CN110229495A - A kind of preparation method of nanocomposite - Google Patents

Abstract

The invention discloses a kind of preparation methods of nanocomposite, which is characterized in that preparation method obtains paste nanometer mixing material the following steps are included: A, liquid medium and nano material be mixed；B, nanometer mixing material described in step A and thermoplastic polymer are mixed to get blend；C, blend in step B is subjected to melt blending, obtains nanocomposite.The method simple process, production cost is low, easily promotes, and the nanocomposite of production impact strength with higher and tensile strength can be used widely in fields such as aerospace, national defence, traffic, sport.

Description

A kind of preparation method of nanocomposite

Technical field

The invention belongs to technical field of composite materials, specifically, being related to a kind of preparation method of nanocomposite.

Background technique

Nanocomposite be using matrixes such as resin, rubber, ceramics and metals as continuous phase, with the metal of nano-scale, The modifying agent such as semiconductor, rigid particles and other inorganic particulates, fiber, carbon nanotubes are dispersed phase, pass through preparation side appropriate Method disperses modifying agent uniformity in basis material, forms the compound system that a phase contains nano-sized materials, this one Based material is referred to as nanocomposite.Using thermoplastic polymer as the nanocomposite of matrix because its high intensity, high abrasion, The excellent combinations characteristic such as high rebound, high tenacity, tear-resistant, processable, recyclable, has been widely used in national defence, automobile, fortune The fields such as dynamic, medical treatment, coating.The preparation method of thermoplastic nanocomposites mainly uses in-situ inserted and fusion intercalation at present Method preparation.Because in-situ inserted industrial investment is big, the period is long, it is more difficult to a wide range of to promote and apply；Fusion intercalation can be in general plastics It is carried out in mixing facilities, it is easy to process, however need carry out the intercalation processing that organises to nano material early period, it is not easy to it obtains completely The nano composite material of removing.With nanocomposite answering extensively in fields such as aerospace, national defence, traffic, sport With to the impact resistance of nanocomposite, tensile strength etc. has higher requirement, accordingly, it is desirable to provide a kind of method is simple Single, production cost is low, easily promotes, the preparation method of the nanocomposite of impact strength and tensile strength with higher.

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 is just because of high-temperature gasification, and then montmorillonite cannot be dispersed in polyamide very well, so that properties of product promotion is limited；In addition, covering De- soil mud, which needs to increase on feed way certain pressure, to inject twin-screw for mud, simultaneously because the processing of twin-screw Section is short, increases the feeding section of montmorillonite mud halfway, it is necessary to increase twin-screw length, cause technique more complicated, cost It is higher.

In view of this present invention is specifically proposed.

Summary of the invention

The technical problem to be solved in the present invention is that it is simple to overcome the deficiencies of the prior art and provide a kind of method, it is produced into This is low, easily promotes, the preparation method of the nanocomposite of impact strength and tensile strength with higher.

In order to solve the above technical problems, the present invention provides a kind of preparation method of nanocomposite, comprising the following steps:

A, liquid medium and nano material are mixed, obtain paste nanometer mixing material；

B, nanometer mixing material described in step A and thermoplastic polymer are mixed to get blend；

C, blend in step B is subjected to melt blending, obtains nanocomposite.

In above scheme, nano material is entered by liquid medium, lower be made with certain tack is being sufficiently stirred Paste nanometer mixing material, the paste nanometer mixing material, which mixes to mix thoroughly with thermoplastic polymer, can be directly added into charging Area, without midway feeding, saves technique and reduces costs without applying pressure.In addition, nano material polymerize with thermoplasticity Be added after object mixing, then through melt blending, the thermoplastic polymer of melting can envelope nano material to form protective layer, when into Entering the liquid medium gasification of nano material can generate huge when the vapour pressure in nano material is greater than melt of thermoplastic polymers pressure Big interior violence separates nano material, and isolated nano material is just evenly dispersed into thermoplastic polymer.

In above scheme, in step, dispersion of the liquid medium in nano material, institute can be promoted by physics mode Stating physics mode includes but is not limited to that the modes such as ultrasound, colloid mill, ball milling, vortex, etching auxiliary, gas shock stir, described The frequency of ultrasound is 800~1000Hz, and power is 200~1000W.

In above scheme, latex can also be added and envelope the paste nanometer mixing material that step A is obtained, the cream Glue includes: styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin Resin emulsion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, One of pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of, preferably styrene-acrylic emulsion, silicone acrylic emulsion, acrylate and vinyl acetate emulsion, One of styrene-acrylic latex is a variety of.

Latex is added in above scheme to coat nanometer mixing material, protective layer is formed, when nanometer mixing material and thermoplastic Property polymer melting when being blended, the liquid medium into nano material gasifies, when vapour pressure in protective layer is greater than polymer Melt can generate implosive force when pressing, and the nano material of reunion is separated, and receive using continuous stirring and/or shearing, separation Rice material can be highly dispersed in the thermoplastic polymer of melting.

In above scheme, the melting extrusion technique in step C can be mixing, mill, screw rod (parallel/taper/mono-/bis -/tri- Screw rod).

In above scheme, when using double screw extruder, the present invention solves nano material very well and polymerize with thermoplasticity The case where object has skidded, can not feed simultaneously when feeding, realizes thermoplastic polymer and nano material and deposits in liquid medium Mixed feeding in case, and without pressure is applied when feeding, in addition, in polymer and nano material in melting process In can make nano material in thermoplastic polymer by the implosive force of the shearing force of double screw extruder and liquid medium gasification Dispersion it is more abundant.

In above scheme, when using double screw extruder, technological parameter are as follows: engine speed 30-80Hz, main feeding hopper Revolving speed is 10-30Hz, and extrusion temperature is 150-200 DEG C of an area, two 230-280 DEG C of areas, three 230-280 DEG C of areas, four area 230-280 DEG C, five 230-280 DEG C of areas；It is preferred that engine speed is 60-80Hz, main feeding hopper revolving speed is 20-30Hz, and extrusion temperature is an area 150-180 DEG C, two 245-260 DEG C of areas, three 245-260 DEG C of areas, four 245-260 DEG C of areas, five 245-260 DEG C of areas.

Further, the auxiliary agent to improve paste nanometer mixing material consistency is additionally added in step A, the 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, One of synthetic water soluble high molecular and its prepolymer are a variety of；Wherein in preferably synthetic water soluble polymer and its prepolymer It is one or more；

Preferably, the mass parts ratio of the auxiliary agent and nano material is 0.01~50:1；It is preferred that 0.1~5:1；More preferably 0.2~1:1.

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, prevent liquid medium from gasifying in advance Evolution.Due to generating the reaction temperature of paste nanometer mixing 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 include surfactant, water soluble polymer and One of its prepolymer is a variety of, preferably water soluble polymer and its prepolymer, more preferable poly-aspartate, lecithin, sea Mosanom, polymeric acid, polyvinylamine, hyaluronic acid；

Wherein 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 and heterocyclic type.

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 is synthesized

(1) polymeric type water soluble polymer

Polymer amide, polymeric 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；

Further, the consistency of the paste nanometer mixing material is 0~100mm, but is not 0.

In above scheme, liquid medium is mixed to form the paste nano material with certain self-adhering-type with nano material and mixes Object, when its consistency be 0~100mm, but be 0 when, the paste nanometer mixing material of formation can be by thermoplastic polymer Particle adheres to and realizes common charging.

Further, step B obtains the blend of paste nanometer mixing material adherency thermoplastic polymer；

Preferably, age resister, the mass parts of the age resister and thermoplastic polymer are additionally added in the blend Number is than being 0.1~1:100；It is preferred that 0.2~0.4:100；More preferable 0.3~0.4:100.

In above scheme, paste nano material and thermoplastic polymer with certain consistency are mixed, the paste Nanometer mixing material is just adhered to thermoplastic polymer surface, since this paste nanometer mixing material itself also has oneself certain Viscosity forms the blend for passing through the mutual adhesion of paste nanometer mixing material between thermoplastic polymer particles, just so as to reality Existing thermoplastic polymer and nano material are fed jointly in the presence of liquid medium.

In above scheme, age resister can also be added in stepb to reduce liquid medium to nanocomposite The mass parts ratio of the influence of energy, the age resister and thermoplastic polymer is 0.1~1:100；It is preferred that 0.2~0.4:100； More preferable 0.3~0.4:100.

The age resister be selected from amine antioxidants, have ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, by Hinder 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 One of thiophosphoric acid zinc is a variety of；It is preferred that anti-aging agent RD, antioxidant A W, antioxidant 4010NA, antioxidant 3114, antioxygen Agent 264.

Further, include: in step C

(1) liquid medium, nano material in heat temperature raising, thermoplastic polymer and nanometer mixing material are in the first stirring Under be mixed, soften and interpenetrate cladding；

(2) after the boiling point that temperature is greater than liquid medium, liquid medium portion gasification, the gasification carries out blend Second stirring；

In above scheme, thermoplastic polymer further contacts mixing by being stirred continuously with liquid medium, nano material, As temperature increases, thermoplastic polymer starts to soften, and the polymer of softening coats nano material, thus formed polymer with Nano material interpenetrates the blend of cladding.As temperature further increases, after temperature is greater than liquid medium boiling point, liquid Media fraction gasification futher stirs blend to realize to will appear bubbling phenomenon in blend.

Further, in step C when blend melt blending, it is greater than or equal to thermoplastic polymer plasticization temperature in temperature When, the liquid medium gasification in nanometer mixing material, the gasification separates the nano material of reunion.

In above scheme, when on the plasticization temperature or plasticization temperature that temperature is increased to thermoplastic polymer, into receiving Liquid medium in rice material further gasifies, and the gasification can generate huge energy and separate the nano material of reunion, Nano material after separation is just under continuous stirring in the evenly dispersed thermoplastic polymer to melting.

Further, in step C when blend melt blending, it is greater than or equal to thermoplastic polymer plasticization temperature in temperature When, the liquid medium gasification in nanometer mixing material, the gasification uniformly transfers heat in the blend；

Preferably, the gasification softens thermoplastic polymer, and reduces partial polymer plasticization temperature.

In above scheme, when polymer and nano material melt blending, into the liquid medium gas between nano material Change, the heat in blend can be transmitted constantly under this gasification, be heated evenly blend, in addition, because liquid medium Gasification, polymer are also further softened, so that the infiltration cladding of polymer and nano material is more abundant.In addition, it is plasticized Temperature is also because the presence of steam decreases.

Further, the boiling point of the liquid medium is lower than the plasticization temperature of thermoplastic polymer, and preferably boiling point is lower than 180 DEG C, more preferable water；

The mass parts ratio of the liquid medium and nano material is 3~100:1；It is preferred that 5~50:1；More preferable 5~ 20:1。

In above scheme, the boiling point of liquid medium need to be lower than the plasticization temperature of thermoplastic polymer, and preferably boiling point is lower than 180 DEG C liquid medium.The liquid medium includes isopentane, pentane, petroleum ether, hexane, hexamethylene, isooctane, trifluoro second Acid, trimethylpentane, 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, methyl Isobutyl ketone, tetrahydrofuran, ethyl acetate, isopropanol, chloroform, methyl ethyl ketone, dioxane, pyridine, acetone, nitro first Alkane, acetonitrile, dimethylformamide, methanol, water, methylamine, dimethylamine, ether, pentane, methylene chloride, carbon disulfide, 1,1- dichloro Ethane, trifluoroacetic acid, 1,1,1- trichloroethanes, ethyl alcohol, butanone, 1,2- dichloroethanes, glycol dimethyl ether, triethylamine, third Nitrile, 4-methyl-2 pentanone, ethylenediamine, butanol, acetic acid, glycol monomethyl ether, octane, morpholine ethylene glycol monoethyl ether, dimethylbenzene, In meta-xylene, acetic anhydride, ortho-xylene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE etc. It is one or more.It is preferred that one of o-dichlorohenzene, water, trimethylpentane, isopentane, acetic acid, toluene or a variety of, consider To manufacturing cost and to the pollution problem of environment, more preferable water.

Further, the nano material includes stratified nano materials, flake nano material, granular nano material, fibre One of dimension nano material is a variety of；

The nano material and the mass parts ratio of thermoplastic polymer are 0.1~20:100；It is preferred that 1~10:100；More It is preferred that 3~5:100.

In above scheme, stratified nano materials include anion type laminated nano material, cationic stratified nano materials With non-ionic stratified nano materials, in which: anionic nano material includes hydrotalcite；

Cationic nano material includes montmorillonite, inorganic phosphate, phyllosilicate, kaolin, sepiolite, titanate Deng；

Non-ionic nano material includes:

(1) carbon material: graphene；

(2) graphene analog: the element of the 4th main group of the periodic table of elements, such as silene, germanium alkene, boron alkene, arsenic alkene are black Phosphorus；

(3) transient metal sulfide (TMDs): coordination environment and oxidation state based on metallic atom, transient metal sulfide (TMDs) insulator (HfS2), semiconductor (MoS2), semimetal (TiSe2) and all-metal (NbSe2) can be formed, or even low Transient metal sulfide (TMDs) can show superconductivity under the conditions of temperature.It is reported in the literature at present to have more than 40 laminate transition Metal sulfide；

(4) layered metal oxide: MoO3, V2O3, V2O5, Al2O3, chromium oxide, TiO2, BiOCl, MnO2；

(5) oxide of layered metal hydroxides, perovskite；

(6) metal nitride, carbide: h-BN, nitrogen carbide (g-C3N4)；

(7) two-dimensional metallic organic framework materials: the MOF for having been carried out removing includes: [Cu2Br (IN) 2] n (different cigarette of IN= Acid), Zn-BDC (BDC=terephthalic acid (TPA)), it is brilliant to remove manganese -2,2- dimethyl succinate (MnDMS) block in ethanol, in methanol [Zn2 (bim) 4] (bim=benzimidazole) is removed with the in the mixed solvent of propyl alcohol, in the mixed of n,N-Dimethylformamide and acetonitrile It grows to obtain ultra-thin 2D CuBDC and ZnBDC MOF material by diffusion control MOF in bonding solvent.M-TCPP ultrathin nanometer piece (M =Zn, Cu, Cd, Co；TCPP=5,10,15,20- tetra- (4- carboxyl phenyl) porphines)；

(8) transition metal oxyhalide: LiCoO2, FeOCl etc.；

It is preferred that montmorillonite, phyllosilicate, kaolin, graphene, hydrotalcite, black phosphorus.

In addition to stratified nano materials, non-laminar nano material can be used for the present invention.Wherein non-laminar nano material packet Include flake nano material, granular nano material, fiber nano material etc.；Specifically, non-laminar nano material includes: nano oxygen SiClx, nano-titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nanogold, nano silver, are received nano-nickel oxide Rice silicon, nano-sized carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur, nano lanthanum oxide are nano oxidized Neodymium, nano oxidized erbium, nano-cerium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide, nanometer tungsten oxide, nano silicon carbide One of silicon, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide, nanoscale molybdenum oxide are a variety of.It is preferred that nano silicon oxide, Nano zine oxide, carbon nano-fiber, nanometer tungsten oxide, nano-silicon.

The plasticization temperature of the thermoplastic polymer be not less than 170 DEG C, including copoly type polymer, be blended confuse polymer, Engineering plastics, general-purpose plastics etc., preferably PA6, PA66, PPO, POM, PP, PET, PBT, PA12, PVC, PLA, TPU Long carbon chain Buddhist nun Imperial PA12.

Further, when the nano material is stratified nano materials, liquid medium enters nano material interlayer in step A The paste nanometer mixing material with certain tack is formed, in step C when temperature is greater than or equal to polymer plasticization temperature, Liquid medium gasification separates lamella.

In above scheme, stratified nano materials have unique two-dimentional layer structure, two-dimentional laminate Orienting ordered arrangement shape At three-dimensional crystalline structure uniqueness, so that bedding void can be inserted under certain condition and strut laminate for liquid medium, without broken The original structure of bad stratified nano materials, and the laminate composition and interlamellar spacing of stratified nano materials all have Modulatory character.Institute It states stratified material and is selected from one of cationic layered materials, anion laminated material and nonionic stratified material or a variety of.

In above scheme, when nano material is stratified nano materials, liquid medium enters nano material interlayer, by not When disconnected stirring forms paste nanometer mixing material, thermoplastic polymer and the nanometer mixing material melt blending, in temperature liter During height, stratified nano materials are coated to form protective layer, prevent liquid medium from gasifying too early ease by thermoplastic polymer softening Out.As temperature increases, when reaching liquid medium boiling point, the liquid medium gasification of interlayer is not entered, the gasification is in blend composition In occur bubbling phenomenon to realize futher stir.When temperature is increased to the plasticization temperature or plasticization temperature of thermoplastic polymer On when, the liquid medium into stratified nano materials interlayer further gasifies explosion, and the huge energy of generation is by stratified material Limellar stripping, the lamella of removing are just orderly dispersed under constant stirring in the thermoplastic polymer of melting.

After adopting the above technical scheme, compared with the prior art, the invention has the following beneficial effects:

1, nano material and liquid medium are mixed to form paste nanometer mixing material and thermoplastic polymer by simple process Melt blending together can obtain nanocomposite, without carrying out complicated organic-treating to nano material；

2, on feeding manner, the present invention realize nano material and thermoplastic polymer liquid medium there are the case where It is lower to feed simultaneously, eliminate the charging of nano material midway and need to increase spiro rod length, production cost is lower, easily popularization, especially with Water is liquid medium, can more reduce environmental pollution.

3, nano material melting mixing together with thermoplastic polymer, enables nano material to be preferably dispersed to thermoplasticity In polymer, its impact strength of nanocomposite and tensile strength being obtained by this method while being promoted.

A specific embodiment of the invention is described in further detail with reference to the accompanying drawing.

Detailed description of the invention

Fig. 1 is graphene SEM figure in paste nanometer mixing material of the present invention；

Fig. 2 is graphene TEM figure in paste nanometer mixing material of the present invention；

Fig. 3 is that the SRD of PLA laminated nm-silicate composite material schemes；

Fig. 4 is that the SRD of PPO laminated nm-silicate composite material schemes；

Fig. 5 is that the SRD of TPU layer shape silicate nanometer composite material schemes；

Fig. 6 is the XRD diagram of not scattered phyllosilicate.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, the technical solution in embodiment is clearly and completely described, the following examples are intended to illustrate the invention, but It is not intended to limit the scope of the invention.

Embodiment 1

PA66/ Nano composite material of montmorillonite

Raw material: 100 parts of PA66,0.1 part of montmorillonite of 10 parts of water

Preparation method:

1, the water of above-mentioned parts by weight is slowly stirred lower addition montmorillonite powder, is sufficiently stirred to form paste montmorillonite mixing Material, the consistency of this mixing material are 36mm；

2, PA66 mixes investment twin-screw extrusion machine inlet thoroughly after mixing with montmorillonite mixing material；

3, PA66 and the further melting mixing of montmorillonite, through extruding pelletization, drying is compound to get PA66/ montmorillonite-based nano Material.

The engine speed of the extrusion equipment is 80Hz, and main feeding hopper revolving speed is 30Hz, extrusion temperature are as follows: 1 180 DEG C of area, 2 280 DEG C of area, 3 280 DEG C of areas, 4 280 DEG C of areas, 5 280 DEG C of areas, the linear velocity of screw speed are 0.9m/s.

Embodiment 2

PA6/ graphene nanocomposite material

Raw material: 1 part of oil of 100 parts of PA6,40 parts of water, 10 parts of graphene Water Soluble Maleic Anhydride

Preparation method:

1, the water of above-mentioned parts by weight is stirred at 1000HZ, the ultrasound condition of 200W, is slowly added to graphene powder, surpassed Water Soluble Maleic Anhydride oil is added after sound 30min, is continued ultrasound 60min, is ultimately formed paste graphene mixing material, this mixing material The consistency of material is 87mm；

2, PA6 is mixed with paste graphene mixing material and is mixed thoroughly, puts into twin-screw extrusion machine inlet；

3, PA6 and the further melting mixing of graphene, it is dry to get PA6 graphene nano composite wood through extruding pelletization Material.

The engine speed of the extrusion equipment is 30Hz, and main feeding hopper revolving speed is 10Hz, extrusion temperature are as follows: 1 150 DEG C of area, 2 230 DEG C of area, 3 245 DEG C of areas, 4 245 DEG C of areas, 5 245 DEG C of areas, the linear velocity of screw speed are 0.9m/s.

Embodiment 3

PPO/ laminated nm-silicate composite material

Raw material: 100 parts of PPO, 100 parts of water, 20 parts of phyllosilicate, 0.2 part of water-soluble epoxy resin anti-aging agent RD 0.2 part

1, the water of above-mentioned parts by weight is stirred at 1000HZ, the ultrasound condition of 1000W, is slowly added to laminar silicic acid salt fines End adds water-soluble epoxy resin after ultrasonic 30min, continues ultrasound 60min, obtains paste phyllosilicate mixing material, this The consistency of mixing material is 68mm；

2, PPO is mixed with phyllosilicate mixing material, anti-aging agent RD and is mixed thoroughly, is added in mixer；

3, by PPO and phyllosilicate, further melt blending, the compound 3h of mixing are dry through being granulated in 280 DEG C of mixers Dry PPO/ laminated nm-silicate composite material to obtain the final product.

Embodiment 4

POM/ nano zine oxide nanocomposite

Raw material: 100 parts of POM, 100 parts of trimethylpentane, 0.5 part of nano zine oxide, 2.5 parts of lecithin antioxidant A W 0.3 part

Preparation method:

1, the trimethylpentane of above-mentioned parts by weight is stirred at 800HZ, the ultrasound condition of 1000W, then by nano oxygen Change zinc alkene powder to be slowly added into trimethylpentane, lecithin is added after ultrasonic 30min, continues ultrasound 60min, obtain paste and receive Rice zinc oxide mixing material, the consistency of this mixing material are 43mm；

2, POM is mixed and is mixed thoroughly with paste nano zine oxide mixing material, anti-aging agent RD, be added in mixer；

3, by POM and nano zine oxide, further melt blending, the compound 3h of mixing are dry through being granulated in 300 DEG C of mixers Dry POM/ nano zine oxide nanocomposite to obtain the final product.

Embodiment 5

PLA/ laminated nm-silicate composite material

Raw material: 100 parts of PLA, 30 parts of water, 3 parts of phyllosilicate, 0.4 part of antioxidant 3114 of 12 parts of sodium alginate

Preparation method:

1, the water of above-mentioned parts by weight is slowly stirred lower addition laminar silicic acid salt powder, adds sodium alginate, sufficiently stirs It mixes to form paste phyllosilicate mixing material, the consistency of this mixing material is 59mm；

2, PLA is mixed with phyllosilicate mixing material, antioxidant 3114 and is mixed thoroughly, double screw extruder feeding is added Area；

3, dry to get PLA/ phyllosilicate through extruding pelletization by PLA and the further melting mixing of phyllosilicate Nanocomposites.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 30Hz, extrusion temperature are as follows: 1 200 DEG C of area, 2 245 DEG C of area, 3 230 DEG C of areas, 4 230 DEG C of areas, 5 245 DEG C of areas, the linear velocity of screw speed are 0.9m/s.

Embodiment 6

TPU/ laminated nm-silicate composite material

Raw material: 100 parts of TPU, 25 parts of toluene, 5 parts of phyllosilicate, 0.5 part of antioxidant 2246 of 1 part of polymeric acid

1, the toluene of above-mentioned parts by weight is slowly stirred lower addition laminar silicic acid salt powder, adds polymeric acid, sufficiently Stirring forms paste phyllosilicate mixing material, and the consistency of this mixing material is 77mm；

2, TPU is mixed with phyllosilicate mixing material, antioxidant 2246 and is mixed thoroughly, mixer is added；

3, by TPU and phyllosilicate, further melt blending, mixing compound 3h are passed through after discharging in 300 DEG C of mixers Granulating and drying is up to TPU/ laminated nm-silicate composite material.

Embodiment 7

PBT/ carbon nano-fiber nanocomposite

Raw material: 100 parts of PBT, 20 parts of water, 1 part of carbon nano-fiber, 0.6 part of antioxidant MB of 1 part of polyvinylamine

Preparation method:

1, the water of above-mentioned parts by weight is stirred at 1000HZ, the ultrasound condition of 500W, is slowly added to carbon nano-fiber powder End adds polyvinylamine after ultrasonic 30min, continues ultrasound 60min, ultimately forms paste carbon nano-fiber mixing material, this The consistency of mixing material is 71mm；

2, it is mixed thoroughly after mixing PBT with carbon nano-fiber mixing material, antioxidant MB, double screw extruder charging is added Mouthful；

3, dry to get PBT/ carbon nano-fiber through extruding pelletization by PBT and the further melt blending of carbon nano-fiber Nanocomposite.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C, Two 245 DEG C of areas, three 260 DEG C of areas, four 260 DEG C of areas, five 260 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

Embodiment 8

PA12/ montmorillonite/sepiolite nanocomposite

Raw material: 100 parts of PA12,16 parts of acetic acid, 2 parts of montmorillonite/sepiolite, 0.6 part of hyaluronic acid anti-aging agent 4010NA0.7 part

Wherein the mass ratio of montmorillonite and sepiolite is 1:1.

Preparation method:

1, the acetic acid of above-mentioned parts by weight is slowly stirred lower addition montmorillonite/sepiolite powder, adds hyaluronic acid, fills Stirring is divided to form paste montmorillonite/sepiolite nanometer mixing material, the consistency of this mixing material is 63mm；

2, it is mixed thoroughly after mixing PA12 with montmorillonite/sepiolite nanometer mixing material, antioxidant 4010NA, twin-screw is added Squeeze out machine inlet；

3, by PA12 and the further melt blending of montmorillonite/sepiolite, through extruding pelletization, dry cover to get PA12/ takes off Soil/sepiolite nanocomposite.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C, Two 230 DEG C of areas, three 260 DEG C of areas, four 260 DEG C of areas, five 270 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

Embodiment 9

PVC/ montmorillonite/nano silicon oxide nanocomposite

Raw material: 100 parts of PVC, 80 parts of water+toluene, 8 parts of montmorillonite/nano silicon oxide, 4 parts of lecithin/sodium alginate is anti- 0.8 part of old agent NBC

Wherein the mass ratio of montmorillonite and nano silicon oxide is 1:1, and the mass ratio of water and toluene is 1:1, lecithin and sea The mass ratio of mosanom is 1:1.

Preparation method:

1, the water of above-mentioned parts by weight and toluene are stirred at 800HZ, the ultrasound condition of 500W, be slowly added to montmorillonite and Nano silicon oxide powder adds lecithin and sodium alginate after ultrasonic 30min, continues ultrasound 60min, ultimately forms cream Shape montmorillonite/nano oxidized silica hybrid material, the consistency of this mixing material are 23mm；

2, it is mixed thoroughly after mixing PVC with montmorillonite/nano oxidized silica hybrid material, antioxidant NBC, twin-screw extrusion is added Machine inlet；

3, by PVC and the further melt blending of montmorillonite/nano silicon oxide, through extruding pelletization, dry cover to get PVC/ takes off Soil/nano oxidized silicon composite.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 150 DEG C, Two 180 DEG C of areas, three 200 DEG C of areas, four 200 DEG C of areas, five 210 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

Embodiment 10

Long carbon chain nylon PA12/ nano silicon oxide/nano-sulfur/graphene nanocomposite material

Raw material: 100 parts of long carbon chain nylon PA12,75 parts of toluene/acetic acid nano silicon oxide/15 parts of nano-sulfur/graphene Dicyandiamide formaldehyde resin/1 part of 6 parts of polyvinylamine antioxidant, 1035/ antioxidant NBC

Wherein, the mass ratio of toluene and acetic acid be 1:1, nano silicon oxide, nano-sulfur, graphene three mass ratio be 1: The mass ratio of 1:1 dicyandiamide formaldehyde resin and polyvinylamine is 1:1, and the mass ratio of antioxidant 1035 and antioxidant NBC is 1:1.

Preparation method:

1, the toluene of above-mentioned parts by weight and acetic acid are stirred at 800HZ, the ultrasound condition of 800W, is slowly added to nano oxygen SiClx, nano-sulfur and graphene end powder add dicyandiamide formaldehyde resin and polyvinylamine after ultrasonic 30min, continue ultrasound 60min, ultimately forms paste nano silicon oxide/nano-sulfur/graphene mixing material, and the consistency of this mixing material is 75mm；

2, by long carbon chain nylon PA12 and nano silicon oxide/nano-sulfur/graphene mixing material, antioxidant 1035, anti-old It is mixed thoroughly after agent NBC, mixing, twin-screw extrusion machine inlet is added；

3, long carbon chain nylon PA12 and nano silicon oxide/further melt blending of nano-sulfur/graphene, through extruding pelletization, Drying is to get long carbon chain nylon PA12/ nano silicon oxide/nano-sulfur/graphene nanocomposite material.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C, Two 230 DEG C of areas, three 260 DEG C of areas, four 260 DEG C of areas, five 270 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

Comparative example 1

This comparative example prepares PA66/ Nano composite material of montmorillonite by way of intercalation polymeric

Raw material: 100 parts of PA66,10 parts of water, 0.1 part of montmorillonite, 0.5 part of cetyl quaternary amine catalyst SnCl2 0.5 part

Preparation method:

1, the montmorillonite of above-mentioned parts by weight is mixed with water, is placed in 80 DEG C of thermostatic water-circulator baths, after high-speed stirred 30min, Static 2h, then cetyl quaternary amine is added in montmorillonite aqueous solution, 2h is stirred at 80 DEG C, reaction solution is filtered, is dry, is obtained The montmorillonite to organise；

2, organo montmorillonite is mixed with PA66, and catalyst SnCl2 is added, then put into double screw extruder melting Mixing is dry to get PA66/ Nano composite material of montmorillonite through extruding pelletization.

Comparative example 2

On the basis of embodiment 1, the position of extruder is added in adjustment montmorillonite to this comparative example.

Raw material: same as Example 1

Preparation method:

1, the water of above-mentioned parts by weight is mixed with montmorillonite, it is fully dispersed, montmorillonite mud is made；

2, PA66 is put into twin-screw extrusion machine inlet, PA66 is melted at high temperature；

3, montmorillonite mud is put into the PA66 melted completely, through extruding pelletization, drying to get PA66/ montmorillonite Nanocomposite.

Wherein the technological parameter of double screw extruder is same as Example 1.

Experimental example 1

This experimental example is the product of nanocomposite properties of product and corresponding base-material made from testing example 1-10 It can compare, as shown in table 1.

Table 1:

By the above experimental result it is found that the impact strength and tensile strength of embodiment 1-10 compare its base-material obtains It is promoted.It is obvious that effect is especially promoted in terms of impact strength.This is because the present invention using thermoplastic polymer base-material with Nano material is fed jointly in the presence of liquid medium, and polymer and nano material are mutual during polymer melting Infiltration cladding, and the gasification of liquid medium is so that nano material separates, and is orderly dispersed in the polymer of melting, therefore its is whole Body performance is improved.

Experimental example 2

This experimental example is for comparing the PA66/ montmorillonite as made from embodiment 1, comparative example 1,2 distinct methods of comparative example Nanocomposite and difference of the PA66 monomer in nano material content and performance, as shown in table 2.

Table 2:

Performance parameter	Nylon66 fiber monomer	Embodiment 1	Comparative example 1	Comparative example 2
					Clay content %	0	1.9	1.8	1.8
Tensile strength MPa	80	95	84	82
					Stretch modulus GPa	3	3.5	3.2	3.1
Bending strength MPa	108	120	119	116
					Bending modulus GPa	2.8	3.2	3.0	3.0
Impact strength Kg cm/cm	60	80	42	44
					OTR oxygen transmission rate ml/m2D	48	34	31	33

As above data as can be seen that nylon66 fiber/Nano composite material of montmorillonite as made from the method for embodiment 1 Interior clay content is higher than comparative example 1 and comparative example 2, illustrates sufficiently remove by the method montmorillonite and be scattered in Buddhist nun very well In dragon 66.In addition, product made from embodiment 1 tensile strength, stretch modulus, bending strength, bending modulus, impact strength, It is superior to nylon66 fiber monomer, comparative example 1 and comparative example 2 in terms of OTR oxygen transmission rate, is especially had in terms of impact resistance significant Promotion, this is also further illustrated through the method for embodiment 1, nano material lamella energy high degree of dispersion in the elastomer, in turn Its performance is also greatly improved.

Experimental example 3

1, (as shown in Figure 1) is schemed by the SEM of graphene in test paste nanometer mixing material, as can be seen from the figure sample Product are in relatively transparent state, illustrate that graphene sheet layer is relatively thin, and agglomeration is unobvious；

2, (as shown in Figure 2) is schemed by the TEM of graphene in test paste nanometer mixing material, as can be seen from the figure sample Product lamella is very thin, can be considered that the single-layer graphene peeled away stacks, and the surface folding of sample is because of two-dimensional structure Material be not easy to stablize individualism, fold is stablized conducive to graphene, and the sample further demonstrated is single layer or few Layer graphene.

3, by testing PLA laminated nm-silicate composite material (as shown in Figure 3), PPO phyllosilicate nano respectively The SRD figure of composite material (as shown in Figure 4), TPU layer shape silicate nanometer composite material (as shown in Figure 5), from composite material XRD test result is it is found that the interlamellar spacing peak without phyllosilicate between 2-10 degree, and the XRD of not scattered phyllosilicate Figure is (as shown in Figure 6) to can see obviously interlamellar spacing peak, it was demonstrated that the lamella of composite material layered silicates has been opened.

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 technology people for being familiar with this patent 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 preparation method of nanocomposite, which is characterized in that preparation method the following steps are included:

A, liquid medium and nano material are mixed, obtain paste nanometer mixing material；

B, nanometer mixing material described in step A and thermoplastic polymer are mixed to get blend；

C, blend in step B is subjected to melt blending, obtains nanocomposite.

2. a kind of nanocomposite preparation method according to claim 1, which is characterized in that be additionally added use in step A To improve the auxiliary agent of paste nanometer mixing material consistency, the auxiliary agent include that carboxylate surface active agent, sulfuric acid surface are living Property agent, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant, heterocycle One of type surfactant, nonionic surfactant, natural water soluble high molecular, synthetic water soluble high molecular and its prepolymer Or it is a variety of；One of preferably synthetic water soluble polymer and its prepolymer are a variety of；

Preferably, the mass parts ratio of the auxiliary agent and nano material is 0.01~50:1；It is preferred that 0.1~5:1；More preferable 0.2 ~1:1.

3. a kind of preparation method of nanocomposite according to claim 1 or 2, which is characterized in that the paste is received The consistency of rice mixing material is 0~100mm, but is not 0.

4. a kind of preparation method of nanocomposite according to claim 1, which is characterized in that step B obtains paste The blend of nanometer mixing material adherency thermoplastic polymer；

Preferably, age resister, the mass parts ratio of the age resister and thermoplastic polymer are additionally added in the blend For 0.1~1:100；It is preferred that 0.2~0.4:100；More preferable 0.3~0.4:100.

5. a kind of preparation method of nanocomposite according to claim 1, which is characterized in that include: in step C

(1) liquid medium, nano material in heat temperature raising, thermoplastic polymer and nanometer mixing material mix under the first stirring Splice grafting touches, softens 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 second to blend Stirring.

6. a kind of preparation method of nanocomposite according to claim 1 or 5, which is characterized in that be blended in step C Liquid medium when object melt blending, when temperature is greater than or equal to thermoplastic polymer plasticization temperature, in nanometer mixing material Gasification, the gasification separate the nano material of reunion.

7. a kind of preparation method of nanocomposite described according to claim 1 or 5 or 6, which is characterized in that in step C Liquid when blend melt blending, when temperature is greater than or equal to thermoplastic polymer plasticization temperature, in nanometer mixing material Medium gasification, the gasification uniformly transfer heat in the blend；

Preferably, the gasification softens thermoplastic polymer, and reduces part thermoplastic's polymer plasticization temperature.

8. according to claim 1 or a kind of 5~7 any nanocomposites, which is characterized in that the liquid medium Boiling point is lower than the plasticization temperature of thermoplastic polymer, and preferably boiling point is lower than 180 DEG C, more preferable water；

The mass parts ratio of the liquid medium and nano material is 3~100:1；It is preferred that 5~50:1；More preferable 5~20:1.

9. according to claim 1 or a kind of 5~8 any nanocomposites, which is characterized in that the nano material packet Include one of stratified nano materials, flake nano material, granular nano material, fiber nano material or a variety of；

The nano material and the mass parts ratio of thermoplastic polymer are 0.1~20:100；It is preferred that 1~10:100；More preferable 3 ~5:100.

10. a kind of nanocomposite according to claim 9, which is characterized in that the nano material is laminar nano When material, liquid medium enters the paste nanometer mixing material that the formation of nano material interlayer has certain tack, step in step A In rapid C when temperature is greater than or equal to thermoplastic polymer plasticization temperature, liquid medium gasification separates lamella.