CN110229413A - A kind of PP nanocomposite and preparation method thereof - Google Patents
A kind of PP nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to field of nanocomposite materials, specifically, it is related to a kind of nanometer composite polypropylene material and preparation method thereof, the nanocomposite is as premix through made from melt blending, the premix is formed by being combined with full be adhered between PP GRANULES of the nano material of liquid medium；When the nanocomposite is in some strength and/or range in stiffness, toughness is promoted with the promotion of intensity and/or rigidity.The preparation method includes that liquid medium and nano material are mixed to get paste, and the paste is adhered to PP GRANULES surface progress melt blending and obtains nanocomposite.Nanocomposite provided by the invention has excellent toughness, and process flow is short, at low cost, is suitble to promote the use of.
Description
Technical field
The present invention relates to field of nanocomposite materials, specifically, being related to a kind of PP nanocomposite and its preparation side
Method.
Background technique
It is squeezed out in existing technology frequently with nano material and mixed with polymers, composite material is formed, although such is compound
The tensile strength of material is promoted, but the problems such as due to nano material and the poor compatibility of polymer, leads to such material
Impact resistance it is generally not high.
To solve the above problems, enabling polymer occur in the interlayer of nano material frequently with modes such as intercalation in-situ polymerizations
It reacts to improve the impact resistance of composite material, but the process is time-consuming longer, polymeric reaction condition is harsh, and solvent is not
Easily recycling, can bring the variations such as environmental pollution.
Patent No. CN101081928A proposes a kind of preparation method of polyamide/nano montmorillonite masterbatch, auxiliary using water
Help method to prepare polyamide/nano montmorillonite masterbatch, it is intercalator that preparation method, which is with deionized water, by the montmorillonite of purifying and
Mud is added step-wise to the polyamide that prescription amount melts completely by deionized water mixing, fully dispersed obtained montmorillonite mud, then
Polyamide/nano montmorillonite masterbatch is obtained through extruding pelletization.Preparation method is simple, and production cost is low, but this method is poly-
Montmorillonite mud is added after amide melting, montmorillonite mud is will lead to and has not enough time to be thoroughly mixed with copolymer, interlayer
Water just because of high-temperature gasification, causes polyamide to fail to timely enter interlayer, meanwhile, it is insufficient only by the energy of water generation
Will be completely exfoliated between cheating engaging layer thus cannot obtain the composite material that type is completely exfoliated, properties of product are also received greatly
Influence.
In view of this, the present invention is specifically proposed.
Summary of the invention
The present invention is intended to provide a kind of nanocomposite, including nano material and polypropylene, the nano material are passed through
Interlayer divergence process does not need to carry out intercalation in-situ polymerization, it is multiple can to further increase polypropylene nano while promoting intensity
The toughness of condensation material material.
In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that
A kind of PP nanocomposite, which is characterized in that the nanocomposite is by premix through melt blending system
, the premix is formed by being combined with full be adhered between PP GRANULES of the nano material of liquid medium；It is described
The toughness of nanocomposite is promoted with the promotion of intensity and/or rigidity.
In above scheme, using macromolecule as the nanocomposite of base-material, in the mechanical property lifting process for representing intensity
In, it can be lost in terms of toughness, can even be lower than the toughness of base-material itself sometimes, reduce the scope of application of material；Study carefully
Its reason is due to poor compatibility between the part nano material component in composite material and part macromolecule, in addition, nano material
Itself produces reunions in process, can not it is evenly dispersed in the composite, also result in the scarce of certain mechanical properties
It loses.Nanocomposite provided by the invention is combined with liquid medium in nano material, and the liquid that is combined with is situated between
The nano material adherency of matter is wrapped in PP GRANULES surface and forms mixture, by said mixture through melt blending, using adding
Work temperature-rise period enables liquid medium undergo phase transition, so that nano material is dispersed in polypropylene, greatly improves compound
The toughness of material.
In above scheme, the liquid medium include at least water, can also include isopentane, pentane, petroleum ether, oneself
Alkane, hexamethylene, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, three
Trichlorotrifluoroethane, propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, just
Butanol, butyl acetate, propyl alcohol, methylisobutylketone, tetrahydrofuran, ethyl acetate, isopropanol, ethyl alcohol, chloroform, methyl ethyl ketone,
Dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, ether,
Pentane, methylene chloride, carbon disulfide, 1,1- dichloroethanes, trifluoroacetic acid, 1,1,1- trichloroethanes, ethyl alcohol, butanone, 1,2-
Dichloroethanes, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, butanol, acetic acid, one first of ethylene glycol
Ether, octane, morpholine, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, acetic anhydride, ortho-xylene, N,N-dimethylformamide, ring
One or more of hexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE；Preferably water.
Further scheme of the invention are as follows: the nano material includes stratified nano materials, layered nano material
At least partly lamella is in expansion shape in the composite.
In above scheme, layered nano material belongs to stratiform two-dimension nano materials, in layered nano material
Interlayer interlamellar spacing after combining liquid medium is expanded, and in the process of nanocomposite, is incorporated in stratified nano materials
The liquid medium of interlayer gasifies, so that interlayer is further expanded, enters interlayer convenient for polypropylene and forms composite material, may be used also
To prevent nano material in process from reuniting.Stratified nano materials have unique two-dimentional layer structure, two-dimentional laminate
Orienting ordered arrangement forms three-dimensional crystalline structure uniqueness, so that bedding void can be inserted by layer in liquid medium under certain condition
Plate struts, and without destroying the original structure of layer nano material, and the laminate composition and interlamellar spacing of stratified nano materials all have
Modulatory character.
Further scheme of the invention are as follows: the interlayer of the liquid medium injection stratified nano materials forms full adherency
Paste between PP GRANULES, the consistency of the paste are 0~100mm, but are not 0mm；The paste includes: to receive
Rice 1 parts by weight of material, 0.02~100 parts by weight of liquid medium；Preferably, the paste further includes 0~50 weight of auxiliary agent
Part, but be not 0.
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,
The paste has certain consistency, but consistency is not 0mm, represents the paste to be combined with liquid medium and having
The semisolid of certain fluidity, therefore can be by the nano material paste uniform adhesion for being combined with liquid medium poly- third
Alkene particle surface improves processability with the common feeding of PP GRANULES to the equipment of melt blending.Preferably, in order to
The amount for improving the combined liquid medium of stratified nano materials interlayer, can also be added auxiliary agent.
Further scheme of the invention are as follows: layered nano material include by fixed structure unit by shared angle,
Multilayer space net structure made of side or face accumulation, there are moveable lewis' acids for each interlayer.
In above scheme, there are when moveable ion, which has layered each interlayer of nano material
There is certain ion exchange capacity, preferred ion exchange capacity is 0.1~400mmol/100g range, such ionic stratiform is received
Rice material is usually used in intercalation polymeric technique, enables the interlayer of stratified nano materials and intercalator that ion occurs using acidification or alkalization
Exchange is modified to realize to nano material；And in the present invention, the ion exchange capacity between nano material and liquid medium is lower,
Ion exchange does not almost occur, so that liquid medium enters the paste that nano material interlayer forms high viscosity containing large amount of liquid amount
Object, convenient for further processing.The ionic stratified nano materials include the phyllosilicate of cationic, layered titanate,
The hydrotalcite-based compound of layer dress phosphate and anionic, specifically includes nano montmorillonite, nanometer potasium titanate, kaolin, sea
One or more of afrodite, hydrotalcite.
In above scheme, layered nano material can also be the non-ionic nanometer layer without ion exchange capacity
Shape material, by taking graphene as an example, as seen from Figure 1, graphene sample part is in relatively transparent state, explanation in the paste
Graphene film interlayer is stripped at this, and agglomeration is unobvious.As seen from Figure 2, graphene sample in the paste
Lamella is very thin, and there are the single-layer graphene peeled away stacking in visual range, the surface folding of sample is because of two dimension
The material of structure is not easy to stablize individualism, and fold is stablized conducive to graphene, and the sample further demonstrated is single layer
Or few layer graphene.The non-ionic nano lamellar 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, black phosphorus；
3. transient metal sulfide (TMDs): coordination environment and oxidation state based on metallic atom, transient metal sulfide
(TMDs) insulator (HfS2), semiconductor (MoS can be formed2), semimetal (TiSe2) and all-metal (NbSe2), 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. the 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..
The wherein chemical general formula of layered metal hydroxides are as follows:
[M(II)1-xM(III)x(OH)2]x+[Ax/n n-]·mH2O
M (II) is bivalent metal ion in formula, can be the divalent ions such as magnesium, nickel, cobalt, iron, copper, zinc, and M (III) is trivalent
Metal ion can be aluminium, chromium, iron etc., the closer stable plate layer more easy to form of the radius of divalent metal and trivalent metal
Structure.After these divalent and trivalent ion are carried out efficient combination, binary, ternary even the LDHs chemical combination of quaternary can be formed
Object.
Further scheme of the invention are as follows: the characterization parameter of the nanocomposite intensity includes tensile strength, rigidity
Characterization parameter include bending strength, the characterization parameter of toughness includes impact strength, the tensile strength of the nanocomposite
In 15~35MPa range and/or bending strength in 25~45MPa range, impact strength is strong with tensile strength and/or bending
The promotion of degree and improve 10~80%.
Further scheme of the invention are as follows: the nano material is 0.1~20:100 with polyacrylic mass ratio, preferably
1~10:100, more preferably 3~8:100；The polyacrylic isotactic index is 90~99.5%, preferably 95~99%；Institute
State polyacrylic melt flow rate (MFR) be 0.1~2000g/10min, preferably 0.2~100g/10min, more preferably 0.3~
80g/10min。
In above scheme, due to frequently with polyacrylic isotactic index it is higher, generally greater than 95%, thus it is corresponding its
Crystallinity is higher, and plasticization temperature and heat resistance improve, but will appear the problem of toughness declines, and the application fills polypropylene
Enter the nano material interlayer through interlayer divergence process, so that performance boost of the composite material in terms of toughness is larger.
The present invention also provides a kind of preparation methods of nanometer composite polypropylene material, which is characterized in that the preparation side
Method includes the following steps:
(1) liquid medium and nano material are mixed, obtain paste；
(2) paste will be obtained in step (1) to mix with PP GRANULES, enables paste is full to be adhered to PP GRANULES
Between obtain premix；
(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；
Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste.
In the above method, there is certain consistency semisolid paste since liquid medium and nano material to be mixed to get
Object, therefore slipping phenomenon will not occur for while being added to extrusion equipment after paste and PP GRANULES mixing, it can direct feeding
Nanocomposite, processing easy to produce are prepared, and it is multiple to avoid nanometer caused by liquid medium in the prior art gasifies too early
The poor problem of condensation material performance, through experiments, it was found that, compared with the prior art, nanocomposite made from mixing of the invention
Performance is more superior.
According to above-mentioned preparation method, in step (3), when melt blending, moulded in temperature greater than or equal to thermoplastic polymer
When changing temperature, liquid medium gasification in nanometer mixing material, the gasification separates the nano material of reunion, while the gasification
Heat is uniformly transferred in thermoplastic polymer and nano material；Preferably, the gasification softens thermoplastic polymer, and
Reduce the plasticization temperature of thermoplastic polymer.
According to above-mentioned preparation method, in step (3), it is higher than the boiling point of liquid medium in the temperature of melt blending and reaches poly-
During propylene plasticization temperature, liquid medium gasification separates the nano material of reunion；The boiling point of the liquid medium is lower than
Polyacrylic plasticization temperature, the boiling point are preferably not higher than 180 DEG C, and the liquid medium is preferably water；The liquid medium
Weight ratio with nano material is 0.02~100:1, preferably 5~50:1, more preferably 5~20:1.
In the above method, the application use will be added simultaneously in conjunction with the higher nano material of liquid medium amount and polypropylene to be added
Construction equipment, due to the lyophile media processes (forming paste) previously to nano material, so that the liquid content of nano material
It improves, therefore when entering polypropylene melt tabetisol, although system temperature is already higher than the boiling point of liquid medium, nano material is empty
Contained liquid medium is more so that phase transformation evaporation process can carry out simultaneously with polyacrylic melting process between gap, just makes molten state
Polypropylene can smoothly enter into interlayer, and improve the impact property of final products.And in the prior art, frequently with first to polymer
It carries out melting and adds the technical solution of the nano material containing liquid, and due to the undertreatment to nano material lyophile medium,
So that wherein liquid medium evaporation is too fast, nano material and polyacrylic compatibility are reduced, so that under the toughness of final products
Drop；On the other hand, in the prior art, is first added to polymer melting the time that nano material undoubtedly extends product preparation,
Waste time cost.
According to above-mentioned preparation method, in step (3), the premix that the paste and PP GRANULES are mixed to get is in nothing
Feeding to hot melt process equipment carries out melt blending under pressure condition.
In the above method, hot melt process equipment includes but is not limited to mixer, open mill or screw extruder (parallel/cone
Shape/mono-/bis -/tri- screw rods), when using screw extruder, premix that the shape object and PP GRANULES are mixed to get from
Without pressure feed zone charging, the charging under the conditions of no pressure is realized.It, can be by nano material directly and PP GRANULES in the present invention
Feeding is directly mixed and carried out, has benefited from nano material and forms the paste with certain consistency in conjunction with liquid medium, is prevented
Slipping phenomenon is stopped, on the other hand the content of the liquid medium as contained by nano material is higher, passes through first in premix
When melting zone, liquid medium therein will not too early phase transformation gasification, allow melting polypropylene preferably infiltrate into nanometer
The nanocomposite of good mechanical properties is formed between the gap of material.
According to above-mentioned preparation method, in step (1), the nano material includes stratified nano materials, further includes in stratiform
Auxiliary agent is added in nano material to improve interlayer liquid content, liquid medium contained by the interlayer of layered nano material is enabled to account for paste
The 50~98% of object gross mass, preferably 60~98%, more preferably 80~98%；The matter of the auxiliary agent and stratified nano materials
Amount is than being 0.01~50:1, preferably 0.1~5:1, and more preferably 0.2~1:1, the auxiliary agent includes carboxylate surface active
Agent, sulfate salt surfactant, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary ammonium
Salt surfactant, heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular and its prepolymer, synthesis
One or more of water-soluble macromolecule and its prepolymer.
In the above method, the premix in the present invention during the preparation process, taken polypropylene as the base material, uses lower content
Auxiliary agent, its purpose is between the gap of nano material formed lyophile medium environment, to improve containing for paste
Liquid measure；High-content intercalator used in intercalation polymeric compared to the prior art significantly reduces auxiliary agent to nano combined material
Expect the influence of overall performance.
In above scheme, the ability that liquid medium enters nano material is can be improved in the addition of auxiliary agent, to increase nanometer
The consistency of material blends；In addition, the addition of auxiliary agent can also improve the boiling point of liquid medium, prevent liquid medium from gasifying in advance
Evolution.Due in the present invention generate gel 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 includes but is not limited to one or more of following component:
A. surfactant:
1, anionic surfactant: it is divided into carboxylate, sulfuric acid, sulfonate and phosphate ester salt.
(1) soap kind is higher fatty acid salt, and general formula of molecular structure is (RCOO)-nMn+.With stearic acid, oleic acid, laurel
Acid etc. is more common.According to the difference of its metal ion (Mn+), there are alkali metal soap, alkaling earth metal base and organic amine soap etc..
(2) hydrosulphate is mainly the sulfuric acid ester of sulfated oil and higher aliphatic, general formula of molecular structure ROSO3-M
+, there are commonly lauryl sodium sulfate (also known as " sldium lauryl sulfate "), sodium hexadecyl sulfate (also known as " cetanol sulfuric acid
Sodium "), sodium stearyl sulfate (also known as " stearyl alcohol sodium sulphate ") etc..
(3) sulphonic acid compound mainly has aliphatic sulfonic compound, sulfo group aryl sulfonic acid compound, sulfo group naphthalene sulfonic acids compound etc.
2, cationic surfactant: containing nitrogen-atoms in the hydrophilic group ion of cationic surfactant, according to nitrogen original
The position difference of son in the molecule is divided into amine salt, quaternary ammonium salt and heterocyclic type three classes.Such as benzalkonium chloride (trade name " geramine "), benzene
Prick bromine ammonium (trade name " bromogeramine "), chlorination (bromination) cetyl pyridinium (trade name " Xi Bailin ") etc.
3, zwitterionic surfactant: lecithin, amino acid pattern, betaine type
4, nonionic surfactant: fatty glyceride, fatty acid sorbitan (sapn), polysorbate (tween), alkane
Base phenol polyethenoxy ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester APEO, detergent series.
B. water soluble polymer includes:
1, natural class macromolecule
Starch
Seaweeds: sodium alginate, agar-agar.
Natural plant gum class: Arabic gum, tragacanth gum, locust bean gum, tamarind seed polysaccharide glue, sesbania gum, carrageenan, guar gum, fruit
Glue.
Animal glue class: gelatin, casein, chitosan.
Microbiological gum: xanthan gum, gellan gum, hyaluronic acid.
2, class macromolecule and its prepolymer are synthesized
(1) polymeric type water soluble polymer and its prepolymer
Polyacrylamide, polyacrylic acid, polymethylacrylic acid and its copolymer, polyvinyl alcohol, polyethylene glycol, 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 and its prepolymer
Water soluble amino resin, water soluble phenol resin, water soluble alkyd resin, water-soluble epoxy resin, water-soluble poly
Urethane resin, polyethylene imine, poly-aspartate, poly-epoxy succinic acid, polyamine epichlorohydrin resin, polyamide second two
Urea 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.
Preferably synthetic class macromolecule and its prepolymer.
According to above-mentioned preparation method, nano material and the adding manner of auxiliary agent include being added at one time in the step (1)
It is added in batches；It is respectively 0.01-100g/min that speed, which is added, preferably 5-10g/min, more preferable 7g/min.
According to above-mentioned preparation method, the step (1) further includes implementing physical dispersion, the physics to stratified nano materials
Dispersion includes but is not limited to colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock etc.；Preferably, the physical dispersion
For ultrasound, the frequency of the ultrasonic field is 800~1000Hz, and power is 200~1000W.
In the above method, when layered nano material is non-ionic stratified material, there is more stable molecular structure,
In order to allow the interlayer of such nano material to inject more liquid mediums, the expansion journey of interlayer is promoted using physical dispersion method
Degree, so that liquid medium, which enters nano material interlayer, forms the paste with certain consistency, in order to be further processed.
According to above-mentioned preparation method, the preparation method further includes addition latex shape in the paste made from step (1)
Resulting mixture, the mixture is blended with polypropylene fusion later, and the mass ratio of the latex and paste is 0.1~10:1,
The latex includes styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon cream
Liquid, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, chlorine
One of fourth latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of.
In the above method, after the completion of prepared by the nano material paste for being combined with liquid medium, latex can also be utilized
Mixed processing carried out to paste precast body, and by the paste and polypropylene melt blending simultaneously after latex mixed processing
Following process is carried out, above-mentioned mixed processing has greatly delayed the release rate of interlayer liquid medium, effectively prevent liquid medium
Phase transformation occurs to early, on the other hand, the nanometer when mixed processing of latex and paste further improves liquid medium phase transformation
The scale of material void expansion is conducive to the gap realization filling that polymer travels further into nano material.
According to above-mentioned preparation method, the preparation method further includes before or during melt blending to paste and poly- third
The age resister being added in the premix that alkene particle is formed, the age resister and polyacrylic weight ratio are 0.1~1:100,
Preferably 0.3:100；The age resister is selected from amine antioxidants, phenolic antioxidant, thio-2 acid vinegar kind antioxidant and Asia
One or more of phosphoric acid vinegar kind antioxidant.
In the above method, the age resister includes:
Amine antioxidants: there are ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, hindered amine；
Phenolic antioxidant: alkylation monophenols, alkylation polyphenol, thiobisphenol and polyphenol can be divided into.Alkylation monophenols and
Polyphenol antioxidant principal item has antioxidant 264,1076,2246,1035,1010,3114 and 1790；The main product of thiobisphenol
Kind has antioxidant 2246 and 300；Polyatomic phenol antioxidant principal item has 2,5 1 di-t-butyl hydroquinones and 2,5 12 tertiary pentyls
Quinhydrones；
Thio-2 acid vinegar and phosphorous vinegar kind antioxidant；Its principal item has anti-aging agent TNP, Ultranox624 and Asia
Tricresyl phosphate (2,4 1 di-tert-butyl) ester.
Other type antioxidants: 2 one coloured glaze base benzo miaow trade name antioxidant MBs, nickel dibutyl dithiocarbamate
Trade name antioxidant NBC, there are also zinc dialkyl dithiophosphates.
The age resister specifically includes: anti-aging agent RD, antioxidant A W, antioxidant BLE, antioxidant A, anti-aging agent OD, 4,
4 '-bis- (α-methylbenzyl) diphenylamines, 4,4 '-bis- (α, α-methylbenzyl) diphenylamines, N, N ,-di-sec-butyl-p-phenyl enediamine prevent
Old 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, antioxygen
Agent DLTP, antioxidant TNP, Ultranox624, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, antioxidant MB, antioxidant NBC,
Zinc dialkyl dithiophosphate.
The present invention also provides a kind of premix, the premix includes paste and polypropylene；The paste includes:
1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but be not 0；The paste is covered poly-
Particulate propylene surface forms premix；Preferably, during preparing paste, successively by nano material and auxiliary agent be added to
In liquid medium and dispersed；It is furthermore preferred that the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, quarter
Erosion auxiliary or gas shock；It is further preferred that nano material and the adding manner of auxiliary agent are including being added at one time and in batches
It is added.
The preparation method of above-mentioned nanometer composite polypropylene material specifically comprises the following steps:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01~100g/min and is persistently stirred
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 0.02~100:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) in batches or once with the speed of 0.01~100g/min,
Obtain paste, the consistency of the paste is 0~100mm, and the weight ratio of the auxiliary agent and nano material is 0.001~50:
1；
(3) paste and PP GRANULES that step (2) obtains are mixed to get premix；
(4) by the premix of step (3), feeding hot melting equipment, melt blending simultaneously carry out subsequent add under the conditions of no pressure
Work obtains nanocomposite.
According to the above method, when the hot melting equipment is screw extruder, engine speed is 30~80Hz, and main feeding hopper turns
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 areas 230~
280 DEG C, five 230~280 DEG C of areas；It is preferred that engine speed is 60Hz, main feeding hopper revolving speed is 20Hz, and extrusion temperature is an area 150
~180 DEG C, two 245~260 DEG C of areas, three 245~255 DEG C of areas, four 240~250 DEG C of areas, five 240~260 DEG C of areas.Screw speed
Linear velocity be 0.6~1m/s.
It further include carrying out mixed processing using latex and paste afterwards in step (2), then carry out step according to the above method
(3) technique.
The invention has the benefit that
1. nanometer composite polypropylene material provided by the invention in terms of mechanical property, especially has in terms of impact property
Biggish promotion, and simple process is easy to operate, and the used time is short, is suitable for promoting；
2. the present invention melts the higher nano material of liquid content with polypropylene simultaneously, during composite processing
Heat improve nano material gap between liquid medium molecular energy, promote interlayer liquid medium to undergo phase transition, expanded and received
The gap of rice material, so that the polypropylene of molten state enters realization filling；
3. nano material provided by the invention through auxiliary agent processing formed have compared with containing large amount of liquid amount paste, with polypropylene
Simultaneously during melt-processed, it is incorporated in the time and polypropylene fusion that the interstitial liquid medium of nano material is undergone phase transition
Time matches, and enters between the gap of nano material and is filled conducive to the polypropylene of molten state；
4. nano material provided by the invention is while using liquid medium phase transformation expansion gap, also playing prevents from receiving
The effect that rice material is reunited.
Detailed description of the invention
Fig. 1 is that the SEM of paste laminate nano material graphene of the invention schemes.
Fig. 2 is that the TEM of paste laminate nano material graphene of the invention schemes.
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
In the present embodiment, nano material and polyacrylic mass ratio are 20:100, the liquid medium used for water, use
Auxiliary agent is cetylpyridinium chloride, and it is multiple to be prepared as follows nanometer for laminar nano montmorillonite for the nano material used
Condensation material:
(1) liquid medium is stirred, while nano material is added with the speed of 5.6g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 20:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) in batches or once with the speed of 0.1g/min, obtains cream
Shape object, the consistency of the paste are 32mm, and the weight ratio of the auxiliary agent and nano material is 10:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 30Hz, and main feeding hopper revolving speed is 10Hz, and extrusion temperature is 150 DEG C of an area,
Two 230 DEG C of areas, three 240 DEG C of areas, four 280 DEG C of areas, five 260 DEG C of areas, the linear velocity of screw speed are 0.8m/s.
The tensile strength of finally obtained nanometer composite polypropylene material is 28MPa, bending strength 36MPa, and impact is strong
Degree is 91kgcm/cm.
Embodiment 2
In the present embodiment, nano material and polyacrylic mass ratio are 10:100, used liquid medium be acetone and
The mass ratio of water, acetone and water is 7:93, and used auxiliary agent is polyacrylic acid and polymaleic anhydride, and weight ratio 1:1 is used
Nano material be kaolin, be prepared as follows nanocomposite:
(1) liquid is stirred, while nano material is added with the speed of 10g/min and is persistently dispersed with stirring
Even, the weight ratio of liquid medium and nano material is 100:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.5g/min, obtains paste, it is described
The consistency of paste is 15mm, and the weight ratio of the auxiliary agent and nano material is 50:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 80Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 190 DEG C,
Two 280 DEG C of areas, three 260 DEG C of areas, four 260 DEG C of areas, five 250 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 26MPa, and bending strength is
34MPa, impact strength 80kgcm/cm.
Embodiment 3
In the present embodiment, nano material and polyacrylic mass ratio are 0.1:100, and the liquid medium used uses for water
Auxiliary agent be sodium alginate, the nano material used is nano montmorillonite and kaolin, mass ratio 8:2, as follows
Prepare nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 50:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 15g/min, obtains paste, the cream
The consistency of shape object is 26mm, and the weight ratio of the auxiliary agent and nano material is 0.1:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix feeding mixer of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tensile strength of finally obtained nanometer composite polypropylene material is 26MPa, bending strength 36MPa, and impact is strong
Degree is 83kgcm/cm.
Embodiment 4
In the present embodiment, nano material and polyacrylic mass ratio are 1:100, and the liquid medium used is N, N- dimethyl
Formamide, the auxiliary agent used is polyethylene imine and its oligomer, and the nano material used is layered hydroxide Mg/Al-
LDHs, the age resister used are prepared as follows nanocomposite for anti-aging agent RD:
(1) liquid medium is stirred, while nano material is added with the speed of 15g/min and is persistently dispersed with stirring
Uniformly applying frequency simultaneously is 800~1000Hz, and power is the ultrasound of 200~1000W, the weight of liquid medium and nano material
Than for 5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 100g/min, obtains paste, it is described
The consistency of paste is 83mm, and the weight ratio of the auxiliary agent and nano material is 5:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C,
Two 245 DEG C of areas, three 255 DEG C of areas, four 250 DEG C of areas, five 240 DEG C of areas；The linear velocity of screw speed is 0.9m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 27MPa, and bending strength is
37MPa, impact strength 88kgcm/cm.
Embodiment 5
In the present embodiment, nano material and polyacrylic mass ratio are 3:100, the liquid medium used be hexamethylene with
Water, mass ratio 1:5, the auxiliary agent used is polyamide glyoxal resin, and the nano material used is layered potassium titanate, according to such as
Lower section method prepares nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 20g/min and is persistently dispersed with stirring
Uniformly, the weight ratio of liquid medium and nano material is 0.5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 1g/min, obtains paste, the cream
The consistency of shape object is 43mm, and the weight ratio of the auxiliary agent and nano material is 0.2:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 15Hz, and one area of extrusion temperature is 170 DEG C,
Two 245 DEG C of areas, three 255 DEG C of areas, four 250 DEG C of areas, five 260 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 28MPa, and bending strength is
38MPa, impact strength 84kgcm/cm.
Embodiment 6
In the present embodiment, nano material and polyacrylic mass ratio are 4:100, the liquid medium used for water, use
Auxiliary agent is dicyandiamide formaldehyde resin, and the nano material used is prepared as follows nanocomposite for sepiolite:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 10:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.1g/min, obtains paste, it is described
The consistency of paste is 67mm, and the weight ratio of the auxiliary agent and nano material is 1:1, further, by paste and terpinol
Mixed processing；
(3) paste mixed with terpinol and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 160 DEG C,
Two 245 DEG C of areas, three 280 DEG C of areas, four 260 DEG C of areas, five 260 DEG C of areas；The linear velocity of screw speed is 0.7m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 26MPa, and bending strength is
35MPa, impact strength 94kgcm/cm.
Embodiment 7
In the present embodiment, nano material and polyacrylic mass ratio are 1:100, and the liquid medium used is water and positive penta
The mass ratio 1:2 of alkane, water and pentane, used auxiliary agent be lauryl sodium sulfate, the nano material used for graphene,
It is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 20g/min and is persistently dispersed with stirring
Uniformly applying frequency simultaneously is 800~1000Hz, and power is the ultrasound of 200~1000W, the weight of liquid medium and nano material
Than for 40:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 37g/min, obtains paste, the cream
The consistency of shape object is 56mm, and the weight ratio of the auxiliary agent and nano material is 3:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from feeding open mill, melt blending simultaneously carries out following process, obtains nano combined
Material.
The tensile strength of finally obtained nanometer composite polypropylene material is 27MPa, bending strength 38MPa, and impact is strong
Degree is 82kgcm/cm.
Embodiment 8
In the present embodiment, nano material and polyacrylic mass ratio are 5:100, the liquid medium used for water, use
Auxiliary agent is hyaluronic acid, and the nano material used is prepared as follows nanocomposite for FeOCl:
(1) liquid medium is stirred, while nano material is added with the speed of 0.5g/min and carries out continuing stirring point
It dissipates and applies frequency simultaneously uniformly as 800~1000Hz, power is the ultrasound of 200~1000W, the weight of liquid medium and nano material
Amount is than being 3:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 60g/min, obtains paste, the cream
The consistency of shape object is 27mm, and the weight ratio of the auxiliary agent and nano material is 35:1；
(3) paste and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 200 DEG C,
Two 230 DEG C of areas, three 280 DEG C of areas, four 230 DEG C of areas, five 280 DEG C of areas；The linear velocity of screw speed is 0.6m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 28MPa, and bending strength is
37MPa, impact strength 86kgcm/cm.
Embodiment 9
In the present embodiment, nano material and polyacrylic mass ratio are 18:100, the liquid medium used for water, use
Auxiliary agent is chitosan and ammonia-dimethylamine-epichlorohydrin resin, chitosan and ammonia-dimethylamine-epichlorohydrin resin quality
Than for 10:1, used nano material is vanadic anhydride, it is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 5g/min and is persistently dispersed with stirring
Uniformly applying frequency simultaneously is 800~1000Hz, and power is the ultrasound of 200~1000W, the weight of liquid medium and nano material
Than for 40:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 12g/min, obtains paste, the cream
The consistency of shape object is 59mm, and the weight ratio of the auxiliary agent and nano material is that 6:1 further mixes paste and terpinol
Conjunction processing；
(3) paste mixed with terpinol and polypropylene that step (2) obtains are mixed to get premix；
(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add
Work obtains nanocomposite.
The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 155 DEG C,
Two 275 DEG C of areas, three 270 DEG C of areas, four 260 DEG C of areas, five 230 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 28MPa, and bending strength is
38MPa, impact strength 95kgcm/cm.
Comparative example 1
In this comparative example, on the basis of embodiment 1, the position of extruder is added in adjustment nano material containing liquid, in no pressure
Feeding polypropylene under the conditions of power, in polypropylene after melting zone, interlayer is contained the nano material feeding of liquid medium by pressurization
It is mixed with the polypropylene of molten state.
The difference of comparative example 1 and embodiment is: nano material between polypropylene and gap containing liquid medium is simultaneously non-concurrent
Feeding, but first feeding polypropylene and after polypropylene fusion, the nano material containing liquid is processed between feeding gap of pressurizeing.
The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 23MPa, and bending strength is
29MPa, impact strength 70kgcm/cm.
Mechanics Performance Testing is carried out to Examples 1 to 9 and comparative example 1, respectively obtains tensile strength, bending strength, bending
The performance parameter of modulus and impact strength is as shown in the table:
As seen from the above table, the mechanical property of nanocomposite obtained by Examples 1 to 9 is above the performance ginseng of comparative example 1
Number, especially there is promotion by a relatively large margin in impact strength, to find out its cause, being phase transformation of the present invention using liquid medium to receiving
Rice material has carried out interlayer divergence process, is filled so that entering interlayer with the polypropylene that nano material melts simultaneously, above-mentioned
The heat that processing generates when polymer melting is utilized in interlayer divergence process enables liquid medium evaporation generate implosion and struts interlayer,
Simultaneously using the shearing force for squeezing out processing, interlayer is further peeled off, so that molten state polypropylene realizes the filling of interlayer, to mention
The high impact strength of product.
Further, it is higher to compare other embodiments for the impact strength of embodiment 6 and embodiment 9, to find out its cause, being molten
The processing of mixing latex is carried out before melting processing to nano material paste, so that liquid medium evaporation generates in melting process
Implosive force it is stronger, the expansion effect in nano material gap is more preferable so that it is polyacrylic filling it is more abundant, improve final production
The impact strength of object.
The above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that this hair
It is bright to be not limited to specific embodiment described here, be able to carry out for a person skilled in the art it is various it is apparent variation, again
Adjustment and substitution are without departing from protection scope of the present invention.Therefore, although by above embodiments to the present invention carried out compared with
For detailed description, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, can be with
Including more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (10)
1. a kind of PP nanocomposite, which is characterized in that
The nanocomposite is as premix through made from melt blending, the premix is by being combined with liquid medium
Nano material is full to be adhered to and is formed between PP GRANULES；
The toughness of the nanocomposite is promoted with the promotion of intensity and/or rigidity.
2. nanocomposite according to claim 1, which is characterized in that the nano material includes laminar nano material
Material, at least partly lamella of layered nano material is in expansion shape in the composite；Layered nano material include by
By multilayer space net structure made of shared angle, side or face accumulation, each interlayer exists moveable fixed structure unit
Lewis' acid.
3. composite material according to claim 1 or 2, which is characterized in that
The interlayer of the liquid medium injection stratified nano materials, forms the full paste being adhered between PP GRANULES, institute
The consistency for stating paste is 0~100mm, but is not 0mm；
The paste includes:
1 parts by weight of nano material
0.02~100 parts by weight of liquid medium；
Preferably, the paste further includes,
0~50 parts by weight of auxiliary agent, but be not 0.
4. composite material according to any one of claims 1 to 3, which is characterized in that the nanocomposite intensity
Characterization parameter include tensile strength, the characterization parameter of rigidity includes bending strength, and the characterization parameter of toughness includes impact strength,
The tensile strength of the nanocomposite, in 25~45MPa range, is impacted in 15~35MPa range and/or bending strength
Intensity improves 10~80% with the promotion of tensile strength and/or bending strength.
5. composite material according to claims 1 to 4, which is characterized in that the nano material and polyacrylic mass ratio
For 0.1~20:100, preferably 1~10:100, more preferably 3~8:100；The polyacrylic isotactic index be 90~
99.5%, preferably 95~99%；The polyacrylic melt flow rate (MFR) be 0.1~2000g/10min, preferably 0.2~
100g/10min, more preferably 0.3~80g/10min.
6. a kind of preparation method of nanometer composite polypropylene material, which is characterized in that the preparation method includes the following steps:
(1) liquid medium and nano material are mixed, obtain paste；
(2) paste will be obtained in step (1) to mix with PP GRANULES, enables paste is full to be adhered between PP GRANULES
To premix；
(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；
Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste.
7. preparation method according to claim 6, which is characterized in that in step (3), be higher than liquid in the temperature of melt blending
The boiling point of body medium and during reaching polypropylene plasticization temperature, liquid medium gasification separates the nano material of reunion；Institute
The boiling point of liquid medium is stated lower than polyacrylic plasticization temperature, the boiling point is preferably not higher than 180 DEG C, and the liquid medium is excellent
It is selected as water；The weight ratio of the liquid medium and nano material be 0.02~100:1, preferably 5~50:1, more preferably 5~
20:1。
8. preparation method according to claim 6 or 7, which is characterized in that in step (1), the nano material includes layer
Shape nano material further includes auxiliary agent being added in stratified nano materials to improve interlayer liquid content, enables layered nano material
Interlayer contained by liquid medium account for the 50~98% of paste gross mass, preferably 60~98%, more preferably 80~98%；Institute
The mass ratio for stating auxiliary agent and stratified nano materials is 0.01~50:1, preferably 0.1~5:1, more preferably 0.2~1:1, described
Auxiliary agent includes carboxylate surface active agent, sulfate salt surfactant, sulfosalt surfactant, phosphate ester salt surface-active
Agent, amine salt surfactant, quaternary surfactant, heterocyclic type surfactant, nonionic surfactant are natural water-soluble
Macromolecule, one or more of synthetic water soluble high molecular and its prepolymer.
9. preparation method according to any one of claims 6 to 8, which is characterized in that the preparation method further include
Latex is added in paste made from step (1) and forms mixture, the mixture is blended with polypropylene fusion later, the glue
The mass ratio of cream and paste is 0.1~10:1, and the latex includes styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicon
Acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion,
One of styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are more
Kind.
10. a kind of premix characterized by comprising
The premix includes paste and polypropylene；
The paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not
0；
The paste, which covers, forms premix on PP GRANULES surface；
Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are divided
It dissipates；
It is furthermore preferred that the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, etching auxiliary or gas shock；
It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.
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| CN201810184901.9A CN110229413B (en) | 2018-03-06 | 2018-03-06 | PP (polypropylene) nano composite material and preparation method thereof |
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| CN201810184901.9A CN110229413B (en) | 2018-03-06 | 2018-03-06 | PP (polypropylene) nano composite material and preparation method thereof |
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| WO2024066972A1 (en) * | 2022-09-30 | 2024-04-04 | 金发科技股份有限公司 | High-primer painting rate polypropylene material, preparation method therefor, and use thereof |
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| CN1752112A (en) * | 2004-09-20 | 2006-03-29 | 中国科学院化学研究所 | Montmorillonoid in-situ organises and prepares the method for nano composite polymer-montmorillonoid material |
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| CN1752112A (en) * | 2004-09-20 | 2006-03-29 | 中国科学院化学研究所 | Montmorillonoid in-situ organises and prepares the method for nano composite polymer-montmorillonoid material |
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| WO2024066972A1 (en) * | 2022-09-30 | 2024-04-04 | 金发科技股份有限公司 | High-primer painting rate polypropylene material, preparation method therefor, and use thereof |
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