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WO2014130948A1 - Procédé de recyclage de déchets de silicone au moyen d'un polymère organique et d'un catalyseur de dépolymérisation - Google Patents

Procédé de recyclage de déchets de silicone au moyen d'un polymère organique et d'un catalyseur de dépolymérisation Download PDF

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Publication number
WO2014130948A1
WO2014130948A1 PCT/US2014/018028 US2014018028W WO2014130948A1 WO 2014130948 A1 WO2014130948 A1 WO 2014130948A1 US 2014018028 W US2014018028 W US 2014018028W WO 2014130948 A1 WO2014130948 A1 WO 2014130948A1
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Prior art keywords
silicone
mixture
specific embodiments
heating
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2014/018028
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English (en)
Inventor
Dan J. Julian
Dimitris Katsoulis
Bernard A. Link
Thomas Alexander Peitz
Bizhong Zhu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
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Dow Corning Corp
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Publication of WO2014130948A1 publication Critical patent/WO2014130948A1/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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • 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
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • 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 present invention provides a method that includes: (a) heating a mixture that includes: (i) silicone, (ii) an organic polymer, and (iii) a
  • the method also includes (b) degassing the heated mixture to remove at least a portion of the cyclosiloxane.
  • the present invention also provides a method for recycling a silicone waste.
  • the method includes: (a) heating a mixture that includes (i) a silicone waste, (ii) an organic polymer, and (iii) a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone waste, to provide a heated mixture comprising cyclosiloxane and a residue.
  • the method also includes: (b) degassing the heated mixture to remove at least a portion of the cyclosiloxane, (c) forming an extrudate from the residue; and (d) heating the extrudate, sufficient to depolymerize at least a portion of remaining silicone waste located therein.
  • advantages of the invention include the catalytic depolymerization of silicone waste to cyclosiloxanes, in a continuous manner. In additional specific embodiments, advantages of the invention include the catalytic depolymerization of silicone waste to cyclosiloxanes, at a relatively high conversion. In specific embodiments, advantages of the invention include the catalytic depolymerization of silicone waste to cyclosiloxanes, in a continuous manner with very good process stability at high conversion. In additional specific embodiments, advantages of the invention include the catalytic depolymerization of silicone waste to cyclosiloxanes, at a relatively low temperature.
  • advantages of the invention include the catalytic depolymerization of a relatively diverse and broad array of silicone waste, to cyclosiloxanes.
  • the silicone waste to be depolymerized can vary with respect to the physical form and/or chemical reactivity.
  • advantages of the invention include the catalytic depoplymerization of silicone waste carried out in the presence of an organic thermoplastic polymer (e.g., polyolefm).
  • advantages of the invention include the recycling of an organic polymer (e.g., thermoplastic waste, such as a polyolefm).
  • the method described herein employs an organic polymer, in addition to a depolymerization catalyst, to provide a cyclosiloxane and a residue.
  • the organic polymer can be a waste product, suitable for recycling.
  • silicone refers to a mixed inorganic- organic polymer that includes an Si-O-Si backbone.
  • the silicone polymer can be a linear polymer (e.g., volatile and nonvolatile fluids such as dimethicone), a ring polymer (e.g., volatile fluids such as cyclomethicone), a branched polymer, a crosslinked polymer (e.g. gels, elastomers, sealants, and rubber), or a resin (e.g., structures that cure to create three-dimensional films).
  • the silicone can be a compound of formula
  • each RJ is independently at each occurrence an organic group, such as, e.g., methyl, ethyl, or phenyl, optionally substituted;
  • n is a whole integer greater than 1.
  • the main chain unit,— (SiRJRJO)— is often shortened by the letter D because, as the silicon atom is connected with two oxygen atoms, this unit is capable of expanding within the polymer in two directions.
  • M (trialkyl-) , T (monoalkyl-), and Q (no alkyl) units can be defined corresponding to:
  • each RJ is independently an organic group, such as, e.g., methyl, ethyl, or phenyl, optionally substituted.
  • the present invention includes M, D, Q and T silicone polymers as described above.
  • These polymers consist of an inorganic silicon-oxygen backbone ( ••• -Si-
  • organic side groups attached to each of the silicon atoms, which are four-coordinate.
  • organic side groups can be used to link two or more of these -Si-O- backbones together.
  • silicones can be synthesized with a wide variety of properties and compositions. They can vary in consistency from liquid to gel to rubber to hard plastic.
  • the siloxane can be, e.g., linear polydimethylsiloxane (PDMS).
  • PDMS linear polydimethylsiloxane
  • silicone material refers to a material that includes silicone.
  • the silicone can be present, e.g., in at least about 0.1 wt.% of the silicone material. Additionally, the silicone can be present, e.g., in up to about 100 wt.% of the silicone material.
  • hydrocarbyl refers to a hydrocarbon in which a hydrogen atom is removed. As such, it is derived from an organic compound, and consists of hydrogen and carbon atoms, wherein the carbon atoms are optionally substituted, e.g., with one or more halo.
  • the method described herein includes heating a mixture that includes silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the method described herein produces depolymerized material from a silicone material.
  • the depolymerized material is produced via a de-polymerization of silicone waste material, thereby recycling the silicone waste material.
  • the silicone material can include solid silicones, liquid silicones, dispersions of silicones, a mixture of silicones with organic and inorganic compounds, or a combination thereof.
  • the silicone material includes an organopolysiloxane.
  • the silicone material includes an
  • organopolysiloxane having silicon-bonded groups independently selected from hydrocarbyl.
  • the silicone material includes at least one of a silicone liquid, a silicone fluid, a silicone gum, a silicone gel, a silicone solid, a silicone resin, a cured silicone polymer, an uncured silicone gum, a silicone emulsion, a silicone sealant, a silicone rubber, a silicone oil, a silicone grease, a silicone tubing, liquid silicone rubber, a silicone elastomer, a silicone band, a silicone tubing, a filled silicone polymer, a fiber reinforced silicone polymer, a silicone sheet, a silicone mat, a silicone varnish, and a silicone glove.
  • the silicone material includes at least one of polydimethylsiloxane (PDMS), polymethylhydrogensiloxane, polymethylvinylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, phenylmethyl silicone, and fluoroalkylsilicone.
  • PDMS polydimethylsiloxane
  • polymethylhydrogensiloxane polymethylvinylsiloxane
  • polydiethylsiloxane polymethylethylsiloxane
  • phenylmethyl silicone phenylmethyl silicone
  • fluoroalkylsilicone fluoroalkylsilicone
  • the silicone material includes silicone polymers terminated with at least one of trimethylsiloxy,
  • the silicone can be present in the silicone material, in any suitable amount.
  • the silicone can be present in about 0.1 wt.% to about 100 wt.% of the silicone material.
  • the silicone can be present in the mixture, in any suitable amount.
  • the silicone can be present in at least about 0.1 wt.% of the mixture.
  • the silicone can be present in up to about 99 wt.% of the mixture. In specific embodiments, the silicone is present in about 1 wt.% to about 99 wt.% of the mixture.
  • the silicone is present in at least about 1 wt.% of the mixture. In additional specific embodiments, the silicone is present in at least about 10 wt.% of the mixture. In additional specific embodiments, the silicone is present in at least about 25 wt.% of the mixture. In additional specific embodiments, the silicone is present in at least about 50 wt.% of the mixture. In additional specific embodiments, the silicone is present in at least about 75 wt.% of the mixture. In additional specific embodiments, the silicone is present in at least about 90 wt.% of the mixture.
  • the silicone is present in up to about 98 wt.% of the mixture. In additional specific embodiments, the silicone is present in up to about 97 wt.% of the mixture. In additional specific
  • the silicone is present in up to about 96 wt.% of the mixture. In additional specific embodiments, the silicone is present in up to about 95 wt.% of the mixture. In additional specific embodiments, the silicone is present in up to about 90 wt.% of the mixture.
  • the silicone is present in about 10 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 20 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 30 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 40 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 50 wt.% to about 99 wt.% of the mixture. In additional specific specific embodiments, the silicone is present in about 60 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 70 wt.% to about 99 wt.% of the mixture. In additional specific embodiments, the silicone is present in about 80 wt.% to about 99 wt.% of the mixture.
  • any suitable amount of silicone can be depolymerized, employing the method described herein.
  • at least about 50 wt.% of the silicone is depolymerized, employing the method described herein.
  • at least about 75 wt.% of the silicone is depolymerized, employing the method described herein.
  • at least about 90 wt.% of the silicone is depolymerized, employing the method described herein.
  • at least about 95 wt.% of the silicone is depolymerized, employing the method described herein.
  • at least about 98 wt.% of the silicone is depolymerized, employing the method described herein.
  • up to about 100 wt.% of the silicone is depolymerized, employing the method described herein.
  • the method described herein employs an organic polymer, in addition to a depolymerization catalyst, to provide a cyclosiloxane and a residue.
  • the organic polymer can be a waste product, suitable for recycling.
  • the organic polymer is a thermoplastic organic polymer. In additional specific embodiments, the organic polymer is a polyolefm.
  • the organic polymer includes at least one of a straight-chain polyolefm or copolymer polyolefm, a branched polyolefm or copolymer polyolefm, a grafted polyolefm or copolymer polyolefm, a borane- grafted polyolefm, a polyolefm with side hydroxyl group, a polyolefm grafted with another polymer, a blend of polyolefm with another polymer, and a polyolefm filled with an inorganic material.
  • the organic polymer includes at least one of polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyisobutylene, poly(ethylene-co-propylene), poly(propylene-co-l,4- hexadiene), poly(isobutylene-co-isoprene), poly(ethylene-co-propylene-co- 1 ,4- hexadiene, PE-g-PVA, PP-g-PMMA, PP-g-PVA, PE-g-PCL, PP-g-PCL, EP-g- PMMA, butyl-g-PMMA, PMMA, PVA, PS, PVC, PVAC, and a polyolefm filled with at least one of mica, calcium carbonate, silica, glass, magnesium oxide, aluminum oxide, and clay.
  • PE polyethylene
  • PP polypropylene
  • PMP polymethylpentene
  • PB-1 polybutene-1
  • the organic polymer is a thermoplastic organic polymer that includes at least one of low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • the organic polymer is a thermoplastic organic polymer that includes at least one of polyoxymethylene, polyoxymethylene copolymer with oxyethylene and others structural units, polymethylmethacrylate (PMMA), PMMA copolymers, polystyrene, polystyrene copolymers, celluloid, celluloid acetate, cyclic olefin copolymers, ethylene -vinyl acetate (EVA), ethylene-vinyl alcohol (EVOH), fluoroplastics, PTFE, acrylonitrile-butadiene- styrene (ABS), polyacrylates, polyamides, polyamide-imide, polyimides, poletherimide, polysulfones, polyethersulfones, polyketones,
  • PMMA polymethylmethacrylate
  • PMMA PMMA copolymers
  • polystyrene polystyrene copolymers
  • celluloid celluloid acetate
  • PEEK polyetheretherketone
  • PVC polyvinyl chloride
  • PVDC polyvinylidene chloride
  • SAN styrene-acrylonitrile
  • the organic polymer can be present in the mixture, in any suitable amount.
  • the organic polymer can be present in about 0.1 wt.% to about 99 wt.% of the mixture.
  • the organic polymer can be present in up to about 99 wt.% of the mixture. In specific embodiments, the organic polymer is present in about 1 wt.% to about 99 wt.% of the mixture.
  • the organic polymer is present in at least about 1 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in at least about 5 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in at least about 10 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in at least about 15 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in at least about 20 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in at least about 25 wt.% of the mixture.
  • the organic polymer is present in up to about 98 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in up to about 97 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in up to about 96 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in up to about 95 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in up to about 90 wt.% of the mixture.
  • the organic polymer is present in about 1 wt.% to about 99 wt.% of the mixture. In additional specific
  • the organic polymer is present in about 1 wt.% to about 75 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in about 1 wt.% to about 50 wt.% of the mixture. In additional specific embodiments, the organic polymer is present in about 1 wt.% to about 25 wt.% of the mixture.
  • the method described herein employs a depolymerization catalyst, in addition to an organic polymer, to provide a cyclosiloxane and a residue.
  • the methods described herein employ a depolymerization catalyst, in addition to an organic polymer, to produce a depolymerized material from a silicone material.
  • the depolymerization catalyst includes an organic base. In additional specific embodiments, the depolymerization catalyst includes an inorganic base.
  • the depolymerization catalyst includes an organic acid. In additional specific embodiments, the depolymerization catalyst includes an inorganic acid.
  • the depolymerization catalyst includes a solid acid selected from at least one of aluminosilicates, acid treated aluminosilicates, zeolites, mixed metal oxides, heteropolyacids, sulfated metal oxides, carbon based solid acids, ion exchange resins, sulfonated polymers, high molecular weight carboxylic acids, and acidic metal salts.
  • a solid acid selected from at least one of aluminosilicates, acid treated aluminosilicates, zeolites, mixed metal oxides, heteropolyacids, sulfated metal oxides, carbon based solid acids, ion exchange resins, sulfonated polymers, high molecular weight carboxylic acids, and acidic metal salts.
  • the depolymerization catalyst includes at least one of a clay, a mixed metal oxide, and a sulfonated metal oxide.
  • the depolymerization catalyst includes at least one of kaolin, smectite, illite, chlorites, and palygorskitem sepiolite.
  • the depolymerization catalyst includes at least one of montmorillonite, saponite, nontronite (ironsmectite), beidellite, bentonite, and hectorite.
  • the depolymerization catalyst includes a clay. In additional specific embodiments, the depolymerization catalyst includes an acid-washed clay.
  • the depolymerization catalyst can be present in the mixture, in any suitable amount.
  • the depolymerization catalyst can be present in about 0.01 wt.% to about 25 wt.% of the mixture.
  • the depolymerization catalyst is present in about 0.01 wt.% to about 25 wt.% of the mixture.
  • the depolymerization catalyst is present in about 0.05 wt.% to about 25 wt.% of the mixture.
  • the depolymerization catalyst is present in about 0.01 wt.% to about 20 wt.% of the mixture.
  • the depolymerization catalyst is present in about 0.01 wt.% to about 15 wt.% of the mixture. In additional specific embodiments, the depolymerization catalyst is present in about 0.01 wt.% to about 10 wt.% of the mixture.
  • the method described herein includes heating a mixture that includes silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the mixture will include no appreciable or significant amount of organic solvent.
  • the heated mixture will include less than about 20 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 10 wt.% organic solvent. In specific embodiments, the mixture will include less than about 1 wt.% organic solvent. In additional specific embodiments, the mixture will include less than about 0.5 wt.% organic solvent. In specific embodiments, the mixture will include less than about 0.1 wt.% organic solvent. In specific embodiments, the mixture will include less than about 0.05 wt.% organic solvent.
  • each of the silicone, organic polymer and depolymerization catalyst Prior to the heating, each of the silicone, organic polymer and depolymerization catalyst can be contacted to provide a mixture. Additionally, each of these components can be mixed together to provide a mixture that is relatively homogeneous. The contacting and/or mixing can be carried out in any suitable manner and employing any suitable device. For example, each of the silicone, organic polymer and depolymerization catalyst can be mixed together, employing at least one of a high shear mechanical device, an extruder, and a twin-screw extruder, equipped with degassing ports.
  • the method described herein includes heating a mixture that includes silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the mixture will include additional substances, such as, e.g., a filler.
  • the mixture can further include at least one of silica, calcium carbonate, and alumina.
  • the method described herein includes heating a mixture that includes silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the heating can be carried out under any suitable conditions sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the heating is carried out for at least about 0.1 minute. In additional specific embodiments, the heating is carried out for at least about 1 minute. In additional specific embodiments, the heating is carried out for at least about 5 minutes. In additional specific embodiments, the heating is carried out for at least about 10 minutes. In additional specific embodiments, the heating is carried out for at least about 30 minutes. In additional specific embodiments, the heating is carried out for at least about 1 hour. In specific embodiments, the heating is carried out for up to about 24 hours. In specific embodiments, the heating is carried out for up to about 12 hours. In additional specific embodiments, the heating is carried out for up to about 8 hours. In additional specific embodiments, the heating is carried out for up to about 6 hours. In additional specific embodiments, the heating is carried out for up to about 4.5 hours.
  • the heating is carried out for about 0.1 minute to about 24 hours. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 2 hours. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 1 hours. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 30 minutes. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 15 minutes. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 10 minutes. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 5 minutes. In additional specific embodiments, the heating is carried out for about 1 hour to about 24 hours. In additional specific embodiments, the heating is carried out for about 1 hour to about 12 hours. In additional specific embodiments, the heating is carried out for about 1 hour to about 8 hours. In additional specific specific specific specific embodiments, the heating is carried out for about 0.1 minute to about 24 hours. In additional specific embodiments, the heating is carried out for about 0.1 minute to about 2 hours. In additional specific embodiments, the heating
  • the heating is carried out for about 1 hour to about 6 hours. In additional specific embodiments, the heating is carried out for about 1 hour to about 4.5 hours.
  • the heating is carried out such that the temperature of the mixture is below the decomposition temperature of the organic polymer. In additional specific embodiments, the heating is carried out such that the temperature of the mixture is at least about 5°C below the decomposition temperature of the organic polymer. In additional specific embodiments, the heating is carried out such that the temperature of the mixture is at least about 10°C below the decomposition temperature of the organic polymer.
  • the heating is carried out such that the mixture reaches a temperature of at least about 60°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 90°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 120°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 150°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 180°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 210°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of at least about 240°C.
  • the heating is carried out such that the mixture reaches a temperature below about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 330°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 320°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 310°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 300°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 290°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature below about 280°C.
  • the heating is carried out such that the mixture reaches a temperature of about 60°C to about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of about 90°C to about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of about
  • the heating is carried out such that the mixture reaches a temperature of about 150°C to about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of about 180°C to about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of about 210°C to about 340°C. In additional specific embodiments, the heating is carried out such that the mixture reaches a temperature of about 240°C to about 340°C.
  • the upper temperature limit is typically determined by the decomposition temperatures of the silicone and more importantly of the organic polymer.
  • the heating is carried out in a batch mode. In additional specific embodiments, the heating is carried out in a continuous fashion.
  • the heating can be carried out in any suitable manner employing any suitable heating device.
  • the heating can be carried out with devices such as a pyrolysis kiln, a fiuidized bed reactor, and/or a twin-screw extruder, equipped with degassing ports.
  • the method described herein includes heating a mixture that includes silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a cyclosiloxane and a residue.
  • the cyclosiloxane includes a compound of formula (I):
  • each of R1 - R ⁇ is independently hydrogen, (C j -C j2 ) alkyl, (Cg-C j2 ) aryl, (Cg-C ⁇ ) aryl (C j -C 1 2 ) alkyl, or (C j -C 1 2 ) alkyl (Cg-C ⁇ ) aryl, optionally substituted with one or more halo; and
  • n is a whole integer from about 3 to about 20.
  • each of R1 AN ⁇ ⁇ R2 is hydrogen, (C j -C 1 2 ) alkyl, (C 6 -C 12 ) aryl, (C 6 -C 12 ) aryl (C r C 12 ) alkyl, or (C r C 12 ) alkyl (C 6 -C 12 ) aryl, optionally substituted with one or more halo.
  • each of R1 and R ⁇ is (C j -C j2 ) alkyl. In specific embodiments, each of R1 and is methyl.
  • n is at least about 3.
  • n is up to about 7.
  • n is up to about 20.
  • n is up to about 25.
  • n is about 3 to about 7.
  • n is 3. In additional specific embodiments, n is 4. In additional specific embodiments, n is 5. In additional specific
  • n is 6. In additional specific embodiments, n is 7. In specific embodiments, the cyclosilane is a mixture of cyclosiloxanes with n ranging from 3 to 12.
  • the depolymerized material can optionally further include an acyclic siloxane oligomer/monomer or a linear siloxane oligomer/monomer.
  • the acyclic siloxane oligomer/monomer or a linear siloxane oligomer/monomer.
  • oligomer/monomer can include one or more (e.g., 2, 3, 4, etc.) acyclic siloxane oligomers/monomers .
  • the depolymerized material or crude cyclosiloxane can optionally be subsequently purified.
  • the cyclosiloxane (crude or purified) can be offered as a commercial product.
  • the cyclosiloxane (crude or purified) can optionally be subsequently polymerized to a polysiloxane.
  • the method described herein includes degassing the heated mixture, to remove at least a portion of the cyclosiloxane, and to collect the condensed vapor as products.
  • the degassing can be carried out under any suitable conditions sufficient to remove at least a portion of the cyclosiloxane.
  • the degassing is carried out by applying a vacuum to the heated mixture. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of less than about 500 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of less than about 400 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of less than about 300 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of less than about 200 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of less than about 100 mm Hg.
  • the degassing is carried out by applying to the heated mixture a vacuum of about 35 mm Hg to about 500 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of about 35 mm Hg to about 400 mm Hg. In more specific embodiments, the degassing is carried out by applying to the heated mixture a vacuum of about 35 mm Hg to about 300 mm Hg. In more specific
  • the degassing is carried out by applying to the heated mixture a vacuum of about 35 mm Hg to about 200 mm Hg.
  • the degassing is carried out by applying to the heated mixture a vacuum of about 35 mm Hg to about 100 mm Hg. Degassing can also be accomplished by applying a vacuum of less than 35 mm Hg.
  • the heated mixture will include no appreciable or significant amount of organic solvent. In additional specific embodiments, the heated mixture will include less than about 20 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 10 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 1 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 0.5 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 0.1 wt.% organic solvent. In additional specific embodiments, the heated mixture will include less than about 0.05 wt.% organic solvent.
  • the degassing is carried out in a batch mode. In additional specific embodiments, the degassing is carried out in a continuous fashion.
  • the method disclosed herein can optionally further include forming an extrudate from the residue.
  • the method disclosed herein can optionally further include heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein.
  • the heating of the extrudate can be carried out under any suitable conditions, sufficient to depolymerize at least a portion of remaining silicone located therein.
  • the heating of the extrudate can be carried out in a pyrolysis kiln or fluidized bed.
  • the heating of the extrudate is carried out at a temperature below the decomposition temperature of the organic polymer. In additional specific embodiments, the heating of the extrudate is carried out at such that the extrudate reaches a temperature of at least about 120°C. In additional specific embodiments, the heating of the extrudate is carried out at such that the extrudate reaches a temperature below about 340°C. In additional specific embodiments, the heating of the extrudate is carried out at such that the extrudate reaches a temperature of about 120°C to about 340°C.
  • At least about 1 wt.% of the remaining silicone (from the extrudate) is depolymerized. In additional specific embodiments, at least about 10 wt.% of the remaining silicone (from the extrudate) is
  • At least about 95 wt.% of the remaining silicone (from the extrudate) is depolymerized.
  • a method comprising: (a) heating a mixture comprising a silicone, an organic polymer, and a depolymerization catalyst, wherein the heating is sufficient to depolymerize at least a portion of the silicone, to provide a heated mixture comprising cyclosiloxane and a residue; and (b) degassing the heated mixture to remove at least a portion of the cyclosiloxane.
  • the method of the above embodiment which is a method for recycling silicone.
  • the silicone comprises solid silicones, liquid silicones, dispersions of silicones, a mixture of silicones with organic and inorganic compounds, or a combination thereof.
  • the silicone comprises at least one of a silicone liquid, a silicone fluid, a silicone gum, a silicone gel, a silicone solid, a silicone resin, a cured silicone polymer, an uncured silicone gum, a silicone emulsion, a silicone sealant, a silicone rubber, a silicone oil, a silicone grease, a silicone tubing, liquid silicone rubber, a silicone elastomer, a silicone band, a silicone tubing, a filled silicone polymer, a fiber reinforced silicone polymer, a silicone sheet, a silicone mat, a silicone varnish, and a silicone glove.
  • silicone comprises an organopolysiloxane having silicon-bonded groups independently selected from hydrocarbyl.
  • the silicone comprises at least one of polydimethylsiloxane (PDMS),
  • polymethylhydrogensiloxane polymethylvinylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, phenylmethyl silicone, and fluoroalkylsilicone.
  • diphenymethylsiloxy dimethylhydroxylsiloxy, chlorodimethylsiloxy, chloromethyldimethylsiloxy, ethyldimethylsiloxy, propyldimethylsiloxy, allyldimethylsiloxy, and hydrogendimethylsiloxy.
  • the organic polymer comprises at least one of a straight-chain polyolefin or copolymer polyolefin, a branched polyolefin or copolymer polyolefin, a grafted polyolefin or copolymer polyolefin, a borane grafted polyolefin, a polyolefin with side hydroxyl group, a polyolefin grafted with another polymer, a blend of polyolefin with another polymer, and a polyolefin filled with an inorganic material.
  • organic polymer comprises at least one of polyethylene (PE), polypropylene
  • PP polymethylpentene
  • PB-1 polybutene-1
  • polyisobutylene poly(ethylene-co-propylene), poly(propylene-co-l ,4-hexadiene),
  • the organic polymer is a thermoplastic organic polymer comprising at least one of low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • the organic polymer is a thermoplastic organic polymer comprising at least one of polyoxymethylene, polyoxymethylene copolymer with oxyethylene and others structural units, polymethylmethacrylate (PMMA), PMMA copolymers, polystyrene, polystyrene copolymers, celluloid, celluloid acetate, cyclic olefin copolymers, ethylene -vinyl acetate (EVA), ethylene-vinyl alcohol (EVOH), fluoroplastics, PTFE, acrylonitrile-butadiene-styrene (ABS), polyacrylates, polyamides, polyamide-imide, polyimides, poletherimide, polysulfones, polyethersulfones, polyketones, polyetheretherketone (PEEK), polycarbonate, polyesters, polycaprolactone, polybutylene terephthalate, polyethylene terephthalate, polylactic acid
  • thermoplastic organic polymer is present in about 1 wt.% to about 95 wt.% of the mixture.
  • the depolymerization catalyst comprises a solid acid selected from at least one of aluminosilicates, acid treated aluminosilicates, zeolites, mixed metal oxides, heteropolyacids, sulfated metal oxides, carbon based solid acids, ion exchange resins, sulfonated polymers, high molecular weight carboxylic acids, and acidic metal salts.
  • the depolymerization catalyst comprises at least one of a clay, a mixed metal oxide, and a sulfonated metal oxide.
  • the depolymerization catalyst comprises at least one of kaolin, smectite, illite, chlorites, and palygorskitem sepiolite.
  • the depolymerization catalyst comprises at least one of montmorillonite, saponite, nontronite (ironsmectite), beidellite, bentonite, and hectorite.
  • the depolymerization catalyst comprises a clay. 28. The method of any one of the above embodiments, wherein the depolymerization catalyst comprises an acid-washed clay.
  • the mixture further comprises at least one of silica, calcium carbonate, and alumina.
  • each of R1 - is at each occurrence independently hydrogen, (C j -C j2 ) alkyl, (C 6 -C 12 ) aryl, (C 6 -C 12 ) aryl (C r C 12 ) alkyl, or (C r C 12 ) alkyl (C 6 -C 12 ) aryl, optionally substituted with one or more halo; and
  • n is a whole integer from about 3 to about 20.
  • cyclosiloxane comprises one or more cyclic polydimethylsiloxanses, each independently containing about 3 to about 7 silicon atoms.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein, wherein the heating of the extrudate is carried out at a temperature below the decomposition temperature of the organic polymer.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein, wherein the heating of the extrudate is carried out at such that the extrudate reaches a temperature of at least about 120°C.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficient to depolymerize at least a portion of remaining silicone located therein, wherein the heating of the extrudate is carried out at such that the the extrudate reaches a temperature below about 340°C.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein, wherein the heating of the extrudate is carried out at such that the extrudate reaches a temperature of about 120°C to about 340°C.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein, wherein the heating the mixture and the heating the extrudate are each carried out, such that the temperature of the heated mixture is below the temperature of the heated extrudate.
  • the method further comprises forming an extrudate from the residue, and heating the extrudate sufficiently to depolymerize at least a portion of remaining silicone located therein, wherein the heating the extrudate is carried out in a pyrolysis kiln or fluidized bed.
  • a method for recycling a silicone waste comprising:
  • the depolymerized material comprises at least one of a cyclic siloxane and an acyclic siloxane monomer.
  • the depolymerized material comprises one or more cyclic siloxanes and one or more acyclic siloxane monomers.
  • the equipment used for this depolymerization step consisted of a 25 mm twin screw extruder on top of which four vacuum ports were installed, and a 1.5 inch diameter single screw extruder connected to the feeding port of the twin screw extruder through a gear pump. The feed rate was calibrated and controlled by the gear pump.
  • the Waste PDMS gum was mixed with 10 wt.% of Montmorillonite K10 and the mixture was fed through the single screw extruder into the twin screw extruder at a rate of 40.57 g/min.
  • the barrel temperature of the twin screw extruder was set at 170 °C, but the actual temperature during the run reached 200 to 210 °C due to the mechanical energy turning into heat.
  • the screw speed was controlled at 300 rpm.
  • a vacuum of 35 to 100 mmHg was maintained.
  • Depolymerization products were collected as condensed vapor from the four vacuum ports on top of the twin screw extruder barrel. Residual solid was collected at exiting die of the twin screw extruder.The extrudate was continuous and vacuum was maintained well during the run. After 2 hours of steady run, 1095.26 g liquid product was collected, along with 3400 g of residual solid. Based on the solid fed into the twin screw extruder and the solid collected at the exiting die, the conversion was calculated to be approximately 48.8%. Some depolymerization products were apparently not completely collected and lost as vented vapor due to incomplete
  • Ring size is expressed as the number of Si atoms in the ring.
  • Example 2 51.1 g of the solid residue collected from the exiting die of the twin screw extruder in Example 1 was placed in a three neck, round bottom flask equipped with a heating mantle, a thermometer, a condenser cooled with water, a receiver under the condenser, and a vacuum pump with accessories.
  • the vacuum was controlled initially at 50 mmHg and then gradually adjusted to 20 mmHg. Temperature was gradually increased and by the time it reached 210 °C liquid product started showing at the bottom of the condenser and was collected. With temperature maintained, liquid collection lasted for an hour. The temperature was increased to 245 °C and maintained for 5 hours, but no additional liquid was collected.
  • compositions of the products were similar to those obtained in Example 1.
  • Example 2 The same equipment as in Example 1 was used except that the gear pump in between the single screw extruder and the twin screw extruder was removed to facilitate flow of mixture with solid cut tubing pellets.
  • a sample of waste silicone medical tubing was obtained and cut into pieces approximately 7 mm by 7 mm in size.
  • a low density polyethylene sample was purchased from Sigma Aldrich with a melt index of 55 g/10 min measured according to ASTM D 1238 at 190 °C/2.16 kg.
  • a mixture of 7 kg tubing, 5.6 kg waste solid PDMS gum as used in Example 1, 1.26 kg Montmorillonite K10, and 1.575 kg polyethylene was made.
  • the feeding rate of the single screw extruder with this mixture was calibrated as a function of screw rotating speed. And the feeding rate was controlled at 14 g/min.
  • the twin screw extruder screw speed was set at 300 rpm and the barrel temperature was set at 160 °C.
  • depolymerization products were collected as condensed vapor from the four vacuum ports, and residual solids were collected at the exiting die of the twin screw extruder.
  • 328.91 g of liquid product was collected along with 1325 g of residual solid.
  • the conversion achieved in this step was 41.53%, and approximately 94% of depolymerization products were collected, a more efficient collection than in Example 1.
  • the composition of the products was identified by GC-MS and the relative amount of each component was determined by GC-FID. Results were included in Table 3.
  • Ring size is expressed as the number of Si atoms in the ring.
  • Example 4 Second stage depolymerization of mixture of waste PDMS gum and waste cured silicone tubing 50 g of the solid residue collected from the exiting die of the twin screw extruder in Example 3 was placed in a three neck, round bottom flask equipped as described in Example 2. A similar heating/vacuum/vapor
  • condensation/collection process was carried out. The final temperature was increased to 260 °C and maintained for 6 hours until no additional liquid was collected. Once the flask is cooled, it was found that 12.9 g of liquid was collected as product, and the solid lost 15.8 g of weight, corresponding to a calculated additional conversion of 25.32% from this step, and a total conversion from both steps, first in example 3 and second in example 4, of 66.85%).
  • Example 4 Approximately 81.6% of the depolymerization product was collected as liquid in Example 4. The composition of the collected products was dominated by cyclic siloxanes but also contained a small amount of T n D m siloxanes.
  • Feeder Bonnot 2.5" diameter single screw extruder.
  • Zone 1 15; Zones 2-5: 150; Zones 6+7: 160; Zones 8+9: 180; Zones 10+11 : 200; Zone 12: 190; and Zonel3: 25 °C.**
  • the process was very unstable. The first 12 minutes, vapor was visibly coming out from the vacuum ports, and the extruded mass was dry and hard, indicating complete depolymerization and removal of cyclics. From 12 to 20 minutes, no vapor was seen coming out from the last two ports. The extruded mass became softer, soft in touch even after cooling. After 20 minutes, no vapor was seen coming out of any of the vacuum ports.
  • the extruded mass was basically the same as the fed gum, no sign of decomposition was seen.
  • vacuum ports were all disassembled and examined. They were all completely clogged by dry powder and dark material. This was in contrast to the previous 12 runs with polyethylene. These runs were successful and stable without ports clogged.

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  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
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Abstract

L'invention concerne un procédé qui consiste : (a) à chauffer un mélange comprenant (i) de la silicone, (ii) un polymère organique, et (iii) un catalyseur de dépolymérisation, le chauffage étant suffisant pour dépolymériser une partie au moins de la silicone, de façon à donner un mélange chauffé comprenant un cyclosiloxane et un résidu. Le procédé consiste ensuite éventuellement (b) à dégazer le mélange chauffé de façon à éliminer une partie au moins du cyclosiloxane, (c) à former un extrudat à partir du résidu, et (d) à chauffer l'extrudat, suffisamment pour dépolymériser une partie au moins de la silicone qui y subsiste.
PCT/US2014/018028 2013-02-25 2014-02-24 Procédé de recyclage de déchets de silicone au moyen d'un polymère organique et d'un catalyseur de dépolymérisation Ceased WO2014130948A1 (fr)

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CN108727590A (zh) * 2018-05-24 2018-11-02 杭州师范大学 一种硅树脂废弃料的回收再利用方法
WO2019000311A1 (fr) * 2017-06-29 2019-01-03 Dow Global Technologies Llc Composition de polyoléfine
EP3744774A1 (fr) 2019-05-28 2020-12-02 Evonik Operations GmbH Procédé de recyclage des silicones
WO2021126671A1 (fr) 2019-12-19 2021-06-24 Dow Global Technologies Llc Composition polyoléfinique
US20220348721A1 (en) * 2021-04-29 2022-11-03 Evonik Operations Gmbh Process for producing endcapped, liquid siloxanes from silicone wastes
WO2025003486A1 (fr) 2023-06-28 2025-01-02 Universite Claude Bernard Lyon 1 Procédé de valorisation des déchets de silicone élastomère pour la production de matériaux silicone recyclés
EP4556521A1 (fr) 2023-07-21 2025-05-21 Nano and Advanced Materials Institute Limited Composition polymère pouvant être retraitée avec réticulations dynamiques

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Publication number Priority date Publication date Assignee Title
WO2019000311A1 (fr) * 2017-06-29 2019-01-03 Dow Global Technologies Llc Composition de polyoléfine
WO2019000654A1 (fr) * 2017-06-29 2019-01-03 Dow Global Technologies Llc Composition de polyoléfine
CN108727590B (zh) * 2018-05-24 2021-03-09 杭州师范大学 一种硅树脂废弃料的回收再利用方法
CN108727590A (zh) * 2018-05-24 2018-11-02 杭州师范大学 一种硅树脂废弃料的回收再利用方法
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EP3744774A1 (fr) 2019-05-28 2020-12-02 Evonik Operations GmbH Procédé de recyclage des silicones
WO2021126671A1 (fr) 2019-12-19 2021-06-24 Dow Global Technologies Llc Composition polyoléfinique
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US20220348721A1 (en) * 2021-04-29 2022-11-03 Evonik Operations Gmbh Process for producing endcapped, liquid siloxanes from silicone wastes
US12060460B2 (en) * 2021-04-29 2024-08-13 Evonik Operations Gmbh Process for producing endcapped, liquid siloxanes from silicone wastes
WO2025003486A1 (fr) 2023-06-28 2025-01-02 Universite Claude Bernard Lyon 1 Procédé de valorisation des déchets de silicone élastomère pour la production de matériaux silicone recyclés
FR3150519A1 (fr) 2023-06-28 2025-01-03 Universite Claude Bernard Lyon 1 Procédé de valorisation des déchets de silicone élastomère pour la production de matériaux silicone recyclés
EP4556521A1 (fr) 2023-07-21 2025-05-21 Nano and Advanced Materials Institute Limited Composition polymère pouvant être retraitée avec réticulations dynamiques

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