WO2010037819A1 - Procédé pour la préparation de bitume modifié par polymère - Google Patents

Procédé pour la préparation de bitume modifié par polymère Download PDF

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Publication number
WO2010037819A1
WO2010037819A1 PCT/EP2009/062765 EP2009062765W WO2010037819A1 WO 2010037819 A1 WO2010037819 A1 WO 2010037819A1 EP 2009062765 W EP2009062765 W EP 2009062765W WO 2010037819 A1 WO2010037819 A1 WO 2010037819A1
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WO
WIPO (PCT)
Prior art keywords
polymer
sulphur
bitumen
process according
styrene
Prior art date
Application number
PCT/EP2009/062765
Other languages
English (en)
Inventor
Vincent Jean Raymond Begon
Norbert Clavel
Hechem Nadjar
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2010037819A1 publication Critical patent/WO2010037819A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • Bitumen may be modified by the addition of a polymer to improve the mechanical properties of the bitumen.
  • the most commonly incorporated polymers are thermoplastic elastomers, particularly styrenic block copolymers such as styrene-butadiene-styrene (SBS) and styrene-isoprene- styrene (SIS) .
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene- styrene
  • the polymer may be cross- linked by the addition of a cross-linking agent, typically elemental sulphur.
  • Sulphur cross-linked polymer-modified bitumens emit increased quantities of hydrogen sulphide during storage or when used, when compared to polymer-modified bitumens that have not been cross-linked.
  • a scavenging agent such as zinc oxide may be added to the formulation to reduce the emission of hydrogen sulphide.
  • the present inventors have sought to provide alternative methods of producing cross-linked polymer-modified bitumen, wherein the emissions of hydrogen sulphide are minimised.
  • the present invention provides a process for preparing sulphur cross-linked polymer- modified bitumen, comprising a step of mixing sulphur with bitumen and polymer, characterised in that the sulphur is in the form of pellets of sulphur that comprise at least 0.25wt% carbon black, and in that the amount of sulphur that is mixed with the bitumen and polymer is from 0.5 to 20wt%, based upon the weight of the polymer.
  • pellets of sulphur comprising at least 0.25wt% carbon black (based upon the weight of the sulphur pellet) can be used as a cross-linking agent and hydrogen sulphide emissions are low even in the absence of a separate scavenging agent.
  • the bitumen used in the process of the invention may be a residue from the distillation of crude oil, a cracked residue, naturally occurring bitumen or a blend of various bitumen types.
  • bitumen that may be conveniently used in the present invention include distillation or "straight run" bitumen, precipitation bitumen, e.g. propane bitumen, oxidised or blown bitumen, naphthenic bitumen, paraffinic bitumen or mixtures thereof.
  • the bitumen in the bitumen composition may be prepared by blending a bitumen with a flux oil, e.g. an aromatic, napthenic or paraffinic flux oil.
  • the penetration at 25°C of the bitumen is preferably between 10 and 400. ⁇ If the bitumen is a blend of bitumen and flux oil, the penetration is preferably between 10 and 400 after the flux oil has been blended with the bitumen.
  • the weight ratio of bitumen to polymer in the blend of bitumen and polymer is preferably at least 4:1, more preferably at least 8:1.
  • Bitumen is typically the least expensive component in the composition so it is desirable to maximise the quantity of bitumen.
  • a weight ratio of greater than 40:1, preferably 20:1 bitumen to polymer is not desirable as there will be insufficient polymer to improve the mechanical properties of the polymer-modified bitumen.
  • the polymer is a polymer that can be cross-linked with sulphur.
  • the polymer is preferably a thermoplastic elastomer.
  • the thermoplastic elastomer may be a homopolyiner such as polybutadiene or may be a random copolymer such as styrene butadiene rubber.
  • the thermoplastic elastomer is most preferably a block copolymer comprising at least one polymer block derived from a vinyl aromatic hydrocarbon and at least one polymer block derived from a conjugated diene.
  • the block copolymer may be linear or radial, symmetric or asymmetric, and may have a structure represented by the formula A-B, A-B-A, B-A-B, A-B-A-B etc. wherein A is the polymer block of a vinyl aromatic hydrocarbon and B is the polymer block of a conjugated diene.
  • the block copolymer preferably contains up to 50% by weight of vinyl aromatic hydrocarbon, more preferably from 25-40wt ⁇ of vinyl aromatic hydrocarbon.
  • the vinyl aromatic hydrocarbon is preferably styrene, o-methylstyrene, p-methylstyrene, p-tert- butylstyrene, 1, 3-dimethylstyrene, ⁇ -methylstyrene, vinylnapthalene or vinylanthracene, and most preferably is styrene.
  • Mixtures of vinyl aromatic hydrocarbons may be used.
  • the conjugated diene preferably has from 4-8 carbon atoms, and more preferably is 1, 3-butadiene, 2-methyl- 1, 3-butadiene (isoprene) , 2, 3-dimethyl-l, 3-butadiene, 1, 3-pentadiene or 1, 3-hexadiene. Most preferably the conjugated diene is 1, 3-butadiene or isoprene. Mixtures of conjugated dienes may be used.
  • the polymer is styrene-butadiene- styrene or styrene-isoprene-styrene.
  • the polymer may be a polymer comprising glycidyl functional groups; preferably either a copolymer wherein at least some of the monomers are glycidyl-containing monomers, or a grafted polymer wherein glycidyl-contai ⁇ ing groups have been grafted onto a polymer backbone.
  • Preferred copolymers are copolymers of ethylene and glycidyl acrylate or methacrylate, or terpolymers of ethylene, alkyl acrylate or methacrylate and glycidyl acrylate or methacrylate.
  • the alkyl acrylate is preferably Ci-e alkyl.
  • Preferred grafted polymers comprise glycidyl acrylate or methacrylate grafted onto a polyethylene backbone.
  • the molecular weight of the polymer is preferably from 50,000 to 500,000.
  • Sulphur in the form of pellets of sulphur that comprise at least 0.25wt% carbon black, is added to the blend of bitumen and polymer.
  • the amount of sulphur that is added is from 0.5 to 20wt%, preferably from 1 to 5wt%, based upon the weight of the polymer.
  • pellets is to any type of sulphur material that has been cast from the molten state into some kind of regularly sized particle, for example flakes, slates or sphere-shaped sulphur such as prills, granules, nuggets and pastilles or half pea sized sulphur.
  • the sulphur pellets typically comprise from 50 to 99wt% of sulphur, based upon the weight of the sulphur pellets, preferably from 60wt% and most preferably from 70wt%; and typically to 95wt%, and preferably to 90wt%. A preferred range is from 60 to 90wt%.
  • the sulphur pellets comprise at least 0.25wt% carbon black.
  • the carbon black plasticises the sulphur, i.e. the sulphur in the pellets is typically amorphous rather than crystalline.
  • the sulphur pellets preferably comprise from 0.25 to 2wt% carbon black, and more preferably comprise from 0.4 to 0.8wt% carbon black. According to WO 03/14321 such sulphur pellets are added as the majority component to bitumen to manufacture paving binders. It does not teach that minor amounts of sulphur pellets that contain at least 0.25wt% carbon provide crosslinking in polymer- modified bitumen or inhibit hydrogen sulphide formation.
  • the sulphur pellets preferably comprise sulphur that has been degassed to remove hydrogen sulphide.
  • the sulphur pellets may comprise other components, for example, they may comprise amyl acetate in a concentration of at least about 0.08wt% based upon the weight of the pellet. They may also comprise free radical inhibitors and/or redox catalysts, e.g. from 0.05 to 6wt% of a compound selected from iodine, amine compounds, copper salts, copper oxides, iron salts, iron oxides, cobalt salts and cobalt oxides. They may also comprise waxes such as paraffin waxes of ethylene bis stearamide. In one preferred embodiment, the sulphur pellets consist of sulphur and carbon black only.
  • Sulphur pellets are mixed with bitumen and polymer.
  • the polymer is added to molten bitumen, and mixed under lower shear to form a blend of bitumen and polymer, and the sulphur pellets are subsequently added and mixed under low shear.
  • the sulphur pellets may be added to molten bitumen and the polymer may be added subsequently, preferably with high shear mixing.
  • the sulphur pellets are preferably mixed with the bitumen and polymer at a temperature of about 180 0 C, and preferably not more than 200 0 C.
  • Example 1 The invention will now be described by reference to examples which are not intended to be limiting of the invention.
  • Example 1 The invention will now be described by reference to examples which are not intended to be limiting of the invention.
  • a cross-linked polymer-modified bitumen formulation was prepared comprising 76.8wt% bitumen (50/70 grade), 18.8wt% SBA (a very hard grade of bitumen), 3.2wt% styrene-butadiene-styrene (DlIOl from Kraton®) , l.lwt% paraffin wax and 0.1wt% sulphur pellets comprising carbon black.
  • a cross-linked polymer-modified bitumen formulation was prepared comprising 76.8wt% bitumen (50/70 grade) , 18.8wt% SBA, 3.2% styrene-butadiene-styrene (DlIOl from Kraton®), l.lwt% paraffin wax and 0.17wt% of elemental sulphur and zinc oxide.
  • bitumen formulation 5Og was placed in a metal tube, which was then sealed. The formulation was heated to 18O 0 C for 24 hours and then cooled. The hydrogen sulphide formed in the formulation was measured by using a Drager pump and reaction tubes that change colour when exposed to hydrogen sulphide. This indicated the presence of lOSppm hydrogen sulphide. The hydrogen sulphide reading in this instance was lower, but a scavenging agent (zinc oxide) was incorporated in this formulation.

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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)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un procédé pour la préparation de bitume modifié par polymère réticulé par du soufre. Le soufre, sous la forme de pastilles de soufre qui comprennent au moins 0,25 % en poids de noir de carbone, est mélangé avec du bitume et du polymère en une quantité de 0,5 à 20 % en poids, sur la base du poids du polymère.
PCT/EP2009/062765 2008-10-02 2009-10-01 Procédé pour la préparation de bitume modifié par polymère WO2010037819A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08305633.3 2008-10-02
EP08305633 2008-10-02

Publications (1)

Publication Number Publication Date
WO2010037819A1 true WO2010037819A1 (fr) 2010-04-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/062765 WO2010037819A1 (fr) 2008-10-02 2009-10-01 Procédé pour la préparation de bitume modifié par polymère

Country Status (1)

Country Link
WO (1) WO2010037819A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012138860A1 (fr) * 2011-04-07 2012-10-11 Shell Oil Company Composition bitumineuse
CN103044930A (zh) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 一种抗老化的嵌缝填充材料及其制备方法
WO2013083807A1 (fr) * 2011-12-08 2013-06-13 Shell Internationale Research Maatschappij B.V. Composition d'asphalte
WO2013132488A1 (fr) * 2012-03-06 2013-09-12 Rubind Inc. Composite de caoutchouc modifié et son procédé de fabrication
CN108059840A (zh) * 2016-11-09 2018-05-22 中国石油化工股份有限公司 一种改性沥青及其制备方法
EP3670606A1 (fr) 2018-12-19 2020-06-24 INDIAN OIL CORPORATION Ltd. Procédé de co-solubilisation pour la préparation de bitume modifié et produit ainsi obtenu

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015193A1 (fr) * 1994-11-10 1996-05-23 Elf Aquitaine Procede de preparation de compositions bitume/polymere, leur application
WO2003014231A1 (fr) * 2001-08-09 2003-02-20 Shell Canada Limited Additifs de soufre pour liants de revetement et leurs procedes de preparation
GB2384240A (en) * 2001-11-21 2003-07-23 Shell Int Research Preparation of polymer-modified bitumen compositions
WO2004018554A2 (fr) * 2002-08-26 2004-03-04 Shell Canada Limited Liants de pavage et leurs procedes de fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015193A1 (fr) * 1994-11-10 1996-05-23 Elf Aquitaine Procede de preparation de compositions bitume/polymere, leur application
WO2003014231A1 (fr) * 2001-08-09 2003-02-20 Shell Canada Limited Additifs de soufre pour liants de revetement et leurs procedes de preparation
GB2384240A (en) * 2001-11-21 2003-07-23 Shell Int Research Preparation of polymer-modified bitumen compositions
WO2004018554A2 (fr) * 2002-08-26 2004-03-04 Shell Canada Limited Liants de pavage et leurs procedes de fabrication

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012138860A1 (fr) * 2011-04-07 2012-10-11 Shell Oil Company Composition bitumineuse
CN103492494A (zh) * 2011-04-07 2014-01-01 国际壳牌研究有限公司 沥青组合物
CN103044930A (zh) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 一种抗老化的嵌缝填充材料及其制备方法
WO2013083807A1 (fr) * 2011-12-08 2013-06-13 Shell Internationale Research Maatschappij B.V. Composition d'asphalte
WO2013132488A1 (fr) * 2012-03-06 2013-09-12 Rubind Inc. Composite de caoutchouc modifié et son procédé de fabrication
CN104302838A (zh) * 2012-03-06 2015-01-21 鲁宾德公司 改性橡胶复合材料及其获得方法
CN108059840A (zh) * 2016-11-09 2018-05-22 中国石油化工股份有限公司 一种改性沥青及其制备方法
EP3670606A1 (fr) 2018-12-19 2020-06-24 INDIAN OIL CORPORATION Ltd. Procédé de co-solubilisation pour la préparation de bitume modifié et produit ainsi obtenu
US11084930B2 (en) 2018-12-19 2021-08-10 Indian Oil Corporation Limited Co-solubilization process for preparing modified bitumen and product obtained thereof

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