CN110229435A - A kind of PVC nanocomposite and preparation method thereof - Google Patents

Abstract

A kind of PVC nanocomposite, by being made including PVC granule, and by the mixing of nano material and liquid medium that PVC granule is coupled through melt blending.The invention also discloses the preparation method of PVC nanocomposite, specific steps include A, by nano material and liquid medium mixing, form nano material mixture paste；B, the nano material mixture in step A is mixed to form blend with PVC granule；C, the blend of step B is passed through into melt blending to get the PVC nanocomposite.The tensile strength and impact strength of the nanocomposite get a promotion on the basis of PVC base-material, and preparation method is simple, and production cost is low, easily promote.

Description

A kind of PVC nanocomposite and preparation method thereof

Technical field

The invention belongs to nanocomposite and its preparation fields, specifically, be related to a kind of PVC nanocomposite and Preparation method.

Background technique

Polyvinyl chloride (PVC) has fire retardant, resist chemical, resistance to as one of maximum plastic product of yield in the world Mill, the excellent and higher mechanical strength of electrical insulating property etc. a little, and can be added as needed additive in process or adopt Miscellaneous plastic products are produced with technique appropriate and equipment.Although widely used, in professional domain using it Performance is also inadequate.At this time, the property different from general composite material that nanocomposite is shown is polychlorostyrene second The study on the modification of alkene indicates a new approach.Numerous studies confirm, polyvinyl chloride and stratified nano materials are combined Nanocomposite can significantly improve its comprehensive performance.The preparation method of PVC nanocomposite mainly uses original position at present Intercalation and the preparation of fusion intercalation method.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；Melting is inserted Layer can carry out in general plastic milling apparatus, easy to process, however need carry out the intercalation that organises to stratified nano materials early period Processing, it is not easy to the polyvinyl chloride nano compound material being completely exfoliated.With development in science and technology, engineer application is to polychlorostyrene More stringent requirements are proposed in impact strength, bending strength and tensile strength performance for vinyl material.

Patent No. CN101081928A is proposed a kind of preparation method of nanocomposite, is prepared using water-assisted growth Polyamide/nano montmorillonite masterbatch, it is intercalator that preparation method, which is with deionized water, by the montmorillonite of purifying and deionization Mud is added step-wise to the polyamide that prescription amount melts completely by water mixing, fully dispersed obtained montmorillonite mud, then through squeezing It is granulated out and obtains polyamide/nano montmorillonite masterbatch.Preparation method is simple, and production cost is low, but this method is in polyamide Montmorillonite mud is added after melting, be will lead to montmorillonite mud and is had not enough time to be thoroughly mixed with copolymer, the water of interlayer 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, montmorillonite Mud, which needs to increase on feed way certain pressure, to inject twin-screw for mud, simultaneously because the processing sections of twin-screw It is short, the feeding section of montmorillonite mud is increased halfway, it is necessary to be increased twin-screw length, be caused technique more complicated, cost is more It is high.

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 overcoming the deficiencies of the prior art and provide a kind of tensile strength and impact is strong It spends while being promoted, and preparation method is simple, production cost is low, PVC nanocomposite easily promoted and preparation method thereof.

In order to solve the above technical problems, the present invention provides a kind of PVC nanocomposite, which is characterized in that the nanometer Composite material by include PVC granule, and by PVC granule be coupled nano material and liquid medium mixing through melt blending It is made.

In above scheme, preparation PVC nanocomposite use by PVC granule and nano material, liquid medium jointly into The mode of material is made.It is coupled between PVC granule with by nano material and liquid medium, forms a kind of not stratified blend. Such mode solves in traditional approach very well, and PVC is blended with nano material, and what nano material skidding can not be fed jointly asks Topic.

Further, the nano material is stratified nano materials, at least partly lamella point of layered nano material It is dissipated in PVC.

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 layer nano material, and the laminate composition and interlamellar spacing of stratified nano materials all have Modulatory character.Work as liquid Body medium enters interlayer, and interlamellar spacing is because liquid medium struts, on the plasticization temperature or plasticization temperature that temperature is increased to PVC When, the liquid medium into stratified nano materials interlayer further gasifies explosion, and the huge energy of generation is by stratified material lamella Removing, the lamella of removing are just orderly dispersed under constant stirring in the PVC of melting.

Preferably, layered nano material includes phyllosilicate, layered titanate, layer dress phosphate, laminated metal Hydroxide, transition metal oxyhalide, lamellar graphite, transient metal sulfide, layered metal oxide, laminated metal nitrogen Compound, laminated metal carbide, two-dimensional metallic organic frame are one or more of；

It is furthermore preferred that nanocomposite XRD diffraction pattern is at 2 2-10 ° of the angles θ when nano material is ionic stratified material Without interlamellar spacing characteristic peak in range.

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 Transient metal sulfide (TMDs) can show superconductivity under cryogenic conditions.It is reported in the literature at present to have more than 40 laminates Transient 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 first The in the mixed solvent of pure and mild propyl alcohol removes [Zn2 (bim) 4] (bim=benzimidazole), in n,N-Dimethylformamide and acetonitrile In the mixed solvent by diffusion control MOF grow to obtain ultra-thin 2D CuBDC and ZnBDC MOF material.M-TCPP is ultra-thin to be received Rice 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.

Further, the liquid medium enters stratified nano materials interlayer, and being formed has the paste of certain consistency will PVC granule is coupled；The consistency of the paste is 0~100mm, but is not 0；

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

In above scheme, intercalation polymeric is to nano-material modified filtering and dry process, this hair compared to the prior art After the interlayer injection liquid medium of bright stratified nano materials, paste continuous, and that there is certain tack is formd Object, the paste have certain consistency, but consistency is not 0mm, represent the paste to be combined with liquid medium, because This can be total to by the nano material paste uniform adhesion for being combined with liquid medium on PVC granule surface with PVC granule With the equipment of feeding to melt blending, processability is improved.

Further, auxiliary agent is also contained in the paste, the auxiliary agent includes carboxylate surface active agent, sulfuric acid Surfactant, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary ammonium salt surface-active Agent, heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular, synthetic water soluble high molecular and its prepolymer One or more of；Wherein one of preferably synthetic water soluble polymer and its prepolymer or 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 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, liquid medium gas in advance is prevented Change evolution.Due in the present invention generate paste nano material reaction temperature at room temperature, the requirement to auxiliary agent is not Height, 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, polyacrylic 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

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 formaldehydes, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin, N, N- dimethyl 1,3- propane diamine and epichlorohydrin resin；

(3) other

Water Soluble Maleic Anhydride oil, dicyandiamide formaldehyde resin, rosin amine-ethylene oxide condensate, poly N-ethylene yl acetamide, water Dissolubility ficoll.

3, semi-synthetic class macromolecule

Modified cellulose and converted starch；

Further, the boiling point of the liquid medium is lower than the plasticization temperature of PVC, and preferably boiling point is lower than 180 DEG C, more preferably Water.

In above scheme, the boiling point of liquid medium need to be lower than the plasticization temperature of PVC, and preferably boiling point is lower than 180 DEG C of liquid Medium.The liquid medium is selected from: isopentane, pentane, petroleum ether, hexane, hexamethylene, isooctane, trifluoroacetic acid, front three Base pentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, chlorotrifluoroethane, propyl ether, toluene, to diformazan Benzene, chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate, propyl alcohol, methyl tert-butyl Ketone, tetrahydrofuran, ethyl acetate, isopropanol, chloroform, methyl ethyl ketone, dioxane, pyridine, acetone, nitromethane, Acetonitrile, dimethylformamide, methanol, water, methylamine, dimethylamine, ether, pentane, methylene chloride, carbon disulfide, 1,1-, bis- chloroethene Alkane, 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, Meta-xylene, acetic anhydride, ortho-xylene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE etc. One of or it is a variety of.It is preferred that o-dichlorohenzene, water, trimethylpentane, isopentane, acetic acid, toluene；In view of manufacturing cost with And the pollution problem to environment, more preferable water.

Further, nano material and the mass parts ratio of PVC are 0.1~20:100 in the mixing；It is preferred that 1~10: 100；More preferable 3~5:100.

Preferably, in the mixing there are also age resister, the mass parts ratio of the age resister and PVC are 0.1~1: 100；It is preferred that 0.2~0.8:100；More preferable 0.3~0.6:100.

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 PVC are 0.1~1:100；It is preferred that 0.2~0.4:100；More preferably 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.It is thio The principal item of bis-phenol has antioxidant 2246 and 300.Polyatomic phenol antioxidant principal item have 2,5 1 di-t-butyl hydroquinones and 2,5 12 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, antioxygen Agent 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246, DBH 2,5 di tert butylhydroquinone, antioxidant DLTP, antioxidant TNP, Ultranox624, phosphorous acid three (the tertiary T base phenyl of 2,4- bis-) ester, antioxidant MB, antioxidant NBC, two One of alkyl zinc dithiophosphate is a variety of；It is preferred that anti-aging agent RD, antioxidant A W, antioxidant 4010NA, antioxidant 3114, antioxidant 264.

Further, which is characterized in that the preparation method comprises the following steps:

A, nano material and liquid medium are mixed, form nano material mixture paste；

B, the nano material mixture in step A is mixed to form blend with PVC granule；

C, the blend of step B is passed through into melt blending to get the PVC nanocomposite.

In above scheme, nano material is entered by liquid medium, lower be made with certain tack is being sufficiently stirred Paste nano material, the paste nano material, which mixes to mix thoroughly with PVC, can be directly added into feed zone, without applying pressure, Without midway feeding, saves technique and reduce costs.In addition, nano material is added after mixing with PVC, then through melt blending, The PVC of melting can envelope nano material to form protective layer, when the liquid medium gasification for entering nano material, nano material When interior vapour pressure is greater than PVC melt pressure, huge interior violence can be generated and separate nano material, isolated nano material is just It is evenly dispersed into PVC.

In above scheme, latex can also be added and envelope the paste nano material mixture that step A is obtained, it is described Latex includes: styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, Rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, neoprene One of latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of, preferably styrene-acrylic emulsion, silicone acrylic emulsion, vinegar third One of lotion, styrene-acrylic latex are a variety of.

In above scheme, latex is added and coats nano material mixture, forms protective layer, then when nano material mixture When with PVC melt blending, the liquid medium into nano material gasifies, when the vapour pressure in protective layer is greater than the melt pressure of PVC When can generate implosive force, the nano material of reunion is separated, using continuous stirring and/or shearing, isolated nano material It can be highly dispersed in the PVC 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 when nano material is fed with PVC very well The case where now skidding, can not feeding simultaneously realizes mixed feeding in the presence of liquid medium of PVC and nano material, And without pressure is applied when feeding, in addition, passing through double screw extruder in melting process in PVC and nano material Shearing force and the implosive force of liquid medium gasification can make nano material more abundant in the dispersion of PVC kind.

Wherein the engine speed of double screw extruder is 30-80Hz, and main feeding hopper revolving speed is 10-30Hz, and extrusion temperature is One 150-200 DEG C of 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 areas；It is preferred that main Machine revolving speed be 60-80Hz, main feeding hopper revolving speed be 20-30Hz, extrusion temperature be 150-180 DEG C of an area, 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, auxiliary agent is additionally added in step A, the auxiliary agent can be added at one time also to be added in batches；

Preferably, can also increase physics mode in step A promotes liquid medium to disperse between nano material, the physics Mode includes colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock.

In above scheme, the ability that liquid medium enters nano material is can be improved in the addition of auxiliary agent, to increase nanometer The consistency of material blends；In addition, the addition of auxiliary agent can also improve the boiling point of liquid medium, liquid medium gas in advance is prevented Change evolution.

It can promote dispersion of the liquid medium in nano material, the physics side in above scheme by physics mode Formula includes but is not limited to that the modes such as ultrasound, colloid mill, ball milling, vortex, etching auxiliary, gas shock stir, the frequency of the ultrasound Rate is 800~1000Hz, and power is 200~1000W.

Further, in step C, when temperature is equal to or higher than PVC plastic temperature, the liquid in nanometer mixing material is situated between Matter gasification, the gasification separate the nano material of reunion；

Preferably, when the nano material is stratified nano materials, liquid medium enters stratified nano materials layer in step A Between form the paste with tack, in step C when temperature is equal to or higher than PVC plastic temperature, into the liquid of interlayer Medium gasification, stratified nano materials lamella is separated.

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

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 layer nano material, and the laminate composition and interlamellar spacing of stratified nano materials all have Modulatory character.It is described Stratified material 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 nano material mixture, PVC and the nano material mixture melt blending, increased in temperature Cheng Zhong, PVC softening, stratified nano materials are coated to form protective layer, prevent liquid medium from gasifying too early evolution.With temperature It increases, when reaching liquid medium boiling point, does not enter the liquid medium gasification of interlayer, the gasification is bubbled in blend composition Phenomenon futher stirs to realize.When on the plasticization temperature or plasticization temperature that temperature is increased to PVC, received into stratiform The liquid medium of rice material interlayer further gasifies explosion, and the huge energy of generation is by stratified material limellar stripping, the piece of removing Layer is just orderly dispersed under constant stirring in the PVC of melting.

The invention also provides a kind of mixings, comprising: paste and PVC；

Paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not 0；The paste is adhered to PVC granule surface and forms mixing；

Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are divided It dissipates.

In above scheme, by the cream that nano material and liquid medium and appropriate amount of addition agent are mixed with to a kind of tack Shape object, when PVC base-material is mixed with paste, paste will be adhered in PVC granule, PVC granule will pass through paste that This is mutually glued.This very good solution that nano material, liquid medium and PVC granule the are formed prior art is skidded because of raw material The problem of cannot feeding jointly.

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

1, simple process, nano material with liquid medium is mixed to form paste and PVC together with melt blending, can obtain To nanocomposite, handled without carrying out complicated organic-treating to nano material；

2, on feeding manner, the present invention realize nano material and PVC in the presence of liquid medium simultaneously into Material eliminates the charging of nano material midway and needs to increase spiro rod length, and production cost is lower, easily promotes, especially using water as liquid Medium can more reduce environmental pollution.

3, nano material melting mixing together with PVC, enables nano material to be preferably dispersed in PVC, thus method Its impact strength of nanocomposite obtained and tensile strength are promoted simultaneously.

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 of the present invention；

Fig. 2 is graphene TEM figure in paste of the present invention.

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

PVC/ graphene nanocomposite material

Raw material: 100 parts of PVC, 40 parts of water graphene, 10 1 part of Fen Ming glue

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 Add gelatin after sound 30min, continue ultrasound 60min, ultimately form paste graphene mixing material, this mixing material it is thick Degree is 22mm；

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

3, PVC and the further melting mixing of graphene, it is dry to get PVC 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, and extrusion temperature is 150 DEG C of an area, Two 220 DEG C of areas, three 230 DEG C of areas, four 250 DEG C of areas, five 230 DEG C of areas, the linear velocity of screw speed are 0.8m/s.

Embodiment 2

PVC/ vanadic anhydride nanocomposite

Raw material: 100 parts of PVC, 100 parts of water, 20 parts of vanadic anhydride, 0.2 part of water-soluble epoxy resin anti-aging agent 0.2 part of RD

1, the water of above-mentioned parts by weight is stirred at 1000HZ, the ultrasound condition of 1000W, is slowly added to vanadic anhydride powder End adds water-soluble epoxy resin after ultrasonic 30min, continues ultrasound 60min, obtains paste vanadic anhydride mixing material, this The consistency of mixing material is 69mm；

2, PVC is mixed with paste vanadic anhydride mixing material and is mixed thoroughly, puts into twin-screw extrusion machine inlet；

3, PVC and the further melting mixing of vanadic anhydride, through extruding pelletization, drying is received to get PVC/ vanadic anhydride Nano composite material.

The engine speed of the extrusion equipment is 80Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 160 DEG C, Two 230 DEG C of areas, three 230 DEG C of areas, four 240 DEG C of areas, five 230 DEG C of areas；The linear velocity of screw speed is 1m/s.

Embodiment 3

PVC/ Nano composite material of montmorillonite

Raw material: 100 parts of PVC, 100 parts of trimethylpentane, 0.5 part of montmorillonite, 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 montmorillonite Powder is slowly added into trimethylpentane, and lecithin is added after ultrasonic 30min, is continued ultrasound 60min, is obtained paste montmorillonite Mixing material, the consistency of this mixing material are 58mm；

2, PVC is mixed and is mixed thoroughly with paste montmorillonite mixing material, anti-aging agent RD, be added in mixer；

3, by PVC and montmorillonite, further melt blending, the compound 3h of mixing are through granulating and drying in 300 DEG C of mixers Obtain PVC/ Nano composite material of montmorillonite.

Embodiment 4

PVC/ Kaolinite Intercalation Nanocomposites

Raw material: 100 parts of PVC, 30 parts of water, 3 parts of kaolin, 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 kaolin powder, adds sodium alginate, shape is sufficiently stirred At paste kaolin mixing material, the consistency of this mixing material is 49mm；

2, PVC is mixed with kaolin mixing material, antioxidant 3114 and is mixed thoroughly, double screw extruder feeding zone is added；

3, by PVC and the further melting mixing of kaolin, through extruding pelletization, drying is nano combined to get PVC/ kaolin Material.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 25Hz, and one area of extrusion temperature is 170 DEG C, Two 240 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas, 5 230 DEG C；The linear velocity of screw speed is 0.8m/s.

Embodiment 5

PVC/ laminated nm-silicate composite material

Raw material: 100 parts of PVC, 25 parts of toluene, 5 parts of phyllosilicate, 1 part of polyacrylic acid antioxidant 2246 0.5 Part

1, the toluene of above-mentioned parts by weight is slowly stirred lower addition laminar silicic acid salt powder, adds polyacrylic acid, sufficiently Stirring forms paste phyllosilicate mixing material, and the consistency of this mixing material is 31mm；

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

3, by PVC 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 PVC/ laminated nm-silicate composite material.

Embodiment 6

PVC/ black phosphorus nanocomposite

Raw material: 100 parts of PVC, 20 parts of water, 0.1 part of black phosphorus, 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 black phosphorus powder, ultrasound Polyvinylamine is added after 30min, is continued ultrasound 60min, is ultimately formed paste black phosphorus mixing material, the consistency of this mixing material For 32mm；

2, it is mixed thoroughly after mixing PVC with black phosphorus mixing material, antioxidant MB, twin-screw extrusion machine inlet is added；

3, dry to get PVC/ black phosphorus nanocomposite through extruding pelletization by PVC and the further melt blending of black phosphorus.

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 250 DEG C of areas, three 250 DEG C of areas, four 240 DEG C of areas, five 240 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

Embodiment 7

PVC/ montmorillonite/sepiolite nanocomposite

Raw material: 100 parts of PVC, 16 parts of acetic acid, 2 parts of montmorillonite/sepiolite, 0.6 part of hyaluronic acid anti-aging agent 0.7 part of 4010NA

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 46mm；

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

3, by PVC and the further melt blending of montmorillonite/sepiolite, through extruding pelletization, it is dry to get PVC/ montmorillonite/ Sepiolite nanocomposite.

The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 15Hz, and one area of extrusion temperature is 170 DEG C, Two 245 DEG C of areas, three 245 DEG C of areas, four 240 DEG C of areas, five 240 DEG C of areas；

Embodiment 8

PVC montmorillonite/black phosphorus nanocomposite

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

Wherein the mass ratio of montmorillonite and black phosphorus is 1:1, and the mass ratio of water and toluene is 1:1, lecithin and sodium alginate Mass ratio be 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 Black phosphorus powder adds lecithin and sodium alginate after ultrasonic 30min, continues ultrasound 60min, ultimately form paste montmorillonite/ Black phosphorus mixing material, the consistency of this mixing material are 26mm；

2, it is mixed thoroughly after mixing PVC with montmorillonite/black phosphorus mixing material, antioxidant NBC, double screw extruder charging is added Mouthful；

3, dry to get PVC/ montmorillonite/black through extruding pelletization by PVC and the further melt blending of montmorillonite/black phosphorus Phosphorus composite material.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 200 DEG C, Two 215 DEG C of areas, three 220 DEG C of areas, four 220 DEG C of areas, five 215 DEG C of areas；The linear velocity of screw speed is 0.7m/s.

Embodiment 9

PVC/ graphene/vanadic anhydride nanocomposite

Raw material: 100 parts of PVC, 75 parts of toluene/acetic acid graphene/vanadic anhydride, 15 parts of dicyandiamide formaldehyde resins/ 1 part of 1035/ antioxidant NBC of 6 parts of antioxidant of polyvinylamine

Wherein, the mass ratio of toluene and acetic acid is 1:1, and the mass ratio of graphene and vanadic anhydride is 1:1, dicyandiamide first The mass ratio of urea formaldehyde 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 graphene And vanadium pentoxide powder, dicyandiamide formaldehyde resin and polyvinylamine are added after ultrasonic 30min, continue ultrasound 60min, most End form is 86mm at paste graphene/vanadic anhydride mixing material, the consistency of this mixing material；

2, by PVC and graphene/vanadic anhydride mixing material, antioxidant 1035, antioxidant NBC, mix after mix thoroughly, add Enter twin-screw extrusion machine inlet；

3, PVC and the further melt blending of graphene/vanadic anhydride, it is dry to get PVC/ graphite through extruding pelletization Alkene/vanadic anhydride nanocomposite.

The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 200 DEG C, Two 250 DEG C of areas, three 250 DEG C of areas, four 250 DEG C of areas, five 250 DEG C of areas；The linear velocity of screw speed is 0.6m/s.

Comparative example 1

This comparative example prepares PVC/ graphene nanocomposite material by way of intercalation polymeric

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

Preparation method:

1, the graphene 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 graphene aqueous solution, 2h is stirred at 80 DEG C, reaction solution is filtered, is dry, The graphene that must be organised；

2, organic graphene is mixed with PVC, and catalyst SnCl2 is added, then put into double screw extruder melting Mixing is dry to get PVC/ graphene nanocomposite material through extruding pelletization.

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

Comparative example 2

On the basis of embodiment 1, the position of extruder, the method assisted using water is added in adjustment graphene to this comparative example Prepare PVC/ graphene nanocomposite material.

Raw material: 100 parts of PVC, 0.1 part of graphene of 10 parts of water

Preparation method:

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

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

3, graphene mud is put into the PVC melted completely, is received through extruding pelletization, drying to get PVC/ graphene Nano composite material.

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:

Classification	Tensile strength (MPa)	Impact strength (kgcm/cm)
			Embodiment 1	45	6
Embodiment 2	46	8
			Embodiment 3	48	6
Embodiment 4	50	7
			Embodiment 5	46	6
Embodiment 6	47	8
			Embodiment 7	49	6
Embodiment 8	50	6
			Embodiment 9	48	7
PVC base-material	40	5

By the above experimental result it is found that the impact strength and tensile strength of embodiment 1-9 compare PVC base-material obtains Larger promotion.This is because the present invention is fed in the presence of liquid medium jointly using PVC base-material and nano material, In PVC melting process, PVC and nano material interpenetrate cladding, and the gasification of liquid medium is so that nano material separation, And it is orderly dispersed in the PVC of melting, therefore its overall performance is improved.

Experimental example 2

This experimental example is received for comparing the PVC/ graphene as made from embodiment 1, comparative example 1,2 distinct methods of comparative example Nano composite material and difference of the PVC monomer in nano material content and performance, as shown in table 2.

Table 2:

Performance parameter	PVC monomer	Embodiment 1	Comparative example 1	Comparative example 2
					Nano material content %	0	2.1	1.8	1.6
Tensile strength MPa	40	45	43	42
					Bending strength MPa	78	100	97	99
Impact strength Kg cm/cm	5	6	4	4

As above data as can be seen that in the PVC/ graphene nanocomposite material as made from the method for embodiment 1 Nano material content is higher than comparative example 1 and comparative example 2, illustrates sufficiently remove and disperse very well by the method graphene In PVC.In addition, product made from embodiment 1 is superior to PVC monomer in tensile strength, bending strength, impact strength, and it is right Although the product tensile strength of ratio 1 and comparative example 2 is promoted, its impact strength declines, this is also furtherly The bright method by embodiment 1, nano material lamella can be highly dispersed in PVC, and then its tensile strength and impact strength are equal It can get a promotion.

Experimental example 3

1, (as shown in Figure 1) is schemed by the SEM of graphene in test paste, as can be seen from the figure sample is in relatively transparent State illustrates 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, as can be seen from the figure sample lamella is very It is thin, it can be considered that the single-layer graphene peeled away stacks, the surface folding of sample is because the material of two-dimensional structure is not easy Stablize individualism, fold is stablized conducive to graphene, and the sample further demonstrated is single layer or few layer graphene.

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 a little change or modification For the equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, according to the technical essence of the invention Any simple modification, equivalent change and modification to the above embodiments, in the range of still falling within the present invention program.

Claims (10)

1. a kind of PVC nanocomposite, which is characterized in that the nanocomposite is by including PVC granule, and by PVC The mixing of nano material and liquid medium that particle is coupled is made through melt blending.

2. a kind of PVC nanocomposite according to claim 1, which is characterized in that the nano material is received for stratiform Rice material, at least partly lamella of layered nano material are dispersed in PVC；

Preferably, layered nano material includes phyllosilicate, layered titanate, layer dress phosphate, laminated metal hydrogen-oxygen Compound, transition metal oxyhalide, lamellar graphite, transient metal sulfide, layered metal oxide, laminated metal nitride, Laminated metal carbide, two-dimensional metallic organic frame are one or more of；

It is furthermore preferred that nanocomposite XRD diffraction pattern is in 2 2-10 ° of the angle θ ranges when nano material is ionic stratified material Interior no interlamellar spacing characteristic peak.

3. a kind of PVC nanocomposite according to claim 2, which is characterized in that the liquid medium enters stratiform Nano material interlayer, being formed, there is the paste of certain consistency to be coupled PVC granule；The consistency of the paste be 0~ 100mm, but be not 0；

Preferably, the mass parts ratio of the liquid medium and stratified nano materials is 3~100:1；It is preferred that 5~50:1；It is more excellent Select 5~20:1.

4. a kind of PVC nanocomposite according to claim 3, which is characterized in that also contain in the paste and help Agent, the auxiliary agent include 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 or a variety of；Wherein preferably synthetic water-soluble high score One of son 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.

5. a kind of PVC nanocomposite according to claim 1 or 3, which is characterized in that the boiling point of the liquid medium Plasticization temperature lower than PVC, preferably boiling point are lower than 180 DEG C, more preferable water.

6. a kind of PVC nanocomposite according to claim 1, which is characterized in that in the mixing nano material with The mass parts ratio of PVC is 0.1~20:100；It is preferred that 1~10:100；More preferable 3~5:100；

Preferably, in the mixing there are also age resister, the mass parts ratio of the age resister and PVC are 0.1~1:100； It is preferred that 0.2~0.8:100；More preferable 0.3~0.6:100.

7. a kind of a kind of preparation method of any PVC nanocomposite of claim 1~6, which is characterized in that described Preparation method the following steps are included:

A, nano material and liquid medium are mixed, form nano material mixture paste；

B, the nano material mixture in step A is mixed to form blend with PVC granule；

C, the blend of step B is passed through into melt blending to get the PVC nanocomposite.

8. a kind of PVC nanocomposite according to claim 7, which is characterized in that auxiliary agent is additionally added in step A, it is described Auxiliary agent can be added at one time also to be added in batches；

Preferably, can also increase physics mode in step A promotes liquid medium to disperse between nano material, the physics mode Including colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock.

9. a kind of preparation method of PVC nanocomposite according to claim 7, which is characterized in that in step C, when When temperature is equal to or higher than PVC plastic temperature, the liquid medium in nanometer mixing material gasifies, described to gasify the nanometer of reunion Material separation；

Preferably, when the nano material is stratified nano materials, liquid medium enters stratified nano materials interlayer shape in step A At the paste with tack, in step C when temperature is equal to or higher than PVC plastic temperature, into the liquid medium of interlayer Gasification, stratified nano materials lamella is separated.

10. a kind of mixing characterized by comprising paste and PVC；

Paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not 0；Institute It states paste and is adhered to PVC granule surface formation mixing；

Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are dispersed.