CN106751584A - A kind of LED fills fire-retardant plastic of high heat conduction and preparation method thereof with oxidative grafting modified carbon fiber Graphene - Google Patents

Abstract

The invention discloses a kind of LED the fire-retardant plastic of high heat conduction is filled with oxidative grafting modified carbon fiber Graphene, and its preparation technology, characterized in that, with magnesia, boron nitride, PBT, EVA, glass fibre, 107 glue, dibutyl tin laurate, tetraethyl orthosilicate, melamine cyanurate, Firebrake ZB, hypo-aluminum orthophosphate, bamboo charcoal, Nano-meter SiO_2₂, dihydroxy dibutyl tin oxide, graphene oxide, carbon fiber etc. be raw material.The present invention is prepared for the heat-conducting silicon rubber of KH550 surface treatments；With dihydroxy dibutyl tin oxide as catalyst, Nano-meter SiO_2 is used₂To polybutylene terephthalate (PBT)（PBT）Carry out activeness and quietness treatment；Composite flame-retardant agent is prepared for using hypo-aluminum orthophosphate, melamine cyanurate；Obtain a kind of LED oxidative grafting modified carbon fibers Graphene filling fire-retardant plastic of high heat conduction.

Description

A kind of LED oxidative grafting modified carbon fibers-Graphene filling fire-retardant shape of high heat conduction Material and preparation method thereof

Technical field

The present invention relates to field of compound material, and in particular to a kind of LED oxidative grafting modified carbon fibers-Graphene filling The fire-retardant plastic of high heat conduction, and its preparation technology.

Background technology

LED has the advantages that small volume, long lifespan, low-carbon environment-friendly, energy-conservation stabilization as a kind of excellent photoelectric device, Being expected in following several years will be as preferably general illumination light source of new generation.As LED develops to light intensity high, high power, Its heat dissipation problem is outstanding day by day, has had a strong impact on light output characteristic and the life-span of device of LED, it has also become high-power LED encapsulation must The key issue that need to be solved., used as LED shell, with light weight, it is easy to machine-shaping, cost is low excellent for heat-conductive composite material Point.

In order to improve the heat conductivility and mechanical property of heat-conductive composite material, to meet the use requirement of LED shell. Ma Jieling is in its master thesis《The research of LED heat-conducting plastic》In, it is with polybutylene terephthalate (PBT) (PBT) Matrix, with magnesia and boron nitride as heat filling, adds ethylene-vinyl acetate copolymer (EVA) and glass fibre to enter it The treatment of row activeness and quietness, heat-conductive composite material is prepared for using double screw extruder, improves the thermal conductivity of heat-conductive composite material Energy and mechanical property, but there is heat conductivility deficiency, and do not possess fire resistance.

The present invention with magnesia, boron nitride as filler, with tetraethyl orthosilicate as vulcanizing agent, be with dibutyl tin laurate Catalyst, is prepared for the heat-conducting silicon rubber of KH550 surface treatments, improves the heat conductivility of silicon rubber；With dihydroxy butyl chloride Change tin is catalyst, uses Nano-meter SiO_2₂To polybutylene terephthalate (PBT)（PBT）Carry out activeness and quietness treatment；Hypo-aluminum orthophosphate (AHP) phosphorus content is high, good flame retardation effect, melamine cyanurate（MCA）It is a kind of typical nitrogen system bittern-free fire retardant, odorless Tasteless, decomposition temperature is high, and low-smoke low-toxicity is prepared for composite flame-retardant agent；Carbon fiber is a kind of novel enhanced material of excellent performance, There is low-density, height than strong and corrosion-resistant；Obtain a kind of LED oxidative graftings modified carbon fiber-Graphene filling high Heat conductive flame-retarding plastic.

The content of the invention

Filled the present invention solves the technical problem of a kind of LED oxidative grafting modified carbon fibers-Graphene is provided The fire-retardant plastic of high heat conduction and its preparation technology, according to the technique make thermal conductivity of composite materials is high, fire resistance is good, energy Preferably improve the radiating of LED.

The technical problems to be solved by the invention are realized using following technical scheme：

Magnesia 5-8, boron nitride 8-13, PBT 10-15, EVA 5-10, glass fibre 4-9,107 glue 2-4, the fourth of tin dilaurate two Base tin 1-3, tetraethyl orthosilicate 1-3, melamine cyanurate 3-8, Firebrake ZB 2-5, hypo-aluminum orthophosphate 2-4, bamboo charcoal 1-3, nanometer SiO₂ 2-5, dihydroxy dibutyl tin oxide 1-2, graphene oxide 2-5, carbon fiber 4-9, KH550 1-2, KH-570 1-2, second Alcohol, acetone, NaOH solution, distilled water, HCl, dense H₂SO₄, dense HNO₃In right amount.

A kind of LED oxidative grafting modified carbon fibers-Graphene fills the preparation method of the fire-retardant plastic of high heat conduction, and it is special Levy and be, carry out according to the following steps：

A. KH550 is mixed with ethanol, heating water bath adds magnesia and boron nitride to 70-90 DEG C, stirs 10-30min, takes Go out to stand 1-2h, upper solution is sucked with suction pipe, after drying 1-2h in 75-95 DEG C, mix with 107 glue, add tin dilaurate Dibutyl tin, tetraethyl orthosilicate, stir 1-2h；

B. to NaOH solution is added in melamine cyanurate, stir, add Firebrake ZB, 65-95 DEG C of reaction 1- of intensification 3h, obtains thick white product, and suction filtration, washing 3-5 times dry 1-3h in 115-165 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-150 DEG C drying 1-2h after, mix with the former, ultra-fine grinding obtains composite flame-retardant agent；

C. PBT is heated to 150-170 DEG C, Nano-meter SiO_2₂, resulting material is added thereto in b, is well mixed, and adds two Hydroxybutyl stannic chloride, after polymerisation 1-2h, move into ice-water bath in and crush, gained sample is done in 105-130 DEG C of vacuum Dry 2-4h；

D. carbon fiber is soaked into 2-4h in acetone, is washed 3-5 times, 2-4h is dried in 70-90 DEG C, with volume ratio 3:1-2 is added Dense H₂SO₄/ dense HNO₃Mixed acid, the stirring reaction 2-5h in 80-90 DEG C of oil bath, is cooled to room temperature, is washed to pH for 6-7, dries Mix with absolute ethyl alcohol afterwards, ultrasonic disperse 1-2h, pH to 3-4 is adjusted with HCl, be slowly added to KH-570, be warming up to 60-80 DEG C of reaction 2-4h, is cooled to room temperature, and alcohol washes, be washed to neutrality, dry oxidative grafting modified carbon fiber；

E. resulting material in d is added graphene oxide into, ultrasonic vibration 2-3h adds carbon fiber and acetone, is well mixed, surpasses Sound oscillation 1-2h；

F. resulting material in a, e and other surplus stocks are put into homogenizer and stir 1-2h, be placed in double screw extruder In, in 200-250 DEG C of melting extrusion, cooled down through air, granulator granulation, 75-95 DEG C of drying 4-8h in baking oven is placed into, take Go out, through injection machine in 235-255 DEG C of injection moulding, obtain a kind of LED oxidative graftings modified carbon fiber-Graphene filling height and lead Thermal resistance fires plastic.

Reaction mechanism of the invention is as follows：

（1）With magnesia, boron nitride as filler, with tetraethyl orthosilicate as vulcanizing agent, with dibutyl tin laurate as catalyst, The heat-conducting silicon rubber of KH550 surface treatments is prepared for, the heat conductivility of silicon rubber is improve.

（2）Hypo-aluminum orthophosphate (AHP) has the advantages that phosphorus content is high, good flame retardation effect, and the addition of synergist bamboo charcoal can promote AHP is degraded and generate phosphoric acid and pyrophosphoric acid, in solid phase, phosphoric acid and pyrophosphoric acid can promote composite degradation into charcoal, and drop The fine and close layer of charcoal produced after solution can prevent oxygen and heat transfer to the anti-flammability for inside polymeric matrix, being conducive to improving material Energy；Melamine cyanurate (MCA) is a kind of typical nitrogen system bittern-free fire retardant, and odorless, tasteless, decomposition temperature is high, and low cigarette is low Poison, is controlled using Firebrake ZB to MCA, makes Firebrake ZB dispersed deposition on MCA surfaces, and MCA is coated, and is separated into smaller Independent reaction system so that the viscosity of reaction system remains at a relatively low level.

（3）Nano-meter SiO_2₂With specific surface area is big, nontoxic, high temperature resistant the features such as, be a kind of excellent reinforcing material；With two Hydroxybutyl stannic chloride is catalyst, using Nano-meter SiO_2₂To polybutylene terephthalate (PBT)（PBT）Carry out at activeness and quietness Reason.

（4）Using dense H₂SO₄/ dense HNO₃Mixed acid carries out surface oxidation treatment and obtains carbon oxide fiber to carbon fiber (CF) (OCF) further reaction obtains KH-570 grafting modified carbon fibers (KCF), oxidation and graft reaction, to recycle KH-570 and OCF Active functional group content and the roughness of carbon fiber surface can be increased, so as to improve the phase between carbon fiber and EVA matrixes Capacitive.

（5）Graphene oxide has radius-thickness ratio high, heat conduction master batch is formed after thermal reduction and forms heat conduction in the composite Path, composite has good mechanical property, an excellent heat conductivility, and preparation process is simple, with low cost.Carbon is fine Dimension is a kind of novel enhanced material of excellent performance, has the advantages that low-density, height than strong and corrosion-resistant.

Specific embodiment

In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below Specific embodiment is closed, the present invention is expanded on further.

Embodiment

A kind of LED oxidative grafting modified carbon fibers-Graphene filling fire-retardant plastic of high heat conduction, by following weight parts G the raw material of () is obtained：

Magnesia 8, boron nitride 13, PBT 15, EVA 10, the glue 4 of glass fibre 9,107, dibutyl tin laurate 1, positive silicic acid Ethyl ester 1, melamine cyanurate 8, Firebrake ZB 5, hypo-aluminum orthophosphate 2, bamboo charcoal 1, Nano-meter SiO_2₂ 5, dihydroxy dibutyl tin oxide 2, Graphene oxide 2, carbon fiber 9, KH550 1, KH-570 1, ethanol, acetone, NaOH solution, distilled water, HCl, dense H₂SO₄, it is dense HNO₃In right amount.

A kind of LED oxidative grafting modified carbon fibers-Graphene fills the preparation method of the fire-retardant plastic of high heat conduction, and it is special Levy and be, carry out according to the following steps：

A. KH550 is mixed with ethanol, heating water bath adds magnesia and boron nitride to 80-90 DEG C, stirs 30min, takes out quiet Put 1h, upper solution sucked with suction pipe, in 85-95 DEG C dry 1h after, mix with 107 glue, add dibutyl tin laurate, Tetraethyl orthosilicate, stirs 1h；

B. to NaOH solution is added in melamine cyanurate, stir, add Firebrake ZB, 1h is reacted in 85-95 DEG C of intensification, Thick white product is obtained, suction filtration, washing 3 times dry 1h in 145-165 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 140-150 DEG C of drying After 1h, mix with the former, ultra-fine grinding obtains composite flame-retardant agent；

C. PBT is heated to 150-160 DEG C, Nano-meter SiO_2₂, resulting material is added thereto in b, is well mixed, and adds two Hydroxybutyl stannic chloride, after polymerisation 2h, move into ice-water bath in and crush, by gained sample in 120-130 DEG C vacuum drying 2h；

D. carbon fiber is soaked into 4h in acetone, is washed 3 times, 2h is dried in 70-80 DEG C, with volume ratio 3:1 adds dense H₂SO₄/ Dense HNO₃Mixed acid, the stirring reaction 2h in 80-90 DEG C of oil bath, is cooled to room temperature, is washed to pH for 6-7, after drying and anhydrous Ethanol mixes, ultrasonic disperse 1h, and pH to 3-4 is adjusted with HCl, is slowly added to KH-570, is warming up to 60-70 DEG C of reaction 2h, is cooled to Room temperature, alcohol washes, be washed to neutrality, dry oxidative grafting modified carbon fiber；

E. resulting material in d is added graphene oxide into, ultrasonic vibration 2h adds carbon fiber and acetone, is well mixed, ultrasound Vibration 1h；

F. resulting material in a, e and other surplus stocks are put into homogenizer and stir 1h, be placed in double screw extruder In, in 230-250 DEG C of melting extrusion, cooled down through air, granulator granulation, 85-95 DEG C of drying 4h in baking oven is placed into, take out, Through injection machine in 245-255 DEG C of injection moulding, a kind of LED oxidative graftings modified carbon fiber-Graphene filling high heat conduction is obtained Fire-retardant plastic.

A kind of LED oxidative grafting modified carbon fibers prepared by above-described embodiment-Graphene filling fire-retardant plastic of high heat conduction Performance test results are as follows：

Thermal conductivity factor is 315.92W/m K, and thermal coefficient of expansion is 13.82 × 10^-6·K^-1(50-150 DEG C), tensile strength is 59.28MPa, bending strength is 45.38MPa, and impact strength is 3.92KJ/m², elongation at break is up to 13.82%.

Claims (2)

1. a kind of LED oxidative grafting modified carbon fibers-Graphene fills the fire-retardant plastic of high heat conduction, it is characterised in that under The raw material for stating weight portion is obtained：

Magnesia 5-8, boron nitride 8-13, PBT 10-15, EVA 5-10, glass fibre 4-9,107 glue 2-4, the fourth of tin dilaurate two Base tin 1-3, tetraethyl orthosilicate 1-3, melamine cyanurate 3-8, Firebrake ZB 2-5, hypo-aluminum orthophosphate 2-4, bamboo charcoal 1-3, nanometer SiO₂ 2-5, dihydroxy dibutyl tin oxide 1-2, graphene oxide 2-5, carbon fiber 4-9, KH550 1-2, KH-570 1-2, second Alcohol, acetone, NaOH solution, distilled water, HCl, dense H₂SO₄, dense HNO₃In right amount.

2. a kind of LED according to claim 1 oxidative grafting modified carbon fibers-Graphene fills the fire-retardant shape of high heat conduction The preparation method of material, it is characterised in that carry out according to the following steps：

KH550 is mixed with ethanol, heating water bath adds magnesia and boron nitride to 70-90 DEG C, stirs 10-30min, takes out 1-2h is stood, upper solution is sucked with suction pipe, after drying 1-2h in 75-95 DEG C, mixed with 107 glue, add tin dilaurate two Butyl tin, tetraethyl orthosilicate, stir 1-2h；

B. to NaOH solution is added in melamine cyanurate, stir, add Firebrake ZB, 65-95 DEG C of reaction 1- of intensification 3h, obtains thick white product, and suction filtration, washing 3-5 times dry 1-3h in 115-165 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-150 DEG C drying 1-2h after, mix with the former, ultra-fine grinding obtains composite flame-retardant agent；

C. PBT is heated to 150-170 DEG C, Nano-meter SiO_2₂, resulting material is added thereto in b, is well mixed, and adds dihydroxy Base dibutyl tin oxide, after polymerisation 1-2h, move into ice-water bath in and crush, by gained sample in 105-130 DEG C vacuum drying 2-4h；

D. carbon fiber is soaked into 2-4h in acetone, is washed 3-5 times, 2-4h is dried in 70-90 DEG C, with volume ratio 3:1-2 is added Dense H₂SO₄/ dense HNO₃Mixed acid, the stirring reaction 2-5h in 80-90 DEG C of oil bath, is cooled to room temperature, is washed to pH for 6-7, dries Mix with absolute ethyl alcohol afterwards, ultrasonic disperse 1-2h, pH to 3-4 is adjusted with HCl, be slowly added to KH-570, be warming up to 60-80 DEG C of reaction 2-4h, is cooled to room temperature, and alcohol washes, be washed to neutrality, dry oxidative grafting modified carbon fiber；

E. resulting material in c is added graphene oxide into, ultrasonic vibration 2-3h adds resulting material and acetone in d, and mixing is equal It is even, sonic oscillation 1-2h；

F. resulting material in a, e and other surplus stocks are put into homogenizer and stir 1-2h, be placed in double screw extruder In, in 200-250 DEG C of melting extrusion, cooled down through air, granulator granulation, 75-95 DEG C of drying 4-8h in baking oven is placed into, take Go out, through injection machine in 235-255 DEG C of injection moulding, obtain a kind of LED oxidative graftings modified carbon fiber-Graphene filling height and lead Thermal resistance fires plastic.