CN110229426A - A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof - Google Patents
A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/20—Oxides; Hydroxides
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- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to field of nanocomposite materials, specifically, it is related to a kind of thermoplastic vulcanizates nanocomposite and preparation method thereof, the nanocomposite is as premix through made from melt blending, the premix is formed by being combined with full be adhered between thermoplastic vulcanizates particle of the nano material of liquid medium, and the thermoplastic vulcanizates includes polar plas and non-polar rubber.The preparation method includes that liquid medium and nano material are mixed to get paste, and the paste is adhered to thermoplastic vulcanizates particle surface progress melt blending and obtains nanocomposite.Nanocomposite provided by the invention has excellent toughness, and process flow is short, at low cost, is suitble to promote the use of.
Description
Technical field
The present invention relates to field of nanocomposite materials, specifically, being related to a kind of nano combined material of thermoplastic vulcanizates
Material and preparation method thereof.
Background technique
It is squeezed out in existing technology frequently with nano material and mixed with polymers, composite material is formed, although such is compound
The tensile strength of material is promoted, but the problems such as due to nano material and the poor compatibility of polymer, leads to such material
Impact resistance it is generally not high.
To solve the above problems, enabling polymer send out between the gap of nano material frequently with modes such as intercalation in-situ polymerizations
It is raw to react 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, using water
Auxiliary law prepares polyamide/nano montmorillonite masterbatch, and it is intercalator that preparation method, which is with deionized water, and the illiteracy of purifying is taken off
Mud is added step-wise to the polyamides that prescription amount melts completely by soil and deionized water mixing, fully dispersed obtained montmorillonite mud
Amine, then polyamide/nano montmorillonite masterbatch is obtained through extruding pelletization.Preparation method is simple, and production cost is low, but this method
It is to add montmorillonite mud after molten polyamide, will lead to montmorillonite mud and have not enough time to be thoroughly mixed with copolymer,
The water of interlayer just because of high-temperature gasification, causes polyamide to fail to timely enter interlayer, meanwhile, only by water generation
Energy, which is not enough to be completely exfoliated between cheating engaging layer, thus cannot obtain the composite material that type is completely exfoliated, properties of product
Receive strong influence.
In view of this, the present invention is specifically proposed.
Summary of the invention
The present invention is intended to provide a kind of nanocomposite, including nano material and thermoplastic vulcanizates, the nanometer
The stretched processing in the gap of material is not needed to carry out intercalation in-situ polymerization, can be further increased while promoting intensity
The toughness of thermoplastic vulcanizates nanocomposites.
In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that
A kind of thermoplastic vulcanizates nanocomposite, which is characterized in that the nanocomposite is by premix
Through made from melt blending, the premix is that the nano material of liquid medium is full to be adhered to thermoplastic vulcanizates by being combined with
It is formed between rubber grain, the thermoplastic vulcanizates includes polar plas and non-polar rubber.
In above scheme, thermoplastic vulcanizates has two phase structure, and the rubber particles of crosslinking are assigned as dispersed phase
For thermoplastic vulcanizates with the high resiliency of friendship and low compression set performance, thermoplastic resin is continuous phase, then is thermoplastic
Property the processing performance that provides of vulcanized rubber.According to the ratio of wherein non-polar rubber and polar plas difference, thermoplastic vulcanizates
The performance of rubber is partial to rubber or plastics respectively, with the reduction of rubber and plastic ratio, although bringing power for thermoplastic vulcanizates
The promotion of performance is learned, but also improves permanent elongation deformation quantity.Staff's discovery of the invention, uses stretched place
Nanocomposite made from the nano material and thermoplastic vulcanizates melting extrusion simultaneously of reason, can be relatively low in rubber and plastic
In the case where still keep lower permanent elongation deformation.
In above scheme, using macromolecule as the nanocomposite of base-material, in the mechanical property lifting process for representing intensity
In, it can be lost in terms of toughness, can even be lower than the toughness of base-material itself sometimes, reduce the scope of application of material；Study carefully
Its reason is due to poor compatibility between the part nano material component in composite material and part macromolecule, in addition, nanometer material
Material itself produce reunion in process, can not it is evenly dispersed in the composite, also result in certain mechanical properties
Missing.Nanocomposite provided by the invention is combined with liquid medium in nano material, and is combined with liquid for described
The nano material adherency of medium is wrapped in thermoplastic vulcanizates particle surface and forms mixture, by said mixture through melting
It is blended, enables liquid medium undergo phase transition using processing temperature-rise period, so that nano material is dispersed in thermoplastic vulcanizates
In, greatly improve the toughness of composite material.
In above scheme, the liquid medium include at least water, can also include isopentane, pentane, petroleum ether, oneself
Alkane, hexamethylene, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, three
Trichlorotrifluoroethane, propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, just
Butanol, butyl acetate, propyl alcohol, methylisobutylketone, tetrahydrofuran, ethyl acetate, isopropanol, ethyl alcohol, chloroform, methyl ethyl ketone,
Dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, second
Ether, pentane, methylene chloride, carbon disulfide, 1,1- dichloroethanes, 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, ethylene glycol
Monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, acetic anhydride, ortho-xylene, N, N- dimethyl formyl
One or more of amine, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE；Preferably water.
Further scheme of the invention are as follows: the nano material includes the one of zero dimensional nanometer materials or monodimension nanometer material
Kind is a variety of, and the liquid medium injects and fill the gap of nano material, forms the paste with tack.
Further scheme of the invention are as follows: the paste does not include: that the consistency of the paste is 0~100mm, but not
For 0mm；1 parts by weight of nano material, 0.02~100 parts by weight of liquid medium；Preferably, it is also preferable to include help the paste
0~50 parts by weight of agent, but be not 0.
In above scheme, compared to the prior art to nano-material modified filtering and dry process, nanometer of the invention
After material is between liquid medium is injected gap, paste continuous, and that there is certain tack, the paste are formd
Object has certain consistency, but consistency is not 0mm, represents the paste to be combined with liquid medium and having a constant current
The semisolid of dynamic property, therefore can be by the nano material paste uniform adhesion for being combined with liquid medium in thermoplasticity sulphur
Change rubber particle surface and improves machinability with the common feeding of thermoplastic vulcanizates particle to the equipment of melt blending
Energy.Preferably, in order to improve the amount of the combined liquid medium of nano material, auxiliary agent can also be added.
Further scheme of the invention are as follows: in the thermoplastic vulcanizates, the weight of polar plas and non-polar rubber
Than for 20~80:80~20, preferably 30~50:70~50；The polar plas include PU, PVC, PBT, PET, PMMA or
One of PA, non-polar rubber include one in natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers or butyl rubber
Kind.
Further scheme of the invention are as follows: the zero dimensional nanometer materials and monodimension nanometer material include nano silicon oxide, are received
Rice titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nanogold, nano silver, nano-silicon, are received nano-nickel oxide
Rice carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur, nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nanometer
Erbium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, is received nano-cerium oxide
One of rice tellurium oxide, nano oxidized niobium, nano-hafnium oxide or nanoscale molybdenum oxide are a variety of.
In above scheme, the ion exchange capacity between nano material and liquid medium is lower, and ion exchange does not almost occur,
So that liquid medium enters the paste that nano material forms high viscosity containing large amount of liquid amount, convenient for further processing.
Further scheme of the invention are as follows: the mass ratio of the nano material and thermoplastic vulcanizates is 0.1~20:
100, preferably 1~10:100, more preferably 3~8:100.
The present invention also provides a kind of preparation methods of thermoplastic vulcanizates nanocomposite, which is characterized in that institute
Preparation method is stated to include the following steps:
(1) liquid medium and nano material are mixed, obtain paste；
(2) paste will be obtained in step (1) to mix with thermoplastic vulcanizates particle, enables paste is full to be adhered to
Premix is obtained between thermoplastic vulcanizates particle；
(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；
Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste
Object.
In the above method, there is certain consistency semisolid paste since liquid medium and nano material to be mixed to get
Object, therefore slipping phenomenon will not occur for while being added to extrusion equipment after paste and thermoplastic vulcanizates particle mixing, it can
Direct feeding prepares nanocomposite, processing easy to produce, and avoids liquid medium in the prior art and gasify too early and cause
The poor problem of nanocomposite performance, 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.
According to above-mentioned preparation method, in step (3), when melt blending, moulded in temperature greater than or equal to thermoplastic polymer
When changing temperature, liquid medium gasification in nanometer mixing material, the gasification separates the nano material of reunion, while the gas
Change uniformly transfers heat in thermoplastic polymer and nano material；Preferably, the gasification is soft by thermoplastic polymer
Change, and reduces the plasticization temperature of thermoplastic polymer.
According to above-mentioned preparation method, in step (3), it is higher than the boiling point of liquid medium in the temperature of melt blending and reaches
During thermoplastic vulcanizates plasticization temperature, liquid medium gasification separates the nano material of reunion；The liquid is situated between
The boiling point of matter is lower than the plasticization temperature of thermoplastic vulcanizates, and the boiling point is preferably not higher than 180 DEG C, the liquid medium
Preferably water；The weight ratio of the liquid medium and nano material is 0.02~100:1, preferably 5~50:1, more preferably 5
~20:1.
In the above method, the application use will combine the higher nano material of liquid medium amount and thermoplastic vulcanizates
Process equipment is added simultaneously, due to the lyophile media processes (forming paste) previously to nano material, so that nanometer material
The liquid content of material improves, therefore when entering thermoplastic vulcanizates melting zone, although system temperature is already higher than liquid medium
Boiling point, but contained liquid medium is more between nano material gap makes the molten of phase transformation evaporation process and thermoplastic vulcanizates
The process of melting can carry out simultaneously, just make molten state thermoplastic vulcanizates that can smoothly enter into the gap of nano material, and improve
The impact property of final products.And in the prior art, the nano material containing liquid is added frequently with first melting is carried out to polymer
Technical solution, and due to the undertreatment to nano material lyophile medium, so that wherein liquid medium evaporation is too fast, drop
The low compatibility of nano material and thermoplastic vulcanizates, so that the toughness of final products declines；On the other hand, existing skill
In art, is first added to polymer melting the time that nano material undoubtedly extends product preparation, waste time cost.
According to above-mentioned preparation method, in step (3), what the paste and thermoplastic vulcanizates particle were mixed to get
Premix feeding to hot melt process equipment under the conditions of no pressure carries out melt blending.
In the above method, hot melt process equipment includes but is not limited to mixer, open mill or screw extruder (parallel/cone
Shape/mono-/bis -/tri- screw rods), when using screw extruder, the shape object and thermoplastic vulcanizates particle are mixed to get
Premix realizes the charging under the conditions of no pressure from without pressure feed zone charging.In the present invention, can by nano material directly with
Thermoplastic vulcanizates particle directly mixes and carries out feeding, has benefited from nano material and form in conjunction with liquid medium to have
The paste of certain consistency, it is therefore prevented that slipping phenomenon, on the other hand the content of the liquid medium as contained by nano material is higher,
Therefore premix pass through the first melting zone when, liquid medium therein will not too early phase transformation gasification so that melting thermoplasticity
Vulcanized rubber can preferably infiltrate between the gap of nano material the nanocomposite for forming good mechanical properties.
According to above-mentioned preparation method, the step (1) further includes auxiliary agent being added in nano material to improve nano material
Liquid content, the liquid medium for enabling the nano material be combined accounts for the 50~98% of paste gross mass, preferably 60~
98%, more preferably 80~98%.
According to above-mentioned preparation method, the mass ratio of the auxiliary agent and nano material is 0.01~50:1, preferably 0.1~
5:1, more preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfate salt surfactant, sulfonate
Surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant, heterocyclic type surface-active
Agent, nonionic surfactant, natural water soluble high molecular, one or more of synthetic water soluble high molecular and its prepolymer.
In the above method, the premix in the present invention during the preparation process, using thermoplastic vulcanizates as base-material, is used
The auxiliary agent of lower content, its purpose is to form the environment of lyophile medium between the gap of nano material, to improve
The liquid content of paste；High-content intercalator used in intercalation polymeric compared to the prior art, significantly reduces auxiliary agent pair
The influence of nanocomposite overall performance.
In above scheme, the ability that liquid medium enters nano material is can be improved in the addition of auxiliary agent, to increase nanometer
The consistency of material blends；In addition, the addition of auxiliary agent can also improve the boiling point of liquid medium, liquid medium gas in advance is prevented
Change evolution.Due to generating the reaction temperature of gel nano material in the present invention at room temperature, requirement to auxiliary agent
It is not high, therefore it is wider to be suitable for the invention the alternative range of auxiliary agent.
The auxiliary agent includes but is not limited to one or more of following component:
A. surfactant:
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.As benzalkonium chloride (trade name " geramine "),
Benzalkonium bromide (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.
B. 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 macromolecule and its prepolymer are synthesized
(1) polymeric type water soluble polymer and its prepolymer
Polyacrylamide, polyacrylic acid, polymethylacrylic acid and its copolymer, polyvinyl alcohol, polyethylene glycol, polyoxygenated
Ethylene, polyvinylpyrrolidone, polymaleic anhydride, polydimethyl diallyl ammonium chloride, polyvinylamine, poly- divinyl miaow
Oxazoline, sulfonate styrene maleic anhydride copolymer, opens Pu Shi resin at kayexalate.
(2) polycondensation class water soluble polymer and its prepolymer
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 formaldehydes, 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-soluble poly-sucrose.
3, semi-synthetic class macromolecule
Modified cellulose and converted starch.
Preferably synthetic class macromolecule and its prepolymer.
According to above-mentioned preparation method, nano material and the adding manner of auxiliary agent include being added at one time in the step (1)
It is added in batches；It is respectively 0.01-100g/min that speed, which is added, preferably 5-10g/min, more preferable 7g/min.
According to above-mentioned preparation method, the step (1) further includes implementing physical dispersion, the physics point to nano material
Dissipate includes but is not limited to colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock etc.；Preferably, the physical dispersion
For ultrasound, the frequency of the ultrasonic field is 800~1000Hz, and power is 200~1000W.
According to above-mentioned preparation method, the preparation method further includes addition latex shape in the paste made from step (1)
The mass ratio of resulting mixture, the later mixture and thermoplastic vulcanizates melt blending, the latex and paste is
0.1~10:1, the latex include styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane cream
Liquid, fluorine carbon emulsion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex,
One of white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of.
In the above method, after the completion of prepared by the nano material paste for being combined with liquid medium, latex can also be utilized
To paste precast body carry out mixed processing, and by after latex mixed processing paste and thermoplastic vulcanizates it is same
When melt blending carry out following process, above-mentioned mixed processing greatly delayed the release rate of liquid medium between gap, effectively
Prevent liquid medium from phase transformation occurs to early, on the other hand, the mixed processing of latex and paste further improves liquid Jie
The scale that nano material gap is expanded when matter phase transformation is conducive to the gap realization filling that polymer travels further into nano material.
According to above-mentioned preparation method, the preparation method further includes before or during melt blending to paste and heat
The age resister being added in the premix that plasticity vulcanized rubber particles are formed, the age resister and thermoplastic vulcanizates
Weight ratio is 0.1~1:100, preferably 0.3:100；The age resister is selected from amine antioxidants, and phenolic antioxidant is thio
One or more of dipropyl vinegar kind antioxidant and phosphorous vinegar kind antioxidant.
In the above method, the age resister includes:
Amine antioxidants: there are ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, hindered amine；
Phenolic antioxidant: alkylation monophenols, alkylation polyphenol, thiobisphenol and polyphenol can be divided into.Alkylation monophenols and
Polyphenol antioxidant principal item has antioxidant 264,1076,2246,1035,1010,3114 and 1790；Thiobisphenol it is main
Kind has antioxidant 2246 and 300；Polyatomic phenol antioxidant principal item has 2,5 1 di-t-butyl hydroquinones and 2,5 12 uncles penta
Base quinhydrones；
Thio-2 acid vinegar and phosphorous vinegar kind antioxidant；Its principal item has anti-aging agent TNP, Ultranox624 and Asia
Tricresyl phosphate (2,4 1 di-tert-butyl) ester.
Other type antioxidants: 2 one coloured glaze base benzo miaow trade name antioxidant MBs, dibutyl dithiocaarbamate
Nickel trade name antioxidant NBC, there are also zinc dialkyl dithiophosphates.
The age resister specifically includes: 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 2246,2,5- di-t-butyl hydrogen
Quinone, antioxidant TNP, Ultranox624, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, antioxidant MB, is prevented anti-oxidant DLTP
Old agent NBC, zinc dialkyl dithiophosphate.
The present invention also provides a kind of premix, the premix includes paste and thermoplastic vulcanizates, the heat
Plasticity vulcanized rubber includes polar plas and non-polar rubber；The paste includes: 1 parts by weight of nano material, liquid medium
5-100 parts by weight, auxiliary agent 0-50 parts by weight, but be not 0；The paste is covered in thermoplastic vulcanizates particle surface shape
At premix；Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium simultaneously
Dispersed；It is furthermore preferred that the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, etching auxiliary or air-flow
Impact；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 preparation method of above-mentioned thermoplastic vulcanizates composite material specifically comprises the following steps:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01~100g/min and is persistently stirred
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 0.02~100:1；
(2) it is once added in batches or into the lasting agitating solution of step (1) and helps with the speed of 0.01~100g/min
Agent, obtains paste, and the consistency of the paste is 0~100mm, and the weight ratio of the auxiliary agent and nano material is 0.001~
50:1；
(3) paste and thermoplastic vulcanizates particle that step (2) obtains are mixed to get premix；
(4) by the premix of step (3), feeding hot melting equipment, melt blending simultaneously carry out subsequent add under the conditions of no pressure
Work obtains nanocomposite.
According to the above method, when the hot melting equipment is screw extruder, engine speed is 30~80Hz, main feeding hopper
Revolving speed is 10~30Hz, and extrusion temperature is 150~200 DEG C of an area, two 220~260 DEG C of areas, three 220~260 DEG C of areas, 4th area
230~250 DEG C, five 210~250 DEG C of areas；It is preferred that engine speed is 50Hz, main feeding hopper revolving speed is 15Hz, extrusion temperature one
150~180 DEG C of area, two 245~255 DEG C of areas, three 240~250 DEG C of areas, four 240~250 DEG C of areas, five 230~250 DEG C of areas.Spiral shell
The linear velocity of bar revolving speed is 0.6~1m/s.
It further include carrying out mixed processing using latex and paste afterwards in step (2), then walked according to the above method
Suddenly the technique of (3).
The invention has the benefit that
1. thermoplastic vulcanizates nanocomposite provided by the invention has a distinct increment in tearing strength, have
Stable permanent elongation deformation, and simple process is easy to operate, and the used time is short, is suitable for promoting；
2. the present invention melts the higher nano material of liquid content with thermoplastic vulcanizates simultaneously, composite material is utilized
Heat in process improves the molecular energy of the liquid medium combined between nano material gap, and sky interstitial liquid is promoted to be situated between
Matter is undergone phase transition, and has expanded the gap of nano material, is filled out so that the thermoplastic vulcanizates of molten state enters gap realization
It fills；
3. nano material provided by the invention through auxiliary agent processing formed have compared with containing large amount of liquid amount paste, with thermoplastic
Property vulcanized rubber simultaneously during melt-processed, time and thermoplasticity sulphur that the liquid medium combined between gap is undergone phase transition
Changing the rubber melting time matches, and enters the gap of nano material conducive to the thermoplastic vulcanizates of molten state and is filled；
4. nano material provided by the invention is while using liquid medium phase transformation expansion gap, also playing is prevented
The effect that nano material is reunited.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the technology in embodiment
Scheme 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
In the present embodiment, the thermoplastic vulcanizates be EPDM/PA6, wherein rubber and plastic ratio be 70/30, nano material with
The mass ratio of thermoplastic vulcanizates is 15:100, and the liquid medium used is water, and the auxiliary agent used is water-soluble alcohol acid tree
Rouge, the nano material used are prepared as follows nanocomposite for nano oxidized praseodymium:
(1) liquid medium is stirred, while nano material is added with the speed of 3.5g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 14:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) in batches or once with the speed of 0.1g/min, obtained
Paste, the consistency of the paste are 40mm, and the weight ratio of the auxiliary agent and nano material is 20:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 10Hz, and extrusion temperature is 170 DEG C of an area,
Two 260 DEG C of areas, three 220 DEG C of areas, four 250 DEG C of areas, five 210 DEG C of areas, the linear velocity of screw speed are 0.8m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 56KN/m, permanently
Tensile deformation is 18%.
Embodiment 2
In the present embodiment, the thermoplastic vulcanizates be EPDM/PA6, wherein rubber and plastic ratio be 20/80, nano material with
The mass ratio of thermoplastic vulcanizates is 10:100, and used liquid medium is pyridine and water, and the mass ratio of pyridine and water is
1:4, used auxiliary agent are gellan gum and hyaluronic acid, and weight ratio 1:2, the nano material used presses for nano zine oxide
Nanocomposite is prepared according to following method:
(1) liquid is stirred, while nano material is added with the speed of 15g/min and is persistently dispersed with stirring
Even, the weight ratio of liquid medium and nano material is 90:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 5g/min, obtains paste, the cream
The consistency of shape object is 58mm, and the weight ratio of the auxiliary agent and nano material is 10:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 50Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C,
Two 250 DEG C of areas, three 235 DEG C of areas, four 240 DEG C of areas, five 245 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 58KN/m, permanently
Tensile deformation is 20%.
Embodiment 3
In the present embodiment, the thermoplastic vulcanizates be EPDM/PA6, wherein rubber and plastic ratio be 50/50, nano material with
The mass ratio of thermoplastic vulcanizates is 1:10, and the liquid medium used is water, and the auxiliary agent used is poly dimethyl allyl
Ammonium chloride, for nano-titanium dioxide and nano aluminium oxide, mass ratio 8:2 is prepared as follows the nano material used
Nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01g/min and carries out continuing stirring
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 0.1:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 15g/min, obtains paste, it is described
The consistency of paste is 73mm, and the weight ratio of the auxiliary agent and nano material is 4.5:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 30Hz, and main feeding hopper revolving speed is 10Hz, and one area of extrusion temperature is 150 DEG C,
Two 220 DEG C of areas, three 220 DEG C of areas, four 230 DEG C of areas, five 210 DEG C of areas；The linear velocity of screw speed is 0.9m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 59KN/m, permanently
Tensile deformation is 21%.
Embodiment 4
In the present embodiment, the thermoplastic vulcanizates be EPDM/PET, wherein rubber and plastic ratio be 70/30, nano material with
The mass ratio of thermoplastic vulcanizates is 7:100, and for isobutanol, the auxiliary agent used uses the liquid medium used for glycine betaine
Nano material be carbon nano-fiber, the age resister used is prepared as follows nano combined for antioxidant 4010NA
Material:
(1) liquid medium is stirred, while nano material is added with the speed of 12g/min and carries out continuing stirring point
Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material
Weight ratio is 6:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 100g/min, obtains paste, it is described
The consistency of paste is 75mm, and the weight ratio of the auxiliary agent and nano material is 0.05:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix feeding mixer of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tearing strength of finally obtained thermoplastic vulcanizates nanocomposite is 61KN/m, permanent elongation deformation
It is 23%.
Embodiment 5
In the present embodiment, the thermoplastic vulcanizates be EPDM/PET, wherein rubber and plastic ratio be 80/20, nano material with
The mass ratio of thermoplastic vulcanizates is 4:100, and the liquid medium used is dimethylbenzene and water, mass ratio 1:15, use
Auxiliary agent is fatty acid sorbitan, and the nano material used is prepared as follows nanocomposite for Nanometer-sized Neodymium Oxide:
(1) liquid medium is stirred, while nano material is added with the speed of 0.5g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 0.5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 1g/min, obtains paste, the cream
The consistency of shape object is 47mm, and the weight ratio of the auxiliary agent and nano material is 0.1:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix feeding open mill of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tearing strength of finally obtained thermoplastic vulcanizates nanocomposite is 65KN/m, permanent elongation deformation
It is 16%.
Embodiment 6
In the present embodiment, the thermoplastic vulcanizates be SBR/PBT, wherein rubber and plastic ratio be 70/30, nano material with
The mass ratio of thermoplastic vulcanizates is 4:100, and for water, the auxiliary agent used uses the liquid medium used for polyethylene glycol oxide
Nano material be nano silicon oxide, the age resister used is prepared as follows nano combined for Ultranox624
Material:
(1) liquid medium is stirred, while nano material is added with the speed of 0.2g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 10:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.1g/min, obtains paste, it is described
The consistency of paste is 48mm, and the weight ratio of the auxiliary agent and nano material is 5:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 45Hz, and main feeding hopper revolving speed is 25Hz, and one area of extrusion temperature is 180 DEG C,
Two 260 DEG C of areas, three 240 DEG C of areas, four 250 DEG C of areas, five 250 DEG C of areas；The linear velocity of screw speed is 0.7m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 63KN/m, permanently
Tensile deformation is 19%.
Embodiment 7
In the present embodiment, the thermoplastic vulcanizates be SBR/PBT, wherein rubber and plastic ratio be 50/50, nano material with
The mass ratio of thermoplastic vulcanizates is 2:100, and the liquid medium used is water and diethyl ether, the mass ratio of water and diethyl ether
5:1, used auxiliary agent are fatty acid methyl ester APEO, and the nano material used is nano-hafnium oxide, according to such as lower section
Method prepares nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 10g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 20:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 33g/min, obtains paste, it is described
The consistency of paste is 78mm, and the weight ratio of the auxiliary agent and nano material is 3.3:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix feeding open mill of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tearing strength of finally obtained thermoplastic vulcanizates nanocomposite is 62KN/m, permanent elongation deformation
It is 25%.
Embodiment 8
In the present embodiment, the thermoplastic vulcanizates be EPDM/PA6, wherein rubber and plastic ratio be 80/20, nano material with
The mass ratio of thermoplastic vulcanizates be 6:100, the liquid medium used for water, the auxiliary agent used for dicyandiamide formaldehyde resin,
The nano material used is prepared as follows nanocomposite for nano zine oxide:
(1) liquid medium is stirred, while nano material is added with the speed of 0.5g/min and carries out continuing stirring point
Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material
Weight ratio is 5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 20g/min, obtains paste, it is described
The consistency of paste is 46mm, and the weight ratio of the auxiliary agent and nano material is 60:1；
(3) paste and thermoplastic vulcanizates that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 25Hz, and one area of extrusion temperature is 160 DEG C,
Two 245 DEG C of areas, three 240 DEG C of areas, four 245 DEG C of areas, five 235 DEG C of areas；The linear velocity of screw speed is 0.6m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 55KN/m, permanently
Tensile deformation is 20%.
Embodiment 9
In the present embodiment, the thermoplastic vulcanizates be EPDM/PA6, wherein rubber and plastic ratio be 50/50, nano material with
The mass ratio of thermoplastic vulcanizates is 18:100, and the liquid medium used is water, and the auxiliary agent used is water soluble amino resin
With ammonia-epichlorohydrin resin, water soluble amino resin and ammonia-epichlorohydrin resin mass ratio are 10:1, used
Nano material is carbon nanotube, is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 12g/min and carries out continuing stirring point
Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material
Weight ratio is 48:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 15g/min, obtains paste, it is described
The consistency of paste is 85mm, and the weight ratio of the auxiliary agent and nano material is 5:1, further, by paste and carboxyl fourth
Benzene latex mixed processing；
(3) paste mixed with carboxylic styrene butadiene latex that step (2) obtains is mixed to get with thermoplastic vulcanizates
Premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 80Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 200 DEG C,
Two 240 DEG C of areas, three 220 DEG C of areas, four 230 DEG C of areas, five 210 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 64KN/m, permanently
Tensile deformation is 15%.
Comparative example 1
In this comparative example, on the basis of embodiment 1, the position of extruder is added in adjustment nano material containing liquid, in no pressure
Feeding thermoplastic vulcanizates under the conditions of power, in thermoplastic vulcanizates after melting zone, pressurization will contain liquid between gap
The nano material feeding of medium is mixed with the thermoplastic vulcanizates of molten state.
The difference of comparative example 1 and embodiment is: containing the nano material of liquid medium between thermoplastic vulcanizates and gap
And non-concurrent feeding, but first feeding thermoplastic vulcanizates and after thermoplastic vulcanizates melting, feeding gap of pressurizeing
Between be combined with the nano material of liquid medium and processed.
The tearing strength for the thermoplastic vulcanizates nanocomposite that final extruding pelletization obtains is 32KN/m, permanently
Tensile deformation is 35%.
Mechanics Performance Testing is carried out to Examples 1 to 9 and comparative example 1, respectively obtains tearing strength and permanent elongation deformation
Performance parameter it is as shown in the table:
As seen from the above table, the mechanical property of nanocomposite obtained by Examples 1 to 9 is above the performance ginseng of comparative example 1
Number, promoted especially in tearing strength it is obvious, to find out its cause, be the present invention using liquid medium phase transformation to nano material into
It has gone divergence process, has been filled so that entering between gap with the thermoplastic vulcanizates that nano material melts simultaneously, above-mentioned sky
The heat that processing generates when polymer melting is utilized in divergence process between gap enables liquid medium evaporation generate implosion and struts gap,
Simultaneously using the shearing force for squeezing out processing, gap is further peeled off, so that molten state thermoplastic vulcanizates realizes filling, from
And improve the mechanical property of product.
Further, the rubber and plastic ratio in embodiment 9 is not high, but tool compares Examples 1 to 8 with minimum permanent drawing
Deformation is stretched, relevant staff of the invention thinks, while the nano material of stretched processing promotes the rigidity of product,
Thermoplastic vulcanizates microfacies interface energy is also improved, the compatibility of co-mixing system is increased, to play stable dimensions
Effect, so that permanent elongation deformation is smaller.
The above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that this hair
It is bright to be not limited to specific embodiment described here, be able to carry out for a person skilled in the art it is various it is apparent variation, again
Adjustment and substitution are without departing from protection scope of the present invention.Therefore, although by above embodiments to the present invention carried out compared with
To be described in detail, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, may be used also
To include more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (10)
1. a kind of thermoplastic vulcanizates nanocomposite, which is characterized in that
The nanocomposite is as premix through made from melt blending, the premix is by being combined with liquid medium
Nano material is full to be adhered to and is formed between thermoplastic vulcanizates particle, the thermoplastic vulcanizates include polar plas and
Non-polar rubber.
2. nanocomposite according to claim 1, which is characterized in that the nano material includes zero dimensional nanometer materials
Or monodimension nanometer material is one or more, the liquid medium injects and fills the gap of nano material, and being formed has self-adhesion
The paste of property；The zero dimensional nanometer materials and monodimension nanometer material include nano silicon oxide, and nano-titanium oxide is nano oxidized
Zirconium, 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, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium,
One of nano-hafnium oxide or nanoscale molybdenum oxide are a variety of.
3. composite material according to claim 1 or 2, which is characterized in that the consistency of the paste is 0~100mm, but
It is not 0mm；
The paste includes:
1 parts by weight of nano material
0.02~100 parts by weight of liquid medium；
The paste it is also preferable to include,
0~50 parts by weight of auxiliary agent, but be not 0.
4. composite material according to any one of claims 1 to 3, which is characterized in that in the thermoplastic vulcanizates,
The weight ratio of polar plas and non-polar rubber is 20~80:80~20, preferably 30~50:70~50；The polar plas
Including one of PU, PVC, PBT, PET, PMMA or PA, non-polar rubber include natural rubber, butadiene-styrene rubber, butadiene rubber,
One of EP rubbers or butyl rubber.
5. composite material described in any one according to claim 1~4, which is characterized in that the nano material and thermoplasticity
The mass ratio of vulcanized rubber is 0.1~20:100, preferably 1~10:100, more preferably 3~8:100.
6. a kind of preparation method of thermoplastic vulcanizates nanocomposite, which is characterized in that the preparation method includes such as
Lower step:
(1) liquid medium and nano material are mixed, obtain paste；
(2) paste will be obtained in step (1) to mix with thermoplastic vulcanizates particle, enables paste is full to be adhered to thermoplasticity
Premix is obtained between vulcanized rubber particles；
(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；
Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste.
7. preparation method according to claim 6, which is characterized in that high in the temperature of melt blending in the step (3)
In liquid medium boiling point and during reaching thermoplastic vulcanizates plasticization temperature, liquid medium gasification, by receiving for reunion
Rice material separation；The boiling point of the liquid medium is lower than the plasticization temperature of thermoplastic vulcanizates, and the boiling point is preferably not high
In 180 DEG C, the liquid medium is preferably water；The weight ratio of the liquid medium and nano material is 0.02~100:1, preferably
For 5~50:1, more preferably 5~20:1.
8. preparation method according to claim 6 or 7, which is characterized in that the step (1) further includes in nano material
Auxiliary agent is added to improve the liquid content of nano material, the liquid medium for enabling the nano material be combined accounts for paste gross mass
50~98%, preferably 60~98%, more preferably 80~98%；The auxiliary agent and the mass ratio of nano material be 0.01~
50:1, preferably 0.1~5:1, more preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfuric acid table
Face activating agent, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant,
Heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular, in synthetic water soluble high molecular and its prepolymer
It is one or more of.
9. preparation method according to any one of claims 6 to 8, which is characterized in that the preparation method further include
Latex is added in paste made from step (1) and forms mixture, the mixture and thermoplastic vulcanizates melting later is altogether
Mixed, the mass ratio of the latex and paste is 0.1~10:1, and the latex includes styrene-acrylic emulsion, acrylic acid ester emulsion, propylene
Yogurt liquid, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, water-base epoxy
Resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, in styrene-acrylic latex
It is one or more.
10. a kind of premix characterized by comprising
The premix includes paste and thermoplastic vulcanizates, and the thermoplastic vulcanizates includes polar plas and non-pole
Property rubber；
The 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；
The paste, which is covered, forms premix in thermoplastic vulcanizates 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 the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, etching auxiliary or gas shock；
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.
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