CN110229510A - A kind of PA66 nanocomposite and preparation method thereof - Google Patents
A kind of PA66 nanocomposite and preparation method thereof Download PDFInfo
- Publication number
- CN110229510A CN110229510A CN201810183428.2A CN201810183428A CN110229510A CN 110229510 A CN110229510 A CN 110229510A CN 201810183428 A CN201810183428 A CN 201810183428A CN 110229510 A CN110229510 A CN 110229510A
- Authority
- CN
- China
- Prior art keywords
- nano
- paste
- nano material
- polyamide
- liquid medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to field of nanocomposite materials, specifically, it is related to a kind of PA66 nanocomposite and preparation method thereof, the nanocomposite is as premix through made from melt blending, the premix is formed by being combined with full be adhered between polyamide 66 particle of the nano material of liquid medium.The preparation method includes that liquid medium and nano material are mixed to get paste, and the paste is adhered to polyamide 66 particle surface progress melt blending and obtains nanocomposite.Nanocomposite provided by the invention has excellent toughness, and process flow is short, at low cost, is suitble to promote the use of.
Description
Technical field
The present invention relates to field of nanocomposite materials, specifically, being related to a kind of PA66 nanocomposite and its preparation
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 send out between the gap of nano material frequently with modes such as intercalation in-situ polymerizations
It is raw to react to improve the impact resistance of composite material, but the process is time-consuming longer, polymeric reaction condition is harsh, and molten
Agent is not easily recycled, and can bring the variations such as environmental pollution.
Patent No. CN101081928A proposes a kind of preparation method of polyamide/nano montmorillonite masterbatch, using water
Auxiliary law prepares polyamide/nano montmorillonite masterbatch, and it is intercalator that preparation method, which is with deionized water, and the illiteracy of purifying is taken off
Mud is added step-wise to the polyamides that prescription amount melts completely by soil and deionized water mixing, fully dispersed obtained montmorillonite mud
Amine, then polyamide/nano montmorillonite masterbatch is obtained through extruding pelletization.Preparation method is simple, and production cost is low, but this method
It is to add montmorillonite mud after molten polyamide, will lead to montmorillonite mud and have not enough time to be thoroughly mixed with copolymer,
The water of interlayer just because of high-temperature gasification, causes polyamide to fail to timely enter interlayer, meanwhile, only by water generation
Energy, which is not enough to be completely exfoliated between cheating engaging layer, thus cannot obtain the composite material that type is completely exfoliated, properties of product
Receive strong influence.
In view of this, the present invention is specifically proposed.
Summary of the invention
The present invention is intended to provide a kind of nanocomposite, including nano material and polyamide 66, the nano material
The stretched processing in gap does not need to carry out intercalation in-situ polymerization, can further increase polyamide while promoting intensity
The toughness of 66 nanocomposites.
In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that
A kind of PA66 nanocomposite, which is characterized in that the nanocomposite is by premix through melt blending
Obtained, the premix is formed by being combined with full be adhered between polyamide 66 particle of the nano material of liquid medium.
In above scheme, the amide groups repeated in polyamide molecule segment is one with polar group, this collection
Hydrogen in group can form quite powerful hydrogen bond in conjunction with the oxygen on the carbonyl on the amide group segment of another molecule.
Hydrogen bond is formed such that the structure of polyamide easily crystallizes.And since intermolecular active force is larger, so that poly-
Amide has higher mechanical strength and high plasticization temperature.On the other hand the presence in polyamide molecule due to methylene makes
It is submissiveer to obtain strand, thus also toughness with higher, but during forming composite material with nano material,
Since nano material and the compatibility of polyamide are there are difference, the toughness that will lead to polyamide itself is declined, in addition, poly-
The major defect of amide is that hydrophily is too strong, and the dimensional stability after leading to water suction is deteriorated.
In above scheme, using macromolecule as the nanocomposite of base-material, in the mechanical property lifting process for representing intensity
In, it can be lost in terms of toughness, can even be lower than the toughness of base-material itself sometimes, reduce the scope of application of material；Study carefully
Its reason is due to poor compatibility between the part nano material component in composite material and part macromolecule, in addition, nanometer material
Material itself produce reunion in process, can not it is evenly dispersed in the composite, also result in certain mechanical properties
Missing.Nanocomposite provided by the invention is combined with liquid medium in nano material, and is combined with liquid for described
The nano material adherency of medium is wrapped in polyamide 66 particle surface and forms mixture, by said mixture through melt blending, benefit
It enables liquid medium undergo phase transition with processing temperature-rise period, so that nano material is dispersed in polyamide 66, greatlys improve
The toughness of composite material.
In above scheme, the liquid medium include at least water, can also include isopentane, pentane, petroleum ether, oneself
Alkane, hexamethylene, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, three
Trichlorotrifluoroethane, propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, just
Butanol, butyl acetate, propyl alcohol, methylisobutylketone, tetrahydrofuran, ethyl acetate, isopropanol, ethyl alcohol, chloroform, methyl ethyl ketone,
Dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, second
Ether, pentane, methylene chloride, carbon disulfide, 1,1- dichloroethanes, trifluoroacetic acid, 1,1,1- trichloroethanes, ethyl alcohol, butanone,
1,2- dichloroethanes, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, butanol, acetic acid, ethylene glycol
Monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, acetic anhydride, ortho-xylene, N, N- dimethyl formyl
One or more of amine, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE；Preferably water.
In above scheme, staff of the invention it was unexpectedly observed that polyamide hydrophilic it is too strong and absorb water after size it is steady
Qualitative variation, although using the liquid medium based on water to infuse between nano material gap in the technical solution of the application
Liquid, but merged using the higher nano material of water content with polyamide 66 and its copolymer after fluid injection and mix and squeeze out
During processing, the dimensional stability of polyamide 66 is not impacted included in the interstitial water body of nano material, very
To also improving the impact strength of polyamide 66 composite material.
Further scheme of the invention are as follows: the nano material includes the one of zero dimensional nanometer materials or monodimension nanometer material
Kind is a variety of, and the liquid medium injects and fill the gap of nano material, forms the paste with tack.
Further scheme of the invention are as follows: the paste includes: 1 parts by weight of nano material, liquid medium 0.02~
100 parts by weight；Preferably, it is also preferable to include, 0~50 parts by weight of auxiliary agent for the paste, but are not 0.
Further scheme of the invention are as follows: the consistency of the paste is 0~100mm, but is not 0mm.
In above scheme, compared to the prior art to nano-material modified filtering and dry process, nanometer of the invention
After material is between liquid medium is injected gap, paste continuous, and that there is certain tack, the paste are formd
Object has certain consistency, but consistency is not 0mm, represents the paste to be combined with liquid medium and having a constant current
The semisolid of dynamic property, therefore can be by the nano material paste uniform adhesion for being combined with liquid medium in polyamide 66
Particle surface improves processability with the common feeding of polyamide 66 particle to the equipment of melt blending.Preferably, in order to
The amount for improving the combined liquid medium of nano material, can also be added auxiliary agent.
Further scheme of the invention are as follows: the zero dimensional nanometer materials and monodimension nanometer material include nano silicon oxide, are received
Rice titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nanogold, nano silver, nano-silicon, are received nano-nickel oxide
Rice carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur, nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nanometer
Erbium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, is received nano-cerium oxide
One of rice tellurium oxide, nano oxidized niobium, nano-hafnium oxide or nanoscale molybdenum oxide are a variety of.
In above scheme, the ion exchange capacity between nano material and liquid medium is lower, and ion exchange does not almost occur,
So that liquid medium enters the paste that nano material forms high viscosity containing large amount of liquid amount, convenient for further processing.
Further scheme of the invention are as follows: the mass ratio of the nano material and polyamide 66 is 0.1~20:100, excellent
It is selected as 1~10:100, more preferably 4:100.
The present invention also provides a kind of preparation methods of polyamide 66 nanocomposite, 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 polyamide 66 particle, enables paste is full to be adhered to polyamide
Premix is obtained between 66 particles；
(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；
Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste
Object.
In the above method, there is certain consistency semisolid paste since liquid medium and nano material to be mixed to get
Object, therefore slipping phenomenon will not occur for while being added to extrusion equipment after paste and polyamide 66 particle mixing, can directly feed
Material prepares nanocomposite, processing easy to produce, and avoids nanometer caused by liquid medium in the prior art gasifies too early
The poor problem of composite property, through experiments, it was found that, it is compared with the prior art, nano combined made from mixing of the invention
Material property is more superior.
According to above-mentioned preparation method, in step (3), when melt blending, moulded in temperature greater than or equal to thermoplastic polymer
When changing temperature, liquid medium gasification in nanometer mixing material, the gasification separates the nano material of reunion, while the gas
Change uniformly transfers heat in thermoplastic polymer and nano material；Preferably, the gasification is soft by thermoplastic polymer
Change, and reduces the plasticization temperature of thermoplastic polymer.
According to above-mentioned preparation method, in step (3), it is higher than the boiling point of liquid medium in the temperature of melt blending and reaches
During polyamide 66 plasticization temperature, liquid medium gasification separates the nano material of reunion；The boiling of the liquid medium
Point is lower than the plasticization temperature of polyamide 66, and the boiling point is preferably not higher than 180 DEG C, and the liquid medium is preferably water；It is described
The weight ratio of liquid medium and nano material is 0.02~100:1, preferably 5~50:1, more preferably 5~20:1.
In the above method, the application use will add simultaneously in conjunction with the higher nano material of liquid medium amount with polyamide 66
Enter process equipment, due to the lyophile media processes (forming paste) previously to nano material, so that nano material contains
Liquid measure improves, therefore when entering polyamide 66 melting zone, although system temperature is already higher than the boiling point of liquid medium, receives
Contained liquid medium is more between rice material void carry out the melting process of phase transformation evaporation process and polyamide 66 can simultaneously,
Just make molten state polyamide 66 that can smoothly enter into the gap of nano material, and improves the impact property of final products.And show
Have in technology, adds the technical solution of the nano material containing liquid frequently with first melting is carried out to polymer, and due to nanometer
The undertreatment of material lyophile medium reduces nano material and polyamide 66 so that wherein liquid medium evaporation is too fast
Compatibility, so that the toughness of final products declines；On the other hand, in the prior art, a nanometer material first is added to polymer melting
Material undoubtedly extends the time of product preparation, wastes time cost.
According to above-mentioned preparation method, in step (3), premix that the paste and polyamide 66 particle are mixed to get
Feeding to hot melt process equipment carries out melt blending under the conditions of no pressure.
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 polyamide 66 particle 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 polyamide in the present invention
66 particles directly mix and carry out feeding, have benefited from nano material and form the cream with certain consistency in conjunction with liquid medium
Shape object, it is therefore prevented that slipping phenomenon, on the other hand the content of the liquid medium as contained by nano material is higher, in premix
When by the first melting zone, liquid medium therein will not too early phase transformation gasification, allow melting polyamide 66 preferably
It infiltrates between the gap of nano material and forms the nanocomposite of good mechanical properties.
According to above-mentioned preparation method, the step (1) further includes auxiliary agent being added in nano material to improve nano material
Liquid content, the liquid medium for enabling the nano material be combined accounts for the 50~98% of paste gross mass, preferably 60~
98%, more preferably 80~98%.
According to above-mentioned preparation method, the mass ratio of the auxiliary agent and nano material is 0.01~50:1, preferably 0.1~
5:1, more preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfate salt surfactant, sulfonate
Surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant, heterocyclic type surface-active
Agent, nonionic surfactant, natural water soluble high molecular, one or more of synthetic water soluble high molecular and its prepolymer.
In the above method, the premix in the present invention during the preparation process, using polyamide 66 as base-material, is used lower
The auxiliary agent of content, its purpose is to form the environment of lyophile medium between the gap of nano material, to improve paste
Liquid content；It is multiple to nanometer to significantly reduce auxiliary agent for high-content intercalator used in intercalation polymeric compared to the prior art
The influence of condensation material overall performance.
In above scheme, the ability that liquid medium enters nano material is can be improved in the addition of auxiliary agent, to increase nanometer
The consistency of material blends；In addition, the addition of auxiliary agent can also improve the boiling point of liquid medium, liquid medium gas in advance is prevented
Change evolution.Due to generating the reaction temperature of gel nano material in the present invention at room temperature, requirement to auxiliary agent
It is not high, therefore it is wider to be suitable for the invention the alternative range of auxiliary agent.
The auxiliary agent includes but is not limited to one or more of following component:
A. surfactant:
1, anionic surfactant: it is divided into carboxylate, sulfuric acid, sulfonate and phosphate ester salt.
(1) soap kind is higher fatty acid salt, and general formula of molecular structure is (RCOO)-nMn+.With stearic acid, oleic acid, laurel
Acid etc. is more common.According to the difference of its metal ion (Mn+), there are alkali metal soap, alkaling earth metal base and organic amine soap etc..
(2) hydrosulphate is mainly the sulfuric acid ester of sulfated oil and higher aliphatic, general formula of molecular structure ROSO3-
M+, there are commonly lauryl sodium sulfate (also known as " sldium lauryl sulfate "), sodium hexadecyl sulfate (also known as " cetanol sulfuric acid
Sodium "), sodium stearyl sulfate (also known as " stearyl alcohol sodium sulphate ") etc..
(3) sulphonic acid compound mainly has aliphatic sulfonic compound, sulfo group aryl sulfonic acid compound, sulfo group naphthalene sulfonic acids compound etc.
2, cationic surfactant: containing nitrogen-atoms in the hydrophilic group ion of cationic surfactant, according to nitrogen original
The position difference of son in the molecule is divided into amine salt, quaternary ammonium salt and heterocyclic type three classes.As benzalkonium chloride (trade name " geramine "),
Benzalkonium bromide (trade name " bromogeramine "), chlorination (bromination) cetyl pyridinium (trade name " Xi Bailin ") etc.
3, zwitterionic surfactant: lecithin, amino acid pattern, betaine type
4, nonionic surfactant: fatty glyceride, fatty acid sorbitan (sapn), polysorbate (tween), alkane
Base phenol polyethenoxy ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester APEO, detergent series.
B. water soluble polymer includes:
1, natural class macromolecule
Starch
Seaweeds: sodium alginate, agar-agar.
Natural plant gum class: Arabic gum, tragacanth gum, locust bean gum, tamarind seed polysaccharide glue, sesbania gum, carrageenan, guar gum, fruit
Glue.
Animal glue class: gelatin, casein, chitosan.
Microbiological gum: xanthan gum, gellan gum, hyaluronic acid.
2, class macromolecule and its prepolymer are synthesized
(1) polymeric type water soluble polymer and its prepolymer
Polyacrylamide, polyacrylic acid, polymethylacrylic acid and its copolymer, polyvinyl alcohol, polyethylene glycol, polyoxygenated
Ethylene, polyvinylpyrrolidone, polymaleic anhydride, polydimethyl diallyl ammonium chloride, polyvinylamine, poly- divinyl miaow
Oxazoline, sulfonate styrene maleic anhydride copolymer, opens Pu Shi resin at kayexalate.
(2) polycondensation class water soluble polymer and its prepolymer
Water soluble amino resin, water soluble phenol resin, water soluble alkyd resin, water-soluble epoxy resin, water-soluble poly
Urethane resin, polyethylene imine, poly-aspartate, poly-epoxy succinic acid, polyamine epichlorohydrin resin, polyamide second
Two urea formaldehydes, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin,
N, N- dimethyl 1,3- propane diamine and epichlorohydrin resin.
(3) other
Water Soluble Maleic Anhydride oil, dicyandiamide formaldehyde resin, rosin amine-ethylene oxide condensate, poly N-ethylene yl acetamide,
Water-soluble poly-sucrose.
3, semi-synthetic class macromolecule
Modified cellulose and converted starch.
Preferably synthetic class macromolecule and its prepolymer.
According to above-mentioned preparation method, nano material and the adding manner of auxiliary agent include being added at one time in the step (1)
It is added in batches；It is respectively 0.01-100g/min that speed, which is added, preferably 5-10g/min, more preferable 7g/min.
According to above-mentioned preparation method, the step (1) further includes implementing physical dispersion, the physics point to nano material
Dissipate includes but is not limited to colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock etc.；Preferably, the physical dispersion
For ultrasound, the frequency of the ultrasonic field is 800~1000Hz, and power is 200~1000W.
According to above-mentioned preparation method, the preparation method further includes addition latex shape in the paste made from step (1)
The mass ratio of resulting mixture, the later mixture and polyamide 66 melt blending, 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
Lotion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream,
One of polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of.
In the above method, after the completion of prepared by the nano material paste for being combined with liquid medium, latex can also be utilized
Mixed processing is carried out to paste precast body, and the paste after latex mixed processing is melted simultaneously with polyamide 66
It is blended and carries out following process, above-mentioned mixed processing has greatly delayed the release rate of liquid medium between gap, effectively prevent liquid
Phase transformation occurs to early in body medium, and on the other hand, the mixed processing of latex and paste further improves liquid medium phase transformation
When nano material gap expansion scale, be conducive to polymer travel further into nano material gap realize filling.
According to above-mentioned preparation method, the preparation method further includes before or during melt blending to paste and poly-
The weight ratio of the age resister that is added in the premix that 66 particle of amide is formed, the age resister and polyamide 66 is 0.1~
1:100, preferably 0.3:100；The age resister is selected from amine antioxidants, phenolic antioxidant, thio-2 acid vinegar class antioxygen
One or more of agent and phosphorous vinegar kind antioxidant.
In the above method, the age resister includes:
Amine antioxidants: there are ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, hindered amine；
Phenolic antioxidant: alkylation monophenols, alkylation polyphenol, thiobisphenol and polyphenol can be divided into.Alkylation monophenols and
Polyphenol antioxidant principal item has antioxidant 264,1076,2246,1035,1010,3114 and 1790；Thiobisphenol it is main
Kind has antioxidant 2246 and 300；Polyatomic phenol antioxidant principal item has 2,5 1 di-t-butyl hydroquinones and 2,5 12 uncles penta
Base quinhydrones；
Thio-2 acid vinegar and phosphorous vinegar kind antioxidant；Its principal item has anti-aging agent TNP, Ultranox624 and Asia
Tricresyl phosphate (2,4 1 di-tert-butyl) ester.
Other type antioxidants: 2 one coloured glaze base benzo miaow trade name antioxidant MBs, dibutyl dithiocaarbamate
Nickel trade name antioxidant NBC, there are also zinc dialkyl dithiophosphates.
The age resister specifically includes: anti-aging agent RD, antioxidant A W, antioxidant BLE, antioxidant A, anti-aging agent OD,
4,4 '-bis- (α-methylbenzyl) diphenylamines, 4,4 '-bis- (α, α-methylbenzyl) diphenylamines, N, N ,-di-sec-butyl-p-phenyl enediamine,
Anti-aging agent 4030, antioxidant 4010, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 1076, antioxidant
2216, antioxidant 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246,2,5- di-t-butyl hydrogen
Quinone, antioxidant TNP, Ultranox624, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, antioxidant MB, is prevented anti-oxidant DLTP
Old agent NBC, zinc dialkyl dithiophosphate.
The present invention also provides a kind of premix, the premix includes paste and polyamide 66；The paste packet
It 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 covers
Premix is formed in polyamide 66 particle surface；Preferably, it during preparing paste, nano material and will successively help
Agent is added into liquid medium and is dispersed；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 disposable add
Enter and is added in batches.
The preparation method of above-mentioned polyamide 66 composite material specifically comprises the following steps:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01~100g/min and is persistently stirred
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 0.02~100:1；
(2) it is once added in batches or into the lasting agitating solution of step (1) and helps with the speed of 0.01~100g/min
Agent, obtains paste, and the consistency of the paste is 0~100mm, and the weight ratio of the auxiliary agent and nano material is 0.001~
50:1；
(3) paste and polyamide 66 particle that step (2) obtains are mixed to get premix；
(4) by the premix of step (3), feeding hot melting equipment, melt blending simultaneously carry out subsequent add under the conditions of no pressure
Work obtains nanocomposite.
According to the above method, when the hot melting equipment is screw extruder, engine speed is 30~80Hz, main feeding hopper
Revolving speed is 10~30Hz, and extrusion temperature is 260~290 DEG C of an area, two 260~290 DEG C of areas, three 280~290 DEG C of areas, 4th area
280~290 DEG C, five 280~290 DEG C of areas.The linear velocity of screw speed is 0.6~1m/s.
It further include carrying out mixed processing using latex and paste afterwards in step (2), then walked according to the above method
Suddenly the technique of (3).
The invention has the benefit that
1. polyamide 66 nanocomposite provided by the invention is in terms of mechanical property, especially in terms of impact property
With 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 polyamide 66 simultaneously, composite processing mistake is utilized
Heat in journey improves the molecular energy of the liquid medium combined between nano material gap, and liquid medium between gap is promoted to occur
The gap of nano material has been expanded in phase transformation, realizes filling so that the polyamide 66 of molten state enters gap；
3. nano material provided by the invention through auxiliary agent processing formed have compared with containing large amount of liquid amount paste, with polyamides
During amine 66 while melt-processed, when the time and polyamide 66 that the liquid medium combined between gap is undergone phase transition melt
Between match, enter the gap of nano material conducive to the polyamide 66 of molten state and be filled；
4. nano material provided by the invention is while using liquid medium phase transformation expansion gap, also playing is prevented
The effect that nano material is reunited.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the technology in embodiment
Scheme is clearly and completely described, and the following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
In the present embodiment, the mass ratio of nano material and polyamide 66 is 12:100, and the liquid medium used is adopted for water
Auxiliary agent is lauryl sodium sulfate, and the nano material used is prepared as follows nano combined for nano yttrium oxide
Material:
(1) liquid medium is stirred, while nano material is added with the speed of 8g/min and is persistently dispersed with stirring
Uniformly, the weight ratio of liquid medium and nano material is 24:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) in batches or once with the speed of 0.1g/min, obtained
Paste, the consistency of the paste are 46mm, and the weight ratio of the auxiliary agent and nano material is 20:1；
(3) paste and polyamide 66 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 260 DEG C of an area,
Two 290 DEG C of areas, three 280 DEG C of areas, four 285 DEG C of areas, five 280 DEG C of areas, the linear velocity of screw speed are 0.8m/s.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 98MPa, and bending strength is
134MPa。
Embodiment 2
In the present embodiment, the mass ratio of nano material and polyamide 66 is 10:100, and used liquid medium is acetonitrile
And water, the mass ratio of acetonitrile and water are 6:4, used auxiliary agent is polyacrylic acid and polyamine epichlorohydrin resin, weight
Than for 1:1, the nano material used is prepared as follows nanocomposite for nano oxidized praseodymium:
(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 35mm, and the weight ratio of the auxiliary agent and nano material is 50:1；
(3) paste and polyamide 66 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 270 DEG C,
Two 285 DEG C of areas, three 290 DEG C of areas, four 280 DEG C of areas, five 285 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 97MPa, and bending strength is
133MPa。
Embodiment 3
In the present embodiment, the mass ratio of nano material and polyamide 66 is 0.1:100, and the liquid medium used is adopted for water
Auxiliary agent is sesbania gum, and the nano material used is nano-cerium oxide and nano oxidized erbium, mass ratio 7:3, according to as follows
Method prepares nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 0.01g/min and carries out continuing stirring
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 50:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 10g/min, obtains paste, it is described
The consistency of paste is 29mm, and the weight ratio of the auxiliary agent and nano material is 0.1:1；
(3) paste and polyamide 66 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 270 DEG C,
Two 275 DEG C of areas, three 290 DEG C of areas, four 290 DEG C of areas, five 290 DEG C of areas；The linear velocity of screw speed is 0.9m/s.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 96MPa, and bending strength is
136MPa。
Embodiment 4
In the present embodiment, the mass ratio of nano material and polyamide 66 is 7:100, the liquid medium used for hexamethylene,
The auxiliary agent used is polyvinylamine and its prepolymer, and for the nano material used for carbon nano-fiber, the age resister used is anti-
Old agent 4010, is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 15g/min and carries out continuing stirring point
Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material
Weight ratio is 5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 80g/min, obtains paste, it is described
The consistency of paste is 44mm, and the weight ratio of the auxiliary agent and nano material is 5:1；
(3) paste and polyamide 66 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 polyamide 66 nanocomposite is 100MPa, bending strength 135MPa.
Embodiment 5
In the present embodiment, the mass ratio of nano material and polyamide 66 is 4:100, and the liquid medium used is ethylene glycol
Dimethyl ether and water, mass ratio 1:15, the auxiliary agent used is sodium hexadecyl sulfate, and the nano material that uses is nano oxidized
Lanthanum is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 40g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 0.8:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 16g/min, obtains paste, it is described
The consistency of paste is 28mm, and the weight ratio of the auxiliary agent and nano material is 0.8:1；
(3) paste and polyamide 66 that step (2) obtains are mixed to get premix；
(4) by the premix feeding open mill of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tensile strength of finally obtained polyamide 66 nanocomposite is 99MPa, bending strength 134MPa.
Embodiment 6
In the present embodiment, the mass ratio of nano material and polyamide 66 is 4:100, and the liquid medium used uses for water
Auxiliary agent be casein, the nano material used is Nanometer-sized Neodymium Oxide, and the age resister used is Ultranox624, according to such as
Lower section method prepares nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 0.02g/min and carries out continuing stirring
It is uniformly dispersed, the weight ratio of liquid medium and nano material is 20:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.1g/min, obtains paste, it is described
The consistency of paste is 71mm, and the weight ratio of the auxiliary agent and nano material is 2:1, further, by paste and phenylpropyl alcohol cream
Liquid mixed processing；
(3) paste mixed with styrene-acrylic emulsion and polyamide 66 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 270 DEG C,
Two 285 DEG C of areas, three 290 DEG C of areas, four 290 DEG C of areas, five 280 DEG C of areas；The linear velocity of screw speed is 0.7m/s.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 109MPa, and bending strength is
143MPa。
Embodiment 7
In the present embodiment, the mass ratio of nano material and polyamide 66 is 2:100, and the liquid medium used is water and neighbour
The mass ratio 10:1 of dichloro-benzenes, water and o-dichlorohenzene, used auxiliary agent are fatty alcohol polyoxyethylene ether, the nanometer material of use
Material is nano-hafnium oxide, is prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 20g/min and carries out continuing stirring point
It dissipates uniformly, the weight ratio of liquid medium and nano material is 40:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 4g/min, obtains paste, the cream
The consistency of shape object is 84mm, and the weight ratio of the auxiliary agent and nano material is 12:1；
(3) paste and polyamide 66 that step (2) obtains are mixed to get premix；
(4) by the premix feeding open mill of step (3), melt blending simultaneously carries out following process, obtains nano combined material
Material.
The tensile strength of finally obtained polyamide 66 nanocomposite is 97MPa, bending strength 136MPa.
Embodiment 8
In the present embodiment, the mass ratio of nano material and polyamide 66 is 6:100, and the liquid medium used uses for water
Auxiliary agent be sodium alginate, the nano material used is prepared as follows nanocomposite for nano oxidized tellurium:
(1) liquid medium is stirred, while nano material is added with the speed of 0.5g/min and carries out continuing stirring point
Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material
Weight ratio is 4.5:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 21g/min, obtains paste, it is described
The consistency of paste is 15mm, and the weight ratio of the auxiliary agent and nano material is 42:1；
(3) paste and polyamide 66 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 290 DEG C,
Two 290 DEG C of areas, three 285 DEG C of areas, four 285 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 polyamide 66 nanocomposite that final extruding pelletization obtains is 101MPa, and bending strength is
132MPa。
Embodiment 9
In the present embodiment, the mass ratio of nano material and polyamide 66 is 18:100, and the liquid medium used is adopted for water
Auxiliary agent is fatty acid methyl ester APEO and poly-aspartate, fatty acid methyl ester APEO and poly-aspartate
Mass ratio be 3:1, used nano material be nano europium oxide, be prepared as follows nanocomposite:
(1) liquid medium is stirred, while nano material is added with the speed of 8g/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
Amount is than being 30:1；
(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 15g/min, obtains paste, it is described
The consistency of paste is 29mm, and the weight ratio of the auxiliary agent and nano material is 6:1, further, by paste and rosin tree
Fat liquor mixed processing；
(3) paste mixed with rosin resin lotion and polyamide 66 that step (2) obtains are mixed to get premix
Material；
(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 285 DEG C,
Two 290 DEG C of areas, three 290 DEG C of areas, four 290 DEG C of areas, five 280 DEG C of areas；The linear velocity of screw speed is 1m/s.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 108MPa, and bending strength is
145MPa。
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 polyamide 66 under the conditions of power pressurizes in polyamide 66 after melting zone by the nanometer material between gap containing liquid medium
Material feeding is mixed with the polyamide 66 of molten state.
The difference of comparative example 1 and embodiment is: the nano material between polyamide 66 and gap containing liquid medium is not same
When feeding, but first feeding polyamide 66 and after polyamide 66 melting is combined with liquid medium between feeding gap of pressurizeing
Nano material is processed.
The tensile strength for the polyamide 66 nanocomposite that final extruding pelletization obtains is 85MPa, and bending strength is
112MPa。
Mechanics Performance Testing is carried out to Examples 1 to 9 and comparative example 1, respectively obtains tensile strength, the property of bending strength
Energy parameter is as shown in the table:
| Tensile strength (MPa) | Bending strength (MPa) | |
| Embodiment 1 | 98 | 134 |
| Embodiment 2 | 97 | 133 |
| Embodiment 3 | 96 | 136 |
| Embodiment 4 | 100 | 135 |
| Embodiment 5 | 99 | 134 |
| Embodiment 6 | 109 | 143 |
| Embodiment 7 | 97 | 136 |
| Embodiment 8 | 101 | 132 |
| Embodiment 9 | 108 | 145 |
| Comparative example 1 | 85 | 112 |
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 bending strength, to find out its cause, being the phase transformation pair that the present invention utilizes liquid medium
Nano material has carried out divergence process, is filled so that entering between gap with the polyamide 66 that nano material melts simultaneously, on
The heat that processing generates when polymer melting is utilized in divergence process between gap is stated, enables liquid medium evaporation generate implosion and struts
Gap, while using the shearing force for squeezing out processing, gap is further peeled off, so that molten state polyamide 66 realizes filling, thus
Improve the bending strength and impact strength of product.
Further, it is higher to compare Examples 1 to 8 for the mechanical property of embodiment 6 and embodiment 9, to find out its cause, be
The processing of mixing latex is carried out before melt-processed to nano material paste, so that liquid medium evaporates in melting process
The implosive force of generation is stronger, and the expansion effect in nano material gap is more preferable, so that the filling of polyamide 66 is more abundant, improves
The mechanical strength of final product.
The above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that this hair
It is bright to be not limited to specific embodiment described here, be able to carry out for a person skilled in the art it is various it is apparent variation, again
Adjustment and substitution are without departing from protection scope of the present invention.Therefore, although by above embodiments to the present invention carried out compared with
To be described in detail, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, may be used also
To include more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (10)
1. a kind of PA66 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 polyamide 66 particle.
2. nanocomposite according to claim 1, which is characterized in that the nano material includes zero dimensional nanometer materials
Or monodimension nanometer material is one or more, the liquid medium injects and fills the gap of nano material, and being formed has self-adhesion
The paste of property.
3. composite material according to claim 1 or 2, which is characterized in that the consistency of the paste is 0~100mm, but
It is not 0mm；
The paste includes:
1 parts by weight of nano material
0.02~100 parts by weight of liquid medium；
The paste it is also preferable to include,
0~50 parts by weight of auxiliary agent, but be not 0.
4. composite material according to any one of claims 1 to 3, which is characterized in that the zero dimensional nanometer materials and one
Dimension nano material includes nano silicon oxide, nano-titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nano oxidized
Nickel, nanogold, nano silver, nano-silicon, nano-sized carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur,
Nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nano oxidized erbium, nano-cerium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide,
One of nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nano oxidized niobium, nano-hafnium oxide or nanoscale molybdenum oxide or
It is a variety of.
5. composite material described in any one according to claim 1~4, which is characterized in that the nano material and polyamide
66 mass ratio is 0.1~20:100, preferably 1~10:100, more preferably 4:100.
6. a kind of preparation method of polyamide 66 nanocomposite, 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 polyamide 66 particle, enables paste is full to be adhered to polyamide 66 particle
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.
7. preparation method according to claim 6, which is characterized in that high in the temperature of melt blending in the step (3)
In liquid medium boiling point and during reaching polyamide 66 plasticization temperature, liquid medium gasification, by the nano material of reunion
Separation；The boiling point of the liquid medium is lower than the plasticization temperature of polyamide 66, and the boiling point is preferably not higher than 180 DEG C, described
Liquid medium is preferably 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 the step (1) further includes in nano material
Auxiliary agent is added to improve the liquid content of nano material, the liquid medium for enabling the nano material be combined accounts for paste gross mass
50~98%, preferably 60~98%, more preferably 80~98%；The auxiliary agent and the mass ratio of nano material be 0.01~
50:1, preferably 0.1~5:1, more preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfuric acid table
Face activating agent, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant,
Heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular, in synthetic water soluble high molecular and its prepolymer
It is one or more of.
9. preparation method according to any one of claims 6 to 8, which is characterized in that the preparation method further include
Latex is added in paste made from step (1) and forms mixture, the mixture and polyamide 66 melt blending, described later
The mass ratio of latex and paste is 0.1~10:1, and the 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 resins cream
One of liquid, styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex or
It is a variety of.
10. a kind of premix characterized by comprising
The premix includes paste and polyamide 66；
The paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not
0；
The paste, which is covered, forms premix in polyamide 66 particle surface；
Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are divided
It dissipates；
It is furthermore preferred that the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, etching auxiliary or gas shock；
It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810183428.2A CN110229510B (en) | 2018-03-06 | 2018-03-06 | PA66 nano composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810183428.2A CN110229510B (en) | 2018-03-06 | 2018-03-06 | PA66 nano composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110229510A true CN110229510A (en) | 2019-09-13 |
| CN110229510B CN110229510B (en) | 2021-02-02 |
Family
ID=67861784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810183428.2A Active CN110229510B (en) | 2018-03-06 | 2018-03-06 | PA66 nano composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110229510B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229508A (en) * | 2018-03-06 | 2019-09-13 | 中国科学院化学研究所 | A kind of PA66 nanocomposite and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705004A (en) * | 2009-11-05 | 2010-05-12 | 上海金发科技发展有限公司 | Method for preparing polymer/montmorillonite nano composite material |
| CN106142381A (en) * | 2015-04-01 | 2016-11-23 | 合肥杰事杰新材料股份有限公司 | A kind of Graphene/Nylon Nanocomposite and reactive extrursion preparation method thereof |
| WO2017012116A1 (en) * | 2015-07-23 | 2017-01-26 | Dow Global Technologies Llc | Thermally conductive particles formed by spray-drying process |
-
2018
- 2018-03-06 CN CN201810183428.2A patent/CN110229510B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705004A (en) * | 2009-11-05 | 2010-05-12 | 上海金发科技发展有限公司 | Method for preparing polymer/montmorillonite nano composite material |
| CN106142381A (en) * | 2015-04-01 | 2016-11-23 | 合肥杰事杰新材料股份有限公司 | A kind of Graphene/Nylon Nanocomposite and reactive extrursion preparation method thereof |
| WO2017012116A1 (en) * | 2015-07-23 | 2017-01-26 | Dow Global Technologies Llc | Thermally conductive particles formed by spray-drying process |
Non-Patent Citations (1)
| Title |
|---|
| HASEGAWA N等: ""Nylon6/Na-montmorillonite nanocomposites prepared by compounding Nylon 6 with Na-montmorillonite slurry"", 《POLYMER》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229508A (en) * | 2018-03-06 | 2019-09-13 | 中国科学院化学研究所 | A kind of PA66 nanocomposite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110229510B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102618107B (en) | Conductive graphite cream and preparation method thereof | |
| CN104388095B (en) | Double-component nano high-polymer sand stabilization material and sand stabilization method thereof | |
| CN110229495A (en) | A kind of preparation method of nanocomposite | |
| CN110229424A (en) | A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof | |
| CN106084738A (en) | A kind of TPU antistatic film of carbon nano-tube modification | |
| CN110229510A (en) | A kind of PA66 nanocomposite and preparation method thereof | |
| CN110229473A (en) | A kind of PET nanocomposite and preparation method thereof | |
| CN106046496A (en) | Preparation method of activated carbon nanotube modified polyethylene antistatic thin film | |
| CN110229426A (en) | A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof | |
| CN110229504A (en) | A kind of nylon elastomer nanocomposite and preparation method thereof | |
| CN110229393A (en) | A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof | |
| CN110229453A (en) | A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof | |
| CN110229503A (en) | A kind of PA6 nanocomposite and preparation method thereof | |
| CN104610505B (en) | High toughening efficiency and the nylon toughener of high fluidity and preparation method thereof | |
| CN110229457A (en) | A kind of ABS nanocomposite and preparation method thereof | |
| CN110229509A (en) | A kind of long carbon chain nylon nanocomposite and preparation method thereof | |
| CN106432899A (en) | Activated carbon nanotube modified polypropylene (PP) antistatic film | |
| CN110229412A (en) | A kind of PP nanocomposite and preparation method thereof | |
| CN110229502A (en) | A kind of PA6 nanocomposite and preparation method thereof | |
| CN110229459A (en) | A kind of POM nanocomposite and preparation method thereof | |
| CN110229413A (en) | A kind of PP nanocomposite and preparation method thereof | |
| CN110229494A (en) | A kind of PPO nanocomposite and preparation method thereof | |
| CN110229490A (en) | A kind of PC nanocomposite and preparation method thereof | |
| CN110229434A (en) | A kind of PS nanocomposite and preparation method thereof | |
| CN110229392A (en) | A kind of thermoplastic vulcanizates nanocomposite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |