CN110229506A - A kind of mixing and preparation method thereof - Google Patents

A kind of mixing and preparation method thereof Download PDF

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Publication number
CN110229506A
CN110229506A CN201810185073.0A CN201810185073A CN110229506A CN 110229506 A CN110229506 A CN 110229506A CN 201810185073 A CN201810185073 A CN 201810185073A CN 110229506 A CN110229506 A CN 110229506A
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nano
thermoplastic polymer
mixing
liquid medium
auxiliary agent
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CN110229506B (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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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 a kind of mixings, cover object including thermoplastic polymer and the paste covered on thermoplastic polymer particles surface, cover the nano material, liquid medium and the auxiliary agent that are 1:5-100:0-50 containing mass ratio in object.Further relate to a kind of preparation method of mixing as described above, comprising: (1) mix nano material, liquid medium and auxiliary agent, obtained paste covers object；(2) object will be covered to mix with thermoplastic polymer, and will make to cover object and is covered in thermoplastic polymer particles surface, mixing is made.It is of the invention to cover object and be added under passive state into reaction system, processing easy to produce, this is covered after object mixes with thermoplastic polymer, it covers on thermoplastic polymer particles surface, obtained mixing will not skid after being added in the equipment such as extruder, nanocomposite, processing easy to produce can be directly prepared, and avoids the problem that nanocomposite performance is poor caused by liquid medium in the prior art gasifies too early.

Description

A kind of mixing and preparation method thereof
Technical field
The present invention relates to a kind of mixings 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 mixing, nano combined material made from the mixing Expect that performance is more superior.
In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that
A kind of mixing covers object including thermoplastic polymer and the paste covered on thermoplastic polymer particles surface, glues Cover the nano material, liquid medium and the auxiliary agent that are 1:5-100:0-50 containing mass ratio in object.
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 one kind to cover object, tool Body, the mixture of nano material and liquid medium viscosity under the action of auxiliary agent increases to form paste, and the object that covers is half Solid can be added under passive state into reaction system, processing easy to produce, this covers object can be mixed with thermoplastic polymer It closes, and covers on thermoplastic polymer particles surface, obtain mixing, which will not beat after being added in the equipment such as extruder It is sliding, nanocomposite can be directly prepared, it is not necessary that other materials, processing easy to produce are added during the preparation process, and is avoided The poor problem of nanocomposite performance caused by liquid medium gasifies too early in the prior art, through experiments, it was found that, compared to The prior art, nanocomposite performance made from mixing of the invention are more superior.Auxiliary agent of the invention also improves liquid It is poor to further avoid nanocomposite performance caused by liquid medium in the prior art gasifies too early for the boiling point of medium Problem.
Preferably, the mass ratio of nano material, liquid medium and auxiliary agent is 1:5-20:2-10；It is furthermore preferred that nanometer material The mass ratio of material, liquid medium and auxiliary agent is 1:10:5
Covering object consistency is 0-100mm, but is not 0.Consistency corresponds to standard JBJ/T70-2009.
The mass ratio for covering the nano material and thermoplastic polymer in object is 0.1-20:100；It is preferred that 1-10:100；More It is preferred that 4:100.
Mixing further includes age resister, and the mass ratio of age resister and thermoplastic polymer is 0.1:100~1:100；It is excellent Select 0.3:100.
Covering the nano material in object is the mixed of one or more of the nano material of zero dimension, one-dimensional nano material It closes.Covering the nano material in object is non-laminar nano material.
Covering the nano material in object is nano silicon oxide, nano-titanium oxide, nano zircite, nano zine oxide, nanometer Aluminium oxide, nano-nickel oxide, nanogold, nano silver, nano-silicon, nano-sized carbon, carbon nano-fiber, carbon nanotube, are received nano-graphite Rice boron powder, nano-sulfur, nano lanthanum oxide, it is Nanometer-sized Neodymium Oxide, nano oxidized erbium, nano-cerium oxide, nano oxidized praseodymium, nano oxidized It is yttrium, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide, nano oxidized The mixing of one or more of molybdenum.
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 thermoplastic polymer, 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.
Thermoplastic polymer includes:
1, copoly type thermoplastic polymer, such as SDS styrenic elastomer, TPU polyurethane elastomer, polyesters elasticity Body, polyamide-based elastomer, ethylene octane copolymer.
2, blending type thermoplastic polymer, such as TPO rubber plastic blend, TPV thermoplastic vulcanizates, wherein TPV thermoplasticity sulphur Changing rubber includes (1) non-polar rubber non-polar plastic, such as EPDM/PP, NR/PE or PP, IIR/PP；(2) polar rubber & Non-polar plastic, such as NBR/PP, acrylic rubber/PP；(3) non-polar rubber & polar plas, such as EPDM/PA6, EPDM/PBT； (4) polar rubber & polar plas, such as acrylic rubber/polyester, NBR/PA.
3, engineering plastics, as PA, PC, polyformaldehyde, polyphenylene oxide, polyester, polyimides, polysulfones, poly(aryl ether ketone), fluoroplastics, Chlorinated polyether.
4, general-purpose plastics, such as PE, PP, PVC, PS, acrylic resin, phenolic resin, amino resins, epoxy resin, poly- ammonia Ester.
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 the preparation methods of a kind of as above any mixing, comprising:
(1) nano material, liquid medium and auxiliary agent are mixed, obtained paste covers object；
(2) object will be covered to mix with thermoplastic polymer, and will make to cover object and is covered in thermoplastic polymer particles surface, be made Mixing.
During the melt blending for covering object and thermoplastic polymer, all hot melt processing technologies can be used, 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, is made and cover object.
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。
Nanocomposite is made through melt blending in mixing of the invention, and preparation method specifically includes:
(1) nano material, liquid medium and auxiliary agent are mixed, is made and covers object；
(2) object and thermoplastic polymer mixing will be covered, makes to cover object and covers on thermoplastic polymer particles surface, be made Mixing；
(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.
In step (3), comprising:
(1) heat temperature raising, thermoplastic polymer with cover in object liquid medium, nano material first stirring under mix It contacts, 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, and at this stage, thermoplastic polymer is gradually Soften and under stirring with cover object and interpenetrate, so that thermoplastic polymer is contacted with each other with liquid medium and nano material Cladding.
In step (3), when mixing melt blending, when temperature is greater than or equal to thermoplastic polymer plasticization temperature, cover Liquid medium in object further gasifies, and the nano material of reunion is separated.
In the melt blending stage, thermoplastic polymer is in molten condition, at this point, liquid medium gasifies, makes the nanometer reunited Material is separated from each other, and thermoplastic polymer is flow between nano material, to improve nano material in thermoplastic polymer Dispersion effect.
In step (3), when mixing melt blending, liquid medium gasification promotes the mobility of the mixing and promotes heat Conduction, liquid medium gasification softens hot thermoplastic polymer, and reduces its plasticization temperature.
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, thermoplastic polymer coats nano material and liquid medium, obtains Mixture, in melt blending, while mixture is by external shear action, also by the gasification of internal liquid medium, two Under person's effect, explosion occurs for mixture, and while liquid medium escapes, the thermoplastic polymer of molten condition enters nano material Between.To realize explosion, the melt pressure of thermoplastic polymer should be greater than the vapour pressure of liquid medium.The present invention is also possible that first right It covers object to be coated, then the object that covers of cladding is mixed with thermoplastic elastomer (TPE), coating includes: styrene-acrylic emulsion, acrylic acid Ester lotion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin resin lotion, terpinol, the third cream of vinegar Liquid, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, Styrene-acrylic latex.Above-mentioned cladding has greatly delayed interlayer liquid medium in the release rate in melt blending stage, effectively prevent liquid Phase transformation occurs to early in body medium, on the other hand, the scale of the expansion of interlayer when further improving liquid medium phase transformation, and favorably Interlayer, which is traveled further into, in polymer realizes filling.
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.And liquid medium enters stratified nano materials interlayer in step (1), molten Melt the blending stage, the liquid medium gasification of stratified nano materials interlayer makes at least partly lamella separation, the thermoplasticity of molten condition Polymer flows between isolated lamella, to improve dispersion effect of the nano material in thermoplastic polymer.Lamella does not divide From stratified nano materials interlamellar spacing increase, the thermoplastic polymer of molten condition flows into interlayer, to improve thermoplasticity polymerization The compatibility of object and stratified nano materials.Wherein, auxiliary agent makes more liquid mediums enter stratified nano materials interlayer, thus into One step improves the interlamellar spacing of stratified nano materials.In melt blending, explosion also occurs for the interlayer of stratified nano materials, make to The separation of small part lamella, the thermoplastic polymer of molten condition enter between the lamella of separation, the unsegregated laminar nano of lamella Material interlamellar spacing increases, and the thermoplastic polymer of molten condition enters interlayer.
Compared with prior art, the invention has the following beneficial effects:
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 one kind to cover object, tool Body, the mixture of nano material and liquid medium viscosity under the action of auxiliary agent increases to form paste, and the object that covers is half Solid can be added under passive state into reaction system, processing easy to produce, this covers object can be mixed with thermoplastic polymer It closes, and covers on thermoplastic polymer particles surface, obtain mixing, which will not beat after being added in the equipment such as extruder It is sliding, nanocomposite can be directly prepared, it is not necessary that other materials, processing easy to produce are added during the preparation process, and is avoided The poor problem of nanocomposite performance caused by liquid medium gasifies too early in the prior art.
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 PA6, 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 PP, 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 PC, 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 PPO, 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 POM, 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 for covering object.2 gained of embodiment is nano combined Material property is better than comparative example 2, it follows that the present invention first mixes with thermoplastic polymer by that will cover object, 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 mixing, which is characterized in that including thermoplastic polymer and cover the paste on thermoplastic polymer particles surface Object is covered, the nano material, liquid medium and the auxiliary agent that are 1:5-100:0-50 containing mass ratio in object are covered.
2. a kind of mixing according to claim 1, which is characterized in that covering object consistency is 0-100mm, but is not 0.
3. a kind of mixing according to claim 1 or 2, which is characterized in that cover the nano material and thermoplastic poly in object The mass ratio for closing object is 0.1-20:100；It is preferred that 1-10:100；More preferable 4:100.
4. a kind of mixing according to claim 1 to 3, which is characterized in that further include age resister, age resister with The mass ratio of thermoplastic polymer is 0.1:100~1:100；It is preferred that 0.3:100.
5. a kind of mixing according to claim 1 to 4, which is characterized in that covering the nano material in object is zero dimension The mixing of one or more of nano material, one-dimensional nano material；
Preferably, covering nano material in object is nano silicon oxide, nano-titanium oxide, nano zircite, and nano zine oxide is received Rice 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 oxygen Change yttrium, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide, nano oxygen Change the mixing of one or more of molybdenum.
6. a kind of mixing according to claim 1 to 4, which is characterized in that auxiliary agent includes carboxylate surface active agent, Sulfate salt surfactant, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary ammonium salt Surfactant, heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular, synthetic water soluble high molecular；
Preferably, the boiling point of liquid medium is lower than the plasticization temperature of thermoplastic polymer, and liquid medium includes water.
7. a kind of preparation method of any mixing of claim 1-5 characterized by comprising
(1) nano material, liquid medium and auxiliary agent are mixed, obtained paste covers object；
(2) object will be covered to mix with thermoplastic polymer, and will make to cover object and is covered in thermoplastic polymer particles surface, and be made mixed Material.
8. a kind of mixing according to claim 7, which is characterized in that in step (1), successively add nano material and auxiliary agent Enter into liquid medium and disperse, is made and covers object.
9. a kind of mixing according to claim 8, which is characterized in that dispersing mode include ultrasound, shearing, stirring, ball milling, Colloid mill.
10. a kind of mixing according to claim 8, which is characterized in that nano material and the adding manner of auxiliary agent include one Secondary property is added and is added in batches.
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