CN110229393B - Thermoplastic vulcanized rubber nano composite material and preparation method thereof - Google Patents
Thermoplastic vulcanized rubber 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 thermoplastic vulcanized rubber nano composite material and a preparation method thereof. The preparation method comprises the steps of mixing a liquid medium and the nano material to obtain a paste, and adhering the paste to the surface of thermoplastic vulcanized rubber 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 thermoplastic vulcanized rubber nano composite material and a preparation method thereof.
Background
In the prior art, a nano material and a polymer are often mixed and extruded to form a composite material, and although the tensile strength of the composite material is improved, the impact resistance of the composite material is generally low due to the problems of poor compatibility of the nano material and the polymer and the like.
In order to solve the above problems, intercalation in-situ polymerization and other methods are often adopted to enable the polymer to react among the gaps of the nano material so as to improve the impact resistance of the composite material, but the process takes a long time, the polymerization reaction conditions are harsh, the solvent is not easy to recover, and environmental pollution and other derivative problems are caused.
Patent No. CN101081928A proposes a method for preparing polyamide/nano montmorillonite master batch, which adopts water-assisted method to prepare polyamide/nano montmorillonite master batch, and the preparation method comprises using deionized water as intercalation agent, mixing purified montmorillonite and deionized water, fully dispersing to obtain montmorillonite slurry, gradually adding the slurry into polyamide whose formula amount is completely melted, and then extruding and granulating to obtain polyamide/nano montmorillonite master batch. The preparation method is simple, the production cost is low, but the montmorillonite slurry is added after the polyamide is melted, the montmorillonite slurry cannot be mixed with the copolymer completely, the polyamide cannot enter the interlayer in time due to the fact that interlayer water is gasified at high temperature, meanwhile, the energy generated by water gasification is not enough to strip the montmorillonite layers completely, and the product performance of the composite material cannot be completely stripped.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nano composite material, which comprises a nano material and thermoplastic vulcanized rubber, wherein gaps of the nano material are subjected to expansion treatment, intercalation in-situ polymerization is not required, and the toughness of the thermoplastic vulcanized rubber 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 thermoplastic vulcanizate nanocomposite, wherein said nanocomposite was prepared by melt blending a premix formed by interpenetration adhesion of a nanomaterial bound to a liquid medium between thermoplastic vulcanizate particles, said thermoplastic vulcanizate comprising a non-polar plastic and a polar rubber.
In the scheme, the thermoplastic vulcanized rubber is prepared from polar rubber and non-polar plastic, and due to different molecular structures and polarities, a certain amount of compatibilizer is required to be added to improve the interfacial tension of two phases and reduce the difference of surface energy, so that the vulcanized rubber is finely dispersed. The workers of the invention find that the compatibility of a blending system can be improved by adopting the nano composite material prepared by simultaneously melting and extruding the layered nano material subjected to interlayer expansion treatment and thermoplastic vulcanized rubber, so that the solvent resistance of the blending system is improved, and the tear resistance of the product is improved.
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 prepared by combining a liquid medium in a nano material, adhering and wrapping the nano material combined with the liquid medium on the surface of thermoplastic vulcanized rubber particles to form a mixture, melting and blending the mixture, and performing phase change on the liquid medium by utilizing a processing and heating process, so that the nano material is uniformly dispersed in the thermoplastic vulcanized rubber, and the toughness of the composite material is greatly improved.
In the above embodiment, the liquid medium at least includes water, and may further include isopentane, n-pentane, petroleum ether, hexane, cyclohexane, isooctane, trifluoroacetic acid, trimethylpentane, cyclopentane, heptane, butyl chloride, trichloroethylene, carbon tetrachloride, trichlorotrifluoroethane, propyl ether, toluene, p-xylene, chlorobenzene, o-dichlorobenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate, propanol, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate, isopropanol, ethanol, chloroform, methyl ethyl ketone, dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, diethyl ether, pentane, dichloromethane, carbon disulfide, 1, 1-dichloroethane, trifluoroacetic acid, 1,1, 1-trichloroethane, ethanol, butanone, ethyl chloride, toluene, p-xylene, chlorobenzene, o-dichlorobenzene, diethyl ether, ethyl chloride, n-butyl chloride, ethyl acetate, toluene, carbon disulfide, toluene, carbon disulfide, toluene, acetone, ethyl acetate, ethyl chloride, ethyl acetate, ethyl chloride, 1-ethyl chloride, 1, 1-ethyl chloride, 1-ethyl acetate, 1, 1-ethyl acetate, ethyl, 1, 2-dichloroethane, ethylene glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2-pentanone, ethylenediamine, butanol, acetic acid, ethylene glycol monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, xylene, m-xylene, acetic anhydride, o-xylene, N-dimethylformamide, cyclohexanone, cyclohexanol, furfural and N-methylformamide; preferably water.
The further scheme of the invention is as follows: the nano material comprises one or more of zero-dimensional nano material or one-dimensional nano material, and the liquid medium is injected into and fills the gaps of the nano material to form a paste with self-adhesion.
The further scheme of the invention is as follows: the paste comprises: the thickness of the paste is 0-100 mm, but not 0 mm; 1 part by weight of nano material and 0.02-100 parts by weight of liquid medium; preferably, the paste further comprises 0-50 parts by weight of an auxiliary agent, but not 0.
In the scheme, compared with the process of modifying, filtering and drying the nano material in the prior art, the nano material forms a continuous paste with certain self-adhesiveness after the liquid medium is injected into the gaps, the paste has certain consistency but not 0mm, and represents that the paste is a semisolid combined with the liquid medium and having certain fluidity, so that the nano material paste combined with the liquid medium can be uniformly adhered to the surface of thermoplastic vulcanized rubber particles and is fed to a melting and blending device together with the thermoplastic vulcanized rubber 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: in the thermoplastic vulcanized rubber, the weight ratio of the nonpolar plastic to the polar rubber is 20-80: 80-20, preferably 30-50: 70-50; the non-polar plastic comprises one of polyethylene, polypropylene, polystyrene or ABS, and the polar rubber comprises one of chloroprene rubber, nitrile rubber, HNBR, XNBR, fluororubber, polyether rubber, polysulfide rubber or acrylic rubber.
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 thermoplastic vulcanized rubber is 0.1-20: 100, preferably 1-10: 100, and more preferably 3-8: 100.
The invention also provides a preparation method of the thermoplastic vulcanized rubber 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 thermoplastic vulcanized rubber particles, and enabling the paste to be sufficiently adhered among the thermoplastic vulcanized rubber particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
preferably, the step (1) further comprises mixing and stirring the liquid medium, the nano material and the auxiliary agent to obtain the paste.
In the method, because the liquid medium and the nano material are mixed to obtain the semisolid paste with a certain consistency, the paste and the thermoplastic vulcanized rubber particles are mixed and then added into the extrusion equipment without slipping, 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 premature 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 the thermoplastic vulcanized rubber, the liquid medium is gasified, and the agglomerated nano material is separated; the boiling point of the liquid medium is lower than the plasticizing temperature of the thermoplastic vulcanized rubber, 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 thermoplastic vulcanized rubber are simultaneously added into the processing equipment, and the lyophilic medium of the nano material is treated (namely a paste is formed) in the prior art, so that the liquid content of the nano material is improved, and when the nano material enters the melting zone of the thermoplastic vulcanized rubber, although the system temperature is higher than the boiling point of the liquid medium, the liquid medium contained in the gaps of the nano material is more, so that the phase-change evaporation process and the melting process of the thermoplastic vulcanized rubber can be simultaneously carried out, the molten thermoplastic vulcanized rubber can smoothly enter the gaps of the nano material, and the impact property 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, so that the compatibility of the nano material and the thermoplastic vulcanized rubber 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 thermoplastic vulcanized rubber particles are mixed to obtain a premix, and the premix is fed to a hot melting processing device under a non-pressure condition for melting and blending.
In the above method, the hot-melt processing apparatus 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 thermoplastic vulcanizate 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 thermoplastic vulcanized rubber particles for feeding, and the nano material and the liquid medium are combined to form a paste with a certain consistency, so that the slipping phenomenon is prevented.
According to the preparation method, the step (1) further comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98%, preferably 60-98% and more preferably 80-98% of the total mass of the paste.
According to the preparation method, the mass ratio of the auxiliary agent to the nano material is 0.01-50: 1, preferably 0.1-5: 1, and more preferably 0.2-1: 1, and the auxiliary agent comprises one or more of a carboxylate surfactant, a sulfate salt surfactant, a sulfonate surfactant, a phosphate salt surfactant, an amine salt surfactant, a quaternary ammonium salt surfactant, a heterocyclic surfactant, a nonionic surfactant, a natural water-soluble polymer, a synthetic water-soluble polymer and a prepolymer thereof.
In the method, the premix in the invention takes thermoplastic vulcanized rubber as a base material and adopts a lower content of auxiliary agent in the preparation process, and the aim is to form an environment of lyophilic medium in the gaps of the nano material so as to improve the liquid content of the paste; compared with the high-content intercalation agent used in the intercalation polymerization in the prior art, the method greatly reduces the influence of the auxiliary agent on the overall performance of the nano composite material.
In the scheme, the addition of the auxiliary agent can improve the capability of a liquid medium entering the nano material, so that the consistency of the nano material mixture is increased; in addition, the addition of the auxiliary agent can also increase the boiling point of the liquid medium and prevent the liquid medium from gasifying and escaping in advance. The reaction temperature for generating the gel-like nano material in the invention can be at room temperature, and the requirement on the auxiliary agent is not high, so that the auxiliary agent applicable to the invention has wider alternative range.
The auxiliary agent includes but is not limited to one or more of the following components:
A. surfactant (b):
1. anionic surfactant: classified into carboxylates, sulfate ester salts, sulfonates, and phosphate ester salts.
(1) The soap is higher fatty acid salt, and the molecular structure general formula is (RCOO) -nMn +. Stearic acid, oleic acid, lauric acid and the like are commonly used. Depending on the metal ion (Mn +) thereof, there are alkali metal soaps, alkaline earth metal soaps, organic amine soaps and the like.
(2) The sulfated product is mainly sulfated oil and sulfate of higher fatty alcohol, and has molecular structure formula of ROSO3-M +, and commonly used sodium dodecyl sulfate (also known as "sodium lauryl sulfate"), sodium hexadecyl sulfate (also known as "sodium cetyl sulfate"), and sodium octadecyl sulfate (also known as "sodium stearyl sulfate").
(3) The sulfonic acid compound is mainly aliphatic sulfonic acid compound, sulfoaryl sulfonic acid compound, sulfonaphthalene sulfonic acid compound, etc
2. Cationic surfactant: the hydrophilic ions of the cationic surfactant contain nitrogen atoms, and are classified into amine salts, quaternary ammonium salts and heterocyclic rings according to the positions of the nitrogen atoms in the molecule. Such as benzalkonium chloride (trade name "benzalkonium chloride"), benzalkonium bromide (trade name "benzalkonium bromide"), cetylpyridinium chloride (bromide) (trade name "cetylpyridinium chloride"), etc
3. Zwitterionic surfactant: lecithin, amino acid type, betaine type
4. Nonionic surfactant: fatty glyceride, sorbitan fatty acid, polysorbate, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene, fatty acid methyl ester polyoxyethylene, and detergent.
B. The water-soluble polymer includes:
1. natural polymer
Starches
Marine algae species: sodium alginate and agar.
Vegetable gums: gum arabic, gum tragacanth, locust bean gum, tamarind seed polysaccharide gum, sesbania gum, carrageenan, guar gum, pectin.
Animal glue: gelatin, casein and chitosan.
Microbial glue: xanthan gum, gellan gum, hyaluronic acid.
2. Synthetic polymer and prepolymer thereof
(1) Water-soluble polymer and prepolymer thereof
Polyacrylamide, polyacrylic acid, polymethacrylic acid and copolymers thereof, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polymaleic anhydride, polydimethyldiallyl ammonium chloride, polyvinylamine, polydivinyl imidazoline, sodium polystyrene sulfonate, sulfonated styrene maleic anhydride copolymer and Kelvin resin.
(2) Condensed water-soluble polymer and prepolymer thereof
The water-soluble epoxy resin is prepared from water-soluble amino resin, water-soluble phenolic resin, water-soluble alkyd resin, water-soluble epoxy resin, water-soluble polyurethane resin, polyethyleneimine, polyaspartic acid, polyepoxysuccinic acid, polyamide epichlorohydrin resin, polyamide glyoxal resin, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin, N-dimethyl-1, 3-propane diamine and epichlorohydrin resin.
(3) Others
Water-soluble maleic anhydride oil, dicyandiamide-formaldehyde resin, rosin amine-ethylene oxide polycondensate, poly N-vinyl acetamide and water-soluble polysucrose.
3. Semi-synthetic polymer
Modified cellulose and modified starch.
Synthetic polymers and prepolymers thereof are preferred.
According to the preparation method, the adding modes of the nano material and the auxiliary agent in the step (1) comprise one-time adding and batch adding; the addition rate is 0.01-100g/min, preferably 5-10g/min, more preferably 7 g/min.
According to the preparation method, the step (1) further comprises the step of carrying out physical dispersion on the nano material, wherein the physical dispersion comprises but is not limited to colloid milling, ball milling, ultrasound, vortex, etching assistance, airflow impact and the like; preferably, the physical dispersion is ultrasonic, the frequency of the ultrasonic field is 800-1000 Hz, and the power is 200-1000W.
According to the preparation method, the 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 the thermoplastic vulcanized rubber, 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 thermoplastic vulcanized rubber are simultaneously melted and blended for subsequent processing, so that the release rate of the liquid medium in gaps is greatly delayed, the premature phase change of the liquid medium is effectively prevented, and on the other hand, the size of the expansion of the gaps of the nano material during the phase change of the liquid medium is further increased by the mixing treatment of the latex and the paste, which is beneficial for the polymer to further enter the gaps of the nano material to realize the filling.
According to the above production method, the production method further comprises adding an age resistor to a premix formed of the paste and the thermoplastic vulcanizate particles before or during melt blending, the weight ratio of the age resistor to the thermoplastic vulcanizate being 0.1 to 1:100, preferably 0.3: 100; the anti-aging agent is selected from one or more of amine antioxidant, phenol antioxidant, thiodipropionic acid vinegar antioxidant and phosphorous acid vinegar antioxidant.
In the above method, the anti-aging agent comprises:
amine antioxidant: ketone amine condensates, secondary diarylamines, substituted p-phenylenediamines, hindered amines;
phenol antioxidant: and can be classified into alkylated monophenols, alkylated polyphenols, thiobisphenols and polyphenols. The main varieties of alkylated monophenol and polyphenol antioxidants are antioxidants 264, 1076, 2246, 1035, 1010, 3114 and 1790; the main varieties of thiobisphenols are anti-aging agents 2246 and 300; the main varieties of the polyphenol antioxidant comprise 2, 5-di-tert-butyl hydrogen and 2, 5-di-tert-amyl hydroquinone;
thiodipropionic acid vinegar and phosphorous acid vinegar antioxidants; the main varieties of the antioxidant are antioxidant TNP, Ultranox624 and tris (2, 4-di-tert-butyl phenyl) phosphite.
Other types of antioxidants: 2-thiobenzimida is commercially available as antioxidant MB, nickel dibutyldithiocarbamate is commercially available as antioxidant NBC, and zinc dialkyldithiophosphate is also available.
The anti-aging agent specifically comprises: antioxidant RD, antioxidant AW, antioxidant BLE, antioxidant A, antioxidant OD, 4 '-bis (alpha-methylbenzyl) diphenylamine, 4' -bis (alpha, alpha-methylbenzyl) diphenylamine, N, -di-sec-butyl p-phenylenediamine, antioxidant 4030, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 1076, antioxidant 2216, antioxidant 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246, 2, 5-di-tert-butylhydroquinone, antioxidant DLTP, antioxidant TNP, Ultranox624, tris (2, 4-di-tert-butylphenyl) phosphite, antioxidant MB, antioxidant NBC and zinc dialkyldithiophosphate.
The invention also provides a premix comprising a paste and a thermoplastic vulcanizate, the thermoplastic vulcanizate comprising a non-polar plastic and a polar rubber; 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 vulcanized rubber 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 thermoplastic vulcanized rubber composite material specifically comprises the following steps:
(1) stirring the liquid medium, adding the nano material at the speed of 0.01-100g/min, and continuously stirring and dispersing uniformly, wherein the weight ratio of the liquid medium to the nano material is 0.02-100: 1;
(2) adding an auxiliary agent to the continuously stirred solution obtained in the step (1) in batches or at one time at a speed of 0.01-100g/min to obtain a paste, wherein the thickness of the paste is 0-100 mm, and the weight ratio of the auxiliary agent to the nano material is 0.001-50: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber 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 150-200 ℃ in a first area, 220-260 ℃ in a second area, 220-260 ℃ in a third area, 230-250 ℃ in a fourth area and 210-250 ℃ in a fifth area; preferably, the rotating speed of the main machine is 50Hz, the rotating speed of the main feeding hopper is 15Hz, the extrusion temperature is 150-180 ℃ in the first zone, 245-255 ℃ in the second zone, 240-250 ℃ in the third zone, 240-250 ℃ in the fourth zone and 230-250 ℃ in the fifth zone. The linear speed of the screw rotating speed is 0.6-1 m/s.
The method also comprises the step of mixing the latex and the paste after the step (2) and then performing the process of the step (3).
The invention has the beneficial effects that:
1. the thermoplastic vulcanized rubber nanocomposite provided by the invention has the advantages of great improvement in solvent resistance and tearing strength, simple process, easy operation, short time and suitability for popularization;
2. the invention melts the nano material with higher liquid content and the thermoplastic vulcanized rubber at the same time, utilizes the heat in the processing process of the composite material to improve the molecular energy of the liquid medium combined between the gaps of the nano material, promotes the phase change of the liquid medium between the gaps, expands the gaps of the nano material, and is beneficial to the filling of the thermoplastic vulcanized rubber in a molten state into the gaps;
3. the nano material provided by the invention is processed by the aid to form a paste with higher liquid content, and in the process of simultaneous melting and processing with the thermoplastic vulcanized rubber, the time of phase change of a liquid medium combined among gaps is matched with the melting time of the thermoplastic vulcanized rubber, so that the molten thermoplastic vulcanized rubber can enter the gaps of the nano material to be filled;
4. the nano material provided by the invention plays a role in preventing the nano material from agglomerating while expanding the gap by utilizing the phase change of the liquid medium.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
In this embodiment, the thermoplastic vulcanizate is NBR/PP, wherein the rubber-to-plastic ratio is 70/30, the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 15:100, the liquid medium used is water, the additive used is tamarind seed polysaccharide gum, and the nanomaterial used is nano praseodymium oxide, and the nanocomposite is prepared by the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 4.2g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 16: 1;
(2) adding an auxiliary agent to the continuously stirred solution obtained in the step (1) in batches or at one time at the speed of 0.1g/min to obtain a paste, wherein the thickness of the paste is 28mm, and the weight ratio of the auxiliary agent to the nano material is 20: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber 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 150 ℃ in a first area, 220 ℃ in a second area, 220 ℃ in a third area, 230 ℃ in a fourth area, 210 ℃ in a fifth area, and the linear speed of the rotating speed of the screw is 0.8 m/s.
The swelling index of the thermoplastic vulcanized rubber nanocomposite obtained by final extrusion granulation is 0.72, and the tear strength is 47 KN/m.
Example 2
In this embodiment, the thermoplastic vulcanizate is NBR/PP, wherein the rubber-to-plastic ratio is 20/80, the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 10:100, the adopted liquid medium is isobutanol and water, the mass ratio of the isobutanol and water is 1:9, the adopted auxiliaries are an aliphatic sulfonate and a sulfonaphthalene sulfonate, the weight ratio is 1:1, the adopted nanomaterial is nano zinc oxide, and the nanocomposite is prepared according to the following method:
(1) stirring the liquid, adding the nano material at the speed of 20g/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 18mm, 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 thermoplastic vulcanized rubber 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 50Hz, the rotating speed of a main feeding hopper is 15Hz, the extrusion temperature of a first zone is 180 ℃, a second zone is 250 ℃, a third zone is 235 ℃, a fourth zone is 240 ℃ and a fifth zone is 245 ℃; the linear speed of the screw speed was 1 m/s.
The swelling index of the thermoplastic vulcanized rubber nanocomposite obtained by final extrusion granulation is 0.76, and the tear strength is 45 KN/m.
Example 3
In the embodiment, the thermoplastic vulcanized rubber is NBR/PP, wherein the rubber-plastic ratio is 50/50, the mass ratio of the nano material to the thermoplastic vulcanized rubber is 0.1:100, the adopted liquid medium is water, the adopted auxiliary agent is sodium polystyrene sulfonate, the adopted nano material is nano titanium dioxide and nano aluminum oxide, and the mass ratio is 9:1, and the nano composite material is prepared according to the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 0.01g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 0.1: 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 79mm, and the weight ratio of the auxiliary agent to the nano material is 30: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber 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 45Hz, the rotating speed of a main feeding hopper is 25Hz, the extrusion temperature of a first zone is 180 ℃, a second zone is 260 ℃, a third zone is 240 ℃, a fourth zone is 250 ℃ and a fifth zone is 250 ℃; the linear speed of the screw speed was 0.9 m/s.
The swelling index of the thermoplastic vulcanized rubber nano composite material obtained by final extrusion granulation is 0.75, and the tear strength is 50 KN/m.
Example 4
In this embodiment, the thermoplastic vulcanizate is acrylic rubber/PP, wherein the rubber-plastic ratio is 70/30, the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 7:100, the adopted liquid medium is propanol, the adopted auxiliary agent is xanthan gum, the adopted nanomaterial is carbon nanofiber, the adopted antiaging agent is antioxidant 4010NA, and the nanocomposite is prepared according to 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 6: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 100g/min to obtain a paste, wherein the thickness of the paste is 58mm, 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 thermoplastic vulcanized rubber 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 resulting thermoplastic vulcanizate nanocomposite had a swelling index of 0.77 and a tear strength of 48 KN/m.
Example 5
In the embodiment, the thermoplastic vulcanized rubber is acrylic rubber/PP, wherein the rubber-plastic ratio is 80/20, the mass ratio of the nano material to the thermoplastic vulcanized rubber is 4:100, the adopted liquid medium is N, N-dimethylformamide and water, the mass ratio is 4:1, the adopted auxiliary agent is alkylphenol ethoxylate, the adopted nano material is nano neodymium oxide, and the nano composite material is prepared according to the following method:
(1) stirring the liquid medium, adding the nano material at the speed of 0.5g/min, continuously stirring and uniformly dispersing, wherein the weight ratio of the liquid medium to the nano material is 0.5: 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 0.1: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, carrying out melt blending and subsequent processing to obtain the nano composite material.
The resulting thermoplastic vulcanizate nanocomposite had a swelling index of 0.74 and a tear strength of 46 KN/m.
Example 6
In this embodiment, the thermoplastic vulcanizate is polyether rubber/ABS, wherein the rubber-to-plastic ratio is 70/30, the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 4:100, the liquid medium used is water, the adjuvant used is carrageenan, the nanomaterial used is nano silica, the antiaging agent used is Ultranox624, and the nanocomposite is prepared according to the following method:
(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 20: 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 59mm, and the weight ratio of the auxiliary agent to the nano material is 6: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber 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 in a first zone is 200 ℃, a second zone is 240 ℃, a third zone is 220 ℃, a fourth zone is 230 ℃ and a fifth zone is 210 ℃; the linear speed of the screw speed was 0.7 m/s.
The swelling index of the thermoplastic vulcanized rubber nanocomposite obtained by final extrusion granulation is 0.7, and the tear strength is 49 KN/m.
Example 7
In this embodiment, the thermoplastic vulcanizate is polyether rubber/ABS, wherein the rubber-to-plastic ratio is 50/50, the mass ratio of the nano material to the thermoplastic vulcanizate is 2:100, the adopted liquid medium is water and acetic acid, the mass ratio of the water and the acetic acid is 8:1, the adopted additive is polymaleic anhydride, the adopted nano material is nano hafnium oxide, and the nano composite material is prepared according to the following method:
(1) stirring a liquid medium, 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 20: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at a speed of 27g/min to obtain a paste, wherein the thickness of the paste is 82mm, and the weight ratio of the auxiliary agent to the nano material is 54: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber to obtain a premix;
(4) and (4) feeding the premix obtained in the step (3) into an open mill, carrying out melt blending and subsequent processing to obtain the nano composite material.
The resulting thermoplastic vulcanizate nanocomposite had a swelling index of 0.71 and a tear strength of 50 KN/m.
Example 8
In this embodiment, the thermoplastic vulcanizate is NBR/PP, wherein the rubber-to-plastic ratio is 80/20, the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 6:100, the liquid medium used is water, the assistant used is polyvinylpyrrolidone, the nanomaterial used is nano zinc oxide, and the nanocomposite is prepared according to the following method:
(1) stirring a liquid medium, adding a nano material at the speed of 0.5g/min, continuously stirring and uniformly dispersing, and applying ultrasonic waves with the frequency of 800-1000 Hz and the power of 200-1000W, wherein the weight ratio of the liquid medium to the nano material is 6: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 30g/min to obtain a paste, wherein the thickness of the paste is 56mm, and the weight ratio of the auxiliary agent to the nano material is 45: 1;
(3) mixing the paste obtained in the step (2) with thermoplastic vulcanized rubber 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 25Hz, the extrusion temperature in a first zone is 160 ℃, a second zone is 245 ℃, a third zone is 240 ℃, a fourth zone is 245 ℃ and a fifth zone is 235 ℃; the linear speed of the screw speed was 0.6 m/s.
The final extrusion granulation yielded a thermoplastic vulcanizate nanocomposite having a swelling index of 0.73 and a tear strength of 52 KN/m.
Example 9
In the embodiment, the thermoplastic vulcanized rubber is NBR/PP, wherein the rubber-plastic ratio is 70/30, the mass ratio of the nano material to the thermoplastic vulcanized rubber is 18:100, the adopted liquid medium is water, the adopted auxiliary agents are chitosan and benzalkonium bromide, the mass ratio of the chitosan to the benzalkonium bromide is 10:1, the adopted nano material is a carbon nano tube, 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 12g/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 60: 1;
(2) adding an auxiliary agent into the continuously stirred solution obtained in the step (1) at the speed of 12g/min to obtain a paste, wherein the thickness of the paste is 65mm, the weight ratio of the auxiliary agent to the nano material is 7.2:1, and further, mixing the paste with an acrylic emulsion;
(3) mixing the paste mixed with the acrylic emulsion obtained in the step (2) with thermoplastic vulcanized rubber 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 10Hz, the extrusion temperature in a first zone is 170 ℃, a second zone is 260 ℃, a third zone is 220 ℃, a fourth zone is 250 ℃ and a fifth zone is 210 ℃; the linear speed of the screw speed was 1 m/s.
The swelling index of the thermoplastic vulcanized rubber nanocomposite obtained by final extrusion granulation is 0.8, and the tear strength is 51 KN/m.
Comparative example 1
In this comparative example, the position where the liquid-containing nanomaterial was fed to the extruder was adjusted based on example 1, and the thermoplastic vulcanizate was fed under no pressure, and after the thermoplastic vulcanizate passed through the melting zone, the nanomaterial containing the liquid medium in the voids was mixed with the molten thermoplastic vulcanizate under pressure.
Comparative example 1 differs from the examples in that: the thermoplastic vulcanizate and the nanomaterial containing the liquid medium in the gaps are not simultaneously fed, but the thermoplastic vulcanizate is fed firstly and the nanomaterial with the liquid medium combined in the gaps is processed by pressurizing and feeding after the thermoplastic vulcanizate is melted.
The swelling index of the thermoplastic vulcanizate nanocomposite obtained by final extrusion granulation was 1.19 and the tear strength was 31 KN/m.
Mechanical property tests are carried out on examples 1-9 and comparative example 1, and the performance parameters of the swelling index and the tear strength are respectively obtained as shown in the following table:
as can be seen from the above table, the mechanical properties of the nanocomposite obtained in examples 1 to 9 are all higher than the performance parameters of comparative example 1, and especially the tear strength is significantly improved, but the reason for this is that the present invention uses the phase change of the liquid medium to expand the nanomaterial, so that the thermoplastic vulcanizate melted simultaneously with the nanomaterial enters into the gaps to be filled, the gap expansion uses the heat generated by the melting of the polymer to evaporate the liquid medium to generate implosion and open the gaps, and simultaneously uses the shearing force of the extrusion process to further strip the gaps, so that the thermoplastic vulcanizate in the molten state is filled, thereby improving the mechanical properties of the product.
Furthermore, the related workers think that the strength of the product is improved by the expanded nano material, and the microphase interface energy of the thermoplastic vulcanized rubber is also improved, so that the compatibility between two phases of the product is improved, the swelling index is reduced, and the solvent resistance of the 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 greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (14)
1. A thermoplastic vulcanizate nanocomposite, characterized in that,
the nano composite material is prepared by melt blending a premix formed by filling and adhering a nano material combined with a liquid medium between thermoplastic vulcanized rubber particles, wherein the thermoplastic vulcanized rubber comprises non-polar plastics and polar rubber; the nano material comprises one or more of a zero-dimensional nano material or a one-dimensional nano material, the liquid medium is injected into and fills gaps of the nano material to form a self-adhesive paste, and the thickness of the paste is 0-100 mm but not 0 mm;
the nano composite material is prepared by the following method:
(1) mixing and stirring a liquid medium, a nano material and an auxiliary agent to obtain a paste, and adding latex into the paste, wherein the mass ratio of the latex to the paste is 0.1-10: 1;
(2) mixing the mixture of the paste and the latex obtained in the step (1) with thermoplastic vulcanized rubber particles, and enabling the paste to be sufficiently adhered to the thermoplastic vulcanized rubber particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the liquid medium is water, and the weight ratio of the liquid medium to the nano material is 5-50: 1;
the step (1) also comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.2-1: 1.
2. The nanocomposite of claim 1, wherein the zero-dimensional nanomaterial and the one-dimensional nanomaterial comprises one or more of nano silicon oxide, nano titanium oxide, nano zirconium oxide, nano zinc oxide, nano aluminum oxide, nano nickel oxide, nano gold, nano silver, nano silicon, nano carbon, carbon nanofiber, carbon nanotube, nano graphite, nano boron powder, nano sulfur, nano lanthanum oxide, nano neodymium oxide, nano erbium oxide, nano cerium oxide, nano praseodymium oxide, nano yttrium oxide, nano europium oxide, nano tungsten oxide, nano silicon carbide, nano tellurium oxide, nano niobium oxide, nano hafnium oxide, or nano molybdenum oxide.
3. The composite material of claim 1, wherein the thermoplastic vulcanizate has a weight ratio of non-polar plastic to polar rubber of 20-80: 80-20; the non-polar plastic comprises one of polyethylene, polypropylene, polystyrene or ABS, and the polar rubber comprises one of chloroprene rubber, nitrile rubber, HNBR, XNBR, fluororubber, polyether rubber, polysulfide rubber or acrylic rubber.
4. The composite material of claim 3, wherein the weight ratio of the non-polar plastic to the polar rubber is 30-50: 70-50.
5. The composite material according to any one of claims 1 to 4, wherein the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 0.1 to 20: 100.
6. The composite material according to claim 5, wherein the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 1-10: 100.
7. The composite material of claim 6, wherein the mass ratio of the nanomaterial to the thermoplastic vulcanizate is 3-8: 100.
8. A method for preparing a thermoplastic vulcanizate nanocomposite as claimed in any of claims 1 to 7, comprising the steps of:
(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 thermoplastic vulcanized rubber particles, and enabling the paste to be sufficiently adhered to the thermoplastic vulcanized rubber particles to obtain a premix;
(3) carrying out melt blending on the premix in the step (2) to obtain a nano composite material;
the liquid medium is water, and the weight ratio of the liquid medium to the nano material is 5-50: 1;
the step (1) also comprises the step of adding an auxiliary agent into the nano material to improve the liquid content of the nano material, so that the liquid medium combined with the nano material accounts for 50-98% of the total mass of the paste; the mass ratio of the auxiliary agent to the nano material is 0.2-1: 1.
9. The method of claim 8, wherein in the step (3), the liquid medium is gasified 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 thermoplastic vulcanizate is reached, and the agglomerated nanomaterial is separated.
10. The preparation method according to claim 8, wherein the weight ratio of the liquid medium to the nanomaterial is 5-20: 1.
11. The method according to claim 8, wherein the auxiliary agent comprises one or more of a carboxylate surfactant, a sulfate surfactant, a sulfonate surfactant, a phosphate surfactant, an amine salt surfactant, a quaternary ammonium salt surfactant, a heterocyclic surfactant, a nonionic surfactant, a natural water-soluble polymer, a synthetic water-soluble polymer, and a prepolymer thereof.
12. The method according to claim 8, wherein the liquid medium combined with the nanomaterial accounts for 60-98% of the total mass of the paste.
13. The method according to claim 12, wherein the liquid medium combined with the nanomaterial accounts for 80-98% of the total mass of the paste.
14. The preparation method of claim 8, wherein the latex comprises one or more of styrene-acrylic emulsion, acrylate emulsion, acrylic emulsion, silicone-acrylic emulsion, aqueous polyurethane emulsion, fluorocarbon emulsion, rosin resin emulsion, terpineol, vinyl acetate-acrylic emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, natural latex, white latex, neoprene latex, pure acrylic latex, carboxylic styrene-butadiene latex and styrene-acrylic latex.
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