CN107987444A - A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications - Google Patents

A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications Download PDF

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Publication number
CN107987444A
CN107987444A CN201711319464.9A CN201711319464A CN107987444A CN 107987444 A CN107987444 A CN 107987444A CN 201711319464 A CN201711319464 A CN 201711319464A CN 107987444 A CN107987444 A CN 107987444A
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pmma
graphene
preparation
composite materials
temperature
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周慧
刘文斌
时杰
刘日鑫
唐惠东
肖雪军
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Changzhou Vocational Institute of Engineering
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Changzhou Vocational Institute of Engineering
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
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    • B29C2945/76494—Controlled parameter
    • B29C2945/76498—Pressure
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

The invention discloses a kind of graphene/PMMA, preparation method and applications, belong to organic material field, its component and content are configured to：0~2 part of graphene；100 parts of polymethyl methacrylate；0~0.2 part of surfactant；500 parts~1000 parts of solvent.In preparation method, the content of the graphene of use is relatively low, and graphene realizes dispersed in PMMA, and while thermal conductivity increase, light transmittance declines seldom.The present invention also provides the application of above-mentioned graphene/PMMA composite materials, has preferable dispersiveness, thermal conductivity, hardness height, wear-resisting, can be applied to the lighting areas such as LED lens material.

Description

A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications
Technical field
The invention belongs to organic material field, and in particular to a kind of graphene/PMMA, preparation method and applications.
Background technology
For LED compared with the light sources such as traditional incandescent lamp, fluorescent lamp, operating current is very small, and the electric energy of consumption is only tradition The 1/10 of light source, without using the mercury of serious pollution environment, has that energy saving, luminous efficiency is high, environmentally friendly, small, light, long lifespan The advantages that, it is known as 21 century new light sources.LED is in advertising media's video screen, automobile lamp, backlight electric power, mark at present It is widely applied with indicative illumination, Landscape Lighting, room lighting (White LED).
And LED lens are to contribute to lift the light extraction efficiency of LED together with being closely connected with LED, change the light field point of LED The optical system of cloth.High transparency light diffusion resin is the main material for making LED lens, mainly there is PMMA (polymethylacrylic acid Methyl esters), PC (makrolon), organosilicon, the resin of the high transparency such as PS (polystyrene).PMMA light transmittances 92%, processability Can good, anti-ultraviolet ageing, but its moisture absorption is strong, poor toughness, inflammable；PC light transmittances 89%, good mechanical properties, moisture absorption is small, hinders Combustion property is good, but ultraviolet or irradiation with radiation easily turn to be yellow；Organosilicon is flexible, ageing-resistant, heat-proof aging, ultraviolet-resistant aging, often For directly encapsulating LED component.With the lifting of LED demands, the market of LED lens also gradually expands, and has a extensive future, right The heat conductivility of its lens material and the requirement of refractive index are further lifted.
Polymer is filled by high heat conduction inorganic matter, prepares inorganic matter/polymer bond's composite material.Due to good Good heat conductivility high polymer is expensive, and it is method widely used at present that filling, which prepares thermal conductive polymer,.
Graphene is with carbon carbon sp2The carbon simple substance for the hexagonal lattice structure that hydridization forms, forms big conjugated bonds, graphite The lattice structure of alkene determines that its bonding is extremely stable, therefore its heat endurance in the case of not chemically reacting is very high. The mean free path of the phonon of graphene is far longer than the phonon of the high-heat conductivity graphite material and other materials on ordinary meaning certainly By journey, its phonon free path about 775nm, the face heat conduction coefficient of graphene is up to 5000W/ (mK) left and right, Ke Yiyong Make good heat sink material.
The content of the invention
It is an object of the invention to overcome the shortcomings of the prior art, using graphene protrude mechanics, heat conduction and thoroughly Photosensitiveness, there is provided one kind has thermal conductive resin, finely dispersed graphene/PMMA composite materials, can be applicable to LED lens material Field.
To achieve the above objectives, the technical solution adopted by the present invention is to provide one kind and has thermal conductive resin, is uniformly dispersed Graphene/PMMA composite materials, its component and content form as follows：
Technical solution of the present invention provides a kind of preparation method of graphene/PMMA composite materials as described above, and use is molten Liquid mixing method, comprises the following steps：
(1) by polymethyl methacrylate (PMMA) and appropriate solvent under magnetic agitation effect 2~8h of magnetic agitation, obtain To PMMA polymer solution；The mass ratio of PMMA and solvent is 1: 5~20；
(2) surfactant is added in PMMA polymer solution, weighs the graphene of PMMA mass 0~2%, continue magnetic Power stirs 15~30min, 0.5~1h of ultrasonic disperse, and high speed homogenization dispersion machine disperses 5~20min；
(3) mixed solution obtained by step (2) is warming up to 50~100 DEG C, removes solvent and dries, up to graphite after crushing Alkene/PMMA masterbatch；
(4) by graphene/PMMA masterbatch, with PMMA through mixing 5~10min in high-speed mixer, mixture, graphite are obtained The mass ratio of alkene/PMMA masterbatch and PMMA are 1: 1~100；
(5) by mixture in extruding pelletization on double screw extruder, temperature is 150~230 DEG C, screw speed for 20~ 30r/min；
(6) by the precise injection machine injection molding of above-mentioned pellet, injection temperature is 180~240 DEG C, injection pressure for 80~ 130MPa, mould temperature are 40~80 DEG C, that is, are obtained a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.
In above-mentioned preparation scheme, graphene is heat-conducting type graphene, and powdered, its lamella is thin, and easily scattered, heat conductivility is excellent It is different, the mass fraction ＜ 1% of its O, 450~500m of specific surface area2/g；
In above-mentioned preparation scheme, polymethyl methacrylate is optical grade, powdered；
In above-mentioned preparation scheme, one kind in surfactant OP-10, Tween-80, Tween-20, Span -60 etc., profit In the scattered of graphene；
In above-mentioned preparation scheme, solvent is one in acetone, butanone, dimethylformamide, tetrahydrofuran, chloroform etc. Kind or several compoundings.
The present invention also provides the application of above-mentioned graphene/PMMA composite materials, there is preferable dispersiveness, thermal conductivity, firmly Degree is high, wear-resisting, can be applied to the lighting areas such as LED lens material.
Best Applying Condition：Polymethyl methacrylate and the mass ratio of solvents tetrahydrofurane are 1：10,35 DEG C of magnetic force stir Mix 4h；Continue magnetic agitation 15min after adding graphene, ultrasonic disperse 40min and high speed homogenization disperse 5min；50 DEG C of removings are molten Agent, drying.With optical grade PMMA through mixing 10min in high-speed mixer after broken；Extruding-out process parameter：Temperature 210~ 250 DEG C, 20~30r/min of screw speed；Pellet precise injection machine injection molding, 180~240 DEG C of injection temperature, injection pressure 80~130MPa of power, 60 DEG C of mould temperature.
Beneficial effect：
(1) the present invention provides a kind of preparation method of graphene/PMMA heat-conductive composite materials, in preparation method, adopt The content of graphene is relatively low, and graphene realizes dispersed in PMMA, and while thermal conductivity increase, light transmittance declines Seldom.
(2) graphene/PMMA heat-conductive composite material raw material sources prepared by the present invention enrich, and preparation process is simple, is easy to Operation, and the requirement to equipment is low, and dispersal device is only increased on the basis of the preparation process of conventional lenses material PMMA.
(3) graphene/PMMA heat-conductive composite materials prepared by the present invention have good thermal conductivity, heat endurance, hardness High, wear-resisting, service life extends.
Figure of description
Fig. 1 is the thermal conductivity factor result of the material sample prepared by 1 technical solution of the embodiment of the present invention；
Fig. 2 is the dsc analysis result of the material sample prepared by 1 technical solution of the embodiment of the present invention.
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Comparative example：
The preparation of PMMA
10ml methyl methacrylate monomers are measured, after addition 0.01g benzoyl peroxides stir evenly, in 85~90 DEG C Under the conditions of 30~40min of prepolymerization；Gained performed polymer is cast in mould, and the low temperature polymerization 8h under the conditions of 45 DEG C, 100 DEG C of bars High temperature polymerization 2h under part, after the natural cooling demoulding, that is, obtains PMMA.
Embodiment 1：
Weigh 10g PMMA to be placed in 100ml tetrahydrofurans, 35 DEG C of magnetic agitation 4h, obtain PMMA polymer solution；Claim The graphene of 0.05g is taken, continues magnetic agitation 15min, then ultrasonic disperse 30min, disperses on last high speed homogenization dispersion machine 5min；Gained mixed solution is warming up to 50 DEG C of removing solvents and dries, up to graphene/PMMA masterbatch after crushing；By graphene/ PMMA masterbatch, with optical grade PMMA powders of the 100g through 85 DEG C of dry 3h through mixing 10min in high-speed mixer, is mixed Material；By mixture in double screw extruder extruding pelletization, temperature is 210~250 DEG C, and screw speed is 20~30r/min；Pellet With precise injection machine injection molding, injection temperature is 180~240 DEG C, and injection pressure is 80~130MPa, and mould temperature is 40~80 DEG C, that is, obtain a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.Its thermal conductivity factor, thermogravimetric analysis As a result, light transmittance, dispersiveness are similar to Example 1.
Embodiment 1：
Weigh 10g PMMA to be placed in 100ml tetrahydrofurans, 35 DEG C of magnetic agitation 4h, obtain PMMA polymer solution；Claim The graphene of 0.044g is taken, continues magnetic agitation 15min, then ultrasonic disperse 30min, disperses on last high speed homogenization dispersion machine 5min；Gained mixed solution is warming up to 50 DEG C of removing solvents and dries, up to graphene/PMMA masterbatch after crushing；By graphene/ PMMA masterbatch, with optical grade PMMA powders of the 100g through 85 DEG C of dry 3h through mixing 10min in high-speed mixer, is mixed Material；By mixture in double screw extruder extruding pelletization, temperature is 210~250 DEG C, and screw speed is 20~30r/min；Pellet With precise injection machine injection molding, injection temperature is 180~240 DEG C, and injection pressure is 80~130MPa, and mould temperature is 40~80 DEG C, that is, obtain a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.Its thermal conductivity factor, thermogravimetric analysis As a result, light transmittance, dispersiveness are similar to Example 1.
Embodiment 2：
Weigh 10g PMMA to be placed in 100ml tetrahydrofurans, 35 DEG C of magnetic agitation 4h, obtain PMMA polymer solution；Claim The graphene of 0.11g is taken, continues magnetic agitation 15min, then ultrasonic disperse 30min, disperses on last high speed homogenization dispersion machine 5min；Gained mixed solution is warming up to 50 DEG C of removing solvents and dries, up to graphene/PMMA masterbatch after crushing；By graphene/ PMMA masterbatch, with optical grade PMMA powders of the 100g through 85 DEG C of dry 3h through mixing 10min in high-speed mixer, is mixed Material；By mixture in double screw extruder extruding pelletization, temperature is 210~250 DEG C, and screw speed is 20~30r/min；Pellet With precise injection machine injection molding, injection temperature is 180~240 DEG C, and injection pressure is 80~130MPa, and mould temperature is 40~80 DEG C, that is, obtain a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.Its thermal conductivity factor, thermogravimetric analysis As a result, light transmittance, dispersiveness are similar to Example 1.
Embodiment 3：
Weigh 10g PMMA to be placed in 100ml tetrahydrofurans, 35 DEG C of magnetic agitation 4h, obtain PMMA polymer solution；Claim The graphene of 0.22g is taken, continues magnetic agitation 15min, then ultrasonic disperse 30min, disperses on last high speed homogenization dispersion machine 5min；Gained mixed solution is warming up to 50 DEG C of removing solvents and dries, up to graphene/PMMA masterbatch after crushing；By graphene/ PMMA masterbatch, with optical grade PMMA powders of the 100g through 85 DEG C of dry 3h through mixing 10min in high-speed mixer, is mixed Material；By mixture in double screw extruder extruding pelletization, temperature is 210~250 DEG C, and screw speed is 20~30r/min；Pellet With precise injection machine injection molding, injection temperature is 180~240 DEG C, and injection pressure is 80~130MPa, and mould temperature is 40~80 DEG C, that is, obtain a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.Its thermal conductivity factor, thermogravimetric analysis As a result, light transmittance, dispersiveness are similar to Example 1.
Embodiment 4
Weigh 10g PMMA to be placed in 100ml dimethylformamides, 35 DEG C of magnetic agitation 4h, it is molten to obtain PMMA polymer Liquid；Weigh the graphene of 0.044g, continue magnetic agitation 15min, then ultrasonic disperse 30min, on last high speed homogenization dispersion machine Scattered 5min；Gained mixed solution is warming up to 50 DEG C of removing solvents and dries, up to graphene/PMMA masterbatch after crushing；By stone Black alkene/PMMA masterbatch, with optical grade PMMA powders of the 100g through 85 DEG C of dry 3h through mixing 10min in high-speed mixer, obtains Mixture；By mixture in double screw extruder extruding pelletization, temperature is 210~250 DEG C, and screw speed is 20~30r/min； Pellet precise injection machine injection molding, injection temperature are 180~240 DEG C, and injection pressure be 80~130MPa, mould temperature is 40~ 80 DEG C, that is, obtain a kind of with thermal conductive resin, finely dispersed graphene/PMMA composite materials.Its thermal conductivity factor, thermogravimetric point It is similar to Example 1 to analyse result, light transmittance, dispersiveness.
The performance of each embodiment is as shown in table 1.
The performance of 1 graphene of table/PMMA composite materials

Claims (9)

  1. A kind of 1. graphene/PMMA composite materials, it is characterised in that：Its component and quality ratio content are as follows：
    The surfactant is OP-10, one kind in Tween-80, Tween-20, Span -60；The solvent is acetone, fourth One or more in ketone, dimethylformamide, tetrahydrofuran, chloroform etc..
  2. A kind of 2. preparation method of graphene/PMMA composite materials, it is characterised in that：Using solution mixing method, including following step Suddenly：
    (1) by 3~12% optical-grade polymethylmethacrylacontinuous (PMMA) and solvent under magnetic agitation effect magnetic agitation 2 ~8h, obtains PMMA polymer solution；The mass ratio of PMMA and solvent is 1: 5~20；
    (2) surfactant is added in PMMA polymer solution, weighs the graphene of PMMA mass 0~2%, continued magnetic force and stir 15~30min, 0.5~1h of ultrasonic disperse are mixed, high speed homogenization dispersion machine disperses 5~20min；
    (3) mixed solution obtained by step (2) is warming up to 50~100 DEG C, removes solvent and dries, and broken rear graphene to obtain the final product/ PMMA masterbatch；
    (4) by graphene/PMMA masterbatch, the optical grade PMMA with different proportion is obtained through mixing 5~10min in high-speed mixer To mixture；The mass ratio of graphene/PMMA masterbatch and PMMA are 1: 1~100；
    (5) it is 150~230 DEG C in extruding pelletization on double screw extruder, temperature by mixture, screw speed is 20~30r/ min；
    (6) by the precise injection machine injection molding of above-mentioned pellet, injection temperature is 180~240 DEG C, injection pressure for 80~ 130MPa, mould temperature are 40~80 DEG C, that is, obtain graphene/PMMA composite materials.
  3. 3. preparation method according to claim 2, it is characterised in that the surfactant is OP-10, Tween-80, spits One kind in temperature -20, Span -60；The solvent is in acetone, butanone, dimethylformamide, tetrahydrofuran, chloroform etc. One or more.
  4. 4. the preparation method according to Claims 2 or 3, it is characterised in that in the step (2), weigh PMMA mass 0~ 2% graphene.
  5. 5. preparation method according to claim 4, it is characterised in that in the step (2), weigh PMMA mass 0~2% Graphene.
  6. 6. according to the preparation method described in Claims 2 or 3 or 5, it is characterised in that the time of step (2) ultrasonic disperse For 20~40min.
  7. 7. preparation method according to claim 4, it is characterised in that the time of step (2) ultrasonic disperse for 20~ 40min。
  8. 8. preparation method according to claim 2, it is characterised in that：Polymethyl methacrylate and solvents tetrahydrofurane Mass ratio is 1：10,35 DEG C of magnetic agitation 4h；Add magnetic agitation 15min, ultrasonic disperse 40min and high speed homogenization after graphene Scattered 5min；50 DEG C of removing solvents, drying；With optical grade PMMA through mixing 10min in high-speed mixer after broken；Extrusion molding Technological parameter：210~250 DEG C of temperature, 20~30r/min of screw speed；Pellet precise injection machine injection molding, injection temperature 180~240 DEG C, 80~130MPa of injection pressure, 60 DEG C of mould temperature, that is, obtain graphene/PMMA composite materials.
  9. A kind of 9. application of graphene/PMMA composite materials as described in claim 1-8 any one, it is characterised in that：Should For LED lens material lighting area.
CN201711319464.9A 2017-12-12 2017-12-12 A kind of graphene/PMMA heat-conductive composite materials, preparation method and applications Pending CN107987444A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN108753087A (en) * 2018-05-29 2018-11-06 厦门海莱照明有限公司 A kind of copper foil graphene acrylic resin high-heat-conductive composite material and preparation method thereof
CN109082054A (en) * 2018-07-11 2018-12-25 望江县天长光学仪器有限公司 A kind of ageing-resistant optical lens material
CN109679261A (en) * 2018-12-29 2019-04-26 厦门十一维科技有限公司 High thermal conductivity oriented graphite alkene/PMMA composite material preparation method
CN112175332A (en) * 2020-10-15 2021-01-05 厦门恒美达工贸有限公司 Preparation method of novel plastic raw material

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CN103524825A (en) * 2013-09-03 2014-01-22 东莞上海大学纳米技术研究院 Preparation method and product of heat conduction macromolecule-graphene composite material
CN104650517A (en) * 2014-12-09 2015-05-27 王瑜玉 Preparation method of graphene oxide composite material
CN106543675A (en) * 2016-10-31 2017-03-29 青岛德通纳米技术有限公司 A kind of preparation method of Graphene 3D printing wire rod

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CN103524825A (en) * 2013-09-03 2014-01-22 东莞上海大学纳米技术研究院 Preparation method and product of heat conduction macromolecule-graphene composite material
CN104650517A (en) * 2014-12-09 2015-05-27 王瑜玉 Preparation method of graphene oxide composite material
CN106543675A (en) * 2016-10-31 2017-03-29 青岛德通纳米技术有限公司 A kind of preparation method of Graphene 3D printing wire rod

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108753087A (en) * 2018-05-29 2018-11-06 厦门海莱照明有限公司 A kind of copper foil graphene acrylic resin high-heat-conductive composite material and preparation method thereof
CN109082054A (en) * 2018-07-11 2018-12-25 望江县天长光学仪器有限公司 A kind of ageing-resistant optical lens material
CN109679261A (en) * 2018-12-29 2019-04-26 厦门十一维科技有限公司 High thermal conductivity oriented graphite alkene/PMMA composite material preparation method
CN112175332A (en) * 2020-10-15 2021-01-05 厦门恒美达工贸有限公司 Preparation method of novel plastic raw material

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