WO2006037278A1 - Procede de regeneration de dechets elastomeres - Google Patents

Procede de regeneration de dechets elastomeres Download PDF

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Publication number
WO2006037278A1
WO2006037278A1 PCT/CN2005/001648 CN2005001648W WO2006037278A1 WO 2006037278 A1 WO2006037278 A1 WO 2006037278A1 CN 2005001648 W CN2005001648 W CN 2005001648W WO 2006037278 A1 WO2006037278 A1 WO 2006037278A1
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Prior art keywords
powder
mesh
rubber
materials
masterbatch
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PCT/CN2005/001648
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English (en)
Chinese (zh)
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Min Duo Chen
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Min Duo Chen
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Publication of WO2006037278A1 publication Critical patent/WO2006037278A1/fr

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    • 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
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08J2317/00—Characterised by the use of reclaimed rubber
    • 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
    • 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
    • C08J2417/00—Characterised by the use of reclaimed rubber
    • 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
    • C08J2421/00—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention provides a new regeneration method of the old discarded elastomer, which is mixed with the regenerating auxiliary agent group and the compounding agent, and is used for mixing the blocks, chips, grains and powder of the old discarded elastomer.
  • Fragmentation, fractionation, heat, kneading, etc., ij has a kind of plastic which has no odor at room temperature and high temperature and is not more than new elastomer, and has no dust flying property. It can be used as a raw material for rubber and plastic products.
  • the invention relates to a rubber powder or a fine rubber powder masterbatch or a masterbatch.
  • the invention mainly relates to the recycling of old waste elastomers and solid wastes, and belongs to the technical field of waste recycling. Background technique
  • the reclaimed rubber produced by the current reclaimed rubber production method has good physical and mechanical properties, it is used in a large amount of aromatic hydrocarbon materials which are odorous and rich in carcinogenicity such as benzo(a)pyrene.
  • aromatic hydrocarbon materials which are odorous and rich in carcinogenicity
  • desulfurization active agent also mainly uses a few ⁇ materials which have malodorous and will produce toxic and polluting hydrogen sulfide and other gases (this is due to these desulfurization active agents It is necessary to have desulfurization activity when ⁇ is less than 7, for example, a tar-like material (referred to as 420) containing 2,2-disulfide bis(6-tert-butyl-p-methylphenol), so that the obtained product materials have The stench that cannot be removed! Especially in the production of reclaimed rubber by high-temperature regeneration method and the use of reclaimed rubber, the smell is even worse!
  • CN1087099A, CN112727 1.A and other patents propose a regeneration scheme at room temperature, but these reconstituted solutions at room temperature are found through practical application, and the obtained product is plasticized. The degree of chemicalization is poor, and the powder is too coarse. In downstream applications, its physical properties and economy are not better than reclaimed rubber; CN1087099A softener group still needs to use a lot of odorous tar, and the obtained product is used at high temperature downstream.
  • the degree of air pollution is the same as that of reclaimed rubber; there is no mention of cheap softeners in the additives proposed by CN1127271.A; CN1087099A, CN1127271. A can not obtain rubber compound with good plasticization or rubber with small particle size. product.
  • Fine rubber powder products are better, but the existing technology may be contrary to the traditional concept of "pure product".
  • the added powder accessories will not exceed 5%, so the obtained product has a larger particle size and its fineness is only It can reach about 60 mesh, and such products are difficult to obtain in a wide range of applications in downstream industries.
  • Dust can be used as a plastic or rubber powder masterbatch or a masterbatch product for the raw materials of the rubber and plastic products industry, so that the old waste elastomer can be environmentally friendly and cheap as much as possible in the use of recycled and recycled products.
  • the solid waste is reused by the synergistic cycle of the old abandoned elastomer. Therefore, it can also be said that the present invention is a method for recycling old disposable elastomer portable solid waste.
  • the old abandoned elastic regeneration method of the present invention is conceived as follows:
  • a regenerating auxiliary group containing the powder auxiliary material system may be added to improve the pulverization efficiency; the powder auxiliary material added when the fine pulverizing the elastic body may be separated after the pulverizing operation, but not separated Better.
  • the regenerating auxiliary agent group contains the softener material component, but the softener material component does not use the malodorous material, such as: coal tar, pine tar, aromatic oil, odorous asphalt, rubber cracking oil, etc.
  • the oil-containing degreased sludge produced by the degreasing and purifying operation of the oil-containing kernel, fruit or/and oil and fat industry of an inexpensive oil plant is directly used.
  • the amount of the softener used is less than the conventional amount, so that the obtained plasticized rubber powder or fine rubber masterbatch or masterbatch is odorless or substantially odorless; in the softener component Further, a polymer material having a grafting function or/and an active monomer (emulsion) is added, so that the damaged and broken polymer chain in the old discarded elastomer can be graft-repaired.
  • the desulfurization active agent component is added to the regeneration auxiliary agent group, and the desulfurization active agent adopts small odor, low toxicity (or is not easy to remain), does not emit pollutant gas such as hydrogen sulfide during desulfurization reaction, and has a feeding material. Convenient, low-cost and other material components to reduce or eliminate pollution caused during production and use.
  • the low-toxic, non-toxic anti-oxidant antioxidant component is added to the regenerating auxiliary group to reduce the hydrocarbon chain aging of the elastomer during the heat regeneration treatment.
  • a powder auxiliary component is added to the regenerating auxiliary agent group, wherein the powder auxiliary material refers to a porous powder material having an adsorption odor characteristic or/and an industrial residue or/and an animal or plant bone, shell, leaf, root, and straw.
  • the powder auxiliary materials may be aqueous materials, which can reduce the dewatering operation in the production of current powder excipients; Including a surface generated in the process of rough and hard as a micro-sickle-like filler particles, the powder filler particles can be cut under the shear force to chew some of the hydrocarbon chain, plasticity of the rubber, added to the rubber Easy-sliding surface rough (hollow) microbead powder, which counteracts the disadvantage of less plasticity caused by softener, so that the obtained plasticized rubber powder or fine rubber powder masterbatch or masterbatch has easy extrusion and low cost.
  • a lubricating anti-friction agent component is added to the regenerating auxiliary agent group, wherein the lubricating anti-friction agent means: having a frictional resistance that reduces ineffective pulverization when the rubber is pulverized, thereby reducing heat generation during fine pulverization.
  • the new method proposed by the present invention has a wide selection range of the harmless regenerating auxiliary agent system, and contains a collection of regenerative auxiliary materials which are not derived from non-renewable resources such as petroleum and coal, and can be more A variety of elastomer processing equipment can be implemented to achieve the purpose of easy promotion.
  • the harmless regenerating auxiliary group system proposed by the invention can also independently form an auxiliary product for elastic body regeneration, or Used as a complex of elastomer; when preparing odorless plasticized rubber powder or fine rubber powder masterbatch or masterbatch containing more powder auxiliary materials, the method of the present invention produces a product containing more rubber, and then Add more powder excipients or / and softeners, etc., for the later added system consisting mainly of powder excipients or / and softener materials, referred to as compounding agents.
  • the product added with the compounding agent has a small amount of glue, which is a low-grade old abandoned elastomer, and finds a way to recycle.
  • the invention combines the old discarded elastomer with the regenerating auxiliary agent group and the compounding material, and then puts it into a conventional elastomer processing machine, and performs mixing, crushing, splitting, heat, kneading and granulation treatment to obtain the foregoing
  • a odorless plasticized rubber powder or a fine rubber masterbatch or masterbatch product which can be packaged in a vacuum bag to facilitate product transportation and improve product storage stability.
  • the product of the present invention refers to an old waste elastomer or an old waste elastomer and solid waste, which does not have a large amount of dust, and does not emit harmful odors at room temperature to high temperature when the product is used. Smog' and the masterbatch or masterbatch of plasticized rubber powder or fine rubber powder with various beneficial functions for the rubber and rubber industry's rubber compound; it can be used as the old waste elastomer portable solid waste after being recycled. form.
  • the product of the invention can be used as a product carrier for carrying all kinds of old waste elastomers to carry solid waste, and then to produce rubber and auxiliary materials for rubber and plastic products; and to use the invention according to the invention in the rubber and plastic products industry.
  • the product can reduce or eliminate the dust during rubber mixing, reduce or eliminate harmful gas pollution during the processing of products and products, reduce the cost of formula and process, and improve the sex/ratio of rubber and plastic products.
  • the technical solution of the implementation concept relates to: a method for regenerating an old discard elastomer and an application of the product and product obtained by regenerating the old discard elastomer; the method also relates to a regenerating auxiliary agent group for regenerating treatment; the method is characterized in that, when regenerating the old discarded elastomer block, chips, granules and powder, it is necessary to perform harmless processing with the cooperation of the regenerating auxiliary agent group, the regeneration
  • the auxiliary group materials include at least one or more of the following materials, which can be selected by the industrial department according to the needs of downstream industries.
  • the specific regenerating auxiliary group materials include:
  • odorless softener materials such as the use of odorless plant kernels, fruit or / and oil-containing destaining sludge or / and elastomers commonly used softening complexes as softeners, and the lower limit of the amount of softener is more than the existing
  • the technique is generally used in a small amount, and the purpose thereof is to make the plasticized rubber powder or the fine rubber powder masterbatch or the masterbatch obtained by the processing odorless or substantially odorless, and in addition, in the softener material group, the grafting function can also be added.
  • the polymer material or the emulsion-like active monomer the purpose of which is to obtain the graft repair of the damaged and broken polymer chain in the old abandoned elastomer, but these are all dependent on the different needs of the downstream products of the invention; (2) Odorless desulfurization activator materials; (3) Antioxidant antioxidant materials; (4) Powder excipients, such as the use of commonly used adsorbents, or / and industrial residues, or / and animal and plant bones, shells, Leaf, root, skin, straw dust, or / and minerals, or / and elastomers commonly used for reinforcing fillers; and (5) adding anti-friction lubricant materials.
  • the old discarded elastomer has a weight percentage of 95 to 70% of plasticized rubber pellets or a fine rubber powder mixture of 80 mesh or less, or a further addition of the compounding agent to obtain another weight percentage of the old discarded elastomer of less than 70 ⁇ 5% non-dusting, at room temperature ⁇ 180 °C does not emit coal tar, pine tar, aromatic oil, odorous jade, rubber hydrocarbon oil and other harmful smells, smoke and rubber and rubber industry Masterbatch or masterbatch of plasticized rubber powder or fine rubber powder with softening, chewing, reinforcing, ⁇ true filling, vulcanization activity function, and finally packaged into products by vacuum, and supplied to the market.
  • the masterbatch or masterbatch product of the present invention in the range of 5 to 95% by weight of the old discarded elastomer, Some products are processed in one step after adding the regeneration auxiliary materials; some products need to be further added to the compounding materials, then stirred or / and kneaded, granulated and then can be completed, in short, by the industrial sector according to downstream industries Different requirements, according to the idea of the present invention, self-distribution within the above content range. In addition, if the downstream industry needs to process at 180 ⁇ 240 °C, as long as it has the conditions of sealing or / and pressure operation, the efficacy and advantages of the product of the invention can also be exerted.
  • the regenerating auxiliary agent material is a combination of one or more of the following auxiliary materials: (1) an odorless softener material, (2) Stinky desulfurization activator materials, (3) anti-oxidant anti-aging agent materials, (4) powder excipients, (5) and anti-friction lubricant materials;
  • the odorless softener-type material of (1) comprises at least one or more of the following materials, and further comprises a softener group composed of one or more materials, wherein the softener-based material comprises: a) oily plant kernels, fruit materials, (b) vegetable oils, resins and derivatives, (c) oily and decolorizing sludge materials, and (d) elastomers commonly used as softeners;
  • Oily plant kernels and fruit materials including but not limited to: Tung oil tree kernels, olive kernels, coconut kernels, cotton kernels, rapeseed, peanut kernels, soybeans, palm kernels, safflower seeds, sunflower seeds, tea Ziren, Linseed, Suziren, Rubber Seeds, Olive Oil, Blackberry Seeds, Wenguan Nuts, Mountain Almonds, Hairy Hazelnuts, Hazelnuts, Pistacia chinensis, ' ⁇ , Walnut Kernels, Samara Oil Tree Seeds , immature pine cones;
  • Vegetable oils, resins and derivatives including but not limited to: corn germ oil, rice bran oil, cottonseed oil, rapeseed oil, peanut oil, soybean oil, palm oil, sunflower oil, olive oil, tea oil, coconut Kernel oil, tung oil, linseed oil, black scorpion seed oil, sage oil, restaurant oil, rosin, tall oil, Taikoo oil, hydrogenated rosin, dehydrogenated rosin, rosin glyceride, rosin pentaerythritol ester, xylene rosin Resin, rosin ester, pine resin, metase resin, eucalyptus resin, peach resin, waste peanut pulp;
  • Desiccant-containing mud-containing materials including but not limited to: oil-containing live charcoal or white clay sludge discarded in the decolorization and purification section of the grease factory;
  • Common softeners for elastomers including but not limited to: lubricating oils, engine oils, white oils, halogenated paraffin oils, paraffin oils, third-line oils, six-line oils, transformer oils, polybutene oils, C 4 ⁇ 18 fatty acids, Vaseline, halogenated paraffin, paraffin, beeswax, animal oil, black ointment, white ointment, odorless asphalt, epoxidized soybean oil, alkyl phenolic resin, bismuth resin, phenolic phenolic resin, petroleum resin, octyl phenolic resin , coumarone, styrene resin, polyvinyl acetal resin, zinc resinate, low molecular weight polyethylene wax, low molecular weight polypropylene wax, stearic acid, palmitic acid, oleic acid, palmitic acid, polyvinyl alcohol, Pentanol, hexanol, heptanol, o
  • the weight content of the softener in the product is: 2 ⁇ 30%, but 3 ⁇ 20% is preferred;
  • the "odorless desulfurization activator type material" referred to in (2) includes a group A selected from the group consisting of the following group A (having a chain-breaking effect on the elastomer sulfur bond in the range of pH 5 to 12 without generating hydrogen sulfide).
  • the odorless desulfurization activator materials are compounded in the following weight ratios.
  • Group A / Group B / Group C 100 ⁇ 2% / 0 ⁇ 98% / 0 ⁇ 98%, the dosage is: 0.1 ⁇ 5 parts/100 parts (based on the weight of tire rubber powder or old discarded elastomer powder) ) is better;
  • the group A materials mentioned therein include, but are not limited to, potassium iron oxalate, ferrous oxalate, iron oxalate, zinc stannate, calcium oxalate, calcium peroxide, calcium hydrogen peroxide adduct, sodium hydrogen peroxide, Copper hydrogen peroxide, zinc oxalate, zinc oxalate, polyferric sulfate, sodium thiosulfate, sodium sulfite, sodium hydrogen sulfite, zinc ferrous sulfate, basic ferric chloride, ferrous chloride, barium hydroxide, Barium phosphate, basic ferric sulfate, copper ferrous sulfate, zinc chloride, zinc silicate, zinc carbonate, basic zinc carbonate, zinc phosphate, zinc sulphate, zinc hydroxide, ferrous hydrogen phosphate, zinc monohydrogen phosphate , ferrous zinc hydrogen phosphate, copper ferrous hydrogen phosphate, zinc sulfate, copper sulfate,
  • ⁇ group materials including but not limited to: rosin, hydrogenated rosin, xylene rosin resin, texyl phenolic resin, coumarone, Taikoo oil, cottonseed oil, rapeseed oil, peanut oil, soybean oil, palm oil, sunflower oil, Olive oil, tea oil, paraffin, stearic acid, beeswax, rubber, desulfurized plasticized rubber powder, thermoplastic elastomer;
  • Group C materials including but not limited to: hemihydrate gypsum powder, clay powder, calcium sulfate composite silica powder; (3) said "antioxidant anti-aging agent materials", said anti-oxidant antioxidants
  • the material comprises at least one or more selected from the materials listed below, and the amount thereof is 0.1 to 5 parts per 100 parts (based on the weight of the tire rubber powder or the old discarded elastomer powder), Anti-oxidant antioxidant materials, including -
  • antioxidant ⁇ 3-hydroxybutanal-2-naphthylamine
  • anti-aging agent ⁇ 3-hydroxybutanal-2-naphthylamine
  • antioxidant ⁇ 6-ethoxy-2,2,4-trimethyl-1, 2-dihydroquinoline
  • antioxidant BLE acetone and diphenylamine high temperature reactant
  • antioxidant 264 N-phenyl-B-naphthylamine
  • anti-aging agent D 2,6-di-tert-butyl a mixture of 4-methylphenol (abbreviated as antioxidant 264), a hydrocarbonated bisphenol (referred to as antioxidant 651), N-cyclohexyl-p-ethoxyaniline (referred to as antioxidant CEA), N-cyclohexyl- P-methoxyaniline (referred to as anti-aging agent CMA), hydroquinone benzyl ether (referred to as antioxidant MBA), 2,2,-methylene bis(4-methyl-6-tert-butanethylamine
  • antioxidant AA 6-eth
  • powder-based excipients comprising: (a) having an odor Adsorbed powdered powder, (b) Industrial slag powder, (c) Bone, leaf, root, straw, rod, shell, and skin powder of animal and plant, (d) inorganic mineral powder (e) Elastomers are commonly used as reinforcing filler powders, (f) particulate materials with a rough surface after calcination, (g) polycrystalline composite materials, and (h) Particles subject to fineness; where said:
  • (b) including but not limited to: chimney ash, steel slag powder, red mud disposed of in aluminum plants, aluminum ash disposed of in aluminum plants, alkaline sludge disposed of in soda ash plants, salt sludge discarded in chlor-alkali plants, citric acid plants, Lactic acid plant, ⁇ white powder factory, phosphoric acid plant, gypsum abandoned by power plant, gypsum iron hydroxide mixed sludge rejected by steel plant, slag containing ginkgo leaf fiber discarded by ginkgo ketone factory, fiber containing discarded by Chinese medicine factory Dregs, fiber-containing sludge rejected by the artificial board factory, pectin factory, tea factory, fiber-containing sludge rejected by paper mills, decolorized and deactivated activated carbon discarded by chemical plants such as sugar, oil, medicine, amino acid, etc.
  • clay slag and activated clay slag, sugar cane, stevia, beet fiber slag, mining tailings slag mud, chemical plant abandoned iron hydroxide mud, sulfuric acid plant abandoned slag, pigment factory row Abandoned mixed pigment sludge, black sludge from carbon black plant, miscellaneous waste glass, miscellaneous waste ceramics, brick powder, boron sludge abandoned by boron salt plant, slag dumped by strontium salt factory, strontium salt factory Disposable slag, zinc ash discarded in galvanizing plant, coal gangue abandoned in coal mine, furnace Ash, a phenol resin powder waste, wastepaper powder, powder waste textile fibers, river sludge;
  • (c) including but not limited to: rice husk ash, rice husk powder, straw ash powder, straw powder, husk powder, peanut shell powder, cork powder, wood flour, charcoal powder, leaf powder, bamboo leaf powder, hay Powder, bark powder, shell powder, bone powder, waste leather powder, coconut shell powder, coir powder, bamboo powder;
  • (d) including but not limited to: fiber serpentine - asbestos, crocidolite, actinolite - asbestos, asbestos, blue asbestos, white tremolite - asbestos, vermiculite, ochre, basalt, iron alum Stone, sodium alumite, magnesium alumite, bauxite, diaspore, aluminox hydroxyaluminite, gibbsite, chromite, celestite, barite, calcined kaolin, acid clay, bentonite, Clay, attapulgite, earth, serpentine, scale serpentine, magnesia wax serpentine, nickel-magnesium wax serpentine, hard serpentine, wax serpentine, talc, attapulgite, oblique stone, stellar Pyroxene, forsterite, enstatite, hydrotalcite, flaky talc, Dongqingshi, mountain cork, diopside, calcium forsterite, magnesia, pyroxene, green opal,
  • (f) including but not limited to: calcined kaolin powder, calcined clay, calcined diatomaceous earth, fly ash, calcined attapulgite, calcined bentonite, hollow microbead powder;
  • D 2 ?? Dn of the auxiliary powder (filler) one or more than one feed material in the general formula.
  • E 2 ... a ⁇ as a listed below or a Any of the above compounds newly formed in water, including but not limited to:
  • thermoplastic elastomers including but not limited to: old abandoned thermoplastic elastomers, waste plastics;
  • the above materials need not be dehydrated and dried first, but it is necessary to control the composition of a plurality of materials to have a pH of 5 to 12, wherein the composition has a pH of 5 to 9. And it is better that the combined material has PH buffering property, and the specific gravity is less than or equal to 2.70; the weight of the material is: 2 ⁇ 1800 parts (dry basis) / 100 parts (based on the weight of the old discarded elastomer powder)
  • the preferred dosage range is: 2 ⁇ 30 parts (dry basis) / 100 parts (based on the weight of the old discarded elastomer powder), and the amount of the powder auxiliary in the regeneration auxiliary group is 5 ⁇ 100 by weight. % is suitable; the reason why the above materials do not need to be dehydrated first is because the product of the invention is heated and heated during the processing, and an appropriate amount of water can prevent the rubber from being scorched.
  • anti-friction lubricant material comprises at least one or more of the materials listed below;
  • the anti-friction lubricant material includes : (a) cationic surfactants, (b) anionic surfactants, (c) nonionic surfactants, (d) amphoteric surfactants, (e) silicone materials, and (f) a plant-derived surfactant; the above-mentioned anti-friction lubricant, the amount of which is used by weight 0.2 to 5% of the amount of free water in the recycled material is preferred;
  • (a) including but not limited to: octadecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, triethanolamine monooleate, decyl phosphate diethanol ammonium salt, Octadecyldimethylhydroxyethyl quaternary ammonium nitrate salt, trishydroxyethyl quaternary ammonium methyl sulfate;
  • (b) including but not limited to: saponified rosin, saponified shellac, saponified stearic acid, saponified fat, sodium dioctyl sulfosuccinate, 1,2-dibutylnaphthalene-6-sulfonic acid Sodium, n-butyl oleate sodium salt, ricinoleic acid butyl sulfate di(or tri)ethanolamine salt, hydrazine-oleoylmethyltaurate sodium, decahydrate sodium sulfate, p-methoxy fatty acid amide Sodium benzene sulfonate, sodium decyl sulfonate, sodium decyl sulfonate, sodium alkyl oxyethylene ether sulfate, sodium benzyl naphthalene sulfonate, Taikoo oil, sodium dinaphthoquinone disulfonate, sub Sodium dimethyl carbaryl naphthalen
  • (c) including but not limited to: epoxy oxime condensate of C7 ⁇ C9 linear fat, coconut oil thioglycolamide, fatty alcohol ethoxylate, C12 ⁇ C18 fatty alcohol ethoxylate, twelve Nonylphenol ethoxylate, octane phenol polyoxyethylene ether-10, polyethylene castor oil, sorbitan oleic acid polyoxyethylene ether, sorbitan stearate, sorbitan monooleic acid Ester, sorbitan stearate polyoxyethylene ether, polypropylene glycol and ethylene oxide adduct, coconut oleyl polyoxyethylene ether, polyethylene glycol octyl phenyl ether;
  • (d) including but not limited to: N-dodecyl alanine, dodecyl betaine;
  • (e) including but not limited to: methyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, bis-[3-triethoxysilylpropyl] tetrasulfide, I-mercaptopropyltrimethoxysilane ⁇ , dimethyldimethoxysilane, methyltrimethoxysilane, methyltriacetoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, two Methyldiethoxysilane;
  • the old waste elastomer regeneration method of the present invention comprises two steps, that is, pre-pulverizing the old waste elastomer to a fine particle of 20 mesh but thicker than 80 mesh, and then 100 parts of the old disposable elastomer (dry weight) Calculate), add 5.3 ⁇ 43 parts of regenerating auxiliary group materials, put them in rubber mechanical device for mixing, crushing, splitting, heat and kneading to obtain a kind of plastic rubber powder or elastomer fine glue with particle size finer than 80 mesh.
  • Powder mixed product including plasticized masterbatch or masterbatch with 95% ⁇ 70% old discard elastomer content, or masterbatch or masterbatch of fine rubber powder with 95% ⁇ 70% old elastomer content
  • the production method comprises the steps of further processing the fine rubber powder masterbatch or the masterbatch having a content of 95% to 70% of the old discarded elastomer or the fine powder masterbatch or the masterbatch having a particle size of less than 80 mesh to a content of less than 70% to 5% of the old East elastomer.
  • the method for regenerating the old disposable elastomer includes at least the following two Step in which,
  • Step (1) is to mix the old discarded elastomer particles having a particle size of 20 mesh or less than 80 mesh and the regenerating auxiliary agent in proportion, and then placed in a rubber processing machine, including mixing, crushing, sieving, Heating desulfurization and kneading and other harmless recycling processing, obtaining plasticized rubber compound, masterbatch, or obtaining more than 95% fine powder mixture with a particle size finer than 80 mesh, and returning the material of less than 80 mesh to the above rubber processing machine Loop processing
  • the processing process of the step (1) comprises: operating at room temperature ⁇ 240 ° C; operating pressure is normal pressure ⁇ 3.5 MPa ; adjusting the pH value of the material system by means of the regenerating auxiliary agent material, so that the pH value of the material system is stable at 5 ⁇ 12;
  • the material ratio in weight percentage is: 95% ⁇ 70% of the old discarded elastomer particles, and 5% ⁇ 30% of the regeneration auxiliary group; under the above process conditions, the regeneration described in step (1) is completed.
  • a kind of plastic rubber powder masterbatch and masterbatch product with a content of 95% ⁇ 70% of the old discarded elastomer are obtained.
  • masterbatch or masterbatch product of fine rubber powder are obtained.
  • Step (2) The product obtained in the step (1) and the compounding agent are separately weighed and placed together in a mixing machine, and after being stirred or kneaded and mixed, the plasticized rubber powder or/and the particle size are obtained.
  • the product obtained in the step (1) accounts for 98% to 5%; the compounding agent comprises the regenerating auxiliary group material contained in the product obtained in the step (1), which accounts for 2% to 95%; under the above process conditions, processing is performed.
  • the regenerating auxiliary agent group mentioned in the step (1) comprises at least one or more of the following functional materials;
  • the functional material includes an odorless softener-like material, and the odorless desulfurizing activator Class materials, anti-oxidant anti-aging agent materials, powder excipients with filling function or/and chewing function powder materials, and anti-friction lubricant materials;
  • the regenerating auxiliary group includes a regenerating auxiliary agent group or a pre-processed independent auxiliary group product.
  • the regenerating auxiliary agent group is prepared by using the foregoing materials in the following weight composition ratio or is produced in advance, and the components thereof include:
  • Odorless softener materials 0 ⁇ 30 parts /100 parts (based on the weight of old disposable elastomer powder)
  • Odorless desulfurizer materials 0 ⁇ 5 parts/100 parts (based on the weight of old abandoned elastomer powder),
  • Antioxidant anti-aging agent materials 0 ⁇ 5 parts/100 parts (based on the weight of old abandoned elastomer powder),
  • Powder excipients 0 ⁇ 30 /100 parts (based on the weight of old abandoned elastomer powder),
  • lubricating anti-friction materials 0 ⁇ 0.5 parts/100 parts (based on the weight of old discarded elastomer powder); the starting amount of all kinds of materials can not be zero at the same time, the sum of all kinds of materials is combined: 5.3 ⁇ 43 parts/100 parts (based on the weight of the old disposable elastomer powder).
  • the compounding agent mentioned in the step (2) is mainly composed of a powder auxiliary material and/or an odorless softener material, and the sum of the two accounts for 80 to 100% of the total amount of the compounding agent, and according to downstream industrial processing needs. Adding one or more functional materials of about 20% to about 0% of the total amount of the complexing agent, said functional material being the functional material mentioned in the group of the regenerating auxiliary agent.
  • the compounding agent in the step (2) is characterized in that the powder auxiliary material involved in the compounding agent in the step (2) is a kind of powder type auxiliary material having a light filling function, and at least the materials listed below
  • the powder auxiliary material involved in the compounding agent in the step (2) is a kind of powder type auxiliary material having a light filling function, and at least the materials listed below
  • adsorbent powders industrial soil powders, bones, leaves, roots, straws, rods, shells, skin powders, inorganic mineral powders, Elastomers are commonly used to reinforce filler powders.
  • the present invention Since the regenerating auxiliary agent group material or the compounding material involved in the method for regenerating the old discarded elastomer according to the present invention does not use harmful materials such as coal tar, pine tar, aromatic, IS oil, etc., the present invention As a regenerating auxiliary group material or compounding material used as an independent regenerative auxiliary material, and the products treated by the same, the natural odor of harmful substances such as coal tar, pine tar and aromatic oil will not be present.
  • the inventors found through experiments at room temperature to 180 ° C that the scent of the product of the present invention and the new rubber without the existing "recycled rubber" is indistinguishable.
  • the method of the present invention comprises: adding an auxiliary agent containing a powder auxiliary material when the old discarded elastic body is pre-pulverized, since the powder material exerts the isolation effect, thereby improving the efficiency of pulverizing the elastic body; when the powder auxiliary material is used as a grinding aid
  • the weight of the added powder auxiliary material is preferably 3 ⁇ 10% of the weight of the obtained rubber powder mixed product, and is finely taken by the ultra-fine pulverizing mechanism at normal temperature.
  • the fine rubber powder is equal to 80 mesh, it is necessary to add a regenerating auxiliary agent group containing the powder auxiliary material, wherein the weight of the added powder auxiliary material is preferably 5 to 25% by weight of the obtained rubber powder mixed product;
  • it is finer than 80 mesh fine powder, according to the habitual thinking, it can be
  • the powder auxiliary material added at the time of pulverization is removed by a separating device such as a spiral separation device or/and a flotation with an ultrasonic machine, but the inventors have experimentally confirmed that the powder auxiliary material added at the time of pulverization is preferably not removed.
  • the method of the invention comprises: when preparing "plasticized rubber powder or fine rubber powder masterbatch or masterbatch containing old used elastomer in 95 ⁇ 5% Fan J", more powder auxiliary materials in the product, softening
  • the auxiliary agent and the like may be added after the rubber powder is plasticized or ground.
  • the powder auxiliary materials and softeners may be combined separately or together to form an independent "combination agent", and the old abandonment elastic body auxiliary regeneration auxiliary agent group After the regeneration treatment is completed, the "combination agent” may be added according to the requirements of the downstream industry, and then mixed or further kneaded to obtain a plasticized rubber powder or a fine rubber powder masterbatch containing less old and used elastomers. Or masterbatch.
  • the method of the invention comprises: when the plasticized rubber powder or the masterbatch or the masterbatch of the fine rubber powder is used, the non-metallic skeleton powder which is entrained in the raw material (old abandoned elastomer) is not deliberately deliberately Separation, and not separating, is preferred because they can also function as excipients.
  • the old discarded elastomer is processed into a product, which is characterized in that: the plasticized rubber powder or the fine rubber powder masterbatch or the masterbatch does not emit coal tar, pine tar, aromatic hydrocarbon at room temperature ⁇ 180 degrees Celsius.
  • the masterbatch or masterbatch can be processed according to the fineness of the rubber powder used, whether it is plasticized by high temperature, whether it is fed into a roll or extruder, granulation, etc., and its products include at least the following five categories: a. a plasticized rubber powder masterbatch equal to 20 mesh but thicker than 80 mesh rubber powder, in the presence of a regenerating auxiliary agent group, mechanically treated, and subjected to high temperature plasticization and further into a roll or extruder, b.
  • a plasticized masterbatch which is finer than 20 mesh but thicker than 80 mesh rubber powder, in the presence of a regenerating auxiliary agent group, mechanically treated, and plasticized at a high temperature but not subjected to a refining treatment, c.
  • Fine glue powder finer than 80 mesh stored in the regeneration aid group Under the mechanical, mixing, and plasticized fine rubber powder masterbatch processed by a high temperature plasticizing at 80 ° C or more into a roll or extruder, d. using a fine rubber powder finer than 80 mesh, in the regeneration In the presence of the agent group, mechanically mixed, and plasticized fine rubber powder masterbatch plasticized at a temperature of 80 ° C or higher, e.
  • the masterbatch or masterbatch can also be subdivided into softening, chewing, etc. according to its role in the rubber-plastic industry mixing process.
  • the weight percentage introduced is 95 ⁇ 5% of the "regenerating auxiliary group" and "complexing agent" in the present invention; wherein the masterbatch or the masterbatch contains the old discarded elastomer in the range of 76 to 92% by weight. (ie, the upper limit formula containing more old elastomers) and the weight of the masterbatch or masterbatch 10 ⁇ 35 ° /.
  • the old disposable elastomer product in the range ie, the lower limit formula product containing less old abandoned elastomer
  • the plasticized fine powder masterbatch or masterbatch is preferred in the product of the invention, especially used
  • the plasticized fine rubber masterbatch or masterbatch and the fine rubber masterbatch prepared by the 100 mesh sieve fine powder are preferred. If the particle size of the product is divided, at least the particle size is equal to 80 mesh, but thicker than 100 mesh plasticized rubber powder or fine rubber masterbatch or masterbatch product; the particle size is equal to 100 mesh, but coarser than 120 mesh Chemical powder or fine rubber masterbatch or masterbatch product; particle size, etc.
  • the product of the present invention has a "softening” function because: the regenerating auxiliary agent group or/and the compounding agent used contains the odorless softener-like material as described above; the product has "chew”
  • the function is that, at least in the regenerating auxiliary agent group, a micro-bead powder material having a rough surface of a polycrystalline composite particle or/and a sliding surface which is easy to slide in an elastomer is used.
  • the shearing force of the rubber mill has a function of chewing on the elastomer;
  • the product has a "reinforcing" function because the regenerating auxiliary agent group or/and the compounding agent used contains reinforcing materials (for example, carbon black, white carbon black, fiber powder, carbon fiber, activated carbon swelling).
  • the product has a "filling" function because: the regenerating auxiliary group used or / And the compounding agent contains the aforementioned powder auxiliary component, which retains the function of filling in the rubber after exerting the function of isolation; the product has the function of "vulcanization activity", because of the f : regeneration auxiliary group or / and the compounding agent contains a component which promotes vulcanization crosslinking of the elastomer (for example, zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, zinc carbonate, magnesium carbonate).
  • a component which promotes vulcanization crosslinking of the elastomer for example, zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, zinc carbonate, magnesium carbonate.
  • the technical advantage of the application of the product described in the technical solution of the present invention is as follows: in the rubber and plastic B 3 ⁇ 4 industry, when the old abandoned elastomer is used as a raw material for the rubber and plastic products industry or as an auxiliary carrier material. It can reduce or eliminate the dust during rubber mixing, can reduce or eliminate harmful gas pollution during the processing of products and products, can reduce the process cost of the formulation and improve the property/ratio of rubber and plastic products;
  • the masterbatch or masterbatch product processed from the old disposable elastomer has been proved by practice, which is significantly superior to the similar raw and auxiliary materials in the existing rubber and plastics industry, and has broad application prospects. detailed description
  • the above materials are firstly mixed in a closed mixing tank, and then introduced into a rubber normal temperature superfine pulverizer through a spiral conveying pipe for pulverization processing. In this process, since the regenerating auxiliary agent group is added and water is used, the mixture is made.
  • the rubber particles in the material can no longer be agglomerated after being pulverized, and the obtained rubber powder can be easily pulverized into fineness equal to 80 mesh; the reason is that the powder auxiliary materials (referred to as clay) of several different crystal forms contained in the regeneration auxiliary group , alkali mud, gypsum materials) in this process mixed, coated, heated, agglomerated, indurated to form a kind of hard surface with a fine surface, fine particles equal to 200 mesh, when the water-containing powder particles When used as a regenerating aid, it is also a good scavenger for the pulverization of the elastomer.
  • the powder auxiliary particles with a micro-sickle shape (the above-mentioned hard surface) have a shearing effect "F, ⁇ Cutting off some hydrocarbon chains, which not only makes the rubber easy to pulverize, but also makes the product plastic on the subsequent rolls.
  • the heat generated during the pulverization process is taken away by the latent heat of the water.
  • Powder The process can be carried out continuously, and the pulverized material is introduced into the accumulation bin by the suction pipe, and the evaporated water vapor is removed through the spiral separator tube. The experiment proves that the output and fineness of the product mainly depend on the efficiency of the pulverizer used, when the regeneration is added.
  • the radial rubber powder with 90% i 40 mesh sieve can be obtained by pulverizing without the regeneration auxiliary agent.
  • the vulcanized rubber normal temperature ultrafine pulverizer with an hourly output of 100 parts by weight is used as a benchmark, and after adding the regenerating auxiliary agent group of the present invention, it is 5 to 55 (theoretical volume of the regenerating auxiliary group) ml / l OOg (tire rubber) range ⁇ , the fineness of the obtained fine rubber powder product can be increased to 90% through 100 mesh sieve, wherein the rubber powder that can pass the 120 mesh sieve reaches 70%, and the fineness rises regularly.
  • the coarse ones are regularly decreased; the hourly output of the product is increased from 100 parts to more than 150 parts.
  • the flat grinding disc rubber is used to pulverize at room temperature ultra-fine pulverizer.
  • the theoretical specific gravity of the regenerating auxiliary group material is 2.7, equivalent to the regenerative additive group Material was added in an amount of 9.3 (theoretical volume) ml / 100g (the tire rubber), 125 parts of the resulting mixture of a pulverized material which Containing less than 2% free water, fineness of rubber powder: 95% over 80 mesh sieve, of which 90% is over 100 mesh and 70% over 120 mesh.
  • the primary pulverized mixture in the silo was sieved with a mesh of 80 mesh, 100 mesh, 120 mesh (industrial wire braided square mesh screen GB/T5330-1985, eqv IS04783-2:1981), but 80 mesh sieve
  • the material is returned to the mixing tank and then pulverized in the tank.
  • the sifted material is then guided into different silos according to the fineness.
  • At least three kinds of products can be obtained, that is, the granularity is finer than 80 mesh, but greater than 100. 5 ⁇
  • the target product 12.5 parts, the particle size is finely equal to 100 mesh, but greater than 120 mesh product 18.75, the particle size is finer than the 120 mesh product 87. 5 copies.
  • the products obtained by sieving are stored in the prepared silos, and these odorless and chewy products can be directly supplied to the downstream market, and the products can be further processed according to the different needs of the next market.
  • the product is then placed in a mechanical mixer as a raw material and mixed with a multi-functional mixture to obtain another type of odorless chewing function and softening function and desulfurization activity.
  • the particle size is finer than 80 mesh.
  • the above-mentioned compounding agent is mainly composed of a powder type filler component, and then a small amount of a odorless softener-like material, an odorless desulfurizing active agent material, an anti-oxidation anti-aging agent material, and aeronautical friction are added according to the needs of the downstream industry.
  • a odorless softener-like material mainly composed of a powder type filler component, and then a small amount of a odorless softener-like material, an odorless desulfurizing active agent material, an anti-oxidation anti-aging agent material, and aeronautical friction are added according to the needs of the downstream industry.
  • a odorless softener-like material mainly composed of a powder type filler component, and then a small amount of a odorless softener-like material, an odorless desulfurizing active agent material, an anti-oxidation anti-aging agent material, and aeronautical friction are added according to the needs of the downstream industry.
  • the compounding agent is composed of 134 parts of paper fiber sludge (dry powder discarded by paper mill, 120 mesh sieve), hydrated silica composite calcium sulfate dihydrate (inorganic composite composition, Dry powder of 200 mesh sieve) 29 parts, salt mud (dry powder discarded by chlor-alkali plant, dry powder of 200 mesh sieve) 112 parts, and 5 parts of motor oil and 5 parts of rosin, "combined to form a total of 285 parts Agent 1, the pH of which is 8-9.
  • the fine rubber powder masterbatch of the invention not only has a good chewing effect, but also has better mastication effect on natural rubber than the commercially available chewing processing aid A (Note: City The composition of the processing agent A sold is a compound of fatty acid zinc or the like, which is relatively expensive, and the cost of plasticating of the natural rubber is significantly reduced by ifc, which is not only caused by the low price of the fine rubber powder masterbatch of the present invention.
  • the fine rubber powder masterbatch used in the present embodiment has a good pH buffering property in the range of pH 5 to 9 when used as a chewing agent, thereby expanding the operational flexibility of the rubber processing.
  • ML10CTC/1+4 indicates the Mooney viscosity of the rubberized compound
  • 100 ⁇ indicates the detection temperature of the Mooney detector
  • 1+4 indicates that the rubber is preheated for one minute after entering the instrument and then continuously tested for four minutes.
  • the industry believes that the Mooney viscosity is /J, which means that the softer the rubber, the easier the molding is.
  • the mixture is combined, and the above materials are firstly mixed in a closed mixer, and then introduced into a vulcanized rubber normal temperature superfine pulverizer through a spiral conveying pipe to be pulverized, and after sieving, a masterbatch which is finer than 80 mesh is obtained.
  • the suction pipe uses the suction pipe to guide the accumulation of goods, silo, which is more than 85% of the material equal to 100 mesh; the material with a particle size of coarser than 80 can be returned to the pulverizer for continuous pulverization.
  • the above masterbatch product can be further Processing, the above-mentioned masterbatch product is introduced into a spiral separation device (also called a cyclone separation device) or a water-floating separation device with ultrasonic function to remove fine wood powder with water, (fine wood powder with water) Return to the batching tank for recycling), the fine powder that has been separated After drying and sieving, a fine pure rubber powder with a fineness equal to 80 mesh can be obtained, and the yield is 85%.
  • a spiral separation device also called a cyclone separation device
  • a water-floating separation device with ultrasonic function to remove fine wood powder with water, (fine wood powder with water)
  • the anti-friction lubricant is preferably non-foaming, and the anti-friction lubricant selected in this example and in the first embodiment. They are all anti-friction lubricants of the non-foam type.
  • Example 2 It can be seen from Example 2 that this embodiment can obtain at least two types of products, one of which is an odorless fine powder masterbatch with good filling function (the particle size is finer than 80 mesh, the yield is 95%, mother The product is 120 parts); the other type is odorless, fine rubber product equal to 80 mesh (the yield is about 85%, and the pure rubber powder product is 102).
  • the particle size is finer than 80 mesh, the yield is 95%, mother The product is 120 parts
  • the other type is odorless, fine rubber product equal to 80 mesh (the yield is about 85%, and the pure rubber powder product is 102).
  • the fine rubber powder masterbatch prepared according to the present embodiment can replace the existing reclaimed rubber, fine rubber powder and filler, and is used in the coating industry and the rubber and plastics industry, and has good technology. effect.
  • the powder-based auxiliary material in the regenerating auxiliary group which has a chewing action on the high molecular hydrocarbon chain can be obtained by using the regeneration operation process for the elastomer, and five examples of the cooperation in accordance with the above combination principle are given. Listed in Table 2.
  • powder-based auxiliary materials are mixed with each other, and after surface changes such as lamination, heat, dehydration crystallization, etc., the surface becomes rough and hard, and the pH is in the range of 5 to 9 and has PH cushioning property.
  • red (red) mud and salt mud as described in this example can be added to plastic to soften the mixture, thereby saving organic softeners or plasticizers.
  • this type of mud contains a large amount of alkaline materials such as Mg(OH) 2 and MgO (PH>9), there is no PH buffering property, and those skilled in the art have found that there are at least three problems in adding them to rubber and plastics. Will greatly affect the vulcanization system, the second is to saponification reaction with resin such as rosin in the rubber compound formulation and affect the viscosity of the rubber compound, and thirdly, it will greatly accelerate the aging of rubber and plastics.
  • the invention changes the pH of the material to a range of 5-9 and has a pH buffering property by rational mixing of (weak) acidic and (weak) alkaline materials. Use various kinds of newly dehydrated clay in the water phase or mix with other dry powder materials to make the surface of the material particles (dry basis weight): ⁇ Example No. 1# 2# 3# 4# 5 # ⁇ (PH5.0 ⁇ 5.5) ' 20 1 1 1 1 1
  • Silica composite gypsum CaS0 4 ⁇ 2H z O ⁇ 2SiO, ⁇ nH z O Irregularly rough and rough. It is hard and rough; the surface is hard and rough. The particles have a good chewing function for rubber and can therefore be chewed.
  • Chinese patent application: 03116373.4 gives a theoretical interpretation model (ie, micro-squeegee particle chewing model), but the Chinese patent application: 03116373.4 focuses on processing aids, so its proposed chewing function
  • the inorganic particulate content is between 50% and 100% (excluding 50%), and the focus of the present invention is on the recycling of the old abandoned elastomer, and comprehensively considering economic rationality and operability,
  • the content of the particles having a chewing function in the rubber powder system should be selected in the range of 1% to 30%.
  • Example 1 7 parts of cotton seed kernel (oily 39%), 3 parts of restaurant oil, 2 parts of rosin, 2 parts of xylene rosin resin;
  • Example 2 7 parts of coconut kernel (40% oil), 3 parts of motor oil, 1.5 parts of coumarone;
  • Example 3 5.5 parts of rubber seed (50% oil), 3 parts of cottonseed oil, 2 parts of transformer oil, 3 parts of octyl phenolic resin;
  • Example 4 3.5 parts of tea kernel (39% oil), palm kernel 3.5 parts, 3 parts of palm oil, 1 part of hydrogenated rosin, 1 part of bismuth resin;
  • Example 5 9 parts of sludge containing oil and fat and activated carbon or / and clay, 10 parts of eucalyptus, 2 parts of zinc resin.
  • the humectant composition proposed by the invention does not contain odorous materials such as coal tar and pine tar, thereby eliminating the disadvantages of the prior art scheme to produce malodor; for example, 10% of the ash content and 12% of the acetone extract. (plastic) rubber (powder) material, and when using a filler with a chewy function, the softener system is based on the sum of pure oil, fat, wax, ester, acid, alcohol, soap, and traditional use.
  • the amount of the softener of the present invention can be reduced by four to sixty percent, in an amount of from 8 to 12 parts per 100 parts by weight of the tire rubber powder, that is, the amount is: 3.2 to 7.2 parts per 100 parts (by the tire rubber powder)
  • the softener material proposed by the present invention uses a low-cost oil plant, oil-containing kernel, fruit or/and oil-and-fat oil-containing adsorption decolorization slag "waste" produced in the industrial decolorization and purification operation, and comprehensively compared
  • the softener system of the present invention has a higher/near ratio than the softener system of the prior art.
  • Odorless desulfurization activator selection principle In the old waste elastomer regeneration method of the present invention, the regenerating auxiliary agent used contains a class of odorless desulfurization activator, wherein the desulfurization activator , one or more odorless desulfurizer materials can be arbitrarily selected, but in practice, we have found that: by a preferred combination, the obtained odorless desulfurization agent system, in the process of regeneration of the old waste elastomer, not only the pole Good desulfurization activity, and it does not produce hydrogen sulfide or other odorous gases under the condition of pH 5 ⁇ 12; it has no deodorizing activity and excellent desulfurization activity under the condition of pH 5 ⁇ 12.
  • the object pursued by the present inventors is the principle of selecting an odorless desulfurization agent system.
  • this embodiment provides five examples of cooperation:
  • Example 1 10 parts of ferrous zinc rosinate, 20 parts of hemihydrate gypsum powder;
  • Example 2 basic copper carbonate or / and malachite powder 5 parts, glucose 10 parts, 2 parts of Taikoo oil, 2 parts of paraffin, 10 parts of hemihydrate gypsum powder, 10 parts of calcium sulfate composite silica;
  • Example 3 7 parts of ferrous sulfate, 5 parts of calcium sulfate composite silica;
  • Example 4 5 parts of zinc powder, 1 part of coumarone, 3 parts of paraffin, 20 parts of hemihydrate gypsum powder;
  • Example 5 5 parts of zinc oxalate, 5 parts of hexadecanylmethyldiethylammonium halide, 5 parts of di-o-tolylhydrazine, 2 parts of paraffin, 2 parts of rubber, and 3 parts of desulfurized rubber.
  • the desulfurization activator system proposed by the present invention can generate hydrogen sulfide or other odorous gas when it is reacted with the rubber powder under the condition of pH 5-12, and has excellent desulfurization activity.
  • Zinc oxide must be combined with stearic acid and accelerator to form a desulfurization activator system; we propose to contain stearic acid and a promoter together to form a desulfurization activator system, which can eliminate zinc oxide and maintain this
  • the odorless desulfurization active agent of the invention should have the characteristics.
  • one or more of the anti-oxidant antioxidant materials may be arbitrarily selected, but if appropriate combination is employed, It can effectively improve the characteristics of the antioxidant anti-aging agent, and can also reduce the amount of the anti-oxidation antioxidant and reduce the cost of the regeneration treatment.
  • this embodiment provides five group instances:
  • Example 1 6-ethoxy- 2,2,4-trimethyl-1,2-dihydroquinoline 1 part, ammonium ferrous sulfate 1 part, 2-thiol benzoquinazoline 1 part;
  • Example 2 Ammonium ferrous sulfate 1 part, 2-thiol phenylimidazole 1 part, 2, 2, 4-trimethyl-1,2-dihydroquinoline polymer 1 part;
  • Example 3 6-ethoxy- 2,2,4-trimethyl-1,2-dihydroquinoline 1 part, hydroquinone benzyl ether 1 part;
  • Example 4 6-ethoxy- 2,2,4-trimethyl-1,2-dihydroquinoline 2 parts, ammonium ferrous sulfate 1 part;
  • Example 5 Ammonium ferrous sulfate 1 part, 2,2,4-trimethyl-1,2-dihydroquinoline polymer 1 part, hydroquinone benzyl ether 1 part.
  • the parts referred to in the above examples are all by weight.
  • Disposal The above materials are mixed with a mixer and then introduced into a vulcanized rubber normal temperature superfine pulverizer for pulverization and sieving to obtain a fine rubber powder having a chewing function and a pH buffering property which is finer than 80 mesh and less than 100 mesh and odorless.
  • Masterbatch 25 parts; finer than 100 mesh, odorless, 115 parts of fine powder masterbatch with pH buffering function and chewing function.
  • the above masterbatch can be directly used as a product to enter the market, and can be further processed.
  • the material can be packaged, and the finished product is odorless, dust-free, and contains about 70% of the powder excipients with light weight (pH range of 8-9, pH buffering).
  • Plasticized fine rubber masterbatch Since the powder excipients such as leaves or/and bamboo leaves are added in this example, the masterbatch product will contain a little plant leaf aroma.
  • the fine rubber powder masterbatch and plasticized fine rubber powder masterbatch in this case can be used in rubber and plastic industry, and made into different grades and different characteristics of rubber and plastic products.
  • a regenerative auxiliary group consisting of a odorless softener, an odorless desulfurization activator and a chewy powder adjuvant
  • the above materials will be placed in a dynamic desulfurization tank, sealed to 200 ° C, and stirred for 2.5 to 3.5 hours, cooled and discharged.
  • the cotton seed kernel in the regeneration aid group can be observed. It is carbonized and oiled, and the oil is absorbed by the old abandoned elastomer powder.
  • the water vapor in the material and the smell of the rubber with little odor are the same as the current reclaimed rubber just out of the can.
  • the can material is an odorless plasticized rubber powder.
  • the cans are processed in the same way as the current recycled rubber cans, and then kneaded into pieces by an open mill. The refiner is passed into a 0.18 ⁇ 0.30 mm book roll and then cut and cut to obtain the same regrind.
  • Formulated odorless plasticized rubber powder masterbatch The physical properties of the rubber compound are tested according to the national standard (GB/T13460-2003), and the density is 1.18, the Mooney viscosity is 70, the water content is 1.0%, the acetone extract is 12%, the ash content is 8%, the breaking strength is 8.52 MPa, and the tear is broken.
  • the content is only 12%, and the ash content is 8%, which is far lower than the standard of no less than 20% of low-pollution reclaimed rubber grade acetone extract and no more than 10% of ash content specified in GB/T13460-2003.
  • the independent compounding agent refers to a compounding product formed according to a certain composition.
  • the independent compounding agent in this example consists of "activated carbon powder or / and activated clay powder 5 parts, iron hydroxide mud powder or / and gypsum powder 10 parts, alkali mud powder or / and red mud powder 30 parts, slag powder Or / and slag powder 10 parts, talc or / and brucite powder 34 parts, dregs fiber powder or / and waste paper fiber powder 145 parts, (rice ash, gypsum ⁇ silicic acid) complex powder 50 parts "Composition, the amount of the independent compounding agent added was 284 parts. After mixing, the pH is 8 ⁇ 9, which has PH buffering capacity and a specific gravity of less than 2.70.
  • the above materials are fully stirred and mixed and cooled to below 40 °C to discharge the finished product.
  • the finished product is odorless, dust-free, light weight (pH is 8 ⁇ 9, and has pH buffering)
  • the powder auxiliary material is 72% plasticized rubber powder masterbatch, and then the plasticized rubber powder masterbatch is further subjected to roll or extrusion kneading, or granulated to obtain about 72% plasticization of the powder-containing auxiliary material. Masterbatch product of rubber powder.
  • the plasticized rubber powder masterbatch or plasticized rubber powder masterbatch obtained in this example can be used as a substitute for reclaimed rubber and filler in the rubber product industry, and obtain odorless rubber products.
  • An application example of an independent regenerative auxiliary group containing a desulfurization activator system Formulation Take 25 parts of 3# natural rubber by weight, old discarded elastomer: white salt bottle stopper particle size is 28 ⁇ 40 mesh rubber powder 100 parts; independent regeneration auxiliary group: by "5. 2 parts of odorless desulfurization activator, 0.5 parts of stearic acid, 1 part of rosin, 2.5 parts of zinc carbonate, 0.9 parts of ⁇ -cyclohexyl benzothiazole sulfenamide, and 1.5 parts of sulphur regenerative additive", the total amount is 8.4 Share.
  • the above materials are placed in an open mill and kneaded into pieces.
  • the operating conditions are: room temperature, water cooling, zero roll distance book pass 10 times; the obtained film is vulcanized at 150 ° C for 5 minutes on a flat vulcanizing machine, and the obtained rubber material property is :
  • the breaking strength is 7.1 (MPa), the elongation is 480%, the Shore hardness (A) is 52 degrees; and the comparative physical property of the desulfurization activator is only: the breaking strength is 2.58 (MPa), and the elongation is 180. %, Shore hardness (A) 58 degrees.
  • a regenerative auxiliary group composed of a combination of a odorless softener, an odorless desulfurization activator and an antioxidant anti-aging agent
  • Example 5 Take 100 parts of the biased tire rubber particles with a particle size of 20 to 30 mesh and a regenerative auxiliary material: 3 parts of the odorless desulfurization activator of No. 1 in Example 5. The 5 in Example 4. # ⁇ 5 ⁇ , Example 4, No. 1# odorless softener 10 parts and antioxidant AW1 parts, a total of 19 parts of the regeneration aid group.
  • the above materials are placed in a dynamic desulfurization tank, the temperature is sealed to 200 ⁇ 220 degrees Celsius, the stirring and heat preservation operation is 2.5 ⁇ 3.5 hours, and the temperature is discharged. At this time, it can be observed that the cotton kernels in the material have been carbonized and oiled. It has also been absorbed by the rubber powder. The water vapor in the material and the smell of the rubber with little odor are the same. The viscosity of the material is the same as that of the current reclaimed rubber. The material of the can is the same as the current recycled rubber.
  • the treatment is carried out by kneading into a sheet with an open mill, and a reeling machine is used to form a sheet of 0.18 to 0.30 mm of the sheet material, and then the material is cut and cut to obtain a plasticized rubber powder masterbatch which is the same as the current reclaimed rubber but is not odorous.
  • the physical properties of the rubber compound are superior to the A1 grade standard for tire reclaimed rubber specified in the national standard GB/T13460-2003.
  • a regenerative auxiliary group comprising the following odorless softener, odorless desulfurization activator and powder excipients; 100 parts of radial rubber tires having a particle size of 20 to 30 for the weight of the discarded elastomer; and 3 parts of No. 1# odorless desulfurization activator in Example 5. and 7.5 parts of No. 1 No. odor softener in Example 4.
  • Silica composite gypsum (chewable ; decomposable powder excipients) , 60% water, ⁇ 5.5) 5 parts” the composition of the regenerative auxiliary group, the total amount is 15.5 parts.
  • the Mooney value of the rubber is the same as that of the current reclaimed rubber, that is, its "ML100 °C/l+4" value does not exceed 80), and is pinched by an open mill. Smelting into pieces, using a refiner book to form a 0.18-0.30 mm book roll, then cutting and cutting, to obtain the same dosage form of the current reclaimed rubber, the odorless plasticized rubber powder masterbatch, the rubber material properties reach the reclaimed rubber (country Standard GB/T13460—2003) tire reclaimed rubber grade A3, but the quality is better than the current reclaimed rubber products.
  • the acetone extract is only 12% (far less than the national standard low pollution level value) 20% " ), the ash content is 7% (also far below the national standard low pollution level "10%").
  • a regenerative auxiliary group consisting of the following odorless softener, odorless desulfurization activator and powder excipient
  • Test sample formula ⁇ Test sample number: 1# (current formula of a shoe factory) 2#
  • Natural rubber 100 parts 100 parts
  • the weight of the old discarded elastomer is 100 parts of the 40-mesh radial tire rubber powder and 1.85 parts of the No. 1# odorless desulfurization activator in Example 5.
  • Cotton seed kernel (39% oil) 6.8 2 parts, 2 parts of oil, 3 parts of restaurant oil, 3 parts of rosin, 40.7 parts of high abrasion resistant carbon black, alkali mud (discarded by soda ash plant, 30% water, PH>9, based on dry basis), 11 parts, clay 12 parts of the composition of the regenerative auxiliary agent, the total amount is 80.35 parts, the total of the above solids: 180.35 parts;
  • Specific treatment method The above materials are placed in a dynamic desulfurization tank, and a small amount of water is added before the treatment. The amount of water is kept so that the moisture in the treated product is kept below 2%, but the material in the treatment is not cokeed. burn. The temperature is sealed to 170 185 ° C, and the mixture is heated for 3 to 5 hours. The material is quickly cooled and discharged. It is kneaded into a dough or a sheet under a cooling condition by a screw machine or an internal mixer or an open mill, and is passed through a refiner.
  • a 0.30 mm book roll is then cut and cut to obtain a plasticized fine powder masterbatch containing a regenerating auxiliary; this embodiment takes the rubber industry's powdering section and the oil and fat industry's oil press section and filler
  • the processing technology of the drying section of the industry is completed in the heating desulfurization tank of the vulcanized rubber.
  • the rubber compound obtained in this example: the plasticized old discarded elastomer powder is not less than 55%, and the filler content is not less than 34.5%.
  • the odor emitted by the rubber compound is the same as that released by the new rubber during the production process; the dust flying property is small during the operation of this example; the rubber compound of the present example and the reclaimed rubber produced by the prior art are separately pressed in the footwear industry.
  • the physical properties of the vulcanizates of the two are compared as shown in Table 4.
  • a regenerative auxiliary group consisting of the following odorless softener, odorless desulfurization activator, antioxidant anti-aging agent and powder excipient
  • Test sample formula ⁇ Test sample number: 1# The current formula of a shoe factory 2#
  • Mill plastic playing time / dust 3 ⁇ 4 Yang: the long / so too - a - short little ⁇ .. Sulfur ship physical property;
  • Specific treatment method 1 The above materials are mixed under a closed condition, mixed with a mixer and then introduced into a vulcanized rubber normal temperature ultra-fine pulverizer for pulverization; (in the process of i3 ⁇ 4, the mixture is added and the water is contained, so that the mixture is mixed.
  • the rubber particles can no longer be agglomerated after being pulverized, and the obtained rubber powder can be easily pulverized into fineness equal to 80 mesh; in addition, since the added white carbon black cement is in the process, it has a hard and rough surface and has a micro-sickle shape.
  • the particle size of the configuration is finer than 1000 mesh particles.
  • Specific treatment method 2 The above materials are placed in a high-speed mixer for stirring and heating, until 170 ⁇ 20 (TC, then continue to stir for 3 ⁇ 5 minutes, the discharge is cooled, that is, the old abandoned elastomer rubber powder is 45.2% a plasticized fine powder masterbatch which is odorless and has a chewing and vulcanizing activity function for the elastomer; if the plasticized fine powder masterbatch is placed in an internal mixer or an open mill or a refiner or extruder In the middle kneading, the old-made elastomer rubber powder can be obtained in 45.2% of odorless and plasticized fine rubber masterbatch which has the function of chewing and vulcanizing activity of the elastomer.
  • the fine rubber powder masterbatch and plasticizing fine in this case If the rubber powder masterbatch or masterbatch is used in the downstream vulcanized rubber products industry, it should be used in 6.5 ⁇ 11 parts in 100 parts of natural rubber, and added before the plasticing section, no need to add commercially available zinc oxide and gas. Auxiliary material.
  • a plasticized fine masterbatch or a masterbatch containing zirconia in a range of 40 to 75% and having a chewing and vulcanizing activity to the elastomer This can be achieved by referring to the processing method provided in Example 14.
  • the odorless rubber powder masterbatch, the plasticized fine rubber masterbatch or the masterbatch which have the function of chewing and vulcanizing activity for the elastomer can be recycled rubber, zinc oxide, chewing agent, etc. Used in the rubber products industry.
  • the old discarded elastomers include 50 parts of butyl water-filled capsule rubber blocks (5 ⁇ 10cm), 50 pieces of radial tire rubber powder (40-100 mesh), and EPDM rubber particles (18 ⁇ 24 mesh). 5 parts, polyurethane rubber particles (10 ⁇ 18 mesh) 5 parts; and 5 parts of "ferrous ferrous sulfate, silica composite dihydrate gypsum (40 ⁇ 60% water, on a dry basis) 5 parts, in the tire Recycled nylon fiber (l ⁇ 10mm) 20-100 parts" consisting of 28 ⁇ 108 parts of regenerating auxiliary.
  • Treatment method 1 The above materials are mixed and then introduced into a rubber crusher or pulverizer to obtain 138 ⁇ 218 parts of the rubber powder mixture with an average particle size of 24 ⁇ 100.
  • the rubber powder material is odorless and contains 79.7% of the old abandoned elastomer. 46.2%; the material is further mixed with the compounding agent and then processed in Process 2.
  • the composition of the compounding agent was 264 parts. (The above materials are all by weight)
  • Treatment method 2 The above materials are placed in a closed heating stirred tank to be heated to 200-220 ° C for desulfurization and plasticization, and the stirring operation is carried out for about 2 hours. After the material is melted, the cooling is obtained, and an old discarded is obtained. The elastomer is 27.36%, and the viscous compound has been desulfurized and plasticized.
  • the rubber compound obtained in this example has the characteristics of pressure sensitive self-adhesive, anti-(oxygen) anti-aging, etc., and can be used as an excellent waterproof material for construction.
  • the old disposable elastomeric compound such as halogenated butyl rubber, natural latex, thermoplastic elastomer, etc., which are agglomerated and contiguous during crushing and pulverization, can be crushed or pulverized according to the embodiment 1. . . , Example 2.
  • the above materials are firstly placed in a closed mixing tank under closed conditions, and then pulverized by a screw conveyor into a normal temperature grinding disc type rubber fine pulverizer. More than 90% of the obtained materials can pass through a 100 mesh sieve, and then pulverized. After the material is sieved through a 100 mesh sieve, the coarse material is returned to the regrind, and the fine material passing through the 100 mesh sieve is introduced into a closed mixing tank, which can be further processed as a product or as a product after packaging.
  • an independent compounding agent is added in an amount of 115 parts of a 100 mesh sieve, and the compounding agent is "355 parts of carbon black, 10 parts of tall oil or/and waste molasses, and 11 parts of transformer oil".
  • the composition of the mixture is 376 parts; together in a closed stirring coupler, mix and then discharge the package, that is, the odorless, dust-free and reinforcing fine rubber powder masterbatch. 7% ⁇ In this example, the content of the rubber powder in the masterbatch is 18.3%, the content of the auxiliary mixture is 81.7%.
  • the fine rubber powder parent family obtained in this case can be used in the rubber products industry instead of reclaimed rubber, fine rubber powder and carbon black.
  • the specific processing method First, the rubber powder is placed in a stirrer kettle, and then the compounding material is heated and melted, and then added to the stirrer kettle to be mixed with the rubber powder, and then discharged, thereby obtaining a dust-free flying property. Fine gum powder masterbatch.
  • the fine powder masterbatch obtained Physical properties are also excellent (ie better than reclaimed rubber).
  • the masterbatch contains 90% of the rubber powder and 10% of the compounding material.
  • the fine rubber powder parent family obtained in this case can be used in the rubber products industry instead of reclaimed rubber, fine rubber powder and carbon black.
  • Formula taking the weight of the old discarded elastomer by weight to be equal to 100 parts of 100 mesh rubber sole sole vulcanized edge fine rubber powder; and 15 parts of bentonite containing calcium hydrogen phosphate composite silica or calcium sulfate composite silica Emulsion cement consisting of polyvinyl butyral resin and nonionic surfactant (such as fatty alcohol polyoxyethylene ether) (containing 40% solids, 60% water content, on a dry basis), 15 parts, 15 parts of eucalyptus powder, low molecular weight polyethylene (wax) 10 parts "combination of 55" The total amount of materials is 155.
  • nonionic surfactant such as fatty alcohol polyoxyethylene ether
  • the above materials are firstly mixed in the mixing tank, and then extruded into a particle having a particle size of 5 mesh by a screw machine at 120 to 150 ° C, after the particles are naturally cooled (water is naturally dry) That is, a property is comparable to that of a tire reclaimed rubber (compared to a test piece containing a similar amount of rubber powder), but there is no commercially available refining gel malodorous and inexpensive plasticized fine powder masterbatch.
  • the plasticized fine rubber powder masterbatch obtained in this example can be used in the rubber products industry instead of recycled rubber and filler.
  • Example 19 The plasticized fine rubber powder masterbatch obtained in this example can be used in the rubber products industry instead of recycled rubber and filler.
  • Formula Take 5 parts of the rubber mat in the car with a fine particle size finer than 100 mesh by weight; and 10 pieces of waste paper powder, 10 pieces of waste (fabric) fiber powder, waste nylon fiber powder 10 parts, 10 parts of gypsum (dismantled by power plant), 10 parts of decolorized and deactivated activated carbon or / and activated clay residue mixture (discarded by chemical plants such as sugar, oil, medicine, amino acid, etc.), wollastonite, gypsum, hydration 10 parts of silica composite composition, 10 parts of public leaf powder, 5 parts of waste leather powder, 20 parts of transformer oil, 95 parts of compounding agent; total amount of materials: 100 parts.
  • the fine rubber powder masterbatch obtained in this example can be used in the rubber and plastic products industry instead of the ordinary rubber and plastic filler. It has the advantages of light weight, can significantly improve the hardness and tear strength of the rubber compound, and feed dust and dust during rubber mixing.
  • the old waste elastomer has a particle size of less than 100 mesh and contains 90% of the automobile tire rubber fine rubber powder and the buckwheat shell or/and the rice husk powder 10% mixed pulverized material; and 10 parts of the transformer oil.
  • the above compounding agent is first heated and melted, and then poured into the mixing tank and mixed with the old discarded elastomer according to the formula, the temperature when mixing can not exceed 50 ° C, and the stirring speed can be 40 60 rpm. It does not need to be stirred vigorously, and evenly stirred and discharged, that is, a fine rubber powder masterbatch containing 80% of the old abandoned elastomer without dust, no foul smell and having a buckwheat shell or/and a rice husk.
  • the fine rubber powder masterbatch obtained in this example can be used in the rubber and plastic products industry instead of ordinary recycled rubber, fillers, softeners and other rubber and plastic ingredients. It has the advantages of high strength, light weight, and fast dusting during rubber mixing.
  • the weight of the old discarded elastomer is less than 100 mesh, and the car-containing rubber rubber fine powder is 95% and the buckwheat hull or/and rice hull powder is 2.5% and wollastonite* zinc silicate ⁇ calcium sulfate. ⁇ 1. 5 parts; and the mixture of "transformer oil 7 parts, phenolic resin 3.5 parts" composed of U 10. 5 parts; the above materials total: 115. 8 copies.
  • Specific treatment method The above compounding material is first heated and melted, and then poured into the mixing tank and stirred and mixed with the old discarded elastomer.
  • the temperature during mixing does not exceed 50 ° C, and the stirring speed can be 40 ⁇ 60 rpm.
  • No need to stir vigorously, evenly mix and discharge that is, a fine rubber powder masterbatch containing 86.4% of old and abandoned elastomer, no dust, no foul smell and buckwheat shell or / and rice husk.
  • the product obtained in this example retains about 80% of the tensile strength of the original discarded elastomer, whereas the regenerated gum produced by the prior art retains only about 40% to 50% of the tensile strength of the original discarded elastomer.
  • the fine rubber powder masterbatch obtained in this example can replace rubber, plastic, rubber, etc. Ingredients are used in the rubber and plastic products industry, which has the advantages of high strength, light weight, and quick and no feed when mixing rubber.
  • the old pulverized elastomer has a particle size of less than 100 mesh and contains 90% of the automobile glass rubber seal fine rubber powder and 5% of the wollastonite ⁇ zinc silicate ⁇ calcium sulfate ⁇ silica composite composition. 5 ⁇
  • the total amount of the above materials is 11. 5 parts, and a total of 7.2 parts.
  • Specific treatment method Mix the above compounding agent with the old waste elastomer in the mixing tank.
  • the temperature during mixing should be controlled at 100 ⁇ 150°C, the stirring speed is 900 ⁇ 1200 rpm, and the mixture is evenly stirred.
  • Material that is, a plasticized fine rubber powder masterbatch containing 88.9% of old abandoned elastomer (EPDM), no dust and malodor.
  • the epoxy resin masterbatch obtained from this example can be used in the rubber and plastic products industry instead of (3B and 2) reclaimed rubber. It has high strength, easy extrusion, defoaming and rubber mixing. Eat fast and no dust and other excellent.
  • the formula of the desulfurization activator of the example 3 of the present invention is as follows: 5 parts of boron mud, (waste) 5 parts of phenolic resin powder, 12 parts of waste paper powder, wollastonite, zinc silicate, calcium sulfate, silica composite composition, 3 parts, polyethylene glycol octylphenyl 0 ⁇ A portion of the "regeneration auxiliary group 28. 6 parts; total: 139. 6 parts.
  • Specific treatment method 1 The above materials are placed in a closed mixing tank under closed conditions, and water is added according to 8% of the above materials, and the mixture is stirred and mixed, and then introduced into a normal temperature grinding disc type rubber fine pulverizer by a screw conveyor. Medium pulverization, (more than 80% of the obtained material can pass through 100 mesh sieve), and then the pulverized material is sieved through a 100 mesh sieve, and the coarse material is guided back to regrind, and the fine material passing through the 100 mesh sieve is introduced into another sealed mixture. In the tank, further processed, with a fine material of 111.
  • Specific treatment method 2 Mix the above materials together and discharge the package to obtain the fine rubber powder masterbatch with no odor, no dust and filling and reinforcing function.
  • the amount of rubber powder contained in the masterbatch product was 23. 4%, and the rest were auxiliary mixtures.
  • the fine rubber powder masterbatch obtained in this example can be used in the rubber products industry instead of recycled rubber, fine rubber powder and carbon black. It is worth noting that this example does not separate the non-metallic skeleton broken fibers entrained in the old disposable elastomer, and does not need to be separated. This is due to the fact that the present invention has a rigid inorganic fine powder (a hard brown) during fine pulverization. The surface of the grinding aid) exists, so the broken fiber of the skeleton can be ground, and the powdered fiber after grinding can not only strengthen the rubber but also affect the appearance of the surface of the rubber.
  • Specific treatment method 1 The above materials are firstly placed in a closed mixing room under closed conditions, and then introduced into a normal temperature grinding disc type rubber fine pulverizer by a screw conveyor for pulverization treatment (more than 80% of the obtained materials can be obtained) After passing through the 100 mesh sieve, the sieved material is sieved through a 100 mesh sieve, and the coarse material is returned to the mill. The fine material passing through the 100 mesh sieve is introduced into a closed mixing tank. As a product, the package is listed as a product. The intermediate product is further processed. Further processing: 139.
  • the total amount of the above-mentioned 4 total amount of the total amount of the total amount of the total amount of the above-mentioned 4 is a total of 50. 6 parts.
  • Specific treatment method 2 The above materials are placed in a closed agitation tank. After mixing and discharging, the material is packaged to obtain a fine rubber powder masterbatch with no dust and filling and reinforcing functions. ⁇ The masterbatch containing the rubber powder 19. 8%, containing a regenerative auxiliaries and a mixture of compounding agent 80. 2%.
  • the fine rubber powder masterbatch obtained in this example can be used in the rubber products industry instead of recycled rubber, fine rubber powder and carbon black. By the way, this example does not separate the non-metallic skeleton broken fibers entrained in the old disposable elastomer.
  • the surface and the broken fiber of the skeleton are pulverized to a 100 mesh sieve, and the ground powdered fiber can be used for the rubber.
  • the plastic material product has the reinforcing effect of the good, and does not affect the appearance of the surface of the rubber product.
  • the masterbatch or the masterbatch product provided by the present invention does not emit coal tar, pine tar, aromatic oil, odorous jade, rubber hydrocarbon oil and the like in the room to high temperature.
  • Dust when the mill is being machined large ... ⁇ — ⁇ —-. Smaller 'Slightly small, very small, very small, small
  • Vulcanizer test 145 ° C, 20 minutes
  • Vulcanization conditions (145° C/X): 14 15 14 15 14 14 14
  • the method and product of the present invention obviously have many variations, for example, a process in which a powder auxiliary (filler) is surface-treated with a known silicone or the like to obtain an active filler, and is combined with a pulverization process;
  • a powder auxiliary (filler) is surface-treated with a known silicone or the like to obtain an active filler, and is combined with a pulverization process;
  • the old waste elastomer is used as a wetting agent for suppressing the powder growth of the filler, as long as the filler powder can be prevented from flying, the content of the old discarded elastomer in the material can be as low as 5% or less;
  • the coarser material is plasticized at a high temperature, and then combined with the sieved fine material to obtain a masterbatch or a masterbatch; from the range of the composition provided by the present invention, it can be combined to form more recyclable materials.
  • the masterbatch or the masterbatch product of the plasticized rubber powder or the fine rubber powder provided by the invention the masterbatch or the masterbatch of the fine rubber powder is preferred, especially the plastic prepared by using the fine rubber powder of the 100 mesh sieve.
  • the masterbatch or masterbatch of the fine rubber powder is the best.
  • the masterbatch or masterbatch of the plasticized rubber powder or the fine rubber powder provided by the present invention can be obtained by the combination of the simple upper and lower limit masterbatch. Or similar formula.
  • the obtained rubber compound is not only odorless, but also can reduce or eliminate dust pollution caused by materials such as zinc oxide, carbon black, calcium carbonate, clay, fiber powder, etc.
  • the present invention retains and expands the existing reclaimed rubber as a promotion.
  • the advantages of applying powdered softening aids The rubber obtained by the invention has good odorlessness and good mechanical properties, which makes it possible to use recycled elastomer materials in the odorless rubber compound formulation of the downstream products industry, and it is possible to use less new rubber materials.
  • the invention uses the old abandoned elastomer as a wetting agent for suppressing the flying of the filler powder, and can produce a kind of wetting agent.
  • the lower-size masterbatch of the present invention is contained in the rubber-based plastics industry, and the old-fashioned elastomers having low rubber content or poor quality are used in the rubber and plastic products industry. A way to recycle.
  • the method provided by the invention discards the odorous disadvantage of the existing (black) reclaimed rubber by using a sorbent and a odor-free softener such as coal tar in the regenerating auxiliary agent group or the compounding agent; the invention is well solved.
  • the invention solves the old problem well Discarding the powder auxiliary material added during the pulverization of the elastomer and containing a large amount of regenerating auxiliary agent is a problem of remaining or removing after pulverization;
  • the present invention proposes that the antioxidant anti-aging agent can be applied to the regeneration process of the waste elastomer; Under the premise of ensuring the regeneration process of the old abandoned elastomer and the product is odorless and non-polluting, it also simplifies and modifies the process of dust-free rubber and filler products in the downstream application, as well as the development and utilization of forestry and mining products and deterioration.
  • the additive combination provided by the present invention can be completely separated Petroleum, coal and other non-renewable materials.
  • the invention is particularly suitable for the recycling of thermoset elastomers.
  • the products of the present invention do not emit coal tar, pine tar, aromatic oil at room temperature ⁇ 180 degrees Celsius.
  • the smell of odorous asphalt and rubber hydrocarbon oil only a small amount of water vapor is emitted during processing, the acetone extract of the product is low and the ash is controllable; the dehydrated substance of the polycrystalline composite composition can be detected in the product.
  • the product of the invention has less smoke at 180 ⁇ 200 degrees Celsius, acetone extract is low and ash is controllable; and EPDM, Compared with the nitrile reclaimed rubber, the product of the invention has less smoke at 180-200 degrees Celsius, low acetone extract and controllable ash.
  • the polycrystalline ash and other powder materials can be detected in the product of the present invention, although the ash content of the product is improved, it is advantageous for the regeneration treatment and is also beneficial for downstream applications.
  • the plasticized masterbatch or masterbatch product of the invention is characterized in that the rubber powder particles in the material have been swollen or plasticized and sticky, and can not be sieved to define the particle size, but can be sieved.
  • a super-rolled rubber test piece of a fine rubber powder whose particle size is defined to compare its compactness and surface flatness, and to infer its physical properties.
  • the masterbatch or masterbatch product provided by the invention has a deeper social significance in addition to its significant economic value, that is, it can utilize almost all solid waste generated by modern industrial society with large capacity! From this point of view, the masterbatch or masterbatch product provided by the present invention can be seen as a product in which a multi-industry multi-species solid waste recycling reuse point is connected in parallel. In this non-polluting product, the old abandoned elastomer is an important medium for recycling a variety of solid waste. She is a scarce resource! Not waste!
  • the masterbatch or masterbatch product provided by the invention is a carrier for transforming the old waste elastomer and various solid wastes into a raw material of the rubber and plastic products, and is an old waste elastomer and a multi-industry solid waste energy resource.

Abstract

L'invention concerne un procédé de régénération de déchets élastomères consistant à appliquer un traitement de non pollution à ces déchets dans des machines à caoutchouc dotées d'une aide à la régénération. Différents moyens techniques constituent cette aide à la régénération: l'utilisation d'agents adoucissants inodores, composés de nucules végétales, de fruits, de boue décolorée contenant de l'huile et/ou d'agents adoucissants classiques utilisés dans les élastomères, entre autres; la réduction du dosage d'agents adoucissants par l'optimisation de l'association des agents adoucissants présents, ce qui permet de renforcer leurs effets; l'utilisation d'agents actifs inodores; l'utilisation d'antioxydants; l'utilisation d'une poudre de sorbant, de terre tourbeuse industrielle, d'os ou de coquilles d'animaux, de tiges de plantes et/ou d'agents de renforcement classiques utilisés dans les élastomères comme matériau auxiliaire en poudre. Le procédé selon l'invention permet d'obtenir une poudre de caoutchouc fine de 80 mailles ou plus, ou un produit de mélange maître ou caoutchouc maître inodore de poudre de caoutchouc plastique ou de poudre de caoutchouc fine, contenant des déchets élastomères dans une quantité comprise entre 5 et 95 %, et présentant certaines caractéristiques du caoutchouc brut, par exemple des propriétés d'adoucissement, d'élasticité, de renforcement, de remplissage et de vulcanisation. Les produits ainsi obtenus peuvent être utilisés comme matière première ou comme matériau auxiliaire dans le domaine du caoutchouc et du plastique.
PCT/CN2005/001648 2004-10-09 2005-10-08 Procede de regeneration de dechets elastomeres WO2006037278A1 (fr)

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CN102250497A (zh) * 2011-05-26 2011-11-23 芮立 一种新型橡胶用碳黑的制备方法
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CN102634062A (zh) * 2012-04-28 2012-08-15 徐州工业职业技术学院 加入偶联剂制备高强力再生胶的方法
CN102766273A (zh) * 2012-07-05 2012-11-07 南开大学 一种超声波降解废轮胎胶粉中多环芳烃的方法
CN104017624A (zh) * 2013-01-23 2014-09-03 周黎明 用污泥垃圾制造的再生煤及制造方法
CN104194355A (zh) * 2014-09-05 2014-12-10 淮阴工学院 废旧橡胶再生剂的制备方法
CN104804456A (zh) * 2015-03-24 2015-07-29 浙江省东阳市诚基电机有限公司 一种微型马达用胶套及其制备方法
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread
CN105000907A (zh) * 2015-08-17 2015-10-28 长沙鼎成新材料科技有限公司 一种轻质陶粒废水处理的方法
CN105461956A (zh) * 2015-12-30 2016-04-06 仙桃市聚兴橡胶有限公司 一种绿色环保轮胎再生胶生产工艺
CN110483837A (zh) * 2019-08-20 2019-11-22 江苏睿博环保设备有限公司 新型脱硫环保再生胶及制备方法
CN112143059B (zh) * 2020-09-30 2022-08-12 四川远星橡胶有限责任公司 一种高弹性低生热的环保再生胶胶料及其制备方法
CN112143059A (zh) * 2020-09-30 2020-12-29 四川远星橡胶有限责任公司 一种高弹性低生热的环保再生胶胶料及其制备方法
CN112873611A (zh) * 2021-01-14 2021-06-01 宁波拓烯新材料科技有限公司 一种混炼硅橡胶或硅橡胶复合物切片的生产装置和工艺
CN112873611B (zh) * 2021-01-14 2023-07-21 拓烯科技(衢州)有限公司 一种混炼硅橡胶或硅橡胶复合物切片的生产装置和工艺
EP4047054A1 (fr) * 2021-02-18 2022-08-24 Thorn Assets, LDA Composé nanocomposite à base de cuir, de polymère et de graphène
CN113150416A (zh) * 2021-02-26 2021-07-23 三河市长城橡胶有限公司 一种废旧橡胶加工用剪切助剂及利用该助剂获得高分子生态橡胶的方法
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CN115304841A (zh) * 2022-07-14 2022-11-08 河北交科材料科技有限公司 一种用于大掺量橡胶改性沥青的预处理胶粉及其制备方法
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