WO2014084727A1 - Procédé de dévulcanisation d'un vulcanisat de caoutchouc - Google Patents

Procédé de dévulcanisation d'un vulcanisat de caoutchouc Download PDF

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Publication number
WO2014084727A1
WO2014084727A1 PCT/NL2013/050829 NL2013050829W WO2014084727A1 WO 2014084727 A1 WO2014084727 A1 WO 2014084727A1 NL 2013050829 W NL2013050829 W NL 2013050829W WO 2014084727 A1 WO2014084727 A1 WO 2014084727A1
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WIPO (PCT)
Prior art keywords
rubber
rubber vulcanizate
compound
vulcanizate
devulcanization
Prior art date
Application number
PCT/NL2013/050829
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English (en)
Inventor
Sitisaiyidah SAIWARI
Wilma Karola DIERKES
Jacobus Wilhelmus Maria Noordermeer
Original Assignee
Recybem B.V.
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Filing date
Publication date
Application filed by Recybem B.V. filed Critical Recybem B.V.
Publication of WO2014084727A1 publication Critical patent/WO2014084727A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/08—Depolymerisation
    • 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
    • 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
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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 relates to the field of rubber polymers, and particularly to a method of devulcanizing a rubber vulcanizate, such as obtained from waste tire rubber. Description of the Related Art
  • Tires, hoses, belts and other rubber products are therefore conveniently discarded after they have been worn out during their service lifetime.
  • a major amount of rubber vulcanizate from tires and other rubber products is shredded or ground to obtain rubber crumb with relatively small particle size.
  • This crumb is incorporated into various products as a filler, and can for instance be used in rubber formulations for new tires, or in other rubber products. Since the thermosetting network in the filler is substantially unaffected by shredding or grinding, the filler does not co-cure to an appreciable extent with the surrounding material.
  • One aim of the present invention is to provide a method of devulcanizing a rubber vulcanizate that yields de-vulcanized rubber products with better properties than those obtained from known methods.
  • the invention thereto provides a method of devulcanizing a rubber vulcanizate of main chains and sulfur-containing cross-links, the method comprising mixing the rubber vulcanizate with a devulcanizing agent to a temperature sufficient to cause the devulcanizing agent to react with the sulfur of the sulfur-containing cross-links and to substantially prevent abstraction of hydrogen atoms from the rubber vulcanizate main chains by contacting the rubber vulcanizate with an oxidation stabilizer.
  • cured rubber is effectively de-vulcanized.
  • the temperature at which abstraction of hydrogen atoms from the rubber vulcanizate main chains is substantially prevented is defined as the threshold temperature above which an increase in cross-link density is observed in the (partly) de-vulcanized rubber, compared to the cross-link density obtained at a lower devulcanization temperature, as will be explained in more detail below.
  • the devulcanizing agent used in the method according to the invention may be chosen from a wide range of devulcanizing agents, and the choice will for instance depend on the type of rubber vulcanizate to be de-vulcanized.
  • Suitable devulcanizing agents comprise sulfur containing compounds such as disulfides and thiols, amine and amide compounds, phenolic compounds and alcohols.
  • An organosulfur compound is preferably used and in a particular embodiment of the method according to the invention, the organosulfur compound comprises a polysulfide.
  • Yet another embodiment of the invention provides a method, wherein the polysulfide is a disulfide, preferably diphenyldisulfide (DPDS)
  • substantially preventing abstraction of hydrogen atoms from the rubber vulcanizate main chains is effected by substantially eliminating oxygen during the devulcanization step.
  • Another embodiment of the invention provides a method, wherein the oxidation stabilizer comprises a phenolic compound, a phosphorous compound, or an aromatic amine compound, or a combination of both.
  • the phenolic compound comprises tetrakis[methylene-3-(3,5-ditertbutyl-4- hydroxyphenyl)propionate]methane (Irganox 1010) and/or n-octadecyl-[beta]-(4- hydroxy-3,5-ditertbutyl phenyl)propionate (Irganox 1076).
  • Hindered phenolic stabilizers act as hydrogen donor. The stabilizer reacts with peroxy radicals to form hydroperoxides and prevents the abstraction of the hydrogen from polymer molecules.
  • the phosphorous compound comprises a phosphorous acid and its salts (phosphites).
  • the phosphorous compound comprises tris(2,4-ditert-butylphenyl)phosphite (Irgafos 168).
  • Phosphite compounds function as hydroperoxide decomposers, the stabilizer prevents the split of hydroperoxide into extremely active radicals: alkoxy and hydroxyl.
  • the aromatic amine compound comprises an arylene-amine compound, more preferably a p-phenylene diamine compound.
  • a particularly preferred embodiment of the invention provides a method wherein a combination of an organosulfur compound and an oxidation stabilizer is used.
  • Another aspect of the invention relates to a method, wherein the temperature during devulcanization is between 180°C and 320°C, and more preferred between 220°C and 280°C. Raising the temperature may increase the speed of devulcanization but preferably measures have to be taken to substantially prevent abstraction of hydrogen atoms from the rubber vulcanizate main chains.
  • the relatively high temperatures of the indicated range help in decreasing shear stresses acting on the rubber vulcanizate during devulcanization, which lowers the risk for main chain scission.
  • Still another aspect of the invention relates to a method, wherein the amount of devulcanizing agent ranges from 0.01 to 10 wt%, relative to the total weight of the rubber vulcanizate, and more preferred from 0.1 to 5 wt%, relative to the total weight of the rubber vulcanizate.
  • Yet another aspect of the invention relates to a method, wherein the amount of oxidation stabilizer ranges from 0.1 to 5 wt%, relative to the total weight of the rubber vulcanizate, and more preferred from 0.5 to 2 wt%, relative to the total weight of the rubber vulcanizate.
  • the devulcanization is performed in an internal mixer or an extruder.
  • the extruder is preferably of the co- rotating twin screw extruder type.
  • the screw configuration of the extruder may among others comprise transporting elements, kneading elements and pressuring elements.
  • Another aspect of the invention is directed to a method, further comprising mixing the rubber vulcanizate with a swelling agent and/or solvent. It is known that energies of carbon-sulfur and sulfur-sulfur bonds in a rubber vulcanizate network are lower than that of carbon-carbon bonds and that carbon-sulfur and sulfur-sulfur bonds are more easily broken up by shear stress during mixing in for instance an extruder. Adding a swelling agent increases mobility of the devulcanizing agent and other aids and allows higher shear stresses, leading to an increased efficiency of devulcanization of the rubber.
  • the solvent or swelling agent is selected from the group consisting of one or more of toluene, naphtha, terpenes, benzene, cyclohexane, diethyl carbonate, ethyl acetate, ethyl benzene, isophorone, isopropyl acetate, methyl ethyl ketone and derivatives thereof.
  • the method of the invention may be used for devulcanizing any known rubber vulcanizate.
  • the rubber vulcanizate comprises natural rubber ( R), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR, CIIR or BIIR), ethylene-propylene rubber (EPM), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber ( BR), acrylic rubber (ACM), ethylene-propylene-diene rubber (EPDM), or mixtures thereof.
  • R natural rubber
  • BR butadiene rubber
  • IR isoprene rubber
  • IIR butyl rubber
  • IIR ethylene-propylene rubber
  • SBR styrene-butadiene rubber
  • chloroprene rubber CR
  • BR nitrile rubber
  • ACM acrylic rubber
  • EPDM ethylene-propylene-diene rubber
  • Filled rubbers may comprise fillers such as carbon black, silica, organic and inorganic fibers, and others.
  • Table I shows the chemical names and structures of thermal stabilizers used in embodiments of the method in accordance with the invention.
  • SBR styrene-butadiene-rubber compound
  • Table III shows the devulcanization conditions, as used in the Examples.
  • Figure 1 shows a schematic diagram of the sol fraction obtained as a function of the devulcanization temperature for de-vulcanized SBR obtained by several embodiments of the invention compared to untreated vulcanized SBR;
  • Figure 2 shows a schematic diagram of the crosslink density obtained as a function of devulcanization temperature for de-vulcanized SBR obtained by several embodiments of the invention compared to untreated vulcanized SBR;
  • Figure 3 shows a schematic diagram of the sol fraction generated during
  • Figure 4 shows a schematic diagram of the sol fraction as a function of the
  • devulcanization temperature for de-vulcanized SBR obtained by several embodiments of the invention compared to untreated vulcanized SBR;
  • Figure 5 shows a schematic diagram of the crosslink density as a function of devulcanization temperature for de-vulcanized SBR obtained by several embodiments of the invention compared to untreated vulcanized SBR;
  • Figure 6 shows a schematic diagram of the sol fraction generated during
  • styrene-butadiene-rubber SBR
  • SBR 1723 an oil extended emulsion-polymerized SBR containing 37.5 phr of Treated Distillate Aromatic Extract (TDAE) oil, obtained from Dow Chemical, Germany.
  • TDAE Treated Distillate Aromatic Extract
  • the polymer contained 23.5 wt% styrene and 76.5 wt% butadiene, and its Mooney viscosity ML(l+4) measured at 100°C was 40 MU.
  • Zinc oxide (ZnO) and stearic acid were obtained from Flexsys, the Netherlands.
  • the curatives sulfur and N-tert-butyl-2-benzothiazylsulfenamide (TBBS) were obtained from Merck.
  • TDAE oil used as devulcanizing processing oil was supplied by Hansen&Rosenthal, Germany.
  • Diphenyldisulfide (DPDS) used as devulcanization aid was obtained from Sigma- Aldrich, Germany.
  • the three types of oxidation stabilizers used were obtained from Ciba Specialty Chemicals Inc., Switzerland. Chemical names and structures of the stabilizers are given in Table I.
  • Plasticorder 350S mixer with a mixing chamber volume of 350 cm 3 .
  • the compounding formulation was as shown in Table II.
  • the mixer was operated at a rotor speed of 60 rpm; a fill factor of 0.75 and an initial temperature of 50°C were used.
  • the final compound temperature before dumping was in the range of 70-90 °C.
  • the compound was tested for its cure characteristics using a RPA 2000 dynamic mechanical curemeter from Alpha Technologies at 170 °C, 0.833 Hz and 0.2 degree strain, according to ISO 6502.
  • the compounds were then vulcanized for t C;90 + 5 minutes in a Wickert WLP1600 laboratory compression molding press at 170 °C and 100 bar, into 2 mm thick sheets.
  • the vulcanized SBR sheets were subsequently ground in a Universal Cutting Mill Pulverisette 19 (Fritsch, Germany) with a 2 mm screen.
  • the particle size of the ground rubber was in the range of 0.85-2.00 mm.
  • thermo-chemical devulcanization was performed in a batch process in an internal mixer Brabender Plasticorder PL-2000, having a chamber volume of 50 ml and a cam-type rotor. A fill factor of 0.7 and a constant rotor speed of 50 rpm were used.
  • the devulcanization temperature was varied from 180 to 300 °C and the devulcanization time was 5 minutes. The variations of the experimental conditions used are given in Table III.
  • Rubber soluble fraction The soluble (Sol) and insoluble (Gel) fractions of the reclaimed materials were determined by extraction in a Soxhlet apparatus.
  • the vulcanized and de- vulcanized SBR samples were extracted initially for 48 hrs in acetone in order to remove low molecular polar substances like remains of accelerators and curatives, followed by an extraction for 72 hrs in tetrahydrofuran (THF) to remove the apolar components: oil and non-cross-linked polymer residues or soluble polymer released from the network by the devulcanization process.
  • THF tetrahydrofuran
  • the extraction was followed by drying the samples in a vacuum oven at 40°C and determining the weight loss until constant weight.
  • the sol fraction was defined as the sum of the soluble fractions in acetone and THF. Correction for the oil contained in the original SBR was made.
  • the gel fraction was calculated by the following equation: weight of rubber dissolved in solvents
  • Crosslink density The extracted SBR samples were subsequently swollen in toluene for 72 hrs at room temperature. The weight of the swollen vulcanizates was measured after removal of surface liquid with absorption paper. The crosslink density was calculated according to the Flory-Rehner equations (2) and (3):
  • V s solvent molar volume
  • the sol fractions and crosslink densities of the remaining gel as a function of the devulcanization temperature of SBR devulcanizates in presence of DPDS are depicted in figures 1 and 2, respectively.
  • the increase of the rubber sol fraction and decrease of crosslink density indicate the extent to which the rubber network is broken.
  • Thermo-chemical devulcanization of sulfur-cured SBR using DPDS as devulcanization aid shows an increase of rubber soluble fraction with increasing devulcanization temperature up to 220°C; above this temperature, the sol fractions decrease again. Furthermore, it can be seen in Figure 2 that above this temperature of 220°C a significant increase in crosslink density is observed again.
  • the DPDS devulcanization agent appears to scavenge radicals formed during the reclaiming process.
  • high devulcanization temperature i.e. above 220°C
  • a more extensive generation of reactive radicals occurs.
  • the experimentally determined sol fractions of DPDS de-vulcanized SBR at various devulcanization temperatures as a function of the relative decrease in crosslink density are shown in figure 3. Also shown are theoretical curves (solid and dashed line), which have been generated by the method developed by M.M.
  • Horikx J.Polym.Sci., 19, 1956, 335, in which the rubber sol fraction of the devulcanizates and the crosslink density of the rubber gel fractions are correlated.
  • Horikx in particular derived a theoretical relationship between the soluble fraction generated after degradation of a polymer network and the relative decrease in crosslink density, as a result of either main-chain scission or crosslink breakage. This treatment of polymer degradation can equally well be applied to rubber reclaiming, where also a mix of main-chain scission and crosslink breakage takes place.
  • main-chain scission takes place, the relative decrease in crosslink density is given by:
  • Si is the soluble fraction of the rubber network before degradation or reclaiming
  • Sf is the soluble fraction of the reclaimed vulcanizate
  • Vi is the crosslink density of the network prior to treatment
  • Vf is the crosslink density of the reclaimed vulcanizate.
  • the soluble fraction is related to the relative decrease in crosslink density by:
  • an increase of the devulcanization temperature to 220 °C results in a shift of the data point to the right hand side of the graph, which indicates a small increase in sol fraction and a large decrease of crosslink density.
  • a further increase of the devulcanization temperature to 260°C results in a shift of the experimental data points to the left hand side of the graph, which is contrary to the expected decrease of cross-link density.
  • This reversion phenomenon is even more pronounced for devulcanization temperatures up to 300°C and beyond; for this temperature the data point is even found at the utmost left hand side of the graph. This may indicate a less efficient devulcanization above temperatures of 220°C, in which the crosslink density of the de-vulcanized rubber is increased rather than decreased with increasing treatment temperature.
  • Particularly preferred embodiments of the method of the invention use combinations of DPDS and oxidation stabilizers as devulcanization aids. A more efficient
  • devulcanization aid with oxidation stabilizers results in a more efficient and controlled devulcanization.
  • devulcanization aid at least for devulcanization temperatures up to 220°C.
  • the devulcanization efficiency of known methods of devulcanizing a rubber vulcanizate is affected by uncontrolled degradation and oxidation.
  • the method according to the invention in which a rubber vulcanizate is treated with an organosulfur compound to a temperature sufficient to cause the organosulfur compound to react with the sulfur of the sulfur-containing cross-links and to substantially prevent abstraction of hydrogen atoms from the rubber vulcanizate main chains offers improved devulcanizing efficiency.
  • Embodiments wherein an organosulfur compound such as DPDS is used as devulcanization aid show a decrease of the crosslink density in first instance but an increase of the devulcanization temperature results in an increase of crosslink density again above a temperature threshold which depends on the specific rubber vulcanizate used, but for SBR is 220°C.
  • Embodiments using a combination of an organosulfur compound and one or more oxidation stabilizers results in a more efficient devulcanization, especially at high devulcanization temperatures. A decrease in crosslink density without creating more sol fraction is provided.
  • organosulfur compound scavenges formed reactive radicals, preventing recombination of the rubber network, while the stabilizers appear to suppress the reaction of oxygen, which accelerates the degradation of the polymers and recombination into new cross-links.
  • a synergistic effect is also observed which results in an increasingly efficient devulcanization of a rubber vulcanizate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de dévulcanisation d'un vulcanisat de caoutchouc appliqué sur les chaînes principales et les réticulations contenant du soufre. Le procédé consiste à traiter le vulcanisat de caoutchouc avec un agent de dévulcanisation à une température suffisante pour provoquer la réaction de l'agent de dévulcanisation avec le soufre des réticulations contenant du soufre et pour empêcher sensiblement l'abstraction des atomes d'hydrogène des principales chaînes du vulcanisat de caoutchouc par mise en contact du vulcanisat de caoutchouc avec un stabilisateur à l'oxydation. Le procédé de l'invention concerne une dévulcanisation plus efficace, particulièrement à des températures de dévulcanisation élevées.
PCT/NL2013/050829 2012-11-27 2013-11-18 Procédé de dévulcanisation d'un vulcanisat de caoutchouc WO2014084727A1 (fr)

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NL2009888A NL2009888C2 (en) 2012-11-27 2012-11-27 A method of devulcanizing a rubber vulcanizate.
NL2009888 2012-11-27

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018093260A1 (fr) 2016-11-18 2018-05-24 Rijksuniversiteit Groningen Procédé de récupération de caoutchouc, et compositions de caoutchouc reconstitué pouvant être obtenues par ce procédé
EP3514200A1 (fr) * 2018-01-22 2019-07-24 Kargro Recycling B.V. Procédé de dévulcanisation d'un caoutchouc vulcanisé
EP3662004A4 (fr) * 2017-07-31 2020-11-25 Rubreco Inc. Nettoyage des évents de moules en caoutchouc
US11713362B2 (en) 2020-12-28 2023-08-01 Industrial Technology Research Institute Depolymerizer and recycled rubber

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019030701A1 (fr) 2017-08-10 2019-02-14 Avonisys Ag Méthode d'élimination de caoutchouc de moules de vulcanisation

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US4211676A (en) * 1977-06-07 1980-07-08 Bridgestone Tire Company Limited Process for reclaiming scrap vulcanized rubber
US20090082475A1 (en) * 2007-09-20 2009-03-26 Zhang Yuncan Process for devulcanization of rubber
WO2010020987A1 (fr) * 2008-08-18 2010-02-25 Innovert Investments A.L. Ltd Procédé et composition chimique pour la régénération de matériaux élastomères durcis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4211676A (en) * 1977-06-07 1980-07-08 Bridgestone Tire Company Limited Process for reclaiming scrap vulcanized rubber
US20090082475A1 (en) * 2007-09-20 2009-03-26 Zhang Yuncan Process for devulcanization of rubber
WO2010020987A1 (fr) * 2008-08-18 2010-02-25 Innovert Investments A.L. Ltd Procédé et composition chimique pour la régénération de matériaux élastomères durcis

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018093260A1 (fr) 2016-11-18 2018-05-24 Rijksuniversiteit Groningen Procédé de récupération de caoutchouc, et compositions de caoutchouc reconstitué pouvant être obtenues par ce procédé
CN110198974A (zh) * 2016-11-18 2019-09-03 格罗宁根大学 用于使橡胶再生的方法及由此得到的翻新橡胶组合物
US11041059B2 (en) 2016-11-18 2021-06-22 Rijksuniversiteit Groningen Method for reclaiming rubber, and renewed rubber compositions obtainable thereby
EP3662004A4 (fr) * 2017-07-31 2020-11-25 Rubreco Inc. Nettoyage des évents de moules en caoutchouc
EP3514200A1 (fr) * 2018-01-22 2019-07-24 Kargro Recycling B.V. Procédé de dévulcanisation d'un caoutchouc vulcanisé
NL2020302B1 (en) * 2018-01-22 2019-07-29 Kargro Recycling B V A method of devulcanizing a rubber vulcanizate
US11713362B2 (en) 2020-12-28 2023-08-01 Industrial Technology Research Institute Depolymerizer and recycled rubber

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