WO2010072832A1 - Composition de bitume modifiée et son procédé de fabrication - Google Patents

Composition de bitume modifiée et son procédé de fabrication Download PDF

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Publication number
WO2010072832A1
WO2010072832A1 PCT/EP2009/067904 EP2009067904W WO2010072832A1 WO 2010072832 A1 WO2010072832 A1 WO 2010072832A1 EP 2009067904 W EP2009067904 W EP 2009067904W WO 2010072832 A1 WO2010072832 A1 WO 2010072832A1
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WO
WIPO (PCT)
Prior art keywords
bitumen
weight
acid
composition
sbs
Prior art date
Application number
PCT/EP2009/067904
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English (en)
Inventor
Akira Seo
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 WO2010072832A1 publication Critical patent/WO2010072832A1/fr

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    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • This invention relates to a bitumen composition suitable for road paving, waterproofing materials, adhesives and the like.
  • Bitumen has hitherto been used in a wide variety of fields such as road paving and waterproofing.
  • Styrene- butadiene-styrene block copolymers have generally been used as a reinforcing material for the bitumen.
  • SES Styrene- butadiene-styrene block copolymers
  • the stability of the SBS decreases when it is dispersed in the bitumen, and in particular/ at the storage temperatures applicable during commercial uses lot the order of 150 to 1.80oC), the bitumen and SBS separate readily, so that there have been problems with the SBS floating up.
  • the aim of the present invention is to offer a bitumen composition suitable for road paving, waterproofing materials, adhesives and the like, and especially, a bitumen composition capable of improving stability and strength, and also a method of manufacture thereof as well as an asphalt composition comprising the bitumen composition.
  • the present invention provides a bitumen composition characterised in that it contains 2 to less than 8% by weight of a styrene-butadiene-styrene block copolymer (SBS) and 0.3 to 3% by weight of a polycyclic diterpene comprising one or more carboxyl groups and having in its molecular formula 20 carbon atoms, and the remaining portion comprising bitumen.
  • SBS styrene-butadiene-styrene block copolymer
  • the present invention provides an asphalt composition comprising a bitumen composition as described herein and filler and/or aggregate.
  • the bitumen composition comprises bitumen that contains not more than 5% by weight relative to the total weight of said bitumen composition of an aromatic- based oil. More preferably, the bitumen composition comprises bitumen that contains not more than 5% by weight relative to the total weight of said bitumen composition of an aromatic-based oil, wherein the aromatic-based oil is an extract obtained by solvent extraction of a solvent deasphalted oil obtained by deasphalting a vacuum distillation residual oil from a crude oil.
  • the bitumen composition of the present invention improves both storage stability by making the softening point difference between the top part and the bottom part of a container in a storage test not more than 3°C, and at the same time improves strength by making the DS value not less than 6000 (rotations/mm) , this value being a criterion for anti-rutting performance in road paving.
  • the bitumen composition; the method of manufacture thereof; and the asphalt composition are described in detail below by way of preferred embodiments of the invention.
  • the inventor has carried out intensive tests and research in order to overcome the above-mentioned problems and to manufacture bitumen compositions in such manner that they can exhibit the desired stability and strength.
  • SBS styrene-butadiene-styrene block copolymer
  • polycyclic diterpene comprising one or more carboxyl groups and having in its molecular formula 20 carbon atoms (resin acid)
  • the SBS has a chemical structure in which a butadiene block is sandwiched between styrene blocks, and by attaching a polycyclic diterpene (resin acid) of carbon number 20 and having carboxyl groups to the double bonds forming this butadiene block, it becomes possible to improve the stability of the SBS in the bitumen composition, that is its tendency not to separate and float up, and ils performance.
  • a polycyclic diterpene (resin acid) of carbon number 20 and having carboxyl groups to the double bonds forming this butadiene block
  • the amount of SBS incorporated per the total weight of the bitumen composition of this invention is less than 2% by weight, in practice the degree of improvement in temperature susceptibility and enhancement of physical strength is inadequate, and problems will arise in that it is not possible to improve the temperature dependence of the bitumen's properties and characteristics, and it becomes difficult to obtain suitable properties and characteristics over a wide range of temperatures.
  • the amount of SBS incorporated exceeds 8% by weight, the viscosity of the bitumen composition ultimately obtained becomes too large, and this will also cause a considerable deterioration in workability when using it for paving roads.
  • the polycyclic diterpene is incorporated to the amount of 0.3 to 3% by weight relative to the total weight of the bitumen composition of this invention. If the amount of this polycyclic diterpene is less than 0.3% by weight, the stability of the bitumen composition is not sufficiently improved. On the other hand, if the amount of polycyclic diterpene exceeds 3% by weight, the cost of the bitumen composition increases without a further significant increase in stability. In other words, even if the amount of polycyclic diterpene exceeds 3% by weight, stability will not be improved significantly beyond this, yet it will be disadvantageous as regards raw material costs .
  • bitumen For raising the softening point of bitumen or when a bitumen having specific properties is to be produced the bitumen may be oxidized with an oxygen-containing gas to produce blown bitumen. Bitumen may be combined with aggregate or filler to provide asphalt.
  • asphalt The term "asphalt" in the present description is used no describe a mixture comprising bitumen and aggregate or filler.
  • bitumen composition of this invention can always restrict the softening point differential to 3°C or less. Also, the bitumen composition of this invention produced by effecting the method of manufacture mentioned above can improve the strength. The strength of this bitumen composition is assessed from the DS value on the basis of the wheel-tracking test described in "Hoso Hyoka - Shiken-ho Benran" [Handbook of Methods of Evaluating and Testing Pavement] , edited by Ninon Doro Kyokai [Japan Road Association] .
  • This DS value can be obtained from the undermentioned Formula (2), and so can be obtained from the number of rotations of tyre travel in the period from 45 minutes to 60 minutes relative to the amount of deformation ⁇ nan) of the bitumen composition in the period from 45 minutes to 60 minutes.
  • the higher this DS value the less the amount of deformation of the bitumen composition, and so the more resistant the material is to rutting, which means its strength is higher.
  • No. of tyre passes in the period from 45 min to 60 min (rev ⁇ Anount of deformation ir. the period from 45 i_in to 60 tr.in
  • bitumen composition of this invention in particular if extract is restricted to not more than 5% by weight, it becomes possible, in mixtures with aggregate of dense granularity (maximum grain size of aggregate 13 min) as used on general road paving, to regulate more or less the above-mentioned DS value to not less than 6000 (rotations/minute ⁇ .
  • the point has been made in "Hoso Hyoka - Shiken-ho Benran" [Handbook of Methods of Evaluating and Testing Pavement] , edited by Nihon Doro Kyokai [Japan Road Association] that if the DS value is not less than 6000 (rotations/minute) , virtually no problems will arise as regards the strength aspect, of the bitumen composition.
  • bitumen composition of this invention when mixed with aggregate, i.e. the asphalt composition of the invention, is especially suitable for road paving, but use of the bitumen composition is not limited to this and the bitumen composition is of course capable of being used for waterproofing materials, adhesives and so on.
  • a styrene-butadiene-styrene block copolymer was used in which the bromine number was 220 (g/100 g: JIS K0070), ⁇ he molecular weight was approximately 150000 and the amount of styrene was 32% by mass and in which the amount of styrene block copolymer present on both terminals of the elastomer molecules was 16% by mass .
  • Experiments 1 to 6 in which acid A (straight chain) was mixed therein were prepared, along with Experiments 1 to 5, in which rosin B was mixed in, Experiment 6, in which rosin C was mixed in, Experiment 7, in which abietic acid was mixed in, and Experiment 8, in which dehydroabietic acid was mixed in.
  • the proportions of straight bitumen, propane-deasphalted bitumen (PDA) and extract in the blend were such as to make ⁇ he needle penetration 40 to 50.
  • the acid A referred to here was a mixture comprised of 7% by weight of monomer acid of straight-chain carbon number 18, 76% by weight of dimer acid of carbon number 36 and 7% by weight of trimer acid of carbon number 54, with acid number 190 (mgK0H/g: JIS K0070) and iodine number 110 (g/100g: JIS K0070) .
  • the average molecular weight was approximately 590.
  • Rosin B was a disproportionated gum rosin with acid number 156 ⁇ rrgKOH/g: JI3K0070) and softening point 77.0oC (JIS K2207) .
  • Rosin C was a tall oil rosin with acid number 170 ⁇ mgKOH/g: JISK0070) , saponification number 178 (mgKOH/g: JlS K0070) ar.d softening point 77.0oC (JIS K2207) .
  • the manufacturing conditions for all compositions were mixing and agitation for about 2 hours with a mixing temperature of 195oC and a homomixer speed of 3500 rotations per minute.
  • the amount manufactured was 1.8 kg in all cases.
  • Table 1 also shows the results of the measurement of properties for each of the Comparative Examples and Examples of Embodiment manufactured.
  • the properties measured were needle penetration (1/10 mm), softening point (oC), viscosity at 18OoC (mPa.s), storage stability, and DS value.
  • data were taken for 25°C measured under the conditions of JIS K2207.
  • For the softening point measurements were also made under the conditions of JIS K2207.
  • the viscosity was measured under the conditions of JPI-5S-54-99 "Bitumen - Method for Testing Viscosity using a Rotating Viscometer”.
  • the measurement temperature was 180oC and measurements were undertaken at 20 spindle rotations/minute using a spindle SC4-21.
  • bitumen composition of this invention (approx. 250 g) was injected and sealed up to a depth of 12 cm In an aluminium cylinder can of internal diameter 5.2 cm and height 13 cm, and heated for 48 hours at 170oC. Then the softening points of the top 4 cm and the bottom 4 cm of the bitumen composition inside the aluminium cylinder were measured in accordance with JI3 K2207. Table 1 shows the absolute value of the differential value between the softening points of the top part and the bottom part, that is the absolute softening-point differential.
  • a wheel tracking test is a test designed to confirm experimentally the degree to which this rutting occurs. It is a test carried out in order to evaluate the dynamic stability which is an indicator of flow-resistance properties in paving materials. Specifically, a tyre to which a specified load has been applied is run backwards and forwards over the experimental sample (test piece) for 1 hour in a constant temperature tank maintained at 6OoC, and the amount of deformation is measured. The DS value is calculated on the basis of the above-mentioned Mathematical Formula (2) from the amount of deformation in the period from 45 minutes to 60 minutes from the start of the test. In Table 1 given above, first of all the trend of
  • Comparative Examples 1 to 4 shows that the DS value improves as the extract is reduced. However, reducing the extract showed a tendency for the absolute value of the difference between, the softening point of the top part and the softening point of the bottom part to increase. In Comparative Example 4 in particular, the extract was reduced to 4% by weight, but as a result, whilst the DS value was improved to 7875 (rotations per minute) , the absolute softening-point differential deteriorated to 19.9oC. Also, as shown by Comparative Examples 5 and 6, if the extract is reduced to 4% by weight, it means that even if acid A, that is the proportion of carboxyl groups contained, is increased or reduced, it is not possible to improve the storage stability.
  • SIS styrene-isoprene-styrene block copolymer
  • the bromine number was 220 (g/100 g: JIS K0070)
  • the molecular weight was approximately 220000
  • the amount of styrene was 15% by mass
  • the amount of the styrene block copolymer present on both terminals of the elastomer molecules was 7.5% by mass.
  • Pi to P3 were examples relating to addition of guru rosin, but there was virtually no change in softening point regardless of the amount of gum rosin added or whether or not any was added.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention a pour objet une composition de bitume caractérisée en ce qu'elle contient de 2 à moins de 8 % en poids d'un copolymère séquencé de styrène-butadiène-styrène (SBS) et de 0,3 à 3 % en poids d'un diterpène polycyclique comprenant un ou plusieurs groupes carboxyle et ayant dans sa formule moléculaire 20 atomes de carbone, le reste étant du bitume. La présente invention a, en outre, pour objet un procédé de fabrication d'une composition de bitume, ledit procédé étant caractérisé en ce que de 2 à 8 % en poids d'un copolymère séquencé de styrène-butadiène-styrène (SBS) et en ce que de 0,3 à 3 % en poids d'un diterpène polycyclique comprenant un ou plusieurs groupes carboxyle et ayant dans sa formule moléculaire 20 atomes de carbone sont incorporés dans le bitume à une température comprise entre 190 et 210°C. L'invention décrit également une composition d'asphalte comprenant la composition de bitume selon l'invention et un agrégat et/ou une charge et un procédé de fabrication de ladite composition d'asphalte.
PCT/EP2009/067904 2008-12-24 2009-12-23 Composition de bitume modifiée et son procédé de fabrication WO2010072832A1 (fr)

Applications Claiming Priority (2)

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JP2008-328553 2008-12-24
JP2008328553A JP4361958B1 (ja) 2008-12-24 2008-12-24 アスファルト組成物及びその製造方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125167A1 (fr) * 2009-05-01 2010-11-04 Shell Internationale Research Maatschappij B.V. Composition styrène-butadiène
WO2011054911A1 (fr) * 2009-11-06 2011-05-12 Shell Internationale Research Maatschappij B.V. Composition d'asphalte
WO2014013399A1 (fr) * 2012-07-14 2014-01-23 Indian Oil Corporation Limited Procédé pour la production de diverses qualités de bitume en termes de viscosité
US9481794B2 (en) 2014-11-03 2016-11-01 Flint Hills Resources, Lp Asphalt binders containing a glyceride and fatty acid mixture and methods for making and using same

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5615690B2 (ja) * 2010-12-27 2014-10-29 昭和シェル石油株式会社 ポリマー改質アスファルト組成物
JP6071538B2 (ja) * 2012-12-26 2017-02-01 昭和シェル石油株式会社 ポリマー改質アスファルト組成物
JP6309329B2 (ja) * 2014-04-08 2018-04-11 昭和シェル石油株式会社 改質アスファルト組成物
JP6545059B2 (ja) * 2015-09-29 2019-07-17 昭和シェル石油株式会社 ポリマー改質アスファルト組成物
JP6127194B1 (ja) * 2016-04-08 2017-05-10 前田道路株式会社 再生舗装用混合物および舗装体
JP6912951B2 (ja) * 2016-09-26 2021-08-04 出光興産株式会社 ポリマー改質アスファルト組成物
WO2018055976A1 (fr) * 2016-09-26 2018-03-29 昭和シェル石油株式会社 Composition d'asphalte modifié par un polymère

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH10237309A (ja) 1996-12-29 1998-09-08 Bridgestone Corp 排水性舗装用アスファルトバインダ−
JP2000053865A (ja) 1998-08-06 2000-02-22 Nisshin Kasei Kk 道路舗装用改質アスファルト、その製造方法、並びに道路舗装用改質アスファルトにおける相分離抑制方法
US20020058734A1 (en) * 2000-09-01 2002-05-16 Harlan C. Wayne Asphalt emulsion
WO2008077913A1 (fr) * 2006-12-26 2008-07-03 Shell Internationale Research Maatschappij B.V. Composition d'asphalte et feuille adhésive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10237309A (ja) 1996-12-29 1998-09-08 Bridgestone Corp 排水性舗装用アスファルトバインダ−
JP2000053865A (ja) 1998-08-06 2000-02-22 Nisshin Kasei Kk 道路舗装用改質アスファルト、その製造方法、並びに道路舗装用改質アスファルトにおける相分離抑制方法
US20020058734A1 (en) * 2000-09-01 2002-05-16 Harlan C. Wayne Asphalt emulsion
WO2008077913A1 (fr) * 2006-12-26 2008-07-03 Shell Internationale Research Maatschappij B.V. Composition d'asphalte et feuille adhésive

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FRONTIER REFINING, INC.: "Material Safety Data Sheet, Asphalt Cement, AC-10", 11 September 2003 (2003-09-11), pages 1 - 12, XP002580476, Retrieved from the Internet <URL:http://www.frontieroil.com/attachments/contentmanagers/106/PrdctsSpec_AsphMSDS.pdf> [retrieved on 20100429] *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010125167A1 (fr) * 2009-05-01 2010-11-04 Shell Internationale Research Maatschappij B.V. Composition styrène-butadiène
WO2011054911A1 (fr) * 2009-11-06 2011-05-12 Shell Internationale Research Maatschappij B.V. Composition d'asphalte
WO2014013399A1 (fr) * 2012-07-14 2014-01-23 Indian Oil Corporation Limited Procédé pour la production de diverses qualités de bitume en termes de viscosité
US9481794B2 (en) 2014-11-03 2016-11-01 Flint Hills Resources, Lp Asphalt binders containing a glyceride and fatty acid mixture and methods for making and using same
US10167390B2 (en) 2014-11-03 2019-01-01 Flint Hills Resources, Lp Asphalt binders containing a glyceride and fatty acid mixture and methods for making and using same
US11578210B2 (en) 2014-11-03 2023-02-14 Flint Hill Resources, Lp Asphalt binders containing a glyceride and fatty acid mixture and methods for making and using same

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JP2010150346A (ja) 2010-07-08

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