CN104497558A - Novel heat conduction nylon composite material and preparation method thereof - Google Patents
Novel heat conduction nylon composite material and preparation method thereof Download PDFInfo
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- CN104497558A CN104497558A CN201410704641.5A CN201410704641A CN104497558A CN 104497558 A CN104497558 A CN 104497558A CN 201410704641 A CN201410704641 A CN 201410704641A CN 104497558 A CN104497558 A CN 104497558A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of high polymer composite materials and particularly relates to a novel heat conduction nylon composite material and a preparation method thereof. The heat conduction nylon composite material is prepared from the following raw materials in percentage by mass: 20-40% of PA6 resin, 15-40% of heat conduction filler, 10-20% of reinforcing filler, 20-40% of a halogen-free flame retardant, 1-3% of flexibilizer, 0.1-0.5% of a coupling agent, 0.4-1.0% of a surface modifier, 0.4-1.0% of a lubricant, 0.1-0.5% of an antioxidant and 0.1-5% of toner, based on 100% in total. Through a hot and cold impact test for over 1000 hours at (-)40 DEG C-120 DEG C, the color of the heat conduction material disclosed by the invention can be regulated to be black, white, self-colored, grey, red, green, and the like without causing incomplete curing of addition type heat conduction silica gel, and thus, the novel heat conduction nylon composite material is halogen-free, flame retardant, and relatively low in carbon footprint.
Description
Technical field
The present invention relates to technical field of polymer composite materials, be specifically related to a kind of Novel heat-conducting nylon composite materials and preparation method thereof.
Background technology
The illumination of existing power-type LED is general adopts conventional aluminum alloy heat-sink shell, has good heat conductivity, efficiency of thermal transfer advantages of higher, also has that quality is large, a shortcoming such as electrical insulating property and erosion resistance is poor, manufacturing procedure is complicated, production efficiency is low, electroplating surface pollution.In the every field of the modern life, polymer composite product is light with its quality, electrical isolation, corrosion-resistant, easy processing, production efficiency are high, without the need to the unique advantages such as spray treatment progressively substituted metal material.Therefore replace conventional aluminum alloy with heat-conductivity polymer composite, meet environment protection and Sustainable development requirement as LED illumination radiator shell.
As LED radiator shell, except requiring that material has except high thermal conductivity, also require that polymer composite is by the thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, various color can be made into the demand of satisfied different client, good electrical insulating property to get an electric shock hidden danger to eliminate human consumer, excellent halogen-free flameproof performance with avoid the sub-component of LED electrical cause in the situation such as short circuit, current overload fire hazard and poison gas dangerous.Under some ad hoc structure (as part candle lamp), light fixture slip-stick artist also uses the silica gel protected power supply of addition thermal conductive when designing, and this requires that thermally conductive material must friendly contact with heat conductive silica gel, and namely thermally conductive material can not affect the solidification of heat conductive silica gel.
" the reply climate change development in science and technology ad hoc planning of " 12 " country " clearly proposes, promote China to slow down and acclimatization change technique Innovation and application, support low-carbon economy develops, and supports the target of " 12 " period and the Carbon emission of the year two thousand twenty per GDP.Therefore, reduce the carbon footprint of polymer composite as much as possible, meet national industrial policies requirement.
Current commercially available heat-conductivity polymer composite is there are no by the report of thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, color is main mainly with black, white, true qualities, the thermally conductive material of halogen-free flameproof all can cause addition thermal conductive silica gel to solidify not exclusively substantially, and the carbon footprint of the thermally conductive material that bromine antimony is fire-retardant is again far away higher than halogen-free flame-retarded heat-conducting material.
Patent of invention CN 102408710 B adopts nylon66 fiber, boron nitride, silicon carbide, aluminium nitride, high heat conduction nylon 66 composite material prepared by the raw materials such as aluminum oxide, and patent of invention CN 102775767 B adopts nylon 6, Graphite Powder 99, aluminum fibers etc. have prepared the nylon 6 composite material of high heat conduction, and patent of invention CN 103602060 A adopts nylon 6, threadiness heat conductive filler, insulating heat-conductive powder, heat conduction abrasion-resistant powder etc. has prepared heat conduction abrasion-proof insulating nylon 6 composite material, and patent of invention CN 103613923 A adopts nylon resin, magnesium oxide, aluminum oxide, aluminium nitride, boron nitride, silicon nitride, multi-walled carbon nano-tubes, natural graphite flakes, Graphene particle has prepared high Heat conduction nylon composite material, and patent of invention CN 103483809 A adopts nylon resin, heat conductive filler magnesium oxide, magnesium nitride, ball-aluminium oxide, class ball-aluminium oxide, aluminium nitride, boron nitride, pitch fibers, halloysite, carbon nanotube, graphite, silicon carbide, boehmite etc., Non-halogen Flame Retardant Melamine-poly-phosphate (MP), trimeric cyanamide-polyphosphoric acid salt (MP), trimeric cyanamide-focusing phosphoric acid salt, alkyl hypophosphite, alkyl metaphosphate, alkyl phosphite, ammonium polyphosphate (APP), aluminium hydroxide, magnesium hydroxide, expanded graphites, high-fluidity polyamide base halogen-free flame-retarded heat-conducting matrix material prepared by magnesium sulfate heptahydrate and molybdenum oxide etc., patent of invention CN1926192A adopts phospho acid aluminium as the filling-modified polymeric amide of fire retardant, prepare flame-retardant polyamide composite material, patent of invention CN101157798A discloses the high-efficiency and continuous polymerization process of a kind of high whiteness super-dispersed nylon 6 dragon 6/ nano montmorillonite composite material, patent of invention ZL200910193532.0 discloses the filling-modified thermal-conducting electric-insulating polyphenyl thioether of a kind of inorganic heat conductive filler and polyamide blended alloy, patent of invention CN103087389A discloses a kind of high heat conduction high-ductility composite material and preparation method thereof, and this patent adopts graphite to mix with granulated filler and fills polyethylene terephthalate and prepare the matrix material that thermal conductivity is up to 1.6 W/mK.
More than invent the heat-conductivity polymer composite related to have no and mention by the thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, also do not mention and how to avoid addition thermal conductive silica gel solidify not exclusively, how to break through the allotment of the color except black, white, true qualities and reduce the problem of material carbon footprint.
Summary of the invention
The object of the invention is for above-mentioned deficiency of the prior art, a kind of Novel heat-conducting nylon composite materials and preparation method thereof is provided, this material is by the thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, color can furnishing black, white, true qualities, grey, redness, green, metallic color etc., addition thermal conductive silica gel can not be caused to solidify not exclusively, there is because of halogen-free flameproof lower carbon footprint.
Object of the present invention is achieved through the following technical solutions.
A kind of Novel heat-conducting nylon composite materials, comprises the raw material of following mass percent:
PA6 resin 20-40%
Heat conductive filler 15-40%
Reinforcing filler 10 ~ 20%
Halogen-free flame retardants 20 ~ 40%
Toughner 1-3%
Coupling agent 0.1-0.5%
Surface-modifying agent 0.4-1.0%
Lubricant 0.4-1.0%
Oxidation inhibitor 0.1-0.5%
Toner 0.1 ~ 5%
Wherein, the mass percent sum of above-mentioned raw materials is 100%.
Wherein, described heat conductive filler is hexagonal boron nitride, and purity is more than 99.8%; The Mohs' hardness of hexagonal boron nitride is less than 4, and whiteness is more than 95%, and median size is between 1 μm-30 μm, and the effect of hexagonal boron nitride is the thermal conductivity promoting material.
Wherein, described reinforcing filler is one or more the mixture in glass fibre, wollastonite, ZnOw; The effect of reinforcing filler is the tensile strength improving material, reduces the thermal expansivity of material, makes the thermal expansivity of material close to the aluminium inserts in LED lamp cup.
Wherein, described toner is selected according to needing the kind of color matching, and described toner is one or both the mixture in black smoke, titanium dioxide, red iron oxide, phthalein viridescent, silver powder and pearlescence; The toner that color matching is selected for white is titanium dioxide, match colors as the toner of black selection is black smoke, the toner that color matching is grey single selection is black smoke and titanium dioxide take mass ratio as the mixture that 1-2:2-5 mixes, the toner that color matching is selected for redness is red iron oxide, color matching is that phthalein is dark green for the toner of green choice, the mixture of the toner selected for metallic color of matching colors to be silver powder and pearlescence with mass ratio be 1-3:2-4 mixing.
Wherein, described halogen-free flame retardants is mineral compound fire retardant, and mineral compound fire retardant is one or more the mixture in magnesium hydroxide, aluminium hydroxide, zinc borate, and described mineral compound fire retardant is not phosphorous, element sulphur; Phosphorus, element sulphur can make the platinum catalyst inside heat conductive silica gel lose efficacy, and cause silica gel not solidify completely.
Wherein, described oxidation inhibitor is oxidation inhibitor that are not phosphorous, sulphur two kinds of elements.Phosphorus, element sulphur can make the platinum catalyst inside heat conductive silica gel lose efficacy, and cause silica gel not solidify completely.
Preferably, a kind of Novel heat-conducting nylon composite materials, comprises the raw material of following mass percent:
PA6 resin 20-30%
Heat conductive filler 30-40%
Reinforcing filler 10 ~ 15%
Halogen-free flame retardants 20 ~ 30%
Toughner 2-3%
Coupling agent 0.3-0.5%
Surface-modifying agent 0.8-1.0%
Lubricant 0.8-1.0%
Oxidation inhibitor 0.1-0.3%
Toner 0.1 ~ 0.3%.
More preferably, a kind of Novel heat-conducting nylon composite materials, comprises the raw material of following mass percent:
PA6 resin 25-35%
Heat conductive filler 15-25%
Reinforcing filler 13 ~ 17%
Halogen-free flame retardants 25 ~ 35%
Toughner 2-3%
Coupling agent 0.2-0.4%
Surface-modifying agent 0.7-0.9%
Lubricant 0.7-0.9%
Oxidation inhibitor 0.2-0.4%
Toner 0.2 ~ 4%.
Wherein, described halogen-free flame retardants is mineral compound fire retardant magnesium hydroxide, aluminium hydroxide and zinc borate is mixture that the ratio of 5:5:1-7:3:1 mixes in mass ratio.
Wherein, described reinforcing filler is made up of glass fibre and ZnOw, and the mass ratio of glass fibre and ZnOw is 2:1; Or reinforcing filler is made up of wollastonite and ZnOw, the mass ratio of wollastonite and ZnOw is 2:1.
Wherein, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as the mixture of 1:1-1:3.
Wherein, the normal direction thermal conductivity of described matrix material is at more than 1.0W/mK, and volume resistance is 1x10
14-1x10
15Ω cm, UL94 flame retardant rating is 1.5mm thickness V0 level.
Wherein, the relative viscosity of described PA6 resin is one or both mixture in 2.0 or 2.5.
Wherein, described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
A preparation method for Novel heat-conducting nylon composite materials, comprises following procedure of processing:
Step a. presses composition of raw materials mass percent, mixes 30-60 second by mixed cylinder under 100-150 rev/min of speed of PA6 resin, toughner and coupling agent;
Step b. presses composition of raw materials mass percent, adds oxidation inhibitor, remix 30-60 second;
Step c presses composition of raw materials mass percent, adds heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 2-5 minute;
Steps d. by the compound in step c by meshing co rotating twin screw extrusion melting at 180 DEG C-250 DEG C, mixing, extrude; Meanwhile, side drawing-in device is used at Section 6 gun barrel, reinforcing filler to be fed;
The material strip extruded in step e. steps d is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, packaging.
beneficial effect of the present invention:
The halogen-free flame retardants magnesium hydroxide that this programme uses, aluminium hydroxide and zinc borate, all materials that nature exists, and halogen containing flame-retardant is as brominated epoxy resin, brominated Polystyrene etc., all synthetic, namely from petroleum cracking, produce carbon raw material, extract bromo element from seawater, produced by chemosynthesis, the carbon footprint of the halogen-free flame retardants that the carbon footprint of whole process necessarily natively exists than nature is high, therefore, this programme halogen-free flameproof and there is lower carbon footprint.
The normal direction thermal conductivity of the nylon composite materials that the present invention obtains is at more than 1.0W/mK, and volume resistance is 1x10
14-1x10
15Ω cm, UL94 flame retardant rating is 1.5mm thickness V0 level, thermally conductive material of the present invention is by the thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, color can furnishing black, white, true qualities, grey, redness, green etc., again because halogen-free flameproof and there is lower carbon footprint, guarantee addition thermal conductive silica gel completion of cure.
Embodiment
The invention will be further described with the following Examples.
embodiment 1:
By composition of raw materials mass percent: PA6 resin 25.0%, heat conductive filler 35%, reinforcing filler 10%, toughner 2.2%, halogen-free flame retardants 25%, coupling agent 0.4%, surface-modifying agent 1%, lubricant 1%, oxidation inhibitor 0.2%, toner 0.2%.30 seconds are mixed by load weighted PA6 resin, toughner and the mixed cylinder of coupling agent under 100 revs/min of speed, then oxidation inhibitor and toner is added, remix 30 seconds, then add heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 3 minutes.By the raw material mixed by meshing co rotating twin screw extrusion melting, mixing, extrude, meanwhile, use side drawing-in device at Section 6 gun barrel, reinforcing filler to be fed.The temperature of twin screw extruder controls as follows: first paragraph 180 DEG C ~ 200 DEG C, second segment 240 DEG C ~ 250 DEG C, 3rd section 240 DEG C ~ 250 DEG C, the 4th section 235 DEG C ~ 245 DEG C, the 5th section 235 DEG C ~ 245 DEG C, 6th section 180 DEG C ~ 200 DEG C, 7th section 180 DEG C ~ 200 DEG C, the 8th section 180 DEG C ~ 200 DEG C, head and die temperature control at 240 DEG C ~ 250 DEG C, screw speed 350 revs/min, head pressure is 14 ~ 18MPa.The material strip extruded is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, finally packs.
Wherein, described reinforcing filler is glass fibre; Match colors as the toner of black selection is black smoke; Described halogen-free flame retardants is mineral compound fire retardant magnesium hydroxide, aluminium hydroxide and zinc borate is mixture that the ratio of 5:5:1 mixes in mass ratio; The mixture that described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as 1:1; The relative viscosity of described PA6 resin is 2.0; Described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
embodiment 2:
By composition of raw materials mass percent: PA6 resin 30.0%, heat conductive filler 20%, reinforcing filler 15%, toughner 2.5%, halogen-free flame retardants 30%, coupling agent 0.3%, surface-modifying agent 0.8%, lubricant 0.8%, oxidation inhibitor 0.3%, toner 0.3%.30 seconds are mixed by load weighted PA6 resin, toughner and the mixed cylinder of coupling agent under 100 revs/min of speed, then oxidation inhibitor and toner is added, remix 30 seconds, then add heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 3 minutes.By the raw material mixed by meshing co rotating twin screw extrusion melting, mixing, extrude, meanwhile, use side drawing-in device at Section 6 gun barrel, reinforcing filler to be fed.The temperature of twin screw extruder controls as follows: first paragraph 180 DEG C ~ 200 DEG C, second segment 240 DEG C ~ 250 DEG C, 3rd section 240 DEG C ~ 250 DEG C, the 4th section 235 DEG C ~ 245 DEG C, the 5th section 235 DEG C ~ 245 DEG C, 6th section 180 DEG C ~ 200 DEG C, 7th section 180 DEG C ~ 200 DEG C, the 8th section 180 DEG C ~ 200 DEG C, head and die temperature control at 240 DEG C ~ 250 DEG C, screw speed 350 revs/min, head pressure is 14 ~ 18MPa.The material strip extruded is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, finally packs.
Wherein, described reinforcing filler is made up of glass fibre and ZnOw, and the mass ratio of glass fibre and ZnOw is 2:1; Described toner is selected according to needing the kind of color matching, the mixture of the toner of matching colors as grey single selection to be black smoke and titanium dioxide with mass ratio be 1:2 mixing; Described halogen-free flame retardants is mineral compound fire retardant, and mineral compound fire retardant is magnesium hydroxide; The mixture that described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as 1:2; The relative viscosity of described PA6 resin is 2.5; Described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
embodiment 3:
By composition of raw materials mass percent: PA6 resin 35%, heat conductive filler 15%, reinforcing filler 12%, toughner 1.1%, halogen-free flame retardants 35%, coupling agent 0.2%, surface-modifying agent 0.6%, lubricant 0.6%, oxidation inhibitor 0.4%, toner 0.1%.30 seconds are mixed by load weighted PA6 resin, toughner and the mixed cylinder of coupling agent under 100 revs/min of speed, then oxidation inhibitor and toner is added, remix 30 seconds, then add heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 3 minutes.By the raw material mixed by meshing co rotating twin screw extrusion melting, mixing, extrude, meanwhile, use side drawing-in device at Section 6 gun barrel, reinforcing filler to be fed.The temperature of twin screw extruder controls as follows: first paragraph 180 DEG C ~ 200 DEG C, second segment 240 DEG C ~ 250 DEG C, 3rd section 240 DEG C ~ 250 DEG C, the 4th section 235 DEG C ~ 245 DEG C, the 5th section 235 DEG C ~ 245 DEG C, 6th section 180 DEG C ~ 200 DEG C, 7th section 180 DEG C ~ 200 DEG C, the 8th section 180 DEG C ~ 200 DEG C, head and die temperature control at 240 DEG C ~ 250 DEG C, screw speed 350 revs/min, head pressure is 14 ~ 18MPa.The material strip extruded is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, finally packs.
Wherein, described reinforcing filler is made up of wollastonite and ZnOw, and the mass ratio of wollastonite and ZnOw is 2:1;
Described toner is selected according to needing the kind of color matching, and described toner is one or both the mixture in black smoke, titanium dioxide, red iron oxide, phthalein viridescent, silver powder and pearlescence; The toner that color matching is selected for redness is red iron oxide; Described halogen-free flame retardants is mineral compound fire retardant, and mineral compound fire retardant is aluminium hydroxide; The mixture that described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as 1:3; The mixture of the relative viscosity of described PA6 resin to be 2.0,2.5 with mass ratio be 1:1; Described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
embodiment 4:
By composition of raw materials mass percent: PA6 resin 20%, heat conductive filler 40%, reinforcing filler 18%, toughner 2.1%, halogen-free flame retardants 18%, coupling agent 0.1%, surface-modifying agent 0.4%, lubricant 0.4%, oxidation inhibitor 0.5%, toner 0.5%.Mix 30 seconds by load weighted PA6 resin, toughner and the mixed cylinder of coupling agent under 100 revs/min of speed, then add oxidation inhibitor, remix 30 seconds, then add heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 3 minutes.By the raw material mixed by meshing co rotating twin screw extrusion melting, mixing, extrude, meanwhile, use side drawing-in device at Section 6 gun barrel, reinforcing filler to be fed.The temperature of twin screw extruder controls as follows: first paragraph 180 DEG C ~ 200 DEG C, second segment 240 DEG C ~ 250 DEG C, 3rd section 240 DEG C ~ 250 DEG C, the 4th section 235 DEG C ~ 245 DEG C, the 5th section 235 DEG C ~ 245 DEG C, 6th section 180 DEG C ~ 200 DEG C, 7th section 180 DEG C ~ 200 DEG C, the 8th section 180 DEG C ~ 200 DEG C, head and die temperature control at 240 DEG C ~ 250 DEG C, screw speed 350 revs/min, head pressure is 14 ~ 18MPa.The material strip extruded is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, finally packs.
Wherein, the mixture of described reinforcing filler to be glass fibre, wollastonite, ZnOw with mass ratio the be ratio of 1:1:1; Described toner is selected according to needing the kind of color matching, the mixture of the toner selected for metallic color of matching colors to be silver powder and pearlescence with mass ratio be 2:3 mixing; Described halogen-free flame retardants is mineral compound fire retardant magnesium hydroxide, aluminium hydroxide and zinc borate is mixture that the ratio of 7:3:1 mixes in mass ratio; The mixture that described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as 1:3; The relative viscosity of described PA6 resin is 2.5; Described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
the material characteristic of the novel nylon matrix material that embodiments of the invention 1-4 obtains is as follows:
Performance test:
The standard test methods that thermal conductivity measures solid conductive heat by ASTM E1461 flicker method is tested;
Volume resistance is tested by ASTM D257 insulating material direct current resistance and conductivity test method;
Flame retardant rating is tested by UL94 plastic material combustion testing standard;
Thermal shock is tested: material injection is become LED lamp cup, at-40 DEG C, places half an hour, place half an hour at then changing 120 DEG C in 3 minutes, so circulation 1000 times.
Silica gel solidifies test: material injection is become LED lamp cup, and pour into Lamp cup after being stirred evenly by two for platinum catalysis component high-temperature silicon disulfide rubber, take out, taken out by the silica gel after solidification at 80 DEG C after drying half an hour, whether observation surface exists does not solidify phenomenon completely.
The normal direction thermal conductivity of the nylon composite materials that the present invention obtains is at more than 1.0W/mK, and volume resistance is 1x10
14-1x10
15Ω cm, UL94 flame retardant rating is 1.5mm thickness V0 level, thermally conductive material of the present invention is by the thermal shock test of more than 1000 hours at-40 DEG C ~ 120 DEG C, and color can furnishing black, white, true qualities, grey, redness, green etc., guarantees addition thermal conductive silica gel completion of cure.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a Novel heat-conducting nylon composite materials, is characterized in that: the raw material comprising following mass percent:
PA6 resin 20-40%
Heat conductive filler 15-40%
Reinforcing filler 10-20%
Halogen-free flame retardants 20-40%
Toughner 1-3%
Coupling agent 0.1-0.5%
Surface-modifying agent 0.4-1.0%
Lubricant 0.4-1.0%
Oxidation inhibitor 0.1-0.5%
Toner 0.1-5%
Wherein, the mass percent sum of above-mentioned raw materials is 100%;
Wherein, described heat conductive filler is hexagonal boron nitride, and purity is more than 99.8%;
Wherein, described reinforcing filler is one or more the mixture in glass fibre, wollastonite, ZnOw;
Wherein, described toner is selected according to needing the kind of color matching, and described toner is one or both the mixture in black smoke, titanium dioxide, red iron oxide, phthalein viridescent, silver powder and pearlescence;
Wherein, described halogen-free flame retardants is mineral compound fire retardant, and mineral compound fire retardant is one or more the mixture in magnesium hydroxide, aluminium hydroxide, zinc borate, and described mineral compound fire retardant is not phosphorous, element sulphur;
Wherein, described oxidation inhibitor is oxidation inhibitor that are not phosphorous, sulphur two kinds of elements.
2. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: the raw material comprising following mass percent:
PA6 resin 20-30%
Heat conductive filler 30-40%
Reinforcing filler 10-15%
Halogen-free flame retardants 20-30%
Toughner 2-3%
Coupling agent 0.3-0.5%
Surface-modifying agent 0.8-1.0%
Lubricant 0.8-1.0%
Oxidation inhibitor 0.1-0.3%
Toner 0.1-0.3%.
3. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: the raw material comprising following mass percent:
PA6 resin 25-35%
Heat conductive filler 15-25%
Reinforcing filler 13-17%
Halogen-free flame retardants 25-35%
Toughner 2-3%
Coupling agent 0.2-0.4%
Surface-modifying agent 0.7-0.9%
Lubricant 0.7-0.9%
Oxidation inhibitor 0.2-0.4%
Toner 0.2-4%.
4. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: described halogen-free flame retardants is mineral compound fire retardant magnesium hydroxide, aluminium hydroxide and zinc borate is mixture that the ratio of 5:5:1-7:3:1 mixes in mass ratio.
5. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: the mixture of described reinforcing filler to be glass fibre or wollastonite and ZnOw with mass ratio be 2:1.
6. a kind of Novel heat-conducting nylon composite materials according to claim 1, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid take mass ratio as the mixture of 1:1-1:3.
7. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: the normal direction thermal conductivity of described matrix material is at more than 1.0W/mK, and volume resistance is 1x10
14-1x10
15Ω cm, UL94 flame retardant rating is 1.5mm thickness V0 level.
8. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: the relative viscosity of described PA6 resin is one or both mixture in 2.0 or 2.5.
9. a kind of Novel heat-conducting nylon composite materials according to claim 1, is characterized in that: described toughner is maleic anhydride graft terpolymer EP rubber; Described coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described surface-modifying agent is high molecular weight silicone; Described lubricant is ethylene-acrylic acid copolymer.
10. the preparation method of a kind of Novel heat-conducting nylon composite materials described in claim 1-9 any one, is characterized in that: comprise following procedure of processing:
Step a. presses composition of raw materials mass percent, mixes 30-60 second by mixed cylinder under 100-150 rev/min of speed of PA6 resin, toughner and coupling agent;
Step b. presses composition of raw materials mass percent, adds oxidation inhibitor, remix 30-60 second;
Step c presses composition of raw materials mass percent, adds heat conductive filler, halogen-free flame retardants, surface-modifying agent, lubricant remix 2-5 minute;
Steps d. by the compound in step c by meshing co rotating twin screw extrusion melting at 180 DEG C-250 DEG C, mixing, extrude; Meanwhile, side drawing-in device is used at Section 6 gun barrel, reinforcing filler to be fed;
The material strip extruded in step e. steps d is air-cooled through transport tape, dicing machine pelletizing, air knife are dry, packaging.
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| CN108003607A (en) * | 2017-12-19 | 2018-05-08 | 大连理工常州研究院有限公司 | A kind of flame retardant type Heat conduction nylon composite material and preparation method thereof |
| CN108003607B (en) * | 2017-12-19 | 2020-03-31 | 大连理工常州研究院有限公司 | Flame-retardant heat-conducting nylon composite material and preparation method thereof |
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| CN108892947A (en) * | 2018-05-24 | 2018-11-27 | 暨南大学 | A kind of halogen-free flame-retarded heat-conducting nylon material |
| CN108892947B (en) * | 2018-05-24 | 2020-09-25 | 广州润锋科技股份有限公司 | Halogen-free flame-retardant heat-conducting nylon material |
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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 |
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