CN110229490B - PC (polycarbonate) nano composite material and preparation method thereof - Google Patents
PC (polycarbonate) nano composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the field of nano composite materials, in particular to a PC nano composite material which is prepared by melting and blending mixed materials; the mixed material comprises PC, and the PC particles are combined with nano materials and a liquid medium. Also relates to a preparation method of the PC nano composite material, which comprises the following steps: (1) mixing the nanometer material and the liquid medium to prepare a paste; (2) mixing the paste with PC to make the paste be adhered on the surface of PC particles to obtain a mixed material; (3) and melting and blending the mixed materials to prepare the nano composite material. The mixed material can not slip after being added into equipment such as an extruder, and can be used for directly preparing the nano composite material without adding other substances in the preparation process, so that the production and processing are convenient, the problem of poor performance of the nano composite material caused by premature 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.
Description
Technical Field
The invention relates to the field of nano composite materials, in particular to a nano composite material taking PC as a base 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 a PC nano composite material, and the product performance of the PC nano composite material is more excellent.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
a PC nano composite material is prepared by mixing materials through melting and blending;
the mixed material comprises PC, and the PC particles are combined with nano materials and a liquid medium.
The mixed material can not slip after being added into equipment such as an extruder, and can be used for directly preparing the nano composite material without adding other substances in the preparation process, so that the production and processing are convenient, the problem of poor performance of the nano composite material caused by premature 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 surface of the PC particle is adhered with a paste formed by mixing the nano material and the liquid medium.
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, so that inconvenience is brought to production and processing.
Preferably, the paste further comprises an auxiliary agent.
Specifically, the viscosity of the mixture of the nano material and the liquid medium is increased under the action of the auxiliary agent to form a paste, the auxiliary agent of the invention also improves the boiling point of the liquid medium, and the problem of poor performance of the nano composite material caused by premature gasification of the liquid medium in the prior art is further avoided.
The paste comprises: 1 part of nano material, 5-100 parts of liquid medium and 0-50 parts of auxiliary agent, but not 0.
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 ratio of the nano material to the PC is 0.1-20: 100; preferably 1-10: 100; more preferably 4: 100.
The PC particles are also combined with an anti-aging agent, and the mass ratio of the anti-aging agent to the PC is 0.1: 100-1: 100; preferably 0.3: 100;
the nano material is one or a mixture of several of zero-dimensional nano material and one-dimensional nano material.
The nano material is one or a mixture of several 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 and nano molybdenum oxide.
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 PC, preferably below 180 ℃, and the liquid medium comprises water.
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 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 mixed material, which comprises: paste and PC; 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 PC particles to form a mixed material;
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 dispersion mode comprises ultrasound, shearing, stirring, ball milling and colloid milling;
further preferably, the addition modes of the nano material and the auxiliary agent comprise one-time addition and batch addition.
The invention also provides a preparation method of the PC nano composite material, which comprises the following steps:
(1) mixing the nanometer material and the liquid medium to prepare a paste;
(2) mixing the paste with PC to make the paste be adhered on the surface of PC 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.
And (2) adding an auxiliary agent into the step (1).
All hot melt processing techniques can be used during melt blending of the paste with PC, such as internal mixing, roll mixing, screws (parallel/conical/single/double/triple screws).
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 step (3) comprises the following steps:
(1) heating, and mixing and contacting PC with the liquid medium and the nano material in the paste 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, PC is gradually softened and mutually permeates with the paste under the stirring action, so that the PC, 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 PC, the liquid medium in the paste is further gasified, and the agglomerated nano materials are separated.
In the stage of melt blending, the PC is in a molten state, at the moment, the liquid medium is gasified, the agglomerated nanometer materials are separated from each other, and the PC flows among the nanometer materials, so that the dispersing effect of the nanometer materials in the PC 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, and the gasification of the liquid medium can help to soften PC.
And (2) adding an anti-aging agent into the step (1).
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 materials before melt blending, the PC coats the nano materials and the liquid medium to obtain a mixture, the mixture is subjected to external shearing action and gasification action of the internal liquid medium during melt blending, the mixture is exploded under the action of the external shearing action and the internal liquid medium, and the PC in a molten state enters between the nano materials while the liquid medium escapes; to achieve blasting, the melt pressure of the PC 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.
The nano material in the paste can also be a layered nano material, such as montmorillonite and graphene, when the nano material is a layered nano material, the liquid medium enters the interlayer of the layered nano material in the step (1), and when the temperature in the step (3) is higher than the plasticizing temperature of the polymer, the liquid medium is gasified, and the lamella is separated. The assistant makes more liquid medium enter the layered nanometer material layer to form paste. And the liquid medium in the step (1) enters between the layered nano-material layers, the liquid medium between the layered nano-material layers is gasified in the melt blending stage, at least part of the sheet layers are separated, and the thermoplastic polymer in the molten state flows between the separated sheet layers, so that the dispersion effect of the nano-material in the thermoplastic polymer is improved. 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. Wherein, the assistant enables more liquid media to enter the interlayer of the layered nano material, thereby further improving the interlayer spacing of the layered nano material. During melt blending, the interlayer of the layered nano material is also exploded to separate at least part of the sheets, the thermoplastic polymer in a molten state enters between the separated sheets, the spacing between the layers of the layered nano material which is not separated from the sheets is increased, and the thermoplastic polymer in a molten state enters between the layers.
Compared with the prior art, the invention has the following beneficial effects:
the mixed material can not slip after being added into equipment such as an extruder, and can be used for directly preparing the nano composite material without adding other substances in the preparation process, so that the production and processing are convenient, the problem of poor performance of the nano composite material caused by premature 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.
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 first, adhesive coating
The nano material is nano silicon oxide, the liquid medium is water, the auxiliary agent is pectin, the thermoplastic polymer is PC, 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, so as to prepare the sticky cover, and the consistency of the sticky cover is 5 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 5 parts by weight
0.005 part by weight of anti-aging agent
And mixing the sticky cover, 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 nano carbon, the liquid medium is isopentane, the auxiliary agent is chitosan, the thermoplastic polymer is PC, and the anti-aging agent is antioxidant TNP.
Preparation of first, adhesive coating
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, so as to prepare the sticky cover, and the consistency of the sticky cover is 20 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 sticky cover, 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 nano silicon carbide, 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 first, adhesive coating
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, so as to prepare the sticky cover, and the consistency of the sticky cover is 50 mm.
Secondly, preparation of mixed materials
100 parts by weight of thermoplastic polymer
Age resister 1 part by weight
And mixing the sticky cover, 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 nano yttrium oxide, the liquid medium is acetonitrile, the auxiliary agent is polyacrylic acid, the thermoplastic polymer is PC, and the anti-aging agent is antioxidant 1790.
Preparation of first, adhesive coating
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, so as to prepare the sticky cover, and the consistency of the sticky cover is 80 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 500 parts by weight
Age resister 5 parts by weight
And mixing the sticky cover, 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 a carbon nano tube, the liquid medium is chloroform, the auxiliary agent is polyaspartic acid, the thermoplastic polymer is PC, and the anti-aging agent is an antioxidant 4020.
Preparation of first, adhesive coating
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, so as to prepare the sticky cover, and the consistency of the sticky cover is 100 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 1000 parts by weight
Age resister 10 parts by weight
And mixing the sticky cover, 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 nano boron powder, the liquid medium is carbon disulfide, the auxiliary agent is dicyandiamide formaldehyde resin, the thermoplastic polymer is PC, and the anti-aging agent is antioxidant 1035.
Preparation of first, adhesive coating
1 part by weight of nano material
Liquid medium 10 parts by weight
Auxiliary agent 2 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, so as to prepare the sticky cover, and the consistency of the sticky cover is 20 mm.
Secondly, preparation of mixed materials
Thermoplastic Polymer 25 parts by weight
0.2 parts by weight of age resister
And mixing the sticky cover, 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 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 auxiliary agents were added during the preparation of the adhesive coating.
Comparative example 2
The only difference from example 2 is that the melt blending of the clay is added after the thermoplastic has reached the 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.
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 (18)
1. A PC nano composite material is characterized in that the PC nano composite material is prepared by melting and blending mixed materials;
the mixing material comprises PC, wherein nano materials and liquid media are combined on PC particles, and the nano materials are one or a mixture of more of zero-dimensional nano materials and one-dimensional nano materials;
the PC nano composite material is prepared by the following method:
(1) mixing the nano material, the liquid medium and the auxiliary agent to prepare paste;
(2) coating the paste with a coating material to obtain a coated paste;
(3) mixing the coated paste with PC to make the paste adhere to the surface of PC particles to obtain a mixed material;
(4) melting and blending the mixed materials to prepare a PC nano composite material;
the auxiliary agent 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, natural water-soluble polymers and synthetic water-soluble polymers;
the covering comprises: 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.
2. The PC nanocomposite material of claim 1, wherein the nanomaterial is 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, and nano molybdenum oxide.
3. PC nanocomposite material according to claim 1, characterized in that the paste has a consistency of 0-100mm, but not 0.
4. A PC nanocomposite as claimed in claim 3 wherein the paste comprises: 1 part of nano material, 5-100 parts of liquid medium and 0-50 parts of auxiliary agent, but not 0.
5. The PC nanocomposite material of claim 4, wherein the mass ratio of nanomaterial to PC is 0.1-20: 100.
6. The PC nanocomposite material of claim 5, wherein the mass ratio of nanomaterial to PC is 1-10: 100.
7. The PC nanocomposite material of claim 6, wherein the mass ratio of nanomaterial to PC is 4: 100.
8. The PC nanocomposite material of claim 5, wherein the PC particles are further combined with an anti-aging agent, and the mass ratio of the anti-aging agent to the PC is 0.1:100 to 1: 100.
9. The PC nanocomposite material of claim 8, wherein the mass ratio of the age resister to the PC is 0.3: 100.
10. The PC nanocomposite of claim 1, wherein the liquid medium has a boiling point below the plasticizing temperature of the thermoplastic polymer, and the liquid medium comprises water.
11. A method for preparing a PC nano composite material is characterized by comprising the following steps:
(1) mixing the nano material, the liquid and the auxiliary agent medium to prepare paste;
(2) coating the paste with a coating material to obtain a coated paste;
(3) mixing the coated paste with PC to make the paste adhere to the surface of PC particles to obtain a mixed material;
(4) adding the mixed materials into a double-screw extruder for melt blending to prepare a nano composite material;
the nano material is one or a mixture of several of zero-dimensional nano material and one-dimensional nano material;
the auxiliary agent 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, natural water-soluble polymers and synthetic water-soluble polymers;
the covering comprises: 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.
12. The method according to claim 11, wherein the step (3) comprises:
(1) heating, and mixing and contacting PC with the liquid medium and the nano material in the paste 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.
13. The method of claim 11, wherein in the step (3), the liquid medium in the paste is further gasified at a temperature higher than or equal to the plasticizing temperature of PC during melt blending of the mixed materials, and the agglomerated nanomaterial is separated.
14. A method according to claim 13, wherein in the step (3), when the mixed materials are melt-blended, the liquid medium is gasified to promote fluidity of the mixed materials and heat conduction, and the gasification of the liquid medium can help softening the PC.
15. A mixing material, characterized by comprising: paste and PC; 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 one or a mixture of several of zero-dimensional nano material and one-dimensional nano material;
the mixed material is prepared by the following method:
(1) mixing the nano material, the liquid medium and the auxiliary agent to prepare paste;
(2) coating the paste with a coating material to obtain a coated paste;
(3) mixing the coated paste with PC to make the paste adhere to the surface of PC particles to obtain a mixed material;
the auxiliary agent 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, natural water-soluble polymers and synthetic water-soluble polymers;
the covering comprises: 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.
16. The mixing material according to claim 15, characterized in that the nanomaterial and the adjuvant are added to the liquid medium and dispersed in sequence during the preparation of the paste.
17. The mixing material according to claim 16, wherein the dispersing means comprises ultrasound, shearing, stirring, ball milling, colloid milling.
18. The mixing material according to claim 17, characterized in that the manner of addition of the nanomaterial and the auxiliary agent comprises a single addition and a batch addition.
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