CN109486092A - A kind of high heat dissipation plastic shell of television ABS alloy material - Google Patents
A kind of high heat dissipation plastic shell of television ABS alloy material Download PDFInfo
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- CN109486092A CN109486092A CN201811372837.3A CN201811372837A CN109486092A CN 109486092 A CN109486092 A CN 109486092A CN 201811372837 A CN201811372837 A CN 201811372837A CN 109486092 A CN109486092 A CN 109486092A
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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 discloses a kind of high heat dissipation plastic shell of television ABS alloy materials, including following raw material: ABS resin, polyimide microsphere, polyethylene terephthalate, bisphenol A polycarbonate, maleic anhydride inoculated polypropylene, two-dimensional layer heat filling, antioxidant, ionomer, calcium carbonate, melamine resin lubricate oil microcapsule, diisononyl phthalate.High heat dissipation plastic shell of television of the present invention has good heating conduction with ABS alloy material, lightweight, processing easy to form, endurance, corrosion-resistant and electrical insulation capability are excellent, pass through the reasonable screening and the adjustment of resin matrix Phase stracture of heat filling, achieve the purpose that while promoting material thermal conductivity maintenance material mechanical performance, while playing the role of save the cost.
Description
Technical field
The present invention relates to household electrical appliances plastics and its preparation technical fields, more particularly to a kind of high heat dissipation plastic shell of television
Use ABS alloy material.
Background technique
Heat Conduction Material is widely used in the fields such as heat exchange, heat dissipation, electric.Conventional thermal conductive material be mostly metal such as copper,
Silver, aluminium, magnesium, gold etc., metal nitride such as AlN, BN, Si3N4Deng metal oxide such as aluminium oxide, silica, magnesia, oxygen
Change zinc etc. and some nonmetallic materials such as graphite, carbon fiber, carbon black etc..But some fields are not only to the heating conduction of material
It requires, it is also necessary to which material has the performances such as good electrical insulating property, corrosion resistance, lightweight and easy processing.
Many high molecular polymers may be used to prepare heat-conductive composite material at present, wherein most popular has poly- second
Alkene, polypropylene, nylon, polyphenylene sulfide, polyethylene terephthalate, polystyrene, acrylonitrile-butadiene-styrene (ABS) are total
Polymers etc..In order to improve the heating conduction of polymer-based material, heat filling such as nitride AlN, BN, Si3N4, carbide SiC,
Metal oxide aluminium, silica, magnesia, zinc oxide and some nonmetallic materials graphite, carbon fiber and carbon black at
For the hot spot of researchers' concern.
A kind of night-television machine scattering plastics of the disclosure of the invention of application number 201710947516.0, including it is following heavy
The Raw material processing of amount part forms: 50~80 parts of ABS resin, 5~10 parts of PC resin, 20~40 parts of polytetrafluoroethylene (PTFE), (3- ammonia third
Base) 6~12 parts of trimethoxy silane, 1~3 part of N-phenylmaleimide, 0.5~2 part of glyceryl tristearate, luminescent powder 8
~15 parts, 4~8 parts of glycidyl methacrylate, 0.5~1.5 part of antioxidant XH-245.
Summary of the invention
The invention discloses a kind of high heat dissipation plastic shell of television ABS alloy materials, including following raw material: ABS tree
Rouge, polyimide microsphere, polyethylene terephthalate, bisphenol A polycarbonate, maleic anhydride inoculated polypropylene, two dimension
Stratiform heat filling, antioxidant, ionomer, calcium carbonate, melamine resin lubricate oil microcapsule, the different nonyl of phthalic acid two
Ester.
Specifically, high heat dissipation plastic shell of television ABS alloy material of the present invention, the original including following parts by weight
Material: 40~60 parts by weight of ABS resin, 30~40 parts by weight of polyimide microsphere, 20~30 weight of polyethylene terephthalate
Part is measured, 10~25 parts by weight of bisphenol A polycarbonate, 1~8 parts by weight of maleic anhydride inoculated polypropylene, two-dimensional layer is thermally conductive to be filled out
Expect 15~20 parts by weight, 0.5~1 parts by weight of antioxidant, 1~3 parts by weight of ionomer, 6~10 parts by weight of calcium carbonate, melamine
0.5~1 parts by weight of resin lubrication oil microcapsule, 2~4 parts by weight of diisononyl phthalate.
Further, the two-dimensional layer heat filling be one of redox graphene, graphite phase carbon nitride or
The mixture of the two.
Preferably, the two-dimensional layer heat filling is the redox graphene@graphite phase carbon nitride two that face face combines
Stratiform heat filling is tieed up, is obtained by the following method: graphite phase carbon nitride is removed using sodium hydrate aqueous solution at negatively charged
The nanoscale twins class graphite phase carbon nitride of lotus, with the modified positively charged reduction-oxidation graphite of diallyl dimethyl ammoniumchloride
The redox graphene@graphite phase carbon nitride two-dimensional layer heat filling of face face combination is prepared in alkene electrostatic self-assembled.
Further, the redox graphene@graphite phase carbon nitride two-dimensional layer heat filling system that the face face combines
Preparation Method are as follows:
(1) sodium hydroxide for 1~5g graphite phase carbon nitride being added to 30~100mL molar concentration, 1~5mol/L is water-soluble
In liquid, 50~70 DEG C are heated to, in 50~70 DEG C with stirring 10~20 hours, obtains mixed liquor；Mixed liquor use is shut off point
The dialysis membrane of 3000~4000Da of son amount is dialysed as medium to dialyzate using deionized water to be in neutrality, and dialyzate is collected；It will dialysis
Liquid is diluted with water, and obtains the graphite phase carbon nitride dispersion liquid of 0.5~1mg/mL of concentration；
(2) graphene oxide dispersion of 150~300mL concentration, 0.2~0.5mg/mL is placed in reaction unit, successively
Diallyl dimethyl ammoniumchloride aqueous solution, the 2~6mL mass fraction 2~4% of 150~400mg mass fraction 35% is added
Ammonium hydroxide and 1.5~6mL hydrazine hydrate, ultrasonic disperse 10~40 minutes, obtain ultrasonic disperse liquid；Ultrasonic disperse liquid is heated to 80
~100 DEG C, in 80~100 DEG C back flow reaction 2~3 hours；20~30 DEG C are naturally cooled to, then with 8000~12000 revs/min
Zhongli's heart 20~30 minutes, supernatant liquor is abandoned, collecting bottom precipitation is redox graphene；Redox graphene is used
It after water washing is in neutrality to washing lotion, is dispersed in water, obtains the redox graphene dispersion liquid of 0.1~0.5mg/mL of concentration；
(3) by the redox graphene dispersion liquid that concentration is 0.1~0.5mg/mL be added dropwise to concentration be 0.5~
The graphite phase carbon nitride dispersion liquid of 1mg/mL uses the variation of Zeta potential analyzer detection Zeta potential；When Zeta potential connects
Nearly 0mv stops the addition of redox graphene dispersion liquid, and redox graphene dispersion liquid and graphite phase carbon nitride are dispersed
The mixed liquor of liquid is freeze-dried, and it is thermally conductive to obtain the redox graphene@graphite phase carbon nitride two-dimensional layer that the face face combines
Filler.
Why select graphite phase carbon nitride and graphene combination to prepare heat filling, is on the one hand since graphite-phase nitrogenizes
Carbon density is minimum, and energy is also minimum, is the most stable phase in carboritride.It compares metal oxide filler, has stronger
Atom between associative key, have more complete crystalline structure, the phon scattering in thermal diffusion process can be substantially reduced, have more
High thermal coefficient.Graphite phase carbon nitride material has very strong hardness simultaneously, also has excellent toughness, low coefficient of friction
With excellent antiwear characteristic.
The present invention using sodium hydrate aqueous solution by being removed graphite phase carbon nitride at negatively charged nanoscale twins class
Graphite phase carbon nitride, and the modified positively charged redox graphene electrostatic self-assembled of diallyl dimethyl ammoniumchloride,
Compound to obtain still for laminar structured redox graphene@graphite phase carbon nitride two-dimensional layer heat filling, the two is vertical
Histogram " face-to-face " superposition upwards, not only can be improved the thermal coefficient of material, maintains the insulation performance of material itself,
The mechanical performances such as shock resistance, toughness, the hardness of high heat dissipation plastic shell of television can also be improved.In addition, two-dimensional layer is thermally conductive
The characteristic of semiconductor of filler, stratiform blocking effect and catalysis carbon-forming effect can be formed by being added in high molecular material, improve its heat
Stability and flame retardant property have good flame retardant effect.
According to any of the above-described kind of technical solution, the raw material of the high heat dissipation plastic shell of television ABS alloy material is also
Including 3~7 parts by weight of triphenyl phosphite.
In some technical solutions of the invention, the polyimide microsphere the preparation method comprises the following steps: by 2~10g polyethers acyl
Imines is added in 100~400mL DMAc, is stirred 5~25 minutes, and 2~10g polyvinyl alcohol is added, and stirs 10~30 points
Clock obtains component A；2~10g polyvinyl alcohol is dissolved into 100~400mL water, stirs 15~30 minutes, obtains component B；It will
Component B is added in isometric component A, after being heated to 50~60 DEG C, stirring 2~3 hours, with 6000~12000 revs/min
Bottom precipitation is collected in centrifugation 20~30 minutes；By its water washing of bottom precipitation, drying obtains the polyimide microsphere.
In some technical solutions of the invention, the polyimide microsphere the preparation method comprises the following steps:
(1) 2~10g polyetherimide is added in 100~400mL DMAc, is stirred 5~25 minutes, add 2~
10g polyvinyl alcohol stirs 10~30 minutes, obtains component A；2~10g polyvinyl alcohol is dissolved into 100~400mL water, is stirred
It mixes 15~30 minutes, obtains component B；Component B is added in isometric component A, is heated to 50~60 DEG C, stirring 2~3 is small
Shi Hou is centrifuged 20~30 minutes with 6000~12000 revs/min, collects bottom precipitation；By its water washing of bottom precipitation, dry
It is dry, obtain the polymeric matrix microballoon；
(2) 0.3~0.9g of 8~10g of Aluminium chloride hexahydrate and surface promoter is weighed, 5~10mL water, 10 are dissolved in
In the mixed solution of~15mL dehydrated alcohol and 1~3g formamide, stirred 10~20 minutes with 800~1200 revs/min；Then
Propylene oxide is added, after being stirred 10~30 seconds with 800~1200 revs/min, stops stirring and stands 12~16 hours, coagulated
Glue；Gel is 4~7 hours dry at 60~80 DEG C, it crushed 40~60 meshes, obtain presoma；Presoma is heated to 400
~500 DEG C, 2~3 hours are kept the temperature in air atmosphere, is then passed through ammonia with 100~300 ls/h of flow velocity, it is warming up to 1100~
1300 DEG C, 1~2 hour is kept the temperature, aluminium nitride microballoon is obtained；
(3) polymeric matrix microballoon is added in acetone, ultrasonic disperse 10~20 minutes, obtain concentration 0.5~
The polymeric matrix microballoon dispersion liquid of 2.5mg/mL；Aluminium nitride microballoon is distributed in acetone simultaneously, 10~30 points of ultrasonic disperse
Clock obtains the aluminium nitride microballoon dispersion liquid of 0.5~2.2mg/mL of concentration；It is under 300~500 revs/min of stirrings, aluminium nitride is micro-
Ball dispersion liquid is added to polymeric matrix microballoon dispersion liquid, point of aluminium nitride microballoon dispersion liquid and polymeric matrix microballoon dispersion liquid
The mass ratio of dispersion liquid is (0.3~0.5): 1, continue stirring 30~60 minutes, obtains complex microsphere dispersion liquid；By complex microsphere point
Dispersion liquid is centrifuged 30~40 minutes at 4000~6000 revs/min, removes supernatant, collects sediment at 110~120 DEG C dry 3
~4 hours, obtain the polyimide microsphere.
The surface promoter is the mixture of one or both of blocked polyethers F127, sucrose.Preferably, described
Surface promoter is the mixture that polyethers F127 and sucrose are formed with mass ratio 1:1.
The technical solution further preferred as the present invention, before polymeric matrix microballoon and aluminium nitride microballoon are compound,
Aluminium nitride microballoon carries out functional modification, then carry out the compound of polymeric matrix microballoon and aluminium nitride microballoon.
Two kinds of technical solutions are provided in the embodiment of the present invention, functional modification are carried out to aluminium nitride microballoon:
First, the polyimide microsphere the preparation method comprises the following steps:
(1) 2~10g polyetherimide is added in 100~400mL DMAc, is stirred 5~25 minutes, add 2~
10g polyvinyl alcohol stirs 10~30 minutes, obtains component A；2~10g polyvinyl alcohol is dissolved into 100~400mL water, is stirred
It mixes 15~30 minutes, obtains component B；Component B is added in isometric component A, is heated to 50~60 DEG C, stirring 2~3 is small
Shi Hou is centrifuged 20~30 minutes with 6000~12000 revs/min, collects bottom precipitation；By its water washing of bottom precipitation, dry
It is dry, obtain the polymeric matrix microballoon；
(2) 0.3~0.9g of 8~10g of Aluminium chloride hexahydrate and surface promoter is weighed, 5~10mL water, 10 are dissolved in
In the mixed solution of~15mL dehydrated alcohol and 1~3g formamide, stirred 10~20 minutes with 800~1200 revs/min；Then
Propylene oxide is added, after being stirred 10~30 seconds with 800~1200 revs/min, stops stirring and stands 12~16 hours, coagulated
Glue；Gel is 4~7 hours dry at 60~80 DEG C, it crushed 40~60 meshes, obtain presoma；Presoma is heated to 400
~500 DEG C, 2~3 hours are kept the temperature in air atmosphere, is then passed through ammonia with 100~300 ls/h of flow velocity, it is warming up to 1100~
1300 DEG C, 1~2 hour is kept the temperature, aluminium nitride microballoon is obtained；
(3) 1~3g aluminium nitride microballoon, 0.01~0.04g silane coupling agent and 120~200mL are added into reaction unit
Acetone, stirring 20~after forty minutes, add 0.1~0.5g water；50~60 DEG C are then heated to, reacts 3~6 in 50~60 DEG C
Hour；After reaction, 20~30 DEG C are naturally cooled to, is centrifuged 30~50 minutes with 4000~9000 revs/min, bottom is collected
Solid；Bottom solid is washed with dehydrated alcohol, it is 2~4 hours dry in 100~110 DEG C, it is micro- to obtain silane-modified aluminium nitride
Ball；
(4) polymeric matrix microballoon is added in acetone, ultrasonic disperse 10~20 minutes, obtain concentration 0.5~
The polymeric matrix microballoon dispersion liquid of 2.5mg/mL；Silane-modified aluminium nitride microballoon is distributed in acetone simultaneously, ultrasound point
It dissipates 10~30 minutes, obtains the silane-modified aluminium nitride microballoon dispersion liquid of 0.5~2.2mg/mL of concentration；300~500 turns/
Under minute stirring, silane-modified aluminium nitride microballoon dispersion liquid is added to polymeric matrix microballoon dispersion liquid, it is silane-modified
The mass ratio of the dispersion liquid of aluminium nitride microballoon and polymeric matrix microballoon dispersion liquid is (0.3~0.5): 1, continue stirring 30~60
Minute, obtain complex microsphere dispersion liquid；Complex microsphere dispersion liquid is centrifuged 30~40 minutes at 4000~6000 revs/min, is removed
Supernatant is removed, collection sediment is 3~4 hours dry at 110~120 DEG C, obtains the polyimide microsphere.
Second, the polyimide microsphere the preparation method comprises the following steps:
(1) 2~10g polyetherimide is added in 100~400mL DMAc, is stirred 5~25 minutes, add 2~
10g polyvinyl alcohol stirs 10~30 minutes, obtains component A；2~10g polyvinyl alcohol is dissolved into 100~400mL water, is stirred
It mixes 15~30 minutes, obtains component B；Component B is added in isometric component A, is heated to 50~60 DEG C, stirring 2~3 is small
Shi Hou is centrifuged 20~30 minutes with 6000~12000 revs/min, collects bottom precipitation；By its water washing of bottom precipitation, dry
It is dry, obtain the polymeric matrix microballoon；
(2) 0.3~0.9g of 8~10g of Aluminium chloride hexahydrate and surface promoter is weighed, 5~10mL water, 10 are dissolved in
In the mixed solution of~15mL dehydrated alcohol and 1~3g formamide, stirred 10~20 minutes with 800~1200 revs/min；Then
Propylene oxide is added, after being stirred 10~30 seconds with 800~1200 revs/min, stops stirring and stands 12~16 hours, coagulated
Glue；Gel is 4~7 hours dry at 60~80 DEG C, it crushed 40~60 meshes, obtain presoma；Presoma is heated to 400
~500 DEG C, 2~3 hours are kept the temperature in air atmosphere, is then passed through ammonia with 100~300 ls/h of flow velocity, it is warming up to 1100~
1300 DEG C, 1~2 hour is kept the temperature, aluminium nitride microballoon is obtained；
(3) 0.3~1g aluminium nitride microballoon, 60~180mL dehydrated alcohol, 0.2~0.5g, tri- (hydroxyl are added into reaction unit
Methyl) aminomethane and 200~400mL water, ultrasound 1~2 hour；Add 0.1~0.3g Dopamine hydrochloride, stirring 10~12
Hour, it is centrifuged 20~40 minutes with 3000~9000 revs/min, collects bottom solid；Bottom solid is washed with dehydrated alcohol,
It is 2~4 hours dry in 60~80 DEG C, obtain the modified aluminium nitride microballoon of dopamine；
(4) polymeric matrix microballoon is added in acetone, ultrasonic disperse 10~20 minutes, obtain concentration 0.5~
The polymeric matrix microballoon dispersion liquid of 2.5mg/mL；The modified aluminium nitride microballoon of dopamine is distributed in acetone simultaneously, ultrasound
Dispersion 10~30 minutes obtains the modified aluminium nitride microballoon dispersion liquid of the dopamine of 0.5~2.2mg/mL of concentration；300~500
Under rev/min stirring, the modified aluminium nitride microballoon dispersion liquid of dopamine is added to polymeric matrix microballoon dispersion liquid, dopamine
The mass ratio of the dispersion liquid of modified aluminium nitride microballoon dispersion liquid and polymeric matrix microballoon dispersion liquid is (0.3~0.5): 1, after
Continuous stirring 30~60 minutes, obtains complex microsphere dispersion liquid；Complex microsphere dispersion liquid is centrifuged 30 at 4000~6000 revs/min
~40 minutes, supernatant is removed, collection sediment is 3~4 hours dry at 110~120 DEG C, obtains the polyimide microsphere.
Further, the ionomer is the ionomer of the base groups containing sulfobetaines.
Further, the ionomer of the base groups containing sulfobetaines is acrylamide-[2- (methylacryloyl
Oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer and/or acrylamide-[3- (ethylene methacrylic acyl
Amine) propyl] dimethyl-(3- sulfonic acid) ammonium ion polymer.Preferably, the ionomer is acrylamide-[3- (methyl
Ethernamine) propyl] dimethyl-(3- sulfonic acid) ammonium ion polymer and acrylamide-[2- (methylacryloyl oxygroup) second
Base] mixture that is formed with mass ratio 1:1 of dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer.
By the way that aluminium nitride to be centered around around polyimide matrix particle in the present invention, formed using polyimides as core,
Aluminium nitride is the compound particle of shell, and this special construction structure evenly dispersed compared to aluminium nitride is more advantageous to thermal conducting path
Formation, be more advantageous to the transmitting of phonon, lead to the promotion of thermal conductivity of material, and avoid the occurrence of aluminium nitride and polymer matrix
Interface compatibility problem between body, the raising for preventing thermal coefficient cause the decline of polymer comprehensive performance.
High heat dissipation plastic shell of television ABS alloy material of the present invention has a good heating conduction, lightweight, easily
In processing and forming, endurance, corrosion-resistant and electrical insulation capability are excellent, pass through the reasonable screening of heat filling and resin matrix
The adjustment of Phase stracture, achieve the purpose that and meanwhile promoted material thermal conductivity maintain material mechanical performance, while play saving at
This effect.
Specific embodiment
Raw material is described below in embodiment:
ABS resin, purchased from the odd beauty in Taiwan, trade mark PA-746H.
Polyethylene terephthalate is purchased from Suzhou Li Tuo plastic cement Co., Ltd, trade mark CB-602.
Bisphenol A polycarbonate is purchased from Chengdu Jin Teng Chemical trade Co., Ltd, average molecular weight 3.57 × 104。
Maleic anhydride inoculated polypropylene is purchased from Heyuan City, Guangdong Province Dongyuan County Zi Heng plastic molding and processing plant, the trade mark 2206.
Antioxidant, is purchased from Tangshan Ke Ao chemical assistant Co., Ltd, and No. CAS: 27676-62-6, chemical name 1,3,5- tri-
(3,5- di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6- triketone.
Calcium carbonate is purchased from Shijiazhuang City rising star woods Chemical Co., Ltd., 1250 mesh.
Diisononyl phthalate, No. CAS: 68515-48-0.
It lubricates the specifically used melamine resin of oil microcapsule and lubricates oil microcapsule, referenced patent application number 201410363639.6
Example IV be prepared.
The embodiment one of graphite phase carbon nitride, referenced patent application number 201810541402.0 is prepared.
The embodiment two of redox graphene, referenced patent application number 201280056867.8 is prepared.
Triphenyl phosphite, No. CAS: 101-02-0.
Diallyl dimethyl ammoniumchloride, No. CAS: 26062-79-3.
Polyetherimide is provided, trade mark 1100R by the letter plasticizing Co., Ltd in Dongguan City day.
Polyvinyl alcohol is provided, trade mark 088-50 by Ao Teng commerce and trade Co., Ltd, Zhengzhou City.
Aluminium chloride hexahydrate, No. CAS: 7784-13-6.
Formamide, No. CAS: 75-12-7.
Propylene oxide, No. CAS: 75-56-9.
Blocked polyethers F127, No. CAS: 9003-11-6.
Sucrose, No. CAS: 57-50-1.
The preparation of graphene oxide dispersion: graphene oxide is dispersed in water, under conditions of ultrasonic power 300W
Dispersion 20 minutes, obtains graphene oxide dispersion.
Acrylamide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ion is poly-
Object and acrylamide-[3- (ethylene methacrylic amide) propyl] dimethyl-(3- sulfonic acid) ammonium ion polymer are closed with reference to husky brave " containing sulphur
The synthesis and its SOLUTION PROPERTIES of base betaine group polyacrylamide " (University Of Tianjin's journal, the o. 11th of volume 46,2003 11
Month) be prepared, wherein initiator additional amount is 0.1%, and initiator proportion is K2S2O8: NaHSO3=1:1, reaction temperature 60
DEG C, the reaction time 6 hours.
Silane coupling agent, specifically used KH550, No. CAS: 919-30-2.
Three (methylol) aminomethanes, No. CAS: 77-86-1.
Dopamine hydrochloride, No. CAS: 62-31-7.
Notch impact strength is tested by GB/T 1043.1-2008, and using XJZ-50 radial-boom impact tester, pendulum is most
Large impact energy 5J.
Tensile strength is tested by GB/T 1040.2-2006, using CMT6104 microcomputer controlled electronic universal tester, is stretched
Rate 5mm/min.
Thermal coefficient is tested using NETZSCH-LFA47 type laser heat conducting instrument, and 25 DEG C of test temperature；Thermally conductive sample
Preparation: by squeezing out, grain is hot-forming under conditions of 235 DEG C of temperature, hot pressing pressure 50MPa, obtains 10mm × 10mm × 1mm
Determination of conductive coefficients sample.
Volume resistivity is tested according to ASTM-D257, enterprising in EST-121 type number ultra-high resistance micro current instrument
Row.
Limit oxygen index is tested by GB/T2406-93, and sample size is 100mm × 10mm × 4mm, in JF-3 type oxygen index (OI)
It is carried out on instrument.
Embodiment 1
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of graphite phase carbon nitride, 1 parts by weight of antioxidant, acrylamide-
3 parts by weight of [2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer, calcium carbonate
8 parts by weight, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate.
Polyimide microsphere the preparation method comprises the following steps: 2.5g polyetherimide is added in 100mL DMAc, with 100 turns/
Minute stirring 20 minutes, adds 2.5g polyvinyl alcohol, is stirred 20 minutes with 100 revs/min, obtains component A；By the poly- second of 2.5g
Enol is dissolved into 100mL deionized water, is stirred 20 minutes with 100 revs/min, is obtained component B；Component B is added to equal bodies
In long-pending component A, 60 DEG C are heated to 2 DEG C, after being stirred 2 hours with 500 revs/min, is centrifuged 30 minutes with 8000 revs/min,
Collect bottom precipitation；Bottom precipitation is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained described poly-
Acid imide microballoon.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
Embodiment 2
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of redox graphene, 1 parts by weight of antioxidant, acryloyl
3 parts by weight of amine-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer, carbon
Sour 8 parts by weight of calcium, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate.
Polyimide microsphere the preparation method comprises the following steps: 2.5g polyetherimide is added in 100mL DMAc, with 100 turns/
Minute stirring 20 minutes, adds 2.5g polyvinyl alcohol, is stirred 20 minutes with 100 revs/min, obtains component A；By the poly- second of 2.5g
Enol is dissolved into 100mL deionized water, is stirred 20 minutes with 100 revs/min, is obtained component B；Component B is added to equal bodies
In long-pending component A, 60 DEG C are heated to 2 DEG C, after being stirred 2 hours with 500 revs/min, is centrifuged 30 minutes with 8000 revs/min,
Collect bottom precipitation；Bottom precipitation is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained described poly-
Acid imide microballoon.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
Embodiment 3
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate.
Polyimide microsphere the preparation method comprises the following steps: 2.5g polyetherimide is added in 100mL DMAc, with 100 turns/
Minute stirring 20 minutes, adds 2.5g polyvinyl alcohol, is stirred 20 minutes with 100 revs/min, obtains component A；By the poly- second of 2.5g
Enol is dissolved into 100mL deionized water, is stirred 20 minutes with 100 revs/min, is obtained component B；Component B is added to equal bodies
In long-pending component A, 60 DEG C are heated to 2 DEG C, after being stirred 2 hours with 500 revs/min, is centrifuged 30 minutes with 8000 revs/min,
Collect bottom precipitation；Bottom precipitation is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained described poly-
Acid imide microballoon.
The two-dimensional layer heat filling is that graphite phase carbon nitride and redox graphene are mixed with what mass ratio 1:1 was formed
Close object.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
Embodiment 4
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate.
Polyimide microsphere the preparation method comprises the following steps: 2.5g polyetherimide is added in 100mL DMAc, with 100 turns/
Minute stirring 20 minutes, adds 2.5g polyvinyl alcohol, is stirred 20 minutes with 100 revs/min, obtains component A；By the poly- second of 2.5g
Enol is dissolved into 100mL deionized water, is stirred 20 minutes with 100 revs/min, is obtained component B；Component B is added to equal bodies
In long-pending component A, 60 DEG C are heated to 2 DEG C, after being stirred 2 hours with 500 revs/min, is centrifuged 30 minutes with 8000 revs/min,
Collect bottom precipitation；Bottom precipitation is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained described poly-
Acid imide microballoon.
The two-dimensional layer heat filling is that the redox graphene@graphite phase carbon nitride two-dimensional layer that face face combines is led
Hot filler, it is specific the preparation method comprises the following steps:
(1) 1g graphite phase carbon nitride is added in the sodium hydrate aqueous solution of 40mL molar concentration 2mol/L, with 2 DEG C/
Minute is heated to 60 DEG C, is stirred 12 hours in 60 DEG C with 100 revs/min, obtains mixed liquor；Mixed liquor use is shut off molecular weight
The dialysis membrane of 3500Da is dialysed as medium to dialyzate using deionized water to be in neutrality, and dialyzate is collected；Dialyzate is diluted with water,
Obtain the graphite phase carbon nitride dispersion liquid of concentration 1mg/mL；
(2) graphene oxide dispersion of 160mL concentration 0.25mg/mL is placed in reaction unit, sequentially adds 180mg
The diallyl dimethyl ammoniumchloride aqueous solution of mass fraction 35%, the ammonium hydroxide of 3mL mass fraction 3% and 2mL hydrazine hydrate,
Ultrasonic disperse 20 minutes under conditions of ultrasonic power 300W obtain ultrasonic disperse liquid；Ultrasonic disperse liquid is heated with 2 DEG C/min
To 95 DEG C, in 95 DEG C back flow reaction 2 hours；30 DEG C are then naturally cooled to, is centrifuged 30 minutes with 12000 revs/min, upper layer is abandoned
Clear liquid, collecting bottom precipitation is redox graphene；Redox graphene is washed with water to after washing lotion is in neutrality, point
Yu Shuizhong is dissipated, the redox graphene dispersion liquid of concentration 0.2mg/mL is obtained；
(3) the redox graphene dispersion liquid that concentration is 0.2mg/mL is added dropwise to concentration using micropipette rifle
For the graphite phase carbon nitride dispersion liquid of 1mg/mL, the variation of Zeta potential analyzer detection Zeta potential is used；Work as Zeta potential
Close to 0mv, stop the addition of redox graphene dispersion liquid, by redox graphene dispersion liquid and graphite phase carbon nitride point
The mixed liquor of dispersion liquid is freeze-dried, and is obtained the redox graphene@graphite phase carbon nitride two-dimensional layer that the face face combines and is led
Hot filler.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
1 Examples 1 to 4 height of table heat dissipation plastic shell of television tests table with ABS alloy material
As known from Table 1, the redox graphene graphite phase carbon nitride two that embodiment 4 is prepared using electrostatic self-assembled method
Stratiform heat filling is tieed up, can be dispersed in the higher reduction-oxidation graphite of thermal diffusion coefficient is more uniform in resin matrix,
More effective thermally conductive chains are formed, avoids and reduction-oxidation graphite is used alone or nitrogenizes reduction-oxidation graphite and graphite-phase
Carbon physical mixed is easy to reunite leads to thermally conductive chain length and a limited number of defects together, so embodiment 4 uses use
It is simple that the thermal diffusion coefficient for the resin composite materials that the heat filling of electrostatic self-assembled method preparation is filled is greater than embodiment 3
Physical mixed.Moreover, dispersibility of the two-dimentional filler in resin is also improved using the method for electrostatic self-assembled, dispersion is more
Uniform redox graphene@graphite phase carbon nitride two-dimensional layer heat filling is added to form more thermally conductive chains, while
Improving the mechanical property of composite material, reason is probably to form more contact surfaces between face face combines layer by layer filler,
And the random distribution being simply mixed will form hole, be unfavorable for closely piling up.
Embodiment 5
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate, phosphorous acid
4 parts by weight of triphenylmethyl methacrylate.
Polyimide microsphere the preparation method comprises the following steps: 2.5g polyetherimide is added in 100mL DMAc, with 100 turns/
Minute stirring 20 minutes, adds 2.5g polyvinyl alcohol, is stirred 20 minutes with 100 revs/min, obtains component A；By the poly- second of 2.5g
Enol is dissolved into 100mL deionized water, is stirred 20 minutes with 100 revs/min, is obtained component B；Component B is added to equal bodies
In long-pending component A, 60 DEG C are heated to 2 DEG C, after being stirred 2 hours with 500 revs/min, is centrifuged 30 minutes with 8000 revs/min,
Collect bottom precipitation；Bottom precipitation is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained described poly-
Acid imide microballoon.
The two-dimensional layer heat filling is that the redox graphene@graphite phase carbon nitride two-dimensional layer that face face combines is led
Hot filler, specific preparation method is the same as embodiment 4.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
Embodiment 6~11
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate, phosphorous acid
4 parts by weight of triphenylmethyl methacrylate.
The two-dimensional layer heat filling is that the redox graphene@graphite phase carbon nitride two-dimensional layer that face face combines is led
Hot filler, specific preparation method is the same as embodiment 4.
The polyimide microsphere the preparation method comprises the following steps:
(1) 2.5g polyetherimide is added in 100mL DMAc, is stirred 20 minutes, is added with 100 revs/min
2.5g polyvinyl alcohol is stirred 20 minutes with 100 revs/min, obtains component A；2.5g polyvinyl alcohol is dissolved into 100mL deionization
In water, is stirred 20 minutes with 100 revs/min, obtain component B；Component B is added in isometric component A, is heated with 2 DEG C
To 60 DEG C, after being stirred 2 hours with 500 revs/min, it is centrifuged 30 minutes with 8000 revs/min, collects bottom precipitation；Bottom is sunk
Shallow lake is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained the polymeric matrix microballoon；
(2) Aluminium chloride hexahydrate 8.7g and surface promoter 0.6g are weighed, 8mL water, 11mL dehydrated alcohol are dissolved in
In the mixed solution of 2g formamide, stirred 20 minutes with 1200 revs/min；It is subsequently added into propylene oxide, with 1200 revs/min
After stirring 10 seconds, stops stirring and stand 12 hours, obtain gel；Gel is 4 hours dry at 80 DEG C, it crushed 40 meshes,
Obtain presoma；Presoma is heated to 500 DEG C with 5 DEG C/min, keeps the temperature 3 hours in air atmosphere, then with 300 liters of flow velocity/
Hour is passed through ammonia, is warming up to 1300 DEG C with 5 DEG C/min, keeps the temperature 2 hours, obtain aluminium nitride microballoon；
(3) polymeric matrix microballoon is added in acetone, at power 300W ultrasonic disperse 10 minutes, obtains concentration 1mg/
The polymeric matrix microballoon dispersion liquid of mL；Aluminium nitride microballoon is distributed in acetone simultaneously, is divided in power 300W ultrasonic disperse 30
Clock obtains the aluminium nitride microballoon dispersion liquid of concentration 1mg/mL；Under 500 revs/min of stirrings, aluminium nitride microballoon dispersion liquid is added
To polymeric matrix microballoon dispersion liquid, continues stirring 60 minutes, obtain complex microsphere dispersion liquid；Complex microsphere dispersion liquid is existed
6000 revs/min are centrifuged 40 minutes, remove supernatant, and collection sediment is 3 hours dry at 120 DEG C, obtains the polyimides
Microballoon.
6~11 aluminium nitride microballoon of embodiment prepares composition of raw materials table
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
The high heat dissipation plastic shell of television of 2 embodiment of table 5~11 tests table with ABS alloy material
As can be drawn from Table 2 to draw a conclusion:
1. embodiment 5 is compared with embodiment 4, by adding triphenyl phosphite, press down during plastic extrusion is heated
The generation of ester exchange reaction processed leads to the decline of boundary layer area, reduces the area of interface resistance, thermal resistance reduces, thus body
The thermal coefficient of system increased.
2. embodiment 6~9 is controlled by the content to propylene oxide, while guaranteeing aluminium nitride Sphere growth,
The structure and performance of aluminium nitride microballoon are controlled.
3. using the mixture of F127 and sucrose as surface promoter, height heat dissipation plastic shell of television in embodiment 11
It is better than embodiment 7 or embodiment 10 with the mechanical property and heating conduction of ABS alloy material.Triblock copolymer F127 hydrophilic chain
Section and hydrophobic segment can be assembled respectively, provide effective reaction space for polymerization reaction, while the polyether segment pair in F127
Hydroxyl interaction of hydrogen bond in the alkoxide compound of the winding of aluminium ion aggregation and cladding and hydroxyl and aluminium in F127；
And sucrose molecule is decomposed into a molecule glucose and fructose, and contain polyhydroxy in glucose and fructose molecule, it can pass through
Hydrogen bond action and the aggregation for forming a kind of similar surfaces promotor micelle；Therefore F127 and sucrose are respectively never with approach to nitrogen
The growth and dispersion for changing alumina particles play regulating and controlling effect.
4. polyimide microsphere and aluminium nitride microballoon simple combination are used, it is easy gap occur in interface, leads to material
The thermal conductivity of material is poor, by the way that aluminium nitride microballoon and polyimide microsphere to be used in combination in the present invention, in the interface of material
Shrinkage stress obviously weaken, the interface gaps of composite material are obviously reduced, and material thermal conductivity is caused to improve.
Embodiment 12
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate, phosphorous acid
4 parts by weight of triphenylmethyl methacrylate.
The two-dimensional layer heat filling is that the redox graphene@graphite phase carbon nitride two-dimensional layer that face face combines is led
Hot filler, specific preparation method is the same as embodiment 4.
The polyimide microsphere the preparation method comprises the following steps:
(1) 2.5g polyetherimide is added in 100mL DMAc, is stirred 20 minutes, is added with 100 revs/min
2.5g polyvinyl alcohol is stirred 20 minutes with 100 revs/min, obtains component A；2.5g polyvinyl alcohol is dissolved into 100mL deionization
In water, is stirred 20 minutes with 100 revs/min, obtain component B；Component B is added in isometric component A, is heated with 2 DEG C
To 60 DEG C, after being stirred 2 hours with 500 revs/min, it is centrifuged 30 minutes with 8000 revs/min, collects bottom precipitation；Bottom is sunk
Shallow lake is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained the polymeric matrix microballoon；
(2) Aluminium chloride hexahydrate 8.7g, F127 0.3g and sucrose 0.3g are weighed, it is anhydrous to be dissolved in 8mL water, 11mL
In the mixed solution of ethyl alcohol and 2g formamide, stirred 20 minutes with 1200 revs/min；It is subsequently added into propylene oxide 14mL, with
After 1200 revs/min are stirred 10 seconds, stops stirring and simultaneously stand 12 hours, obtain gel；Gel is dried 4 hours at 80 DEG C, powder
Broken 40 mesh of mistake, obtains presoma；Presoma is heated to 500 DEG C with 5 DEG C/min, keeps the temperature 3 hours in air atmosphere, then
It is passed through ammonia with 300 ls/h of flow velocity, 1300 DEG C is warming up to 5 DEG C/min, keeps the temperature 2 hours, obtain aluminium nitride microballoon；
(3) 2g aluminium nitride microballoon, 0.02g silane coupling agent and 150mL acetone is added, into reaction unit with 100 revs/min
Clock stirs after twenty minutes, adds 0.1g water；Then 60 DEG C are heated to 2 DEG C/min, are reacted 6 hours in 60 DEG C；Reaction terminates
Afterwards, 30 DEG C are naturally cooled to, is centrifuged 30 minutes with 4000 revs/min, bottom solid is collected；By bottom solid with 60 times of its weight
Dehydrated alcohol washing, it is 2 hours dry in 100 DEG C, obtain silane-modified aluminium nitride microballoon；
(4) polymeric matrix microballoon is added in acetone, at power 300W ultrasonic disperse 10 minutes, obtains concentration 1mg/
The polymeric matrix microballoon dispersion liquid of mL；Silane-modified aluminium nitride microballoon is distributed in acetone simultaneously, it is super in power 300W
Sound disperses 30 minutes, obtains the silane-modified aluminium nitride microballoon dispersion liquid of concentration 1mg/mL；It, will under 500 revs/min of stirrings
Silane-modified aluminium nitride microballoon dispersion liquid is added to polymeric matrix microballoon dispersion liquid, continues stirring 60 minutes, obtains compound
Microballoon dispersion liquid；Complex microsphere dispersion liquid is centrifuged 40 minutes at 6000 revs/min, removes supernatant, collects sediment 120
DEG C dry 3 hours, obtain the polyimide microsphere.
Height heat dissipation plastic shell of television is prepared with ABS alloy material by following steps: all raw materials are put into
It is stirred 20 minutes and is discharged with 800 revs/min in high-speed mixer, obtain output mixture；Output mixture is passed through into twin-screw
Extruding pelletization, the barrel temperature of the double screw extruder are 235 DEG C, and screw speed is 60 revs/min.
Embodiment 13
Height heat dissipation plastic shell of television ABS alloy material, is prepared: ABS resin by the raw material of following parts by weight
50 parts by weight, 40 parts by weight of polyimide microsphere, 20 parts by weight of polyethylene terephthalate, bisphenol A polycarbonate 20
Parts by weight, 4 parts by weight of maleic anhydride inoculated polypropylene, 20 parts by weight of two-dimensional layer heat filling, 1 parts by weight of antioxidant, propylene
3 parts by weight of amide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer,
8 parts by weight of calcium carbonate, melamine resin lubricate 0.5 parts by weight of oil microcapsule, 2 parts by weight of diisononyl phthalate, phosphorous acid
4 parts by weight of triphenylmethyl methacrylate.
The two-dimensional layer heat filling is that the redox graphene@graphite phase carbon nitride two-dimensional layer that face face combines is led
Hot filler, specific preparation method is the same as embodiment 4.
The polyimide microsphere the preparation method comprises the following steps:
(1) 2.5g polyetherimide is added in 100mL DMAc, is stirred 20 minutes, is added with 100 revs/min
2.5g polyvinyl alcohol is stirred 20 minutes with 100 revs/min, obtains component A；2.5g polyvinyl alcohol is dissolved into 100mL deionization
In water, is stirred 20 minutes with 100 revs/min, obtain component B；Component B is added in isometric component A, is heated with 2 DEG C
To 60 DEG C, after being stirred 2 hours with 500 revs/min, it is centrifuged 30 minutes with 8000 revs/min, collects bottom precipitation；Bottom is sunk
Shallow lake is washed with 80 times of its weight of deionized water, is dried 2 hours in 120 DEG C, is obtained the polymeric matrix microballoon；
(2) Aluminium chloride hexahydrate 8.7g, F127 0.3g and sucrose 0.3g are weighed, it is anhydrous to be dissolved in 8mL water, 11mL
In the mixed solution of ethyl alcohol and 2g formamide, stirred 20 minutes with 1200 revs/min；It is subsequently added into propylene oxide 14mL, with
After 1200 revs/min are stirred 10 seconds, stops stirring and simultaneously stand 12 hours, obtain gel；Gel is dried 4 hours at 80 DEG C, powder
Broken 40 mesh of mistake, obtains presoma；Presoma is heated to 500 DEG C with 5 DEG C/min, keeps the temperature 3 hours in air atmosphere, then
It is passed through ammonia with 300 ls/h of flow velocity, 1300 DEG C is warming up to 5 DEG C/min, keeps the temperature 2 hours, obtain aluminium nitride microballoon；
(3) 0.5g aluminium nitride microballoon, 100mL dehydrated alcohol, 0.4g tri- (methylol) amino first are added into reaction unit
Alkane and 300mL water, ultrasound 1 hour under conditions of ultrasonic power 300W；0.1g Dopamine hydrochloride is added, with 100 revs/min
Stirring 12 hours is centrifuged 20 minutes with 3000 revs/min, collects bottom solid；Bottom solid is anhydrous with 50 times of its weight
Ethanol washing, it is 4 hours dry in 80 DEG C, obtain the modified aluminium nitride microballoon of dopamine；(4) polymeric matrix microballoon is added to
In acetone, at power 300W ultrasonic disperse 10 minutes, the polymeric matrix microballoon dispersion liquid of concentration 1mg/mL is obtained；It simultaneously will be more
The modified aluminium nitride microballoon of bar amine is distributed in acetone, at power 300W ultrasonic disperse 30 minutes, obtains the more of concentration 1mg/mL
The modified aluminium nitride microballoon dispersion liquid of bar amine；Under 500 revs/min of stirrings, the modified aluminium nitride microballoon of dopamine is added to
Polymeric matrix microballoon dispersion liquid continues stirring 60 minutes, obtains complex microsphere dispersion liquid；By complex microsphere dispersion liquid 6000
Revs/min centrifugation 40 minutes, supernatant is removed, it is 3 hours dry at 120 DEG C to collect sediment, obtains the polyimide microsphere.
Embodiment 14
Substantially the same manner as Example 13, difference is only that acrylamide-[2- (methylacryloyl oxygroup) ethyl] two
Methyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer replaces with acrylamide-[3- (ethylene methacrylic amide) propyl] diformazan
Base-(3- sulfonic acid) ammonium ion polymer.
Embodiment 15
Substantially the same manner as Example 13, difference is only that acrylamide-[2- (methylacryloyl oxygroup) ethyl] two
Methyl-(3- propyl sulfonic acid) ammonium hydroxide ionomer replaces with acrylamide-[3- (ethylene methacrylic amide) propyl] diformazan
Base-(3- sulfonic acid) ammonium ion polymer and acrylamide-[2- (methylacryloyl oxygroup) ethyl] dimethyl-(3- sulfonic acid third
Base) mixture that is formed with mass ratio 1:1 of ammonium hydroxide ionomer.
The high heat dissipation plastic shell of television of 3 embodiment of table 12~15 tests table with ABS alloy material
From table 3 it can be seen that embodiment 12 and embodiment 13 are compared to embodiment 11, height heat dissipation plastic shell of television material
The mechanical property and heating conduction of material increase.Silanization aluminium nitride is used compared to embodiment 12, embodiment 13 uses dopamine
Aluminium nitride is modified, good compatibility between aluminium nitride and polyimide matrix, mechanism are as follows: dopamine is one are assigned
Kind combines the catechu with low relative molecular mass of the catechol group of levodopa and the amido functional group of lysine
Phenol amine can be adsorbed on aluminium nitride material surface, oxidation polymerization occurs under mild conditions with good cementation
Poly-dopamine film is generated, interaction is generated with the group of polyimides, improves the compatibility of the two, therefore toughening effect and heat
Conductance is obviously improved.
Table 4 is fire-retardant and insulation performance tests table
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, for the sake of this narrating mode of specification is used for the purpose of clearly, those skilled in the art should be incited somebody to action
As a whole, the technical solutions in the various embodiments may also be suitably combined for specification, and forming those skilled in the art can
With the other embodiments of understanding.
Claims (9)
1. a kind of high heat dissipation plastic shell of television ABS alloy material, which is characterized in that the raw material including following parts by weight:
40~60 parts by weight of ABS resin, 30~40 parts by weight of polyimide microsphere, 20~30 weight of polyethylene terephthalate
Part, 10~25 parts by weight of bisphenol A polycarbonate, 1~8 parts by weight of maleic anhydride inoculated polypropylene, two-dimensional layer heat filling
15~20 parts by weight, 0.5~1 parts by weight of antioxidant, 1~3 parts by weight of ionomer, 6~10 parts by weight of calcium carbonate, melamine tree
0.5~1 parts by weight of grease lubrication oil microcapsule, 2~4 parts by weight of diisononyl phthalate.
2. high heat dissipation plastic shell of television ABS alloy material according to claim 1, which is characterized in that described two
Tie up the mixture that stratiform heat filling is one or both of redox graphene, graphite phase carbon nitride.
3. high heat dissipation plastic shell of television ABS alloy material according to claim 1, which is characterized in that described two
Tie up stratiform heat filling be face face combine redox graphene@graphite phase carbon nitride two-dimensional layer heat filling, by with
Lower method obtains: graphite phase carbon nitride is removed using sodium hydrate aqueous solution into negatively charged nanoscale twins class graphite-phase nitrogen
Change carbon to be prepared with the modified positively charged redox graphene electrostatic self-assembled of diallyl dimethyl ammoniumchloride
The redox graphene@graphite phase carbon nitride two-dimensional layer heat filling that face face combines.
4. high heat dissipation plastic shell of television ABS alloy material according to claim 3, which is characterized in that the face
Face combine redox graphene@graphite phase carbon nitride two-dimensional layer heat filling the preparation method comprises the following steps:
(1) 1~5g graphite phase carbon nitride is added in the sodium hydrate aqueous solution of 30~100mL molar concentration, 1~5mol/L,
50~70 DEG C are heated to, in 50~70 DEG C with stirring 10~20 hours, obtains mixed liquor；Mixed liquor use is shut off molecular weight
The dialysis membrane of 3000~4000Da is dialysed as medium to dialyzate using deionized water to be in neutrality, and dialyzate is collected；By dialyzate plus
Water dilution, obtains the graphite phase carbon nitride dispersion liquid of 0.5~1mg/mL of concentration；
(2) graphene oxide dispersion of 150~300mL concentration, 0.2~0.5mg/mL is placed in reaction unit, is sequentially added
The ammonia of the diallyl dimethyl ammoniumchloride aqueous solution of 150~400mg mass fraction 35%, 2~6mL mass fraction 2~4%
Water and 1.5~6mL hydrazine hydrate ultrasonic disperse 10~40 minutes, obtain ultrasonic disperse liquid；Ultrasonic disperse liquid is heated to 80~
100 DEG C, in 80~100 DEG C back flow reaction 2~3 hours；20~30 DEG C are naturally cooled to, then with 8000~12000 revs/min
Supernatant liquor is abandoned in centrifugation 20~30 minutes, and collecting bottom precipitation is redox graphene；By redox graphene water
After washing is in neutrality to washing lotion, it is dispersed in water, obtains the redox graphene dispersion liquid of 0.1~0.5mg/mL of concentration；
(3) the redox graphene dispersion liquid that concentration is 0.1~0.5mg/mL is added dropwise to concentration is 0.5~1mg/mL
Graphite phase carbon nitride dispersion liquid, use Zeta potential analyzer detection Zeta potential variation；When Zeta potential is close to 0mv,
The addition for stopping redox graphene dispersion liquid, by the mixed of redox graphene dispersion liquid and graphite phase carbon nitride dispersion liquid
Liquid freeze-drying is closed, the redox graphene graphite phase carbon nitride two-dimensional layer heat filling that the face face combines is obtained.
5. high heat dissipation plastic shell of television ABS alloy material according to any one of claims 1 to 4, feature
It is, the raw material of the high heat dissipation plastic shell of television ABS alloy material further includes 3~7 parts by weight of triphenyl phosphite.
6. high heat dissipation plastic shell of television ABS alloy material according to claim 5, which is characterized in that described poly-
Acid imide microballoon the preparation method comprises the following steps: 2~10g polyetherimide is added in 100~400mL DMAc, stir 5~25 points
Clock adds 2~10g polyvinyl alcohol, stirs 10~30 minutes, obtains component A；2~10g polyvinyl alcohol is dissolved into 100~
In 400mL water, stirs 15~30 minutes, obtain component B；Component B is added in isometric component A, is heated to 50~60
DEG C, it after stirring 2~3 hours, is centrifuged 20~30 minutes with 6000~12000 revs/min, collects bottom precipitation；By bottom precipitation
With its water washing, drying obtains the polyimide microsphere.
7. high heat dissipation plastic shell of television ABS alloy material according to claim 5, which is characterized in that described poly-
Acid imide microballoon the preparation method comprises the following steps:
(1) 2~10g polyetherimide is added in 100~400mL DMAc, is stirred 5~25 minutes, it is poly- to add 2~10g
Vinyl alcohol stirs 10~30 minutes, obtains component A；2~10g polyvinyl alcohol is dissolved into 100~400mL water, stirring 15~
30 minutes, obtain component B；Component B is added in isometric component A, after being heated to 50~60 DEG C, stirring 2~3 hours,
It is centrifuged 20~30 minutes with 6000~12000 revs/min, collects bottom precipitation；By its water washing of bottom precipitation, drying is obtained
To the polymeric matrix microballoon；
(2) weigh 0.3~0.9g of 8~10g of Aluminium chloride hexahydrate and surface promoter, be dissolved in 5~10mL water, 10~
In the mixed solution of 15mL dehydrated alcohol and 1~3g formamide, stirred 10~20 minutes with 800~1200 revs/min；Then plus
Enter propylene oxide, after being stirred 10~30 seconds with 800~1200 revs/min, stops stirring and stand 12~16 hours, coagulated
Glue；Gel is 4~7 hours dry at 60~80 DEG C, it crushed 40~60 meshes, obtain presoma；Presoma is heated to 400
~500 DEG C, 2~3 hours are kept the temperature in air atmosphere, is then passed through ammonia with 100~300 ls/h of flow velocity, it is warming up to 1100~
1300 DEG C, 1~2 hour is kept the temperature, aluminium nitride microballoon is obtained；
(3) polymeric matrix microballoon is added in acetone, ultrasonic disperse 10~20 minutes, obtains 0.5~2.5mg/mL of concentration
Polymeric matrix microballoon dispersion liquid；Aluminium nitride microballoon is distributed in acetone simultaneously, ultrasonic disperse 10~30 minutes, is obtained dense
Spend the aluminium nitride microballoon dispersion liquid of 0.5~2.2mg/mL；Under 300~500 revs/min of stirrings, by aluminium nitride microballoon dispersion liquid
It is added to polymeric matrix microballoon dispersion liquid, the matter of the dispersion liquid of aluminium nitride microballoon dispersion liquid and polymeric matrix microballoon dispersion liquid
Amount is than being (0.3~0.5): 1, continue stirring 30~60 minutes, obtains complex microsphere dispersion liquid；Complex microsphere dispersion liquid is existed
4000~6000 revs/min are centrifuged 30~40 minutes, remove supernatant, and it is small in 110~120 DEG C of dryings 3~4 to collect sediment
When, obtain the polyimide microsphere.
8. high heat dissipation plastic shell of television ABS alloy material according to claim 7, which is characterized in that the table
Face promotor is the mixture of one or both of blocked polyethers F127, sucrose.
9. high heat dissipation plastic shell of television ABS alloy material according to claim 1, which is characterized in that it is described from
Sub- polymer is the ionomer of the base groups containing sulfobetaines.
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| CN201811372837.3A Withdrawn CN109486092A (en) | 2018-11-19 | 2018-11-19 | A kind of high heat dissipation plastic shell of television ABS alloy material |
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| CN111147641A (en) * | 2020-01-22 | 2020-05-12 | Oppo广东移动通信有限公司 | Composite board, shell assembly and electronic equipment |
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| CN112745624A (en) * | 2020-12-22 | 2021-05-04 | 金发科技股份有限公司 | ACS/PET-based alloy with short molding period and preparation method and application thereof |
| CN112745624B (en) * | 2020-12-22 | 2022-08-19 | 金发科技股份有限公司 | ACS/PET-based alloy with short molding period and preparation method and application thereof |
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