CN104194248A - Method for in-situ modification of ABS (acrylonitrile-butadiene-styrene) resin by graphene - Google Patents
Method for in-situ modification of ABS (acrylonitrile-butadiene-styrene) resin by graphene Download PDFInfo
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Abstract
The invention belongs to the technical field of materials and particularly relates to a method for in-situ modification of ABS (acrylonitrile-butadiene-styrene) resin by graphene. The method comprises the following steps: (1) preparing a PB emulsion from butadiene by virtue of emulsion polymerization; (2) then grafting styrene, polymerizing acrylonitrile, agglomerating and drying to obtain ABS aggregates; (3) preparing SAN (styrene-acrylonitrile) particles by bulk polymerization or suspension polymerization; and (4) mixing and granulating the ABS aggregates and the SAN particles. Graphene can be added randomly in the steps (1), (2) and (3) to obtain a graphene modified ABS resin composite material by virtue of in-situ modification. The method is simple in technical process, easy to implement and suitable for industrialized production. The obtained composite material is remarkably enhanced in heat conductivity, electric conductivity and mechanical property and has a considerable economic value, thereby creating a new path for graphene modified ABS resin.
Description
Technical field
The invention belongs to nano-polymer composite material technical field, particularly a kind of method of graphene in-situ modified ABS resin.
Background technology
ABS resin is the mixture of polyhutadiene and vinyl cyanide (A) and the graft copolymer of vinylbenzene (B) monomer and the free multipolymer (SAN) of styrene-acrylonitrile, and it has the advantages such as rigidity is strong, hardness is large, good dimensional stability and processing fluidity.It has also preserved good toughness simultaneously, is a kind of engineering plastics of excellent performance.In addition, ABS resin also has good stability, use range extensively and cost performance advantages of higher, is widely used in the aspects such as automobile, electronic apparatus, building materials, universal machine and general merchandise.
Along with the expansion of ABS resin Application Areas, the status of mineral filler in ABS resin industry is more and more outstanding.Particularly, along with the fast development of nanoscale science and technology, a lot of nano inorganic materials have been endowed unique physics and chemical property, as wear resistance, electroconductibility, thermal conductivity, flame retardant resistance, erosion resistance, resistance to air loss etc.Therefore utilize inorganic nano material to carry out modification to ABS resin, be realize ABS resin high performance, multifunction, become more meticulous, one of the main path of Developing New Variety, become a key areas of current Materials science research and development.
Current inorganic materials mainly concentrates on hollow glass microballoon, carbon fiber, nano-calcium carbonate, polynite, silicon-dioxide to the modification of ABS resin, yet it has defect in various degree on to the improvement of the enhancing of ABS resin, toughness reinforcing and over-all properties.
Graphene be current known rigidity maximum one of inorganic nano material, its Young's modulus 1TPa, becomes the ideal material of high performance composite reinforce.Studies have shown that, Graphene and functionalization graphene thereof can be given traditional new performance of common material, such as the good performance such as electricity, mechanics, optics, calorifics and high stability thereof.Therefore Graphene is the desirable nano-composite material of ABS resin.
The preparation method of matrix material mainly contains solution mixing, melting mixing, in-situ polymerization at present.Adopt solution blended process not only in technological process, to need a large amount of solvents, not environmental protection, and also process energy consumption is high, and process is long, and yield is low, almost cannot industrialization.And employing scorification, Graphene is difficult to reach the dispersion of nanoscale.Situ aggregation method is when existing, to add nanometer inorganic filler at polymerization monomer in early stage, now monomer viscosity is mixed with abundant and nanometer inorganic filler compared with I, during handling the dispersiveness of nano material well, with the compatibility problem of base material, nanoparticulate dispersed can not only be realized even, can keep the characteristic of nanoparticle again, and can on original polymerization reaction kettle, carry out, possess industrialization possibility.
At present, adopt graphene in-situ modified to prepare the existing relevant report of graphene composite material.Chinese patent application notification number CN102827315A discloses " a kind of graphene oxide/polystyrene nano composite material and preparation method thereof ", this method be take water as dispersion medium, take stannic oxide/graphene nano sheet as solid surfactant, under the collaborative stabilization of salt, simply, effectively prepared stable Pickering emulsion, after in-situ emulsion polymerization, obtain graphene oxide/polystyrene nano composite material.Chinese patent application notification number CN103254400A discloses " a kind of preparation method of graphene oxide/aqueous polyurethane nano matrix material ", this method is refered in particular to and is first utilized γ-aminopropyl triethoxysilane to carry out finishing to graphene oxide, reduce the wetting ability of graphene oxide lamella, improve its dispersed in organic solvent and and polymkeric substance between consistency, recycling situ aggregation method is prepared graphene oxide/aqueous polyurethane nano matrix material.Chinese patent application publication No. CN103805046A discloses " in-situ method is prepared aqueous polyurethane composite electrically-conducting paint and the method thereof of graphene-containing ", this method is carried out amination modified with diamine to graphene oxide, with chemical method reduction, recover again the conjugation conduction system of Graphene, utilize Graphene surface-NH
2with the aqueous polyurethane in-situ polymerization of-NCO end-blocking, make the water polyurethane electric conduction paint of graphene-containing.China Patent No. ZL201110242497.4 discloses " preparation method of polyamide-amine in-situ intercalation graphene composite material ", and this method adopts situ aggregation method polymerization between multi-layer graphene to generate daiamid, obtains daiamid intercalated graphite alkene matrix material.China Patent No. ZL201210319394.8 disclose " method of Graphene-the development of PVC nanocomposites is prepared in emulsion by in-situ polymerization; first this method prepares graphene oxide dispersion liquid; secondly by graphene oxide and vinylchlorid or with the in-situ emulsion polymerization of vinylchlorid and function monomer mixture, finally carry out the aftertreatment of composite emulsions.
At present, utilize the in-situ modified ABS resin of Graphene to there is not yet report.As fully visible, utilize graphene in-situ modified ABS resin to can be Graphene/ABS matrix material and open up a new route.
Summary of the invention
The object of the present invention is to provide a kind of method of in-situ modified ABS resin.The method has been introduced Graphene in the process of emulsion graft polymerization SAN blending method, by changing addition and the addition manner of Graphene, thereby can in a big way, regulate heat conduction, conduction and the mechanical property of matrix material to obtain the matrix material of excellent performance.
For achieving the above object, solution of the present invention is:
A method for graphene in-situ modified ABS resin, comprises the following steps:
(1) emulsifying agent, divinyl, initiator, other auxiliary agents are added in polymeric kettle, at 50-70 ℃, by letex polymerization, prepare PB latex;
(2), at 30-90 ℃, emulsifying agent, initiator and PB latex, vinylbenzene, acrylonitrile monemer are added reactor to pass through emulsion grafting polymerization, cohesion, are dried to obtain ABS pellet;
(3) adopt mass polymerization or suspension polymerization to prepare SAN(styrene-acrylonitrile) particle;
(4) ABS pellet and SAN particle are obtained to Graphene/ABS matrix material by continuous mixing, extruding pelletization under the condition of 200-250 ℃;
Described Graphene can optionally add in above-mentioned steps (1), (2), (3), adopts mechanical dispersion method that it is fully mixed, and obtains the matrix material of Graphene modified ABS resin by in-situ polymerization.
Described Graphene is graphene powder or graphene dispersing solution.Further, add the preferred graphene dispersing solution form of Graphene in step (1) or (2), this Graphene is wetting ability more preferably; In step (3), add the preferred graphene powder form of Graphene, this Graphene is lipophilicity more preferably; Described Graphene is the Graphene with or without polar group, and described polar group is hydroxyl, amino, carboxyl, sulfonic group, cl radical, fluorin radical or sulfydryl.
Described initiator is that one or both of Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, diisobutyryl peroxide, sodium bisulfite, Sulfothiorine are composite.
Described emulsifying agent is one or both of potassium stearate, potassium oleate, potassium rosinate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Preferred potassium oleate further.
Described dispersion agent is a kind of of active calcium phosphate, polyvinyl alcohol, methylene dinaphthalene sodium disulfonate or two kinds; Be preferably further polyvinyl alcohol.
Described other auxiliary agents are terminator, molecular weight regulator, oxidation inhibitor; Wherein terminator is Sodium dimethyldithiocarbamate 40min; Molecular weight regulator is mercaptan; Oxidation inhibitor is 2,2 ,-methylene-bis (4-methyl-6 tert.-butyl phenol), the positive octadecanol ester of β (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, phosphorous acid esters a kind of or two kinds.
The method of described mechanical dispersion comprises mechanical stirring; Vibrator vibration; Ultra-sonic oscillation; Planetary type ball-milling; Basket ball milling; Stirring-type ball milling; Horizontal ball milling; Sand mill grinds; One or more during triple-roller mill grinding, colloidal mill grind.
In described Graphene/ABS matrix material, polybutadiene rubber content is 5-35%, and acrylonitrile content is 5-35%, and styrene content is 35-75%, and Graphene content is 0.1-10%.
The present invention compared with prior art has following characteristics and beneficial effect:
(1) the present invention adopts emulsion graft polymerization SAN blending method to come in-situ polymerization Graphene/ABS matrix material to have the advantages such as less investment, production cost be low, and advantages of simple technological process, is easy to scale operation; (2) in ABS polymerization process, add Graphene and can utilize the feature that monomer viscosity is less, fully strongthener is mixed with out the matrix material of performance homogeneous, and polymerization is owing to being polymerization in the situation that Graphene participates in position, matrix can form good interface with Graphene, increase the switching performance at both interfaces, and then improve the overall performance of matrix material, can access the matrix material of excellent performance; (3) the method can regulate heat conduction, conduction and the mechanical property of matrix material in a big way, is a kind of upgrade method of new generation that adopts nanotechnology transformation ABS.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
Embodiment 1
Step 1: the PB latex of preparing graphene-containing
According to following composition of raw materials, carry out emulsion polymerizing preparation butadiene latex, described umber is all parts by weight: 100 parts of divinyl, 0.5 part of Potassium Persulphate, 5 parts, mercaptan, 1 part of oleic acid potash soap, 70 parts of deionized waters, 5 parts of Graphenes.
Divinyl, oleic acid potash soap, mercaptan, Potassium Persulphate, Graphene, deionized water and stirring are evenly formed to solution, add together in polymeric kettle, carry out letex polymerization at 55 ℃, when transformation efficiency reaches 80%, material continues approximately 16 hours residence time in still.After reaction, latex enters degassing vessel decompression devolatilisation.Latex after degassed after 4 days, is sent into storage tank for next step raw material as grafting through ageing.
Step 2: the ABS pellet of preparing graphene-containing
According to following composition of raw materials, carry out emulsion graft polymerization and prepare ABS pellet, described umber is all parts by weight: 60 parts of polybutadiene latexs, 30 parts of vinylbenzene, 15 parts of vinyl cyanide, 100 parts of deionized waters, 0.3 part of hydrogen phosphide cumene, 2.0 parts, 0.01 part, ferrous sulfate, rosin potash soap, fatty acid potassium soap compound emulsifying agent.
Rosin potash soap, fatty acid potassium soap compound emulsifying agent, ferrous sulfate, polybutadiene latex, vinylbenzene, acrylonitrile monemer, deionized water are added and mixed, be warming up to 90 ℃, add hydrogen phosphide cumene initiated polymerization.ABS emulsion after polymerization enters steel basin, adds dilute sulphuric acid simultaneously, cohesion at 90 ℃, and the ABS fine particle in mother liquor that is suspended in obtaining after cohesion is sent to dry after belt filter wash.Dried ABS pellet is for next step blending.
Step 3: adopt mass polymerization to prepare SAN(styrene-acrylonitrile) particle
According to following formula, carry out mass polymerization and prepare SAN(styrene-acrylonitrile) particle: 70 parts of vinylbenzene, vinyl cyanide is 30 parts, and benzoyl peroxide is 0.1 part, and ethylbenzene is 10 parts, and described umber is that parts by weight take.
Styrene monomer, vinyl cyanide and solvent ethylbenzene are entered to polymeric kettle after mixing, be slowly warming up to 130 ℃, after reaction, from polymeric kettle material flash distillation out, remove the volatiless such as vinyl cyanide and styrene monomer, ethylbenzene.The SAN of melting sends to extrusion pelletizing, then retains with ABS granular mixing and uses.
Step 4: blending and granulation
ABS pellet, auxiliary agent mix in mixing tank with SAN pellet, adopt the blending of mechanical stirring wet method.Then enter extruding pelletization in twin screw extruder.Finally deliver to finished product ABS feed bin packing and get final product to obtain Graphene/ABS matrix material.
Embodiment 2
Step 1: preparation PB latex
According to following composition of raw materials, carry out emulsion polymerizing preparation butadiene latex, described umber is all parts by weight: 100 parts of divinyl, 0.5 part of Potassium Persulphate, 5 parts, mercaptan, 1 part of oleic acid potash soap, 70 parts of deionized waters.
Divinyl, oleic acid potash soap, mercaptan, Potassium Persulphate, deionized water and stirring are evenly formed to solution, add together in polymeric kettle, carry out letex polymerization at 55 ℃, when transformation efficiency reaches 80%, material continues approximately 16 hours residence time in still.After reaction, latex enters degassing vessel decompression devolatilisation.Latex after degassed after 4 days, is sent into storage tank for next step raw material as grafting through ageing.
Step 2: the ABS pellet of preparing graphene-containing
According to following composition of raw materials, carry out emulsion graft polymerization and prepare ABS pellet, described umber is all parts by weight: 60 parts of polybutadiene latexs, 30 parts of vinylbenzene, 15 parts of vinyl cyanide, 100 parts of deionized waters, 0.3 part of hydrogen phosphide cumene, 0.01 part, ferrous sulfate, rosin potash soap, 2.0 parts of fatty acid potassium soap compound emulsifying agents, 5 parts of Graphenes.
Rosin potash soap, fatty acid potassium soap compound emulsifying agent, ferrous sulfate, polybutadiene latex, vinylbenzene, acrylonitrile monemer, Graphene, deionized water are added and mixed, be slowly warming up to 90 ℃, add hydrogen phosphide cumene initiated polymerization.ABS emulsion after polymerization enters steel basin, adds dilute sulphuric acid simultaneously, cohesion at 90 ℃, and the ABS fine particle in mother liquor that is suspended in obtaining after cohesion is sent to dry after belt filter wash.Dried ABS pellet is for next step blending.
Step 3: adopt mass polymerization to prepare SAN(styrene-acrylonitrile) particle
According to following formula, carry out mass polymerization and prepare SAN(styrene-acrylonitrile) particle: 70 parts of vinylbenzene, vinyl cyanide is 30 parts, and benzoyl peroxide is 0.1 part, and ethylbenzene is 10 parts, and described umber is that parts by weight take.
Styrene monomer, vinyl cyanide and solvent ethylbenzene are entered to polymeric kettle after mixing, be slowly warming up to 130 ℃, after reaction, from polymeric kettle material flash distillation out, remove the volatiless such as vinyl cyanide and styrene monomer, ethylbenzene.The SAN of melting sends to extrusion pelletizing, then retains with ABS granular mixing and uses.
Step 4: blending and granulation
ABS pellet, auxiliary agent mix in mixing tank with SAN pellet, adopt the blending of mechanical stirring wet method.Then enter extruding pelletization in twin screw extruder.Finally deliver to finished product ABS feed bin packing and get final product to obtain Graphene/ABS matrix material.
Embodiment 3
Step 1: preparation PB latex
According to following composition of raw materials, carry out emulsion polymerizing preparation butadiene latex, described umber is all parts by weight: 100 parts of divinyl, 0.5 part of Potassium Persulphate, 5 parts, mercaptan, 1 part of oleic acid potash soap, 70 parts of deionized waters.
Divinyl, oleic acid potash soap, mercaptan, Potassium Persulphate, deionized water and stirring are evenly formed to solution, add together in polymeric kettle, carry out letex polymerization at 55 ℃, when transformation efficiency reaches 80%, material continues approximately 16 hours residence time in still.After reaction, latex enters degassing vessel decompression devolatilisation.Latex after degassed after 4 days, is sent into storage tank for next step raw material as grafting through ageing.
Step 2: preparation ABS pellet
According to following composition of raw materials, carry out emulsion graft polymerization and prepare ABS pellet, described umber is all parts by weight: 60 parts of polybutadiene latexs, 30 parts of vinylbenzene, 15 parts of vinyl cyanide, 100 parts of deionized waters, 0.3 part of hydrogen phosphide cumene, 2.0 parts, 0.01 part, ferrous sulfate, rosin potash soap, fatty acid potassium soap compound emulsifying agent.
Rosin potash soap, fatty acid potassium soap compound emulsifying agent, ferrous sulfate, polybutadiene latex, vinylbenzene, acrylonitrile monemer, deionized water are added and mixed, be slowly warming up to 90 ℃, add hydrogen phosphide cumene initiated polymerization.ABS emulsion after polymerization enters steel basin, adds dilute sulphuric acid simultaneously, cohesion at 90 ℃, and the ABS fine particle in mother liquor that is suspended in obtaining after cohesion is sent to dry after belt filter wash.Dried ABS pellet is for next step blending.
Step 3: adopt mass polymerization to prepare the SAN(styrene-acrylonitrile of graphene-containing) particle
According to following formula, carry out mass polymerization and prepare SAN(styrene-acrylonitrile) particle: 70 parts of vinylbenzene, vinyl cyanide is 30 parts, benzoyl peroxide is 0.1 part, 5 parts of Graphenes, ethylbenzene is 10 parts, described umber is that parts by weight take.
Styrene monomer, vinyl cyanide, Graphene and solvent ethylbenzene are entered to polymeric kettle after mixing, be slowly warming up to 130 ℃, after reaction, from polymeric kettle material flash distillation out, remove the volatiless such as vinyl cyanide and styrene monomer, ethylbenzene.The SAN of melting sends to extrusion pelletizing, then retains with ABS granular mixing and uses.
Step 4: blending and granulation
ABS pellet, auxiliary agent mix in mixing tank with SAN pellet, adopt the blending of mechanical stirring wet method.Then enter extruding pelletization in twin screw extruder.Finally deliver to finished product ABS feed bin packing and get final product to obtain Graphene/ABS matrix material.
Embodiment 4
Step 1: the PB latex of preparing graphene-containing
According to following composition of raw materials, carry out emulsion polymerizing preparation butadiene latex, described umber is all parts by weight: 100 parts of divinyl, 0.5 part of Potassium Persulphate, 5 parts, mercaptan, 1 part of oleic acid potash soap, 70 parts, 10 parts Graphene emulsions of deionized water (Graphene content 10%).
Divinyl, oleic acid potash soap, mercaptan, Potassium Persulphate, Graphene emulsion, deionized water and stirring are evenly formed to solution, add together in polymeric kettle, carry out letex polymerization at 55 ℃, when transformation efficiency reaches 80%, material continues approximately 16 hours residence time in still.After reaction, latex enters degassing vessel decompression devolatilisation.Latex after degassed after 4 days, is sent into storage tank for next step raw material as grafting through ageing.
Step 2: the ABS pellet of preparing graphene-containing
According to following composition of raw materials, carry out emulsion graft polymerization and prepare ABS pellet, described umber is all parts by weight: 60 parts of polybutadiene latexs, 30 parts of vinylbenzene, 15 parts of vinyl cyanide, 100 parts of deionized waters, 0.3 part of hydrogen phosphide cumene, 2.0 parts, 0.01 part, ferrous sulfate, rosin potash soap, fatty acid potassium soap compound emulsifying agent.
Rosin potash soap, fatty acid potassium soap compound emulsifying agent, ferrous sulfate, polybutadiene latex, vinylbenzene, acrylonitrile monemer, deionized water are added and mixed, be warming up to 90 ℃, add hydrogen phosphide cumene initiated polymerization.ABS emulsion after polymerization enters steel basin, adds dilute sulphuric acid simultaneously, cohesion at 90 ℃, and the ABS fine particle in mother liquor that is suspended in obtaining after cohesion is sent to dry after belt filter wash.Dried ABS pellet is for next step blending.
Step 3: adopt mass polymerization to prepare SAN(styrene-acrylonitrile) particle
According to following formula, carry out mass polymerization and prepare SAN(styrene-acrylonitrile) particle: 70 parts of vinylbenzene, vinyl cyanide is 30 parts, and benzoyl peroxide is 0.1 part, and ethylbenzene is 10 parts, and described umber is that parts by weight take.
Styrene monomer, vinyl cyanide and solvent ethylbenzene are entered to polymeric kettle after mixing, be slowly warming up to 130 ℃, after reaction, from polymeric kettle material flash distillation out, remove the volatiless such as vinyl cyanide and styrene monomer, ethylbenzene.The SAN of melting sends to extrusion pelletizing, then retains with ABS granular mixing and uses.
Step 4: blending and granulation
ABS pellet, auxiliary agent mix in mixing tank with SAN pellet, adopt the blending of mechanical stirring wet method.Then enter extruding pelletization in twin screw extruder.Finally deliver to finished product ABS feed bin packing and get final product to obtain Graphene/ABS matrix material.
Embodiment 5
Step 1: preparation is containing the PB latex of graphene oxide
According to following composition of raw materials, carry out emulsion polymerizing preparation butadiene latex, described umber is all parts by weight: 100 parts of divinyl, 0.5 part of Potassium Persulphate, 5 parts, mercaptan, 1 part of oleic acid potash soap, 70 parts, 5 parts graphene oxides of deionized water.
Divinyl, oleic acid potash soap, mercaptan, Potassium Persulphate, graphene oxide, deionized water and stirring are evenly formed to solution, add together in polymeric kettle, carry out letex polymerization at 55 ℃, when transformation efficiency reaches 80%, material continues approximately 16 hours residence time in still.After reaction, latex enters degassing vessel decompression devolatilisation.Latex after degassed after 4 days, is sent into storage tank for next step raw material as grafting through ageing.
Step 2: preparation is containing the ABS pellet of graphene oxide
According to following composition of raw materials, carry out emulsion graft polymerization and prepare ABS pellet, described umber is all parts by weight: 60 parts of polybutadiene latexs, 30 parts of vinylbenzene, 15 parts of vinyl cyanide, 100 parts of deionized waters, 0.3 part of hydrogen phosphide cumene, 2.0 parts, 0.01 part, ferrous sulfate, rosin potash soap, fatty acid potassium soap compound emulsifying agent.
Rosin potash soap, fatty acid potassium soap compound emulsifying agent, ferrous sulfate, polybutadiene latex, vinylbenzene, acrylonitrile monemer, deionized water are added and mixed, be warming up to 90 ℃, add hydrogen phosphide cumene initiated polymerization.ABS emulsion after polymerization enters steel basin, adds dilute sulphuric acid simultaneously, cohesion at 90 ℃, and the ABS fine particle in mother liquor that is suspended in obtaining after cohesion is sent to dry after belt filter wash.Dried ABS pellet is for next step blending.
Step 3: adopt mass polymerization to prepare SAN(styrene-acrylonitrile) particle
According to following formula, carry out mass polymerization and prepare SAN(styrene-acrylonitrile) particle: 70 parts of vinylbenzene, vinyl cyanide is 30 parts, and benzoyl peroxide is 0.1 part, and ethylbenzene is 10 parts, and described umber is that parts by weight take.
Styrene monomer, vinyl cyanide and solvent ethylbenzene are entered to polymeric kettle after mixing, be slowly warming up to 130 ℃, after reaction, from polymeric kettle material flash distillation out, remove the volatiless such as vinyl cyanide and styrene monomer, ethylbenzene.The SAN of melting sends to extrusion pelletizing, then retains with ABS granular mixing and uses.
Step 4: blending and granulation
ABS pellet, auxiliary agent mix in mixing tank with SAN pellet, adopt the blending of mechanical stirring wet method.Then enter extruding pelletization in twin screw extruder.Finally deliver to finished product ABS feed bin packing and get final product to obtain graphene oxide/ABS matrix material.
Claims (5)
1. a method for graphene in-situ modified ABS resin, comprises the following steps:
(1) emulsifying agent, divinyl, initiator, other auxiliary agents are added in polymeric kettle, at 50-70 ℃, by letex polymerization, prepare PB latex;
(2), at 30-90 ℃, emulsifying agent, initiator and PB latex, vinylbenzene, acrylonitrile monemer are added reactor to pass through emulsion grafting polymerization, cohesion, are dried to obtain ABS pellet;
(3) adopt mass polymerization or suspension polymerization to prepare SAN(styrene-acrylonitrile) particle;
(4) ABS pellet and SAN particle are obtained to Graphene/ABS matrix material by continuous mixing, extruding pelletization under the condition of 200-250 ℃;
Described Graphene can optionally add in above-mentioned steps (1), (2), (3), adopts mechanical dispersion method that it is fully mixed, and obtains the matrix material of Graphene modified ABS resin by in-situ polymerization.
2. the method for a kind of graphene in-situ modified ABS resin as claimed in claim 1, is characterized in that described Graphene is graphene powder or graphene dispersing solution.
3. the method for a kind of graphene in-situ modified ABS resin as claimed in claim 1, it is characterized in that described Graphene is for the Graphene with or without polar group, described polar group is hydroxyl, amino, carboxyl, sulfonic group, cl radical, fluorin radical or sulfydryl.
4. the method for a kind of graphene in-situ modified ABS resin as claimed in claim 1, the method that it is characterized in that described mechanical dispersion comprises that mechanical stirring, vibrator vibration, ultra-sonic oscillation, planetary type ball-milling, basket ball milling, stirring-type ball milling, horizontal ball milling, sand mill grind, triple-roller mill grinds, one or more in grinding of colloidal mill.
5. the method for a kind of graphene in-situ modified ABS resin as claimed in claim 1, it is characterized in that in described Graphene/ABS matrix material, polybutadiene rubber content is 5-35%, acrylonitrile content is 5-35%, and styrene content is 35-75%, and Graphene content is 0.1-10%.
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| ES2570391A1 (en) * | 2016-01-18 | 2016-05-18 | Univ Cartagena Politecnica | Abs doped with graphene (Machine-translation by Google Translate, not legally binding) |
| CN106957469A (en) * | 2015-04-03 | 2017-07-18 | 3M创新有限公司 | Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof |
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| CN107141698A (en) * | 2017-05-15 | 2017-09-08 | 南通强生光电科技有限公司 | A kind of graphene is combined multi-functional resins of ABS and preparation method thereof |
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| CN106957469A (en) * | 2015-04-03 | 2017-07-18 | 3M创新有限公司 | Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof |
| CN106957469B (en) * | 2015-04-03 | 2018-11-23 | 3M创新有限公司 | Limit element, check valve, composition, elastomeric material, grafting graphite and preparation method thereof |
| ES2570391A1 (en) * | 2016-01-18 | 2016-05-18 | Univ Cartagena Politecnica | Abs doped with graphene (Machine-translation by Google Translate, not legally binding) |
| CN106987109A (en) * | 2017-04-13 | 2017-07-28 | 郭峰 | The method that a kind of nanometer of dawsonite/stannic acid lanthanum/graphene oxide composite flame-proof is modified PC/ABS alloys |
| CN107286559A (en) * | 2017-04-24 | 2017-10-24 | 劳富文 | The graphene color masterbatch preparation method of ABS material |
| CN107141698A (en) * | 2017-05-15 | 2017-09-08 | 南通强生光电科技有限公司 | A kind of graphene is combined multi-functional resins of ABS and preparation method thereof |
| CN107141698B (en) * | 2017-05-15 | 2020-06-26 | 南通强生光电科技有限公司 | Graphene composite ABS multifunctional resin and preparation method thereof |
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| CN107501845B (en) * | 2017-08-25 | 2020-01-31 | 天津大学 | Preparation of graphene/ABS nano composite material by master batch-ball milling-hot pressing method |
| CN113136007A (en) * | 2021-03-26 | 2021-07-20 | 林轩 | Preparation method of porous ABS graft polymer particles easy to dry |
| CN113943470A (en) * | 2021-08-19 | 2022-01-18 | 创合新材料科技江苏有限公司 | High-temperature-resistant and non-deformable plastic ABS and preparation method thereof |
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