CN103937177B - A kind of high heat conduction modified plastics and preparation method thereof - Google Patents
A kind of high heat conduction modified plastics and preparation method thereof Download PDFInfo
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- CN103937177B CN103937177B CN201410166502.1A CN201410166502A CN103937177B CN 103937177 B CN103937177 B CN 103937177B CN 201410166502 A CN201410166502 A CN 201410166502A CN 103937177 B CN103937177 B CN 103937177B
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Abstract
The invention discloses a kind of high heat conduction modified plastics and preparation method thereof, this heat-conducting plastic comprises following weight percent composition: heat conduction additive, host plastic, coupling agent, dispersion agent, the mixture surface that described heat conduction additive is made up of two or three in heat conductive filler sapphire whisker, magnesium oxide powder and platelet boron nitride is formed by water solution polymerization process coated with conductive polymkeric substance.The present invention is at heat conduction additive surface aggregate skim conductive polymers, the high thermal conduction characteristic utilizing the metalloid key of conductive polymers to have is to connect the host plastic such as heat conduction additive and polyethylene terephthalate, polypropylene, polyethylene, nylon, make heat conduction additive and host plastic well compatible, and then prepare high heat conduction modified plastics.The thermal conductivity detecting the modified plastics that application method of the present invention is prepared through authoritative institution reaches 4.20W/m.K.
Description
[technical field]
The present invention relates to a kind of high heat conduction modified plastics and preparation method thereof, belong to technical field of polymer materials.
[background technology]
Modified plastics belongs to the intermediates in petrochemical industry chain, and it is on the basis of general-purpose plastics and engineering plastics, through filling, the method processing such as blended, enhancing and the novel plastic goods that go out.It is that plastics substrate processes primarily of five large general-purpose plastics and five large-engineering plastics, has fire-retardant, the feature such as anti-impact, high tenacity, workability.Modified plastics is typical technical progress and the benefited industry of consumption upgrading, have benefited from the production capacities such as global household electrical appliances, computer, power tool and toy to accelerate to shift to China, rely on the cost advantage in labor force and other production factors, China has become the manufacturing powerhouse in these fields, and takes this development having promoted domestic modified plastic industry.Consumption upgrading makes the industry entry rapid growth period such as automobile, building of China, and along with people's improving constantly material performance requirement, China is just becoming the maximum potential market of global modified plastics and major demands motive force of growth.
The developmental level of the modified plastic industry current overall context of China is lower, the industrial scale of enterprise inside the circle is generally less than normal, and it is many that the market situation of product also presents primary products, intermediate unstable product quality, the feature that high-grade products lack, far can not meet the needs of China's 21 century Economic development.Therefore, modified plastics, as the important component part of in new chemical materials field, is also classified as one of sciemtifec and technical sphere given priority to by country.Since two thousand seven China puts into effect every policy successively and advances modified plastic industry development.
Nowadays the key point preparing modification heat-conducting plastic is the consistency improving filler for plastic.In the actual production of our country, modifying plastics generally adopts blending method: directly joined in polymeric matrix by nanoparticle and mix.Blending method is simple to operate, but nanoparticle is easily reunited, inorganic nano-particle is difficult to be uniformly dispersed in conductive polymer matrix, and composite structure has uncertainty, and therefore this method needs the modifying surface process to nanoparticle before blended usually.Surface treatment method conventional at present has: add surface tension and surface free energy that tensio-active agent reduces nanoparticle, to improve the dispersion situation of nanoparticle; Add coupling agent, make between nanoparticle and matrix, there is strong interaction, this interaction can be covalent bonds, can be that the coupling agent be adsorbed on particle makes the segment of matrix polymer form ring-type, being caught wherein by nanoparticle, also can be that the segment of polymkeric substance and the cross-linked network of surface-modifying agent run through mutually.Our general actual production is now all directly add silane coupling agent and additive is blended, but this surface treatment also has skewness, and selective single shortcoming, the heat-conducting plastic localized thermal conductivity heterogeneity produced can be caused, can not get stable product.
Chinese Patent Application No.: 200510057168.7 describe a kind of inorganic oxide conductive powder/polyaniline conductive polymer matrix material and preparation method, its method selects single conductive polymer polyanilinc, the quality of aniline monomer is 2-40 times of inorganic oxide conductive powder quality, is not suitable for industrial production.
Chinese Patent Application No.: 201210326715.7 describe a kind of electric-insulating polyphenyl thioether height heat-conducting plastic and preparation method thereof, its method is by blended to polymeric substrate, glass fibre, conductive carbon black and properties-correcting agent, by the conductivity of carbon black, to reach the object preparing conductive plastics.This patent needs to consume a large amount of carbon black, considerably increases the cost of preparation.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of heat conduction additive and host plastic consistency good, the high heat conduction modified plastics that thermal conductivity is high.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high heat conduction modified plastics.
The present invention to achieve these goals, by the following technical solutions:
A kind of high heat conduction modified plastics, is characterized in that comprising following weight percent composition:
Heat conduction additive 50-70%
Host plastic 25-45%
Coupling agent 0.1-2%
Dispersion agent 3-5%,
The mixture Surface coating conductive polymers that described heat conduction additive is made up of two or three in heat conductive filler sapphire whisker, magnesium oxide powder and platelet boron nitride forms.
Sapphire whisker in the present invention, magnesium oxide powder and platelet boron nitride are micron order, sapphire whisker, magnesium oxide powder and platelet boron nitride by weight 1-5:4-8:1-3 mix between two or three kinds mix, the preferred mass of sapphire whisker, magnesium oxide powder and platelet boron nitride is than being 3:6:1.
In the present invention, sapphire whisker, magnesium oxide powder and the surface coated conductive polymers of platelet boron nitride mixture are the one in polyaniline, polypyrrole and Polythiophene, and the monomer of often kind of conductive polymers is respectively aniline monomer, pyrrole monomer and thiophene monomer.
The present invention selects fibrous alumina, magnesium oxide powder and platelet boron nitride between two or three kinds blended, allows heat conductive filler fully contact each other, forms netted and thermal conducting path that is chain-like structure.Select suitable tensio-active agent and coupling agent, hydrophilic radical is connected with additive surface, is adsorbed on additive surface, make lipophilic group outside, can be better compatible with plastics.
The high thermal conduction characteristic that the present invention utilizes the metalloid key of conductive polymers to have is to connect heat conduction additive and host plastic, and compared to selecting single conductive polymer polyanilinc, the present invention can select between polyaniline, polypyrrole, Polythiophene.And the quality of aniline monomer is 0.03-0.08 times of heat conduction additive quality, is suitable for industrial mass production.
Compared to a large amount of uses of conductive carbon black, the present invention better can reach economical, simple and easy, object easily.
Host plastic in the present invention is two or more the mixture in polyethylene terephthalate, polypropylene, polyethylene, nylon and nylon66 fiber, and each component in host plastic mixture is by waiting mass ratio mixing.
Coupling agent in the present invention is the one in maleic anhydride graft compatilizer, silane coupling agent and Aluminate.
Dispersion agent in the present invention is polyvinylpyrrolidone.
A preparation method for above-mentioned high heat conduction modified plastics, is characterized in that comprising the following steps:
A, preparation heat conduction additive: by heat conductive filler mixture water solution polymerization process at mixture surface aggregate growth skim conductive polymers, obtain heat conduction additive;
B, prepare modified plastics: heat conduction additive prepared by step a and host plastic, coupling agent and dispersion agent blended; join in the feeder of twin screw extruder; control extrusion temperature 200-270 DEG C, melt moment of torsion 30-70Nm, granulation in dicing machine.
In the present invention, the concrete steps of water solution polymerization process generation conductive polymers are:
By the monomer of conductive polymers, water and protonic acid according to volume ratio 1:15:1 mixing, then join in heat conductive filler mixture and mix, stir, then add initiator for reaction 26-30h in batches, obtain heat conduction additive; Conductive polymers monomer wherein and the mass ratio of heat conductive filler mixture are 1-3:10-15, and the amount of substance ratio of initiator and conductive polymers monomer is 1:1.
Protonic acid is wherein sulfuric acid or hydrochloric acid, and initiator is Potassium Persulphate.
The high heat conduction modified plastics masterbatch that granulation obtains can be processed further, through base, and reason base, heating base, blows in advance, stretching base, and high pressure blows, and cooling is blown, and demoulding program forms product, finally integrates unitizing; Also in twin screw extruder, directly can carry out base at plastics of the present invention after hybrid reaction, reason base, heating base, blows in advance, stretching base, and high pressure blows, and cooling is blown, and demoulding program forms the step of product.
The present invention, relative to prior art, has following advantage:
The present invention is at heat conduction additive surface aggregate skim conductive polymers, the high thermal conduction characteristic utilizing the metalloid key of conductive polymers to have is to connect the host plastic such as heat conduction additive and polyethylene terephthalate, polypropylene, polyethylene, nylon, make heat conduction additive and host plastic well compatible, and then prepare high heat conduction modified plastics.The thermal conductivity detecting the modified plastics that application method of the present invention is prepared through authoritative institution reaches about 4.20W/m.K.
The present invention prepares simple and easy, and cost is low, is suitable for suitability for industrialized production.
[embodiment]
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
The weight percent composition of high heat conduction modified plastics is: magnesium oxide powder 32%, platelet boron nitride 32%, nylon 16%, nylon66 fiber 16%, maleic anhydride graft compatilizer 1%, dispersion agent 3%;
The preparation method of embodiment 1 is:
A, first magnesium oxide powder and platelet boron nitride are mixed into heat conductive filler mixture, then the mixture that aniline monomer, water and hydrochloric acid mix according to volume ratio 1:15:1 is added, add the initiator for reaction 28h with amount of substances such as aniline monomers more in batches, at heat conductive filler mixture Surface coating skim polyaniline, obtain heat conduction additive, wherein the mass ratio of aniline monomer and heat conductive filler mixture is 1:10;
B, by heat conduction additive and host plastic, coupling agent and dispersion agent blended, join in the feeder of twin screw extruder, control extrusion temperature 240-250 DEG C, melt moment of torsion 40Nm, granulation in dicing machine.
Embodiment 2:
The weight percent composition of high heat conduction modified plastics is: sapphire whisker 48%, platelet boron nitride 18%, polypropylene 16%, polyethylene 12%, silane coupling agent 2%, dispersion agent 4%;
The preparation method of embodiment 2 is:
A, first sapphire whisker and platelet boron nitride are mixed into heat conductive filler mixture, add the mixture that pyrrole monomer, water and sulfuric acid mix according to volume ratio 1:15:1 again, add the initiator for reaction 26h with amount of substances such as pyrrole monomers more in batches, at heat conductive filler mixture Surface coating skim polypyrrole, obtain heat conduction additive, wherein the mass ratio of pyrrole monomer and heat conductive filler mixture is 1:3;
B, by heat conduction additive and host plastic, coupling agent and dispersion agent blended, join in the feeder of twin screw extruder, control extrusion temperature 260-270 DEG C, melt moment of torsion 50Nm, granulation in dicing machine.
Embodiment 3:
The weight percent composition of high heat conduction modified plastics is: sapphire whisker 30%, magnesium oxide powder 20%, polyethylene terephthalate 15%, polypropylene 16%, polyethylene 12%, Aluminate 2%, dispersion agent 5%;
The preparation method of embodiment 3 is:
A, first sapphire whisker and magnesium oxide powder are mixed into heat conductive filler mixture, add the mixture that thiophene monomer, water and hydrochloric acid mix according to volume ratio 1:15:1 again, add the initiator for reaction 30h with amount of substances such as thiophene monomers more in batches, at heat conductive filler mixture Surface coating skim Polythiophene, obtain heat conduction additive, wherein the mass ratio of thiophene monomer and heat conductive filler mixture is 1:5;
B, by heat conduction additive and host plastic, coupling agent and dispersion agent blended, join in the feeder of twin screw extruder, control extrusion temperature 220-230 DEG C, melt moment of torsion 70Nm, granulation in dicing machine.
Embodiment 4:
The weight percent composition of high heat conduction modified plastics is: sapphire whisker 21%, magnesium oxide powder 42%, platelet boron nitride 7%, nylon 13%, nylon66 fiber 12%, maleic anhydride graft compatilizer 1%, dispersion agent 4%;
The preparation method of embodiment 4 is:
A, first sapphire whisker, magnesium oxide powder and platelet boron nitride are mixed into heat conductive filler mixture, add the mixture that aniline monomer, water and hydrochloric acid mix according to volume ratio 1:15:1 again, add the initiator for reaction 29h with amount of substances such as aniline monomers more in batches, at heat conductive filler mixture Surface coating skim polyaniline, obtain heat conduction additive, wherein the mass ratio of aniline monomer and heat conductive filler mixture is 1:15;
B, by heat conduction additive and host plastic, coupling agent and dispersion agent blended, join in the feeder of twin screw extruder, control extrusion temperature 240-260 DEG C, melt moment of torsion 40Nm, granulation in dicing machine.
Embodiment 5:
The weight percent composition of high heat conduction modified plastics is: sapphire whisker 20%, magnesium oxide powder 20%, platelet boron nitride 10%, polyethylene terephthalate 15%, nylon 15%, nylon66 fiber 15%, maleic anhydride graft compatilizer 0.1%, dispersion agent 4.9%;
The preparation method of embodiment 5 is:
A, first sapphire whisker, magnesium oxide powder and platelet boron nitride are mixed into heat conductive filler mixture, add the mixture that aniline monomer, water and sulfuric acid mix according to volume ratio 1:15:1 again, add the initiator for reaction 27h with amount of substances such as aniline monomers more in batches, at heat conductive filler mixture Surface coating skim polyaniline, obtain heat conduction additive, wherein the mass ratio of aniline monomer and heat conductive filler mixture is 1:8;
B, by heat conduction additive and host plastic, coupling agent and dispersion agent blended, join in the feeder of twin screw extruder, control extrusion temperature 200-210 DEG C, melt moment of torsion 30Nm, granulation in dicing machine.
Carry out hot physical property detection to embodiment 1-5, detection method is ASTME1461 laser method, and testing tool is thermal conductivity instrument FL4010, and test result is as shown in table 1.
Table 1:
From the test data in table 1, the applying modified carbon material of the present invention heat-conducting plastic thermal conductivity be stabilized in about 4.20W/m.K.
Claims (5)
1. a high heat conduction modified plastics, is characterized in that comprising following weight percent composition:
Described heat conduction additive is by heat conductive filler sapphire whisker, the mixture Surface coating conductive polymers that magnesium oxide powder and platelet boron nitride three kinds form forms, described sapphire whisker, magnesium oxide powder and platelet boron nitride in mass ratio 1-5:3-7:1-3 mix, described sapphire whisker, magnesium oxide powder and platelet boron nitride are micron order, described conductive polymers is polyaniline, one in polypyrrole and Polythiophene, described coupling agent is maleic anhydride graft compatilizer, one in silane coupling agent and Aluminate, described host plastic is polyethylene terephthalate, polypropylene, polyethylene, two or more mixture in nylon66 fiber.
2. the high heat conduction modified plastics of one according to claim 1, is characterized in that described dispersion agent is polyvinylpyrrolidone.
3. a preparation method for the high heat conduction modified plastics according to any one of claim 1-2, is characterized in that comprising the following steps:
A, preparation heat conduction additive: by heat conductive filler mixture water solution polymerization process at mixture surface aggregate growth skim conductive polymers, obtain heat conduction additive;
B, prepare modified plastics: heat conduction additive prepared by step a and host plastic, coupling agent and dispersion agent blended; join in the feeder of twin screw extruder; control extrusion temperature 200-270 DEG C, melt moment of torsion 30-70Nm, granulation in dicing machine.
4. the preparation method of a kind of high heat conduction modified plastics according to claim 3, is characterized in that the concrete steps of described water solution polymerization process generation conductive polymers are:
By the monomer of conductive polymers, water and protonic acid according to volume ratio 1:15:1 mixing, then join in heat conductive filler mixture and mix, stir, then add initiator for reaction 26-30h in batches, obtain heat conduction additive; Wherein said conductive polymers monomer and the mass ratio of heat conductive filler mixture are 1-3:10-15, and the amount of substance ratio of described initiator and conductive polymers monomer is 1:1.
5. the preparation method of a kind of high heat conduction modified plastics according to claim 4, it is characterized in that described protonic acid is sulfuric acid or hydrochloric acid, described initiator is Potassium Persulphate.
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| CN108641306A (en) * | 2018-03-15 | 2018-10-12 | 苏州甫众塑胶有限公司 | A kind of heat conductive flame-retarding material and preparation method thereof being exclusively used in LED lamp of automobile radiator |
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