CN110229504B - Nylon elastomer nano composite material and preparation method thereof - Google Patents

Nylon elastomer nano composite material and preparation method thereof Download PDF

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CN110229504B
CN110229504B CN201810184672.0A CN201810184672A CN110229504B CN 110229504 B CN110229504 B CN 110229504B CN 201810184672 A CN201810184672 A CN 201810184672A CN 110229504 B CN110229504 B CN 110229504B
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paste
liquid medium
nylon elastomer
oxide
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CN110229504A (en
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马永梅
张京楠
曹新宇
郑鲲
连思铭
尚欣欣
叶钢
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Institute of Chemistry CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
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    • 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
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    • 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

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Abstract

The invention relates to the field of nano composite materials, in particular to a nylon elastomer nano composite material and a preparation method thereof. The preparation method comprises the steps of mixing a liquid medium and the nano material to obtain a paste, and adhering the paste to the surface of nylon elastomer particles to perform melt blending to obtain the nano composite material. The nano composite material provided by the invention has the advantages of excellent toughness, short process flow and low cost, and is suitable for popularization and use.

Description

Nylon elastomer nano composite material and preparation method thereof
Technical Field
The invention relates to the field of nano composite materials, in particular to a nylon elastomer nano composite material and a preparation method thereof.
Background
In the prior art, a nano material and a polymer are often mixed and extruded to form a composite material, and although the tensile strength of the composite material is improved, the impact resistance of the composite material is generally low due to the problems of poor compatibility of the nano material and the polymer and the like.
In order to solve the above problems, intercalation in-situ polymerization and other methods are often adopted to enable the polymer to react among the gaps of the nano material so as to improve the impact resistance of the composite material, but the process takes a long time, the polymerization reaction conditions are harsh, the solvent is not easy to recover, and environmental pollution and other derivative problems are caused.
Patent No. CN101081928A proposes a method for preparing polyamide/nano montmorillonite master batch, which adopts water-assisted method to prepare polyamide/nano montmorillonite master batch, and the preparation method comprises using deionized water as intercalation agent, mixing purified montmorillonite and deionized water, fully dispersing to obtain montmorillonite slurry, gradually adding the slurry into polyamide whose formula amount is completely melted, and then extruding and granulating to obtain polyamide/nano montmorillonite master batch. The preparation method is simple, the production cost is low, but the montmorillonite slurry is added after the polyamide is melted, the montmorillonite slurry cannot be mixed with the copolymer completely, the polyamide cannot enter the interlayer in time due to the fact that interlayer water is gasified at high temperature, meanwhile, the energy generated by water gasification is not enough to strip the montmorillonite layers completely, and the product performance of the composite material cannot be completely stripped.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nano composite material, which comprises a nano material and a nylon elastomer, wherein gaps of the nano material are subjected to expansion treatment, intercalation in-situ polymerization is not required, and the toughness of the nylon elastomer nano composite material can be further improved while the strength is improved.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a nylon elastomer nanocomposite, wherein the nanocomposite is prepared by melt blending a premix formed by filling and adhering nanomaterials combined with a liquid medium between nylon elastomer particles.
In the above scheme, the nylon elastomer is mainly a block or graft copolymer, and the biggest characteristic of the macromolecular chain structure is that the nylon elastomer simultaneously comprises a hard segment and a soft segment which are different in chemical structure. Wherein T of hard segmentgAnd TmHigher, soft segment T in glassy or semi-crystalline state in the macromolecular chaingAnd TmLower, imparting flexibility and extensibility to the polymer. The hard segment of the nylon elastomer is classified into nylon 6, nylon 66, nylon 12, and the like according to the type of polyamide used.
In the scheme, the nano composite material taking the macromolecule as the base material has loss in toughness in the process of improving the mechanical property representing the strength, and sometimes even is lower than the toughness of the base material, so that the application range of the material is reduced; the reason for this is that some nano-material components in the composite material have poor compatibility with some polymers, and in addition, the nano-material itself generates agglomeration during the processing process and cannot be uniformly dispersed in the composite material, thereby causing some mechanical property deficiencies. The nano composite material provided by the invention is combined with the liquid medium in the nano material, the nano material combined with the liquid medium is adhered and wrapped on the surface of nylon elastomer particles to form a mixture, the mixture is subjected to melt blending, and the liquid medium is subjected to phase change by utilizing the processing and heating process, so that the nano material is uniformly dispersed in the nylon elastomer, and the toughness of the composite material is greatly improved.
In the above embodiment, the liquid medium at least includes water, and may further include isopentane, n-pentane, petroleum ether, hexane, cyclohexane, isooctane, trifluoroacetic acid, trimethylpentane, cyclopentane, heptane, butyl chloride, trichloroethylene, carbon tetrachloride, trichlorotrifluoroethane, propyl ether, toluene, p-xylene, chlorobenzene, o-dichlorobenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate, propanol, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate, isopropanol, ethanol, chloroform, methyl ethyl ketone, dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, diethyl ether, pentane, dichloromethane, carbon disulfide, 1, 1-dichloroethane, trifluoroacetic acid, 1,1, 1-trichloroethane, ethanol, butanone, ethyl chloride, toluene, p-xylene, chlorobenzene, o-dichlorobenzene, diethyl ether, ethyl chloride, n-butyl chloride, ethyl acetate, toluene, carbon disulfide, toluene, carbon disulfide, toluene, acetone, ethyl acetate, ethyl chloride, ethyl acetate, ethyl chloride, 1-ethyl chloride, 1, 1-ethyl chloride, 1-ethyl acetate, 1, 1-ethyl acetate, ethyl, 1, 2-dichloroethane, ethylene glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2-pentanone, ethylenediamine, butanol, acetic acid, ethylene glycol monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, xylene, m-xylene, acetic anhydride, o-xylene, N-dimethylformamide, cyclohexanone, cyclohexanol, furfural and N-methylformamide; preferably water.
The further scheme of the invention is as follows: the nano material comprises one or more of zero-dimensional nano material or one-dimensional nano material, and the liquid medium is injected into and fills the gaps of the nano material to form a paste with self-adhesion.
The further scheme of the invention is as follows: the paste comprises: the thickness of the paste is 0-100 mm, but not 0 mm; 1 part by weight of nano material and 0.02-100 parts by weight of liquid medium; preferably, the paste further comprises 0-50 parts by weight of an auxiliary agent, but not 0.
In the scheme, compared with the process of modifying, filtering and drying the nano material in the prior art, the nano material forms a continuous paste with certain self-adhesion after the liquid medium is injected into the gaps, the paste has certain consistency but not 0mm, and represents that the paste is a semisolid combined with the liquid medium and having certain fluidity, so that the nano material paste combined with the liquid medium can be uniformly adhered to the surface of nylon elastomer particles and is fed to a melting and blending device together with the nylon elastomer particles, and the processability is improved. Preferably, in order to increase the amount of the liquid medium to which the nanomaterial is bound, an auxiliary agent may be further added.
The further scheme of the invention is as follows: the nylon elastomer comprises polyamide, polyether and dicarboxylic acid, and the polyamide comprises one of PA6, PA66 or PA 12.
In the scheme, the mass ratio of the polyamide to the polyether is 15-95: 85-5, said polyether is composed of alkylene oxide units, including but not limited to PEG, PPG, tetrahydrofuran, polytrimethylene ether glycol, etc., said polyether can be used to polycondense with polyamide blocks containing terminal carboxyl groups, and can also be aminated, converted to a polyether diamine, and polycondensed with polyamide blocks containing terminal carboxyl groups.
The further scheme of the invention is as follows: the zero-dimensional nano material and the one-dimensional nano material comprise one or more of nano silicon oxide, nano titanium oxide, nano zirconium oxide, nano zinc oxide, nano aluminum oxide, nano nickel oxide, nano gold, nano silver, nano silicon, nano carbon, carbon nano fiber, carbon nano tube, nano graphite, nano boron powder, nano sulfur, nano lanthanum oxide, nano neodymium oxide, nano erbium oxide, nano cerium oxide, nano praseodymium oxide, nano yttrium oxide, nano europium oxide, nano tungsten oxide, nano silicon carbide, nano tellurium oxide, nano niobium oxide, nano hafnium oxide or nano molybdenum oxide.
In the scheme, the ion exchange amount between the nano material and the liquid medium is low, and almost no ion exchange occurs, so that the liquid medium enters the nano material to form a paste with high viscosity and high liquid content, and further processing is facilitated.
The further scheme of the invention is as follows: the mass ratio of the nano material to the nylon elastomer is 0.1-20: 100, preferably 1-10: 100, and more preferably 3-8: 100.
The invention also provides a preparation method of the nylon elastomer nano composite material, which is characterized by comprising the following steps:
(1) mixing and stirring the liquid medium and the nano material to obtain paste;
(2) mixing the paste obtained in the step (1) with nylon elastomer particles, and enabling the paste to be sufficiently adhered among the nylon elastomer particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
preferably, the step (1) further comprises mixing and stirring the liquid medium, the nano material and the auxiliary agent to obtain the paste.
In the method, because the liquid medium and the nano material are mixed to obtain the semisolid paste with a certain consistency, the paste and the nylon elastomer particles are mixed and then added into an extrusion device without slipping, the nano composite material can be prepared by direct feeding, the production and the processing are convenient, the problem of poor performance of the nano composite material caused by premature gasification of the liquid medium in the prior art is solved, and experiments show that the nano composite material prepared by the mixed material has more excellent performance compared with the prior art.
According to the preparation method, in the step (3), during melt blending, when the temperature is higher than or equal to the plasticizing temperature of the thermoplastic polymer, the liquid medium in the nano mixed material is gasified, the gasification separates the agglomerated nano material, and simultaneously the gasification uniformly transfers heat in the thermoplastic polymer and the nano material; preferably, the gasification softens the thermoplastic polymer and lowers the plasticizing temperature of the thermoplastic polymer.
According to the preparation method, in the step (3), in the process that the temperature of melt blending is higher than the boiling point of the liquid medium and reaches the plasticizing temperature of the nylon elastomer, the liquid medium is gasified, and the agglomerated nanometer materials are separated; the boiling point of the liquid medium is lower than the plasticizing temperature of the nylon elastomer, the boiling point is preferably not higher than 180 ℃, and the liquid medium is preferably water; the weight ratio of the liquid medium to the nano material is 0.02-100: 1, preferably 5-50: 1, and more preferably 5-20: 1.
In the method, the nano material with high combined liquid medium content and the nylon elastomer are simultaneously added into the processing equipment, and the liquid content of the nano material is improved due to the previous treatment (namely forming paste) on the lyophilic medium of the nano material, so that when the nano material enters a nylon elastomer melting zone, although the system temperature is higher than the boiling point of the liquid medium, the liquid medium contained in the gaps of the nano material is more, so that the phase change evaporation process and the melting process of the nylon elastomer can be simultaneously carried out, the molten nylon elastomer can smoothly enter the gaps of the nano material, and the impact performance of a final product is improved. In the prior art, the technical scheme of firstly melting the polymer and then adding the liquid-containing nano material is adopted, and due to insufficient treatment on the nano material lyophilic medium, the liquid medium is evaporated too fast, so that the compatibility of the nano material and the nylon elastomer is reduced, and the toughness of the final product is reduced; on the other hand, in the prior art, the addition of the nano material after the polymer is melted undoubtedly prolongs the time for preparing the product, and wastes the time cost.
According to the preparation method, in the step (3), the premix obtained by mixing the paste and the nylon elastomer particles is fed to a hot melting processing device under the non-pressure condition for melting and blending.
In the above method, the hot-melt processing equipment includes, but is not limited to, an internal mixer, an open mill, or a screw extruder (parallel/conical/single/double/triple screw), and when the screw extruder is used, the premix obtained by mixing the dough with the nylon elastomer particles is fed from a non-pressure feeding zone to achieve feeding under a non-pressure condition. According to the invention, the nano material can be directly mixed with the nylon elastomer particles for feeding, and the nano material and the liquid medium are combined to form a paste with a certain consistency, so that the slipping phenomenon is prevented.
According to the preparation method, the step (1) further comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98%, preferably 60-98% and more preferably 80-98% of the total mass of the paste.
According to the preparation method, the mass ratio of the auxiliary agent to the nano material is 0.01-50: 1, preferably 0.1-5: 1, and more preferably 0.2-1: 1, and the auxiliary agent comprises one or more of a carboxylate surfactant, a sulfate salt surfactant, a sulfonate surfactant, a phosphate salt surfactant, an amine salt surfactant, a quaternary ammonium salt surfactant, a heterocyclic surfactant, a nonionic surfactant, a natural water-soluble polymer, a synthetic water-soluble polymer and a prepolymer thereof.
In the method, the premix in the invention takes the nylon elastomer as a base material and adopts a lower content of auxiliary agent in the preparation process, and the aim is to form an environment of lyophilic medium in the gaps of the nano material so as to improve the liquid content of the paste; compared with the high-content intercalation agent used in the intercalation polymerization in the prior art, the method greatly reduces the influence of the auxiliary agent on the overall performance of the nano composite material.
In the scheme, the addition of the auxiliary agent can improve the capability of a liquid medium entering the nano material, so that the consistency of the nano material mixture is increased; in addition, the addition of the auxiliary agent can also increase the boiling point of the liquid medium and prevent the liquid medium from gasifying and escaping in advance. The reaction temperature for generating the gel-like nano material in the invention can be at room temperature, and the requirement on the auxiliary agent is not high, so that the auxiliary agent applicable to the invention has wider alternative range.
The auxiliary agent includes but is not limited to one or more of the following components:
A. surfactant (b):
1. anionic surfactant: classified into carboxylates, sulfate ester salts, sulfonates, and phosphate ester salts.
(1) The soap is higher fatty acid salt, and the molecular structure general formula is (RCOO) -nMn +. Stearic acid, oleic acid, lauric acid and the like are commonly used. Depending on the metal ion (Mn +) thereof, there are alkali metal soaps, alkaline earth metal soaps, organic amine soaps and the like.
(2) The sulfated product is mainly sulfated oil and sulfate of higher fatty alcohol, and has molecular structure formula of ROSO3-M +, and commonly used sodium dodecyl sulfate (also known as "sodium lauryl sulfate"), sodium hexadecyl sulfate (also known as "sodium cetyl sulfate"), and sodium octadecyl sulfate (also known as "sodium stearyl sulfate").
(3) The sulfonic acid compound is mainly aliphatic sulfonic acid compound, sulfoaryl sulfonic acid compound, sulfonaphthalene sulfonic acid compound, etc
2. Cationic surfactant: the hydrophilic ions of the cationic surfactant contain nitrogen atoms, and are classified into amine salts, quaternary ammonium salts and heterocyclic rings according to the positions of the nitrogen atoms in the molecule. Such as benzalkonium chloride (trade name "benzalkonium chloride"), benzalkonium bromide (trade name "benzalkonium bromide"), cetylpyridinium chloride (bromide) (trade name "cetylpyridinium chloride"), etc
3. Zwitterionic surfactant: lecithin, amino acid type, betaine type
4. Nonionic surfactant: fatty glyceride, sorbitan fatty acid, polysorbate, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene, fatty acid methyl ester polyoxyethylene, and detergent.
B. The water-soluble polymer includes:
1. natural polymer
Starches
Marine algae species: sodium alginate and agar.
Vegetable gums: gum arabic, gum tragacanth, locust bean gum, tamarind seed polysaccharide gum, sesbania gum, carrageenan, guar gum, pectin.
Animal glue: gelatin, casein and chitosan.
Microbial glue: xanthan gum, gellan gum, hyaluronic acid.
2. Synthetic polymer and prepolymer thereof
(1) Water-soluble polymer and prepolymer thereof
Polyacrylamide, polyacrylic acid, polymethacrylic acid and copolymers thereof, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polymaleic anhydride, polydimethyldiallyl ammonium chloride, polyvinylamine, polydivinyl imidazoline, sodium polystyrene sulfonate, sulfonated styrene maleic anhydride copolymer and Kelvin resin.
(2) Condensed water-soluble polymer and prepolymer thereof
The water-soluble epoxy resin is prepared from water-soluble amino resin, water-soluble phenolic resin, water-soluble alkyd resin, water-soluble epoxy resin, water-soluble polyurethane resin, polyethyleneimine, polyaspartic acid, polyepoxysuccinic acid, polyamide epichlorohydrin resin, polyamide glyoxal resin, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin, N-dimethyl-1, 3-propane diamine and epichlorohydrin resin.
(3) Others
Water-soluble maleic anhydride oil, dicyandiamide-formaldehyde resin, rosin amine-ethylene oxide polycondensate, poly N-vinyl acetamide and water-soluble polysucrose.
3. Semi-synthetic polymer
Modified cellulose and modified starch.
Synthetic polymers and prepolymers thereof are preferred.
According to the preparation method, the adding modes of the nano material and the auxiliary agent in the step (1) comprise one-time adding and batch adding; the addition rate is 0.01-100g/min, preferably 5-10g/min, more preferably 7 g/min.
According to the preparation method, the step (1) further comprises the step of carrying out physical dispersion on the nano material, wherein the physical dispersion comprises but is not limited to colloid milling, ball milling, ultrasound, vortex, etching assistance, airflow impact and the like; preferably, the physical dispersion is ultrasonic, the frequency of the ultrasonic field is 800-1000 Hz, and the power is 200-1000W.
According to the preparation method, the latex is added into the paste prepared in the step (1) to form a mixture, then the mixture and the nylon elastomer are subjected to melt blending, the mass ratio of the latex to the paste is 0.1-10: 1, and the latex comprises one or more of styrene-acrylic emulsion, acrylate emulsion, acrylic emulsion, silicone-acrylic emulsion, waterborne polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, terpineol, vinyl acetate-acrylic emulsion, waterborne epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex, pure acrylic latex, carboxylated styrene-butadiene latex and styrene-acrylic latex.
In the method, after the preparation of the nano material paste combined with the liquid medium is finished, the latex can be used for mixing the paste preform, and the paste subjected to the mixing treatment of the latex and the nylon elastomer are simultaneously melted and blended for subsequent processing, so that the release rate of the liquid medium in gaps is greatly delayed, the premature phase change of the liquid medium is effectively prevented, and on the other hand, the size of the expansion of the gaps of the nano material during the phase change of the liquid medium is further increased by the mixing treatment of the latex and the paste, and the polymer can further enter the gaps of the nano material to realize the filling.
According to the preparation method, the preparation method further comprises the step of adding an anti-aging agent into the premix formed by the paste and the nylon elastomer particles before or during melt blending, wherein the weight ratio of the anti-aging agent to the nylon elastomer is 0.1-1: 100, preferably 0.3: 100; the anti-aging agent is selected from one or more of amine antioxidant, phenol antioxidant, thiodipropionic acid vinegar antioxidant and phosphorous acid vinegar antioxidant.
In the above method, the anti-aging agent comprises:
amine antioxidant: ketone amine condensates, secondary diarylamines, substituted p-phenylenediamines, hindered amines;
phenol antioxidant: and can be classified into alkylated monophenols, alkylated polyphenols, thiobisphenols and polyphenols. The main varieties of alkylated monophenol and polyphenol antioxidants are antioxidants 264, 1076, 2246, 1035, 1010, 3114 and 1790; the main varieties of thiobisphenols are anti-aging agents 2246 and 300; the main varieties of the polyphenol antioxidant comprise 2, 5-di-tert-butyl hydrogen and 2, 5-di-tert-amyl hydroquinone;
thiodipropionic acid vinegar and phosphorous acid vinegar antioxidants; the main varieties of the antioxidant are antioxidant TNP, Ultranox624 and tris (2, 4-di-tert-butyl phenyl) phosphite.
Other types of antioxidants: 2-thiobenzimida is commercially available as antioxidant MB, nickel dibutyldithiocarbamate is commercially available as antioxidant NBC, and zinc dialkyldithiophosphate is also available.
The anti-aging agent specifically comprises: antioxidant RD, antioxidant AW, antioxidant BLE, antioxidant A, antioxidant OD, 4 '-bis (alpha-methylbenzyl) diphenylamine, 4' -bis (alpha, alpha-methylbenzyl) diphenylamine, N, -di-sec-butyl p-phenylenediamine, antioxidant 4030, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 1076, antioxidant 2216, antioxidant 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246, 2, 5-di-tert-butylhydroquinone, antioxidant DLTP, antioxidant TNP, Ultranox624, tris (2, 4-di-tert-butylphenyl) phosphite, antioxidant MB, antioxidant NBC and zinc dialkyldithiophosphate.
The invention also provides a premix which comprises the paste and the nylon elastomer; the paste comprises: 1 part of nano material, 5-100 parts of liquid medium and 0-50 parts of auxiliary agent by weight but not 0; the paste is adhered to the surface of the nylon elastomer particles to form a premix; preferably, in the process of preparing the paste, the nano material and the auxiliary agent are sequentially added into the liquid medium and dispersed; more preferably, the dispersing comprises ultrasound, shearing, stirring, ball milling, colloid milling, vortexing, etching assistance, or air flow impingement; further preferably, the addition modes of the nano material and the auxiliary agent comprise one-time addition and batch addition.
The preparation method of the nylon elastomer composite material specifically comprises the following steps:
(1) stirring the liquid medium, adding the nano material at the speed of 0.01-100g/min, and continuously stirring and dispersing uniformly, wherein the weight ratio of the liquid medium to the nano material is 0.02-100: 1;
(2) adding an auxiliary agent to the continuously stirred solution obtained in the step (1) in batches or at one time at a speed of 0.01-100g/min to obtain a paste, wherein the thickness of the paste is 0-100 mm, and the weight ratio of the auxiliary agent to the nano material is 0.001-50: 1;
(3) mixing the paste obtained in the step (2) with nylon elastomer particles to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) to a hot melting device under a non-pressure condition, melting and blending, and performing subsequent processing to obtain the nano composite material.
According to the method, when the hot melting equipment is a screw extruder, the rotating speed of a main machine is 30-80 Hz, the rotating speed of a main feeding hopper is 10-30 Hz, the extruding temperature is 260-290 ℃ in a first zone, 260-290 ℃ in a second zone, 280-290 ℃ in a third zone, 280-290 ℃ in a fourth zone and 280-290 ℃ in a fifth zone. The linear speed of the screw rotating speed is 0.6-1 m/s.
The method also comprises the step of mixing the latex and the paste after the step (2) and then performing the process of the step (3).
The invention has the beneficial effects that:
1. the nylon elastomer nano composite material provided by the invention has the advantages that the mechanical property, especially the impact property, is greatly improved, the process is simple and easy to operate, the time is short, and the nylon elastomer nano composite material is suitable for popularization;
2. the invention melts the nanometer material with high liquid content and the nylon elastomer at the same time, utilizes the heat in the processing process of the composite material to improve the molecular energy of the liquid medium combined between the gaps of the nanometer material, promotes the phase change of the liquid medium between the gaps, expands the gaps of the nanometer material, and is beneficial to the molten nylon elastomer to enter the gaps to realize the filling;
3. the nano material provided by the invention is processed by the aid to form a paste with higher liquid content, and in the process of simultaneous melting and processing with the nylon elastomer, the time of phase change of a liquid medium combined among gaps is matched with the melting time of the nylon elastomer, so that the molten nylon elastomer can enter the gaps of the nano material to be filled;
4. the nano material provided by the invention plays a role in preventing the nano material from agglomerating while expanding the gap by utilizing the phase change of the liquid medium.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
In this embodiment, the mass ratio of the nanomaterial to the nylon elastomer is 15:100, the nylon elastomer is a PA6 series, the mass ratio of the PA6 to the polyether block is 95:5, the liquid medium used is water, the auxiliary used is lecithin, and the nanomaterial used is nano praseodymium oxide, and the nanocomposite is prepared by the following method:
(1) stirring a liquid medium, adding the nano material at the speed of 8g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 16: 1;
(2) adding an auxiliary agent to the continuously stirred solution obtained in the step (1) in batches or at one time at the speed of 0.1g/min to obtain a paste, wherein the thickness of the paste is 31mm, and the weight ratio of the auxiliary agent to the nano material is 20: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 30Hz, the rotating speed of a main feeding hopper is 10Hz, the extrusion temperature is 260 ℃ in a first area, 290 ℃ in a second area, 280 ℃ in a third area, 285 ℃ in a fourth area, 280 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 0.8 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation had a tensile strength of 54MPa, a flexural strength of 88MPa, and an impact strength of 52 kg. cm/cm.
Example 2
In this embodiment, the mass ratio of the nanomaterial to the nylon elastomer is 10:100, the nylon elastomer is a PA66 system, the mass ratio of PA66 to the polyether block is 95:5, the adopted liquid medium is ethylene glycol dimethyl ether and water, the mass ratio of the ethylene glycol dimethyl ether to the water is 6:4, the adopted additives are polyacrylic acid and heavy polyamine epichlorohydrin resin, the weight ratio is 1:1, the adopted nanomaterial is nano zinc oxide, and the nanocomposite is prepared according to the following method:
(1) stirring the liquid, adding the nano material at the speed of 10g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 100: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 0.5g/min to obtain a paste, wherein the thickness of the paste is 24mm, and the weight ratio of the auxiliary agent to the nano material is 50: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 80Hz, the rotating speed of a main feeding hopper is 30Hz, the extrusion temperature of a first zone is 270 ℃, a second zone is 285 ℃, a third zone is 280 ℃, a fourth zone is 280 ℃ and a fifth zone is 285 ℃; the linear speed of the screw speed was 1 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation has a tensile strength of 55MPa, a bending strength of 87MPa, and an impact strength of 52 kg/cm.
Example 3
In this embodiment, the mass ratio of the nano material to the nylon elastomer is 0.1:100, the nylon elastomer is a PA12 series, the mass ratio of the PA12 to the polyether block is 95:5, the adopted liquid medium is water, the adopted auxiliary agent is kepu resin, the adopted nano material is nano silicon carbide and nano erbium oxide, and the mass ratio is 9:1, and the nano composite material is prepared according to the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 0.01g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 50: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 10g/min to obtain a paste, wherein the thickness of the paste is 69mm, and the weight ratio of the auxiliary agent to the nano material is 0.1: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 60Hz, the rotating speed of a main feeding hopper is 20Hz, the extrusion temperature of a first zone is 270 ℃, a second zone is 275 ℃, a third zone is 290 ℃, a fourth zone is 285 ℃, and a fifth zone is 290 ℃; the linear speed of the screw speed was 0.9 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation had a tensile strength of 53MPa, a flexural strength of 89MPa, and an impact strength of 51 kg. cm/cm.
Example 4
In this embodiment, the mass ratio of the nanomaterial to the nylon elastomer is 7:100, the nylon elastomer is a PA6 series, the mass ratio of PA6 to the polyether block is 70:30, the adopted liquid medium is propyl ether, the adopted auxiliary agent is chitosan, the adopted nanomaterial is carbon nanofiber, the adopted antiaging agent is antioxidant 4010NA, and the nanocomposite is prepared by the following method:
(1) stirring a liquid medium, adding a nano material at a speed of 20g/min, continuously stirring and uniformly dispersing, and applying ultrasonic waves with the frequency of 800-1000 Hz and the power of 200-1000W, wherein the weight ratio of the liquid medium to the nano material is 5: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 80g/min to obtain a paste, wherein the thickness of the paste is 71mm, and the weight ratio of the auxiliary agent to the nano material is 5: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an internal mixer, melting, blending and performing subsequent processing to obtain the nano composite material.
The tensile strength of the finally obtained nylon elastomer nano composite material is 52MPa, the bending strength is 84MPa, and the impact strength is 53 kg-cm/cm.
Example 5
In this example, the mass ratio of the nanomaterial to the nylon elastomer is 4:100, the nylon elastomer is a PA66 series, the mass ratio of PA66 to the polyether block is 70:30, the adopted liquid medium is trichlorotrifluoroethane and water, the mass ratio is 1:15, the adopted auxiliary agent is benzalkonium chloride, the adopted nanomaterial is nano neodymium oxide, and the nanocomposite is prepared according to the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 40g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 0.8: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 16g/min to obtain a paste, wherein the thickness of the paste is 45mm, and the weight ratio of the auxiliary agent to the nano material is 0.8: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, carrying out melt blending and subsequent processing to obtain the nano composite material.
The tensile strength of the finally obtained nylon elastomer nano composite material is 53MPa, the bending strength is 85MPa, and the impact strength is 54 kg-cm/cm.
Example 6
In this embodiment, the mass ratio of the nanomaterial to the nylon elastomer is 4:100, the nylon elastomer is a PA12 series, the mass ratio of PA12 to the polyether block is 70:30, the liquid medium used is water, the assistant used is polyamide glyoxal resin and its prepolymer, the nanomaterial used is nano silica, the antiaging agent used is Ultranox624, and the nanocomposite is prepared by the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 0.2g/min, and continuously stirring and dispersing uniformly, wherein the weight ratio of the liquid medium to the nano material is 20: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 60g/min to obtain a paste, wherein the thickness of the paste is 68mm, the weight ratio of the auxiliary agent to the nano material is 30:1, and further, mixing the paste with the acrylate emulsion;
(3) mixing the paste mixed with the acrylate emulsion obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 60Hz, the rotating speed of a main feeding hopper is 30Hz, the extrusion temperature of a first zone is 270 ℃, a second zone is 285 ℃, a third zone is 280 ℃, a fourth zone is 285 ℃, and a fifth zone is 280 ℃; the linear speed of the screw speed was 0.7 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation has a tensile strength of 53MPa, a flexural strength of 86MPa and an impact strength of 53 kg/cm.
Example 7
In this example, the mass ratio of the nanomaterial to the nylon elastomer is 2:100, the nylon elastomer is a PA6 series, the mass ratio of PA6 to the polyether block is 15:85, the adopted liquid medium is water and dioxane, the mass ratio of water to dioxane is 10:1, the adopted auxiliary agent is fatty acid methyl ester polyoxyethylene ether, the adopted nanomaterial is nano hafnium oxide, and the nanocomposite is prepared according to the following method:
(1) stirring a liquid medium, adding the nano material at the speed of 20g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 40: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 4g/min to obtain a paste, wherein the thickness of the paste is 74mm, and the weight ratio of the auxiliary agent to the nano material is 15: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, carrying out melt blending and subsequent processing to obtain the nano composite material.
The tensile strength of the finally obtained nylon elastomer nano composite material is 51MPa, the bending strength is 85MPa, and the impact strength is 50 kg-cm/cm.
Example 8
In this embodiment, the mass ratio of the nano material to the nylon elastomer is 6:100, the nylon elastomer is a PA66 series, the mass ratio of the PA66 to the polyether block is 15:85, the liquid medium used is water, the assistant used is sodium alginate, and the nano material used is nano zinc oxide, and the nano composite material is prepared by the following method:
(1) stirring a liquid medium, adding a nano material at the speed of 0.5g/min, continuously stirring and uniformly dispersing, and applying ultrasonic waves with the frequency of 800-1000 Hz and the power of 200-1000W, wherein the weight ratio of the liquid medium to the nano material is 6.5: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 9g/min to obtain a paste, wherein the thickness of the paste is 53mm, and the weight ratio of the auxiliary agent to the nano material is 45: 1;
(3) mixing the paste obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 70Hz, the rotating speed of a main feeding hopper is 20Hz, the extrusion temperature of a first zone is 290 ℃, a second zone is 290 ℃, a third zone is 285 ℃, a fourth zone is 285 ℃, and a fifth zone is 290 ℃; the linear speed of the screw speed was 0.6 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation has a tensile strength of 50MPa, a bending strength of 84MPa and an impact strength of 51 kg/cm.
Example 9
In this embodiment, the mass ratio of the nanomaterial to the nylon elastomer is 18:100, the nylon elastomer is a PA12 series, the mass ratio of PA12 to the polyether block is 15:85, the liquid medium used is water, the auxiliaries used are polyamide glyoxal resin and polyaspartic acid, the mass ratio of polyamide glyoxal resin to polyaspartic acid is 3:1, the nanomaterial used is a carbon nanotube, and the nanocomposite is prepared by the following method:
(1) stirring a liquid medium, adding a nano material at the speed of 10g/min, continuously stirring and uniformly dispersing, and applying ultrasonic waves with the frequency of 800-1000 Hz and the power of 200-1000W, wherein the weight ratio of the liquid medium to the nano material is 30: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 15g/min to obtain a paste, wherein the thickness of the paste is 67mm, the weight ratio of the auxiliary agent to the nano material is 9:1, and further mixing the paste with carboxylic styrene-butadiene latex;
(3) mixing the paste mixed with the carboxylic styrene-butadiene latex obtained in the step (2) with a nylon elastomer to obtain a premix;
(4) and (4) melting, blending and carrying out subsequent processing on the premix obtained in the step (3) from a feed screw extruder in a non-pressure feeding area to obtain the nano composite material.
The rotating speed of a main machine of the extrusion equipment is 70Hz, the rotating speed of a main feeding hopper is 30Hz, the extrusion temperature in a first zone is 285 ℃, a second zone is 290 ℃, a third zone is 285 ℃, a fourth zone is 280 ℃ and a fifth zone is 280 ℃; the linear speed of the screw speed was 1 m/s.
The nylon elastomer nanocomposite obtained by final extrusion granulation has a tensile strength of 52MPa, a bending strength of 83MPa, and an impact strength of 50 kg/cm.
Comparative example 1
In this comparative example, on the basis of example 1, the position where the liquid-containing nanomaterial was fed to the extruder was adjusted, the nylon elastomer was fed under a non-pressure condition, and after the nylon elastomer passed through the melting zone, the nanomaterial feed containing the liquid medium in the gaps was mixed with the molten nylon elastomer under pressure.
Comparative example 1 differs from the examples in that: the nylon elastomer and the nano material containing the liquid medium in the gaps are not simultaneously fed, but the nylon elastomer is fed firstly, and after the nylon elastomer is melted, the nano material combined with the liquid medium in the gaps is pressurized and fed for processing.
The nylon elastomer nanocomposite obtained by final extrusion granulation has tensile strength of 43MPa, bending strength of 72MPa and impact strength of 47 kg-cm/cm.
Mechanical property tests were performed on examples 1 to 9 and comparative example 1, and the performance parameters of tensile strength, flexural strength and impact strength were respectively obtained as shown in the following table:
Figure BDA0001589908740000151
Figure BDA0001589908740000161
as can be seen from the above table, the mechanical properties of the nanocomposite obtained in examples 1 to 9 are all higher than the performance parameters of comparative example 1, and the reason for this is that the present invention uses the phase change of the liquid medium to expand the nanomaterial, so that the nylon elastomer melted simultaneously with the nanomaterial enters the gaps to be filled, the gap expansion uses the heat generated by the melting of the polymer, so that the liquid medium is evaporated to generate implosion to prop open the gaps, and the shear force of the extrusion processing is used to further strip the gaps, so that the nylon elastomer melted is filled, thereby improving the mechanical properties of the product.
The foregoing is considered as illustrative of the preferred embodiments of the invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.

Claims (13)

1. A nylon elastomer nano composite material is characterized in that,
the nano composite material is prepared by melt blending of a premix formed by filling and adhering a nano material combined with a liquid medium between nylon elastomer particles; the nano material comprises one or more of a zero-dimensional nano material or a one-dimensional nano material, the liquid medium is injected into and fills gaps of the nano material to form a self-adhesive paste, and the thickness of the paste is 0-100 mm but not 0 mm;
the nano composite material is prepared by the following method:
(1) mixing and stirring a liquid medium, a nano material and an auxiliary agent to obtain a paste, and adding latex into the paste, wherein the mass ratio of the latex to the paste is 0.1-10: 1;
(2) mixing the mixture of the paste and the latex obtained in the step (1) with nylon elastomer particles, and enabling the paste to be sufficiently adhered to the nylon elastomer particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the liquid medium is water, and the weight ratio of the liquid medium to the nano material is 5-50: 1;
the step (1) also comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.2-1: 1.
2. The nanocomposite of claim 1, wherein the zero-dimensional nanomaterial and the one-dimensional nanomaterial comprises one or more of nano silicon oxide, nano titanium oxide, nano zirconium oxide, nano zinc oxide, nano aluminum oxide, nano nickel oxide, nano gold, nano silver, nano silicon, nano carbon, carbon nanofiber, carbon nanotube, nano graphite, nano boron powder, nano sulfur, nano lanthanum oxide, nano neodymium oxide, nano erbium oxide, nano cerium oxide, nano praseodymium oxide, nano yttrium oxide, nano europium oxide, nano tungsten oxide, nano silicon carbide, nano tellurium oxide, nano niobium oxide, nano hafnium oxide, or nano molybdenum oxide.
3. The composite material of claim 1, wherein the nylon elastomer comprises a polyamide, a polyether, and a dicarboxylic acid, the polyamide comprising one of PA6, PA66, or PA 12.
4. The composite material according to claim 1, wherein the mass ratio of the nano material to the nylon elastomer is 0.1-20: 100.
5. The composite material according to claim 4, wherein the mass ratio of the nano material to the nylon elastomer is 1-10: 100.
6. The composite material of claim 5, wherein the mass ratio of the nanomaterial to the nylon elastomer is 3-8: 100.
7. A method for preparing the nylon elastomer nanocomposite material as claimed in any one of claims 1 to 6, wherein the method comprises the following steps:
(1) mixing and stirring a liquid medium, a nano material and an auxiliary agent to obtain a paste, and adding latex into the paste, wherein the mass ratio of the latex to the paste is 0.1-10: 1;
(2) mixing the mixture of the paste and the latex obtained in the step (1) with nylon elastomer particles, and enabling the paste to be sufficiently adhered to the nylon elastomer particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the liquid medium is water, and the weight ratio of the liquid medium to the nano material is 5-50: 1;
the step (1) also comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.2-1: 1.
8. The method of claim 7, wherein in the step (3), during the process that the temperature of the melt blending is higher than the boiling point of the liquid medium and the plasticizing temperature of the nylon elastomer is reached, the liquid medium is gasified, and the agglomerated nanometer materials are separated.
9. The preparation method according to claim 7, wherein the weight ratio of the liquid medium to the nanomaterial is 5-20: 1.
10. The method according to claim 7, wherein the auxiliary agent comprises one or more of a carboxylate surfactant, a sulfate surfactant, a sulfonate surfactant, a phosphate surfactant, an amine salt surfactant, a quaternary ammonium salt surfactant, a heterocyclic surfactant, a nonionic surfactant, a natural water-soluble polymer, a synthetic water-soluble polymer, and a prepolymer thereof.
11. The method according to claim 7, wherein the liquid medium combined with the nanomaterial accounts for 60-98% of the total mass of the paste.
12. The method according to claim 11, wherein the liquid medium combined with the nanomaterial accounts for 80-98% of the total mass of the paste.
13. The preparation method of claim 7, wherein the latex comprises one or more of styrene-acrylic emulsion, acrylate emulsion, acrylic emulsion, silicone-acrylic emulsion, aqueous polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, terpineol, vinyl acetate-acrylic emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex, pure acrylic latex, carboxylic styrene-butadiene latex and styrene-acrylic latex.
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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
CN106832913A (en) * 2017-02-28 2017-06-13 苏州博利迈新材料科技有限公司 A kind of hydrophobicity nylon 66 composite material and preparation method thereof

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