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WO2003014206A1 - Traitement d'elastomeres reticules - Google Patents

Traitement d'elastomeres reticules Download PDF

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Publication number
WO2003014206A1
WO2003014206A1 PCT/GB2002/003477 GB0203477W WO03014206A1 WO 2003014206 A1 WO2003014206 A1 WO 2003014206A1 GB 0203477 W GB0203477 W GB 0203477W WO 03014206 A1 WO03014206 A1 WO 03014206A1
Authority
WO
WIPO (PCT)
Prior art keywords
vulcanised
granules
product
rubber
elastomer
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/GB2002/003477
Other languages
English (en)
Inventor
Christopher Brown
David Brown
Nigel Hodgkinson
William Ferguson Watson
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.)
Watson Brown HSM Ltd Great Britain
Original Assignee
Watson Brown HSM Ltd Great Britain
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 Watson Brown HSM Ltd Great Britain filed Critical Watson Brown HSM Ltd Great Britain
Publication of WO2003014206A1 publication Critical patent/WO2003014206A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2030/00—Pneumatic or solid tyres or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/732—Floor coverings
    • B29L2031/7324—Mats
    • 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 treatment of cross-linked elastomers, and in particular vulcanised rubber (both natural and synthetic, and not limited to vulcanisation with sulphur), and to products produced from such treated materials.
  • the invention relates to the re-cycling of rubber products, such as for instance vehicle tyres.
  • one of the most widely used methods to generate usable material from scrap rubber is to chop and grind the rubber into small granules or fine powders. Fine powders may be incorporated at relatively low levels into new rubber products (sometimes after additional chemical treatment to improve the material properties).
  • a major area of application for granulated material derived from such scrap rubber is in the production of articles such as tiles, mats or other ground surfaces (often used in school playgrounds and athletic tracks) in which the granulated rubber crumb is combined with, and encapsulated by, a binder matrix (such as urethane) which is cured to bind the granules together in a suitable moulded or otherwise formed product.
  • a binder matrix such as urethane
  • a method of treating cross-linked elastomeric material comprising: subjecting the material to mechanical stresses in a processing apparatus to mechanochemically de-vulcanise a portion of the material; and controlling the processing operation such that a predetermined portion of the untreated material remains vulcanised as granules, to thereby produce a flowable material comprising granules of vulcanised elastomer dispersed in a matrix of de- vulcanised elastomer.
  • the mechanical stresses will generally be shear and/or extensional stresses.
  • the predetermined portion of untreated material remaining vulcanised in the treated material need not be predetermined precisely.
  • the predetermination may be to specify an approximate amount, a maximum amount and/or a minimum amount of material to be de-vulcanised.
  • a major application of the present invention is in the re-cycling of re-claimed rubber but the invention may be applied to the treatment of any elastomeric material which responds to mechanochemical processing.
  • the treated material can be readily re-constituted by a simple curing process to re-cure the de-vulcanised material and the resultant products may be completely homogeneous.
  • the treated material may be mixed with additional material prior to curing.
  • additional material may include cured elastomers or elastomer that has not previously been vulcanised and which may be cured together with the treated elastomer in a single stage.
  • Mechanochemistry is essentially a process of inducing chemical reactions in a material solely by the application of mechanical stresses.
  • One significant advantage of mechanochemistry is that there is no need to identify the nature of the cross-links as would be required for chemical de-vulcanisation.
  • Mechanochemistry has for many years been applied to non-vulcanised rubber stock as a means for modifying (usually reducing) the molecular weight of the polymer to facilitate easy processing.
  • the required stresses are imparted to the material in a machine such as a two-roll mill.
  • Mechanochemistry has also been proposed as a method of solubalising reclaimed rubber.
  • Such a process is disclosed in UK patent number 2,300,129 by William Watson.
  • William Watson discloses a method of re-claiming rubber by mechanically mixing the re-claimed material with a minor amount of raw rubber which provides a matrix into which rubber de-vulcanised by the mixing stresses dissolves. The result is a flowable material with properties very close to those of raw rubber which can then be re-cured, and otherwise treated, in conventional ways to produce products having substantially the same properties as the original product.
  • the present invention takes advantage of the possibilities offered by mechanochemistry in producing predictable changes to the chemical nature of a cross- linked elastomer by appropriate control of the processing conditions.
  • the invention recognises that rather than applying mechanochemistry to produce fully de-vulcanised product, the conditions can be controlled to produce a material comprising partly de-vulcanised rubber and partly granules or particles of the original re-claimed rubber.
  • any de- vulcanisation is due only to the mechanochemical process and not as a direct result of a temperature increase in the material.
  • surface regions of the vulcanised granules/particles generally will become tacky through at least partial de- vulcanisation by the mechanochemcial process. This is an additional advantage in that it improves the binding of the remaining vulcanised particles/granules.
  • products produced from a re-cycled material obtained in accordance with the present invention may replace the urethane bound rubber granule products mentioned above.
  • the proportion of de- vulcanised material acts to allow the material to flow (so that it may be processed in conventional rubber processing equipment) and also as a matrix which can be re- cured to bind the granules of rubber together thereby obviating the need to provide a separate binder such as the urethane binder mentioned above.
  • Products according to the present invention are therefore cheaper to produce and posses better physical properties than the prior art products mentioned above.
  • the invention modifies the known mechanochemical process to reach a practical compromise between the required time and energy input in treating the reclaimed material and the usefulness of the final product.
  • the products of the present invention also tend to be stronger and more robust than the prior art materials formed using a urethane binder material.
  • the method in accordance with the present invention may be controlled to vary the amount of the original material which is de-vulcanised and the amount which remains as vulcanised granules. Products of quite different physical characteristics can thereby be produced from treated material in accordance with the present invention.
  • the portion of the original material which is de- vulcanised should preferably be sufficient to ensure that the treated material is sufficiently flowable to allow subsequent processing using conventional rubber processing equipment.
  • the de- vulcanised portion of the material is therefore preferably at least 10% of the material (by weight) although it may well be more than 90%.
  • the proportion of de- vulcanised material to vulcanised granules has an effect on the density of products made from the treated material.
  • the portion of de-vulcanised material should preferably be between 10% and 75% of the material (by weight).
  • the size of the granules in the un-vulcanised portion of the material also has an effect on the characteristics of the treated material, and thus products made from that material. This can also be varied by appropriate control of the mixing process. It is envisaged that for most commercial applications of the treated material (for instance for the production of impact absorbing tiles) the granule size should be less than about 15mm and preferably less than 10mm (e.g. of the order of 0.8 to 7mm).
  • the treated material according to the present invention may be formed (e.g. moulded or extruded) and cured in accordance with entirely conventional methods.
  • the material could be cured and moulded in a single process, in a press for example.
  • the bulk density of the final product can further be varied by controlling the fill-in factor of the mould and the forming process.
  • the material can, for instance, be compressed to reduce the number or size of voids (i.e. air spaces formed at the granule sites) to increase density.
  • the material in untreated form may be in sheets, slabs, granules, irregular sized and shaped fragments etc. No particular pre-processing is required
  • the material should, however, be as free from unwanted contaminants as possible. For instance, if the untreated material is reclaimed rubber from scrap tyres, all metal should preferably be removed from the material. However, this is not essential as the de-vulcanised material can serve to bind such contaminants into the final product.
  • a further important advantage of the present invention is that there is no requirement to mix the original vulcanised material with an amount of raw rubber or similar elastomer.
  • the treated material of the present invention may be derived entirely from re-claimed material.
  • products according to the present invention preferably comprise entirely re-cycled elastomer.
  • products of the present invention are themselves 100% re-cyclable by the method according to the present invention.
  • additives common to conventional rubber formulation technology may be added to the material, for instance to suit requirements of subsequent re-curing of the de-vulcanised portion of the material (which may be based on any conventional curing system such as, but not limited to, one utilising sulphur as a vulcanising agent).
  • mixers could be used to impart the required stresses on the material in the mixing process of the present invention.
  • the material could be cycled through a conventional two-roll mill.
  • UK patent number 2,300,129 mentioned above discloses a form of mixer specifically designed for mechanochemistry.
  • the mixer generally moves the material through a series of high stress and relaxation zones whilst an integrated cooling system maintains optimum mixing temperatures.
  • the basic high shear mixer described in this patent has been further developed by Watson Brown HSM Limited which produces mixers suitable for operation of the present invention.
  • the mixer comprises a first member that is mounted for movement relative to a second member and has a grooved surface that is opposed to, and separated by a gap from, a grooved surface of the second member.
  • the arrangement is such that one or more grooves and lands of each grooved surface are traversed within the gap by one or more grooves and lands of the other surface during movement of the first member for shearing and splitting material entered into the gap.
  • Each groove has walls that are inclined both to the respective grooved surface and outwardly from one another upwardly of the groove.
  • the grooves are also configured to draw material entering the gap progressively further in to the gap forcing it along the grooves to well up for mixing distributively with material moving backwardly of the grooves in the gap.
  • a further advantage of the above form of mixer is that the temperature of the material being mixed can be readily controlled by way of an integral water cooling system. For instance, by maintaining temperatures below a curing temperature curatives can be introduced during the high stress mechanochemical process without any danger of the material actually curing within the mixer. This obviates the need to provide a separate mixing stage for addition of a curative (e.g. vulcanising agent such as sulphur) to the material after it has been subjected to the mechnochemical mixing process. This is in addition to the advantages of low temperature operation mentioned above.
  • a curative e.g. vulcanising agent such as sulphur
  • Granulated rubber re-claimed from scrap tyres was mixed in a Watson Brown HMS Limited high shear mixer.
  • the untreated material supplied to the mixer comprised granules of between 3mm and 7mm diameter.
  • the material in the mixer was maintained at a temperature below 80°C (and preferably below 60°C) by the recirculating water cooling system.
  • the mixing was stopped before all of the material had been de- vulcanised, so that a portion of the original material remained as granules (of a size of approximately 7mm) dispersed within a matrix of well fluidised material.
  • the treated material was then transferred to a conventional two-roll mill where curatives were added (i.e. sulphur and associated accelerators).
  • curatives i.e. sulphur and associated accelerators.
  • the material was then moulded by conventional means, using a heated press.
  • 0.5- 2% sulphur was added to the treated material which was then cured at 150°C for 10 to 30 minutes.
  • a range of products were produced from the treated material having a density determined primarily by the fill factor of the mould, ranging from a relatively soft compressible material (which typical may be porous) to a substantially solid article.
  • the final product may be coloured on one or more of its surfaces by the use of a coloured material, which may be derived entirely from re-cycled rubber having been generated by the process according to the present invention.
  • the covered layer may thus be co-moulded along with the bulk of the material.
  • appropriate pigments could be added to the material before it is cured.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention se rapporte à un procédé servant à traiter (recycler) des matériaux élastomères réticulés et consistant à cet effet à soumettre un tel matériau à des contraintes mécaniques dans un appareil de traitement pour dévulcaniser par voie mécanochimique une partie dudit matériau. L'opération de traitement est contrôlée pour qu'une partie prédéterminée du matériau non traité reste vulcanisée sous la forme de granules, afin de produire un matériau coulant comprenant des granules d'élastomère vulcanisé dispersées dans une matrice d'élastomère dévulcanisé.
PCT/GB2002/003477 2001-08-03 2002-07-29 Traitement d'elastomeres reticules Ceased WO2003014206A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0119102A GB0119102D0 (en) 2001-08-03 2001-08-03 Treatment of cross-linked elastomers
GB0119102.2 2001-08-03

Publications (1)

Publication Number Publication Date
WO2003014206A1 true WO2003014206A1 (fr) 2003-02-20

Family

ID=9919854

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2002/003477 Ceased WO2003014206A1 (fr) 2001-08-03 2002-07-29 Traitement d'elastomeres reticules

Country Status (2)

Country Link
GB (1) GB0119102D0 (fr)
WO (1) WO2003014206A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013075216A1 (fr) 2011-11-25 2013-05-30 Watson Brown Hsm Ltd. Procédé de dévulcanisation d'un matériau élastomère réticulé
EP2782732A1 (fr) 2011-11-25 2014-10-01 Rep International Appareil de traitement d'un matériau de rebut élastomère thermodurci et réticulé

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4104435A1 (de) * 1991-02-14 1992-08-20 Bayer Ag Verfahren zur herstellung von formkoerpern aus gummiabfaellen
WO1995004640A1 (fr) * 1993-08-05 1995-02-16 Movetech, Inc. Procede de recyclage de pneus
RU2098275C1 (ru) * 1991-04-24 1997-12-10 Фирма "Архтехстром" Способ регенерации вулканизованных отходов резины
RU2098272C1 (ru) * 1991-04-15 1997-12-10 Фирма "Архтехстром" Способ переработки отходов шинного производства
JPH10287765A (ja) * 1997-04-11 1998-10-27 Yamabishi Ind Co Ltd 加硫ゴムの再生方法
EP0887372A1 (fr) * 1995-12-19 1998-12-30 Kabushiki Kaisha Toyota Chuo Kenkyusho Caoutchouc dévulcanisé, procédé de production et procédé de fabrication d'objets moulés en caoutchouc régénéré à partir de caoutchouc dévulcanisé
US5904885A (en) * 1997-12-04 1999-05-18 Illinois Institute Of Technology Process for recycling of rubber materials
EP0997252A2 (fr) * 1998-10-28 2000-05-03 Bridgestone Corporation Caoutchouc régénéré et procédé pour régénérer du caoutchouc vulcanisé
WO2001023464A1 (fr) * 1999-09-28 2001-04-05 Dsm N.V. Procede de devulcanisation d'un caoutchouc
EP1201390A1 (fr) * 1999-06-08 2002-05-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Procede de recuperation de caoutchouc reticule

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4104435A1 (de) * 1991-02-14 1992-08-20 Bayer Ag Verfahren zur herstellung von formkoerpern aus gummiabfaellen
RU2098272C1 (ru) * 1991-04-15 1997-12-10 Фирма "Архтехстром" Способ переработки отходов шинного производства
RU2098275C1 (ru) * 1991-04-24 1997-12-10 Фирма "Архтехстром" Способ регенерации вулканизованных отходов резины
WO1995004640A1 (fr) * 1993-08-05 1995-02-16 Movetech, Inc. Procede de recyclage de pneus
EP0887372A1 (fr) * 1995-12-19 1998-12-30 Kabushiki Kaisha Toyota Chuo Kenkyusho Caoutchouc dévulcanisé, procédé de production et procédé de fabrication d'objets moulés en caoutchouc régénéré à partir de caoutchouc dévulcanisé
JPH10287765A (ja) * 1997-04-11 1998-10-27 Yamabishi Ind Co Ltd 加硫ゴムの再生方法
US5904885A (en) * 1997-12-04 1999-05-18 Illinois Institute Of Technology Process for recycling of rubber materials
EP0997252A2 (fr) * 1998-10-28 2000-05-03 Bridgestone Corporation Caoutchouc régénéré et procédé pour régénérer du caoutchouc vulcanisé
EP1201390A1 (fr) * 1999-06-08 2002-05-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Procede de recuperation de caoutchouc reticule
WO2001023464A1 (fr) * 1999-09-28 2001-04-05 Dsm N.V. Procede de devulcanisation d'un caoutchouc

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 01 29 January 1999 (1999-01-29) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013075216A1 (fr) 2011-11-25 2013-05-30 Watson Brown Hsm Ltd. Procédé de dévulcanisation d'un matériau élastomère réticulé
US8673989B2 (en) 2011-11-25 2014-03-18 New Rubber Technologies Holdings, Inc. Method of devulcanizing a cross-linked elastomeric material
EP2782732A1 (fr) 2011-11-25 2014-10-01 Rep International Appareil de traitement d'un matériau de rebut élastomère thermodurci et réticulé

Also Published As

Publication number Publication date
GB0119102D0 (en) 2001-09-26

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