CN103642198A - Graphene/carbon black thermoplastic resin master batch with high dispersibility and preparation method thereof - Google Patents
Graphene/carbon black thermoplastic resin master batch with high dispersibility and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene/carbon black thermoplastic resin master batch with high dispersibility and a preparation method thereof. The graphene/carbon black compound in the master batch is formed in an electrostatic self-assembly manner, and comprises 10-50% of graphene, 5-20% of carbon black, 0.5-10% of surfactant, 10-65% of carrier resin and 2-10% of assistant. The preparation method comprises the following steps: (1) compounding and dispersing graphene by adopting the surfactant to control the positive electricity of the graphene surface; (2) forming a stable graphene/carbon black compound from the modified graphene and carbon black with positive electricity through electrostatic incorporation in a self-assembly manner; (3) preparing the graphene/carbon black thermoplastic resin master batch with high dispersibility by matching with a solution blended process, a melt-blending method and an in-situ polymerization method; (4) adding the assistant to extrude and pelletize, so as to prepare the graphene/carbon black/thermoplastic resin master batch particles after processing the master batch. By adopting the obtained master batch, the problems of difficult charging of graphene powder, uneven dispersion, dust pollution, unstable product performance and the like are solved.
Description
Technical field
The present invention relates to a kind of Graphene masterbatch and technology of preparing thereof being applied in thermoplastic material processing, be specially Graphene/carbon black thermoplastic resin masterbatch of a kind of polymolecularity and preparation method thereof.
Background technology
Since 2004, the An Deliehaimu of Britain graceful Chester university and the Constantine Nuo Woxiaoluofu method that first passage micromechanics is peeled off in test have successfully obtained after Graphene, Graphene just becomes Materials science, information science, new forms of energy, one of the study hotspot in the subject crossing fields such as chemistry.Graphene intensity is the highest in test material, reach 130Gpa, more than 100 times of (Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene of steel, Science, 2008,321:385-388), and there are very high specific conductivity and thermal conductivity, reach respectively 6000S/cm (Approaching ballistic transport in suspended graphene, Nature Nanotechnology, 2008,3:491-495) and 5300Wm
-1k
-1(Superior thermal conductivity of single-layer grapheme, Nano Letters, 2008; 8:902 – 7), therefore aspect the enhancing as polymeric matrix, conduction and heat conductive filler, be considered to have prospects for commercial application widely.
In the preparation process of Graphene/polymer composites, the dispersion of Graphene in polymeric matrix is a very crucial problem.This is because Graphene has very large specific surface area, and active high easily reunion, causes original excellent properties to be lost.In order to address this problem, current more investigator adopts graphene oxide that surface contains a large amount of functional groups as filler, thereby be beneficial to, Graphene is carried out modification and reaches the object being scattered in resin.Summer and raw etc. is dispersed in polymer latex Ruzhong graphene oxide, and in latex, introduce reductive agent and carry out in-situ reducing graphene oxide, through breakdown of emulsion, cohesion, dry, obtain graphene/polymer nano composite material (seeing that bulletin is for the Chinese invention patent of CN 101864098) again.Zheng Weitao etc. are placed in the ultrasonic dispersion of solvent by graphene oxide, add polyethylene powders mechanical stirring, after being dried, composite particles are added heat reduction in hydrazine hydrate to become graphene composite particle (seeing that bulletin is the Chinese invention patent of CN 102585335).But due to graphene oxide in oxidising process by the oxygenant that is used havoc graphene film protocrystal structure and seriously reduced the performances such as its conduction, heat conduction.
At present, in order to enhance productivity, the production of most polymer based composites all adopts masterbatch completion method.Thermoplastic resin material has workability as masterbatch carrier, suppresses filler oxidation and reunites, and keeping can making again system have higher long-acting stability on the functional basis of mineral filler, has therefore been subject to paying attention to and application widely.
To sum up, in the present invention, the carbon black adding by electrostatic self-assembled mode in Graphene not only can improve the performance of matrix material by synergy, and the carbon black pellet adding is evenly dispersed in Graphene surface, effectively reduces the reunion degree of Graphene.The composite granule obtaining is prepared into masterbatch with resin-bonded again, can solves again graphene powder and in the practical application of modified plastic rubber, bring problems: graphene powder is fluffy, directly extrude and process difficulty, power consumption is large; The reinforced difficulty of powder, powder disperse in plastic cement that inequality, product properties are unstable, dust pollution.Therefore, prepare Graphene masterbatch and have industrial application meaning.
Summary of the invention
The object of the present invention is to provide a kind of Graphene/carbon black thermoplastic resin masterbatch with polymolecularity and preparation method thereof, it is simple that the method has technical process, and production cost is low, the finely dispersed advantage of Graphene in masterbatch.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Graphene/carbon black thermoplastic resin masterbatch with polymolecularity, it is characterized in that: in described masterbatch, Graphene/carbon black mixture adopts electrostatic self-assembled to form, according to weight percent, comprise: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Adopt solution blended process
1. configure polymer mixing solutions: control the ratio of solvent, masterbatch carrier is dissolved in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: Graphene/carbon black mixture is joined in above-mentioned mixed solution, utilize dispersing apparatus, prepare the Graphene/carbon black/macromolecular solution of high dispersed degree;
In described step 2, in solution blended process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
In described step 2, in solution blended process, solvent is one or more the mixture in the corresponding thermal plastic high polymer solvent of water, ethanol, acetone, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride solubilized.
In described step 2, precipitation agent is that water, ethanol, propyl alcohol, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride and macromolecule solvent dissolve each other in insoluble high molecular solvent one or more.
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Melt-blending process
1. prepare Graphene/carbon black/macromolecule mixture: thermoplasticity masterbatch carrier is added to high-speed mixer with together with Graphene/carbon black electrostatic self-assembled mixture in step 1, under the condition of rotating speed 500-2500r/min, mix 3-15 minute;
2. masterbatch aftertreatment: by the material mixing of above-mentioned acquisition, add auxiliary agent and adopt the conventional processing units of thermoplastic material to carry out extruding pelletization, obtain the masterbatch pellet that can dilute application.
In described step 2, in melt-blending process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Situ aggregation method
1. prepare Graphene/carbon black/macromolecule mixture: after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator are mixed, stir, Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, processes and obtains masterbatch after completion of the reaction according to differential responses.
2. masterbatch aftertreatment: masterbatch is carried out to press filtration and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopt the conventional processing units of thermoplastic material to carry out extruding pelletization, can dilute the masterbatch pellet of application.
In described step 2 situ polymerization, monomer used is acrylic acid or the like, alkene class, maleic anhydride; Described initiator is azo-initiator, peroxide initiator, metal species initiator, methylaluminoxane.
Described acrylic monomer is vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methyl methacrylate; Vinyl monomer is ethene, vinylbenzene, vinylchlorid, divinyl; Described azo-initiator is azo-bis-isobutyl cyanide, azo two cyanogen in different heptan; Peroxide initiator is benzoyl peroxide, tertbutyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide; Metal species initiator is metallocene initiator.
Feature of the present invention and beneficial effect:
1, the present invention adopts surface-modifying agent to regulate the charging property of Graphene and by electrostatic self-assembled technology, prepares Graphene/carbon black hybrid material, has effectively avoided the reunion of Graphene in last handling process, and then has been conducive to obtain the Graphene masterbatch of good dispersity.
2, the present invention adopts three kinds of methods to prepare the Graphene/carbon black/resin concentrates of polymolecularity, realized dispersed in masterbatch carrier of Graphene/carbon black hybrid material, solved the reinforced difficulty of graphene with high specific surface, in plastic cement, disperseed the problems such as uneven, product properties is unstable, Graphene dust pollution.
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.The present invention has disclosed a kind of Graphene/carbon black thermoplastic resin masterbatch with polymolecularity, wherein Graphene/carbon black mixture adopts electrostatic self-assembled to form, according to weight percent, comprise: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.
Described tensio-active agent is one or both compounds of nonionogenic tenside, cats product.
Described nonionogenic tenside is fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, polyoxyethylene alkyl amine, polyxyethylated alcohol amide glyceryl ester; Described cats product is oxide compound, the quaternary ammonium salt of amine salt, amine.
Described auxiliary agent is one or more in polyethylene wax, phthalate, epoxy ester series, aliphatic dibasic acid ester, phosphoric acid ester, polyester, citrate plasticizer.
A kind of preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Adopt solution blended process
1. configure polymer mixing solutions: control the ratio of solvent, masterbatch carrier is dissolved in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: Graphene/carbon black mixture is joined in mixed solution, select suitable dispersing apparatus, prepare the Graphene/carbon black/macromolecular solution of high dispersed degree;
In described step 1, surface modifying method comprises dry method modification, one or more in wet-process modified.
Dispersing apparatus in described step 1 is one or more in conventional stirrer, homogenizer, ball mill, sand mill.
In described step 2, in solution blended process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
In described step 2, in solution blended process, solvent is one or more the mixture in the corresponding thermal plastic high polymer solvent of water, ethanol, acetone, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride solubilized.
In described step 2, precipitation agent is that water, ethanol, propyl alcohol, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride and macromolecule solvent dissolve each other in insoluble high molecular solvent one or more.
In described step 2, thermoplastic material common equipment is one or more in single screw extrusion machine, twin screw extruder, three-screw extruder, Banbury mixer, mill, rolling press, plastic breaker.
A kind of preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Melt-blending process
1. prepare Graphene/carbon black/macromolecule mixture: thermoplasticity masterbatch carrier is added to high-speed mixer with together with Graphene/carbon black electrostatic self-assembled mixture in step 1, under the condition of rotating speed 500-2500r/min, mix 3-15 minute;
2. masterbatch aftertreatment: by the material mixing of above-mentioned acquisition, add auxiliary agent and adopt the conventional processing units of thermoplastic material to carry out extruding pelletization, obtain the masterbatch pellet that can dilute application.
In described step 1, surface modifying method comprises dry method modification, one or more in wet-process modified.
Dispersing apparatus in described step 1 is one or more in conventional stirrer, homogenizer, ball mill, sand mill.
In described step 2, in melt-blending process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
The preferred single screw extrusion machine of fusion apparatus in described step 2, auxiliary agent is one or more in polyethylene wax, phthalic ester, epoxy plasticizer, glutarate, adipic acid ester, phosphoric acid ester, polyester plasticizer.
In described step 2, thermoplastic material common equipment is one or more in single screw extrusion machine, twin screw extruder, three-screw extruder, Banbury mixer, mill, rolling press, plastic breaker.
A kind of preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: Graphene is carried out to surface modification treatment with tensio-active agent, regulate the charging property on Graphene surface, obtaining the electropositive Graphene of surface band disperses, jitter time is 0.5-20 hour, by this graphene dispersing solution press filtration, dry, break up the Graphene that obtains clad surface promoting agent; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, Graphene/carbon black electrostatic self-assembled mixture is dried to obtain in press filtration, and jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Situ aggregation method
1. prepare Graphene/carbon black/macromolecule mixture: after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator are mixed, stir, Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, processes and obtains masterbatch after completion of the reaction according to differential responses.
2. masterbatch aftertreatment: masterbatch is carried out to press filtration and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopt thermoplastic material common equipment to carry out aftertreatment, can dilute the masterbatch pellet of application.
In described step 1, surface modifying method comprises dry method modification, one or more in wet-process modified.
Dispersing apparatus in described step 1 is one or more in conventional stirrer, homogenizer, ball mill, sand mill.
In described step 2 situ polymerization, solvent used is one or more the mixture in the corresponding monomer of solubilized, initiator, the polymer solvents such as dimixo-octyl phthalate, water, ethanol, acetone, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF), methylene dichloride.
In described step 2 situ polymerization, monomer used is acrylic acid or the like, alkene class, maleic anhydride; Described initiator is azo-initiator, peroxide initiator, metal species initiator, methylaluminoxane.
Described acrylic monomer is vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methyl methacrylate; Vinyl monomer is ethene, vinylbenzene, vinylchlorid, divinyl; Described azo-initiator is azo-bis-isobutyl cyanide, azo two cyanogen in different heptan; Peroxide initiator is benzoyl peroxide, tertbutyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide; Metal species initiator is metallocene initiator.
In described step 2, thermoplastic material common equipment is one or more in single screw extrusion machine, twin screw extruder, three-screw extruder, Banbury mixer, mill, rolling press, plastic breaker.
Embodiment 1
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts solution blended process, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in sand mill, add 10g cetyl trimethylammonium bromide, 5kg water and 200g Graphene, sand milling, after 3 hours, filters and obtains surperficial electropositive graphene uniform dispersion.By the press filtration of Graphene aqueous dispersions, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 125g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 2 hours, press filtration, dries, breaks up and to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, be equipped with thermoplastic polyurethane/DMF solution: by 450g thermoplastic polyurethane, be dissolved in 2000mlDMF, be made into mixing solutions.
Step 4, prepare Graphene/carbon black/TPU/DMF mixing solutions: the above-mentioned Graphene/carbon black mixture making is joined in TPU/DMF solution, and sand milling, after 2 hours, makes Graphene/carbon black/TPU/DMF solution of high dispersed degree.
Step 5, be settled out Graphene/carbon black/TPU masterbatch: 1500ml water is joined in finely dispersed Graphene/carbon black/TPU/DMF solution, Graphene/carbon black/TPU is precipitated out from DMF solvent;
Step 6, masterbatch aftertreatment: the Graphene/carbon black being settled out/TPU mixture is carried out press filtration, oven dry, pulverizes to obtain dry state masterbatch, add 50g DISPERBYK-170 as dispersion agent, adopt single screw extrusion machine to carry out extruding pelletization to masterbatch and obtain Graphene/carbon black/TPU masterbatch.
Embodiment 2
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts situ aggregation method, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in sand mill, add 16g Cetyltrimethylammonium bromide, 5kg water and 200g Graphene, sand milling, after 4 hours, filters and obtains surperficial electropositive graphene uniform dispersion.By the press filtration of Graphene aqueous dispersions, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 50g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 5 hours, and press filtration is dried and broken up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, outfit acrylonitrile-butadiene-styrene (ABS)/DMF solution: 500gABS resin dissolves, in 2000mlDMF solvent, is made into mixing solutions;
Step 4, prepare Graphene/carbon black/ABS/DMF mixing solutions: by the compound ABS/DMF of the joining solution of the above-mentioned Graphene/carbon black making, sand milling, after 5 hours, makes Graphene/carbon black/ABS/DMF solution of high dispersed degree.
Step 5, be settled out Graphene/carbon black/ABS masterbatch: 1500ml water is joined in finely dispersed Graphene/carbon black/ABS/DMF solution, Graphene/carbon black/ABS is precipitated out from DMF solvent;
Step 6, masterbatch aftertreatment: the Graphene/carbon black being settled out/ABS mixture is carried out press filtration, oven dry, pulverizes to obtain dry state masterbatch, add 30g polyethylene wax as dispersion agent, adopt single screw extrusion machine to carry out extruding pelletization to masterbatch and obtain Graphene/carbon black/ABS masterbatch.
Embodiment 3
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts melt-blending process, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in sand mill, add 20g hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, 5kg water and 200g Graphene, sand milling, after 5 hours, filters and obtains surperficial electropositive graphene uniform dispersion.By this graphene dispersing solution press filtration, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 120g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 8 hours, and press filtration is dried and broken up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, prepare Graphene/carbon black/polycarbonate: 600g polycarbonate is added to high-speed mixer together with above-mentioned Graphene/carbon black electrostatic self-assembled mixture, under the condition of rotating speed 1500r/min, mix 10 minutes;
Step 4, masterbatch aftertreatment: add 30g polyester wax as dispersion agent, and adopt twin screw extruder after above-mentioned mixing of materials, controlled working temperature melt extrudes granulation at 250-290 ℃ to masterbatch and obtains Graphene/carbon black/PC masterbatch.Screw speed is 120 revs/min.Granulation adopts water ring granulation mode, is then dried cooling.
Embodiment 4
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts melt-blending process, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in homogenizer, add 30g Trimethyllaurylammonium bromide, 5g polyoxyethylene nonylphenol ether, 5kg water and 200g Graphene, stir after 5 hours, filter and obtain surperficial electropositive graphene uniform dispersion.By this graphene dispersing solution press filtration, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 60g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 6 hours, and press filtration is dried and broken up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, prepare Graphene/carbon black/polypropylene: 500g polypropylene is added to high-speed mixer together with above-mentioned Graphene/carbon black electrostatic self-assembled mixture, under the condition of rotating speed 1000r/min, mix 15 minutes;
Step 4, masterbatch aftertreatment: add 30g petroleum wax, with above-mentioned mixing of materials evenly after, adopt twin screw extruder controlled working temperature at 200-260 ℃, masterbatch is melt extruded to granulation and obtains Graphene/carbon black/PP masterbatch.Screw speed is 160 revs/min.Granulation adopts water ring granulation mode, is then dried cooling.
Embodiment 5
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts situ aggregation method, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in sand mill, add 30g Trimethyllaurylammonium bromide, 10g ethoxylated dodecyl alcohol, 5kg water and 200g Graphene, sand milling, after 5 hours, filters and obtains surperficial electropositive graphene uniform dispersion.By this graphene dispersing solution press filtration, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 60g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 6 hours, and press filtration is dried and broken up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, prepare Graphene/carbon black/polyethylene: in the polymerization bottle with agitator of the deoxygenation that dewaters, add new toluene, above-mentioned Graphene/carbon black mixture, the 3ml metallocene catalyst (1 * 10 steaming of 1000ml
-3m), the methylaluminoxane (1M) of 10ml, under mechanical stirring, (350rpm) is warming up to 60 ℃, passes into 3.0 atmospheric ethylene gas, polyreaction continues to stop passing into ethylene gas after 5 hours stops polymerization.After cooling, polymerisate is poured in the industrial spirit of hcl acidifying (alcohol consumption is 5 times of toluene amount), polyethylene is fully precipitated, suction filtration is isolated Graphene/carbon black/polyethylene solid and is used industrial spirit repetitive scrubbing.
Step 4, masterbatch aftertreatment: Graphene/carbon black/polyethylene composite is carried out press filtration, oven dry, pulverized to obtain dry state masterbatch, add 20g polyethylene wax as dispersion agent, adopt single screw extrusion machine to carry out extruding pelletization to masterbatch and obtain Graphene/carbon black/PE masterbatch.
Embodiment 6
A preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, adopts situ aggregation method, realizes as follows:
Step 1, adjusting Graphene surface electrical behavior: in sand mill, add 25g Trimethyllaurylammonium bromide, 5kg water and 200g Graphene, sand milling, after 5 hours, filters and obtains surperficial electropositive graphene uniform dispersion.By this graphene dispersing solution press filtration, dry, break up the Graphene that obtains clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: 60g carbon black is added in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of the above-mentioned surface band making in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 6 hours, and press filtration is dried and broken up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, prepare Graphene/carbon black/polyvinyl chloride: in thering is the polymerization bottle of agitator, add above-mentioned Graphene/carbon black mixture, 1.5kg deionized water, dibenzoyl peroxide initiator 2.5g, appropriate sodium bicarbonate regulates pH value to 7-8 left and right, and closed reactor, stirs 10min; In reactor, add vinyl chloride monomer 900g(1L), stirring makes system even, setting temperature of reaction is 60 ℃, intensification initiated polymerization, and still internal pressure raises and rises with temperature, tend towards stability gradually, last stage reaction pressure drop, to 0.8MPa, adds polyreaction terminator, stirs after 20min, make it to mix, polyreaction stops.
Step 4, masterbatch aftertreatment: remove unreacted vinyl chloride monomer, discharging, centrifugal, be dried, pulverize and to obtain dry state masterbatch, add 40g epoxyfatty acid, adopt single screw extrusion machine to carry out extruding pelletization to masterbatch and obtain Graphene/carbon black/PVC masterbatch.
In sum, the present invention adopts surface-modifying agent regulate the charging property of Graphene and pass through electrostatic self-assembled technology, prepare Graphene/carbon black hybrid material, effectively avoided the reunion of Graphene in last handling process, and then be conducive to obtain the Graphene masterbatch of good dispersity.The problems such as Graphene/carbon black/resin concentrates solved the reinforced difficulty of graphene with high specific surface, it is uneven to disperse in plastic cement, product properties is unstable, Graphene dust pollution.
Claims (10)
1. Graphene/carbon black thermoplastic resin masterbatch with polymolecularity, it is characterized in that: in described masterbatch, Graphene/carbon black mixture adopts electrostatic self-assembled to form, according to weight percent, comprise: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.
2. a preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Adopt solution blended process
1. configure polymer mixing solutions: control the ratio of solvent, masterbatch carrier is dissolved in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: Graphene/carbon black mixture is joined in mixed solution, utilize dispersing apparatus, prepare the Graphene/carbon black/macromolecular solution of high dispersed degree;
3. be settled out Graphene/carbon black/polymer masterbatch: add a certain amount of precipitation agent, solid mixture is separated from solvent;
4. masterbatch aftertreatment: isolated solid mixture is carried out to press filtration and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopt the conventional processing units of thermoplastic material to carry out extruding pelletization, can dilute the masterbatch pellet of application.
3. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 2, is characterized in that: in described step 2, in solution blended process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
4. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 2, it is characterized in that: in described step 2, in solution blended process, solvent is one or more the mixture in the corresponding thermal plastic high polymer solvent of water, ethanol, acetone, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride solubilized.
5. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 2, it is characterized in that: in described step 2, precipitation agent is that water, ethanol, propyl alcohol, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride and macromolecule solvent dissolve each other in insoluble high molecular solvent one or more.
6. a preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Melt-blending process
1. standby Graphene/carbon black/macromolecule mixture: thermoplasticity masterbatch carrier is added to high-speed mixer with together with Graphene/carbon black electrostatic self-assembled mixture in step 1, mix 3-15 minute under the condition of rotating speed 500-2500r/min;
2. masterbatch aftertreatment: by the material mixing of above-mentioned acquisition, add auxiliary agent and adopt thermoplastic material common equipment to carry out extruding pelletization, obtain the masterbatch pellet that can dilute application.
7. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 6, is characterized in that: in described step 2, in melt-blending process, masterbatch carrier is thermal plastic high polymer; Described thermal plastic high polymer is polyethylene, polystyrene, polypropylene, thermoplastic polyurethane, polycarbonate, polyvinyl chloride, polymeric amide, acrylics or other polyolefine and multipolymer thereof.
8. a preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: with tensio-active agent, Graphene is carried out to surface modification treatment, regulate the charging property on Graphene surface, obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour
;add the Graphene of the coated promoting agent in surface in carbon black solution, after being uniformly dispersed, press filtration with dry to obtain Graphene/carbon black electrostatic self-assembled mixture, jitter time is 0.5-20 hour;
The preparation of step 2, Graphene/carbon black/thermoplastic resin:
Situ aggregation method
1. prepare Graphene/carbon black/macromolecule mixture: after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator are mixed, stir, Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, processes and obtains masterbatch after completion of the reaction according to differential responses;
2. masterbatch aftertreatment: masterbatch is carried out to press filtration and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopt the conventional processing units of thermoplastic material to carry out extruding pelletization, can dilute the masterbatch pellet of application.
9. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 8, is characterized in that: in described step 2 situ polymerization, monomer used is acrylic acid or the like, alkene class, maleic anhydride; Described initiator is azo-initiator, peroxide initiator, metal species initiator, methylaluminoxane.
10. the preparation method with Graphene/carbon black thermoplastic resin masterbatch of polymolecularity as claimed in claim 9, is characterized in that: described acrylic monomer is vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methyl methacrylate; Vinyl monomer is ethene, vinylbenzene, vinylchlorid, divinyl; Described azo-initiator is azo-bis-isobutyl cyanide, azo two cyanogen in different heptan; Peroxide initiator is benzoyl peroxide, tertbutyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide; Metal species initiator is metallocene initiator.
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Address after: Siming District in Fujian province Narcissus 361000 Xiamen Road, No. 33 sea light building 24C Patentee after: XIAMEN KNANO GRAPHENE TECHNOLOGY CORPORATION LIMITED Address before: Siming District in Fujian province Narcissus 361000 Xiamen Road, No. 33 sea light building 24C Patentee before: Xiamen Knano Graphene Technology Corporation Limited |
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