WO2004087794A1 - Compound powder, its preparation method and use - Google Patents
Compound powder, its preparation method and use Download PDFInfo
- Publication number
- WO2004087794A1 WO2004087794A1 PCT/CN2004/000309 CN2004000309W WO2004087794A1 WO 2004087794 A1 WO2004087794 A1 WO 2004087794A1 CN 2004000309 W CN2004000309 W CN 2004000309W WO 2004087794 A1 WO2004087794 A1 WO 2004087794A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber latex
- rubber
- particles
- inorganic particles
- composite powder
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31707—Next to natural rubber
Definitions
- the present invention relates to a powder, and more particularly, the present invention relates to a composite powder containing rubber particles and inorganic particles, and a preparation method and application thereof. Background technique
- Vulcanized powder rubber refers to discrete rubber powders with a gel content of more than 60%, which can flow freely without adding a release agent after drying.
- the preparation method of the fully vulcanized powder rubber uses rubber emulsion as a raw material, and the particle diameter of the rubber is fixed through irradiation crosslinking with or without a crosslinking assistant, and then the fully vulcanized powder rubber is obtained by a precipitation or spray drying method.
- the average particle size of the obtained fully vulcanized powder rubber particles is 20 to 2000 nm, which can be used as a toughening agent for plastics and has a good toughening effect.
- the powder rubber is used to toughen the plastic, the strength, modulus and thermal properties of the plastic are often reduced.
- inorganic particle modified plastics Since the 1980s, new concepts of inorganic particle modified plastics have appeared abroad. However, due to the large surface energy of the inorganic particles, the inorganic particles can easily agglomerate when blended with plastics without special treatment, which greatly reduces the modification effect on plastics.
- the current development of polyamide / clay nanocomposites using nanoclay materials to increase the rigidity of polyamides is very rapid (such as "Polymer-inorganic nanocomposites", published by the Chemical Industry Press in December 2002, nano Materials and Applied Technology Series).
- the clays used to prepare polyamide / clay nanocomposites are generally layered clays. This layered clay has a nano-scale lamellar structure, is a natural nano material, and is very suitable for preparing nano composite materials.
- the organic polymer cannot enter the layers of the clay platelet and peel off into a nano-sized dispersed phase. and so Before preparing this polymer clay nanocomposite, the clay must be specially treated, and the surface-treated clay should be replaced with various organisms to obtain nano-precursor materials containing organic functional groups for further nanocompositing.
- the process of preparing nano-precursor materials is also called clay organication.
- the organically treated clay is replaced with organic functional groups such as organic cations between layers to make it easier for polymer monomers or polymer macromolecules to be inserted (see Polymer-Inorganic Nanocomposites, pp. 21-22).
- Intercalation compounding of organicized clay can be used to disperse layered clay in the form of nanosheets in a polymer matrix to produce a polymer / clay nanocomposite.
- This nanocomposite has high strength, high modulus, and high heat. Deformation temperature and other characteristics.
- Organically treating montmorillonite can facilitate intercalation and compounding, but complicates the preparation process of the composite material. Summary of the invention
- the present inventors have conducted extensive and in-depth research in the field of plastic toughening, with a view to developing a toughening that can better maintain the strength, modulus and thermal properties of the plastic while toughening the plastic Agent.
- compounding powdered rubber with inorganic particles can obtain a composite powder containing organic elastic particles and inorganic rigid particles.
- the organic elastic particles in it help prevent the agglomeration of inorganic particles. Therefore, applying this composite powder to toughen plastic can obtain better toughness than when elastic particles and inorganic particles are used alone. Effect, at the same time, it can also reduce the adverse effects of the elastic particles on resin rigidity and heat resistance.
- the composite powder can be well applied to the preparation of thermoplastic elastomers.
- the object of the present invention is to provide a composite powder which can be used for toughening plastics and preparing thermoplastic elastomers.
- Another object of the present invention is to provide a method for preparing the composite powder.
- Another object of the present invention is to provide the application of the composite powder in the preparation of toughened plastics and thermoplastic elastomers.
- One aspect of the present invention provides a composite powder including powder rubber particles having a crosslinked structure and inorganic particles distributed between the powder rubber particles.
- Another aspect of the present invention provides a method for preparing the composite powder, comprising mixing a slurry of irradiated or non-irradiated rubber latex and inorganic particles in a ratio corresponding to a desired ratio of rubber particles to inorganic particles. Stir well, then dry it.
- Another aspect of the present invention provides a plastic toughened using the composite powder.
- Another aspect of the present invention provides a thermoplastic elastomer including the composite powder.
- Fig. 1 is a transmission electron microscope photomicrograph of a slice of the composition of Example 15.
- the large shaded parts in the picture are the aggregates of rubber particles and inorganic particles dispersed in the plastic matrix, and the dark dots in the shadows are the inorganic particles evenly distributed in the aggregates.
- Fig. 2 is a transmission electron microscope photomicrograph of a slice of the composition of Example 17.
- the large shaded parts in the picture are the aggregates of rubber particles and inorganic particles dispersed in the plastic matrix, and the dark spots in the shadows are the inorganic particles distributed in the agglomerates.
- Fig. 3 is a transmission electron microscope photograph of a section of the polyamide composition of Example 14.
- the round shaded part is styrene-butadiene rubber particles
- the bar-shaped shaded part is sodium-based montmorillonite. It clearly shows that the rubber particles and montmorillonite are both hooked.
- the montmorillonite sheet is on the polyamide matrix. Completely peeled off.
- the composite powder of the present invention includes powder rubber particles having a crosslinked structure and inorganic particles distributed between the powder rubber particles, wherein the weight ratio of the powder rubber particles to the inorganic particles is 99.5: 0.5-20: 80, preferably 99: 1- 50: 50.
- the inorganic particles that can be used can be various kinds of inorganic particles available in the prior art. As long as the size range is within the scope of the present invention, the effect required by the invention can be achieved, and it is not affected by itself. Restrictions on substance types, except for inorganic particles that are unstable in water.
- the shape of the individual particles of these inorganic particles varies, and may be spherical, ellipsoidal, plate-shaped, needle-shaped, or irregular. From a three-dimensional point of view, at least one dimension of the individual particles has an average size of 0.2 to 500 nm, preferably 0.5 to 100 nm.
- the inorganic particles may be selected from one or a combination of the following: a metal element or an alloy, such as gold, silver, copper, iron, or their respective alloys, etc .; a metal oxide, such as alumina (A1 2 0 3 ), magnesium oxide ( MgO), titanium dioxide (Ti0 2 ), iron oxide (Fe 2 0 3 ), iron oxide (Fe 3 0 4 ), silver oxide (Ag 2 0), zinc oxide (ZnO), etc .; metal or non-metal Nitrides, such as aluminum nitride (A1N), silicon nitride (SiN 4 ), etc .; non-metal carbides, such as silicon carbide (SiC), etc .; non-metal oxides, such as silicon dioxide (Si0 2 ), etc .; metal hydrogen.
- a metal element or an alloy such as gold, silver, copper, iron, or their respective alloys, etc .
- a metal oxide such as alumina (A1 2 0
- Oxides such as aluminum hydroxide ( ⁇ 1 ( ⁇ ) 3 ), rhenium hydroxide (Mg (OH) 2 ), etc .; metal salts, including metal carbonates, silicates, sulfates, etc., such as calcium carbonate (CaC0 3 ), barium sulfate (BaS0 4 ), calcium sulfate (CaS0 4 ), silver chloride (AgCl), etc .; ores, such as asbestos, talc, kaolin, mica, feldspar, wollastonite, montmorillonite, etc.
- the powdered rubber particles having a crosslinked structure contained in the composite powder of the present invention are rubber particles of a homogeneous structure, that is, the individual rubber particles are homogeneous in composition, and the inside of the particles is observed under the observation of existing micro-technology. No delamination or equal heterogeneity was found.
- Its gel content is 60% by weight or more, preferably 75% by weight or more; more preferably 80% by weight or more.
- the composite powder of the present invention can be prepared by the method for preparing a fully vulcanized powder rubber disclosed in the international patent application WO 01 / 40356A1 (the disclosure of which is incorporated herein by reference) filed by the applicant on September 18, 2000. It is to mix the latex after irradiation with the slurry of inorganic particles before drying.
- the composite powder may also adopt the Chinese patent application 00130386.4 (CN 1353131A, which is filed on November 3, 2000) It is prepared by the method for preparing crosslinked powder rubber disclosed herein, except that the crosslinked synthetic rubber latex is mixed with a slurry of inorganic particles before drying.
- the composite powder of the present invention may optionally further include a water-soluble plastic nucleating agent, and the nucleating agent is present in an amount such that the weight ratio of the rubber particles to the nucleating agent in the composite powder is
- the composite powder of the present invention includes an agglomerate composed of powdered rubber particles and inorganic particles.
- inorganic particles are uniformly distributed in or on the inner surface of the agglomerate, and the rubber content itself has a gel content of 60% by weight or more. It is preferably 75% by weight or more, and more preferably 80% by weight. /. Or higher.
- the composite powder may contain discrete inorganic particles in addition to aggregates composed of powdered rubber particles and inorganic particles. Especially when the content of the inorganic particles is high, the inorganic particles dispersed outside the aggregates tend to appear.
- This agglomerated state of the composite powder of the present invention can be maintained in a composition obtained after melt blending with a non-polar plastic (such as polypropylene, polyethylene).
- a non-polar plastic such as polypropylene, polyethylene.
- the composition was sliced and directly observed under a transmission electron microscope to obtain a photograph reflecting this aggregated state (see Fig. 1).
- the composite powder of the present invention is prepared by mixing a slurry of irradiated or non-irradiated rubber latex and inorganic particles at a ratio corresponding to a desired ratio of rubber particles to inorganic particles, mixing and stirring uniformly, and then drying.
- the composite powder of the present invention is prepared by the following method:
- the slurry of the inorganic particles and the irradiated rubber latex are mixed uniformly to obtain a mixed emulsion.
- the mixed emulsion is dried.
- the slurry of the inorganic particles that is, the suspension of the inorganic particles in water
- the inorganic particles do not have a commercial-grade slurry, they can also be made by themselves, that is, the inorganic particles are dispersed into a stable suspension with an appropriate amount of water by using a general dispersing device, and then mixed with a rubber emulsion.
- the inorganic particles used in the preparation method of the composite powder of the present invention may be various kinds of inorganic particles available in the prior art, as long as the size range is within the scope of the present invention, the effect required by the invention can be achieved, and is not subject to itself.
- the shape of individual particles of these inorganic particles varies, and can be spherical, ellipsoidal, flake, needle, or irregular. From a three-dimensional perspective, the average size of a single particle in at least one dimension is 0.2 to 500 nm, preferably 0.5 to 100 nm.
- the inorganic particles may be selected from one or a combination of the following: a metal element or an alloy, such as gold, silver, copper, iron, or their respective alloys, etc .; a metal oxide, such as alumina (A1 2 0 3 ), magnesium oxide ( MgO), titanium dioxide (Ti ⁇ 2 ), iron oxide (Fe 2 0 3 ), iron oxide
- metal or non-metal nitrides such as aluminum nitride (A1N), silicon nitride (SiN 4 ), etc .
- non-metal carbides Such as silicon carbide (SiC), etc .
- non-metal oxides such as silicon dioxide (Si0 2 ), etc .
- metal hydroxides such as aluminum hydroxide ( ⁇ 1 ( ⁇ ) 3 ), magnesium hydroxide (Mg (OH) 2 ), Etc .
- metal salts including metal carbonates, silicates, sulfates, etc., such as calcium carbonate (CaC0 3 ), barium sulfate (BaS0 4 ), calcium sulphate (CaS0 4 ), silver chloride (AgCl) Etc .
- ores such as asbestos, talc, kaolin, mica, feldspar, wollast
- the weight of the rubber contained in the rubber latex or the crosslinked rubber latex described in the method for preparing the composite powder of the present invention that is, the dry weight of the rubber latex or the solid content of the rubber latex
- the weight of the inorganic particles contained in the inorganic particle slurry (Dry weight of inorganic particle slurry)
- the mixed emulsion may further include an aqueous solution containing an inorganic particle slurry, a water-soluble plastic nucleating agent, and a irradiated rubber latex (in method b) or with Crosslinked rubber latex (in method a) is uniformly mixed and Got.
- the ratio of the dry weight of the irradiated rubber latex or crosslinked rubber latex to the weight of the nucleating agent in the nucleating agent aqueous solution is 99: 1-50: 50, preferably 97: 3-70: 30.
- the composite powder thus prepared can improve the toughness of the plastic and also promote the crystallization of the crystalline plastic, thereby further improving the rigidity of the plastic.
- the nucleating agent commonly used in the prior art can achieve the effect to be achieved by the invention.
- sodium benzoate Generally, sodium benzoate .
- an inorganic particle slurry and an optional aqueous solution of a water-soluble plastic nucleating agent can be added to the irradiated rubber latex or crosslinked synthetic rubber latex while stirring, and thoroughly stirred Make it mix well.
- concentration of the rubber latex and the concentration of the inorganic nanoparticle slurry and the nucleating agent aqueous solution are no special requirements for the concentration of the rubber latex and the concentration of the inorganic nanoparticle slurry and the nucleating agent aqueous solution.
- the drying method used in the drying process is the same as the international patent application WO 01 / 40356A1 and the international patent application WO 01/98395 filed by the applicant on June 15, 2001 (the priority application is June 2000)
- the drying method when preparing fully vulcanized powder rubber in Chinese Patent Application Publication CN 1383439A) filed on the 15th that is, the drying process can be performed with a spray dryer, and the inlet temperature can be controlled at 100 ⁇ 200. C, outlet temperature can be controlled at 20 ⁇ 80 ° C.
- the gel content of the rubber contained in the composite powder obtained by the above two methods is consistent with the gel content of the crosslinked synthetic rubber latex in method a, and the gel content of the rubber latex after irradiation in method b. .
- the inventors have found through experimental research that some synthetic rubber latexes undergo a certain crosslinking reaction between the rubber molecules during the synthesis process, so that the obtained rubber latex has a certain degree of crosslinking.
- crosslinked synthetic rubber latex or crosslinked synthetic rubber latex.
- the gum content should be 80% by weight or more, preferably 85% by weight or more.
- this type of crosslinked rubber latex due to its high degree of crosslinking, it can be dried without further irradiation and crosslinking. A rubber powder was obtained.
- crosslinked synthetic rubber latex is used as a latex raw material.
- the type of cross-linked synthetic rubber latex is selected from the group consisting of cross-linked styrene-butadiene rubber latex, cross-linked carboxyl styrene-butadiene rubber latex, cross-linked polybutadiene rubber latex, cross-linked nitrile rubber latex, and cross-linked carboxylic butadiene rubber latex.
- Latex such as natural rubber latex, styrene-butadiene rubber latex, carboxyl styrene-butadiene rubber latex, nitrile rubber latex, carboxyl-nitrile rubber latex, polybutadiene rubber latex, neoprene latex, silicone rubber latex, acrylic rubber latex , Styrene-butadiene rubber latex, isoprene rubber latex, butyl rubber latex, ethylene-propylene rubber latex, polysulfide rubber latex, acrylate-butadiene rubber latex, polyurethane rubber latex, and fluoro rubber latex.
- natural rubber latex such as natural rubber latex, styrene-butadiene rubber latex, carboxyl styrene-butadiene rubber latex, nitrile rubber latex, carboxyl-nitrile rubber latex, polybutadiene rubber latex, neoprene latex, silicone rubber late
- the rubber latex used in the composite powder preparation method b of the present invention actually includes the crosslinked synthetic rubber latex in the method a described above, that is, the crosslinked synthetic rubber latex can be used to prepare the compound of the present invention without irradiation.
- the powder (as described in method a) can also be irradiated to prepare the composite powder of the present invention (such as method b).
- the gel content of rubber in the composite powder obtained by the latter is higher than that of the former.
- the solid content (dry rubber content) of the rubber latex is not particularly limited, and is generally 20 to 70% by weight, preferably 30 to 60% by weight, and more preferably 40 to 50% by weight.
- the average particle diameter of the rubber particles in the rubber latex is
- the rubber particles After the rubber latex is irradiated, the rubber particles reach a higher gel content (60% by weight or higher), or for a cross-linked synthetic rubber latex, in which the particle size of the rubber particles is fixed due to the high gel content, Therefore, after the rubber latex is mixed and sprayed with the inorganic particle slurry, whether the rubber particles are agglomerated or free, the particle size of the individual rubber particles can still be consistent with the rubber particles in the original rubber latex, with an average particle size of 20-2000 nm. Preferably 30-1500 nm, more preferably 50-500 nm.
- the nano-components (including crosslinking auxiliary, irradiation dose, high-energy radiation source for irradiation, etc.) for irradiating the rubber latex are the same as those of International Patent Application WO 01 / 40356A1 and International Conditions used in the irradiation method for preparing a fully vulcanized powder rubber in patent application WO 01/98395.
- the rubber latex may be irradiated without using a cross-linking aid, or a cross-linking aid may be used.
- the crosslinking assistant used is selected from the group consisting of monofunctional crosslinking assistant, difunctional crosslinking assistant, trifunctional crosslinking assistant, tetrafunctional crosslinking assistant or polyfunctional crosslinking assistant, and any combination thereof.
- the monofunctional crosslinking assistant include (but are not limited to): octyl (meth) acrylate, isooctyl (meth) acrylate, glycidyl (meth) acrylate;
- co-agents include (but are not limited to): 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (fluorenyl) ) Acrylate, triethylene glycol di (fluorenyl) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene;
- examples of the trifunctional crosslinking assistant include (but
- (fluorenyl) acrylate refers to acrylate or methacrylate.
- crosslinking auxiliaries can be used in any combination as long as they contribute to dredging under irradiation.
- the variation is generally 0.1-10% by weight of the dry rubber weight in the latex, preferably 0.5-9% by weight, and more preferably 0.7-7% by weight.
- the method for preparing the composite powder b of the present invention is selected from a cobalt source, an ultraviolet ray source, or a high-energy electron accelerator, and a cobalt source is preferred.
- Irradiated dose can be 0.1 ⁇ 30
- Mr ad preferably 0.5 ⁇ 20 Mrad.
- the radiation dose depends on the type and formulation of the rubber latex. In general, the radiation dose should be such that the gel content of the rubber latex after irradiation vulcanization It reaches 60% by weight or more, preferably 75% by weight or more, and more preferably 80% by weight or more.
- the composite powder of the present invention prepared by the co-spraying method of the rubber latex and the inorganic particle slurry described above includes agglomerates composed of rubber particles and inorganic particles, and inorganic particles are uniformly distributed on the inside or the inner surface of the agglomerates.
- the rubber strand particles themselves have a gel content of 60% by weight or more, preferably 75% by weight or more, and more preferably 80% by weight or more.
- the composite powder may contain discrete inorganic particles in addition to aggregates composed of rubber particles and inorganic particles. Especially when the content of inorganic particles is high, inorganic particles dispersed outside the agglomerates tend to appear.
- This agglomerated state of the composite powder of the present invention can be maintained in a composition obtained after melt blending with a non-polar plastic (such as polypropylene, polyethylene).
- a non-polar plastic such as polypropylene, polyethylene.
- the composition was sliced and directly observed under a transmission electron microscope to obtain a photograph reflecting this aggregated state (see Fig. 1).
- the composite powder of the present invention is processed through ordinary blending:
- a plastic matrix the rubber strand particles therein help the inorganic particles to be uniformly dispersed in the matrix, and are not easy to agglomerate in large quantities.
- a non-polar resin polypropylene, polyethylene
- inorganic particles are evenly distributed in the agglomerate composed of rubber particles and rubber particles, which brings a good modification effect.
- the rubber particles in the composite powder of the present invention can achieve single particle dispersion in the resin matrix after melt blending. The particles are uniformly dispersed among the rubber particles, so the ideal dispersion of the rubber particles in the resin can help the dispersion of the inorganic particles.
- the composite powder method can be used to make montmorillonite in a polar resin matrix such as nylon without the need for complicated organic treatments with the help of rubber particles.
- the state of peeling ⁇ : is reached (as shown in Fig. 2).
- the method for preparing the composite powder of the invention is simple, convenient and easy to apply. Applying this composite powder to toughening plastics can obtain a better toughening effect than when using pure rubber elastic particles, and at the same time, it can also reduce the adverse impact of resin particles on rigidity and heat resistance due to the bow of the elastic particles.
- the composite powder of the present invention can also be used for preparing thermoplastics. Elastomer.
- the composite powder of the present invention is extremely easy to be incorporated into a plastic matrix, so it can be mixed with various plastics to make various toughened plastics and thermoplastic elastomers.
- the basic preparation method is to mix the composite powder and plastic of the present invention in a certain proportion in a conventional mixing equipment and under conventional process conditions, and if necessary, add a proper amount of a conventional processing aid and a compatibilizer.
- the weight ratio of the composite powder to plastic of the present invention is
- Toughened plastic can be nylon, polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene ether (PPO), polyether (PPS), polyacryl Imine, polysulfone, epoxy resin, unsaturated polyester, phenolic resin, amino resin, alkyd resin, diallyl phthalate, silicone resin and copolymers and blends thereof.
- the weight ratio of the composite powder to plastic of the present invention is
- plastics are nylon, polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene ether (PPO), polyphenylene sulfide (PPS), polyimide Amines, polysulfones and their copolymers and blends.
- Example 1 The lower section was then stained with Os0 4 and observed with a transmission electron microscope.
- Example 1 The lower section was then stained with Os0 4 and observed with a transmission electron microscope.
- the carbonic acid slurry fine chemical plant of Beijing University of Chemical Technology, solid content 47.3%, the average size of the particles in one dimension of 40 ⁇ 60nm
- the latex after irradiation are mixed at a ratio of 50: 50 of their dry weight, and stirred for 1 hour
- the mixed liquid is spray-dried by a spray dryer.
- the inlet temperature of the spray dryer is 140 ° C-160 ° C
- the outlet temperature is 40 ° C-60 ° C.
- the dried ⁇ is collected in a cyclone separator.
- 500g of calcium carbonate powder (fine chemical plant of Beijing University of Chemical Technology, the average size of particles in one dimension is 40 ⁇ 60nm) is mixed with 1 kg of water in a container, and then the mixture is made into a suspension with a high shear ⁇ : emulsifier ,
- the prepared suspension and the carboxylated styrene-butadiene emulsion after irradiation (same as in Example 1) were mixed at a dry weight ratio of 50:50, and stirred for 1 hour, and then the mixture was spray-dried by a spray dryer, sprayed
- the inlet temperature of the dryer is 140 ° C. C-160 ° C
- outlet temperature is 40 ° C-60, collect the dried carboxylated styrene-butadiene rubber ⁇ carbonate hook compound powder 2 in a cyclone separator.
- 50Gy / min ChargeThe gel content of the rubber particles in the latex after irradiation is 90.0%.
- the latex and calcium carbonate slurry (same as in Example 1) after irradiation are mixed at a ratio of 90: 10 of their dry weight, and stirred for 1 hour, then Spray-dry the mixture with a spray dryer
- the inlet temperature is 140 ° C-160 ° C and the outlet temperature is 40 ° C-60 ° C.
- the dried styrene-butadiene oak calcium carbonate composite powder 1 is collected in a cyclone.
- a commercially available styrene-butadiene latex (same as Example 3) with a solid content of 45% by weight was directly mixed with a calcium carbonate slurry (same as Example 1) at a ratio of 80:20 of each dry weight, stirred for 1 hour, and then the mixed solution Spray dry with a spray dryer.
- the inlet temperature of the spray dryer is 140 ° C-160 ° C, and the outlet temperature is 40 ° C-60 ° C.
- the dried styrene-butadiene oak calcium carbonate composite powder is collected in a cyclone. 2.
- styrene-butadiene latex (same as Example 3) with a solid content of 45% by weight was directly mixed with a calcium carbonate slurry (same as Example 1) and an aqueous solution of sodium benzoate (Wuhan Organic Industry Co., Ltd.) at a dry weight of 80: 20 : 10 ratio mixing, stirring for 1 hour, and then spraying the mixture through a spray dryer, the inlet temperature of the spray dryer is 140 ° C-160 ° C, the outlet temperature is 40 ° C-60'C, in a cyclone The dried nucleating agent-containing lower benzene-like / calcium carbonate composite powder was collected in the separator.
- Sodium-based montmorillonite (produced by Qinghe Chemical Plant in Zhangjiakou, Hebei, the particles can be dispersed into flakes with a thickness of 1 to 20 nm and a length of 200 to 100 nm) are mixed with water at a concentration of 5% by weight, dispersed by a high-shear disperser and left to stand After the above, the dispersion was again dispersed by a high-shear disperser to obtain a stable fully peeled suspension between the layers.
- the irradiated styrene-butadiene latex (same as Example 3) and the prepared sodium-based montmorillonite slurry were mixed at a ratio of 90:10 of each dry weight, stirred for 1 hour, and then the mixture was spray-dried by a spray dryer.
- the inlet temperature of the spray dryer is 140.
- C-160 ° C, outlet temperature is ⁇ ⁇ ⁇ ⁇ , collect the dried styrene-butadiene-montmorillonite composite powder 1 in a cyclone separator.
- styrene-butadiene latex and sodium-based montmorillonite slurry were mixed at a respective dry weight of 99: 1, the rest were the same as in Example 6, and styrene-butadiene rubber was obtained after spray drying ⁇ / Montmorillonite composite powder 2.
- Silica powder (Shenyang Chemical Co., Ltd., whose average particle size in one dimension is 7 to 30 nm) is mixed with water at a concentration of 5% by weight, and a high-shear disperser is used to obtain a stable suspension.
- carboxybutyronitrile latex (Xanl production, XNBRL, solid content 45%, average particle size of rubber particles in the latex is 50nm) and place it in a container.
- the gel content of the rubber particles in the latex after irradiation was 96.1%.
- the irradiated emulsion and the prepared silica slurry were mixed at a ratio of 90:10 of each dry weight, stirred for 1 hour, and then the mixture was spray-dried by a spray dryer, and the inlet temperature of the spray dryer was 140 ° C-16 (TC, outlet temperature is 40'C-60'C, collect the dried carboxyl nitrile rubber / silica composite powder in a cyclone.
- Example 8 Except that the silica slurry used in Example 8 was changed to calcium carbonate slurry (the same as in Example 1), the rest were the same as in Example 8. After spray drying, a carboxybutyronitrile rubber calcium carbonate composite powder was obtained.
- Titanium dioxide powder (Beijing University of Chemical Technology, whose average particle size in one dimension is 40-60 nm) is mixed with water at a concentration of 20% by weight, and dispersed by a high-shear disperser to obtain a stable suspension.
- the irradiated styrene-butadiene emulsion (same as Example 3) was mixed with the prepared titanium dioxide slurry at a ratio of 95: 5 of each dry weight, and stirred for 1 hour, and then the mixture was spray-dried by a spray dryer, and a spray dryer
- the inlet temperature is 140 ° C-160 ° C
- the outlet temperature is 40 ° C-60 ° C.
- the dried styrene-butadiene rubber / titanium dioxide composite powder is collected in a cyclone.
- the average size of magnesium hydroxide powder (Beijing University of Chemical Technology) 20 ⁇ 40nm) mixed with water at a concentration of 20% by weight, and dispersed by a high-shear disperser to obtain a stable suspension.
- nitrile latex blue rubber latex development center, brand: butyronitrile 26, solid content 45%, average particle diameter of rubber particles in the latex
- 100Kg put in a container, and add trihydroxymethylpropane dropwise with stirring. After 112.5 g of triacrylate was added, stirring was continued for one hour.
- the irradiated latex and the sodium-based montmorillonite slurry (same as Example 6) were mixed at a 95: 5 ratio of their respective dry weights, stirred for 1 hour, and then the mixture was spray-dried by a spray dryer, and the inlet temperature of the spray dryer It is 140 "0-160 ° 0 and outlet temperature is 40" C -60 ° C.
- the dried styrene-butadiene rubber / montmorillonite composite powder is collected in a cyclone.
- Metal 1 powder (Shandong Zhengyuan Nano Materials Engineering Co., Ltd., average size
- 20 ⁇ 80nm) 50g is mixed with 1kg of water in a container, and then the mixture is made into a suspension with a high-shear dispersing emulsifier. Each dry weight is mixed at a ratio of 1:99, stirred for 1 hour, and then the mixture is spray-dried by a spray dryer.
- the inlet temperature of the spray dryer is 140 -160 ° C.
- the outlet temperature is 40 ° C-60 ° C, and the dried styrene-butadiene rubber-metal silver composite powder is collected in a cyclone separator.
- the styrene-butadiene rubber / montmorillonite composite powder prepared in Example 12 was mixed with nylon 6 (produced by Ube, Japan, brand: 1013B) and antioxidant 1010 (produced by Ciba Gage, Switzerland) according to the following composition. Ingredients: 100 parts by weight of nylon, 15 parts by weight of styrene-butadiene-montmorillonite composite powder, and 0.3 parts by weight of an antioxidant.
- the ZSK-25 twin-screw extruder of German WP company was used for blending and pelletizing. The temperatures of each section of the extruder were: 220 235 ° C> 235. C, 235 ° C, 235 ° C and 235 ° C (head temperature). The pellets were made into standard splines by injection molding and tested for various mechanical properties. The results are shown in Table 1. Figure 3 is a photomicrograph of the section.
- Example 14 The nylon pellets and styrene-butadiene rubber powder in Example 14 (the styrene-butadiene rubber latex after irradiation in Example 12 was not mixed with the montmorillonite slurry and directly spray-dried) and the antioxidant 1010 were as follows The composition is mixed: 100 parts by weight of nylon, 15 parts by weight of styrene-butadiene rubber powder, and 0.3 parts by weight of an antioxidant. Standard splines are prepared through the same extrusion and injection process conditions as in Example 14, and various mechanics are performed. Performance test and mechanical test results are listed in Table 1.
- Example 14 After mixing the nylon pellets and antioxidants in Example 14, the standard splines were made under the same extrusion and injection molding process conditions as in Example 14, and various mechanical properties were tested. The results of the mechanical tests are shown in Table 1. .
- Example 5 Lioyang Petrochemical Branch, brand: B-200, melt index 0.35g / 10min
- antioxidant 1010 (Produced by Ciba Gaki, Switzerland) with the following composition: Polypropylene 100 parts by weight of ene, 10 parts by weight of composite powder, and 0.25 parts by weight of antioxidant 1010 based on 100 parts by weight of polypropylene and composite powder rubber, mixed in a high-speed stirrer for one minute, using German WP company ZSK-25 twin-screw extruder for blending and pelletizing, the temperature of each section of the extruder is 165 ° C, 190 ° C, 195 ° C, 195 ° C, 195 ° C, 195 ° C (head temperature) .
- the pellets were made into standard splines by the injection method, and the properties of the composite powder toughened polypropylene
- Example 15 The polypropylene powder (Luoyang Petrochemical Branch, brand: B-200, melt index 0.35g / 10min) and the antioxidant 1010 (produced by Ciba Gage, Switzerland) in Example 15 were mixed at a weight ratio of 100: 0.25. After that, the sample was extruded and injection molded into a standard spline, and various mechanical properties were tested. The results are shown in Table 1.
- styrene-butadiene-sodium benzoate powder rubber (take 1 kg of the styrene-butadiene emulsion of Example 3, add 45 g of sodium benzoate, and continue stirring for one hour.
- the mixed emulsion is spray-dried by a spray dryer.
- the inlet temperature of the spray dryer is 125 ° C ⁇ 145 ° C, outlet temperature is 45 V ⁇ 60 C.
- the weight ratio of styrene-butadiene rubber and sodium benzoate in this powder is 100.
- Example 15 10) Instead of the styrene-butadiene-carbonate composite powder containing a nucleating agent, the remaining conditions are the same as those in Example 15.
- the pellets obtained by melt blending were made into standard splines by injection method, and various mechanical properties were tested. The results are shown in Table 1. (Stretching strong cantilever miscellaneous mouth cantilever county mouth bend female thermal deformation punching 3 ⁇ 4GPa)
- Example 14 60.8 25 116 90.1 85.7 2.01 692
- Example 1 562 40 107 615 79 ⁇ 8 1.83 665
- Example 2 82.4 3 ⁇ 4 ⁇ 16 34.4 29.8 111 2.41 67.4
- Example 15 34.6 120 221 315 36.0 157 116.4
- Male example 4 33.9 119 186 35.9 1.53 116.0
- Polypropylene (a homopolypropylene powder produced by Daqing Huake Co., Ltd. with a melt index of 0.4 g / 10min) and the styrene-butadiene rubber ⁇ calcium carbonate composite powder 2 prepared in Example 4 were used at a high speed of 50/50 by weight Mix evenly in the mixer. Extrude and pelletize with ZSK-25 twin-screw extruder from WP Germany. The temperature of each section of the extruder is: 170 ° C, 190 ° C, 200 ° C, 210 ° C, 220 ° C and 210 ° C (head temperature). The pellets were made into standard splines by injection molding, and various performance tests were performed. The results of the measured fully vulcanized thermoplastic elastomers are listed in Table 2.
- the styrene-butadiene rubber carbonic acid hook composite powder 2 was replaced with styrene-butadiene powder rubber (the styrene-butadiene rubber latex after irradiation in Example 3 was obtained by directly spray-drying without mixing calcium carbonate slurry), and the same as in Example 16.
- the pellets were made into standard splines by injection molding, and various performance tests were performed. The results of the fully vulcanized thermoplastic elastomers are shown in Table 2.
- Premix 1 Homemade method:
- the premix 1 was changed to the premix 2 (home-made), and the rest were the same as in Example 17. Test various performances. The test results are shown in Table 3.
- the carboxylated nitrile rubber emulsion after irradiation in the same carboxylated nitrile rubber emulsion as in Example 8 was added with 5% by weight of the dry weight of the carboxylated nitrile rubber emulsion, and a crosslinking assistant trimethylolpropane triacrylic acid was added. After esterification, it was vulcanized by irradiation, the irradiation dose was 1 Mrad), and carboxybutyronitrile powder rubber was obtained by spray drying, and the inlet temperature of the spray dryer was 140 ° C. C-160 ° C, outlet temperature is 40 ° C-60 ° C.
- the nitrile powder rubber had a gel content of 90.0% and an average particle diameter of 90 nm. 20 parts of this powder rubber was mixed with 100 parts of an epoxy resin prepolymer (same as Example 17), and three times were ground with a three-roll mill to prepare a premix 2. Comparative Example 8
- Nano-scale carbonic acid 5 (fine chemical plant of Beijing University of Chemical Technology, average particle size in one dimension of 40 ⁇ 60mn) 40 parts were mixed with 100 parts of epoxy resin prepolymer (same as in Example 17), and three parts were ground with a three-roll mill Pass to make premix 3. Comparative Example 9
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES04725660.7T ES2576577T3 (es) | 2003-04-03 | 2004-04-05 | Polvo de material compuesto, su método de preparación y uso |
JP2006504208A JP4989216B2 (ja) | 2003-04-03 | 2004-04-05 | 複合体粉末、その製造および使用 |
EP04725660.7A EP1621571B1 (en) | 2003-04-03 | 2004-04-05 | Compound powder, its preparation method and use |
CNB2004800091166A CN100558796C (zh) | 2003-04-03 | 2004-04-05 | 复合粉末及其制备方法和用途 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN03109108.3 | 2003-04-03 | ||
CNB031091083A CN1239587C (zh) | 2003-04-03 | 2003-04-03 | 一种复合粉末及其制备方法和用途 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004087794A1 true WO2004087794A1 (en) | 2004-10-14 |
Family
ID=33102893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2004/000309 WO2004087794A1 (en) | 2003-04-03 | 2004-04-05 | Compound powder, its preparation method and use |
Country Status (6)
Country | Link |
---|---|
US (2) | US8362128B2 (zh) |
EP (1) | EP1621571B1 (zh) |
JP (1) | JP4989216B2 (zh) |
CN (2) | CN1239587C (zh) |
ES (1) | ES2576577T3 (zh) |
WO (1) | WO2004087794A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100417681C (zh) * | 2004-10-27 | 2008-09-10 | 中国石油化工股份有限公司 | 一种高强度全硫化聚烯烃热塑性弹性体及其制备方法 |
Families Citing this family (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE602004030248D1 (de) * | 2003-07-30 | 2011-01-05 | Polyone Corp | Nukleiertes thermoplastisches elastomer enthaltende zusammensetzung und zugehörige verfahren |
US7566437B2 (en) * | 2006-03-31 | 2009-07-28 | Umicore Ag & Co. Kg | Process for manufacture of silver-based composite powders for electrical contact materials and composite powders so produced |
EP2049592B1 (en) * | 2006-07-27 | 2011-10-19 | Dow Global Technologies LLC | Shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
DE102006041308A1 (de) * | 2006-09-01 | 2008-03-20 | Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh | Verfahren zum Einbringen von Hartstoffen in eine Reifenlauffläche |
DE102007019942A1 (de) * | 2007-04-27 | 2008-11-06 | Continental Aktiengesellschaft | Kautschukmischung mit verbesserter Rückprallelastizität |
CN101772546B (zh) * | 2007-08-02 | 2012-05-23 | 陶氏环球技术公司 | 用来增强热固性聚合物性能的两亲性嵌段共聚物和无机纳米填料 |
EP2195160A1 (en) * | 2007-10-02 | 2010-06-16 | Dow Global Technologies Inc. | Multilayer coextruded shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
EP2229416B1 (en) * | 2008-01-08 | 2018-04-04 | Dow Global Technologies LLC | High tg epoxy systems for composite application |
KR100891297B1 (ko) | 2008-01-15 | 2009-04-06 | 한국신발피혁연구소 | 플라스틱 사출 성형이 가능한 속가교형 고무 조성물 및 그제조 방법 |
CN102027067B (zh) * | 2008-02-08 | 2014-03-26 | 埃姆斯专利股份公司 | 耐水解性聚酰胺弹性体混合物、由该混合物生产的成型件及该混合物的用途 |
JP4518195B2 (ja) * | 2008-06-10 | 2010-08-04 | 横浜ゴム株式会社 | 天然ゴムマスターバッチの製造方法 |
US20230045778A9 (en) * | 2008-07-30 | 2023-02-09 | Brilliant Light Power, Inc. | Heterogeneous hydrogen-catalyst solid fuel reaction mixture and reactor |
EP2315795B1 (en) * | 2008-08-18 | 2012-09-19 | Dow Global Technologies LLC | Process for forming and devolatilizing brominated polybutadiene polymer particles |
CN101724187B (zh) * | 2008-10-31 | 2011-08-31 | 中国石油化工股份有限公司 | 一种橡胶组合物及其制备方法 |
DE102009006936A1 (de) * | 2009-01-30 | 2010-08-05 | Tesa Se | Trennmittel insbesondere für ein Klebeband |
US8129015B2 (en) * | 2009-05-14 | 2012-03-06 | International Automotive Components North America, Inc. | Modified moldable urethane with tunable haptics |
CN102050973B (zh) * | 2009-10-30 | 2012-11-21 | 中国石油化工股份有限公司 | 一种轮胎胎面胶复合材料及其制备方法 |
JP5434610B2 (ja) * | 2010-01-12 | 2014-03-05 | 富士ゼロックス株式会社 | 静電荷像現像用トナー、静電荷像現像剤、トナーカートリッジ、プロセスカートリッジ、画像形成方法及び画像形成装置 |
CN102268174B (zh) * | 2010-06-04 | 2016-08-17 | 中国石油化工股份有限公司 | 一种高耐热性高韧性环氧树脂组合物及其制备方法 |
CN102321281A (zh) * | 2011-08-09 | 2012-01-18 | 上海华明高技术(集团)有限公司 | 碳酸钙与有机弹性体组合物及其制备方法 |
CN103035864B (zh) * | 2011-09-30 | 2017-06-06 | 天津东皋膜技术有限公司 | 具有压缩弹性热关断耐高温的涂层隔膜 |
DE102011054628A1 (de) * | 2011-10-20 | 2013-04-25 | Minervius Gmbh | Verfahren zur Herstellung von Nanokompositen aus anorganischen Nanopartikeln und Polymeren |
SG11201401845PA (en) * | 2011-10-26 | 2014-09-26 | China Petroleum & Chemical | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof |
TWI546343B (zh) * | 2011-10-26 | 2016-08-21 | China Petro Chemical Technology Dev Company Ltd | A rubber composition and its preparation method and vulcanized rubber thereof |
JP6199889B2 (ja) | 2011-12-20 | 2017-09-20 | ダウ グローバル テクノロジーズ エルエルシー | エポキシ樹脂複合材料 |
US9594999B2 (en) | 2012-04-03 | 2017-03-14 | X-Card Holdings, Llc | Information carrying card comprising crosslinked polymer composition, and method of making the same |
US9122968B2 (en) | 2012-04-03 | 2015-09-01 | X-Card Holdings, Llc | Information carrying card comprising a cross-linked polymer composition, and method of making the same |
CN102690468B (zh) * | 2012-05-23 | 2013-08-21 | 航天科工武汉磁电有限责任公司 | 薄型射频噪声抑制材料及其制备方法 |
CN102827408B (zh) * | 2012-07-05 | 2014-05-28 | 安徽邦尼新材料有限公司 | 一种聚烯烃增强增韧母料及其生产方法 |
EP2973236B1 (en) | 2013-03-15 | 2019-01-09 | X-Card Holdings, LLC | Methods of making a core layer for an information carrying card, and resulting products |
EP3882923A3 (en) | 2014-05-29 | 2022-06-22 | Brilliant Light Power, Inc. | Electrical power generation systems and methods regarding same |
CN104761733A (zh) * | 2015-03-29 | 2015-07-08 | 安徽同丰橡塑工业有限公司 | 一种粘结型粉末氯丁橡胶的制备方法 |
EP3371252A1 (de) * | 2015-11-06 | 2018-09-12 | ARLANXEO Deutschland GmbH | Nanokomposits enthaltend ein schichtsilikat und einen kautschuk |
TWI729144B (zh) | 2016-05-30 | 2021-06-01 | 美商明亮光源能源公司 | 熱光伏打電力產生器、其網路及用於彼等之方法 |
CN108017744B (zh) * | 2016-11-03 | 2021-07-30 | 中国石油化工股份有限公司 | 一种粉末羧基丁苯橡胶及其制备方法和应用 |
CN106633883A (zh) * | 2016-12-13 | 2017-05-10 | 安庆市吉美装饰材料有限责任公司 | 一种具有防静电功能的保温板 |
CN107043534A (zh) * | 2017-04-07 | 2017-08-15 | 北京隆轩橡塑有限公司 | 一种高强增韧的聚酰胺66复合材料及其制备方法 |
CN107556621A (zh) * | 2017-10-13 | 2018-01-09 | 铜陵市永创变压器电子有限公司 | 一种纳米氧化铝‑丁苯橡胶‑微孔聚丙烯复合减震垫材料的制备方法 |
EP3762871A4 (en) | 2018-03-07 | 2021-11-10 | X-Card Holdings, LLC | METAL CARD |
CN109705569B (zh) * | 2018-12-13 | 2021-02-19 | 中广核俊尔新材料有限公司 | 一种低线性膨胀系数的导电聚苯醚/聚酰胺合金及其制备方法 |
MY198073A (en) * | 2019-11-07 | 2023-07-31 | Kossan Sdn Bhd | Polymeric/inorganic composite particle formulation and methods of producing rubber articles using said formulation |
CN111849048B (zh) * | 2020-07-23 | 2022-04-12 | 陕西师范大学 | 一种金属粉-橡胶颗粒复合的声子材料、制备方法及应用 |
CN113024849A (zh) * | 2021-03-05 | 2021-06-25 | 江苏麒祥高新材料有限公司 | 一种粉末状改性胶及其制备方法 |
CN113185915A (zh) * | 2021-05-28 | 2021-07-30 | 北京化工大学 | 一种耐高温有机硅树脂涂料的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4912151A (en) * | 1988-03-23 | 1990-03-27 | Huels Aktiengesellschaft | Method of manufacturing pourable pulverulent rubber-filler mixtures starting with rubber solutions |
CN1174210A (zh) * | 1997-05-24 | 1998-02-25 | 中国石油化工总公司 | 超细碳酸钙填充粉末丁苯橡胶的制备方法 |
CN1304425A (zh) * | 1998-04-07 | 2001-07-18 | 粉末橡胶联合股份有限公司 | 粉状填料橡胶粉、应用及其制备方法 |
CN1353131A (zh) * | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | 一种交联型粉末橡胶及其制备方法和用途 |
CN1383439A (zh) * | 2000-06-15 | 2002-12-04 | 中国石油化工股份有限公司 | 全硫化粉末硅橡胶及其制备方法和用途 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL264042A (zh) * | 1960-04-26 | |||
JPS5968333A (ja) * | 1982-10-12 | 1984-04-18 | Toray Silicone Co Ltd | 線状オルガノポリシロキサンブロツクを含有するポリマもしくはポリマ組成物の球状硬化物およびその製造方法 |
US5166227A (en) * | 1989-08-17 | 1992-11-24 | Zeon Chemicals Usa, Inc. | Free flowing particles of an emulsion polymer having SiO2 incorporated therein |
US5017630A (en) * | 1989-08-17 | 1991-05-21 | Zeon Chemicals Usa, Inc. | Free flowing particles of an emulsion polymer having SiO2 incorporated therein |
JP2844886B2 (ja) * | 1989-09-05 | 1999-01-13 | 東亞合成株式会社 | 重合体粉末 |
JPH06192483A (ja) * | 1992-12-24 | 1994-07-12 | Denki Kagaku Kogyo Kk | アクリル系粉末ゴム組成物及びその製造方法 |
US6365663B2 (en) * | 1996-04-01 | 2002-04-02 | Cabot Corporation | Elastomer composite blends and methods-II |
US6525139B2 (en) * | 1996-12-24 | 2003-02-25 | Bridgestone Sport Co., Ltd. | Golf ball |
DE19924366A1 (de) * | 1999-05-27 | 2000-11-30 | Pku Pulverkautschuk Union Gmbh | Kautschukpulver, die hohe Mengen an Füllstoffen enthalten, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP2003515644A (ja) | 1999-12-03 | 2003-05-07 | チュンクオ シュユウ ファコン ジトゥアン コンス | 制御可能な粒度を有する全硫化粉末ゴム,その調製方法及び用途 |
EP1111001B1 (en) * | 1999-12-23 | 2006-06-14 | Rohm And Haas Company | Plastics additives composition, process and blends thereof |
DE10016280A1 (de) * | 2000-04-03 | 2001-10-04 | Basf Ag | Schlagzähe thermoplastische Formmassen aus syndiotaktischem Polystyrol, Glasfasern und Acrylat-Schlagzähmodifier |
JP5443661B2 (ja) * | 2000-08-22 | 2014-03-19 | 中国石油化工股▲分▼有限公司 | 強化されたプラスチック及びその調製 |
ATE325155T1 (de) * | 2001-03-02 | 2006-06-15 | Southern Clay Prod Inc | Herstellung von polymernanoverbundmaterialien durch dispersiondestabilisierung |
EP1245598A3 (en) * | 2001-03-28 | 2003-07-16 | Techno Polymer Co., Ltd. | Rubber-reinforced thermoplastic resin and rubber-reinforced thermoplastic resin composition |
JP2004530785A (ja) * | 2001-06-29 | 2004-10-07 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | ナノスケール充填剤立体障害性とアミン系光安定剤との相乗的組み合わせ |
JP2003111871A (ja) * | 2001-10-09 | 2003-04-15 | Sumitomo Rubber Ind Ltd | ゴルフボールおよびその製造方法 |
US7101922B2 (en) * | 2001-12-18 | 2006-09-05 | The Goodyear Tire & Rubber Company | Method for preparing elastomer/silica composite |
US7041741B2 (en) * | 2004-01-08 | 2006-05-09 | Teknor Apex Company | Toughened polymer compositions |
-
2003
- 2003-04-03 CN CNB031091083A patent/CN1239587C/zh not_active Expired - Lifetime
-
2004
- 2004-04-05 US US10/818,950 patent/US8362128B2/en active Active
- 2004-04-05 EP EP04725660.7A patent/EP1621571B1/en not_active Expired - Lifetime
- 2004-04-05 WO PCT/CN2004/000309 patent/WO2004087794A1/zh active Application Filing
- 2004-04-05 CN CNB2004800091166A patent/CN100558796C/zh not_active Expired - Lifetime
- 2004-04-05 JP JP2006504208A patent/JP4989216B2/ja not_active Expired - Lifetime
- 2004-04-05 ES ES04725660.7T patent/ES2576577T3/es not_active Expired - Lifetime
-
2012
- 2012-12-31 US US13/731,895 patent/US8957135B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4912151A (en) * | 1988-03-23 | 1990-03-27 | Huels Aktiengesellschaft | Method of manufacturing pourable pulverulent rubber-filler mixtures starting with rubber solutions |
CN1174210A (zh) * | 1997-05-24 | 1998-02-25 | 中国石油化工总公司 | 超细碳酸钙填充粉末丁苯橡胶的制备方法 |
CN1304425A (zh) * | 1998-04-07 | 2001-07-18 | 粉末橡胶联合股份有限公司 | 粉状填料橡胶粉、应用及其制备方法 |
CN1383439A (zh) * | 2000-06-15 | 2002-12-04 | 中国石油化工股份有限公司 | 全硫化粉末硅橡胶及其制备方法和用途 |
CN1353131A (zh) * | 2000-11-03 | 2002-06-12 | 中国石油化工股份有限公司 | 一种交联型粉末橡胶及其制备方法和用途 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1621571A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100417681C (zh) * | 2004-10-27 | 2008-09-10 | 中国石油化工股份有限公司 | 一种高强度全硫化聚烯烃热塑性弹性体及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1239587C (zh) | 2006-02-01 |
EP1621571B1 (en) | 2016-03-16 |
ES2576577T3 (es) | 2016-07-08 |
CN1852939A (zh) | 2006-10-25 |
JP2006522175A (ja) | 2006-09-28 |
EP1621571A4 (en) | 2006-11-08 |
CN1536006A (zh) | 2004-10-13 |
US20050031870A1 (en) | 2005-02-10 |
US20130225713A1 (en) | 2013-08-29 |
US8957135B2 (en) | 2015-02-17 |
JP4989216B2 (ja) | 2012-08-01 |
US8362128B2 (en) | 2013-01-29 |
CN100558796C (zh) | 2009-11-11 |
EP1621571A1 (en) | 2006-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2004087794A1 (en) | Compound powder, its preparation method and use | |
JP4405814B2 (ja) | 新規なベーマイト粒子及びそれを含むポリマー | |
Zhang et al. | Silane-grafted silica-covered kaolinite as filler of styrene butadiene rubber | |
CN102786726B (zh) | 一种含氧化石墨烯的高性能xnbr橡胶硫化胶及其制备方法 | |
Zhou et al. | Preparation and properties of powder styrene–butadiene rubber composites filled with carbon black and carbon nanotubes | |
WO2020143162A1 (zh) | 鞋底用超轻石墨烯橡胶发泡胶粒及其制备方法 | |
WO2001040356A1 (fr) | Caoutchouc en poudre entierement vulcanise a diametre de particules regulable, son procede de preparation et des utilisations | |
Poompradub et al. | In situ generated silica in natural rubber latex via the sol–gel technique and properties of the silica rubber composites | |
Shimpi et al. | Synthesis of nanoparticles and its effect on properties of elastomeric nanocomposites | |
CN112375369A (zh) | 一种界面超分子增强纳米复合材料及其制备方法 | |
CN109384967A (zh) | 一种高导热氮化硼/天然橡胶复合材料及其制备方法 | |
Qiao | Elastomeric nano-particle and its applications in polymer modifications | |
TWI289576B (en) | Rubber powders which contain large amounts of fillers, a process for preparing them and their use | |
WO2013150973A1 (ja) | 樹脂複合材料の製造方法及び樹脂複合材料 | |
CN101787197B (zh) | 聚碳酸酯/丙烯腈-丁二烯-苯乙烯/层状硅酸盐纳米复合材料及其制备方法 | |
Mohammadi et al. | Improvement of nanosilica effects on the performance of mechanically processed styrene-butadiene rubber by rational hybridization with nanodiamond | |
WO2006129362A1 (ja) | カーボンブラック | |
CN104650293B (zh) | 一种高分散性石墨烯原位改性石油树脂的制备方法 | |
CN109749168B (zh) | 一种纳米氧化锌/橡胶复合材料及制备方法 | |
CN1233722C (zh) | 一种聚丙烯组合物及其制备方法 | |
Sahoo et al. | Effect of carbon nanotubes and processing methods on the properties of carbon nanotube/polypropylene composites | |
Paran et al. | Fabrication methods of carbon-based rubber nanocomposites | |
CN106366393B (zh) | 一种高性能橡胶的制备方法 | |
You et al. | Morphology and performance of unsaturated polyester nanocomposites modified with organoclay and thermoplastic polyurethane | |
KR101642052B1 (ko) | 열전도성 조성물, 열전도성 점착 시트 및 이의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 20048091166 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006504208 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004725660 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2004725660 Country of ref document: EP |