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CN104371318A - Polyamide composite material with high thermal conductivity and high heat resistance and preparation method thereof - Google Patents

Polyamide composite material with high thermal conductivity and high heat resistance and preparation method thereof Download PDF

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Publication number
CN104371318A
CN104371318A CN201410657249.XA CN201410657249A CN104371318A CN 104371318 A CN104371318 A CN 104371318A CN 201410657249 A CN201410657249 A CN 201410657249A CN 104371318 A CN104371318 A CN 104371318A
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Prior art keywords
high heat
heat resistance
heat conduction
polyamide compoiste
material according
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Pending
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CN201410657249.XA
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Inventor
刘引烽
徐华根
张阳
周海堤
王宇翔
朱逸莉
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Priority to CN201410657249.XA priority Critical patent/CN104371318A/en
Publication of CN104371318A publication Critical patent/CN104371318A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a polyamide composite material with high thermal conductivity and high heat resistance and a preparation method thereof. The composite material comprises the following components in percentage by mass: 20%-50% of matrix resin, 40%-65% of composite heat-conducting fillers, 4%-12% of a halogen-free flame retardant, 0.5%-2% of a coupling agent, 0.2-1% of an antioxidant and 0.2%-1% of a lubricating dispersant. PA46 resin with a symmetrical molecular chain structure and high crystallinity is taken as the matrix resin; different heat-conducting fillers with different shapes and particle sizes are added to be overlapped between the heat-conducting fillers; and meanwhile, a small amount of flame retardant is added, so that the polyamide composite material disclosed by the invention has excellent heat-conducting property, flame retardant property and insulating property, and meets the operating requirements of electronic and electrical appliances, is high in design freedom, and can be widely applied to the fields such as LED lampshades, printed circuit boards and electrical devices.

Description

High heat conduction high heat resistance polyamide compoiste material and preparation method thereof
Technical field
The present invention relates to a kind of polyamide compoiste material and preparation method thereof, particularly a kind of high heat conduction high heat resistance polyamide compoiste material and preparation method thereof.
Background technology
Plastics have the advantage such as light weight, high-strength, insulation, good molding processibility and designability, but when being used for the aspects such as electrical and electronic component, indicating meter framework, computer heat radiation parts and LED when plastics, because the thermal conductivity of plastics is lower, be difficult in time heat be shed, cause the accumulation of heat thus reduce the work-ing life of material and the stability in use of material.Based on this, the development research of heat-conducting plastic enters the visual field of people.Heat-conducting plastic is divided into eigenmode and filled-type, and wherein eigenmode operation easier is large, cost is high, so we mainly pay close attention to HEAT-CONDUCTING PLASTICS FILLED WTTH PARTICLES.The main preparation methods of HEAT-CONDUCTING PLASTICS FILLED WTTH PARTICLES is in polymeric matrix, fill high heat conduction component, by the interaction between heat-conducting plastic, forms similar chain or netted distributional pattern and heat conduction network chain and improve the thermal conductivity of matrix material in system.Single filler forms continuous print path needs more consumption, causes the decline of material mechanical performance and processing characteristics; Mixing heat conductive filler can overlap in the base preferably, is formed stacking more closely, forms reticulated structure, thus improves the heat conductivility of material.
Can be used for filled with polymer material modification has a variety of with the heat conductive filler obtaining thermal conductive resin matrix material, such as, hexagonal boron nitride, spherical alumina, crystal whisker-shaped silicon carbide, aluminium nitride, magnesium oxide, crystalline flake graphite, expanded graphite, Graphene, carbon nanotube, metal powders etc., wherein boron nitride can increase substantially the heat conductivility of material and don't the insulating property of loss material as heat conductive filler, the high and relative moderate of thermal conductivity.However, single boron nitride loaded polymer material is still difficult to the cooling requirements meeting some high-end radiating element.In order to reach certain thermal conductivity, the hexagonal boron nitride loading level of needs is very high.For this reason, other filler different types of to itself and different shapes carries out mixing as heat conductive filler by we, can improve the heat conductivility of material further.
Number of patent application 200780011249.0 discloses and utilizes PA66 for resin matrix, aluminum oxide is the preparation of the heat conduction PA of filler, because the thermal conductivity of the single filling of aluminum oxide is not high, the thermal conductivity of disclosed heat conduction PA in this way not high, and resistance toheat is outstanding not.PA46 is the fatty polyamide by butanediamine and hexanodioic acid polycondensation, although there be the molecular structure similar to polyamide 66, the acid amides group number on the chain of each given length of PA46 is more, and chain structure is more symmetrical; And the chain structure of high degree of symmetry causes its degree of crystallinity high (being about 70%), and crystallization velocity is fast, and thus fusing point higher (295 DEG C), heat-drawn wire is also high, and its life-time service temperature (CUT 5000hours) can reach 163 DEG C.These characteristics cause the matrix material using PA46 as matrix can reach higher thermal conductivity compared to other material; Meanwhile, as thermally conductive material, must have certain thermotolerance, PA46 also has excellent performance in this regard.Therefore, the present invention take PA46 as matrix resin, adopts composite heat-conducting filler to fill, to obtain the heat-conductive composite material of high heat conductance, high heat resistance.
Summary of the invention
An object of the present invention be to overcome exist in prior art defect, a kind of high heat conduction high heat resistance polyamide compoiste material is provided.The advantages such as this thermal conductivity of composite materials is high, heat-resisting effect good, good workability, fire retardant insulating.
Two of object of the present invention is the preparation method providing this matrix material.
Object of the present invention can be achieved through the following technical solutions:
A kind of high heat conduction high heat resistance polyamide compoiste material, it is characterized in that the composition of this matrix material and mass percentage content as follows:
Matrix resin 20 ~ 50%;
Composite heat-conducting filler 40 ~ 65%;
Halogen-free flame retardants 4 ~ 12%;
Coupling agent 0.5 ~ 2%;
Oxidation inhibitor 0.2 ~ 1%;
Lubrication dispersing agent 0.2 ~ 1%;
The mass percent sum of each composition is 100% above.
Above-mentioned matrix resin to be degree of crystallinity be 50 ~ 80% PA46 polymeric amide or the polyamide alloy that is main component with PA46 polymeric amide.
Above-mentioned composite heat-conducting filler is that one or more and the crystalline flake graphite in boron nitride, aluminium nitride, magnesium oxide, aluminum oxide, Graphene, carbon nanotube, metal powder combines by a certain percentage.For boron nitride, aluminum oxide and crystalline flake graphite, boron nitride particle diameter is 5 ~ 20 microns, and alumina particle is 20 ~ 50 microns, and crystalline flake graphite is 50 ~ 150 microns, and three's mass percent ratio is:
Crystalline flake graphite: 5 ~ 30%
Aluminum oxide and boron nitride mixture: 95 ~ 70%
Wherein, in aluminum oxide and boron nitride mixture, the mass percent of aluminum oxide is 0 ~ 70.
In above-mentioned heat conductive filler, a kind of aluminium nitride, magnesium oxide, carbon nanotube, the metal powder that also can replace with corresponding size in aluminum oxide and boron nitride.
Above-mentioned halogen-free flame retardants is red phosphorus and phosphorus flame retardant and nitrogenated flame retardant is composite forms, and described phosphorus flame retardant is one or more in Triphenyl phosphate (TPP), tricresyl phosphate second fat, metaphenylene tetraphenyl biphosphonate; Described nitrogenated flame retardant is one or more in trimeric cyanamide, melamine pyrophosphate, polyphosphoric acid melamine.
Above-mentioned coupling agent is KH550, KH560 or KH570.
Above-mentioned oxidation inhibitor is the compound system of Hinered phenols antioxidant, phosphite kind antioxidant or these two kinds of oxidation inhibitor, but is not limited only to this two kinds of oxidation inhibitor or their compound system.
Above-mentioned lubrication dispersing agent is polymeric amide conventional lubricants, such as, with a kind of BAB type multipolymer (TAF or MB-4) containing polar group that ethylenebis fatty acid amide (EBS) is prepared for base-material, but is not limited only to this multipolymer.
Prepare a method for above-mentioned high heat conduction high heat resistance polyamide compoiste material, it is characterized in that the concrete steps of the method are: above-mentioned raw materials is put into discharging after high-speed mixer and mixing 3 ~ 5min, obtain mixture; Then, control processing temperature and the screw speed of twin screw extruder, mixture is placed in twin screw extruder extruding pelletization, obtains product.
During above-mentioned extruding pelletization, the processing conditions of twin screw extruder is generally: when matrix resin is PA46, and the processing temperature controlling twin screw extruder is 280 ~ 320 DEG C, screw speed 180 ~ 600 revs/min; When matrix resin is when taking PA46 as the polyamide alloy of main component, according to concrete all types of alloys, the processing conditions reference data provided according to material supplier, the suitably processing temperature of adjustment twin screw extruder and screw speed.
The present invention compared with prior art, has the following advantages:
1, the matrix resin that the present invention adopts is the PA46 resin that the regular degree of crystallinity of molecular chain structure is high, and good heat conduction effect, thermotolerance is strong.The thermal conductivity of matrix material generally can reach 2.3 more than W/mK, and when mixing heat conductive filler loading level is 58%, heat-conductive composite material is through preferred, and its thermal conductivity can reach 4.2 W/mK.
2, the present invention adopts composite heat-conducting filler, and utilize the effective overlap joint between different shapes and the heat conductive filler of particle diameter to improve the thermal conductivity of material, obtain matrix material good heat conduction effect, filler cost is low.
3, the present invention adds a certain amount of fire retardant, makes the fire-retardant rank of matrix material reach V0(UL-94).
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Embodiment 1-6
A kind of high heat conduction high heat resistance polyamide compoiste material formula and preparation method thereof, comprises the following steps:
(1) get the raw materials ready according to the component in table 1 and content, halogen-free flame retardants is red phosphorus and phosphorus system composite fire retardant; Boron nitride is hexagonal system boron nitride, is of a size of 5 microns; Aluminum oxide is heat conduction ball-aluminium oxide, is of a size of 50 microns; Graphite is crystalline flake graphite, is of a size of 104 microns; Coupling agent is silane coupling agent; Oxidation inhibitor is Hinered phenols antioxidant, phosphite kind antioxidant compound system; Lubrication dispersing agent is a kind of BAB type multipolymer containing polar group that ethylenebis fatty acid amide (EBS) is prepared for base-material.
(2) above-mentioned raw materials is put into discharging after high-speed mixer and mixing 3-5min, obtain mixture, then control the processing temperature 280-320 DEG C of twin screw extruder, screw rod revolution 180-600 rev/min, the mixture mixed is placed in twin screw extruder extruding pelletization, obtains product.
Table 1 embodiment 1-6 formula for raw stock
Carry out performance test comparison according to the sample 1-6 that embodiment 1-6 obtains, adopt ASTM standard, test performance contrast is as shown in table 2.
The batten test result of table 2 embodiment 1-6
Embodiment 1 is for adding more polymeric matrix and less crystalline flake graphite, and according to test result, we can find out, the thermal conductivity of material is lower, but surface resistivity is higher, good insulating.Embodiment 4 adds more crystalline flake graphite, and six side's shape boron nitride, has suitable ratio between spherical alumina and sheet crystalline flake graphite, add-on is suitable, can conveniently process, and has very high thermal conductivity, and surface resistivity reaches insulating requirements, and flame retardant properties reaches V0, and resistance to elevated temperatures is good.
Simultaneously, we are not to add fire retardant systems, to adopt the single heat conductive filler of boron nitride and boron nitride and aluminum oxide binary composite heat-conducting filler to fill the system of PA46, and using PA66 but not PA46 polymeric amide as matrix resin system as a comparison, show the present invention and adopt compound PA46 to be matrix resin and adopt composite heat-conducting filler and add the comprehensive advantage of fire retardant.Contrast experiment is embodiment 7-10, and concrete grammar is as follows:
(1) get the raw materials ready according to the component in table 3 and content, halogen-free flame retardants is red phosphorus and phosphorus system composite fire retardant; Boron nitride is hexagonal system boron nitride, is of a size of 5 microns; Aluminum oxide is heat conduction ball-aluminium oxide, is of a size of 50 microns; Graphite is crystalline flake graphite, is of a size of 104 microns; Coupling agent is silane coupling agent; Oxidation inhibitor is Hinered phenols antioxidant, phosphite kind antioxidant compound system; Lubrication dispersing agent is a kind of BAB type multipolymer containing polar group that ethylenebis fatty acid amide (EBS) is prepared for base-material.
(2) above-mentioned raw materials is put into discharging after high-speed mixer and mixing 3-5min, obtain mixture, then control the processing temperature 280-320 DEG C of twin screw extruder, screw rod revolution 180-600 rev/min, is placed in twin screw extruder extruding pelletization, obtains product by mixture.When embodiment 10 adopts PA66 to be matrix resin, the processing temperature of twin screw extruder is 250-270 DEG C.
Table 3 embodiment 7-10 formula for raw stock
The sample obtained to embodiment 7-10 does performance test, and adopt ASTM standard, test performance result is as shown in table 4.
The batten test result of table 4 embodiment 7-10
Do not add fire retardant in embodiment 7, therefore, the flame retardant properties of matrix material reduces greatly, only reaches V2 level; Embodiment 8 is for adding less polymeric matrix and single heat conductive filler boron nitride, although the filler added is a lot, according to test result, we can find out, the thermal conductivity of material is lower; Embodiment 9 adopts binary composite heat-conducting filler boron nitride and alumina filled in less PA46 matrix resin, and its thermal conductivity is also lower.Adopt PA66 to substitute the embodiment 10 of PA46 compared with the embodiment 4 of same recipe, thermal conductivity is also lower, and temperature capacity declines larger.
Can draw from above-described embodiment, the excellent performance of fire retardant insulating heat-conducting plastic of the present invention, flame retardant properties can reach V0, and surface resistivity is 10 13Ω/cm, thermal conductivity preferably can reach 4.2 W/mK.Wherein graphite guide good in thermal property, but on-insulated, so can not use when component design too much.The present invention focuses on and uses molecular chain structure is symmetrical and degree of crystallinity is high PA46 resin to fill for matrix and the shape heat conductive filler different with particle diameter, add a certain amount of fire retardant simultaneously, by the overlap joint of mixed fillers, pile up tightr, give that materials'use temperature is high, good insulation preformance, good flame retardation effect and thermal conductivity advantages of higher, there are good market outlook.
Need to be illustrated, the present invention is not limited to the raw material of above-mentioned specific embodiment, proportioning and working method thereof, and those skilled in the art can make various distortion or amendment within the scope of the claims and not affect flesh and blood of the present invention.

Claims (14)

1. a high heat conduction high heat resistance polyamide compoiste material, it is characterized in that the composition of this matrix material and mass percentage content as follows:
Matrix resin 20 ~ 50%;
Composite heat-conducting filler 40 ~ 65%;
Halogen-free flame retardants 4 ~ 12%;
Coupling agent 0.5 ~ 2%;
Oxidation inhibitor 0.2 ~ 1%;
Lubrication dispersing agent 0.2 ~ 1%;
The mass percent sum of each composition is 100% above.
2. high heat conduction high heat resistance polyamide compoiste material according to claim 1, is characterized in that described matrix resin to be degree of crystallinity is the PA46 polymeric amide of 50 ~ 80% or the polyamide alloy that is main component with PA46 polymeric amide.
3. high heat conduction high heat resistance polyamide compoiste material according to claim 1, is characterized in that described composite heat-conducting filler is that one or more mixtures in boron nitride, aluminium nitride, magnesium oxide, aluminum oxide, Graphene, carbon nanotube, metal powder and crystalline flake graphite combine by a certain percentage.
4. high heat conduction high heat resistance polyamide compoiste material according to claim 3, is characterized in that described boron nitride is hexagonal system; Described aluminum oxide and magnesium oxide are spherical; Described graphite is flaky graphite.
5. high heat conduction high heat resistance polyamide compoiste material according to claim 4, is characterized in that described boron nitride particle diameter is 5 ~ 20 microns; Described alumina particle is 20 ~ 50 microns; Described crystalline flake graphite is 50 ~ 150 microns.
6. high heat conduction high heat resistance polyamide compoiste material according to claim 4, is characterized in that the combination of described composite heat-conducting filler in mass percent ratio is:
Crystalline flake graphite: 5 ~ 30%
Aluminum oxide and boron nitride mixture: 95 ~ 70%
Wherein, in aluminum oxide and boron nitride mixture, the mass percent of aluminum oxide is 0 ~ 70.
7. high heat conduction high heat resistance polyamide compoiste material according to claim 6, is characterized in that in described composite heat-conducting filler, and the aluminium nitride of a kind of corresponding size in aluminum oxide and boron nitride, magnesium oxide or carbon nanotube are replaced.
8. high heat conduction high heat resistance polyamide compoiste material according to claim 1, it is characterized in that described halogen-free flame retardants is red phosphorus and phosphorus flame retardant and nitrogenated flame retardant is composite forms, described phosphorus flame retardant is one or more in Triphenyl phosphate (TPP), tricresyl phosphate second fat, metaphenylene tetraphenyl biphosphonate; Described nitrogenated flame retardant is one or more in trimeric cyanamide, melamine pyrophosphate, polyphosphoric acid melamine.
9. high heat conduction high heat resistance polyamide compoiste material according to claim 1, is characterized in that described coupling agent is KH550, KH560 or KH570.
10. high heat conduction high heat resistance polyamide compoiste material according to claim 1, is characterized in that described oxidation inhibitor is Hinered phenols antioxidant, phosphite kind antioxidant, any compound system.
11. high heat conduction high heat resistance polyamide compoiste materials according to claim 1, is characterized in that a kind of BAB type multipolymer containing polar group of described lubrication dispersing agent for preparing for base-material with ethylenebis fatty acid amide (EBS).
12. high heat conduction high heat resistance polyamide compoiste materials according to claim 10, is characterized in that described lubrication dispersing agent is: TAF or MB-4.
13. 1 kinds of methods preparing high heat conduction high heat resistance polyamide compoiste material according to claim 1, is characterized in that the concrete steps of the method are: above-mentioned raw materials is put into discharging after high-speed mixer and mixing 3 ~ 5min, obtain mixture; Then, control processing temperature and the screw speed of twin screw extruder, mixture is placed in twin screw extruder extruding pelletization, obtains product.
14. high heat conduction high heat resistance polyamide compoiste materials according to claim 12, it is characterized in that the processing conditions of twin screw extruder during described extruding pelletization is generally: when matrix resin is PA46, the processing temperature controlling twin screw extruder is 280 ~ 320 DEG C, screw speed 180 ~ 600 revs/min; When matrix resin is when taking PA46 as the polyamide alloy of main component, according to concrete all types of alloys, the processing conditions reference data provided according to material supplier, the suitably processing temperature of adjustment twin screw extruder and screw speed.
CN201410657249.XA 2014-11-19 2014-11-19 Polyamide composite material with high thermal conductivity and high heat resistance and preparation method thereof Pending CN104371318A (en)

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CN104761856A (en) * 2015-04-16 2015-07-08 浙江乔兴建设集团湖州智能科技有限公司 Novel environment-friendly high-temperature-resistant polyvinyl chloride cable material and preparation method thereof
CN104788951A (en) * 2015-05-04 2015-07-22 武汉轻工大学 LED (light-emitting diode) high-thermal-conductivity composite material and preparation method thereof
CN105462246A (en) * 2015-12-30 2016-04-06 广东聚石化学股份有限公司 Graphene/metal powder composite-modification ultrahigh-heat-conductivity nylon and preparing method thereof
CN105504761A (en) * 2015-12-30 2016-04-20 张桂华 Formula of novel rubber with high stability performance and preparation method thereof
CN109082109A (en) * 2018-06-08 2018-12-25 厦门泰启力飞科技有限公司 A kind of polyamide and graphene high heat conducting nano composite material and preparation method thereof
CN109456591A (en) * 2018-09-04 2019-03-12 徐州市华天塑业有限公司 A kind of Environmentally-frieflame-retardant flame-retardant nylon composition
CN109553963A (en) * 2018-10-30 2019-04-02 广东格瑞新材料股份有限公司 A kind of heat sink material and preparation method thereof
CN110305443A (en) * 2019-06-03 2019-10-08 泰能环保科技(浙江)有限公司 A kind of graphene composite heat conducting material and preparation method thereof
CN110951254A (en) * 2019-11-24 2020-04-03 上海大学 Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof
CN113025041A (en) * 2021-04-13 2021-06-25 南京翌动新材料科技有限公司 Preparation method of high-thermal-conductivity ceramic polymer composite material
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CN116444983A (en) * 2023-04-17 2023-07-18 金发科技股份有限公司 Polyamide composite material and preparation method and application thereof
CN117343586A (en) * 2023-11-13 2024-01-05 慈溪市中一涂料有限公司 PTFE energy-gathering coating

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CN103524873A (en) * 2013-09-25 2014-01-22 吴江市天源塑胶有限公司 Heat-conducting flame-retardant plastic
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761856A (en) * 2015-04-16 2015-07-08 浙江乔兴建设集团湖州智能科技有限公司 Novel environment-friendly high-temperature-resistant polyvinyl chloride cable material and preparation method thereof
CN104788951A (en) * 2015-05-04 2015-07-22 武汉轻工大学 LED (light-emitting diode) high-thermal-conductivity composite material and preparation method thereof
CN105462246A (en) * 2015-12-30 2016-04-06 广东聚石化学股份有限公司 Graphene/metal powder composite-modification ultrahigh-heat-conductivity nylon and preparing method thereof
CN105504761A (en) * 2015-12-30 2016-04-20 张桂华 Formula of novel rubber with high stability performance and preparation method thereof
CN109082109A (en) * 2018-06-08 2018-12-25 厦门泰启力飞科技有限公司 A kind of polyamide and graphene high heat conducting nano composite material and preparation method thereof
CN109456591A (en) * 2018-09-04 2019-03-12 徐州市华天塑业有限公司 A kind of Environmentally-frieflame-retardant flame-retardant nylon composition
CN109553963A (en) * 2018-10-30 2019-04-02 广东格瑞新材料股份有限公司 A kind of heat sink material and preparation method thereof
CN109553963B (en) * 2018-10-30 2021-03-05 广东格瑞新材料股份有限公司 Heat dissipation material and preparation method thereof
CN110305443A (en) * 2019-06-03 2019-10-08 泰能环保科技(浙江)有限公司 A kind of graphene composite heat conducting material and preparation method thereof
CN110951254A (en) * 2019-11-24 2020-04-03 上海大学 Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof
CN113025041A (en) * 2021-04-13 2021-06-25 南京翌动新材料科技有限公司 Preparation method of high-thermal-conductivity ceramic polymer composite material
CN115403857A (en) * 2021-05-27 2022-11-29 伊利诺斯工具制品有限公司 Heat-conducting insulating film and battery pack comprising same
CN115073905A (en) * 2022-07-12 2022-09-20 四川大学 High-thermal-conductivity electrical insulation composite material and preparation method and application thereof
CN116444983A (en) * 2023-04-17 2023-07-18 金发科技股份有限公司 Polyamide composite material and preparation method and application thereof
CN117343586A (en) * 2023-11-13 2024-01-05 慈溪市中一涂料有限公司 PTFE energy-gathering coating

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Application publication date: 20150225