CN106977922A - A kind of highly heat conductive polyphenylene sulfide composite material and preparation method thereof - Google Patents

A kind of highly heat conductive polyphenylene sulfide composite material and preparation method thereof Download PDF

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CN106977922A
CN106977922A CN201710247541.8A CN201710247541A CN106977922A CN 106977922 A CN106977922 A CN 106977922A CN 201710247541 A CN201710247541 A CN 201710247541A CN 106977922 A CN106977922 A CN 106977922A
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polyphenylene sulfide
temperature
composite material
antioxidant
area
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董磊
冉汉青
侯兴忠
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Dongguan Bailixing New Material Co Ltd
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Dongguan Bailixing New Material Co Ltd
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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
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/02—Polythioethers; Polythioether-ethers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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Abstract

The invention discloses a kind of highly heat conductive polyphenylene sulfide composite material and preparation method thereof, include the component of following percentage by weight：High-crystallinity polyphenylene sulfide 30 ~ 50%；CNT 5 ~ 10%；Heat conduction master batch 30 ~ 60%；Toughener 3 ~ 5%；Surface modifier 0.5 ~ 2%；Antioxidant 0.1 ~ 1%；Wherein heat conduction master batch includes following components in percentage by weight：High-crystallinity diphenyl sulfide 20 ~ 40%；Microspheric heat filling 15 ~ 35%；Microplate type heat filling 15 ~ 35%；Surface modifier 1 ~ 3%；Antioxidant 0.1 ~ 0.5%.Preparation process includes：Ith, the preparation of high-crystallinity polyphenylene sulfide；IIth, the preparation of heat conduction master batch；IIIth, prepared by the processing of high-heat-conductive composite material.The preparation for processing of composite is as follows：（1）Weigh the gained high-crystallinity polyphenylene sulfide of above-mentioned steps I, CNT, heat conduction master batch, toughener, surface modifier and antioxidant made from step II；（2）Said components are put into blender mixing 5~15 minutes in proportion；（3）Step is gathered（2）The raw material mixed is thrown into double screw extruder, melting extrusion, granulation.While composite prepared by this method has high-termal conductivity, with preferable mechanical performance, use requirement can be met.

Description

A kind of highly heat conductive polyphenylene sulfide composite material and preparation method thereof
Technical field
Electric neck is can be widely applied to the invention belongs to polyphenylene sulfide modified engineered plastic field, more particularly to one kind The highly heat conductive polyphenylene sulfide composite material in domain and preparation method thereof.
Background technology
Polyphenylene sulfide（PPS）Also known as polyphenylene sulfide, is the extraordinary high score of crystallinity for having a large amount of phenyl ring on a kind of molecular backbone Sub- material.PPS has excellent corrosion resistance, radiation resistance and itself has self-extinguishment, non-modified PPS materials resistance Combustion grade can just reach V0/ 1.5mm, good dimensional stability and heat resistance（260 DEG C of high temperature are resistant to, temperature is used for a long time It can reach 200~220 DEG C）, not only cause PPS to have wide application in the high-end technical field such as Aero-Space, and extensively should For the civilian industry such as automobile, electric, machine-building field.But the toughness of PPS materials in itself is poor, It must be modified, can be only achieved use requirement.And non-modified PPS material conducts heat rates only have 0.226W/mK, itself leads Hot property is not good, and it is to widen the key problem in technology in PPS materials applications field to improve PPS thermal conductivity of material.
At this stage, polyphenylene sulfide（PPS）Heat conduction research is concentrated mainly on is entered using a large amount of inorganic heat fillings to PPS materials Row is modified, and the preparation method is with low cost, is adapted to large-scale promotion, and thermal conductivity of material can meet use requirement, but body A large amount of heat fillings are added in system to be difficult to be uniformly dispersed, and material property will be caused to decline, it is impossible to meet use requirement.
The A of Chinese patent CN 105062072, disclose a kind of polyphenyl thioether composite material and preparation method thereof, the patent Propose and PPS is modified using big or middle and small particle inorganic heat filling compounding, the heat-conductive composite material heat conduction of preparation Rate can reach more than 10W/mK, but mechanical property is poor.The A of Chinese patent CN 101113240, disclose a kind of heat conduction Polyphenyl thioether composite material, the patent is equally used as PPS heat fillings, the heat conduction composite wood of preparation using inorganic matters such as magnesia Material thermal conductivity is only 0.85W/mK, but declining by a relatively large margin occurs in the mechanical property of composite, it is difficult to met using will Ask.
The content of the invention
The purpose of the present invention proposes a kind of highly heat conductive polyphenylene sulfide primarily directed to above-mentioned of the prior art not enough Composite and preparation method thereof.The heat-conductive composite material that the present invention is announced has excellent heat conductivility, and mechanical performance can To meet the use requirement in each field, meanwhile, preparation cost, which does not have, significantly to be increased.
To realize the purpose of the present invention, the invention provides following technical scheme：
A kind of highly heat conductive polyphenylene sulfide composite material, based on quality 100%, includes：
High-crystallinity polyphenylene sulfide 30 ~ 50%；
CNT 5 ~ 10%；
Heat conduction master batch 35 ~ 60%；
Toughener 3 ~ 5%；
Surface modifier 0.5 ~ 2%；
Antioxidant 0.1 ~ 1%；
The heat conduction master batch includes based on quality 100%：
High-crystallinity polyphenylene sulfide 28 ~ 40%；
Microspheric heat filling 15 ~ 35%；
Microplate type heat filling 15 ~ 35%；
Surface modifier 1 ~ 3%；
Antioxidant 0.1 ~ 0.5%；
The high-crystallinity polyphenylene sulfide includes based on quality 100%：
Linear polyphenylthioether 95 ~ 98%；
Stabilizer 0.5 ~ 3%；
Antioxidant 0.1 ~ 1%；
Nucleator 0.5 ~ 1%.
Preferably, the linear polyphenylthioether weight average molecular weight is 20000~50000.
Preferably, the stabilizer be double-resorcinol group triazine, double -2,2,6, the 6- tetramethyl piperidine alcohol esters of decanedioic acid, 1- methyl -8-（1,2,2,6,6- pentamethyl -4- piperidines）Sebacate and double（1,2,2,6,6- pentamethyl -4- piperidines）Decanedioic acid The mixture of one or both of ester.
Preferably, the nucleator is nano silicon, nano-calcium carbonate, methylene bis (2,4- di-tert-butyl phenoxy group) The mixture of one or both of sodium phosphate, aryl carboxylic acid diamides or dibenzal sorbitol.
Preferably, the toughener is ethylene-octene-maleic anhydride terpolymer, ethylene-methyl acrylate-methyl One kind in benzene olefin(e) acid ethylene oxidic ester terpolymer, thermoplastic polyester elastomer or maleic anhydride graft thermoplastic polyurethane Or two kinds of interworking thing.
Preferably, the surface modifier is monoalkoxy phosphate titanate coupling agent, the coupling of pyrophosphoric acid type titanate esters One or more of mixtures in agent, aliphatic acid titanate coupling agent or Silane coupling agent KH550.
Preferably, the heat filling is microspheric heat filling or microplate type heat filling, and the microspheric heat conduction is filled out Material particle diameter is the mesh of 2000 mesh~2500, is one kind of magnesia, aluminum oxide or aluminium nitride；The heat filling is microplate type heat conduction Filler is one kind of graphene, boron nitride or silicon nitride.
Preferably, the antioxidant be antioxidant 1010, high-temperature anti-oxidant 412S, high-temperature anti-oxidant PEPQ, One or both of antioxidant PEP36 or antioxidant 626 mixture.
A kind of preparation method of highly heat conductive polyphenylene sulfide composite material, comprises the following steps：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 95 ~ 98%；
Stabilizer 0.5 ~ 3%；
Antioxidant 0.1 ~ 1%；
Nucleator 0.5~1%
The said components weighed are put into high-speed mixer, incorporation time is 5~15min, obtains premix, premix is placed in In banbury, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenyl using 180 DEG C of heat treatment half an hour After thioether crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury For：250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 28 ~ 40%；
Microspheric heat filling 15 ~ 35%；
Microplate type heat filling 15 ~ 35%；
Surface modifier 1 ~ 3%；
Antioxidant 0.1 ~ 0.5%；
Said components are put into blender mixing 5~15 minutes in proportion；The above-mentioned raw material mixed is thrown into double spiral shells In bar extruder, melting extrusion granulation obtains heat conduction master batch；Heat filling has aluminum oxide, magnesia, zinc oxide, aluminium nitride, nitrogen Change boron, carborundum etc.；Wherein, especially based on micron grade aluminum oxide, silicon powder, nano aluminium oxide, nitride is as high heat conduction The filling powder in field；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 30 ~ 50%；
CNT 5 ~ 10%；
Heat conduction master batch 35 ~ 60%；
Toughener 3 ~ 5%；
Surface modifier 0.5 ~ 2%；
Antioxidant 0.1 ~ 1%；
Said components are put into blender mixing 5~15 minutes in proportion；The above-mentioned raw material mixed is thrown into double spiral shells In bar extruder, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, the temperature in the area of temperature control one for 240~ 290℃；The temperature in the area of temperature control two is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；The temperature in the area of temperature control five is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven Spend for 260~310 DEG C；The temperature in the area of temperature control eight is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature For 260~310 DEG C；Rotating speed is 350~450r/min.
Beneficial effects of the present invention：
1. passing through stabilization processes before matrix material processing of the present invention, the reactable of base material in process in itself is relatively low, The degree of cross linking of process base material is greatly lowered, and polyphenylene sulfide strand has higher regularity, and crystallinity is higher, more holds Easily form passage of heat.
Change 2. first addition coupling agent in heat conduction master batch, preparation process is made in inorganic heat filling by the present invention as surface Property agent, heat filling and polyphenylene sulfide base material form chemical bridged linkage in the presence of coupling agent, beneficial to point of heat filling Dissipate；The formation of this chemical bridged linkage, contributes to heat conduction master batch further disperseing in heat-conductive composite material.
3. the present invention prepares conductive agglomerate using microspheric and microplate type heat filling compounding, microplate type filler has larger Surface area, be more likely formed heat conduction network, but the easy viscosity of increase material, and microspheric heat filling surface area is smaller, to material The viscosity influence very little of material, both interworkings as heat conduction master batch heat filling, formed heat conduction network while, to material Performance impact is smaller.
4. the present invention is using CNT as one of heat filling, its heat transfer efficiency is higher but expensive, the present invention Simply as auxiliary heat conduction filler, addition is less will not to increase considerably material cost, but contribute to form perfect Thermal conducting path.
Embodiment
Embodiment 1
A kind of preparation method of highly heat conductive polyphenylene sulfide composite material, comprises the following steps：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 95%；
Stabilizer 3%；
Antioxidant 1%；
Nucleator 1%
The said components weighed are put into high-speed mixer, incorporation time is 15min, obtains premix, premix is placed in close In mill, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenylene sulfide using 180 DEG C of heat treatment half an hour After ether crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury For：250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 40%；
Microspheric heat filling 25%；
Microplate type heat filling 33.9%；
Surface modifier 1%；
Antioxidant 0.1%；
Said components are put into blender mixing 5 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains heat conduction master batch；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
The % of high-crystallinity polyphenylene sulfide 30；
CNT 10%；
Heat conduction master batch 52%；
Toughener 5%；
Surface modifier 2%；
Antioxidant 1%；
Said components are put into blender mixing 5 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
The linear polyphenylthioether weight average molecular weight is 20000~50000.
The stabilizer is double-resorcinol group triazine.
The nucleator is nano silicon.
The toughener is ethylene-octene-maleic anhydride terpolymer.
The surface modifier is monoalkoxy phosphate titanate coupling agent.
The heat filling is microspheric heat filling or microplate type heat filling, and the microspheric heat filling particle diameter is The mesh of 2000 mesh~2500, is one kind of magnesia, aluminum oxide or aluminium nitride.
The antioxidant is antioxidant 1010.
The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, the temperature in the area of temperature control one for 240~ 290℃；The temperature in the area of temperature control two is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；The temperature in the area of temperature control five is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven Spend for 260~310 DEG C；The temperature in the area of temperature control eight is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature For 260~310 DEG C；Rotating speed is 350~450r/min.
Embodiment 2
A kind of preparation method of highly heat conductive polyphenylene sulfide composite material, comprises the following steps：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 98%；
Stabilizer 0.5%；
The % of antioxidant 0.1；
Nucleator 0.5%
The said components weighed are put into high-speed mixer, incorporation time is 5min, obtains premix, premix is placed in into banburying In machine, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenylene sulfide using 180 DEG C of heat treatment half an hour After crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury is： 250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 40%；
Microspheric heat filling 35%；
Microplate type heat filling 23.5%；
The % of surface modifier 1；
Antioxidant 0.5%；
Said components are put into blender mixing 15 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains heat conduction master batch；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 50%；
The % of CNT 5；
Heat conduction master batch 37%；
Toughener 5%；
Surface modifier 2%；
Antioxidant 1%；
Said components are put into blender mixing 15 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
The linear polyphenylthioether weight average molecular weight is 20000~50000.
The stabilizer is the double -2,2,6,6- tetramethyl piperidine alcohol esters of decanedioic acid.
The toughener is ethylene-methyl acrylate-methylbenzene olefin(e) acid ethylene oxidic ester terpolymer.
The surface modifier is pyrophosphoric acid type titanate coupling agent.
The heat filling is microspheric heat filling or microplate type heat filling, and the heat filling is microplate type heat conduction Filler is one kind of graphene, boron nitride or silicon nitride.
The antioxidant is high-temperature anti-oxidant 412S.
The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, the temperature in the area of temperature control one for 240~ 290℃；The temperature in the area of temperature control two is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；The temperature in the area of temperature control five is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven Spend for 260~310 DEG C；The temperature in the area of temperature control eight is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature For 260~310 DEG C；Rotating speed is 350~450r/min.
Embodiment 3
A kind of preparation method of highly heat conductive polyphenylene sulfide composite material, comprises the following steps：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 96%；
Stabilizer 2%；
Antioxidant 1%；
Nucleator 1%
The said components weighed are put into high-speed mixer, incorporation time is 15min, obtains premix, premix is placed in close In mill, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenylene sulfide using 180 DEG C of heat treatment half an hour After ether crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury For：250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 40%；
Microspheric heat filling 30%；
Microplate type heat filling 26.5%；
Surface modifier 3%；
Antioxidant 0.5%；
Said components are put into blender mixing 8 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains heat conduction master batch；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
The % of high-crystallinity polyphenylene sulfide 30；
The % of CNT 5；
Heat conduction master batch 60%；
Toughener 3%；
Surface modifier 1.5%；
Antioxidant 0.5%；
Said components are put into blender mixing 10 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
The linear polyphenylthioether weight average molecular weight is 20000~50000.
The stabilizer is 1- methyl -8-（1,2,2,6,6- pentamethyl -4- piperidines）Sebacate.
The nucleator is methylene bis (2,4- di-tert-butyls phenoxy group) sodium phosphate.
The toughener is thermoplastic polyester elastomer.
The surface modifier is aliphatic acid titanate coupling agent.
The heat filling is microspheric heat filling or microplate type heat filling, and the microspheric heat filling is nitridation Aluminium, its particle diameter is the mesh of 2000 mesh~2500.
The antioxidant is antioxidant PEP36.
The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, the temperature in the area of temperature control one for 240~ 290℃；The temperature in the area of temperature control two is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；The temperature in the area of temperature control five is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven Spend for 260~310 DEG C；The temperature in the area of temperature control eight is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature For 260~310 DEG C；Rotating speed is 350~450r/min.
Embodiment 4
A kind of preparation method of highly heat conductive polyphenylene sulfide composite material, comprises the following steps：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 97%；
Stabilizer 2%；
Antioxidant 0.5%；
Nucleator 0.5%
The said components weighed are put into high-speed mixer, incorporation time is 12min, obtains premix, premix is placed in close In mill, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenylene sulfide using 180 DEG C of heat treatment half an hour After ether crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury For：250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 35%；
Microspheric heat filling 26.5%；
Microplate type heat filling 35%；
Surface modifier 3%；
Antioxidant 0.5%；
Said components are put into blender mixing 13 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains heat conduction master batch；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 40%；
CNT 7%；
Heat conduction master batch 47.5%；
Toughener 4%；
Surface modifier 1%；
Antioxidant 0.5%；
Said components are put into blender mixing 12 minutes in proportion；The above-mentioned raw material mixed is thrown into and squeezed in twin-screw Go out in machine, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
The linear polyphenylthioether weight average molecular weight is 20000~50000.
The stabilizer is double（1,2,2,6,6- pentamethyl -4- piperidines）Sebacate.
The nucleator is nano silicon and nano-calcium carbonate in mass ratio 1:3 compositions..
The toughener is maleic anhydride graft thermoplastic polyurethane.
The surface modifier is Silane coupling agent KH550.
The heat filling is microspheric heat filling graphene.
The antioxidant is antioxidant 1010.
The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, the temperature in the area of temperature control one for 240~ 290℃；The temperature in the area of temperature control two is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；The temperature in the area of temperature control five is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven Spend for 260~310 DEG C；The temperature in the area of temperature control eight is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature For 260~310 DEG C；Rotating speed is 350~450r/min.
Table 3：The performance test results of each embodiment
Unit Testing standard Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Bending modulus Mpa ASTM D790 5100 5300 5300 5500
Bending strength Mpa ASTM D790 96 102 100 98
Tensile strength Mpa ASTM D638 93 97 93 90
Elongation at break % ASTM D639 4 3 3 2
Notch impact strength J/m ASTM D256 105 100 96 110
Thermal conductivity W/m·K ASTM E1461 7.4 7.8 7.7 8.8
Specific insulation Ω·cm GB/T1400-2600 1015 1015 1014 1014
Note：Extension test condition is 5mm/min, and crooked test condition is 1.3mm/min.
As shown in Table 3, by the highly heat conductive polyphenylene sulfide composite material obtained by the material mixture ratio and processing technology of the present invention Not only there is high thermal conductivity, and with excellent mechanical performance.Appropriate CNT and heat conduction master batch by adding, it is multiple The thermal conductivity of condensation material is all higher than 7W/mK, while mechanical performance is excellent, can meet performance of the association area to Heat Conduction Material It is required that.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, any to be familiar with this area Technical staff the invention discloses technical scope in, the change or replacement that can be readily occurred in, should all cover the present invention Within protection domain.Therefore, protection scope of the present invention should be defined by scope of the claims.

Claims (10)

1. a kind of highly heat conductive polyphenylene sulfide composite material, it is characterised in that：Based on quality 100%, include：
High-crystallinity polyphenylene sulfide 30 ~ 50%；
CNT 5 ~ 10%；
Heat conduction master batch 35 ~ 60%；
Toughener 3 ~ 5%；
Surface modifier 0.5 ~ 2%；
Antioxidant 0.1 ~ 1%；
The heat conduction master batch includes based on quality 100%：
High-crystallinity polyphenylene sulfide 28 ~ 40%；
Microspheric heat filling 15 ~ 35%；
Microplate type heat filling 15 ~ 35%；
Surface modifier 1 ~ 3%；
Antioxidant 0.1 ~ 0.5%；
The high-crystallinity polyphenylene sulfide includes based on quality 100%：
Linear polyphenylthioether 95 ~ 98%；
Stabilizer 0.5 ~ 3%；
Antioxidant 0.1 ~ 1%；
Nucleator 0.5 ~ 1%.
2. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The linear polyphenylthioether is divided equally again Son amount is 20000~50000.
3. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The stabilizer is double-isophthalic two Double -2,2,6,6- tetramethyl piperidines the alcohol esters of phenolic group triazine, decanedioic acid, 1- methyl -8-（1,2,2,6,6- pentamethyl -4- piperidines）The last of the ten Heavenly stems Two acid esters and double（1,2,2,6,6- pentamethyl -4- piperidines）The mixture of one or both of sebacate.
4. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The nucleator is nanometer titanium dioxide In silicon, nano-calcium carbonate, methylene bis (2,4- di-tert-butyls phenoxy group) sodium phosphate, aryl carboxylic acid diamides or dibenzal sorbitol One or two kinds of mixtures.
5. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The toughener be ethylene-octene- Maleic anhydride terpolymer, ethylene-methyl acrylate-methylbenzene olefin(e) acid ethylene oxidic ester terpolymer, thermoplastic polyester The interworking thing of one or both of elastomer or maleic anhydride graft thermoplastic polyurethane.
6. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The surface modifier is single alcoxyl Base phosphate titanate coupling agent, pyrophosphoric acid type titanate coupling agent, aliphatic acid titanate coupling agent or Silane coupling agent KH550 In one or more of mixtures.
7. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The heat filling is led for microspheric Hot filler or microplate type heat filling, the microspheric heat filling particle diameter is the mesh of 2000 mesh~2500, is magnesia, aluminum oxide Or one kind of aluminium nitride；The heat filling is one kind that microplate type heat filling is graphene, boron nitride or silicon nitride.
8. highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：The antioxidant is antioxidant 1010th, high-temperature anti-oxidant 412S, high-temperature anti-oxidant PEPQ, antioxidant PEP36 or one kind in antioxidant 626 or two The mixture planted.
9. a kind of preparation method of highly heat conductive polyphenylene sulfide composite material as claimed in claim 1, it is characterised in that：Including as follows Step：
1）Prepare high-crystallinity polyphenylene sulfide
Each component is weighed respectively according to following percentage by weight：
Linear polyphenylthioether 95 ~ 98%；
Stabilizer 0.5 ~ 3%；
Antioxidant 0.1 ~ 1%；
Nucleator 0.5~1%
The said components weighed are put into high-speed mixer, incorporation time is 5~15min, obtains premix, premix is placed in In banbury, by the uniform discharge of the melting mixing of banbury, then by crushing and making polyphenyl using 180 DEG C of heat treatment half an hour After thioether crystallization is further improved, the polyphenylene sulfide of granular high-crystallinity is obtained；Wherein, the temperature setting of banbury For：250~290 DEG C；
2）Prepare heat conduction master batch
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 28 ~ 40%；
Microspheric heat filling 15 ~ 35%；
Microplate type heat filling 15 ~ 35%；
Surface modifier 1 ~ 3%；
Antioxidant 0.1 ~ 0.5%；
Said components are put into blender mixing 5~15 minutes in proportion；The above-mentioned raw material mixed is thrown into double spiral shells In bar extruder, melting extrusion granulation obtains heat conduction master batch；
3）Prepare highly heat conductive polyphenylene sulfide composite material
Each component is weighed respectively according to following percentage by weight：
High-crystallinity polyphenylene sulfide 30 ~ 50%；
CNT 5 ~ 10%；
Heat conduction master batch 35 ~ 60%；
Toughener 3 ~ 5%；
Surface modifier 0.5 ~ 2%；
Antioxidant 0.1 ~ 1%；
Said components are put into blender mixing 5~15 minutes in proportion；The above-mentioned raw material mixed is thrown into double spiral shells In bar extruder, melting extrusion granulation obtains highly heat conductive polyphenylene sulfide composite material.
10. the preparation method of highly heat conductive polyphenylene sulfide composite material according to claim 9, it is characterised in that：The step 2）With step 3）Middle double screw extruder includes 10 temperature controlled regions, and the temperature in the area of temperature control one is 240~290 DEG C；The area of temperature control two Temperature is 240~290 DEG C；The temperature in the area of temperature control three is 260~310 DEG C；The temperature in the area of temperature control four is 260~310 DEG C；Temperature control five The temperature in area is 260~310 DEG C；The temperature in the area of temperature control six is 260~310 DEG C；The temperature in the area of temperature control seven is 260~310 DEG C；Temperature The temperature for controlling 8th area is 260~310 DEG C；The temperature in the area of temperature control nine is 260~310 DEG C；Die head temperature is 260~310 DEG C；Rotating speed For 350~450r/min.
CN201710247541.8A 2017-04-17 2017-04-17 A kind of highly heat conductive polyphenylene sulfide composite material and preparation method thereof Pending CN106977922A (en)

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CN108250751A (en) * 2018-02-07 2018-07-06 深圳华力兴新材料股份有限公司 The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k
CN109280387A (en) * 2018-10-24 2019-01-29 新奥石墨烯技术有限公司 Polyphenyl thioether composite material and preparation method thereof
CN109912973A (en) * 2019-01-25 2019-06-21 深圳市高科塑化有限公司 A kind of glass fiber reinforcement PPS-CNT conducing composite material and preparation method thereof
CN110128824A (en) * 2019-03-18 2019-08-16 绍兴裕辰新材料有限公司 Poly arylidene thio-ester granules, preparation method and its molded product
CN112358713A (en) * 2020-11-09 2021-02-12 广州视源电子科技股份有限公司 High-thermal-conductivity insulating PC/ABS composite material and preparation method thereof
CN113105732A (en) * 2021-04-13 2021-07-13 东莞市东翔塑胶有限公司 Resin-based composite material with high thermal conductivity and preparation method thereof
CN114716826A (en) * 2022-05-16 2022-07-08 佛山市达孚新材料有限公司 PPS/PA blend biaxial stretching film and preparation method thereof

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CN102898834A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced electrically and thermally conductive polyphenylene sulfide composite material and preparation method thereof
CN103319893A (en) * 2013-07-11 2013-09-25 四川中物材料有限责任公司 Preparation method of high-heat-conducting polyphenylene sulfide material and prepared material
CN104559148A (en) * 2014-12-16 2015-04-29 惠州力王佐信科技有限公司 High-thermal-diffusion-coefficient high molecular material and preparation method thereof

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CN102898834A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced electrically and thermally conductive polyphenylene sulfide composite material and preparation method thereof
CN103319893A (en) * 2013-07-11 2013-09-25 四川中物材料有限责任公司 Preparation method of high-heat-conducting polyphenylene sulfide material and prepared material
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CN108250751A (en) * 2018-02-07 2018-07-06 深圳华力兴新材料股份有限公司 The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k
CN109280387A (en) * 2018-10-24 2019-01-29 新奥石墨烯技术有限公司 Polyphenyl thioether composite material and preparation method thereof
CN109912973A (en) * 2019-01-25 2019-06-21 深圳市高科塑化有限公司 A kind of glass fiber reinforcement PPS-CNT conducing composite material and preparation method thereof
CN110128824A (en) * 2019-03-18 2019-08-16 绍兴裕辰新材料有限公司 Poly arylidene thio-ester granules, preparation method and its molded product
CN112358713A (en) * 2020-11-09 2021-02-12 广州视源电子科技股份有限公司 High-thermal-conductivity insulating PC/ABS composite material and preparation method thereof
CN113105732A (en) * 2021-04-13 2021-07-13 东莞市东翔塑胶有限公司 Resin-based composite material with high thermal conductivity and preparation method thereof
CN114716826A (en) * 2022-05-16 2022-07-08 佛山市达孚新材料有限公司 PPS/PA blend biaxial stretching film and preparation method thereof
CN114716826B (en) * 2022-05-16 2023-05-23 佛山市达孚新材料有限公司 PPS/PA blend biaxially oriented film and preparation method thereof

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