CN110229457A - A kind of ABS nanocomposite and preparation method thereof - Google Patents

A kind of ABS nanocomposite and preparation method thereof Download PDF

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Publication number
CN110229457A
CN110229457A CN201810184681.XA CN201810184681A CN110229457A CN 110229457 A CN110229457 A CN 110229457A CN 201810184681 A CN201810184681 A CN 201810184681A CN 110229457 A CN110229457 A CN 110229457A
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nano
abs
mixing
liquid medium
paste
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CN110229457B (en
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马永梅
郑鲲
张京楠
曹新宇
尚欣欣
叶钢
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The present invention relates to field of nanocomposite materials, specifically, being related to a kind of ABS nanocomposite, ABS nanocomposite is to be made by mixing through melt blending；Mixing includes ABS, is combined with nano material and liquid medium on ABS particle.Further relate to a kind of preparation method of ABS nanocomposite, comprising: (1) nano material, liquid medium are mixed, paste is made；(2) paste and ABS are mixed, covers paste in ABS particle surface, mixing is made；(3) by mixing melt blending, nanocomposite is made.Mixing of the invention will not skid after being added in the equipment such as extruder, nanocomposite can directly be prepared, it is not necessary that other materials are added during the preparation process, processing easy to produce, and avoid the problem that nanocomposite performance is poor caused by liquid medium in the prior art gasifies too early, through experiments, it was found that compared with the prior art, nanocomposite performance made from mixing of the invention is more superior.

Description

A kind of ABS nanocomposite and preparation method thereof
Technical field
The present invention relates to field of nanocomposite materials, specifically, being related to a kind of using ABS as the nanocomposite of base-material And preparation method thereof.
Background technique
It is squeezed out in existing technology frequently with stratified nano materials and mixed with polymers, forms composite material, although such The tensile strength of composite material is promoted, but the problems such as due to the poor compatibility of stratified nano materials and polymer, is caused The impact resistance of such material is not generally high.
To solve the above problems, enabling polymer in the interlayer of stratified nano materials frequently with modes such as intercalation in-situ polymerizations It reacts to improve the impact resistance of composite material, but the process is time-consuming longer, polymeric reaction condition is harsh, and molten Agent is not easily recycled, and can bring the variations such as environmental pollution.
Patent No. CN101081928A proposes a kind of preparation method of polyamide/nano montmorillonite masterbatch, auxiliary using water Help method to prepare polyamide/nano montmorillonite masterbatch, it is intercalator that preparation method, which is with deionized water, by the montmorillonite of purifying and Mud is added step-wise to the polyamide that prescription amount melts completely by deionized water mixing, fully dispersed obtained montmorillonite mud, then Polyamide/nano montmorillonite masterbatch is obtained through extruding pelletization.Preparation method is simple, and production cost is low, but this method is poly- Montmorillonite mud is added after amide melting, montmorillonite mud is will lead to and has not enough time to be thoroughly mixed with copolymer, interlayer Water just because of high-temperature gasification, causes polyamide to fail to timely enter interlayer, meanwhile, it is insufficient only by the energy of water generation Will be completely exfoliated between cheating engaging layer thus cannot obtain the composite material that type is completely exfoliated, properties of product are also received greatly Influence.
In view of this, the present invention is specifically proposed.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention provides a kind of ABS nanocomposite, properties of product are more Add superior.
In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that
A kind of ABS nanocomposite, ABS nanocomposite are to be made by mixing through melt blending；
Mixing includes ABS, is combined with nano material and liquid medium on ABS particle.
Mixing of the invention will not skid after being added in the equipment such as extruder, can directly prepare nanocomposite, nothing Other materials, processing easy to produce need to be added during the preparation process, and avoid liquid medium in the prior art and gasify too early and lead The poor problem of the nanocomposite performance of cause, through experiments, it was found that, compared with the prior art, received made from mixing of the invention Nano composite material performance is more superior.
The paste that ABS particle surface covers nano material and liquid medium is mixed to form.
Mud made from the prior art is semiliquid, in the preparation process of nanocomposite, is needed in a high voltage state It is added into reaction system, makes troubles to production and processing, to solve the above problems, the present invention provides a kind of paste, institute Stating paste is semisolid, can be added under passive state into reaction system, processing easy to produce, the paste can be with ABS Mixing, and cover in ABS particle surface, obtain mixing.
Preferably, also contain auxiliary agent in paste.
Specifically, the mixture of nano material and liquid medium viscosity under the action of auxiliary agent increases to form paste, this hair Bright auxiliary agent also improves the boiling point of liquid medium, further avoids liquid medium in the prior art and receives caused by gasifying too early The poor problem of nano composite material performance.
Paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not 0。
Preferably, paste includes: 1 parts by weight of nano material, liquid medium 5-20 parts by weight, auxiliary agent 2-10 parts by weight, It but is not 0；
It is furthermore preferred that paste includes: 1 parts by weight of nano material, 10 parts by weight of liquid medium, 5 parts by weight of auxiliary agent, but not It is 0.
The consistency of paste is 0-100mm, but is not 0.Consistency corresponds to standard JBJ/T70-2009.
The mass ratio of nano material and ABS are 0.1-20:100；It is preferred that 1-10:100；More preferable 4:100.
Also incorporate age resister on ABS particle, the mass ratio of age resister and ABS are 0.1:100~1:100；It is preferred that 0.3:100；
Nano material is the mixing of one or more of the nano material of zero dimension, one-dimensional nano material.
Nano material is nano silicon oxide, nano-titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nanometer Nickel oxide, nanogold, nano silver, nano-silicon, nano-sized carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nanometer Sulphur, nano lanthanum oxide, it is Nanometer-sized Neodymium Oxide, nano oxidized erbium, nano-cerium oxide, nano oxidized praseodymium, nano yttrium oxide, nano oxidized One of europium, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide, nanoscale molybdenum oxide Or several mixing.
Auxiliary agent includes carboxylate surface active agent, sulfate salt surfactant, sulfosalt surfactant, phosphate ester salt Surfactant, amine salt surfactant, quaternary surfactant, heterocyclic type surfactant, nonionic surfactant, Natural water soluble high molecular, synthetic water soluble high molecular；
The boiling point of liquid medium is lower than the plasticization temperature of ABS, and preferably shorter than 180 DEG C, liquid medium includes water.
Auxiliary agent includes surfactant, water soluble polymer.
Specifically, surfactant includes:
1, anionic surfactant: it is divided into carboxylate, sulfuric acid, sulfonate and phosphate ester salt.
(1) soap kind is higher fatty acid salt, and general formula of molecular structure is (RCOO)-nMn+.With stearic acid, oleic acid, laurel Acid etc. is more common.According to the difference of its metal ion (Mn+), there are alkali metal soap, alkaling earth metal base and organic amine soap etc..
(2) hydrosulphate is mainly the sulfuric acid ester of sulfated oil and higher aliphatic, general formula of molecular structure ROSO3-M +, there are commonly lauryl sodium sulfate (also known as " sldium lauryl sulfate "), sodium hexadecyl sulfate (also known as " cetanol sulfuric acid Sodium "), sodium stearyl sulfate (also known as " stearyl alcohol sodium sulphate ") etc..
(3) sulphonic acid compound mainly has aliphatic sulfonic compound, sulfo group aryl sulfonic acid compound, sulfo group naphthalene sulfonic acids compound etc.
2, cationic surfactant: containing nitrogen-atoms in the hydrophilic group ion of cationic surfactant, according to nitrogen original The position difference of son in the molecule is divided into amine salt, quaternary ammonium salt and heterocyclic type three classes.Such as benzalkonium chloride (trade name " geramine "), benzene Prick bromine ammonium (trade name " bromogeramine "), chlorination (bromination) cetyl pyridinium (trade name " Xi Bailin ") etc.
3, zwitterionic surfactant: lecithin, amino acid pattern, betaine type
4, nonionic surfactant: fatty glyceride, fatty acid sorbitan (sapn), polysorbate (tween), alkane Base phenol polyethenoxy ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester APEO, detergent series.
Water soluble polymer includes:
1, natural class macromolecule
Starch
Seaweeds: sodium alginate, agar-agar.
Natural plant gum class: Arabic gum, tragacanth gum, locust bean gum, tamarind seed polysaccharide glue, sesbania gum, carrageenan, guar gum, fruit Glue.
Animal glue class: gelatin, casein, chitosan.
Microbiological gum: xanthan gum, gellan gum, hyaluronic acid.
2, class organic polymer and its prepolymer are synthesized
(1) polymeric type water soluble polymer
Polyacrylamide, polyacrylic acid, polymethylacrylic acid and its copolymer, polyvinyl alcohol, polyethylene glycol, polyoxyethylene Alkene, polyvinylpyrrolidone, polymaleic anhydride, polydimethyl diallyl ammonium chloride, polyvinylamine, poly- divinyl imidazoles Quinoline, sulfonate styrene maleic anhydride copolymer, opens Pu Shi resin at kayexalate.
(2) polycondensation class water soluble polymer
Water soluble amino resin, water soluble phenol resin, water soluble alkyd resin, water-soluble epoxy resin, water-soluble poly Urethane resin, polyethylene imine, poly-aspartate, poly-epoxy succinic acid, polyamine epichlorohydrin resin, polyamide second two Urea formaldehyde, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin, N, N- Dimethyl 1,3- propane diamine and epichlorohydrin resin.
(3) other
Water Soluble Maleic Anhydride oil, dicyandiamide formaldehyde resin, rosin amine-ethylene oxide condensate, poly N-ethylene yl acetamide, water Dissolubility ficoll.
3, semi-synthetic class macromolecule
Modified cellulose and converted starch.
Liquid medium includes: isopentane, pentane, petroleum ether, hexane, hexamethylene, isooctane, trifluoroacetic acid, trimethyl Pentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, chlorotrifluoroethane, propyl ether, toluene, paraxylene, Chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate, propyl alcohol, methylisobutylketone, four Hydrogen furans, ethyl acetate, isopropanol, ethyl alcohol, chloroform, methyl ethyl ketone, dioxane, pyridine, acetone, nitromethane, Acetic acid, acetonitrile, dimethylformamide, methanol, water, methylamine, dimethylamine, ether, pentane, methylene chloride, carbon disulfide, 1,1- bis- Chloroethanes, trifluoroacetic acid, 1,1,1- trichloroethanes, ethyl alcohol, butanone, 1,2- dichloroethanes, glycol dimethyl ether, triethylamine, Propionitrile, 4-methyl-2 pentanone, ethylenediamine, butanol, acetic acid, glycol monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, diformazan Benzene, meta-xylene, acetic anhydride, ortho-xylene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE.
Age resister includes:
Antioxidant:
Amine antioxidants have ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, hindered amine.
Phenolic antioxidant, phenolic antioxidant can be divided into alkylation monophenols, alkylation polyphenol, thiobisphenol and polyphenol.Alkane Base single phenol and polyphenol antioxidant principal item have antioxidant 264,1076,2246,1035,1010,3114 and 1790.Thiobis The principal item of phenol has antioxidant 2246 and 300.Polyatomic phenol antioxidant principal item has 2,5 1 di-t-butyl hydroquinones and 2,5 One or two amyl hydroquinones.
Thio-2 acid vinegar and phosphorous vinegar kind antioxidant, principal item have anti-aging agent TNP, Ultranox624 and Asia Tricresyl phosphate (2, the tertiary T base phenyl of soul one or two) ester.
Other type antioxidants, 2 one coloured glaze base benzo miaow trade name antioxidant MBs, nickel dibutyl dithiocarbamate Trade name antioxidant NBC, there are also zinc dialkyl dithiophosphates.
Primary anti-oxidant has: anti-aging agent RD, antioxidant A W, antioxidant BLE, antioxidant A, anti-aging agent OD, 4,4 '-bis- (α- Methylbenzyl) diphenylamines, 4,4 '-bis- (α, α-methylbenzyl) diphenylamines, N, N ,-di-sec-butyl-p-phenyl enediamine, anti-aging agent 4030, Antioxidant 4010, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 1076, antioxidant 2216, antioxidant 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246, DBH 2,5 di tert butylhydroquinone, anti-oxidant DLTP, Antioxidant TNP, Ultranox624, phosphorous acid three (the tertiary T base phenyl of 2,4- bis-) ester, antioxidant MB, antioxidant NBC, dialkyl group two Thiophosphoric acid zinc.
The present invention also provides a kind of mixings, comprising: paste and ABS；Paste includes: 1 parts by weight of nano material, liquid Body medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but be not 0；Paste, which is covered, forms mixing in ABS particle surface；
Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are divided It dissipates；
It is furthermore preferred that dispersing mode includes ultrasound, shearing, stirring, ball milling, colloid mill；
It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.
The present invention also provides a kind of preparation methods of ABS nanocomposite, comprising:
(1) nano material, liquid medium are mixed, paste is made；
(2) paste and ABS are mixed, covers paste in ABS particle surface, mixing is made；
(3) by mixing melt blending, nanocomposite is made.
In the preparation process of nanocomposite, mixing will not skid after being added in the equipment such as extruder, can be direct Nanocomposite is prepared, it is not necessary that other materials, processing easy to produce are added during the preparation process, and is avoided in the prior art The poor problem of nanocomposite performance caused by liquid medium gasifies too early, through experiments, it was found that, compared with the prior art, this Nanocomposite performance made from the mixing of invention is more superior.
Step is additionally added auxiliary agent in (1).
During the melt blending of paste and ABS, all hot melt processing technologies can be used, such as mixing, mill, screw rod (parallel/taper/mono-/bis -/tri- screw rods).
In step (1), successively nano material and auxiliary agent are added into liquid medium and are dispersed, paste is made.
Dispersing mode includes ultrasound, shearing, stirring, ball milling, colloid mill.Nearly all dispersing mode can be used.It is described super The frequency of sound is 800~1000Hz, and power is 200~1000W.
Nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.
Nano material and the addition speed of auxiliary agent are respectively 0.01-100g/min, preferably 5-10g/min, more preferable 7g/ min。
In step (3), comprising:
(1) heat temperature raising, ABS are mixed under the first stirring with the liquid medium in paste, nano material, soften And the cladding that interpenetrates；
(2) after the boiling point that temperature is greater than liquid medium, liquid medium portion gasification, the gasification carries out the to mixing Two stirrings.
In the preparation process of nanocomposite, there are the heat temperature raising stages, at this stage, ABS gradually soften and It is interpenetrated under stirring action with paste, ABS and liquid medium and nano material is made to contact with each other cladding.
Liquid in step (3), when mixing melt blending, when temperature is greater than or equal to ABS plasticization temperature, in paste Medium further gasifies, and the nano material of reunion is separated.
In the melt blending stage, ABS is in molten condition, at this point, liquid medium gasifies, divides the nano material reunited mutually From ABS is flow between nano material, to improve dispersion effect of the nano material in ABS.
In step (3), when mixing melt blending, liquid medium gasification promotes the mobility of the mixing and promotes heat Conduction, liquid medium gasification will be helpful to ABS softening.
Step is additionally added age resister in (1).
In an embodiment of the present invention, double screw extruder includes solid conveying zone, melting zone and melt delivery area, mixing It being added from barrel to solid conveying zone, the engine speed of double screw extruder is 30~80Hz, main feeding hopper revolving speed is 10~ 30Hz, extrusion temperature be 150~200 DEG C of an area, two 230~280 DEG C of areas, three 230~280 DEG C of areas, four 230~280 DEG C of areas, five 230~280 DEG C of area；It is preferred that engine speed is 60Hz, main feeding hopper revolving speed is 20Hz, and extrusion temperature is 150~180 DEG C of an area, Two 245~260 DEG C of areas, three 245~255 DEG C of areas, four 240~250 DEG C of areas, five 240~260 DEG C of areas.The linear velocity of screw speed For 0.6~1m/s.
In mixing before melt blending, ABS coats nano material and liquid medium, obtains mixture, When melt blending, while mixture is by external shear action, also by the gasification of internal liquid medium, under the two effect, Explosion occurs for mixture, and while liquid medium escapes, the ABS of molten condition enters between nano material；To realize explosion, The melt pressure of ABS should be greater than the vapour pressure of liquid medium.The present invention is also possible that and first coats to paste, then by cladding Paste is mixed with thermoplastic elastomer (TPE), and coating includes: styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, the third cream of silicon Liquid, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, butylbenzene Latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex.Above-mentioned cladding is greatly prolonged Delay interlayer liquid medium in the release rate in melt blending stage, effectively prevent liquid medium that phase transformation, another party occurs to early Face, the scale of the expansion of interlayer when further improving liquid medium phase transformation are conducive to polymer and travel further into interlayer reality Now fill.
Nano material in paste may be stratified nano materials, such as montmorillonite, graphene, when nano material is layer When shape nano material, liquid medium enters stratified nano materials interlayer in step (1), and step (3) is moulded in temperature higher than polymer When changing temperature, liquid medium gasification separates lamella.Auxiliary agent makes more liquid mediums enter stratified nano materials interlayer, shape At paste.And liquid medium enters stratified nano materials interlayer in step (1), and in the melt blending stage, stratified nano materials The liquid medium of interlayer gasifies, and makes at least partly lamella separation, the thermoplastic polymer of molten condition flow into isolated lamella it Between, to improve dispersion effect of the nano material in thermoplastic polymer.The unsegregated stratified nano materials interlamellar spacing of lamella Increase, the thermoplastic polymer of molten condition flows into interlayer, to improve the compatible of thermoplastic polymer and stratified nano materials Property.Wherein, auxiliary agent makes more liquid mediums enter stratified nano materials interlayer, to further improve stratified nano materials Interlamellar spacing.In melt blending, explosion also occurs for the interlayer of stratified nano materials, makes at least partly lamella separation, molten The thermoplastic polymer of state enters between the lamella of separation, and the unsegregated stratified nano materials interlamellar spacing of lamella increases, molten The thermoplastic polymer of state enters interlayer.
Compared with prior art, the invention has the following beneficial effects:
Mixing of the invention will not skid after being added in the equipment such as extruder, can directly prepare nanocomposite, nothing Other materials, processing easy to produce need to be added during the preparation process, and avoid liquid medium in the prior art and gasify too early and lead The poor problem of the nanocomposite performance of cause, through experiments, it was found that, compared with the prior art, received made from mixing of the invention Nano composite material performance is more superior.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below to the technical side in embodiment Case is clearly and completely described, and the following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
One, the preparation of object is covered
Nano material is nano silicon oxide, and liquid medium is water, and auxiliary agent is pectin, thermoplastic polymer ABS, anti-aging Agent is antioxidant 264.
1 parts by weight of nano material
10 parts by weight of liquid medium
0.01 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 0.01g/min, is made and covers object, and covering object consistency is 5mm.
Two, the preparation of mixing
5 parts by weight of thermoplastic polymer
0.005 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 30Hz, and main feeding hopper revolving speed is 10Hz, and extrusion temperature is 150 DEG C of an area, two 230 DEG C of areas, three 230 DEG C of areas, four The linear velocity in 230 DEG C of area, five 230 DEG C of areas, screw speed is 0.6m/s, obtains nanocomposite.
Embodiment 2
Nano material is nano-sized carbon, and liquid medium is isopentane, and auxiliary agent is chitosan, thermoplastic polymer ABS, anti-ageing Agent is antioxidant TNP.
One, the preparation of object is covered
1 parts by weight of nano material
5 parts by weight of liquid medium
1.5 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 1g/min, is made and covers object, and covering object consistency is 20mm.
Two, the preparation of mixing
50 parts by weight of thermoplastic polymer
0.1 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 60Hz, and main feeding hopper revolving speed is 20Hz, and extrusion temperature is 180 DEG C of an area, two 230 DEG C of areas, three 230 DEG C of areas, four The linear velocity in 250 DEG C of area, five 250 DEG C of areas, screw speed is 0.8m/s, obtains nanocomposite.
Embodiment 3
Nano material is nanometer silicon carbide, and liquid medium is dimethylamine, and auxiliary agent is xanthan gum, thermoplastic polymer ABS, Age resister is antioxidant 3114.
One, the preparation of object is covered
1 parts by weight of nano material
30 parts by weight of liquid medium
5 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 10g/min, is made and covers object, and covering object consistency is 50mm.
Two, the preparation of mixing
100 parts by weight of thermoplastic polymer
1 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 80Hz, and main feeding hopper revolving speed is 30Hz, and extrusion temperature is 200 DEG C of an area, two 250 DEG C of areas, three 250 DEG C of areas, four The linear velocity in 280 DEG C of area, five 280 DEG C of areas, screw speed is 1m/s, obtains nanocomposite.
Embodiment 4
Nano material is nano yttrium oxide, and liquid medium is acetonitrile, and auxiliary agent is polyacrylic acid, thermoplastic polymer ABS, Age resister is antioxidant 1790.
One, the preparation of object is covered
1 parts by weight of nano material
50 parts by weight of liquid medium
10 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 30g/min, is made and covers object, and covering object consistency is 80mm.
Two, the preparation of mixing
500 parts by weight of thermoplastic polymer
5 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 60Hz, and main feeding hopper revolving speed is 20Hz, and extrusion temperature is 150 DEG C of an area, two 260 DEG C of areas, three 245 DEG C of areas, four The linear velocity in 240 DEG C of area, five 240 DEG C of areas, screw speed is 0.6m/s, obtains nanocomposite.
Embodiment 5
Nano material is carbon nanotube, and liquid medium is chloroform, and auxiliary agent is poly-aspartate, thermoplastic polymer ABS, Age resister is antioxidant 4020.
One, the preparation of object is covered
1 parts by weight of nano material
100 parts by weight of liquid medium
50 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 100g/min, is made and covers object, and covering object consistency is 100mm.
Two, the preparation of mixing
1000 parts by weight of thermoplastic polymer
10 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 60Hz, and main feeding hopper revolving speed is 20Hz, and extrusion temperature is 180 DEG C of an area, two 245 DEG C of areas, three 255 DEG C of areas, four The linear velocity in 240 DEG C of area, five 260 DEG C of areas, screw speed is 1m/s, obtains nanocomposite.
Embodiment 6
Nano material is nano boron powder, and liquid medium is carbon disulfide, and auxiliary agent is dicyandiamide formaldehyde resin, thermoplasticity polymerization Object is ABS, and age resister is antioxidant 1035.
One, the preparation of object is covered
1 parts by weight of nano material
10 parts by weight of liquid medium
2 parts by weight of auxiliary agent
Successively nano material and auxiliary agent are added into liquid medium and are dispersed, wherein the addition of nano material and auxiliary agent Speed is respectively 7g/min, is made and covers object, and covering object consistency is 20mm.
Two, the preparation of mixing
25 parts by weight of thermoplastic polymer
0.2 parts by weight of age resister
Object will be covered, age resister is mixed with thermoplastic polymer, obtain mixing.
Three, the preparation of nanocomposite
By mixing melt blending, wherein mixing is added to double screw extruder solid conveying zone, double screw extruder Engine speed is 30Hz, and main feeding hopper revolving speed is 10Hz, and extrusion temperature is 200 DEG C of an area, two 280 DEG C of areas, three 260 DEG C of areas, four The linear velocity in 250 DEG C of area, five 240 DEG C of areas, screw speed is 1m/s, obtains nanocomposite.
Comparative example 1
Difference with embodiment 2 is only that, is covered in the preparation process of object, and auxiliary agent is added without.
Comparative example 2
Difference with embodiment 2 is only that addition covers object melt blending after thermoplasticity reaches molten condition.
Test example 1
This test detects the mechanical property of embodiment 1-6 and comparative example 1,2 gained nanocomposites, as a result sees Table 1.
Table 1
As can be seen from Table 1,2 gained nanocomposite performance of embodiment is better than comparative example 1, it follows that of the invention The performance for improving nanocomposite by the way that auxiliary agent is added in the preparation process of paste.2 gained of embodiment is nano combined Material property be better than comparative example 2, it follows that the present invention by the way that paste is first mixed with thermoplastic polymer, it is remelted total The mixed performance for improving nanocomposite.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any to be familiar with technology people of the invention Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.

Claims (10)

1. a kind of ABS nanocomposite, which is characterized in that ABS nanocomposite is to be made by mixing through melt blending；
Mixing includes ABS, is combined with nano material and liquid medium on ABS particle.
2. a kind of ABS nanocomposite according to claim 1, which is characterized in that ABS particle surface has covered nanometer The paste that material and liquid medium are mixed to form；
Preferably, also contain auxiliary agent in paste.
3. a kind of ABS nanocomposite according to claim 1 or 2, which is characterized in that nano material is receiving for zero dimension The mixing of one or more of rice material, one-dimensional nano material；
Preferably, nano material is nano silicon oxide, nano-titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, Nano-nickel oxide, nanogold, nano silver, nano-silicon, nano-sized carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, Nano-sulfur, nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nano oxidized erbium, nano-cerium oxide, nano oxidized praseodymium, nano yttrium oxide, nanometer Europium oxide, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide, in nanoscale molybdenum oxide One or more of mixing.
4. a kind of ABS nanocomposite according to claim 1 to 3, which is characterized in that the consistency of paste is 0-100mm, but be not 0；
Preferably, paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but not It is 0.
5. a kind of ABS nanocomposite according to claim 1 to 4, which is characterized in that nano material and ABS's Mass ratio is 0.1-20:100；It is preferred that 1-10:100；More preferable 4:100；
Preferably, age resister is also incorporated on ABS particle, the mass ratio of age resister and ABS are 0.1:100~1:100；It is excellent Select 0.3:100；
It is furthermore preferred that auxiliary agent includes carboxylate surface active agent, sulfate salt surfactant, sulfosalt surfactant, phosphorus Acid esters salt surfactant, amine salt surfactant, quaternary surfactant, heterocyclic type surfactant, non-ionic surface Activating agent, natural water soluble high molecular, synthetic water soluble high molecular；
It is further preferred that the boiling point of liquid medium is lower than the plasticization temperature of thermoplastic polymer, liquid medium includes water.
6. a kind of preparation method of ABS nanocomposite characterized by comprising
(1) nano material, liquid medium are mixed, paste is made；
(2) paste and ABS are mixed, covers paste in ABS particle surface, mixing is made；
(3) by mixing melt blending, nanocomposite is made.
7. preparation method according to claim 6, which is characterized in that step is additionally added auxiliary agent in (1).
8. preparation method according to claim 6, which is characterized in that in step (3), comprising:
(1) heat temperature raising, ABS are mixed under the first stirring with the liquid medium in paste, nano material, soften and mutual Mutually infiltration cladding；
(2) after the boiling point that temperature is greater than liquid medium, liquid medium portion gasification, the gasification carries out second to mixing and stirs It mixes.
9. preparation method according to claim 6, which is characterized in that in step (3), when mixing melt blending, in temperature When greater than or equal to ABS plasticization temperature, the liquid medium in paste further gasifies, and the nano material of reunion is separated；
Preferably, in step (3), when mixing melt blending, liquid medium gasification promotes the mobility and promotion of the mixing The conduction of heat, liquid medium gasification will be helpful to ABS softening.
10. a kind of mixing characterized by comprising paste and ABS；Paste includes: 1 parts by weight of nano material, liquid Jie Matter 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but be not 0；Paste, which is covered, forms mixing in ABS particle surface；
Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are dispersed；
It is furthermore preferred that dispersing mode includes ultrasound, shearing, stirring, ball milling, colloid mill；
It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.
CN201810184681.XA 2018-03-06 2018-03-06 ABS (acrylonitrile butadiene styrene) nano composite material and preparation method thereof Active CN110229457B (en)

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CN113512265A (en) * 2021-07-29 2021-10-19 深圳免喷材料科技有限公司 Preparation method of anodic oxidation effect imitation spraying-free aesthetic ABS material

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CN106832354A (en) * 2017-02-24 2017-06-13 上海纳琳科新材料科技有限公司 A kind of preparation method for optical thin film hardening wear-resistant plastic particle
CN106832355A (en) * 2017-02-24 2017-06-13 先陶纳米材料科技（上海）有限公司 A kind of preparation method of the ultraviolet-resistant particle for optical thin film

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CN106832354A (en) * 2017-02-24 2017-06-13 上海纳琳科新材料科技有限公司 A kind of preparation method for optical thin film hardening wear-resistant plastic particle
CN106832355A (en) * 2017-02-24 2017-06-13 先陶纳米材料科技（上海）有限公司 A kind of preparation method of the ultraviolet-resistant particle for optical thin film

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Publication number Priority date Publication date Assignee Title
CN113512265A (en) * 2021-07-29 2021-10-19 深圳免喷材料科技有限公司 Preparation method of anodic oxidation effect imitation spraying-free aesthetic ABS material

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