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WO2001023464A1 - Procede de devulcanisation d'un caoutchouc - Google Patents

Procede de devulcanisation d'un caoutchouc Download PDF

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Publication number
WO2001023464A1
WO2001023464A1 PCT/NL2000/000621 NL0000621W WO0123464A1 WO 2001023464 A1 WO2001023464 A1 WO 2001023464A1 NL 0000621 W NL0000621 W NL 0000621W WO 0123464 A1 WO0123464 A1 WO 0123464A1
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WO
WIPO (PCT)
Prior art keywords
rubber
process according
atoms
group
amount
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
Application number
PCT/NL2000/000621
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English (en)
Inventor
Martin Duin Van
Jacobus Wilhelmus Maria Noordermeer
Miriam Adriënne Lambertina VERBRUGGEN
Leen Van Der Does
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Koninklijke DSM NV
Original Assignee
DSM NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Priority to AU74581/00A priority Critical patent/AU7458100A/en
Publication of WO2001023464A1 publication Critical patent/WO2001023464A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J11/28—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 by treatment with organic compounds containing nitrogen, sulfur or phosphorus
    • 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
    • C08J11/12—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 dry-heat treatment only
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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 relates to a process for devulcanizing a rubber, which rubber is obtained by vulcanizing with the aid of a sulphur-containing compound a copolymer which contains ethylene monomer units, monomer units of an ⁇ -olefin and monomer units of a polyunsaturated compound, by heating the rubber to such elevated temperature that devulcanization occurs and a recyclable product is obtained.
  • the object of the invention is to provide a rubber devulcanization process in which a higher degree of devulcanization is effected in a simpler manner and at a shorter heating time.
  • This object is achieved through application of the process, which is characterised in that use is made of a rubber obtained by vulcanizing a copolymer which contains monomer units of a polyunsaturated compound according to the formula
  • X is a group having 2-20 C atoms, which group can polymerise with the aid of a co-ordination catalyst and R° is a chain having 2-30 C atoms and containing at least one double carbon-carbon bond, with none of the C atoms of the double bond forming part of a ring structure .
  • a further advantage is that the rubber can be devulcanized with lower concentrations of the devulcanizing agent. Indeed, complete or substantially complete devulcanization of the rubber can be achieved even without adding any devulcanizing agent.
  • the process of the invention can be caried out using polymer processing equipment referred to in the literature.
  • suitable equipment are a press, an oven, a kneader, a stirred vessel, an autoclave or an extruder.
  • an extruder or a kneader is used.
  • Heating during the process of the invention is effected at a temperature of for example 50-400°C, preferably at a temperature of 150-350°C, in particular at a temperature between 250 and 350°C inasmuch as at this temperature devulcanization proceeds very rapidly, the backbone chains of the copolymer decompose only to a limited extent and the devulcanized product obtained is well recyclable.
  • the time during which the rubber is heated is normally less than 5 hours, preferably less than 3 hours, more preferably less than 1 hour and still more preferably less than 30 minutes. In general, a higher temperature calls for a shorter period to obtain a recyclable devulcanized product than a lower temperature .
  • the rubber is preferably heated in an atmosphere which is substantially free of oxygen. This can be achieved by for example saturating with nitrogen the reaction vessel containing the rubber to be devulcanized.
  • rubber articles obtained by vulcanizing the copolymer with a sulphur-containing compound are preferably pretreated using equipment referred to in the literature for the fragmenting, crushing, cutting, grinding and crumbing of rubber or plastic articles.
  • ⁇ -olefins that may be used as a monomer besides ethylene there may be mentioned propylene, butene-1, pentene-1, hexene-1, octene-1 or the branched isomers thereof, such as 4-methylpentene-l, as well as styrene and ⁇ -methylstyrene .
  • Mixtures of these alkenes are also suitable; it is preferred for propylene and/or butene-1 to be used.
  • the molar ratio of ethylene to propylene normally is between 5:1 and 1:5. Preferably between 3:1 and 1:1.
  • a group X that can be polymerised with a co-ordination catalyst is any group that contains at least one double carbon-carbon bond that can be polymerised in the presence of a co-ordination catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst .
  • a co-ordination catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst
  • Examples of a group X that can be polymerised with a co-ordination catalyst are vinyl, norbornyl, dinorbornyl and dicyclopentadienyl .
  • R° is a chain having 2-20 C atoms and at least one double carbon-carbon bond, with none of the C atoms of the double bond forming part of a ring structure. It is preferred for R° to be chosen from chains that satisfy either formulae II or III:
  • R ⁇ -R 8/ Rio and R 14 may be the same or different and may be hydrogen or a hydrocarbon group having 1-5 C atoms;
  • R 11 -R 12 may be the same or different and may represent hydrogen or a hydrocarbon group having 1-5 C atoms and where R i3 represents a hydrocarbon group having 1-5 C atoms;
  • p and q are, independently of each other, 0 or 1 but not at the same time 0;
  • f 0-5, but if p and q are equal to 1 , f cannot be 0 ;
  • g 1-6;
  • n 1-5;
  • Monomer units of a polyunsaturated compound according to formula (I) serve to incorporate unsaturation in the copolymer and may be aliphatic or alicyclic.
  • An aliphatic polyunsaturated compound preferably is a compound with formula (I) , where X is vinyl and R° satisfies formula (II) or (III) and where the double carbon-carbon bonds present may be conjugated or unconjugated.
  • the double carbon-carbon bonds preferably are unconjugated.
  • Examples of aliphatic, conjugated polyunsaturated compounds are 1, 3 -butadiene, isoprene, 2-ethylbutadiene-l , 3 and piperylene.
  • Examples of aliphatic, unconjugated polyunsaturated compounds are 1 , 4 , 9-decatrienes, 1,4- hexadiene, 1 , 5-hexadiene, 4 -methyl -1 , 4-hexadiene, 4- ethylidene-10-methyl-l, 6, 9-decatriene, 9-methyl-l, 5,8- nonatriene, 4-ethylidene-l , 7-nonadiene, 4-ethylidene-8- methyl-1, 7-nonadiene .
  • 1 , 4-hexadiene or 4- ethylidene-8-methyl-l, 7-nonadiene is used as aliphatic, unconjugated polyunsaturated compound.
  • An alicyclic polyunsaturated compound preferably is a compound with formula (I) , where X may be monocyclic or polycyclic, preferably norbornyl , dinorbornyl and dicyclopentadienyl and R° satisfies formula (II) or (III) and where the double carbon- carbon bonds present may be conjugated or unconjugated.
  • the double carbon-carbon bonds preferably are unconjugated. Examples of such polyunsaturated compounds are unconjugated alicyclic dienes, alicyclic trienes or alicyclic tetraenes. Mixtures of the aforementioned polyunsaturated compounds may also be used.
  • Monomer units of a polyunsaturated compound are present in the copolymer in amounts of for example up to 30% by weight, preferably up to 15% by weight, in particular between 2 and 10% by weight relative to the other monomer units.
  • the copolymer needs to be vulcanized in order to obtain a rubber article that is dimensionally stable.
  • the dimensionally stable article is obtained by chemical cross-linking of freely movable macromolecules of the copolymer, as a result of which the article becomes a large, single macromolecules or network, as it were.
  • devulcanization is meant the reduction of the number of cross-links until there is obtained a product that is suitable for recycling. It is possible, for example, to blend the devulcanized rubber with an as-yet unvulcanized copolymer and then to, for example, extrude or roll the so-obtained blend of the devulcanized rubber and the as-yet unvulcanized rubber to form a product.
  • the number of cross-links of the rubber has been strongly reduced by devulcanization, it is also possible to process the devulcanized rubber as such in the manner described above to form a product.
  • the number of cross-links of the rubber is reduced by heating the rubber for a particular period of time.
  • a suitable measure of the rate of progress of this devulcanization process is the amount of polymer that dissolves in a suitable solvent such as tetrahydrofuran (THF) .
  • THF tetrahydrofuran
  • the amount of polymer that can dissolve through extraction with THF is dependent on the number of cross-links of the rubber that are severed. The higher the amount of dissolved polymer, the higher the number of cross-links that are severed.
  • the invention also relates to a devulcanized rubber of which the amount of polymer soluble in tetrahydrofuran is greater than 20% by weight, preferably greater than 30% by weight, in particular greater than 50% by weight.
  • devulcanizing agent there may be used any commercially applicable devulcanizing agent that is capable of severing the cross-links in a rubber that has been vulcanized with a sulphur-containing compound. It is not necessary for the devulcanizing agent to sever all cross-links in the vulcanized rubber.
  • the devulcanizing agent should preferably sever at least a proportion of the cross-links.
  • devulcanizing agents are chosen from the group comprising aromatic and aliphatic disulphides, thiols and amines.
  • aromatic and aliphatic disulphides are diphenyldisulphide, dixylyldisulphide, dibenzyldisulphide and dibutyldisulphide . It is preferred for diphenyldisulphide to be used.
  • the amount of devulcanizing agent to be added preferably is between 0 and 10% by weight, more preferably between 0 and 5% by weight.
  • the invention also relates to a blend of the devulcanized rubber obtained via the process as described and an as-yet unvulcanized rubber, vulcanizing agent, oil, carbon black and any additives.
  • Blending may be by customary techniques and equipment. Preferably, blending operations take place at a temperature of between 50°C and 120°C.
  • customary additives for the polymer composition such as stabilisers, colorants, processing aids such as mould release agents and retardants and fillers or reinforcing (fibrous) materials .
  • the blend of the invention may be used in the customary applications of vulcanized ethylene- alpha-olefin-diene copolymers .
  • Examples of such applications are bicycle tyres, mats, cable sheathing, hoses and shock dampers .
  • the amount of soluble polymer is determined as follows. After extraction with acetone, the rubber is dried in a vacuum oven. The dry, devulcanized rubber, which now is free of devulcanizing agent and oil, is weighed and then extracted with tetrahydrofuran in a Soxhlet extraction apparatus in a nitrogen atmosphere and with exclusion of light for 96 hours. After extraction, the rubber is again dried in a vacuum oven and weighed. The difference yields the amount of soluble polymer. For samples without carbon black and free of devulcanizing agant and oil, this amount is expressed as a percentage relative to the devulcanized rubber sample. For rubber with carbon black, the amount is expressed as the percentage of polymeric portion present in the rubber that is free of devulcanizing agent and oil.
  • the vulcanized rubber was then heated for 2 hours at 266°C and at a pressure of 7.6 MPa in the presence of 2.5% by weight of diphenyldisulphide in a closed oven saturated with nitrogen.
  • the amount of soluble polymer was determined as a measure of the degree of devulcanization.
  • the amount of tetrahydrofuran-soluble polymer relative to the polymeric portion was 55 ⁇ 2 % by weight.
  • Example I was repeated except that the amount of diphenyldisulphide was varied as shown in Table 1.
  • Table 1 Amount of THF-soluble polymer as a function of the amount of diphenyldisulphide
  • Example I was repeated except that the temperature was varied as shown in Table 2.
  • Example I was repeated except that the time was varied as shown in Table 3.
  • Example I was repeated except that no Sunthene 4240 oil and N330 carbon black were added to the EPDM polymer, the devulcanization temperature was 200°C and the amount of diphenyldisulphide was varied as shown in Table 4.
  • N330 carbon black were added to and blended in an internal blender with an EPDM polymer containing 3.3 % by weight of 4 -ethylidene- 8 -methyl -1, 7-nonadiene (EMN) and 56% by weight of ethylene.
  • EPN -ethylidene- 8 -methyl -1, 7-nonadiene
  • the blend was blended in a laboratory blender with 5 pph of zinc oxide, 1 pph of stearic acid, 0.5 pph of mercaptobenzothiazol, 1 pph of tetramethylthiuram disulphide and 1.5 pph of a sulphur-containing compound and then heated.
  • the amount of tetrahydrofuran-soluble polymer of the vulcanized rubber so obtained was between 2 and 3% by weight.
  • the vulcanized rubber was then heated for 2 hours at
  • Example VI was repeated except that the amount of diphenyldisulphide was varied as shown in Table 5.
  • Table 5 Amount of THF-soluble polymer as a function of the amount of diphenyldisulphide
  • Example VI was repeated except that the temperature was varied as shown in Table 6.
  • Example VI was repeated except that the time was varied as shown in Table 7.
  • Table 7 Amount of THF-soluble polymer as a function of time
  • Example VI was repeated except that no Sunthene 4240 oil and N330 carbon black were added to the EPDM polymer, the devulcanization temperature was 200°C and the amount of diphenyldisulphide was varied as shown in Table 8.
  • N330 carbon black were added to and blended in an internal blender with Keltan ® 4802 (an EPDM polymer containing 4.5% by weight of 5-ethylidene-2 -norbornene and 49 % by weight of ethylene) .
  • Keltan ® 4802 an EPDM polymer containing 4.5% by weight of 5-ethylidene-2 -norbornene and 49 % by weight of ethylene
  • the blend was blended in a laboratory blender with 5 pph of zinc oxide, 1 pph of stearic acid, 0.5 pph of mercaptobenzothiazol, 1 pph of tetramethylthiuram disulphide and 1.5 pph of a sulphur-containing compound and then heated.
  • the amount of tetrahydrofuran-soluble polymer of the vulcanized rubber so obtained was 1.0 % by weight.
  • the vulcanized rubber was then heated for 2 hours at 266°C and at a pressure of 7.6 MPa in the presence of
  • the amount of soluble polymer was determined as a measure of the degree of devulcanization.
  • the amount of tetrahydrofuran-soluble polymer was 18% by weight.
  • the amount of tetrahydrofuran-soluble polymer of the vulcanized rubber so obtained was 4.0% by weight .
  • the vulcanized rubber was then heated for 2 hours at 266°C and at a pressure of 7.6 MPa in the presence of 2.5% by weight of diphenyldisulphide in a closed oven saturated with nitrogen.
  • the amount of soluble polymer was determined as a measure of the degree of devulcanization.
  • the amount of tetrahydrofuran-soluble polymer was 21% by weight.
  • Comparative example C Comparative examples A and B were repeated except that no Sunthene 4240 oil and N330 carbon black were added to the EPDM polymer, the devulcanization temperature was 200°C and the amount of diphenyldisulphide was varied. Table 15 Amount of THF-soluble polymer as a function of the amount of diphenyldisulphide

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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de dévulcanisation d'un caoutchouc obtenu par vulcanisation au moyen d'un composé contenant du soufre, d'un copolymère qui contient des unités monomères d'éthylène, des unités monomères d'une α-oléfine et des unités monomères d'un composé polyinsaturé, ledit procédé consistant à porter le caoutchouc à des températures élevées entraînant la dévulcanisation et permettant d'obtenir un produit recyclable. Les unités monomères d'un composé polyinsaturé sont des unités monomères selon la formule X-R0, dans laquelle: X désigne un groupe possédant 2-20 atomes de carbone, qui peut provoquer une polymérisation grâce à un catalyseur de coordination; et R0 désigne une chaîne possédant 2-30 atomes de carbone et contenant au moins une double liaison carbone-carbone, aucun atome de carbone de cette double liaison ne faisant partie d'une structure cyclique.
PCT/NL2000/000621 1999-09-28 2000-09-05 Procede de devulcanisation d'un caoutchouc Ceased WO2001023464A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74581/00A AU7458100A (en) 1999-09-28 2000-09-05 Process for devulcanizing a rubber

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1013155A NL1013155C2 (nl) 1999-09-28 1999-09-28 Werkwijze voor het devulkaniseren van een rubber.
NL1013155 1999-09-28

Publications (1)

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WO2001023464A1 true WO2001023464A1 (fr) 2001-04-05

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003014206A1 (fr) * 2001-08-03 2003-02-20 Watson Brown Hsm Ltd. Traitement d'elastomeres reticules
WO2011158024A1 (fr) * 2010-06-14 2011-12-22 Smithers Rapra Technology Limited Procédés concernant des produits de caoutchouc
EP4116336A1 (fr) 2021-07-09 2023-01-11 The Goodyear Tire & Rubber Company Procédé de dévulcanisation de produit en caoutchouc et produit
US11713362B2 (en) 2020-12-28 2023-08-01 Industrial Technology Research Institute Depolymerizer and recycled rubber
US12291631B2 (en) 2022-01-06 2025-05-06 Industrial Technology Research Institute Reclaiming agent and reclaimed rubber

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104205A (en) * 1976-01-06 1978-08-01 The Goodyear Tire & Rubber Company Microwave devulcanization of rubber
US4469817A (en) * 1981-11-19 1984-09-04 Toyoda Gosei Co., Ltd. Method for reclamation of vulcanized rubber
EP0931809A2 (fr) * 1998-01-26 1999-07-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Composition de caoutchouc et méthode pour sa production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104205A (en) * 1976-01-06 1978-08-01 The Goodyear Tire & Rubber Company Microwave devulcanization of rubber
US4469817A (en) * 1981-11-19 1984-09-04 Toyoda Gosei Co., Ltd. Method for reclamation of vulcanized rubber
EP0931809A2 (fr) * 1998-01-26 1999-07-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Composition de caoutchouc et méthode pour sa production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VERBRUGGEN M. A. L. ET AL: "Mechanisms involved in the recycling of NR and EPDM", RUBBER CHEMISTRY AND TECHNOLOGY, vol. 72, no. 4, 1999, pages 731 - 740, XP002141062 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003014206A1 (fr) * 2001-08-03 2003-02-20 Watson Brown Hsm Ltd. Traitement d'elastomeres reticules
WO2011158024A1 (fr) * 2010-06-14 2011-12-22 Smithers Rapra Technology Limited Procédés concernant des produits de caoutchouc
US11713362B2 (en) 2020-12-28 2023-08-01 Industrial Technology Research Institute Depolymerizer and recycled rubber
EP4116336A1 (fr) 2021-07-09 2023-01-11 The Goodyear Tire & Rubber Company Procédé de dévulcanisation de produit en caoutchouc et produit
US12291631B2 (en) 2022-01-06 2025-05-06 Industrial Technology Research Institute Reclaiming agent and reclaimed rubber

Also Published As

Publication number Publication date
AU7458100A (en) 2001-04-30
NL1013155C2 (nl) 2001-03-29

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