mixes polyphenyl second
Alkene increases material flowability, and the heating conduction of material is improved by being charged with filler, last polyphenyl ether material obtained
With low-dielectric loss outstanding and high thermal conductivity.
(2) hollow glass micropearl that the present invention is added during the preparation process has very low dielectric loss, and self-lubrication
Better performances can be very good to be distributed in system, so as to effectively reduce the dielectric loss factor of material, in addition, this
Invention selection side feed material adds hollow glass micropearl, also for its percentage of damage is reduced, to guarantee hollow glass as far as possible
The integrality of microballon is to reduce dielectric loss；The heat fillings such as the aluminium nitride (AlN) and boron nitride (BN) of addition simultaneously then can be big
The big heating conduction for improving material, by by heat filling in advance and mix lubricant, be higher than lubricant fusing point at a temperature of
It is lubricated pretreatment, lubricant can be made to be evenly coated at the surface of heat filling well, to reduce heat filling table
The frictional force in face, and then improve between the heat filling and other raw materials that occupy significant proportion in polyphenyl ether material or itself
Mix non-uniform problem, also solve in process because it is excessive in heat filling mantle friction, reunite etc. caused by under
Phenomena such as expecting difficult and network blocking plate greatly reduces the difficulty of processing of polyphenyl ether material, reduces screw rod abrasion, because of mixing for each raw material
It closes more evenly but also the heating conduction of last polyphenyl ether material obtained further increases.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
In following each embodiments, unless otherwise specified, the screw speed in expression screw extruder is 220rpm, high speed
Stirring then indicates speed of agitator within the scope of 800~1000rpm.
Embodiment 1
(1) each component raw material is weighed by following parts by weight: 55 parts of polyphenylene oxide, 5 parts of high impact polystyrene, SEBS5 parts, empty
5 parts of heart glass microballoon, 30 parts of boron nitride, 1 part of OP wax, 0.1 part of antioxidant 1010,0.2 part of irgasfos 168.
(2) 100 DEG C of high mixers first are added in boron nitride and OP wax, high-speed stirred 10min obtains pretreatment boron nitride, so
Remaining raw material in addition to hollow glass micropearl is mixed with pretreatment boron nitride through high mixer high speed afterwards, high mixer revolving speed is
800-1000rpm, mixing temperature are 40 DEG C, mix 10min；Double screw extruder is added in mixed material, and simultaneously from side feed
Hollow glass micropearl is added in material mouth, controls the temperature in each area at 260-290 DEG C, product can be obtained in tie rod pelletizing.
Embodiment 2
(1) each component raw material is weighed by following parts by weight: 25 parts of polyphenylene oxide, 25 parts of high impact polystyrene, 5 parts of SBS,
5 parts of hollow glass micropearl, 40 parts of aluminium nitride, 3 parts of PE wax, 0.1 part of antioxidant 1010,0.1 part of irgasfos 168；
(2) 130 DEG C of high mixers first are added in aluminium nitride and PE wax, high-speed stirred 5min obtains pretreatment aluminium nitride, then
By remaining raw material in addition to hollow glass micropearl and aluminium nitride is pre-processed through high mixer high speed mixing, and control high mixer revolving speed is
800-1000rpm, mixing temperature are 60 DEG C, mix 3min；By mixed material through double screw extruder, and simultaneously from side spout
Hollow glass micropearl is added, controls the temperature in each area at 240-275 DEG C, product can be obtained in extruder tie rod pelletizing.
Embodiment 3
(1) each component raw material is weighed by following parts by weight: 20 parts of polyphenylene oxide, 14 parts of high impact polystyrene, SEBS-g-
10 parts of MAH, 6 parts of hollow glass micropearl, 50 parts of aluminium oxide, 2 parts of silicone, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168；
(2) 120 DEG C of high mixers first are added in aluminium oxide and silicone, high-speed stirred 15min obtains pretreatment aluminium oxide, so
Remaining raw material in addition to hollow glass micropearl is mixed with pretreatment aluminium oxide through high mixer high speed afterwards, high mixer revolving speed is
800-1000rpm, mixing temperature are 50 DEG C, mix 6min；By mixed material through double screw extruder, and simultaneously from side spout
Hollow glass micropearl is added, controls the temperature in each area at 250-280 DEG C, product can be obtained in tie rod pelletizing.
Embodiment 4
(1) each component raw material is weighed by following parts by weight: 22 parts of polyphenylene oxide, 8 parts of high impact polystyrene, 8 parts of SBS, nitrogen
Change 50 parts of boron, 12 parts of hollow glass micropearl, 3 parts of silicone oil, 0.2 part of antioxidant 1076,0.2 part of irgasfos 168；
(2) 100 DEG C of high mixers first are added in boron nitride and silicone oil, high-speed stirred 20min obtains pretreatment boron nitride, so
Remaining raw material in addition to hollow glass micropearl is mixed with pretreatment boron nitride through high mixer high speed afterwards, high mixer revolving speed is
800-1000rpm, mixing temperature are 40 DEG C, mix 5min；By mixed material through double screw extruder, and simultaneously from side spout
Hollow glass micropearl is added, controls the temperature in each area at 260-280 DEG C, product can be obtained in tie rod pelletizing.
Embodiment 5
(1) each component raw material is weighed by following parts by weight: 30 parts of polyphenylene oxide, 12 parts of high impact polystyrene, 8 parts of SEBS,
35 parts of aluminium nitride, 15 parts of hollow glass micropearl, 2 parts of OP wax, 0.1 part of antioxidant 1010,0.1 part of irgasfos 168；
(2) 110 DEG C of high mixers first are added in aluminium nitride and OP wax, high-speed stirred 15min obtains pretreatment aluminium nitride, so
Remaining raw material in addition to hollow glass micropearl is mixed with pretreatment aluminium nitride through high mixer high speed afterwards, control high mixer revolving speed is
800-1000rpm, mixing temperature are 40 DEG C, mix 6min；By mixed material through double screw extruder, and simultaneously from side spout
Hollow glass micropearl is added, controls the temperature in each area at 260-280 DEG C, product can be obtained in tie rod pelletizing.
Embodiment 6
(1) each component raw material is weighed by following parts by weight: 20 parts of polyphenylene oxide, 10 parts of high impact polystyrene, 5 parts of SBS,
55 parts of aluminium oxide, 10 parts of hollow glass micropearl, 3 parts of PETS, 0.1 part of antioxidant 1010,0.2 part of irgasfos 168；
(2) 100 DEG C of high mixers first are added in aluminium oxide and PETS, high-speed stirred 10min obtains pretreatment aluminium oxide, so
Afterwards by remaining raw material and pretreatment aluminium oxide in addition to hollow glass micropearl, mixed through high mixer high speed, high mixer revolving speed is
800-1000rpm, mixing temperature are 60 DEG C, mix 5min；Single screw extrusion machine is added in mixed material, and simultaneously from side feed material
Hollow glass micropearl is added in mouth, controls the temperature in each area at 250-280 DEG C, product can be obtained in tie rod pelletizing.
The performance test of product is as shown in table 1.
Table 1
Embodiment 7
(1) each component raw material is weighed by following parts by weight: 35 parts of polyphenylene oxide, 15 parts of high impact polystyrene, 6 parts of SBS,
45 parts of aluminium oxide, 5 parts of hollow glass micropearl, 1 part of PETS, 1 part of silicone oil, 0.1 part of antioxidant 1010,0.2 part of irgasfos 168；
(2) 100 DEG C of high mixers first are added in aluminium oxide, silicone oil and PETS, stir 10min under 800rpm revolving speed, obtains
Aluminium oxide is pre-processed, then by remaining raw material and pretreatment aluminium oxide in addition to hollow glass micropearl, is mixed through high mixer high speed,
Its high mixer revolving speed is 900rpm, and mixing temperature is 60 DEG C, mixes 5min；Single screw extrusion machine is added in mixed material, and same
When from side spout hollow glass micropearl is added, control the temperature in each area at 250-280 DEG C, screw speed 200rpm, tie rod
Product can be obtained in pelletizing.
Embodiment 8
(1) each component raw material is weighed by following parts by weight: 35 parts of polyphenylene oxide, 15 parts of high impact polystyrene, 6 parts of SBS,
16 parts of aluminium oxide, 16 parts of boron nitride, 8 parts of hollow glass micropearl, 2 parts of PETS, 0.1 part of antioxidant 1010, irgasfos 168 0.2
Part；
(2) 100 DEG C of high mixers first are added in aluminium oxide, boron nitride and PETS, stir 10min under 1000rpm revolving speed, obtains
To pretreatment heat filling, then by remaining raw material and pretreatment heat filling in addition to hollow glass micropearl, through high mixer height
Speed mixes, and high mixer revolving speed is 900rpm, and mixing temperature is 60 DEG C, mixes 5min；Single screw rod is added in mixed material to squeeze out
Machine, and hollow glass micropearl is added from side spout simultaneously controls the temperature in each area at 250-280 DEG C, and screw speed is
Product can be obtained in 300rpm, tie rod pelletizing.
Embodiment 9
(1) each component raw material is weighed by following parts by weight: 35 parts of polyphenylene oxide, 15 parts of high impact polystyrene, 6 parts of SBS,
35 parts of aluminium nitride, 5 parts of hollow glass micropearl, 2 parts of PETS, 0.1 part of antioxidant 1010,0.2 part of irgasfos 168；
(2) 100 DEG C of high mixers first are added in aluminium nitride and PETS, stir 10min under 900rpm revolving speed, is pre-processed
Aluminium nitride mixes, height is mixed then by remaining raw material and pretreatment aluminium nitride in addition to hollow glass micropearl through high mixer high speed
Machine revolving speed is 900rpm, and mixing temperature is 60 DEG C, mixes 5min；Single screw extrusion machine is added in mixed material, and simultaneously from side
Hollow glass micropearl is added in spout, controls the temperature in each area at 250-280 DEG C, screw speed 250rpm, tie rod pelletizing is
Product can be obtained.
Comparative example 1
(1) each component raw material is weighed by following parts by weight: 35 parts of polyphenylene oxide, 15 parts of high impact polystyrene, 6 parts of SBS,
35 parts of aluminium nitride, 5 parts of hollow glass micropearl, 2 parts of PETS, 0.1 part of antioxidant 1010,0.2 part of irgasfos 168；
(2) high mixer high speed is added in above-mentioned raw materials to mix, high mixer revolving speed is 900rpm, mixing temperature 60
DEG C, mix 5min；Single screw extrusion machine is added in mixed material, controls the temperature in each area at 250-280 DEG C, screw speed is
Product can be obtained in 250rpm, tie rod pelletizing.
Performance detection is carried out to product made from embodiment 7~9 and comparative example 1, specific performance result is as shown in table 2 below.
Table 2
From the above results, the polyphenyl ether material being prepared compared to conventional mixing method is mixed using of the invention
The heating conduction and dielectric loss performance of polyphenyl ether material obtained by conjunction method and hybrid technique are obviously improved.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (7)
1. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity, which is characterized in that the modified polyphenyl
Ether material includes the component of following parts by weight:
20 ~ 55 parts of polyphenylene oxide,
5 ~ 25 parts of polystyrene,
5 ~ 10 parts of toughener,
35 ~ 65 parts of filler,
1 ~ 3 part of lubricant,
0.2 ~ 0.5 part of antioxidant；
The filler includes 1:(4 ~ 9 in mass ratio) the low dielectric filler and heat filling of addition, wherein the low dielectric
Filler is hollow glass micropearl, and the heat filling is selected from one or more of aluminium nitride, boron nitride or aluminum oxide；
The lubricant is selected from one or more of OP wax, PE wax, silicone oil or pentaerythritol stearate；
Preparation method the following steps are included:
(1) it is 1:(4 ~ 9 by the mass ratio of low dielectric filler and heat filling) 35 ~ 65 parts of filler are weighed, it 1 ~ 3 part of lubricant, will
Heat filling is stirred with lubricant, obtains pretreatment heat filling；
(2) 20 ~ 55 parts of polyphenylene oxide, 5 ~ 25 parts of polystyrene, 5 ~ 10 parts of toughener and 0.2 ~ 0.5 part of antioxidant are weighed again, with step
Suddenly the pretreated filler that (1) obtains is mixed together uniformly, obtains mixture；
(3) mixture for obtaining step (2) is added in screw extruder, and low dielectric filler is added from side spout simultaneously
In screw extruder, the pelletizing of melting extrusion tie rod to get arrive purpose product.
2. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is that the polystyrene is high impact polystyrene.
3. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is that the toughener is selected from styrene and the block copolymer of butadiene, hydrogenated styrene/Butadiene/Styrene are embedding
Section one or more of copolymer or maleic anhydride graft phenylethene-ethylene-butadiene-styrene block copolymer elastomer.
4. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is, the antioxidant be selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters, β-(3,
5- di-tert-butyl-hydroxy phenyl) one of propionic acid n-octadecyl alcohol ester or three [ 2,4- di-tert-butyl-phenyl ] phosphite esters
Or it is several.
5. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is that heat filling is, the process conditions that are stirred uniform in high-speed mixer and mixing with lubricant in step (1) are as follows:
With 800 ~ 1000rpm revolving speed stirring 5 ~ 20 minutes at 100 ~ 130 DEG C.
6. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is, the process conditions mixed in step (2) are as follows: mixed with 800 ~ 1000rpm revolving speed in 30 ~ 60 DEG C of temperature of high mixer
It is combined into 3 ~ 10min.
7. a kind of preparation method of the modified polyphenyl ether material of low-dielectric loss high thermal conductivity according to claim 1, special
Sign is that the extrusion temperature in step (3) in screw extruder is 240 ~ 290 DEG C, and screw speed is 200 ~ 300rpm.
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| CN107513261B (en) * | 2017-08-11 | 2020-09-04 | 深圳市吉塑工程塑料有限公司 | Modified polyphenyl ether aerogel and preparation method thereof |
| EP3591004B8 (en) * | 2018-07-06 | 2021-04-21 | SHPP Global Technologies B.V. | Thermoplastic compositions having good dielctric and ductility properties |
| US20220340802A1 (en) * | 2019-09-23 | 2022-10-27 | Amogreentech Co., Ltd. | Rf heat dissipation plasitc and repeater cabinet implemented by including same |
| CN113150528A (en) * | 2021-01-18 | 2021-07-23 | 浙江华电器材检测研究所有限公司 | High-thermal-conductivity composite material for insulating puncture wire clamp shell and preparation method thereof |
| CN113583310B (en) * | 2021-07-29 | 2023-04-11 | 无锡睿龙新材料科技有限公司 | High-thermal-conductivity hydrocarbon composition, high-frequency copper-clad plate prepared from same and preparation method of high-frequency copper-clad plate |
| CN113930003B (en) * | 2021-12-03 | 2023-09-08 | 海信视像科技股份有限公司 | MPPO material, mineral filled master batch and preparation method thereof |
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| CN103059550A (en) * | 2011-10-18 | 2013-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polystyrene blend alloy material, its preparation method and application |
| CN103421296A (en) * | 2012-05-23 | 2013-12-04 | 上海杰事杰新材料(集团)股份有限公司 | PPO/PS blend alloy material and preparation method thereof |
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| CN103172997A (en) * | 2011-12-22 | 2013-06-26 | 上海杰事杰新材料(集团)股份有限公司 | Low-density polyphenylether/polystyrene (PPO/PS) blend alloy material and preparation method thereof |
| CN103804847B (en) * | 2012-11-09 | 2017-04-12 | 合肥杰事杰新材料股份有限公司 | Polyoxymethylene composition and preparation method thereof |
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| CN103059550A (en) * | 2011-10-18 | 2013-04-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene oxide/polystyrene blend alloy material, its preparation method and application |
| CN103421296A (en) * | 2012-05-23 | 2013-12-04 | 上海杰事杰新材料(集团)股份有限公司 | PPO/PS blend alloy material and preparation method thereof |
| CN103589044A (en) * | 2013-11-15 | 2014-02-19 | 东莞市德诚塑化科技有限公司 | Plastic composition for cable and wire shielding layer and preparation method of plastic composition |
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