CN110229505B - Mixed material and preparation method thereof - Google Patents
Mixed material and preparation method thereof Download PDFInfo
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- CN110229505B CN110229505B CN201810185050.XA CN201810185050A CN110229505B CN 110229505 B CN110229505 B CN 110229505B CN 201810185050 A CN201810185050 A CN 201810185050A CN 110229505 B CN110229505 B CN 110229505B
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Abstract
The invention relates to a mixed material, which comprises the following components: a paste and a thermoplastic polymer; 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 thermoplastic polymer particles to form a compound. Also relates to a preparation method of the mixed material, which comprises the following steps: (1) mixing the nano material, the liquid medium and the auxiliary agent to prepare paste; (2) and mixing the paste with the thermoplastic polymer to enable the paste to be adhered to the surfaces of the thermoplastic polymer particles to obtain the mixed material. The paste can be added into a reaction system under a non-pressure state, so that the production and the processing are convenient, the paste is mixed with a thermoplastic polymer and then is adhered to the surfaces of thermoplastic polymer particles, the obtained mixed material cannot slip after being added into equipment such as an extruder, a nano composite material can be directly prepared, the production and the processing are convenient, and the problem of poor performance of the nano composite material caused by premature gasification of a liquid medium in the prior art is solved.
Description
Technical Field
The invention relates to a mixed material and a preparation method thereof.
Background
In the prior art, a layered 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 layered nano material and the polymer and the like.
In order to solve the above problems, intercalation in-situ polymerization and other ways are often adopted to enable the polymer to react between layers of the layered nano material so as to improve the impact resistance of the composite material, but the flow takes longer time, the polymerization reaction conditions are harsh, the solvent is not easy to recover, and the derived problems of environmental pollution and the like are brought.
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
In order to solve the problems in the prior art, the invention provides the mixed material, and the nano composite material prepared from the mixed material has more excellent performance.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a mixing material, comprising: a paste and a thermoplastic polymer;
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 thermoplastic polymer particles to form a compound.
The invention provides a paste, in particular a paste which is formed by increasing the viscosity of a mixture of a nano material and a liquid medium under the action of an auxiliary agent to form the paste, wherein the paste is semisolid and can be added into a reaction system under a non-pressure state for convenient production and processing, the paste can be mixed with a thermoplastic polymer and is adhered to the surface of thermoplastic polymer particles to obtain a mixed material, the mixed material can not skid after being added into equipment such as an extruder and the like, the nano composite material can be directly prepared, other substances are not required to be added in the preparation process, the production and processing are convenient, and the problem of poor performance of the nano composite material caused by premature gasification of the liquid medium in the prior art is solved, experiments show that compared with the prior art, the nano composite material prepared by the mixed material has more excellent performance. The auxiliary agent of the invention also improves the boiling point of the liquid medium, and further avoids the problem of poor performance of the nano composite material caused by premature gasification of the liquid medium in the prior art.
Preferably, the paste comprises: 1 part of nano material, 5-20 parts of liquid medium and 2-10 parts of auxiliary agent, but not 0;
more preferably, the paste comprises: 1 part of nano material, 10 parts of liquid medium and 5 parts of auxiliary agent, but not 0.
The consistency of the paste is 0-100mm, but not 0. The consistency corresponds to the standard JBJ/T70-2009.
The mass part ratio of the nano material to the thermoplastic polymer in the paste is 0.1-20: 100; preferably 1-10: 100; more preferably 4: 100.
The mixed material also comprises an anti-aging agent, and the mass part ratio of the anti-aging agent to the thermoplastic polymer is 0.1: 100-1: 100; preferably 0.3: 100.
The nano material in the paste is a layered nano material.
The nano material in the paste is one or a mixture of several of phyllosilicate, layered titanate, layered phosphate, layered metal hydroxide, transition metal oxyhalide, layered graphite, transition metal sulfide, layered metal oxide, layered metal nitride, layered metal carbide and two-dimensional metal organic framework.
The auxiliary agent comprises carboxylate surfactant, sulfate surfactant, sulfonate surfactant, phosphate surfactant, amine salt surfactant, quaternary ammonium salt surfactant, heterocyclic surfactant, nonionic surfactant, natural water-soluble polymer and synthetic water-soluble polymer;
the boiling point of the liquid medium is below the plasticizing temperature of the thermoplastic polymer, preferably below 180 ℃, and the liquid medium comprises water.
Specifically, the layered nano material comprises an ionic layered nano material and a non-ionic layered nano material.
The ionic layered nano material comprises:
the cationic nano-layered material comprises: montmorillonite, inorganic phosphate, layered silicate, kaolin, sepiolite and titanate;
the anionic nano-layered material comprises: hydrotalcite like compounds (LDHs)
Secondly, the non-ionic nano-layered material comprises:
1. carbon material: graphene.
2. Graphene analogs: elements of the fourth main group of the periodic table, such as silylene, germylene, borolene, arsylene, etc., and black phosphorus.
3. Transition Metal Sulfides (TMDs): transition Metal Sulfides (TMDs) may form insulators (HfS2), semiconductors (MoS2), semimetals (TiSe2), and all metals (NbSe2) based on the coordination environment and oxidation state of metal atoms, and Transition Metal Sulfides (TMDs) may exhibit superconductivity even under low temperature conditions. More than 40 layered transition metal sulfides are reported in the literature.
4. Layered metal oxide: MoO3, V2O3, V2O5, Al2O3, chromium oxide, TiO2, BiOCl, MnO 2.
5. Layered metal hydroxides, perovskite oxides.
6. Metal nitrides, carbides: h-BN, nitrogen carbide (g-C3N 4).
7. Two-dimensional metal-organic framework material: MOFs that have been stripped include: [ Cu2Br (IN)2] N (IN ═ isonicotinic acid), Zn-BDC (BDC ═ terephthalic acid), manganese-2, 2-dimethylsuccinic acid (MnDMS) bulk crystals were exfoliated IN ethanol, [ Zn2(bim)4] (bim ═ benzimidazole) IN a mixed solvent of methanol and propanol, MOF growth was controlled by diffusion IN a mixed solvent of N, N-dimethylformamide and acetonitrile to give ultrathin 2D CuBDC and ZnBDC MOF materials. M-TCPP ultrathin nanometer sheet (M ═ Zn, Cu, Cd, Co; TCPP ═ 5,10,15, 20-tetra (4-carboxyphenyl) porphin).
8. Transition metal oxyhalides: LiCoO2, FeOCl, and the like.
The auxiliary agent comprises a surfactant and a water-soluble polymer.
Specifically, the surfactant includes:
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.
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 organic polymer and prepolymer thereof
(1) Water-soluble polymer of polymerization type
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
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.
The liquid medium includes: 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, water, methylamine, dimethylamine, diethyl ether, pentane, dichloromethane, carbon disulfide, 1, 1-dichloroethane, trifluoroacetic acid, 1, 1, 1-trichloroethane, ethanol, butanone, 1, 2-dichloroethane, ethylene glycol dimethyl ether, triethylamine, cyclopentane, cyclohexane, ethyl acetate, dimethyl formamide, ethyl acetate, 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, N-methylformamide.
The thermoplastic polymer comprises:
1. copolymerized thermoplastic polymers, such as SDS styrene elastomers, TPU polyurethane elastomers, polyester elastomers, polyamide elastomers, polyolefin elastomers.
2. Blend type thermoplastic polymers such as TPO rubber and plastic blends, TPV thermoplastic vulcanizates, wherein the TPV thermoplastic vulcanizates include (1) non-polar rubbers & non-polar plastics such as EPDM/PP, NR/PE or PP, IIR/PP; (2) polar rubbers & non-polar plastics, such as NBR/PP, acrylic rubber/PP; (3) non-polar rubbers & polar plastics, such as EPDM/PA6, EPDM/PBT; (4) polar rubber & polar plastics, such as acrylic rubber/polyester, NBR/PA.
3. Engineering plastics, such as PA, PC, polyoxymethylene, polyphenylene oxide, polyester, polyimide, polysulfone, polyaryletherketone, fluoroplastic, chlorinated polyether.
4. General-purpose plastics such as PE, PP, PVC, PS, acrylics, phenolics, amino resins, epoxies, polyurethanes.
The anti-aging agent comprises:
antioxidant:
the amine antioxidant includes ketone-amine condensate, secondary diarylamine, substituted p-phenylenediamine and hindered amine.
Phenolic antioxidants, which can be classified as alkylated monophenols, alkylated polyphenols, thiobisphenols and polyphenols. The main classes 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.
The main varieties of the antioxidant comprise antioxidant TNP, Ultranox624 and phosphite tri (2, soul-di-tert-T phenyl).
Other types of antioxidants, 2-sulfobenzimide, commercially available as antioxidant MB, nickel dibutyldithiocarbamate, commercially available as antioxidant NBC, and also zinc dialkyldithiophosphate.
The main antioxidants are: 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-T-butylphenyl) phosphite, antioxidant MB, antioxidant NBC and zinc dialkyldithiophosphate.
The invention also provides a preparation method of the mixed material, which comprises the following steps:
(1) mixing the nano material, the liquid medium and the auxiliary agent to prepare paste;
(2) and mixing the paste with the thermoplastic polymer to enable the paste to be adhered to the surfaces of the thermoplastic polymer particles to obtain the mixed material.
All hot melt processing techniques can be used during melt blending of the paste with the thermoplastic polymer, such as internal mixing, roll mixing, screws (parallel/conical/single/double/triple screws).
In the step (1), the nano material is a layered nano material, and the liquid medium enters between layers of the layered nano material. The assistant makes more liquid medium enter the layered nanometer material layer to form paste.
In the step (1), the nano material and the auxiliary agent are sequentially added into the liquid medium and dispersed to prepare the paste.
The dispersion mode comprises ultrasonic, shearing, stirring, ball milling and colloid milling. Almost all dispersion modes can be used. The frequency of the ultrasonic wave is 800-1000 Hz, and the power is 200-1000W.
The addition modes of the nano material and the auxiliary agent comprise one-time addition and batch addition.
The addition speed of the nano material and the addition speed of the auxiliary agent are respectively 0.01-100g/min, preferably 5-10g/min, and more preferably 7 g/min.
The nanometer composite material is prepared by melt blending the mixed materials, and the preparation method specifically comprises the following steps:
(1) mixing the nano material, the liquid medium and the auxiliary agent to prepare paste;
(2) mixing the paste with a thermoplastic polymer to enable the paste to be adhered to the surfaces of thermoplastic polymer particles to obtain a mixed material;
(3) and melting and blending the mixed materials to prepare the nano composite material.
In the preparation process of the nano composite material, the mixed material is not slipped after being added into equipment such as an extruder, the nano composite material can be directly prepared, other substances are not required to be added in the preparation process, the production and the processing are convenient, the problem of poor performance of the nano composite material caused by early gasification of a 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.
The step (3) comprises the following steps:
(1) heating, and mixing and contacting the thermoplastic polymer, the liquid medium in the paste and the nano material under first stirring, softening, mutually permeating and coating;
(2) and after the temperature is higher than the boiling point of the liquid medium, partially gasifying the liquid medium, and carrying out secondary stirring on the mixed material by gasifying.
In the preparation process of the nano composite material, a heating and temperature rising stage exists, in the stage, the thermoplastic polymer is gradually softened and mutually permeates with the paste under the stirring action, so that the thermoplastic polymer, the liquid medium and the nano material are mutually contacted and coated.
In the step (3), when the mixed materials are melted and blended and the temperature is higher than or equal to the plasticizing temperature of the thermoplastic polymer, the liquid medium in the paste is further gasified, and the agglomerated nanometer materials are separated.
In the melt blending stage, the thermoplastic polymer is in a molten state, at the moment, the liquid medium is gasified, the agglomerated nanometer materials are separated from each other, and the thermoplastic polymer flows to the nanometer materials, so that the dispersion effect of the nanometer materials in the thermoplastic polymer is improved.
In the step (3), when the mixed materials are melted and blended, the liquid medium is gasified to promote the fluidity of the mixed materials and the conduction of heat, the liquid medium is gasified to soften the thermal thermoplastic polymer, and the plasticizing temperature of the thermal thermoplastic polymer is reduced.
The nano material is a layered nano material, the liquid medium enters the interlayer of the layered nano material in the step (1), and the liquid medium is gasified to separate the lamella in the step (3) when the temperature is higher than the plasticizing temperature of the polymer.
When the nano material in the paste is a layered nano material, the liquid medium in the step (1) enters between layers of the layered nano material, the liquid medium between the layers of the layered nano material is gasified in the stage of melt blending, so that at least part of the layers are separated, and the thermoplastic polymer in a molten state flows between the separated layers, thereby improving the dispersion effect of the nano material in the thermoplastic polymer. The interlayer distance of the layered nanometer material layer without the separation of the sheet layers is increased, and the thermoplastic polymer in a molten state flows into the interlayer, so that the compatibility of the thermoplastic polymer and the layered nanometer material is improved.
And (2) adding an anti-aging agent into the step (1).
When the nano material in the paste is a layered nano material, the auxiliary agent enables more liquid media to enter between layers of the layered nano material, so that the interlayer spacing of the layered nano material is further improved.
When the nano material is an ionic layered material, the XRD diffraction pattern of the nano composite material has no characteristic peak of interlayer spacing within the range of 2 theta angle 2-10 degrees.
In the embodiment of the invention, the double-screw extruder comprises a solid conveying area, a melting area and a melt conveying area, the mixed materials are added into the solid conveying area from a charging barrel, the rotating speed of a main machine of the double-screw extruder is 30-80 Hz, the rotating speed of a main feeding hopper is 10-30 Hz, the extrusion temperature is 150-200 ℃ in a first area, 230-280 ℃ in a second area, 230-280 ℃ in a third area, 230-280 ℃ in a fourth area and 230-280 ℃ in a fifth area; preferably, the rotating speed of the main machine is 60Hz, the rotating speed of the main feeding hopper is 20Hz, the extrusion temperature is 150-180 ℃ in the first zone, 245-260 ℃ in the second zone, 245-255 ℃ in the third zone, 240-250 ℃ in the fourth zone and 240-260 ℃ in the fifth zone. The linear speed of the screw rotating speed is 0.6-1 m/s.
In the mixed material before melt blending, the thermoplastic polymer coats the nano materials and the liquid medium to obtain a mixture, when the mixture is melt blended, the mixture is subjected to external shearing action and gasification action of the internal liquid medium, under the action of the external shearing action and the gasification action of the internal liquid medium, the mixture is exploded, and the thermoplastic polymer in a molten state enters between the nano materials while the liquid medium escapes; when the nano material is a layered nano material, the interlayer of the layered nano material is also exploded to separate at least part of the lamella, the thermoplastic polymer in a molten state enters between the separated lamella, the distance between the layers of the layered nano material which is not separated from the lamella is increased, and the thermoplastic polymer in a molten state enters between the layers. To achieve blasting, the melt pressure of the thermoplastic polymer should be greater than the vapor pressure of the liquid medium. The invention may also be such that the paste is coated first and then the coated paste is mixed with the thermoplastic elastomer, the coating comprising: styrene-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. The coating greatly delays the release rate of the interlayer liquid medium in the melt blending stage, effectively prevents the liquid medium from generating phase change prematurely, further improves the scale of interlayer expansion during the phase change of the liquid medium, and is beneficial to the polymer to further enter the interlayer to realize filling.
Compared with the prior art, the invention has the following beneficial effects:
the slurry prepared by the prior art is semi-liquid, and needs to be added into a reaction system under a high pressure state in the preparation process of the nano composite material, which brings inconvenience to production and processing, and in order to solve the problems, the invention provides a paste, in particular, a mixture of a nano material and a liquid medium increases in viscosity under the action of an auxiliary agent to form a paste, the paste is semisolid, can be added into a reaction system under a non-pressure state, is convenient for production and processing, the paste can be mixed with a thermoplastic polymer and adhered to the surface of thermoplastic polymer particles to obtain a mixed material, the mixed material can not slip after being added into equipment such as an extruder, can be directly used for preparing the nano composite material, does not need to add other substances in the preparation process, is convenient for production and processing, and the problem of poor performance of the nano composite material caused by premature gasification of the liquid medium in the prior art is avoided.
Drawings
Fig. 1 is an SEM image of graphene in the paste of the present invention.
Fig. 2 is a TEM image of graphene in paste of the present invention.
FIG. 3 is an XRD diagram of a nanocomposite prepared when the thermoplastic polymer of the present invention is PPO and the nanomaterial is phyllosilicate.
FIG. 4 is an XRD pattern of a nanocomposite prepared when the thermoplastic polymer of the present invention is PLA and the nanomaterial is a layered silicate.
FIG. 5 is an XRD pattern of a nanocomposite made when the thermoplastic polymer of the present invention is TPU and the nanomaterial is a layered silicate.
Fig. 6 is an XRD pattern of the layered silicate.
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 are clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not used for limiting the scope of the present invention.
Example 1
Preparation of paste
The nano material is montmorillonite, the liquid medium is water, the auxiliary agent is pectin, the thermoplastic polymer is PA6, and the anti-aging agent is antioxidant 264.
1 part by weight of nano material
Liquid medium 10 parts by weight
0.01 part by weight of auxiliary agent
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are respectively 0.01g/min, and preparing a paste with the consistency of 2 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 5 parts by weight
0.005 part by weight of anti-aging agent
And mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 30Hz, the rotating speed of a main feeding hopper is 10Hz, the extrusion temperature is 150 ℃ in a first area, 230 ℃ in a second area, 230 ℃ in a third area, 230 ℃ in a fourth area, 230 ℃ in a fifth area, and the linear speed of the rotating speed of the screws is 0.6m/s, so that the nano composite material is obtained.
Example 2
The nano material is kaolin, the liquid medium is isopentane, the auxiliary agent is chitosan, the thermoplastic polymer is PP, and the anti-aging agent is TNP.
Preparation of paste
1 part by weight of nano material
Liquid medium 5 parts by weight
Auxiliary agent 1.5 weight portions
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are respectively 1g/min, and preparing a paste with the consistency of 10 mm.
Secondly, preparation of mixed materials
50 parts by weight of a thermoplastic polymer
0.1 part by weight of age resister
And mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 60Hz, the rotating speed of a main feeding hopper is 20Hz, the extrusion temperature is 180 ℃ in a first area, 230 ℃ in a second area, 230 ℃ 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 0.8m/s, so that the nano composite material is obtained.
Example 3
The nano material is graphene, the liquid medium is dimethylamine, the auxiliary agent is xanthan gum, the thermoplastic polymer is PC, and the anti-aging agent is antioxidant 3114.
Preparation of paste
1 part by weight of nano material
Liquid medium 30 parts by weight
Auxiliary agent 5 parts by weight
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are respectively 10g/min, and preparing a paste with the consistency of 30 mm.
Secondly, preparation of mixed materials
100 parts by weight of thermoplastic polymer
Age resister 1 part by weight
And mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 80Hz, the rotating speed of a main feeding hopper is 30Hz, the extrusion temperature is 200 ℃ in a first area, 250 ℃ in a second area, 250 ℃ in a third area, 280 ℃ in a fourth area, 280 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 1m/s, so that the nano composite material is obtained.
Example 4
The nano material is montmorillonite, the liquid medium is acetonitrile, the auxiliary agent is polyacrylic acid, the thermoplastic polymer is PPO, and the anti-aging agent is antioxidant 1790.
Preparation of paste
1 part by weight of nano material
50 parts by weight of a liquid medium
10 parts by weight of assistant
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are respectively 30g/min, and preparing a paste with the consistency of 80 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 500 parts by weight
Age resister 5 parts by weight
And mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 60Hz, the rotating speed of a main feeding hopper is 20Hz, the extrusion temperature is 150 ℃ in a first area, 260 ℃ in a second area, 245 ℃ in a third area, 240 ℃ in a fourth area, 240 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 0.6m/s, so that the nano composite material is obtained.
Example 5
The nano material is kaolin, the liquid medium is chloroform, the auxiliary agent is polyaspartic acid, the thermoplastic polymer is ABS, and the anti-aging agent is antioxidant 4020.
Preparation of paste
1 part by weight of nano material
Liquid medium 100 parts by weight
50 parts by weight of auxiliary agent
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are respectively 100g/min, and preparing a paste with the consistency of 100 mm.
Secondly, preparation of mixed materials
And mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 60Hz, the rotating speed of a main feeding hopper is 20Hz, the extrusion temperature is 180 ℃ in a first area, 245 ℃ in a second area, 255 ℃ in a third area, 240 ℃ in a fourth area, 260 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 1m/s, so that the nano composite material is obtained.
Example 6
The nano material is graphene, the liquid medium is carbon disulfide, the auxiliary agent is dicyandiamide formaldehyde resin, the thermoplastic polymer is POM, and the anti-aging agent is an antioxidant 1035.
Preparation of paste
1 part by weight of nano material
Liquid medium 10 parts by weight
And sequentially adding the nano material and the auxiliary agent into the liquid medium and dispersing, wherein the adding speeds of the nano material and the auxiliary agent are 7g/min respectively, and preparing a paste with the consistency of 20 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 25 parts by weight
0.2 parts by weight of age resister
Mixing the paste, the anti-aging agent and the thermoplastic polymer to obtain a mixed material, wherein the consistency of the paste is 50 mm.
Preparation of three, nanometer composite material
And (2) melting and blending the mixed materials, wherein the mixed materials are added into a solid conveying area of a double-screw extruder, the rotating speed of a main machine of the double-screw extruder is 30Hz, the rotating speed of a main feeding hopper is 10Hz, the extrusion temperature is 200 ℃ in a first area, 280 ℃ in a second area, 260 ℃ in a third area, 250 ℃ in a fourth area, 240 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 1m/s, so that the nano composite material is obtained.
Comparative example 1
The only difference from example 2 is that no auxiliaries are added during the preparation of the paste.
Comparative example 2
The only difference from example 2 is that the paste was added to melt blend after the thermoplastic reached a molten state.
Test example 1
The mechanical properties of the nanocomposites obtained in examples 1-6 and comparative examples 1, 2 were tested in this test and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the nanocomposite obtained in example 2 has better properties than comparative example 1, and it can be seen that the present invention improves the properties of the nanocomposite by adding an auxiliary agent during the preparation of the paste. The nanocomposite obtained in example 2 was superior in performance to that of comparative example 2, and it can be seen that the present invention improves the properties of the nanocomposite by mixing the paste with the thermoplastic polymer first and then melt-blending.
As can be seen from FIG. 6, the layered silicate has a peak interlayer distance between 2 and 10 degrees, and as can be seen from FIGS. 2 and 5, the nano composite material has no peak interlayer distance between 2 and 10 degrees. It was confirmed that the sheets of the layered silicate had opened.
As can be seen from fig. 1, the obtained sample is in a relatively transparent state, which indicates that the graphene sheet layer is relatively thin and the agglomeration phenomenon is not obvious.
As can be seen from fig. 2, the obtained sample sheet layer is very thin and can be regarded as being formed by stacking peeled single-layer graphene, the surface wrinkles of the sample are due to the fact that the two-dimensional structure material is not stable and exists independently, the wrinkles are beneficial to stabilizing graphene, and the obtained sample is further proved to be single-layer graphene or few-layer graphene.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A mixing material, characterized by comprising: a paste and a thermoplastic polymer;
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 nano material is a layered nano material;
the mixed material is prepared by the following method:
(1) mixing the layered nano material, the liquid medium and the auxiliary agent to prepare a paste;
(2) coating the paste with a coating material to obtain a coated paste;
(3) mixing the coated paste with a thermoplastic polymer to enable the paste to be adhered to the surface of thermoplastic polymer particles to obtain a mixed material;
the covering comprises: acrylate emulsion, aqueous polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex and carboxylic styrene-butadiene latex;
the blend may be melt blended by heating for the preparation of nanocomposites.
2. A mixing material according to claim 1, characterised in that the consistency of the paste is 0-100mm, but not 0.
3. A compound according to claim 1 or 2, characterised in that the ratio of parts by mass of nanomaterial to thermoplastic polymer in the paste is 0.1-20: 100.
4. A compound according to claim 3, characterised in that the ratio of parts by mass of nanomaterial to thermoplastic polymer in the paste is 1-10: 100.
5. A mixing material as claimed in claim 4, characterised in that the ratio of parts by mass of nanomaterial to thermoplastic polymer in the paste is 4: 100.
6. The compound according to claim 1, further comprising an anti-aging agent, wherein the mass part ratio of the anti-aging agent to the thermoplastic polymer is 0.1:100 to 1: 100.
7. A compound according to claim 6, characterised in that the ratio of parts by mass of the age resistor to the thermoplastic polymer is 0.3: 100.
8. A compound according to claim 1, characterised in that the nano-materials in the paste are one or a mixture of several of layered silicates, layered titanates, layered phosphates, layered metal hydroxides, transition metal oxyhalides, layered graphite, transition metal sulphides, layered metal oxides, layered metal nitrides, layered metal carbides, two-dimensional metal organic frameworks.
9. The mixing material as claimed in claim 1, wherein the adjuvant comprises 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.
10. A compound according to claim 9, characterised in that the boiling point of the liquid medium is below the plasticisation temperature of the thermoplastic polymer, and that the liquid medium comprises water.
11. A method for preparing a batch according to any one of claims 1 to 10, characterized in that it comprises:
(1) mixing the layered nano material, the liquid medium and the auxiliary agent to prepare a paste;
(2) coating the paste with a coating material to obtain a coated paste;
(3) and mixing the coated paste with a thermoplastic polymer to enable the paste to be adhered to the surfaces of the thermoplastic polymer particles to obtain the mixed material.
12. The method according to claim 11, wherein in the step (1), the liquid medium enters between the layers of the layered nanomaterial.
13. The method of claim 11, wherein in the step (1), the layered nanomaterial and the auxiliary agent are sequentially added to the liquid medium and dispersed to prepare a paste.
14. The method of claim 13, wherein the dispersing means comprises sonication, shearing, stirring, ball milling, colloid milling.
15. The method according to claim 13 or 14, wherein the layered nanomaterial and the auxiliary agent are added in a manner including a single addition and a batch addition.
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| Nylon 6/Na-montmorillonite nanocomposites prepared by compounding Nylon 6 with Na-montmorillonite slurry;Hasegawa N等;《Polymer》;20030511;第44卷(第10期);2933-2937页 * |
| 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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