CN103642198B - Graphene/carbon black thermoplastic resin master batch with polymolecularity and preparation method thereof - Google Patents
Graphene/carbon black thermoplastic resin master batch with polymolecularity and preparation method thereof Download PDFInfo
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Abstract
A kind of Graphene/carbon black thermoplastic resin master batch with polymolecularity and preparation method thereof, Graphene in this masterbatch/carbon black mixture adopts electrostatic self-assembled to be formed, comprise according to weight percent: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.Its preparation method: (1) adopts surfactant compound dispersed graphite alkene, to regulate and control the positive polarity of graphenic surface; (2) Graphene of modified positively charged and carbon black are formed stable Graphene/carbon black mixture by electrostatic adsorption self-assembly; (3) Graphene/carbon black thermoplastic resin master batch of polymolecularity is prepared with the use of solution blended process, melt-blending process, situ aggregation method; (4) to carry out after process masterbatch and add auxiliary agent extruding pelletization obtaining Graphene/carbon black/thermoplastic resin masterbatch pellet.Gained masterbatch solves the problems such as the reinforced difficulty of graphene powder, dispersion inequality, dust pollution, product properties instability.
Description
Technical field
The present invention relates to a kind of be applied to thermoplastic material processing in Graphene masterbatch and technology of preparing, be specially Graphene/carbon black thermoplastic resin master batch of a kind of polymolecularity and preparation method thereof.
Background technology
Since 2004, after the An Deliehaimu of graceful Chester university of Britain and the Constantine Nuo Woxiaoluofu method that first passage micromechanics is peeled off in test successfully obtains 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 have very high specific conductivity and thermal conductivity, reach 6000S/cm (Approaching ballistic transport in suspended graphene respectively, Nature Nanotechnology, 2008,3:491-495) and 5300Wm
-1k
-1(Superior thermal conductivity of single-layer grapheme, Nano Letters, 2008; 8:902 – 7), be therefore considered to have prospects for commercial application widely as in the enhancing of polymeric matrix, conduction and heat conductive filler.
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, active high easily reunion, causes original excellent properties to be lost.In order to address this problem, current more investigator adopts the graphene oxide of surface containing a large amount of functional group as filler, thus is beneficial to and carries out modification to Graphene and reach the object be scattered in resin.Summer and raw etc. is dispersed in polymer latex Ruzhong graphene oxide, and in latex, introduce reductive agent carry out in-situ reducing graphene oxide, again through breakdown of emulsion, cohesion, drying, obtain graphene/polymer nano composite material (being the Chinese invention patent of CN 101864098 see bulletin).Graphene oxide is placed in solvent ultrasonic disperse by Zheng Weitao etc., adds polyethylene powders mechanical stirring, after drying, composite particles is added heat reduction in hydrazine hydrate and becomes graphene composite particle (being the Chinese invention patent of CN 102585335 see bulletin).But due to graphene oxide in oxidising process by the oxygenant being used havoc graphene film original crystalline structure and seriously reduce 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 system can be made again to have higher long-term stability on the maintenance functional basis of mineral filler, therefore receives and payes attention to and apply widely.
To sum up, in the present invention, the carbon black added by electrostatic self-assembled mode in Graphene can not improve the performance of matrix material by means of only synergy, and the carbon black pellet added is evenly dispersed in graphenic surface, effectively reduces the reunion degree of Graphene.The composite granule obtained is prepared into masterbatch with resin-bonded again, can solves again graphene powder and bring problems in the practical application of modified plastic rubber: graphene powder is fluffy, directly extrude processing and to get up difficulty, power consumption is large; The reinforced difficulty of powder, powder disperses 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 master batch with polymolecularity and preparation method thereof, it is simple that the method has technical process, and production cost is low, the uniform advantage of graphene dispersion in masterbatch.
To achieve these goals, the present invention adopts following technical scheme:
A kind of Graphene/carbon black thermoplastic resin master batch with polymolecularity, it is characterized in that: in described masterbatch, Graphene/carbon black mixture adopts electrostatic self-assembled to be formed, comprise according to weight percent: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.
Have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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: the ratio controlling solvent, be dissolved in by masterbatch carrier in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: joined in above-mentioned mixed solution by Graphene/carbon black mixture, utilize dispersing apparatus, prepare the Graphene/carbon black/macromolecular solution of high uniform dispersion;
be settled out Graphene/carbon black/polymer masterbatch: add a certain amount of precipitation agent, separated from solvent by solid mixture;
masterbatch aftertreatment: carry out press filtration to isolated solid mixture and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts thermoplastic material to commonly use processing units to carry out extruding pelletization, can dilute the masterbatch pellet of application.
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 dichloromethane soluble.
In described step 2 precipitation agent be 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.
Have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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. Graphene/carbon black/macromolecule mixture is prepared: thermoplasticity masterbatch carrier is added high-speed mixer together with the Graphene in step 1/carbon black electrostatic self-assembled mixture, under the condition of rotating speed 500-2500r/min, mixes 3-15 minute;
2. masterbatch aftertreatment: by the material mixed of above-mentioned acquisition, adds auxiliary agent and adopts thermoplastic material to commonly use processing units and carry out extruding pelletization, obtains 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.
Have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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. Graphene/carbon black/macromolecule mixture is prepared: stir after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator mixing, make that Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, carries out process after completion of the reaction obtain masterbatch according to differential responses.
2. masterbatch aftertreatment: carry out press filtration to masterbatch and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts thermoplastic material to commonly use processing units 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 type initiators, 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 type initiators 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 regulate the charging property of Graphene and by electrostatic self-assembled technology, prepare Graphene/carbon black hybrid material, effectively prevent the reunion of Graphene in last handling process, and then is conducive to the Graphene masterbatch obtaining good dispersity.
2, the present invention adopts three kinds of methods to prepare the Graphene/carbon black/resin concentrates of polymolecularity, achieve dispersed in masterbatch carrier of Graphene/carbon black hybrid material, solve the reinforced difficulty of graphene with high specific surface, the problem such as dispersion uneven, product properties is unstable, Graphene dust pollution in plastic cement.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.Present invention is disclosed a kind of Graphene/carbon black thermoplastic resin master batch with polymolecularity, wherein Graphene/carbon black mixture adopts electrostatic self-assembled to be formed, comprise according to weight percent: 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 amine salt, the oxide compound of amine, quaternary ammonium salt.
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 the Graphene/carbon black thermoplastic resin master batch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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: the ratio controlling solvent, be dissolved in by masterbatch carrier in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: join in mixed solution by Graphene/carbon black mixture, select suitable dispersing apparatus, prepare the Graphene/carbon black/macromolecular solution of high uniform dispersion;
be settled out Graphene/carbon black/polymer masterbatch: add a certain amount of precipitation agent, separated from solvent by solid mixture;
masterbatch aftertreatment: carry out press filtration to isolated solid mixture and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts thermoplastic material to commonly use processing units to carry out extruding pelletization, can dilute the masterbatch pellet of application.
In described step 1, surface modifying method comprises dry method modification, wet-process modified in one or more.
Dispersing apparatus in described step 1 is one or more in conventional mixer, 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 dichloromethane soluble.
In described step 2 precipitation agent be 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 the Graphene/carbon black thermoplastic resin master batch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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. Graphene/carbon black/macromolecule mixture is prepared: thermoplasticity masterbatch carrier is added high-speed mixer together with the Graphene in step 1/carbon black electrostatic self-assembled mixture, under the condition of rotating speed 500-2500r/min, mixes 3-15 minute;
2. masterbatch aftertreatment: by the material mixed of above-mentioned acquisition, adds auxiliary agent and adopts thermoplastic material to commonly use processing units and carry out extruding pelletization, obtains the masterbatch pellet that can dilute application.
In described step 1, surface modifying method comprises dry method modification, wet-process modified in one or more.
Dispersing apparatus in described step 1 is one or more in conventional mixer, 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 the Graphene/carbon black thermoplastic resin master batch of polymolecularity that the present invention discloses, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: surface modification treatment is carried out to Graphene with tensio-active agent, regulate the charging property of graphenic surface, obtain the electropositive Graphene of surface band to disperse, jitter time is 0.5-20 hour, by this graphene dispersing solution press filtration, dries, breaks up the Graphene obtaining clad surface promoting agent; Add the Graphene of Surface coating promoting agent 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. Graphene/carbon black/macromolecule mixture is prepared: stir after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator mixing, make that Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, carries out process after completion of the reaction obtain masterbatch according to differential responses.
2. masterbatch aftertreatment: carry out press filtration to masterbatch and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts 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, wet-process modified in one or more.
Dispersing apparatus in described step 1 is one or more in conventional mixer, 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 type initiators, 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 type initiators 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
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt solution blended process, realize as follows:
Step 1, adjustment graphenic surface are electrical: in sand mill, add 10g cetyl trimethylammonium bromide, 5kg water and 200g Graphene, and 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 125g carbon black in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of above-mentioned obtained surface band in carbon black solution, electrostatic adhesion forms Graphene/carbon black mixture, and sand milling is after 2 hours, press filtration, dries, breaks up to obtain Graphene/carbon black electrostatic self-assembled mixture.
Step 3, outfit 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: join in TPU/DMF solution by above-mentioned obtained Graphene/carbon black mixture, sand milling is after 2 hours, the Graphene/carbon black/TPU/DMF solution of obtained high uniform dispersion.
Step 5, be settled out Graphene/carbon black/TPU masterbatch: joined by 1500ml water 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/TPU mixture be settled out is carried out to 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
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt situ aggregation method, realize as follows:
Step 1, adjustment graphenic surface are electrical: in sand mill, add 16g Cetyltrimethylammonium bromide, 5kg water and 200g Graphene, and 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 50g carbon black in 5000ml water, form carbon black solution.Slowly add the electropositive Graphene of above-mentioned obtained surface band in sand mill 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: by 500gABS resin dissolves in 2000mlDMF solvent, be made into mixing solutions;
Step 4, prepare Graphene/carbon black/ABS/DMF mixing solutions: join in ABS/DMF solution by above-mentioned obtained Graphene/carbon black compound, sand milling is after 5 hours, the Graphene/carbon black/ABS/DMF solution of obtained high uniform dispersion.
Step 5, be settled out Graphene/carbon black/ABS masterbatch: joined by 1500ml water 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/ABS mixture be settled out is carried out to 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
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt melt-blending process, realize as follows:
Step 1, adjustment graphenic surface are electrical: in sand mill, add 20g hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride, 5kg water and 200g Graphene, and 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 120g carbon black in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of above-mentioned obtained surface band 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 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, adopt twin screw extruder with after above-mentioned mixing of materials, controlled working temperature melt extrudes granulation at 250-290 DEG C to masterbatch and obtains Graphene/carbon black/PC masterbatch.Screw speed is 120 revs/min.Granulation adopts water ring granulation mode, then carries out drying and cools.
Embodiment 4
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt melt-blending process, realize as follows:
Step 1, adjustment graphenic surface are electrical: 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 60g carbon black in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of above-mentioned obtained surface band 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 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, after even with above-mentioned mixing of materials, adopt twin screw extruder controlled working temperature at 200-260 DEG C, melt extrude granulation obtain Graphene/carbon black/PP masterbatch to masterbatch.Screw speed is 160 revs/min.Granulation adopts water ring granulation mode, then carries out drying and cools.
Embodiment 5
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt situ aggregation method, realize as follows:
Step 1, adjustment graphenic surface are electrical: in sand mill, add 30g Trimethyllaurylammonium bromide, 10g ethoxylated dodecyl alcohol, 5kg water and 200g Graphene, and 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 60g carbon black in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of above-mentioned obtained surface band 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: have in the polymerization bottle of agitator in the deoxygenation that dewaters, add toluene, above-mentioned Graphene/carbon black mixture, 3ml metallocene catalyst (1 × 10 that 1000ml newly steams
-3m), the methylaluminoxane (1M) of 10ml, under mechanical stirring, (350rpm) is warming up to 60 DEG C, passes into 3.0 atmospheric ethylene gas, and polyreaction continues to stop passing into ethylene gas after 5 hours makes polymerization stop.Poured into by polymerisate after cooling (alcohol consumption is 5 times of toluene amount) in the industrial spirit of hcl acidifying, polyethylene is fully precipitated, suction filtration is isolated Graphene/carbon black/polyethylene solids and is used industrial spirit repetitive scrubbing.
Step 4, masterbatch aftertreatment: carry out press filtration, oven dry to Graphene/carbon black/polyethylene composite, pulverize 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
There is a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, adopt situ aggregation method, realize as follows:
Step 1, adjustment graphenic surface are electrical: in sand mill, add 25g Trimethyllaurylammonium bromide, 5kg water and 200g Graphene, and 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 obtaining clad surface promoting agent.
Step 2, prepare Graphene/carbon black mixture: added to by 60g carbon black in 5000ml water, form carbon black solution.In sand mill, slowly add the electropositive Graphene of above-mentioned obtained surface band 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 the polymerization bottle with agitator, add above-mentioned Graphene/carbon black mixture, 1.5kg deionized water, dibenzoyl peroxide initiator 2.5g, appropriate sodium bicarbonate adjust ph is to about 7-8, and closed reactor, stirs 10min; Vinyl chloride monomer 900g(1L is added) in reactor, stirring makes system even, setting temperature of reaction is 60 DEG C, intensification initiated polymerization, and still internal pressure raises with temperature and rises, tend towards stability gradually, last stage reaction pressure drop, to 0.8MPa, adds polyreaction terminator, after stirring 20min, make it to mix, polyreaction stops.
Step 4, masterbatch aftertreatment: remove unreacted vinyl chloride monomer, discharging, centrifugal, dry, pulverize 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 adopt surface-modifying agent regulate Graphene charging property and by electrostatic self-assembled technology, prepare Graphene/carbon black hybrid material, effectively prevent the reunion of Graphene in last handling process, and then be conducive to the Graphene masterbatch obtaining good dispersity.Graphene/carbon black/resin concentrates solves the reinforced difficulty of graphene with high specific surface, in plastic cement, disperses the problems such as inequality, product properties are unstable, Graphene dust pollution.
Claims (10)
1. one kind has the Graphene/carbon black thermoplastic resin master batch of polymolecularity, it is characterized in that: in described masterbatch, Graphene/carbon black mixture adopts electrostatic self-assembled to be formed, described masterbatch comprises according to weight percent: 10-50% Graphene, 5-20% carbon black, 0.5-10% tensio-active agent, 10-65% vector resin, 2-10% auxiliary agent.
2. have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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: the ratio controlling solvent, be dissolved in by masterbatch carrier in solvent, be made into mixing solutions, described solvent load is 20-100ml/g;
2. prepare Graphene/carbon black/polymer mixing solutions: joined in mixed solution, utilize dispersing apparatus by Graphene/carbon black mixture, prepare the Graphene/carbon black/macromolecular solution of high uniform dispersion;
3. Graphene/carbon black/polymer masterbatch is settled out: add a certain amount of precipitation agent, separated from solvent by solid mixture;
4. masterbatch aftertreatment: carry out press filtration to isolated solid mixture and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts thermoplastic material to commonly use processing units to carry out extruding pelletization, can dilute the masterbatch pellet of application.
3. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 2, it 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. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 2, it is characterized in that: the corresponding thermal plastic high polymer of solvent-soluble solution in described step 2 in solution blended process, described solvent is one or more the mixture in water, ethanol, acetone, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride.
5. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 2, it is characterized in that: in described step 2, precipitation agent and macromolecule solvent dissolve each other but not soluble high molecular, described precipitation agent be in water, ethanol, propyl alcohol, benzene, dimethylbenzene, DMF, tetrahydrofuran (THF) or methylene dichloride one or more.
6. have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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. for Graphene/carbon black/macromolecule mixture: thermoplasticity masterbatch carrier is added high-speed mixer together with the Graphene in step 1/carbon black electrostatic self-assembled mixture, mix 3-15 minute under the condition of rotating speed 500-2500r/min;
2. masterbatch aftertreatment: by the material mixed of above-mentioned acquisition, adds auxiliary agent and adopts thermoplastic material common equipment to carry out extruding pelletization, obtains the masterbatch pellet that can dilute application.
7. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 6, it 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. have a preparation method for the Graphene/carbon black thermoplastic resin master batch of polymolecularity, concrete steps comprise:
The preparation of step 1, Graphene/carbon black mixture: carry out surface modification treatment to Graphene with tensio-active agent, regulates the charging property of graphenic surface, and obtain the electropositive Graphene of surface band and disperse, jitter time is 0.5-20 hour; Add the Graphene of Surface coating promoting agent 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. Graphene/carbon black/macromolecule mixture is prepared: stir after monomer, Graphene/carbon black electrostatic self-assembled mixture, solvent, initiator mixing, make that Graphene/carbon black electrostatic self-assembled mixture is evenly dispersed in reaction system, polyreaction is carried out in intensification, carries out process after completion of the reaction obtain masterbatch according to differential responses;
2. masterbatch aftertreatment: carry out press filtration to masterbatch and drying and processing obtains dry state masterbatch, adds auxiliary agent and adopts thermoplastic material to commonly use processing units to carry out extruding pelletization, can dilute the masterbatch pellet of application.
9. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 8, it 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 type initiators, metal species initiator, methylaluminoxane.
10. there is the preparation method of the Graphene/carbon black thermoplastic resin master batch of polymolecularity as claimed in claim 9, it 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 Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Peroxide type initiators 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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Inventor after: Fang Chongqing Inventor after: Hong Jiangbin Inventor after: Jiang Longying Inventor after: Zhao Liping Inventor after: Qiu Shuxuan Inventor before: Zhao Liping Inventor before: Hong Jiangbin Inventor before: Jiang Longying Inventor before: Fang Chongqing Inventor before: Qiu Shuxuan |