CN106589897A - Polyphenyl ether resin mixture - Google Patents
Polyphenyl ether resin mixture Download PDFInfo
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- CN106589897A CN106589897A CN201611051107.4A CN201611051107A CN106589897A CN 106589897 A CN106589897 A CN 106589897A CN 201611051107 A CN201611051107 A CN 201611051107A CN 106589897 A CN106589897 A CN 106589897A
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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
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a high-frequency polyphenyl ether resin mixture low in dielectric constant and dielectric loss. By adding proper modified resin, flexibilizer, compatilizer, inorganic filler, flame retardant and the like in polyphenyl ether resin and conducting optimal combination, the processability of the polyphenyl ether resin mixture can be greatly improved, and the dielectric property, flame resistance, weather resistance, heat resistance, impact resistance and the like all meet all actual use requirements of high-frequency plastic. The polyphenyl ether resin mixture is simple in the operation process, mild in preparation condition, low in production cost and capable of achieving batched and large-scale production easily and has a good industrial production basis and wide application prospect.
Description
Technical field
The present invention relates to the high frequency polyphenylene oxide resin mixture of a kind of low-k, low-dielectric loss.
Background technology
Nowadays, information electronic industries are in the high speed development stage, are just progressively becoming one of pillar industry of various countries.As
The HF plastic of one of information electronic industries critical material, is widely used in communication base station, satellite, automatic vending machine, computer, handss
Machine or even the wearable device for progressively rising, pilotless automobile, unmanned plane and intelligent robot.HF plastic of new generation just court
Low-k, low-dielectric loss, high intensity, high-weatherability, high heat conduction, resistance to transconversion into heat, high flame retardant, lightweight and low cost
Develop Deng direction, related R＆D work has attracted the extensive concern of various countries' industrial quarters and academia.
Polyphenylene oxide resin heat-mechanical performance is excellent, resistance to acids and bases is good, dielectric constant（It is 2.45 during 1MHz）And dielectric loss
（It is 0.0007 during 1MHz）Low, glass transition temperature is high, water absorption is poor, density is low, with self-extinguishment, can be used as of future generation high
Frequency matrix material.But, pure polyphenylene oxide resin melting viscosity is big, it is difficult to process；Its fusing point and glass transition temperature are close, difficult
To bear the high temperature processing technique of HF plastic production.Chinese patent CN201410712708 is with polystyrene as modified resin
The processability of polyphenylene oxide is improved, then with suitable block copolymer as toughener, filling is made with proper amount of inorganic filler
It is standby to have obtained dielectric properties preferably composite.But, on the one hand, real excellent HF plastic needs to meet 10GHz and is
Application demand to higher frequency, the test frequency of CN201410712708 intermediaries unit for electrical property parameters is very low, only 1GHz；Separately
On the one hand, the composite that CN201410712708 is provided can not meet the growing base to the fire-retardant performance of composite
This requirement, the anti-flammability of material is concerning many aspects such as Environmental security, property safety and personal safeties.Chinese patent
CN104774476A is devoted to improving the flame-retarding characteristic of polyphenylene oxide based composites by introducing phosphor-containing flame-proof compositionss.But,
It is single that with phosphorus-containing composition as fire retardant, its addition is high, but because the dielectric loss of its own it is larger, preparation-obtained compound Jie
The dielectric loss factor of electric material is also very big, up to 0.005 ~ 0.007 in the case of 10GHz.Additionally, CN104774476A passes through
Introducing crosslinked agent solidifies polyphenylene oxide matrix composite system.In fact, people further developed the heat of other various polyphenylene oxide resins
The allylation of solidity modified method, such as polyphenylene oxide（《Insulant》, 2001,1,28-33）, cyanate modified polyphenylene oxide
（JP 08239566,1996）, polyolefin modified polyphenylene oxide（JP03269910,1991）With epoxide modified polyphenylene oxide（USP
4853423,1989）Deng, but these method operating processes complexity, cost are high.Chinese patent CN 20091010922 with
Styrene based copolymer containing epoxide group or anhydride group is as compatilizer, with polyethylene terephthalate as modified resin
Improve the processability of polyphenylene oxide.But, after the inorganic filler for introducing regulation and control composite dielectric properties, it will directly damage
Lose the mechanical strength and toughness of composite.Additionally, CN 20091010922 is fire-retardant with bromide fire retardant or organophosphorus compoundses
Agent is the fire retardant of polyphenylene oxide based composites, and the former causes serious environmental issue because burning produces noxious substance,
Progressively it is substituted；The latter then equally exists the higher problem of dielectric loss.
The content of the invention
It is an object of the invention to provide a kind of polyphenylene oxide resin mixture, it contains following several materials as necessary group
Point：1）Resin, wherein polyphenylene oxide resin account for 10 ~ 90wt% of the polyphenylene oxide resin mixture；Modified resin, accounts for the polyphenyl
0 ~ 90wt% of ether resin mixture；2）Compatilizer, accounts for 0 ~ 50wt% of the polyphenylene oxide resin mixture；3）Inorganic filler, accounts for
0 ~ 80wt% of the polyphenylene oxide resin mixture；4）Auxiliary agent, accounts for 0 ~ 50wt% of the polyphenylene oxide resin mixture.
Pin of the present invention by add in polyphenylene oxide resin suitable modified resin, toughener, compatilizer, inorganic filler and
Fire retardant, and optimum organization so that the processability of polyphenylene oxide resin mixture is substantially improved, its dielectric properties, anti-flammability,
Weatherability, thermostability and impact strength etc. have been satisfied by every actual operation requirements of HF plastic.Operating process of the present invention
Simply, preparation condition is gentle, low production cost, it is easy to mass, large-scale production, with good industrialized production basis and
Wide application prospect.
In the present invention, one or more in homopolymer that described polyphenylene oxide resin is as follows or copolymer it is mixed
Compound：
Wherein R1For hydrogen atom, alkyl or aryl, R2For hydrogen atom, alkyl or aryl, R3For hydrogen atom, alkyl or aryl, R4For
Hydrogen atom, alkyl or aryl；Two ends wave represents macromolecular chain.
In the present invention, described modified resin includes polyolefin, polyamide, polyimides, polyether-ketone, polyether-ether-ketone, poly-
Carbonic ester, polyphenylene sulfide, polyether sulphone, polyaryl thioether sulfone, PAEK, polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile,
It is polyaryl thioether sulfone nitrile, polyphenylene quinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyester, polyurethane, polyformaldehyde, poly-
Carbonic ester, acrylonitrile-styrene-acrylic ester copolymer, acrylonitritrile-styrene resin, methacrylate-styrene are common
Polymers, acrylonitrile-butadiene-styrene copolymer, ethylene-tetrafluoroethylene copolymer, butadiene-styrene rubber, nitrile rubber and cellulose
And its mixture of one or more in derivant；The melt index of described modified resin is 3 ~ 30g/min.
In the present invention, described compatilizer includes SEBS, styrene-butadiene-styrene, styrene-isoamyl
Diene-styrene copolymer, styrene-polyolefin-styrol copolymer, also including SEBS, s-B-S
Copolymer, styrene-isoprene-styrene copolymer and styrene-polyolefin-styrol copolymer and maleic anhydride or horse
Come imido copolymer and its derivant, also including described modified resin and maleic anhydride, maleimide, SEBS, benzene
Ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-polyolefin-styrene are common
The mixture of one or more in polymers, polystyrene, polyarylether, the copolymer of poly arylidene thio-ester and its derivant.Above-mentioned phase
Hold agent and there is toughening effect, good mechanical strength and toughness can be kept while superior dielectric performance is obtained.
In the present invention, described inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、Al
(OH)3、Mg(OH)2、BaxSr1-xTiO3(x=1~0)、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、
Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、
MgZrO3、SrZrO3、ZnZrO3, graphite, graphite oxide, fluorographite, Pulvis Talci, mica powder, the one kind in Kaolin and clay
Or several mixture.
In the present invention, described auxiliary agent is the one kind in main flame retardant, secondary fire retardant, antioxidant, releasing agent and coupling agent
Or various mixture.
In the present invention, described main flame retardant is magnalium flame retardant（Such as magnesium hydroxide, aluminium hydroxide）, boron zinc system resistance
Combustion agent（Such as Borax, sodium metaborate, Firebrake ZB）, molybdenum stannum flame retardant（Such as zinc, molybdenum oxide）, antimony oxide and its
The mixture of one or more in derivant；Described secondary fire retardant is phosphorus flame retardant（Such as the double (diphenylphosphines of resorcinol
Acid esters), triphenyl phosphate etc.）And nitrogenated flame retardant（Such as melamine cyanurate, polyphosphoric acid melamine）And its derivant
In one or more of mixture.
In the present invention, described antioxidant is phosphite antioxidant（Such as three (2,4- di-tert-butyl-phenyls) phosphorous
Acid esters, two (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites etc.）, Hinered phenols antioxidant（Such as four [β-
(3,5- di-tert-butyl-hydroxy phenyls) propanoic acid] pentaerythritol ester, hexanediol [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] ester etc.）, suffocated amine antioxidant（Such as secondary diarylamine, ketoamine）, containing sulphur ester antioxidant（Such as thiodipropionic acid dilauryl
Osmanthus ester etc.）, matal deactivator（Such as N, the hydrazides of N- diacetyls adipyl two etc.）, one or more in ZnS, ZnO and MgO
Mixture.
In the present invention, described releasing agent is fatty acid（Such as stearic acid, Palmic acid, lauric acid）, soap（As firmly
Fat acid calcium, zinc stearate etc.）, fatty acid ester（Such as stearyl stearate, glycerol tristearate, the double stearates of tetramethylolmethane
Deng）, amide-type（Erucyl amide）, paraffin, glycerol, vaseline, silicone powder, silicone oil（Such as polydimethylsiloxane）, polyolefin
Wax（Such as Tissuemat E, polypropylene wax）, oxidized polyolefin waxes（Such as OPE, its chlorinated polypropylene wax）, Pulvis Talci,
The mixture of one or more in mica powder, potter's clay and clay and its derivant.
In the present invention, described coupling agent is silane coupler（Such as KH550, KH570）, titanate coupling agent（Such as
TMC-201, TMC-102, DN-101 etc.）, aluminate coupling agent（Such as SG-Al821, DL-411-A, DL-411-B）, borate
Coupling agent, zirconium ester coupling agent（Such as ZR-801, ZR-802）, rare-earth coupling agent（Such as DN-903, DN-931）, phosphate ester idol
Connection agent（Such as DN-27, DN-37）With the mixture of one or more in sulfonyl azide coupling agent and its derivant.
Specific embodiment
A kind of low-k, the height of low-dielectric loss that the present invention is provided are further described by the following examples
Frequency polyphenylene oxide resin mixture.However, the embodiment is merely possible to provide explanation, rather than limit the present invention.
Embodiment 1
By 70 parts of polyphenylene oxide resins（Husky Bick PPO640）, 30 parts of polypropylene（Yanshan Petrochemical K9026）, 15 parts of compatilizer SEBS
（SEBS G1652 rise in section）, 20 parts of aluminium oxidies（Zibo perseverance nation）, 10 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.7 part of silane
Coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 1010（Nanjing Milan chemical industry）, 0.5 part of stearic acid release agent
Zinc（Plastic additive processing company limited is protected in Hebei celebrating）, 30 parts of main flame retardant magnesium hydroxide（The refined precious MAGNIFIN H-5 in the U.S.）、2
Part time combustion inhibitor bisphenol A bis-bis-（Diphenyl phosphoester）（BDP, the normal space chemical industry in Changzhou）Jing high-speed stirred mix homogeneously.Will be above-mentioned mixed
Compound is sent in extruder, fully melts in the shearing, mixing and course of conveying in screw rod, disperses, then Jing head extrusions, drawing
Bar, cooling, pelletizing.The temperature control that each section of screw extruder is 270 ~ 290oBetween C, screw speed is 200rmp/min.System
The standby compound particle for obtaining is molded into the standard batten of test by standard size Jing, and its result is as shown in table 1.
Embodiment 2
By 60 parts of polyphenylene oxide resins（Husky Bick PPO640）, 40 parts of polyether-ether-ketones（Win wound VESTAKEEP1000G）, 20 parts it is compatible
Agent SEBS（SEBS G1652 rise in section）, 20 parts of silicon oxides（Xinyi Hong Run）, 20 parts of titanium oxides（Just magnificent science and technology in Tianjin）、0.8
Part Silane coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 225（Ciba refines）, 0.5 part of releasing agent Hard Fat
Sour zinc（Plastic additive processing company limited is protected in Hebei celebrating）, 10 parts of main flame retardant antimony oxides（Dongguan City Jeff's fire proofing
Company limited）, 20 parts of aluminium hydroxide（Weifang Far East rubber and plastic science and technology）, 3 parts combustion inhibitor bisphenol A bis-bis-（Diphenyl phosphoester）
（BDP, the normal space chemical industry in Changzhou）With Jing high-speed stirred mix homogeneously.Said mixture is sent in extruder, shearing in screw rod,
Fully melt in mixing and course of conveying, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.The temperature that each section of screw extruder
Degree control is 280 ~ 300oBetween C, screw speed is 200rmp/min.The compound particle for preparing is molded by standard size Jing
Into the standard batten of test, its result is as shown in table 1.
Embodiment 3
By 55 parts of polyphenylene oxide resins（Husky Bick PPO646）, 10 parts of polystyrene（Strange U.S. PG-383）, 35 parts of ABS resin（It is strange beautiful
PA-717C）, 25 parts of compatilizer styrene-maleic anhydride copolymers（Cray Willie SMA4000）, 35 parts of titanium oxides（In Tianjin just
Magnificent science and technology）, 0.7 part of Silane coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 215（Ciba refines）、0.8
Part releasing agent pentaerythritol stearate（Shenxian County nova oils and fatss company limited）, 35 parts of main flame retardant magnesium hydroxide（The refined treasured in the U.S.
MAGNIFIN H-5）, 3 parts fire retardant resorcinols it is double (diphenyl phosphoester)（RDP, the normal space chemical industry in Changzhou）Jing high-speed stirred
Mix homogeneously.Said mixture is sent in extruder, is fully melted in the shearing, mixing and course of conveying in screw rod, is disperseed,
Jing head extrusions, tie rod, cooling, pelletizing again.The temperature control that each section of screw extruder is 240 ~ 270oBetween C, screw speed
For 200rmp/min.The compound particle for preparing is molded into the standard batten of test, its result such as table 1 by standard size Jing
It is shown.
Embodiment 4
By 180 parts of polyphenylene oxide resins（Husky Bick PPO646）, 6 parts of ASA resins（BASF ASA778T）, 2 parts of compatilizer benzene second
Alkene-copolymer-maleic anhydride（Cray Willie SMA4000）, 4 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 2 parts of silane couplers
KH550（Nanjing Shuguang Chemical General Plant）, 1 part of antioxidant 1010（Nanjing Milan chemical industry）, 1 part of antioxidant 618（Nanjing Milan
Work）, 1.2 parts of stearic acid release agent calcium（Plastic additive processing company limited is protected in Hebei celebrating）, 2 parts of main flame retardant magnesium hydroxide（It is beautiful
The refined precious MAGNIFIN H-5 of state）, 0.8 part fire retardant resorcinol it is double (diphenyl phosphoester)（RDP, the normal space chemical industry in Changzhou）Jing
High-speed stirred mix homogeneously.Said mixture is sent in extruder, is fully melted in the shearing, mixing and course of conveying in screw rod
Change, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.The temperature control that each section of screw extruder is 285 ~ 305oBetween C,
Screw speed is 200rmp/min.The compound particle for preparing is molded into the standard batten of test by standard size Jing, its
As a result it is as shown in table 1.
Embodiment 5
By 40 parts of polyphenylene oxide resins（Husky Bick PPO640）, 60 parts of ABS resin（Strange U.S. PA-717C）, 10 parts of compatilizer SEBS（Section
Rise SEBS G1652）, 10 parts of silicon oxides（Xinyi Hong Run）, 30 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.8 part it is silane coupled
Agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 1010（Nanjing Milan chemical industry）, 0.5 part of releasing agent Fischer-Tropsch wax（Day
This fine wax Co., Ltd. FT115）, 40 parts of main flame retardant aluminium hydroxide（Weifang Far East rubber and plastic science and technology）With 2 parts fire retardant bis-phenols
A- is double（Diphenyl phosphoester）（BDP, the normal space chemical industry in Changzhou）Jing high-speed stirred mix homogeneously.Said mixture is sent into into extruder
In, fully melt in the shearing, mixing and course of conveying in screw rod, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.Spiral shell
The temperature control that each section of bar extruder is 225 ~ 250oBetween C, screw speed is 200rmp/min.The compound particle for preparing
The standard batten of test is molded into by standard size Jing, its result is as shown in table 1.
Embodiment 6
By 20 parts of polyphenylene oxide resins（Husky Bick PPO646）, 100 parts of polystyrene（Strange U.S. PG-383）, 10 parts of compatilizer SEBS
（SEBS G1652 rise in section）, 10 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 1 part of Silane coupling agent KH550（Nanjing dawn chemical industry
Head factory）, 1 part of antioxidant 1010（Nanjing Milan chemical industry）, part releasing agent silicone powder（The limited public affairs of triumphant outstanding high molecule plastic toughening material
Department）, 55 parts of main flame retardant magnesium hydroxide（The refined precious MAGNIFIN H-5 in the U.S.）With 3 parts fire retardant resorcinol pair (diphenyl
Phosphate ester)（RDP, the normal space chemical industry in Changzhou）Jing high-speed stirred mix homogeneously.Said mixture is sent in extruder, in screw rod
Fully melt in shearing, mixing and course of conveying, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.Each section of screw extruder
Temperature control 215 ~ 235oBetween C, screw speed is 190rmp/min.The compound particle for preparing is by standard size Jing
The standard batten of test is molded into, its result is as shown in table 1.
Comparative example 1
By 115 parts of polyphenylene oxide resins（Husky Bick PPO640）, 20 parts of aluminium oxidies（Zibo perseverance nation）, 10 parts of titanium oxides（In Tianjin just
Magnificent science and technology）, 0.7 part of Silane coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 1010（Nanjing Milan
Work）, 0.5 part of stearic acid release agent zinc（Plastic additive processing company limited is protected in Hebei celebrating）, 30 parts of main flame retardant magnesium hydroxide（It is beautiful
The refined precious MAGNIFIN H-5 of state）, 2 parts combustion inhibitor bisphenol A bis-bis-（Diphenyl phosphoester）（BDP, the normal space chemical industry in Changzhou）Jing is at a high speed
It is uniformly mixed.Said mixture is sent in extruder, fully melt in the shearing, mixing and course of conveying in screw rod,
Dispersion, then Jing head extrusions, tie rod, cooling, pelletizing.The temperature control that each section of screw extruder is 330 ~ 360oBetween C, screw rod
Rotating speed is 200rmp/min.The compound particle for preparing is molded into the standard batten of test, its result by standard size Jing
As shown in table 1.
Comparative example 2
By 70 parts of polyphenylene oxide resins（Husky Bick PPO640）, 30 parts of polypropylene（Yanshan Petrochemical K9026）, 15 parts of compatilizer SEBS
（SEBS G1652 rise in section）, 20 parts of aluminium oxidies（Zibo perseverance nation）, 10 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.7 part of silane
Coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 1010（Nanjing Milan chemical industry）With 0.5 part of releasing agent Hard Fat
Sour zinc（Plastic additive processing company limited is protected in Hebei celebrating）Jing high-speed stirred mix homogeneously.Said mixture is sent into into extruder
In, fully melt in the shearing, mixing and course of conveying in screw rod, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.Spiral shell
The temperature control that each section of bar extruder is 255 ~ 275oBetween C, screw speed is 200rmp/min.The compound particle for preparing
The standard batten of test is molded into by standard size Jing, its result is as shown in table 1.
Comparative example 3
By 70 parts of polyphenylene oxide resins（Husky Bick PPO640）, 30 parts of polypropylene（Yanshan Petrochemical K9026）, 15 parts of compatilizer SEBS
（SEBS G1652 rise in section）, 20 parts of aluminium oxidies（Zibo perseverance nation）, 10 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.7 part of silane
Coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 0.5 part of antioxidant 1010（Nanjing Milan chemical industry）, 0.5 part of stearic acid release agent
Zinc（Plastic additive processing company limited is protected in Hebei celebrating）, 35 parts of combustion inhibitor bisphenol A bis-bis-（Diphenyl phosphoester）（BDP, Changzhou is normal
Space chemical industry）Jing high-speed stirred mix homogeneously.Said mixture is sent in extruder, shearing in screw rod, is kneaded and was conveyed
Fully melt in journey, disperse, then Jing head extrusions, tie rod, cooling, pelletizing.The temperature control that each section of screw extruder 255 ~
275oBetween C, screw speed is 200rmp/min.The compound particle for preparing is molded into the mark of test by standard size Jing
Quasi- batten, its result is as shown in table 1.
As shown in comparative example 1, in the case where introducing modified resin and compatilizer is not added, the processing of polyphenylene oxide compound system
Temperature is up to 330 ~ 360oC, high temperature causes fire retardant magnesium hydroxide to there occurs Partial digestion in process, reduces compound
The fire resistance of dielectric material；Meanwhile, the mechanical performance of composite is also because the effect such as shear at high temperature-degraded also there occurs necessarily
Decline.If the processing characteristics for not selecting fire retardant, polyphenylene oxide compound system is improved, as shown in comparative example 2, but now not
The basic demand of actually used occasion polyphenylene ether HF plastic fire resistance can be met.If additionally, only using phosphorus system etc.
Secondary fire retardant, the fire resistance of composite can ensure that, but because the dielectric loss of phosphorus system grade fire retardant itself is larger, most
The dielectric loss factor of the polyphenylene oxide based composites for preparing eventually also steeply rises, and up to 0.008, as shown in comparative example 3.
Therefore, the present invention by add simultaneously in polyphenylene oxide resin suitable modified resin, toughener, compatilizer, inorganic filler and
Fire retardant, and optimization of C/C composites, reasonable combination so that while the processing characteristics of polyphenylene oxide resin mixture is significantly improved,
Its dielectric properties, anti-flammability, weatherability, thermostability and impact strength etc. have been satisfied by the every actually used of HF plastic will
Ask, shown in the result of embodiment 1 ~ 6.Operating process of the present invention is simple, and preparation condition is gentle, low production cost, it is easy to mass, rule
Modelling is produced, with the basic and wide application prospect of good industrialized production.
Above example is not imposed any restrictions to the content of compositionss in the present invention.Every technology reality according to the present invention
Any trickle amendment, equivalent variations and modification that matter or compositionss composition or content are made to above example, still fall within this
In the range of inventive technique scheme.
Claims (10)
1. a kind of polyphenylene oxide resin mixture, it is characterised in that containing following several materials as necessary component：
1）Resin, wherein polyphenylene oxide resin account for 10 ~ 90wt% of the polyphenylene oxide resin mixture, and modified resin accounts for the polyphenyl
0 ~ 90wt% of ether resin mixture；
2）Compatilizer, accounts for 0 ~ 50wt% of the polyphenylene oxide resin mixture；
3）Inorganic filler, accounts for 0 ~ 80wt% of the polyphenylene oxide resin mixture；
4）Auxiliary agent, accounts for 0 ~ 50wt% of the polyphenylene oxide resin mixture.
2. polyphenylene oxide resin mixture as claimed in claim 1, it is characterised in that described polyphenylene oxide resin is as follows
Homopolymer or copolymer in one or more of mixture：
Wherein R1For hydrogen atom, alkyl or aryl, R2For hydrogen atom, alkyl or aryl, R3For hydrogen atom, alkyl or aryl, R4For
Hydrogen atom, alkyl or aryl, two ends wave represents macromolecular chain.
3. polyphenylene oxide resin mixture as claimed in claim 1, it is characterised in that described modified resin comprising polyolefin,
Polyamide, polyimides, polyether-ketone, polyether-ether-ketone, Merlon, polyphenylene sulfide, polyether sulphone, polyaryl thioether sulfone, polyarylether
Ketone, polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile, polyaryl thioether sulfone nitrile, polyphenylene quinoxaline, phenolic resin, asphalt mixtures modified by epoxy resin
Fat, cyanate ester resin, polyester, polyurethane, polyformaldehyde, Merlon, acrylonitrile-styrene-acrylic ester copolymer, propylene
Nitrile-styrol copolymer, methacrylate-styrol copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-four
The mixture of one or more in fluoride copolymers, butadiene-styrene rubber, nitrile rubber and cellulose and its derivates；It is described to change
Property resin melt index be 3 ~ 30g/min.
4. polyphenylene oxide resin mixture as claimed in claim 1, it is characterised in that described compatilizer includes SEBS, benzene second
Alkene-BS, styrene-isoprene-styrene copolymer, styrene-polyolefin-styrene copolymerized
Thing, also including SEBS, styrene-butadiene-styrene, styrene-isoprene-styrene copolymer and benzene second
Alkene-polyolefin-styrol copolymer and maleic anhydride or the copolymer and its derivant of maleimide, also including described modified
Resin and maleic anhydride, maleimide, SEBS, styrene-butadiene-styrene, styrene-isoprene-benzene
Ethylene copolymer, styrene-polyolefin-styrol copolymer, polystyrene, polyarylether, the copolymer of poly arylidene thio-ester and its spread out
The mixture of one or more in biology.
5. polyphenylene oxide resin mixture as claimed in claim 1, it is characterised in that described inorganic filler is SiO2、Al2O3、
TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、Al(OH)3、Mg(OH)2、BaxSr1-xTiO3(x=1~0)、Mg2TiO4、Bi2
(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、
MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, graphite, graphite oxide, fluorine
One kind or several mixture in graphite, Pulvis Talci, mica powder, Kaolin and clay.
6. polyphenylene oxide resin mixture as claimed in claim 1, it is characterised in that described auxiliary agent is main flame retardant, secondary resistance
The mixture of one or more in combustion agent, antioxidant, releasing agent and coupling agent.
7. polyphenylene oxide resin mixture as claimed in claim 6, it is characterised in that described main flame retardant is that high purity alumina-magnesia is fire-retardant
The mixture of one or more in agent, boron zinc flame retardant, molybdenum stannum flame retardant, antimony oxide and its derivant；It is described
Secondary fire retardant be one or more in phosphorus flame retardant and nitrogenated flame retardant and its derivant of mixture.
8. polyphenylene oxide resin mixture as claimed in claim 6, it is characterised in that described antioxidant is anti-for phosphorous acid esters
Oxidant, Hinered phenols antioxidant, suffocated amine antioxidant, containing in sulphur ester antioxidant, matal deactivator, ZnS, ZnO and MgO
One or more of mixture.
9. polyphenylene oxide resin mixture as claimed in claim 6, it is characterised in that described releasing agent is fatty acid, fat
Hydrochlorate, fatty acid ester, amide-type, paraffin, glycerol, vaseline, silicone powder, silicone oil, polyolefin-wax, oxidized polyolefin waxes, Talcum
The mixture of one or more in powder, mica powder, potter's clay and clay and its derivant.
10. polyphenylene oxide resin mixture as claimed in claim 6, it is characterised in that described coupling agent be silane coupler,
Titanate coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent and
The mixture of one or more in sulfonyl azide coupling agent and its derivant.
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