CN104045896A - Heat-conductive polyethylene composite material and preparation method thereof - Google Patents
Heat-conductive polyethylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heat-conductive polyethylene composite material and a preparation method thereof. The composite material comprises the following components in parts by weight: 15 to 50 parts of polyethylene, 4 to 35 parts of heat-conductive fibers and 23 to 80 parts of heat-conductive granules. The heat-conductive fibers taken as heat-conductive filling materials are added into the polyethylene substrate, so that the heat-conductive polyethylene composite material is formed. Compared with granular heat-conductive filling materials, according to the composite material provided by the invention, after the fibriform heat-conductive fibers enter the polyethylene substrate, an overlapping state can be easily formed between the heat-conductive fibers and the polyethylene substrate, so that the formed overlapping network can easily pass through the whole polyethylene substrate; and thus, the heat in the substrate can be rapidly dispersed under the heat-conductive action of the overlapping network, thereby being favorable for improving the heat transfer efficiency of the composite material. Meanwhile, after the heat-conductive granules are added, the heat-conductive granules can be used for enwrapping joints among the different heat-conductive fibers, so that strong heat-conductive channels are formed among the heat-conductive fibers.
Description
Technical field
The present invention relates to polymer materials manufacture field, in particular to a kind of heat conduction composite polyethylene material and preparation method thereof.
Background technology
Along with scientific and technical development, power to device of electronic applications and LED field and the requirement of integrated level improve day by day, and correspondingly, superpower and high integration make device heat-dissipating amount in normal operation more and more higher.This just requires device to have higher heat transfer property, to reach radiating effect timely.As the important material of preparing of these devices, the heat conductivility of polymer materials has also been subject to increasing challenge.The polymeric matrix of the thermal conductive polymer composite material by adopting of most is polyphenylene sulfide and polymeric amide.But these materials or processing characteristics are poor, or price is higher, should not carry out large-scale manufacture.
Polyethylene is typical thermoplastics, and its body odorless, tasteless, nontoxic, material is soft and tough, density ratio water is low, and has excellent dielectric properties.Meanwhile, poly chemical stability is better, can resistance to most soda acid salt, under normal temperature, be insoluble to any organic solvent.In addition, poly resistance to low temperature is good, still can keep good mechanical property at-60 DEG C.As a kind of engineering plastics, poly temperature flowing is good, processing characteristics excellence, and there is obvious cost advantage.Comprehensive above-mentioned reason, the thermal conductive polymer matrix material taking polyethylene as polymeric matrix becomes new study hotspot.
Patent CN102311568B discloses a kind of preparation method of heat conduction high-density polyethylene material, and cardinal principle is to adopt the granular heat conductive filler filling high-density polyethylenes such as silicon carbide, aluminium nitride, to prepare heat conduction high-density polyethylene material.The thermal conductivity of above-mentioned materials is lower, and its high heat conductance only has 0.69w/ (mk).
Patent CN102311567B discloses the polyethylene thermally conductive material that a kind of nano aluminium oxide is filled, but its thermal conductivity is also lower.In the time that nano aluminium oxide loading level reaches 59%, the thermal conductivity of material only has 0.616w/ (mk).
In sum, the thermal conductivity that how to improve composite polyethylene material becomes investigator's the new focus of attention.
Summary of the invention
The present invention aims to provide a kind of heat conduction composite polyethylene material and preparation method thereof, to solve the lower problem of the heat conductivility of composite polyethylene material in prior art.
To achieve these goals, according to an aspect of the present invention, provide a kind of heat conduction composite polyethylene material, it comprises the polyethylene of 15～50 parts, the heat conducting fiber of 4～35 parts and the heat conduction particle of 23～80 parts by weight.
Further, by weight, heat conducting fiber comprises the macrofiber of 2～20 parts and the staple fibre of 2～15 parts; Long stapled length is 0.7～9mm, and the length of staple fibre is 0.15～0.4mm.
Further, the thermal conductivity >80w/ of above-mentioned heat conducting fiber (mk), the tensile strength >700Mpa of heat conducting fiber.
Further, by weight, heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts.
Further, the initial expansion temperature of expanded graphite is 250～280 DEG C; The particle diameter of expanded graphite is 100～300 orders, and the particle diameter of crystalline flake graphite is 1200～5000 orders.
Further, heat conducting fiber is carbon fiber or steel fiber, is preferably carbon fiber.
Further, by weight, also comprise the fortifying fibre of 1～15 part, preferably fortifying fibre is glass fibre.
Further, by weight, heat conduction composite polyethylene material also comprises: the fire retardant of 1～20 part and the fire retarding synergist of 0.5～6 part, the toughner of optional 3～15 parts and the coupling agent of optional 0.5～3 part, and preferably fire retardant is one or more in decabromodiphynly oxide, TDE or tetrabromo-bisphenol; Preferably fire retarding synergist is one or more in antimonous oxide, sodium antimonate or zinc borate; Preferably toughner is one or more in ethylene-vinyl acetate copolymer, terpolymer EP rubber, ethylene-octene copolymer, styrene-butadiene copolymer; Preferably coupling agent is silane coupling agent.
According to a further aspect in the invention, a kind of preparation method of heat conduction composite polyethylene material is also provided, it comprises the following steps: S1, by weight, by the polyethylene of 15～50 parts, the heat conducting fiber of 4～35 parts, and the heat conduction particle of 23～80 parts mixes in mixing machine, obtain mixture; S2, by mixture extrude, traction and granulation, obtain heat conduction composite polyethylene material.
Further, in step S1, also comprise the fortifying fibre of 1～15 part is by weight added in mixing machine, the step of jointly mixing with polyethylene, heat conducting fiber and heat conduction particle.
Further, in step S1, also comprise the fire retardant of 1～20 part and the fire retarding synergist of 0.5～6 part are by weight added in mixing machine, the step of jointly mixing with polyethylene, heat conducting fiber, heat conduction particle and optional fortifying fibre.
Further, in step S1, in polyethylene is added to mixing machine before, the toughner of polyethylene and 3～15 parts is mixed, and by mixture at-60～-20 DEG C of temperature abrasive dust to particle diameter below 150 μ m.
Further, in step S1, heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts; Before in crystalline flake graphite is added to mixing machine, also comprise crystalline flake graphite is carried out to pretreated step; Crystalline flake graphite is carried out to pretreated step to be comprised: by weight, the coupling agent of 0.3～2 part is dissolved in ethanol, being mixed with concentration is the first mixing solutions of 1～3%wt, the first mixing solutions is sprayed to crystalline flake graphite, and mix in mixing machine, take out the dry rear pretreated crystalline flake graphite that forms.
Further, in step S1, in fortifying fibre is added to mixing machine before, also comprise fortifying fibre carried out to pretreated step; Fortifying fibre is carried out to pretreated step to be comprised: by weight, the coupling agent of 0.2～1 part is dissolved in ethanol, and being mixed with concentration is the second mixing solutions of 1～3%wt, and the second mixing solutions is sprayed to fortifying fibre, after drying, form pretreated fortifying fibre.
Further, in step S2, when mixture is extruded, extrusion temperature is 200～270 DEG C.
Apply heat conduction composite polyethylene material of the present invention and preparation method thereof, by being added in polyethylene matrix heat conducting fiber as heat conductive filler, formed heat conduction composite polyethylene material.Than granular heat conductive filler, be fibrous heat conductive filler and entering after polyethylene matrix, more easily form each other overlap joint state, the overlap joint network forming also more easily runs through whole polyethylene matrix.Under the conduction of heat of such overlap joint network, can impel the heat rapid diffusion in matrix, thereby be conducive to improve the heat transfer efficiency of matrix material, and then improve the radiating effect of matrix material.In addition, in the time that matrix material is subject to external impacts, the overlap joint network that fibrous heat conductive filler forms can also utilize the deformation of self to absorb certain energy, thereby improves the shock resistance of matrix material, makes matrix material have higher mechanical property.Add after heat conduction particle, these heat conduction particles can " wrap up " joint between different heat conducting fiber simultaneously, make the stronger thermal conducting path of formation between heat conducting fiber.Again for example, heat conduction particle can also " pierce " position between heat conducting fiber, impel originally mutually away from heat conducting fiber form thermal conducting path by these heat conduction particles.Under effect in every respect, be conducive to make two kinds of heat conductive fillers mutually to be coordinated, in polyethylene matrix, form more perfect three-dimensional net structure.Thereby further improve the heat conductivility of matrix material, and improve the shock resistance of matrix material.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe the present invention in detail below in conjunction with embodiment.
Introduce as background technology part, existing composite polyethylene material has the poor problem of thermal conductivity.In order to address this problem, inventor provides a kind of heat conduction composite polyethylene material, and by weight, it comprises polyethylene and the heat conducting fiber of 4～35 parts and the heat conduction particle of 23～80 parts of 15～50 parts.
Above-mentioned matrix material of the present invention is that heat conducting fiber and heat conduction particle are added in polyethylene matrix as heat conductive filler simultaneously.Than granular heat conductive filler, be fibrous heat conductive filler and entering after polyethylene matrix, more easily form each other overlap joint state, the overlap joint network forming also more easily runs through whole polyethylene matrix.Under the conduction of heat of such overlap joint network, can impel the heat rapid diffusion in matrix, thereby be conducive to improve the heat transfer efficiency of matrix material, and then improve the radiating effect of matrix material.In addition, in the time that matrix material is subject to external impacts, the overlap joint network that fibrous heat conductive filler forms can also utilize the deformation of self to absorb certain energy, thereby improves the shock resistance of matrix material, makes matrix material have higher mechanical property.Add after heat conduction particle, these heat conduction particles can " wrap up " joint between different heat conducting fiber simultaneously, make the stronger thermal conducting path of formation between heat conducting fiber.Again for example, heat conduction particle can also " pierce " position between heat conducting fiber, impel originally mutually away from heat conducting fiber form thermal conducting path by these heat conduction particles.Under effect in every respect, be conducive to make two kinds of heat conductive fillers mutually to be coordinated, in polyethylene matrix, form more perfect three-dimensional net structure.Thereby further improve the heat conductivility of matrix material, and improve the shock resistance of matrix material.
In above-mentioned matrix material of the present invention, as long as adopt heat conducting fiber as heat conductive filler, just can be at the certain heat conduction network of polyethylene matrix performance.One preferred embodiment in, above-mentioned heat conducting fiber comprises the macrofiber of 2～20 parts and the staple fibre of 2～15 parts; Long stapled length is 0.7～9mm, and the length of staple fibre is 0.15～0.4mm.The in the situation that of fixing heat conductive filler umber, heat conducting fiber collocation different length is used, utilize macrofiber to form the filler network on two-dimensional directional, utilize staple fibre to overlap different two-dimentional filler networks, and then can form three-dimensional filler network.This is just conducive to further improve heat conductivility and the shock resistance of matrix material.
In above-mentioned matrix material of the present invention, the thermal conductivity of the heat conducting fiber adopting self is higher, and the heat conductivility of applying its prepared composite polyethylene material is better.Consider heat conductivility and the use properties of matrix material, preferably, the thermal conductivity >80w/ of heat conducting fiber (mk), the tensile strength >700Mpa of heat conducting fiber.
In above-mentioned matrix material of the present invention, the heat conduction particle of employing can be any heat conduction particle well-known to those skilled in the art, silicon carbide and aluminium nitride that for example background technology part is mentioned.One preferred embodiment in, by weight, above-mentioned heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts.Expanded graphite and crystalline flake graphite all have higher thermal conductivity, and the density of the two is lighter, can make heat transfer property that composite material concurrent is higher and lighter weight.More preferably, the initial expansion temperature of above-mentioned expanded graphite is 250～280 DEG C; The particle diameter of expanded graphite is 100～300 orders, and the particle diameter of crystalline flake graphite is 1200～5000 orders.Initial expansion temperature is the important factor that affects expanded graphite interlamellar spacing.The expanded graphite forming under above-mentioned initial expansion temperature, interlamellar spacing is comparatively suitable, can make the crystalline flake graphite under the above-mentioned particle diameter of part enter interlayer.Thereby can further improve the heat conductivility of expanded graphite, further to improve the heat conductivility of matrix material.
In above-mentioned matrix material of the present invention, the fiber arbitrarily with heat conductivility all can serve as above-mentioned heat conducting fiber.One preferred embodiment in, above-mentioned heat conducting fiber is carbon fiber or steel fiber, steel fiber can be copper fiber, aluminum fiber etc.More preferably, above-mentioned heat conducting fiber is carbon fiber.Carbon fiber has higher thermal conductivity, and has the advantage of high strength, light weight.In order to be conducive to make the high heat conduction of composite material concurrent, high impact resistance and high-intensity excellent properties as heat conducting fiber.In addition, for the consideration that further improves mechanics of composites intensity, above-mentioned matrix material by weight, also comprises the fortifying fibre of 1～15 part, and this fortifying fibre can be glass fibre.
According to the above-mentioned instruction of the present invention, those skilled in the art, for the object of improving composite material combination property, have the ability to select other auxiliary agents, are added in above-mentioned matrix material.One preferred embodiment in, by weight, above-mentioned matrix material also comprises the fire retardant of 1～20 part and the fire retarding synergist of 0.5～6 part.Fire retardant and fire retarding synergist are added in matrix material, can improve the flame retardant properties of matrix material so that this matrix material be more suitable for high integration electron device prepare material.Concrete fire retardant includes but not limited to one or more in decabromodiphynly oxide, TDE or tetrabromo-bisphenol, and fire retarding synergist includes but not limited to one or more in antimonous oxide, sodium antimonate or zinc borate;
More preferably, by weight, the above-mentioned heat conduction composite polyethylene material of stating also comprises 3～15% toughner; Toughner includes but not limited to one or more in ethylene-vinyl acetate copolymer, terpolymer EP rubber, ethylene-octene copolymer, styrene-butadiene copolymer;
Further preferably, by weight, above-mentioned heat conduction composite polyethylene material also comprises the coupling agent of 0.5～3 part; Coupling agent includes but not limited to silane coupling agent.Utilize coupling agent, be conducive to improve the consistency between filler or auxiliary agent and polyethylene matrix, thereby further improve the over-all properties of matrix material.
In above-mentioned matrix material of the present invention, the molecular weight of the polyethylene matrix of employing does not have particular requirement, as long as it has good processing characteristics.Such as, poly weight-average molecular weight can 4 × 10
5～8 × 10
5.
In addition, the present invention also provides a kind of preparation method of heat conduction composite polyethylene material, it comprises the following steps: S1, by weight, the polyethylene of 15～50 parts, the heat conducting fiber of 4～35 parts and the heat conduction particle of 23～80 parts are mixed in mixing machine, and obtain mixture; S2, by described mixture extrude, traction and granulation, obtain described heat conduction composite polyethylene material.Apply fibrous heat conductive filler, can make to form and overlap network between different heat conducting fiber, and then form heat conduction network.Even this just can by the heat in matrix by this heat conduction network transfer out, thereby be conducive to improve the heat conductivility of composite polyethylene material.Meanwhile, in the time that matrix material is subject to external force, such overlap joint network can utilize the deformation absorption portion energy of self, thereby is conducive to improve the shock resistance of matrix material.In addition, add fibrous and granular heat conductive filler simultaneously, be conducive in polyethylene matrix, form more perfect three dimentional heat conduction filler network, thereby further improve the heat conductivility of matrix material.
More preferably, in above-mentioned steps S1, also comprise the fortifying fibre of 1～15 part is by weight added in mixing machine, the step of jointly mixing with polyethylene, heat conducting fiber and heat conduction particle.By adding fortifying fibre, can further improve the mechanical property of matrix material.Further preferably, in above-mentioned steps S1, also comprise the fire retardant of 1～20 part and the fire retarding synergist of 0.5～6 part are by weight added in mixing machine, the step of jointly mixing with polyethylene, heat conducting fiber, heat conduction particle and optional fortifying fibre.By adding fire retardant and fire retarding synergist, can improve the flame retardant properties of matrix material.
In above-mentioned preparation method of the present invention, as long as each raw material is mixed in mixing machine, then mixture is extruded, just can be obtained the matrix material that heat conductivility is higher.One preferred embodiment in, in above-mentioned steps S1, in polyethylene is added to mixing machine before, by polyethylene and by weight 3～15 parts toughner mix, and by mixture at-60～-20 DEG C of temperature abrasive dust to particle diameter below 150 μ m.Polyethylene is ground at low temperatures in pulverizing mill, can make it have less particle diameter, thereby be conducive to the mixing in later stage and extrude processing.Meanwhile, further add toughner, be conducive to further improve the shock resistance of matrix material.
Above-mentioned heat conduction particle can be expanded graphite and crystalline flake graphite, and preferably, in above-mentioned steps S1, heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts; Before in crystalline flake graphite is added to mixing machine, also comprise crystalline flake graphite is carried out to pretreated step; Crystalline flake graphite is carried out to pretreated step to be comprised: by weight, the coupling agent of 0.3～2 part is dissolved in ethanol, being mixed with concentration is the first mixing solutions of 1～3%wt, the first mixing solutions is sprayed to crystalline flake graphite, and mix in mixing machine, take out and form after drying pretreated crystalline flake graphite.Utilize coupling agent to carry out pre-treatment to crystalline flake graphite, can improve the surfactivity of crystalline flake graphite, make itself and polyethylene matrix there is better consistency, and then improve the over-all properties of matrix material.In like manner, in above-mentioned steps S1, in fortifying fibre is added to mixing machine before, also comprise fortifying fibre carried out to pretreated step; Fortifying fibre is carried out to pretreated step to be comprised: by weight, the coupling agent of 0.2～1 part is dissolved in ethanol, and being mixed with concentration is the second mixing solutions of 1～3%wt, and the second mixing solutions is sprayed to described fortifying fibre, after drying, form pretreated described fortifying fibre.
In above-mentioned preparation method of the present invention, when polyethylene, filler mixture are extruded, expressing technique is according to conventional polyethylene expressing technique.One preferred embodiment in, in above-mentioned steps S2, when mixture is extruded, extrusion temperature is 200～270 DEG C.The composite polyethylene material forming at this temperature, the dispersiveness of heat conducting fiber, heat conduction particle, fortifying fibre and other auxiliary agents is better, and the over-all properties of matrix material is relatively high.
Below in conjunction with specific embodiment, the present invention is described in further detail, these embodiment can not be interpreted as restriction the present invention scope required for protection.
Embodiment 1
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 40 | Weight-average molecular weight 4 × 10 5 |
| Carbon fiber is long fine | 5 | Staple length 1mm, thermal conductivity is 90w/ (mk) |
| Carbon fiber short fiber | 3 | Staple length 0.15mm, thermal conductivity is 90w/ (mk) |
| Expanded graphite | 30 | 260 DEG C of initial expansion temperatures; Particle diameter 200 orders |
| Crystalline flake graphite | 3 | Particle diameter 2000 orders |
| Glass fibre | 5 | Staple length 50mm |
| Toughner (terpolymer EP rubber) | 10 | -- |
| Decabromodiphynly oxide | 2.5 | -- |
| Antimonous oxide | 0.5 | -- |
| Silane coupling agent (KH560) | 1 | -- |
Preparation technology:
Polyethylene and toughner particle are carried out to low temperature abrasive dust (abrasive dust temperature is-60 DEG C) in pulverizing mill, to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution is in glass fibre, dry rear for subsequent use.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution, on crystalline flake graphite, and is mixed to 5min in mixing machine, for subsequent use after dry.
Above-mentioned polyethylene after treatment, toughner, glass fibre and crystalline flake graphite are added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 250 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Embodiment 2
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 30 | Weight-average molecular weight 8 × 10 5 |
| Carbon fiber is long fine | 8 | Staple length 3mm, thermal conductivity is 90w/ (mk) |
| Carbon fiber short fiber | 5 | Staple length 0.2mm, thermal conductivity is 90w/ (mk) |
| Expanded graphite | 35 | 260. DEG C of initial expansion temperatures; Particle diameter 100. orders |
| Crystalline flake graphite | 6 | Particle diameter 2000 orders |
| Glass fibre | 5 | Staple length 50mm |
| Toughner (ethylene-octene copolymer) | 7 | -- |
| Decabromodiphynly oxide | 2.5 | -- |
| Antimonous oxide | 0.5 | -- |
| Silane coupling agent (KH560) | 1 | -- |
Preparation technology:
Polyethylene and toughner particle are carried out to low temperature abrasive dust (abrasive dust temperature is-20 DEG C) in pulverizing mill, to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution is in glass fibre, dry rear for subsequent use.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution, on crystalline flake graphite, and is mixed to 5min in mixing machine, for subsequent use after dry.
Above-mentioned polyethylene after treatment, toughner, glass fibre and crystalline flake graphite are added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 270 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Embodiment 3
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 25 | Weight-average molecular weight 6 × 10 5 |
| Carbon fiber is long fine | 15 | Staple length 5mm, thermal conductivity is 90w/ (mk) |
| Carbon fiber short fiber | 5 | Staple length 0.3mm, thermal conductivity is 90w/ (mk) |
| Expanded graphite | 35 | 250 DEG C of initial expansion temperatures; Particle diameter 300 orders |
| Crystalline flake graphite | 6 | Particle diameter 2000 orders |
| Glass fibre | 5 | Staple length 50mm |
| Toughner (ethylene-octene copolymer) | 5 | -- |
| Decabromodiphynly oxide | 2.5 | -- |
| Antimonous oxide | 0.5 | -- |
| Silane coupling agent (KH560) | 1 | -- |
Preparation technology:
Polyethylene and toughner particle are carried out to low temperature abrasive dust (abrasive dust temperature is-30 DEG C) in pulverizing mill, to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution is in glass fibre, dry rear for subsequent use.
The silane coupling agent of 0.5 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution, on crystalline flake graphite, and is mixed to 5min in mixing machine, for subsequent use after dry.
Above-mentioned polyethylene after treatment, toughner, glass fibre and crystalline flake graphite are added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 200 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Embodiment 4
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 55 | Weight-average molecular weight 4 × 10 5 |
| Carbon fiber is long fine | 23 | Staple length 5mm, thermal conductivity is 80w/ (mk) |
| Carbon fiber short fiber | 18 | Staple length 0.2mm, thermal conductivity is 80w/ (mk) |
| Expanded graphite | 15 | 260 DEG C of initial expansion temperatures; Particle diameter 100 orders |
| Crystalline flake graphite | 35 | Particle diameter 2000 orders |
| Glass fibre | 0 | -- |
| Toughner | 0 | -- |
| Decabromodiphynly oxide | 0 | -- |
| Antimonous oxide | 0 | -- |
| Silane coupling agent | 0 | -- |
Preparation technology:
Polyethylene is carried out in pulverizing mill to low temperature abrasive dust (abrasive dust temperature for-60 DEG C), to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
Above-mentioned polyethylene after treatment is added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 280 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Embodiment 5
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 50 | Weight-average molecular weight 4 × 10 5 |
| Carbon fiber is long fine | 20 | Staple length 9mm, thermal conductivity is 90w/ (mk) |
| Carbon fiber short fiber | 15 | Staple length 0.15mm, thermal conductivity is 90w/ (mk) |
| Expanded graphite | 50 | 250 DEG C of initial expansion temperatures; Particle diameter 300 orders |
| Crystalline flake graphite | 3 | Particle diameter 5000 orders |
| Glass fibre | 15 | Staple length 50mm |
| Toughner (ethylene-octene copolymer) | 15 | -- |
| Tetrabromo-bisphenol | 20 | -- |
| Sodium antimonate | 6 | -- |
| Silane coupling agent (KH560) | 3 | -- |
Preparation technology:
Polyethylene and toughner particle are carried out to low temperature abrasive dust (abrasive dust temperature is-60 DEG C) in pulverizing mill, to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
The silane coupling agent of 2 parts is diluted to the solution that concentration is 3wt% in ethanol, this spray solution is in glass fibre, dry rear for subsequent use.
The silane coupling agent of 1 part is diluted to the solution that concentration is 2wt% in ethanol, this spray solution, on crystalline flake graphite, and is mixed to 5min in mixing machine, for subsequent use after dry.
Above-mentioned polyethylene after treatment, toughner, glass fibre and crystalline flake graphite are added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min and obtain mixture;
By said mixture at 270 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Embodiment 6
The present embodiment has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
Preparation technology:
Polyethylene and toughner particle are carried out to low temperature abrasive dust (abrasive dust temperature is-60 DEG C) in pulverizing mill, to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
The silane coupling agent of 0.3 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution is in glass fibre, dry rear for subsequent use.
The silane coupling agent of 0.2 part is diluted to the solution that concentration is 1wt% in ethanol, this spray solution, on crystalline flake graphite, and is mixed to 5min in mixing machine, for subsequent use after dry.
Above-mentioned polyethylene after treatment, toughner, glass fibre and crystalline flake graphite are added in mixing machine, other raw materials are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 240 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Comparative example 1
This comparative example has been prepared a kind of heat conduction composite polyethylene material.
Raw materials:
| Raw material | Consumption (g) | Parameter |
| Polyethylene | 25 | Weight-average molecular weight 3 × 10 5 |
| Carbon fiber is long fine | 23 | Staple length 0.6mm, thermal conductivity is 80w/ (mk) |
| Carbon fiber short fiber | 18 | Staple length 0.1mm, thermal conductivity is 80w/ (mk) |
| Expanded graphite | 0 | -- |
| Crystalline flake graphite | 0 | -- |
| Glass fibre | 0 | -- |
| Toughner (terpolymer EP rubber) | 0 | -- |
| Decabromodiphynly oxide | 0 | -- |
| Antimonous oxide | 0 | -- |
| Silane coupling agent (KH560) | 0 | -- |
Preparation technology:
Polyethylene is carried out in pulverizing mill to low temperature abrasive dust (abrasive dust temperature for-20 DEG C), to grain diameter be 100～150 μ m, for subsequent use after abrasive dust is dry.
Above-mentioned polyethylene after treatment is added in mixing machine, long carbon fiber fibre and carbon fiber short fiber are added in mixing machine in the lump simultaneously, under the power of 3KW, mix 5min, obtain mixture;
By said mixture at 280 DEG C, extrude, traction and granulation, prepare heat conduction composite polyethylene material.
Heat conduction composite polyethylene material prepared in above-described embodiment 1 to 6 and comparative example 1 is carried out to performance characterization.
Performance test, the impact property test of sample is measured according to GBT1043.1-2008, and is expressed as kJ/m
2; Sample Determination of conductive coefficients carries out according to GB-T10297-1998, and is expressed as w/mk; Combustionproperty test is tested according to UL94 standard.Test result is as shown in table 1:
Table 1
From above data with describing, can find out, in polyethylene matrix, add heat conducting fiber and heat conduction particle simultaneously, can make matrix material there is higher heat conductivility.Especially, further add after other auxiliary agents, can further improve the over-all properties of matrix material, make it have higher heat conductivility, shock resistance and flame retardant properties concurrently.Can meet raw-material service requirements in high integration electron device.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (15)
1. a heat conduction composite polyethylene material, is characterized in that, by weight, comprises the polyethylene of 15～50 parts, the heat conducting fiber of 4～35 parts and the heat conduction particle of 23～80 parts.
2. matrix material according to claim 1, is characterized in that, by weight, described heat conducting fiber comprises the macrofiber of 2～20 parts and the staple fibre of 2～15 parts; Described long stapled length is 0.7～9mm, and the length of described staple fibre is 0.15～0.4mm.
3. matrix material according to claim 2, is characterized in that, the thermal conductivity >80w/ (mk) of described heat conducting fiber, the tensile strength >700Mpa of described heat conducting fiber.
4. matrix material according to claim 1, is characterized in that, by weight, described heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts.
5. matrix material according to claim 4, is characterized in that, the initial expansion temperature of described expanded graphite is 250～280 DEG C; The particle diameter of described expanded graphite is 100～300 orders, and the particle diameter of described crystalline flake graphite is 1200～5000 orders.
6. according to the matrix material described in any one in claim 1 to 5, it is characterized in that, described heat conducting fiber is carbon fiber or steel fiber, is preferably carbon fiber.
7. matrix material according to claim 6, is characterized in that, by weight, also comprises the fortifying fibre of 1～15 part, and preferred described fortifying fibre is glass fibre.
8. matrix material according to claim 7, it is characterized in that, by weight, described heat conduction composite polyethylene material also comprises: the fire retardant of 1～20 part, the fire retarding synergist of 0.5～6 part, the toughner of optional 3～15 parts and the coupling agent of optional 0.5～3 part
Preferred described fire retardant is one or more in decabromodiphynly oxide, TDE or tetrabromo-bisphenol;
Preferred described fire retarding synergist is one or more in antimonous oxide, sodium antimonate or zinc borate;
Preferred described toughner is one or more in ethylene-vinyl acetate copolymer, terpolymer EP rubber, ethylene-octene copolymer, styrene-butadiene copolymer;
Preferred described coupling agent is silane coupling agent.
9. a preparation method for heat conduction composite polyethylene material, is characterized in that, comprises the following steps:
S1, by weight, by the polyethylene of 15～50 parts, the heat conducting fiber of 4～35 parts, and the heat conduction particle of 23～80 parts mixes in mixing machine, obtains mixture;
S2, by described mixture extrude, traction and granulation, obtain described heat conduction composite polyethylene material.
10. preparation method according to claim 9, it is characterized in that, in described step S1, also comprise the fortifying fibre of 1～15 part is by weight added in described mixing machine, the step of jointly mixing with described polyethylene, described heat conducting fiber and described heat conduction particle.
11. according to the preparation method described in claim 9 or 10, it is characterized in that, in described step S1, also comprise the fire retardant of 1～20 part and the fire retarding synergist of 0.5～6 part are by weight added in described mixing machine, the step of jointly mixing with described polyethylene, described heat conducting fiber, described heat conduction particle and optional described fortifying fibre.
12. preparation methods according to claim 11, it is characterized in that, in described step S1, in described polyethylene is added to described mixing machine before, the toughner of described polyethylene and 3～15 parts is mixed, and by mixture at-60～-20 DEG C of temperature abrasive dust to particle diameter below 150 μ m.
13. preparation methods according to claim 10, is characterized in that, in described step S1, described heat conduction particle comprises the expanded graphite of 20～50 parts and the crystalline flake graphite of 3～30 parts; Before in described crystalline flake graphite is added to described mixing machine, also comprise described crystalline flake graphite is carried out to pretreated step; Described crystalline flake graphite is carried out to pretreated step to be comprised:
By weight, the coupling agent of 0.3～2 part is dissolved in ethanol, and being mixed with concentration is the first mixing solutions of 1～3%wt, and described the first mixing solutions is sprayed to described crystalline flake graphite, and mix in mixing machine, take out the dry rear pretreated described crystalline flake graphite that forms.
14. preparation methods according to claim 11, is characterized in that, in described step S1, in described fortifying fibre is added to described mixing machine before, also comprise described fortifying fibre carried out to pretreated step; Described fortifying fibre is carried out to pretreated step to be comprised:
By weight, the coupling agent of 0.2～1 part is dissolved in ethanol, being mixed with concentration is the second mixing solutions of 1～3%wt, and described the second mixing solutions is sprayed to described fortifying fibre, after drying, forms pretreated described fortifying fibre.
15. preparation methods according to claim 9, is characterized in that, in described step S2, when described mixture is extruded, extrusion temperature is 200～270 DEG C.
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Effective date of registration: 20170914 Address after: 100084, building 9, building 1, Zhongguancun East Road, Beijing, Haidian District, 04-09A Co-patentee after: Tianjin Huachuang Ruifeng air conditioning equipment Co. Patentee after: Beijing SinoRefine Air Conditioning Technology Co., Ltd. Address before: 100084, building 9, building 1, Zhongguancun East Road, Beijing, Haidian District, 04-09A Patentee before: Beijing SinoRefine Air Conditioning Technology Co., Ltd. |