CN110229503B - PA6 nano composite material and preparation method thereof - Google Patents
PA6 nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of nano composite materials, in particular to a PA6 nano composite material and a preparation method thereof, wherein the nano composite material is prepared by melting and blending a premix, and the premix is formed by filling and adhering a nano material combined with a liquid medium among polyamide 6 particles. 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 polyamide 6 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
Technical Field
The invention relates to the field of nano composite materials, in particular to a PA6 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 in the gaps of the nano material so as to improve the impact resistance of the composite material, but the process takes longer 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 a water-assisted method to prepare the polyamide/nano montmorillonite master batch, and the preparation method comprises the steps of using deionized water as an intercalation agent, mixing purified montmorillonite and the deionized water, fully dispersing to prepare montmorillonite slurry, gradually adding the montmorillonite slurry into polyamide with completely melted formula amount, and then extruding and granulating to obtain the 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 polyamide 6, wherein gaps of the nano material are subjected to expansion treatment, intercalation in-situ polymerization is not required, and the toughness of the polyamide 6 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 PA6 nanocomposite material, wherein the nanocomposite material is prepared by melt blending a premix formed by a liquid medium incorporated with a nanomaterial adhered to particles of polyamide 6.
In the above-mentioned embodiment, the recurring amide group in the polyamide molecule segment is a polar group, and hydrogen in this group can combine with oxygen in the carbonyl group in the amide group segment of another molecule to form a relatively strong hydrogen bond. The formation of hydrogen bonds makes the structure of the polyamide susceptible to crystallization. And the intermolecular force is large, so that the polyamide has high mechanical strength and high plasticizing temperature, on one hand, molecular chains in polyamide molecules are relatively flexible due to the existence of methylene, so that the polyamide also has high toughness, but in the process of forming a composite material with a nano material, the toughness of the polyamide is reduced to some extent due to the difference of compatibility between the nano material and the polyamide, and in addition, the polyamide has the main defect of high hydrophilicity, so that the dimensional stability after water absorption is poor.
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 polyamide 6 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 polyamide 6, 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, methanol, methyl ethyl ketone, dimethyl amine, diethyl ether, pentane, dichloromethane, carbon disulfide, 1, 1-dichloroethane, trifluoroacetic acid, 1,1, 1-trichloroethane, toluene, One or more of ethanol, butanone, 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.
In the above scheme, the staff of the present invention unexpectedly finds that the polyamide has too strong hydrophilicity and the dimensional stability after water absorption is deteriorated, and although the liquid medium mainly containing water is used to inject the liquid into the spaces of the nanomaterial in the technical scheme of the present application, in the process of using the nanomaterial with high water content to blend and mix with the polyamide 6 and the copolymer thereof and extruding the mixture after the liquid injection, the water contained in the spaces of the nanomaterial does not affect the dimensional stability of the polyamide 6, and even the impact strength of the polyamide 6 composite material is improved.
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: 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.
The further scheme of the invention is as follows: the paste has a consistency of 0-100 mm, but not 0 mm.
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-adhesiveness after the liquid medium is injected into 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 surfaces of polyamide 6 particles and can be fed to a melting and blending device together with the polyamide 6 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 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 polyamide 6 is 0.1-20: 100, preferably 1-10: 100, and more preferably 4: 100.
The invention also provides a preparation method of the polyamide 6 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 polyamide 6 particles, and enabling the paste to be fully adhered to the polyamide 6 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 semisolid paste with certain consistency is obtained by mixing the liquid medium and the nano material, the phenomenon of slipping can not occur when the paste and the polyamide 6 particles are mixed and added into an extrusion device, the nano composite material can be prepared by direct feeding, the production and the processing are convenient, and the problem of poor performance of the nano composite material caused by the early gasification of the liquid medium in the prior art is solved.
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 polyamide 6, 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 polyamide 6, 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 polyamide 6 are simultaneously added into the processing equipment, and the liquid content of the nano material is improved due to the previous treatment (namely paste formation) on the lyophilic medium of the nano material, so that when the nano material enters a polyamide 6 melting zone, although the system temperature is higher than the boiling point of the liquid medium, the liquid medium contained in gaps of the nano material is more, so that the phase change evaporation process and the melting process of the polyamide 6 can be simultaneously carried out, the molten polyamide 6 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 usually adopted, and due to insufficient treatment of the nano material lyophilic medium, the liquid medium is evaporated too fast, the compatibility of the nano material and polyamide 6 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 paste and the polyamide 6 particles are mixed to obtain a pre-mixed material, and the pre-mixed material is fed to a hot melting processing device under a non-pressure condition for melt 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 polyamide 6 pellets is fed from a non-pressure feeding zone to achieve feeding under non-pressure conditions. According to the invention, the nano material can be directly mixed with the polyamide 6 particles for feeding, and the nano material is combined with the liquid medium to form a paste with a certain consistency, so that the slipping phenomenon is prevented, and on the other hand, the liquid medium contained in the nano material has a high content, so that the liquid medium in the premix can not be subjected to early phase change gasification when the premix passes through the first melting zone, and the molten polyamide 6 can better penetrate into gaps of the nano material to form the nano composite material with good mechanical property.
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 polyamide 6 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, etc. 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 ester of higher fatty alcohol, and has molecular structure formula of ROSO3-M +, and commonly used sodium lauryl sulfate (also known as "sodium lauryl sulfate"), sodium cetyl sulfate (also known as "sodium cetyl sulfate"), and sodium stearyl sulfate (also known as "sodium stearyl sulfate").
(3) The sulfonic acid compound includes 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 ethoxylate, fatty alcohol ethoxylate, fatty acid methyl ester ethoxylate, 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, polyvinyl amine, 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 selected from the group consisting of 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-propanediamine 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 preparation method further comprises the step of adding latex into the paste prepared in the step (1) to form a mixture, and then melt-blending the mixture and polyamide 6, wherein 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 polyamide 6 are simultaneously melted and blended for subsequent processing, so that the releasing rate of the liquid medium in gaps is greatly delayed, the liquid medium is effectively prevented from being subjected to premature phase change, and on the other hand, the size of the gap expansion 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, which is beneficial for the polymer to further enter the gaps of the nano material to realize the filling.
According to the above preparation method, the preparation method further comprises adding an anti-aging agent to the premix formed by the paste and the polyamide 6 particles before or during melt blending, wherein the weight ratio of the anti-aging agent to the polyamide 6 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-thiobenzimide 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 a paste and polyamide 6; 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 polyamide 6 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 polyamide 6 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 the 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 polyamide 6 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 230-240 ℃ in a first zone, 230-240 ℃ in a second zone, 240-250 ℃ in a third zone, 240-250 ℃ in a fourth zone and 240-250 ℃ 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 carrying out the process of the step (3).
The invention has the beneficial effects that:
1. the polyamide 6 nanocomposite provided by the invention has the advantages of great improvement in mechanical properties, especially impact properties, simple process, easy operation, short time and suitability for popularization;
2. according to the invention, the nano material with high liquid content and the polyamide 6 are melted at the same time, the molecular energy of the liquid medium combined among the gaps of the nano material is improved by utilizing the heat in the processing process of the composite material, the phase change of the liquid medium among the gaps is promoted, the gaps of the nano material are expanded, and the filling of the melted polyamide 6 in the gaps is facilitated;
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 polyamide 6, the time of phase change of a liquid medium combined among gaps is matched with the melting time of the polyamide 6, so that the polyamide 6 in a molten state 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 of the embodiments will be clearly and completely described below, 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 example, the mass ratio of the nanomaterial to polyamide 6 was 15:100, the liquid medium used was water, the auxiliary agent used was cetylpyridinium chloride, and the nanomaterial used was nano alumina, and the nanocomposite was prepared as follows:
(1) stirring a liquid medium, and simultaneously adding the nano material at the speed of 4.5g/min for continuous stirring and uniform dispersion, wherein the weight ratio of the liquid medium to the nano material is 20: 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 46mm, and the weight ratio of the auxiliary agent to the nano material is 10: 1;
(3) mixing the paste obtained in the step (2) with polyamide 6 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 230 ℃ in a first area, 240 ℃ in a second area, 240 ℃ in a third area, 250 ℃ in a fourth area, 250 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 0.8 m/s.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 90MPa and a bending strength of 116 MPa.
Example 2
In this example, the mass ratio of the nanomaterial to the polyamide 6 is 10:100, the adopted liquid medium is acetone and water, the mass ratio of the acetone to the water is 7:93, the adopted auxiliary agent is polyacrylic acid and polymaleic anhydride, the weight ratio is 1:1, the adopted nanomaterial is nano silicon, 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 25mm, 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 polyamide 6 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 235 ℃, a second zone is 235 ℃, a third zone is 250 ℃, a fourth zone is 250 ℃ and a fifth zone is 240 ℃; the linear speed of the screw speed was 1 m/s.
The polyamide 6 nanocomposite obtained by final extrusion and granulation had a tensile strength of 91MPa and a flexural strength of 115 MPa.
Example 3
In this example, the mass ratio of the nano material to the polyamide 6 was 0.1:100, the liquid medium used was water, the auxiliary agent used was sodium alginate, the nano material used was nano zirconia and nano silicon carbide, and the mass ratio was 8:2, and the nanocomposite was prepared as follows:
(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 38mm, 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 polyamide 6 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 polyamide 6 nano composite material is 94MPa, and the bending strength is
118MPa。
Example 4
In this example, the mass ratio of the nanomaterial to the polyamide 6 is 7:100, the liquid medium is N, N-dimethylformamide, the auxiliary agent is polyethyleneimine or its oligomer, the nanomaterial is carbon nanotube, and the antioxidant is antioxidant BLE, and the nanocomposite is prepared by the following method:
(1) stirring a liquid medium, adding a nano material at a speed of 15g/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 100g/min to obtain a paste, wherein the thickness of the paste is 73mm, 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 polyamide 6 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 230 ℃, a second zone is 245 ℃, a third zone is 250 ℃, a fourth zone is 250 ℃ and a fifth zone is 240 ℃; the linear speed of the screw speed was 0.9 m/s.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 95MPa and a bending strength of 119 MPa.
Example 5
In this example, the mass ratio of the nanomaterial to the polyamide 6 was 4:100, the liquid medium used was cyclohexane and water, the mass ratio was 1:8, the auxiliary used was polyamide glyoxal resin, the nanomaterial used was carbon nanofibers, and the nanocomposite was prepared as follows:
(1) stirring the liquid medium, and simultaneously adding the nano material at the speed of 20g/min for continuous stirring and uniform dispersion, 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 the speed of 1g/min to obtain a paste, wherein the thickness of the paste is 49mm, 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 polyamide 6 to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, melting, blending and performing subsequent processing to obtain the nano composite material.
The tensile strength of the finally obtained polyamide 6 nanocomposite material is 92MPa, and the bending strength is 117 MPa.
Example 6
In this example, the mass ratio of the nanomaterial to polyamide 6 was 4:100, the liquid medium used was water, the adjuvant used was tamarind polysaccharide gum, the nanomaterial used was nano niobium oxide, and the antiaging agent used was tris (2, 4-di-tert-butylphenyl) phosphite, and the nanocomposite was prepared as follows:
(1) stirring the liquid medium, adding the nano material at the speed of 0.02g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 10: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 0.1g/min to obtain a paste, wherein the thickness of the paste is 39mm, the weight ratio of the auxiliary agent to the nano material is 2:1, and further, mixing the paste with pure acrylic latex;
(3) mixing the paste mixed with the pure acrylic latex obtained in the step (2) with polyamide 6 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 in a first zone is 230 ℃, a second zone is 235 ℃, a third zone is 240 ℃, a fourth zone is 240 ℃ and a fifth zone is 240 ℃; the linear speed of the screw speed was 0.7 m/s.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 99MPa and a bending strength of 125 MPa.
Example 7
In this example, the mass ratio of the nanomaterial to polyamide 6 was 2:100, the liquid medium used was water and n-pentane, the mass ratio of water to n-pentane was 1:10, the adjuvant used was sodium dodecyl sulfate, the nanomaterial used was nano nickel oxide, and the nanocomposite was prepared as follows:
(1) stirring a liquid medium, and simultaneously adding the nano material at the speed of 20g/min for continuous stirring and uniform dispersion, 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 35g/min to obtain a paste, wherein the thickness of the paste is 81mm, and the weight ratio of the auxiliary agent to the nano material is 7: 1;
(3) mixing the paste obtained in the step (2) with polyamide 6 to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, melting, blending and performing subsequent processing to obtain the nano composite material.
The tensile strength of the finally obtained polyamide 6 nanocomposite is 90MPa, and the bending strength is 115 MPa.
Example 8
In this example, the mass ratio of the nanomaterial to polyamide 6 was 4.5:100, the liquid medium used was water, the adjuvant used was hyaluronic acid, and the nanomaterial used was nano tellurium oxide, and the nanocomposite was prepared as follows:
(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 3.5: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 56g/min to obtain a paste, wherein the thickness of the paste is 37mm, and the weight ratio of the auxiliary agent to the nano material is 28: 1;
(3) mixing the paste obtained in the step (2) with polyamide 6 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 in a first zone is 230 ℃, a second zone is 235 ℃, a third zone is 245 ℃, a fourth zone is 245 ℃ and a fifth zone is 250 ℃; the linear speed of the screw speed was 0.6 m/s.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 92MPa and a bending strength of 116 MPa.
Example 9
In this example, the mass ratio of the nano material to the polyamide 6 is 18:100, the adopted liquid medium is water, the adopted auxiliary agents are chitosan and ammonia-dimethylamine-epichlorohydrin resin, the mass ratio of the chitosan to the ammonia-dimethylamine-epichlorohydrin resin is 10:1, the adopted nano material is nano yttrium oxide, and the nano composite material is prepared according to the following method:
(1) stirring a liquid medium, adding a nano material at the speed of 8g/min, continuously stirring and dispersing uniformly, 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 40: 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 92mm, the weight ratio of the auxiliary agent to the nano material is 9:1, and further, mixing the paste with the fluorocarbon emulsion;
(3) mixing the paste mixed with the fluorocarbon emulsion obtained in the step (2) with polyamide 6 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 of a first zone is 235 ℃, a second zone is 235 ℃, a third zone is 250 ℃, a fourth zone is 250 ℃ and a fifth zone is 240 ℃; the linear speed of the screw speed was 1 m/s.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 100MPa and a bending strength of 128 MPa.
Comparative example 1
In this comparative example, on the basis of example 1, the position of feeding the liquid-containing nanomaterial into the extruder was adjusted, polyamide 6 was fed under a non-pressure condition, and after the polyamide 6 passed through the melting zone, the nanomaterial containing the liquid medium in the voids was mixed with the polyamide 6 in a molten state by pressurization.
Comparative example 1 differs from the examples in that: the polyamide 6 and the nanomaterial containing a liquid medium in the gaps are not fed simultaneously, but the polyamide 6 is fed first and after the polyamide 6 is melted, the nanomaterial with the liquid medium bound in the gaps is pressurized and fed for processing.
The polyamide 6 nanocomposite obtained by final extrusion granulation has a tensile strength of 78MPa and a bending strength of 102 MPa.
Mechanical property tests are carried out on examples 1-9 and comparative example 1, and the performance parameters of tensile strength and bending strength are respectively obtained as shown in the following table:
| tensile Strength (MPa) | Flexural Strength (MPa) | |
| Example 1 | 90 | 116 |
| Example 2 | 91 | 115 |
| Example 3 | 94 | 118 |
| Example 4 | 95 | 119 |
| Example 5 | 92 | 117 |
| Example 6 | 99 | 125 |
| Example 7 | 90 | 115 |
| Example 8 | 92 | 116 |
| Example 9 | 100 | 128 |
| Comparative example 1 | 78 | 102 |
As can be seen from the above table, the mechanical properties of the nanocomposite obtained in examples 1 to 9 are all higher than those of comparative example 1, and especially the bending strength is greatly improved, but the present invention utilizes the phase change of the liquid medium to perform the expansion treatment on the nanomaterial, so that the polyamide 6 melted simultaneously with the nanomaterial enters into the gap to be filled, the gap expansion treatment utilizes the heat generated by the melting of the polymer, so that the liquid medium is evaporated to generate implosion to prop open the gap, and the shear force of the extrusion processing is utilized to further peel off the gap, so that the molten polyamide 6 is filled, thereby improving the bending strength and the impact strength of the product.
Furthermore, the strength of the embodiment 6 and the embodiment 9 is higher than that of the embodiment 1 to 8, and the reason is that the mixed latex treatment is carried out on the nano material paste before the melting processing, so that the implosion force generated by the evaporation of the liquid medium in the melting process is stronger, the expansion effect of the nano material gap is better, the polyamide 6 is more fully filled, and the mechanical strength of the final product is improved.
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 some 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 (20)
1. A PA6 nanocomposite material, 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 among polyamide 6 particles; 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 gap of the nano material to form a paste with self-adhesion;
the nano composite material is prepared by the following method:
(1) mixing and stirring a liquid medium and a nano material 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 polyamide 6 particles, and enabling the paste to be fully adhered to the polyamide 6 particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the latex comprises one or more of acrylate emulsion, waterborne polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, waterborne epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex and carboxylic styrene-butadiene latex.
2. The composite material according to claim 1, characterized in that the consistency of the paste is 0-100 mm, but not 0 mm;
the paste comprises:
1 part by weight of nano material
0.02-100 parts by weight of a liquid medium.
3. The composite material of claim 2, wherein the paste further comprises:
0 to 50 parts by weight of an auxiliary agent, but not 0.
4. The composite material 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.
5. The composite material according to claim 1 or 2, wherein the mass ratio of the nanomaterial to the polyamide 6 is 0.1-20: 100.
6. The composite material according to claim 5, wherein the mass ratio of the nanomaterial to the polyamide 6 is 1-10: 100.
7. The composite material according to claim 6, wherein the mass ratio of the nanomaterial to polyamide 6 is 4: 100.
8. A preparation method of a polyamide 6 nano composite material is characterized by comprising the following steps:
(1) mixing and stirring a liquid medium and a nano material 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 polyamide 6 particles, and enabling the paste to be fully adhered to the polyamide 6 particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the latex comprises one or more of acrylate emulsion, waterborne polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, waterborne epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex and carboxylic styrene-butadiene latex.
9. The method for preparing polyamide 6 nanocomposite as claimed in claim 8, wherein the step (1) further comprises mixing and stirring the liquid medium, the nanomaterial and the auxiliary agent to obtain a paste.
10. The preparation method according to claim 8, 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 polyamide 6 is reached, 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 polyamide 6; the weight ratio of the liquid medium to the nano material is 0.02-100: 1.
11. The method according to claim 10, wherein the liquid medium has a boiling point of not higher than 180 ℃ and is water.
12. The preparation method according to claim 10, wherein the weight ratio of the liquid medium to the nanomaterial is 5-50: 1.
13. The preparation method according to claim 12, wherein the weight ratio of the liquid medium to the nanomaterial is 5-20: 1.
14. The preparation method according to claim 8, wherein the step (1) further comprises adding an auxiliary agent into the nano material to increase 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 0.01-50: 1, and 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.
15. The preparation method according to claim 14, wherein the step (1) further comprises adding an auxiliary agent into the nano material to increase the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 60-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.1-5: 1.
16. The preparation method according to claim 15, wherein the step (1) further comprises adding an auxiliary agent into the nano material to increase the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 80-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.2-1: 1.
17. A premix, comprising:
the premix comprises a paste, latex and polyamide 6;
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 mass ratio of the latex to the paste is 0.1-10: 1, and the latex comprises one or more of acrylate emulsion, water-based polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, water-based epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, chloroprene latex and carboxyl styrene-butadiene latex;
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;
the premix 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 polyamide 6 particles, and enabling the paste and the latex to be fully adhered to the polyamide 6 particles to obtain a premix;
the boiling point of the liquid medium is lower than the temperature of the premix for melt blending in the subsequent step, so that the liquid medium is gasified to separate the agglomerated nanometer materials in the process of reaching the plasticizing temperature of the polyamide 6 in the subsequent melt blending step.
18. A pre-mix according to claim 17 wherein the nanomaterial and adjuvant are added to the liquid medium and dispersed sequentially during the process of making the paste.
19. A pre-mix according to claim 18 wherein the dispersion comprises ultrasound, shear, agitation, ball milling, colloid milling, vortexing, etching aid or air impingement.
20. A pre-mix according to claim 17 or 18 wherein the nanomaterial and adjuvant are added in a manner which includes single addition and batch addition.
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| Polyamide 12 (PA12)/clay nanocomposites fabricated by conventional extrusion and water-assisted extrusion processes;Stoeffler, Karen等;《Journal of applied polymer science》;20131105;第130卷(第3期);1959-1974页 * |
| Relations between Structure and Property of Polyamide 11 Nanocomposites based on Raw Clays Elaborated by Water-Assisted Extrusion;Gregory Stoclet等;《JOURNAL OF APPLIED POLYMER SCIENCE》;20120611;第127卷(第6期);4809-4824页 * |
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