CN106280414B - A kind of nylon base heat-conductive composite material and preparation method thereof - Google Patents
A kind of nylon base heat-conductive composite material and preparation method thereof Download PDFInfo
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- CN106280414B CN106280414B CN201610632928.0A CN201610632928A CN106280414B CN 106280414 B CN106280414 B CN 106280414B CN 201610632928 A CN201610632928 A CN 201610632928A CN 106280414 B CN106280414 B CN 106280414B
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The present invention provides a kind of nylon base heat-conductive composite material and preparation method thereof.Nylon base heat-conductive composite material provided by the invention includes following components：30~60 mass parts nylon, 6,5~25 mass parts expanded graphite, 5~20 mass parts auxiliary packings, 1~5 mass parts silane coupling agent, 0.5~2 mass parts lubricant, 0.2~1 mass parts antioxidant, 1~10 mass parts elastic body toughening agent, 1~20 mass parts fire retardant and 5~15 mass parts glass fibres.Nylon base heat-conductive composite material provided by the invention has good heat conduction, antistatic, flame retarding function, and mechanical property and processing performance are good and of low cost.Preparation method provided by the invention is easy, practical, suitable for large-scale industrial production.
Description
Technical field
The present invention relates to Heat Conduction Material technical field, more particularly to a kind of nylon base heat-conductive composite material and its preparation side
Method.
Background technology
Nowadays, with the development of science and technology, the application of electronic apparatus gradually tends to minimize, and use environment is changeable, this is right
Matched heat sink material performance proposes new requirement, such as the molding of lightweight, easy processing and corrosion-resistant, traditional heat conduction material
Material such as metal and ceramic material have been difficult to meet above-mentioned performance requirement, and therefore, Development of Novel Heat Conduction Material is extremely urgent.
Heat-conducting plastic is since it is with low-density, corrosion-resistant, the inexpensive and characteristics such as easily processed into type, to conventional pilot
The shortcoming of hot material has carried out preferable supplement, and is led in the heat dissipation of microelectronic packaging material, LED illumination, electronic apparatus
Domain is widely used.Therefore, development heat-conducting plastic meaning heavy is big.
At present, the production of heat-conducting plastic is prepared usually with the functional stuffing with high thermal conductivity to not having heat conductivility
Resin matrix be filled to prepare HEAT-CONDUCTING PLASTICS FILLED WTTH PARTICLES.Typically, the filler cost also phase with high thermal conductivity
To higher, such as boron nitride, silicon carbide, aluminium nitride, carbon nanotube, graphene；And the filler such as oxygen that heat conductivility is relatively low
Changing magnesium, aluminium oxide etc. then needs larger loading could be so that material reaches higher thermal conductivity factor, this can cause material
Mechanical property declines to a great extent.The production and processing mode of heat-conducting plastic is mainly melt-blending process, and this processing method is simple
It is convenient, but have higher requirement to the melt flowability of material.Although the use of a large amount of heat fillings can be in resin matrix
It is middle to form more heat conduction network, promote thermal conductivity factor, but the reunion of filler also can cause the mechanical property of material to decline to a great extent
And the rising of material cost.Meanwhile the use of a large amount of heat fillings can make the mobility of material be deteriorated, it is right to a certain extent
The processability of material adversely affects.
Chinese patent CN103613923A provides a kind of high heat conduction nylon that electric conductivity can be controlled according to application requirement
Composite material and its preparation process, but a variety of high cost fillers such as multi-walled carbon nanotube, graphene are arrived involved in the patent, not
Conducive to large-scale production；Chinese patent CN105623258A discloses a kind of heat conduction high temperature resistant nylon composite material and its preparation side
Method, and the fillers such as expanded graphite have been used, but expanded graphite belongs to sheet filler with lappingout graphite powder, is being used alone
And loading it is larger when the mechanical property of material and processing fluidity can be caused to decline to a great extent, be unfavorable for large-scale industry metaplasia
Production.
Invention content
The purpose of the present invention is to provide a kind of nylon base heat-conductive composite materials and preparation method thereof.Buddhist nun provided by the invention
Imperial base heat-conductive composite material has good heat conduction, fire-retardant and anti-static function, and mechanical property and processing performance are good, and cost
It is cheap.
The present invention provides a kind of nylon base heat-conductive composite material, including following components：
Preferably, the grain size of the expanded graphite is 20~150 μm.
Preferably, the auxiliary packing include aluminium oxide, magnesia, calcium carbonate, talcum powder and wollastonite in one kind or
It is a variety of.
Preferably, the silane coupling agent includes N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(methyl
Acryloyl-oxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane
With it is one or more in ethyl trimethoxy silane.
Preferably, the lubricant includes atoleine or stearic acid.
Preferably, the antioxidant include three (2,4- di-tert-butyl-phenyl) phosphite esters, four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, bis- (2.4- di-tert-butyl-phenyls) pentaerythritol diphosphites, N, N'- be bis--(3-
(3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and bis- (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- of N, N'-
It is one or more in benzenedicarboxamide.
Preferably, the elastic body toughening agent includes olefin block copolymers, ethylene-octene random copolymer, ethylene-vinegar
It is one or more in sour ethylene copolymer and above-mentioned three kinds of grafts of any one.
Preferably, the fire retardant include decabromodiphenylethane, brominated Polystyrene and antimony oxide in one kind or
It is a variety of.
Preferably, the glass fiber diameter is 9~13 μm.
The present invention also provides a kind of preparation method of nylon base heat-conductive composite material described in above-mentioned technical proposal, including with
Lower step：
(1) expanded graphite and auxiliary packing are mixed respectively with silane coupling agent, surface treatment obtains the swollen of surface modification
The auxiliary packing that swollen graphite and surface are modified；
The auxiliary packing that the expanded graphite and surface that the surface for (2) obtaining the step (1) is modified are modified and nylon 6,
Antioxidant, lubricant, fire retardant, elastic body toughening agent and glass fibre mixing, obtain mixed material；
(3) mixed material for obtaining the step (2), which is plasticized, squeezes out, and obtains nylon base heat-conductive composite material.
The present invention provides a kind of nylon base heat-conductive composite material, including following components：30~60 mass parts nylon 6,5~
25 mass parts expanded graphites, 5~20 mass parts auxiliary packings, 1~5 mass parts silane coupling agent, 0.5~2 mass parts lubricant,
0.2~1 mass parts antioxidant, 1~10 mass parts elastic body toughening agent, 1~20 mass parts fire retardant and 5~15 mass parts glass
Fiber.
Nylon base heat-conductive composite material provided by the invention is using expanded graphite as main heat filling, and expanded graphite is by common
Flaky graphite expansion after be made, it is of low cost, and with laminar structured and specific surface area it is very big, filler particles each other it
Between mutually can overlap to form network at lower levels, this can cause material to reach higher heat conduction under relatively low amount of filler
Coefficient simultaneously maintains preferable mechanical property；In addition, the electric conductivity that graphite itself has, can assign composite material antistatic work(
Energy；Meanwhile the addition of expanded graphite can also improve the flame retardant property of composite material.
The present invention makes auxiliary packing be compounded with expanded graphite, is on the one hand conducive to expanded graphite by adding in auxiliary packing
Piece layer open makes resin matrix be more easy to, into the laminar structured interior of expanded graphite, promote its interface phase interaction between matrix
With；On the other hand, the thermal conductivity factor of these auxiliary packings is also above matrix, by auxiliary packing and the collocation of expanded graphite,
Intrinsic silicon forms more fine and close and uniform heat conduction network, so as to promote the heat conduction of material and rigidity；Meanwhile auxiliary packing
Use, can also weaken sheet expanded graphite to material melt flowing generate inhibition, and further reduce material into
This.
The present invention is avoided by adding in glass fibre and elastic body toughening agent due to the addition of a large amount of inorganic rigid particles
And the brittleness of material is caused to increase, toughness of material is assigned while the strength of materials is promoted so that the material has excellent comprehensive
Close performance.
The experimental results showed that nylon base heat-conductive composite material thermal conductivity factor provided by the invention is up to 2.86w/ (mk),
Volume resistivity can be down to 4.25 × 103Ω m, vertical combustion rank V-0, tensile strength can up to 49.4MPa, impact strength
Up to 20.7KJ/m2, conventional extruder can be used to squeeze out, and conventional injector can be used to be injection moulded, there is good thermal conductivity
Energy, antistatic property, flame retardant property, processing performance and comprehensive mechanical property.
Specific embodiment
The present invention provides a kind of nylon base heat-conductive composite material, including following components：
Nylon base heat-conductive composite material provided by the invention include 30~60 mass parts nylon 6 (PA6), preferably 35~55
Mass parts, more preferably 40~50 mass parts.The present invention does not have special restriction to the source of the nylon 6, using this field
Well known commercially available nylon 6.In the present invention, in the strand of the nylon 6 containing a large amount of amido bonds, they can be
PA6 molecules interchain forms hydrogen bond, has larger strand intermolecular forces, is conducive to diffusion of the heat in resin matrix, makes
Material reaches higher thermal conductivity factor.
Nylon base heat-conductive composite material provided by the invention include 5~25 mass parts expanded graphites (EG), preferably 10~
20 mass parts, more preferably 13~17 mass parts.In the present invention, the grain size of the expanded graphite is preferably 20~150 μm, more
Preferably 50~120 μm, most preferably 80~90 μm.The present invention does not have the source of the expanded graphite special restriction, adopts
With commercially available expanded graphite well known in the art.In the present invention, after the expanded graphite is expanded by common flaky graphite
It is made, of low cost and very big with laminar structured and specific surface area, filler particles each other can be in relatively low dosage
Lower mutually overlap joint forms network, and material is made to reach higher thermal conductivity factor under relatively low amount of filler and maintains preferable mechanical property
Energy；The electric conductivity that expanded graphite itself has can assign composite material anti-static function；The addition of expanded graphite can also carry
The flame retardant property of high composite material.
Nylon base heat-conductive composite material provided by the invention includes 5~20 mass parts auxiliary packings, preferably 10~15 matter
Measure part.In the present invention, the auxiliary packing preferably includes one in aluminium oxide, magnesia, calcium carbonate, talcum powder and wollastonite
Kind is a variety of, more preferably includes the combination of a kind of and wollastonite or talcum powder in aluminium oxide, magnesia and calcium carbonate.In this hair
In bright, the aluminium oxide, magnesia and calcium carbonate are preferably irregular shape；The talcum powder is preferably lamellar；The silicon
Lime stone is preferably needle-shaped or fibrous.In the present invention, the auxiliary packing is compounded with expanded graphite, is on the one hand conducive to expand
Graphite flake layer is opened, and resin matrix is made to be more easy to, into the laminar structured interior of expanded graphite, promote its interface phase between matrix
Interaction；On the other hand, the thermal conductivity factor of these auxiliary packings is also above matrix, passes through taking for auxiliary packing and expanded graphite
Match, more fine and close and uniform heat conduction network is formed in intrinsic silicon, so as to promote the heat conduction of material and rigidity；It is meanwhile auxiliary
The use of filler is helped, can also weaken the inhibition that sheet expanded graphite generates material melt flowing, and further reduce material
The cost of material.
Nylon base heat-conductive composite material provided by the invention includes 1~5 mass parts silane coupling agent, preferably 2~4 mass
Part.The present invention does not have the type of the silane coupling agent special restriction, using silane well known to those skilled in the art idol
Join agent.In the present invention, the silane coupling agent include N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-
(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl
It is one or more in silane and ethyl trimethoxy silane.In the present invention, the silane coupling agent passes through in expanded graphite
With the coating modification on auxiliary packing surface, the parent of expanded graphite and the surface energy of auxiliary packing, enhancing and polymeric matrix is reduced
And ability.
Nylon base heat-conductive composite material provided by the invention includes 0.5~2 mass parts lubricant, preferably 1~1.5 mass
Part.The present invention does not have the type of the lubricant special restriction, using lubricant well known to those skilled in the art.
In the present invention, the lubricant preferably includes atoleine or stearic acid.
Nylon base heat-conductive composite material provided by the invention includes 0.2~1 mass parts antioxidant, preferably 0.5~0.8 matter
Measure part.The present invention does not have the type of the antioxidant special restriction, is using antioxidant well known to those skilled in the art
It can.In the present invention, the antioxidant preferably includes three (2,4- di-tert-butyl-phenyl) phosphite esters, four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester, bis- (2.4- di-tert-butyl-phenyls) pentaerythritol diphosphites, N, N'- be bis- -
(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -
It is one or more in 1,3- benzenedicarboxamides.
Nylon base heat-conductive composite material provided by the invention include 1~10 mass parts elastic body toughening agent, preferably 5~7
Mass parts.The present invention does not have special restriction to the type of the elastic body toughening agent, and use is well known to those skilled in the art
Elastomer.In the present invention, the elastic body toughening agent preferably include olefin block copolymers (OBC), ethylene-octene without
Advise one kind or more in copolymer (POE), ethylene-vinyl acetate copolymer (EVA) and above-mentioned three kinds of grafts of any one
Kind.In the present invention, the graft is preferably grafted maleic anhydride (MAH) or glycidyl methacrylate (GMA).
In the present invention, the elastic body toughening agent can avoid the addition due to a large amount of inorganic rigid particles and the brittleness of material is caused to increase
Add, assign toughness of material so that the material has excellent comprehensive performance.
Nylon base heat-conductive composite material provided by the invention includes 1~20 mass parts fire retardant, preferably 5~15 mass
Part, more preferably 8~12 mass parts.The present invention does not have the type of the fire retardant special restriction, using art technology
Fire retardant known to personnel.In the present invention, the fire retardant preferably include decabromodiphenylethane, brominated Polystyrene and
It is one or more in antimony oxide, more preferably include one or both of decabromodiphenylethane and brominated Polystyrene with
The combination of antimony oxide.In the present invention, when the fire retardant is one kind in decabromodiphenylethane and brominated Polystyrene
During with the combination of antimony oxide, the decabromodiphenylethane or brominated Polystyrene and antimony oxide mass ratio are preferably 1
~3:1.In the present invention, when the fire retardant includes one or both of decabromodiphenylethane and brominated Polystyrene and three
When aoxidizing the combination of two antimony, the bromine in the decabromodiphenylethane and brominated Polystyrene can be with antimony oxide reaction generation bromine
Change antimony, macromolecular radical is captured, so as to terminate combustion reaction.
Nylon base heat-conductive composite material provided by the invention includes 5~15 mass parts glass fibres, preferably 8~12 mass
Part.The present invention does not have the type of the glass fibre special restriction, using glass fibre well known to those skilled in the art
.In the present invention, the diameter of the glass fibre is preferably 9~13 μm, more preferably 10~12 μm；The glass fibre
Chopped length be preferably 3~4.5mm, more preferably 3.5~4mm.In the present invention, on the one hand the glass fibre can carry
High tensile and bending strength on the other hand with elastic body toughening agent collective effect, can be avoided due to a large amount of inorganic rigid grains
Son addition and the brittleness of material is caused to increase, toughness of material is assigned while the strength of materials is promoted so that the material has
Excellent comprehensive performance.
The present invention also provides the preparation method of nylon base heat-conductive composite material described in above-mentioned technical proposal, including following step
Suddenly：
(1) expanded graphite and auxiliary packing are mixed respectively with silane coupling agent, surface treatment obtains the swollen of surface modification
The auxiliary packing that swollen graphite and surface are modified；
The auxiliary packing that the expanded graphite and surface that the surface for (2) obtaining the step (1) is modified are modified and nylon 6,
Antioxidant, lubricant, fire retardant, elastic body toughening agent and glass fibre mixing, obtain mixed material；
(3) mixed material for obtaining the step (2), which is plasticized, squeezes out, and obtains nylon base heat-conductive composite material.
The present invention mixes expanded graphite and auxiliary packing with silane coupling agent respectively, and surface treatment obtains surface modification
The auxiliary packing that expanded graphite and surface are modified.Operation no special restriction of the present invention to the surface treatment, using this
The technical solution that inorganic filler surface known to field technology personnel is handled.In the present invention, the silane coupling agent is excellent
Choosing is added in the form of silane coupling agent ethyl alcohol and/or acetone soln；The volume of the silane coupling agent and ethyl alcohol and/or acetone
Than being preferably 1:100~150.In the present invention, the surface treatment makes coupling agent be coated on expansion stone preferably by stirring
Ink or auxiliary packing surface.In the present invention, the stirring carries out preferably in high-speed mixer；The rate of the stirring is preferred
For 500~600rpm；The time of the stirring is preferably 8~15min.In the present invention, the ethyl alcohol and/or acetone preferably exist
Naturally volatilization removal after stirring.
The ethyl alcohol and/or acetone solvent remaining for removal, the present invention are preferably dried after surface treatment, obtain surface
The auxiliary packing that modified expanded graphite and surface are modified.Operation no special restriction of the present invention to the drying, uses
The technical solution of drying well known to those skilled in the art.In the present invention, the drying is preferably dried；The drying
Temperature be preferably 40~50 DEG C, more preferably 43~46 DEG C；The time of the drying is preferably 0.5~1.5h.
It is of the invention by the surface treatment and Buddhist nun after obtaining the expanded graphite of surface modification and the auxiliary packing of surface modification
Dragon 6, antioxidant, lubricant, fire retardant, elastic body toughening agent and glass fibre mixing, obtain mixed material.The present invention is to described
The device of mixing does not have special restriction, using the device of mixing well known to those skilled in the art.In the present invention, institute
Mixing is stated to carry out preferably in high-speed mixer.In the present invention, the mixing preferably carries out at normal temperatures；The speed of the mixing
Rate is preferably 500~600rpm, more preferably 540~560rpm；The time of the mixing is preferably 5~8min.
To reduce water content, the present invention is preferably dried before 6 use of nylon.The present invention is to the drying process
The no special restriction of operation, using the technical solution of drying process well known to those skilled in the art.In the present invention
In, the drying is preferably dried in vacuo；The vacuum drying vacuum degree is preferably 0.09~0.1MPa；The vacuum drying
Temperature be preferably 100~120 DEG C, more preferably 105~110 DEG C；The vacuum drying time is preferably 8~12h, more excellent
It is selected as 9~11h.
After completing the mixing, obtained mixed material is plasticized and squeezes out by the present invention, obtains nylon base heat-conductive composite material.
In the present invention, the temperature that the plasticizing squeezes out is preferably 180~260 DEG C, more preferably 200~250 DEG C.The present invention is to described
The device that plasticizing squeezes out does not have special restriction, using plasticizing extrusion device well known to those skilled in the art.In this hair
In bright, the plasticizing squeezes out to be carried out preferably in double screw extruder.In the present invention, the screw rod of the double screw extruder turns
Speed is preferably 200~400rpm, more preferably 250~350rpm.
In order to further illustrate the present invention, with reference to embodiment to nylon base heat-conductive composite material provided by the invention and
Preparation method is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1:
According to 1:150 volume ratios will 5 mass parts silane coupling agent add in ethyl alcohol in dissolves in advance, then with heat filling
Mixing in high-speed mixer, 15min is stirred with the rate of 500rpm, until filler surface is fully soaked, finally at 50 DEG C
Under the conditions of dry 1h, obtain surface modification heat filling.
Nylon 6 dries 9h in 110 DEG C under vacuum before processing.
In parts by mass, by 37 parts of nylon, 6,25 parts of expanded graphites, 20 parts of aluminium oxide, 5 parts of glass fibres, 10 parts of fire retardants
(brominated Polystyrene:Antimony oxide=1:1), 3 parts of POE-g-MAH, 0.4 part of antioxidant and 2 parts of lubricants are in mixed at high speed
It is uniformly mixed in machine, by double screw extruder extruding pelletization, 200~250 DEG C of extrusion temperature, screw speed 200rpm is obtained
Nylon base heat-conductive composite material.
Obtained nylon base heat-conductive composite material is made up after 110 DEG C of drying 8h of injection molding under vacuum
It stretches, the standby test of sample needed for impact property test, injection molding temperature is 220~240 DEG C, injection pressure 50MPa.Stretch sample
Product are dumbbell shape batten, and overall length 150mm, intermediate parallel partial-length is 60mm, width 10mm, thickness 4mm；Non-notch rushes
Batten size is hit as 80 × 10 × 4 (mm)；
Heat conduction sample is then by the hot-forming thin slice for being made as 10 × 10 × 1 (mm), and hot pressing temperature is 235 DEG C, hot pressing pressure
Power 50MPa.
The thermal conductivity factor of nylon base heat-conductive composite material that the present invention is tested using laser heat conducting instrument.
Vertical combustion is tested according to UL-94 standards, and sample size is 130mm × 13mm × 3mm, and control flame is to examination
Sample lower end acts on 10s, and record removes the flaming combustion time t of sample after flame1If sample flame is after burning things which may cause a fire disaster is removed
Extinguish in 30s, then apply flame combustion 10s, and record removes the flaming combustion time t of sample after flame respectively second2With
Glowing time t3Index.Meanwhile see whether flame molten drop and its burning of caused absorbent cotton.Each sample requirement
5 samples are tested, sample classification is then determined according to result of the test.
The average value that limit oxygen index LOI tests measure 10 standard samples with reference to ASTM D2836-74 obtains, sample ruler
Very little is 100 × 6.5 × 3mm.Sample maintains balance combustion in nitrogen oxygen atmosphere stream, i.e., just burns 50mm's long in 180s
Apart from required oxygen percent by volume.
The nylon base heat-conductive composite material performance that the present embodiment is prepared is as shown in table 1.
Embodiment 2:
According to 1:130 volume ratios will 2 mass parts silane coupling agent add in acetone in dissolves in advance, then with heat filling
Mixing in high-speed mixer, 8min is stirred with the rate of 500rpm, until filler surface is fully soaked, finally at 45 DEG C
Under the conditions of dry 1h, obtain surface modification heat filling.
Nylon 6 dries 10h in 110 DEG C under vacuum before processing.
In parts by mass, by 50 parts of nylon, 6,10 parts of expanded graphites, 10 parts of calcium carbonate, 7 parts of glass fibres, 20 parts of fire retardants
(brominated diphenyl methane:Antimony oxide=2:1), 3 parts of EVA, 0.5 part of antioxidant and 1.5 parts of lubricants are in high-speed mixer
It is uniformly mixed, by double screw extruder extruding pelletization, 200~250 DEG C of extrusion temperature, screw speed 300rpm obtains nylon
Base heat-conductive composite material.
Performance is carried out to the nylon base heat-conductive composite material that the present embodiment is prepared according to test method described in embodiment 1
Test, the results are shown in Table 1.
Embodiment 3:
According to 1:110 volume ratios will 1 mass parts silane coupling agent add in acetone in dissolves in advance, then with heat filling
Mixing in high-speed mixer, 8min is stirred with the rate of 500rpm, until filler surface is fully soaked, finally at 45 DEG C
Under the conditions of dry 1h, obtain surface modification heat filling.
Nylon 6 dries 12h in 110 DEG C under vacuum before processing.
In parts by mass, by 60 parts of nylon, 6,10 parts of expanded graphites, 5 parts of talcum powder, 5 parts of glass fibres, 15 parts of fire retardants
(brominated diphenyl methane:Antimony oxide=1:1), 5 parts of OBC-g-GMA, 1 part of antioxidant and 1 part of lubricant are in high-speed mixer
In be uniformly mixed, by double screw extruder extruding pelletization, 200~250 DEG C of extrusion temperature, screw speed 280rpm obtains Buddhist nun
Imperial base heat-conductive composite material.
Performance is carried out to the nylon base heat-conductive composite material that the present embodiment is prepared according to test method described in embodiment 1
Test, the results are shown in Table 1.
Embodiment 4:
According to 1:140 volume ratios will 4 mass parts silane coupling agent add in ethyl alcohol in dissolves in advance, then with heat filling
Mixing in high-speed mixer, 10min is stirred with the rate of 500rpm, until filler surface is fully soaked, finally at 50 DEG C
Under the conditions of dry 1h, obtain surface modification heat filling.
Nylon 6 dries 12h in 110 DEG C under vacuum before processing.
In parts by mass, by 50 parts of nylon, 6,15 parts of expanded graphites, 3 parts of wollastonites, 7 parts of calcium carbonate, 7 parts of glass fibres,
10 parts of fire retardant (brominated Polystyrenes:Antimony oxide=3:1), 6 parts of POE-g-GMA, 0.8 part of antioxidant and 1 part of lubricant
It is uniformly mixed in high-speed mixer, passes through double screw extruder extruding pelletization, 200~250 DEG C of extrusion temperature, screw speed
250rpm obtains nylon base heat-conductive composite material.
Performance is carried out to the nylon base heat-conductive composite material that the present embodiment is prepared according to test method described in embodiment 1
Test, the results are shown in Table 1.
Embodiment 5:
According to 1:150 volume ratios will 4 mass parts silane coupling agent add in acetone in dissolves in advance, then with heat filling
Mixing in high-speed mixer, 12min is stirred with the rate of 500rpm, until filler surface is fully soaked, finally at 45 DEG C
Under the conditions of dry 1h, obtain surface modification heat filling.
Nylon 6 dries 12h in 110 DEG C under vacuum before processing.
In parts by mass, by 40 parts of nylon, 6,15 parts of expanded graphites, 20 parts of magnesia, 10 parts of glass fibres, 10 parts it is fire-retardant
Agent (brominated diphenyl methane:Antimony oxide=2:1), 10 parts of OBC-g-MAH, 0.4 part of antioxidant and 2 parts of lubricants are mixed in high speed
It is uniformly mixed in conjunction machine, by double screw extruder extruding pelletization, 200~250 DEG C of extrusion temperature, screw speed 200rpm is obtained
To nylon base heat-conductive composite material.
Performance is carried out to the nylon base heat-conductive composite material that the present embodiment is prepared according to test method described in embodiment 1
Test, the results are shown in Table 1.
The performance test results of nylon base heat-conductive composite material that 1 embodiment of the present invention of table obtains
As can be seen from the above embodiments, nylon base heat-conductive composite material provided by the invention can be squeezed with conventional extruder
Go out, be injection moulded with conventional injector, there is good thermal conductivity, anti-static function, anti-flammability, processing performance and resultant force
Learn performance.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
Several improvements and modifications can also be made, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of nylon base heat-conductive composite material, composed of the following components：
The auxiliary packing includes one or more in aluminium oxide, magnesia, calcium carbonate and wollastonite；The aluminium oxide, oxygen
It is irregular shape to change magnesium and calcium carbonate；The wollastonite is needle-shaped or fibrous；
The elastic body toughening agent includes olefin block copolymers, ethylene-octene random copolymer, ethene-vinyl acetate copolymerization
It is one or more in object and above-mentioned three kinds of grafts of any one.
2. nylon base heat-conductive composite material according to claim 1, which is characterized in that the grain size of the expanded graphite is 20
~150 μm.
3. nylon base heat-conductive composite material according to claim 1, which is characterized in that the silane coupling agent includes N-
(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-shrink are sweet
It is one or more in oily ether oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane and ethyl trimethoxy silane.
4. nylon base heat-conductive composite material according to claim 1, which is characterized in that the lubricant includes atoleine
Or stearic acid.
5. nylon base heat-conductive composite material according to claim 1, which is characterized in that the antioxidant includes three (2,4-
Di-tert-butyl-phenyl) phosphite ester, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, bis- (2.4- bis-
Tert-butyl-phenyl) pentaerythritol diphosphites, N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself two
It is one or more in amine and bis- (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'-.
6. nylon base heat-conductive composite material according to claim 1, which is characterized in that the fire retardant includes decabrominated dipheny
It is one or more in ethane, brominated Polystyrene and antimony oxide.
7. nylon base heat-conductive composite material according to claim 1, which is characterized in that the glass fiber diameter for 9~
13μm。
8. a kind of preparation method of nylon base heat-conductive composite material described in any one in claim 1~7, including following step
Suddenly：
(1) expanded graphite and auxiliary packing are mixed respectively with silane coupling agent, surface treatment obtains the expansion stone of surface modification
The auxiliary packing that ink and surface are modified；
(2) auxiliary packing and nylon 6, antioxygen that the expanded graphite and surface that the surface for obtaining the step (1) is modified are modified
Agent, lubricant, fire retardant, elastic body toughening agent and glass fibre mixing, obtain mixed material；
(3) mixed material for obtaining the step (2), which is plasticized, squeezes out, and obtains nylon base heat-conductive composite material.
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| CN106675008B (en) * | 2017-01-19 | 2020-08-14 | 广东星联科技有限公司 | High-thermal-conductivity nylon 6 composite material and preparation method thereof |
| CN106916443A (en) * | 2017-03-08 | 2017-07-04 | 四川九洲电器集团有限责任公司 | A kind of heat conduction nylon plastic(s) and the method for preparing heat conduction nylon plastic(s) |
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| CN109836814A (en) * | 2019-01-27 | 2019-06-04 | 余姚市舜辰新材料科技有限公司 | A kind of PA6 formula with heat insulating and corrosion function |
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| CN111171561A (en) * | 2020-02-14 | 2020-05-19 | 中广核瑞胜发（厦门）新材料有限公司 | Flame-retardant heat-conducting high-strength nylon composite material and preparation method thereof |
| CN112778754B (en) * | 2021-01-28 | 2022-04-05 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| CN113956654A (en) * | 2021-10-22 | 2022-01-21 | 安徽众诚塑胶科技有限公司 | High-temperature-resistant nylon master batch and preparation method thereof |
| CN114031934B (en) * | 2021-12-15 | 2023-07-04 | 宁波公牛光电科技有限公司 | Polyamide composite material with high heat conductivity coefficient and preparation method thereof |
| CN115418102B (en) * | 2022-09-24 | 2023-10-20 | 苏州井村塑料科技有限公司 | high-GWIT high-CTI halogen-free flame-retardant PA66 material and preparation method thereof |
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| CN102604372B (en) * | 2012-02-17 | 2013-06-05 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
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