EP0961812A1 - Granules de bitume stabilises par adjonction de polymere - Google Patents

Granules de bitume stabilises par adjonction de polymere

Info

Publication number
EP0961812A1
EP0961812A1 EP98903960A EP98903960A EP0961812A1 EP 0961812 A1 EP0961812 A1 EP 0961812A1 EP 98903960 A EP98903960 A EP 98903960A EP 98903960 A EP98903960 A EP 98903960A EP 0961812 A1 EP0961812 A1 EP 0961812A1
Authority
EP
European Patent Office
Prior art keywords
bitumen
composition
polymer
compositions
styrene
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.)
Withdrawn
Application number
EP98903960A
Other languages
German (de)
English (en)
Inventor
Zhi-Zhong Liang
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.)
Polyphalt Inc
Original Assignee
Polyphalt Inc
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 Polyphalt Inc filed Critical Polyphalt Inc
Publication of EP0961812A1 publication Critical patent/EP0961812A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to compositions of polymer stabilized bitumen granulates and processes for their preparation, as well as commercial application thereof .
  • Asphalt is a black and sticky cementitious material that varies widely in consistency from springy hard to soft "solid" at normal room temperature.
  • Polymers such as rubbers or plastics, are added to improve the performance of the bitumen without changing traditional means for storage and transportation.
  • German Patent DE-PS 29 33 339 there is described the preparation of a pulverulant bitumen concentrate by spraying the hot liquid bitumen onto about 10% to 80 wt% of silica so that the silica is completely covered with bitumen.
  • the asphalt coated composites tend to stick together during storage, due to the static pressure forces.
  • novel bituminous compositions of high dispersed polymer concentration which are able to be pelletized or granulated and the pellets or granules so formed retain their free flowing condition.
  • the pellets or granules may be readily diluted with bitumen to a lower polymer loading level while the dispersed polymer remains stabilized and is able to impart performance-enhancing properties to the resulting bituminous composition.
  • a bituminous composition suitable for granulating or pelletizing into stable free-flowing pellets or granules which comprises about 10 to about 50 wt% of at least one crystalline and/or rigid polymer which has been stabilized or incorporated into the bitumen using at least one rubber in an amount of about 3 to about 25 wt%.
  • the crystalline or rigid polymer (s) are present preferably in an amount of about 15 to about 30 wt% while the rubber (s) are present preferably in an amount of about 5 to about 15 wt%.
  • Bitumen is the major component of the composition and may be present in an amount of from about 45% to about 85%, preferably about 50 to about 75% by wt .
  • the bitumen composition retains the ability to improve performance as a polymer modified asphalt, resists polymer phase separation upon dilution with asphalt, and acts as a binder after the composition has been melted.
  • bitumen which is used herein may have a wide penetration range, from soft to hard base. Bitumen is the major component of the composition from which the pellets or granules are formed, and may be present in an amount of up to about 85 wt% of the composition.
  • bitumen compositions of the invention exhibits considerable homogeneity and storage stability upon dilution with bitumen to a lower polymer concentration and pellets formed therefrom are free-flowing and are readily and rapidly dispersible in bitumen for use.
  • any other shapes and forms may be provided, such as bricks, pucks and sheets of bituminous composition.
  • bitumen used herein means a class of black or dark-colored (solid, semi-solid or viscous) cementitious substances, natural or manufactured, composed principally of high molecular weight hydrocarbons of which asphalts, tars, pitches and asphaltites are typical.
  • asphaltt used herein means a dark, brown to black, cementitious material, solid or semi-solid in consistency, in which the predominating constituents are bitumens that occur in nature, as such, or are obtained as residue in petroleum refining.
  • the provision of the high levels of dispersed polymer phase achieved herein can be effected using a variety of different stabilization systems for the dispersed polymer phases, as discussed in detail below.
  • Such stabilization systems include steric stabilization, depletion stabilization and domain stabilization.
  • one or more additional polymers may be incorporated into the steric ⁇ stabilized compositions of the aforementioned patents.
  • Such additional polymers are generally copolymers and may contain residual unsaturation.
  • Such additional copolymers are often incompatible with bitumen and hence normally separate or coalesce rapidly when stirring of the composition is stopped.
  • WO 94/22957 when such copolymers are incorporated into the stabilized polyolefin compositions of WO 93/07219, they become stabilized and resist separation from the bitumen.
  • copolymers which can be employed herein are already somewhat compatible with bitumen or can be rendered so by suitable processing.
  • the presence of the dispersed polyolefin phase in bituminous compositions comprising such materials at worst does not destabilize such materials and frequently may improve such stability.
  • Copolymers which may be incorporated into the bituminous compositions according to the invention include elastomeric copolymer, including: - styrenic copolymers, such as styrene-butadiene rubber (SBR) , styrene-butadiene-styrene block copolymers (SBS) , styrene-ethylene-butadiene- styrene block copolymers (SEBS) and styrene- isoprene-styrene block copolymers (SIS) ; - olefinic copolymers, such as polypropylene copolymers, ethylene-vinyl acetate compolymers (EVA) , ethylene methacylate copolymers (EMA) and ethylene propylene diene copolymers (EPDM) .
  • SBR styrene-butadiene rubber
  • SBS styrene-
  • compositions of WO 94/22957 may but do not necessarily employ components, such as process oils, which render the polymers more compatible with the bitumen.
  • the polymeric materials may be present in the bitumen composition in the form of particle dispersions, strand-like dispersions, solutions and combinations in which the (co) polymer (s) is stabilized against separation.
  • WO 97/28220 the disclosure of which is incorporated herein by reference, wherein the inventor herein is namely as inventor, there is described the stabilization of polyolefins in bitumen by the mechanism of depletion stabilization by the utilization of a macromolecular material decreased in the bituminous phase and stabilizing the dispersed polyolefin against separation without the necessity of forming chemical bonds or physical attachments between the macromolecular material and the particulate polyolefin.
  • the macromolecular material dissolved in the bituminous phase provides a potential energy barrier to coalescence and flocculation of the dispersed polymer phase to maintain a stable dispersion of the particulate polyolefin phase.
  • the macromolecules used in the depletion stabilization of the dispersion of polyolefin particles in bitumen may be any desired material, including the unsaturated polymers or copolymers which are elastomeric, such as a polybutadiene, a styrene- butadiene-styrene (SBS) block copolymer, random styrene- butadiene copolymers (SBR) , or other polybutadiene based copolymer, which may be provided in the form of devulcanized or otherwise dissociated rubber vulcanate.
  • SBS styrene- butadiene-styrene
  • SBR random styrene- butadiene copolymers
  • other polybutadiene based copolymer which may be provided in the form of devulcanized or otherwise dissociated rubber vulcanate.
  • macromolecular material which may be employed includes natural rubber, polyisoprenes and nitrile- butadiene rubbers. Such macromolecules may have a molecular weight of about 5,000 to about 300,000 or higher, provided that the molecules are soluble in or can be fully digested into the bitumen.
  • the crystalline polyolefins used in the invention may be virgin or recycled polyethylene (PE) , polypropylene (PP) , comingled PE/PP and/or maleic anhydride functionalized polyethylene in the case of steric stabilization, which may be either high or low density and/or high or low melt flow.
  • the percentage of the functionalized polyethylene based on the total amount of the crystalline polyolefin polymers used generally is in the range from 3 to 100% by wt, preferably from 10 to 20% by wt, based on the total amount of crystalline polymers used.
  • the functionalized polyethylene is the anchor polymer in the steric stabilization systems, which functions as a receiving structure to combine with non-functionalized polyethylene which is blended in.
  • An effective dispersion temperature for the polyethylene or other polyolefin is obtained at least about 10°C above the melting or fusion temperature of the polyolefin being dispersed, depending on factors, such as polymer molecular weight, matrix viscosity and shear force of mixing.
  • a grade of polyethylene having a melting or fusion point of 130° to 135°C can be dispersed at a temperature of above about 140°C.
  • a stabilizer system in the present invention including steric stabilization and depletion stabilization.
  • Most polyethylenes thus may be dispersed and stabilized by a stabilizer in the present invention.
  • Most polyethylene used in consumer products have fusion temperatures in the acceptable range and polyethylene blends, such as are obtained as pelletized, flaked or powdered of recycled material, are suitable for dispersal in bitumens and may be stabilized according to the present invention.
  • the synthetic rubbers which serve as co- stabilizers with the functionalized polyethylene for the dispersion of the crystalline polymers in bitumen in steric stabilization may be a diene rubber, which may have a wide range of molecular weights, as described in the above-mentioned U.S.
  • BR polybutadiene
  • SBS styrene-diene rubbers
  • SBR styrene-diene rubbers
  • treated diene rubber vulcanate such as devulcanized rubber, tire rubber produced according to the procedure of WO 94/14896, combined with a small proportion of amine-functionalized diene based polymer, such as amine functionalized poly (butadiene-co-acrylonitride) , from about 3% to about 35% by wt., preferably from about 5 to about 20% by wt . , based on the total amount of the rubber stabilizer component.
  • Two rubbers used as co- stabilizers, namely the unfunctionalized and the functionalized rubber are co-cross-linked and in-situ compatibilized into bitumen, which may be effected in presence of sulfur or other suitable reagent.
  • WO 97/30121 the disclosure of which is incorporated herein by reference, wherein the inventor named herein is the inventor, there is described the provision of a composition of an elastomeric triblock copolymer comprising at least two polystyrene segments and stabilized and compatibilized in bitumen.
  • a dispersed particulate polymer phase consisting of polystyrene or the rigid styrene-based copolymers miscible in the molten state with polystyrene is dispersed in the bituminous phase and is normally incompatible with the bituminous phase and is stabilized against separation from the bituminous phase by the elastomeric triblock copolymer by domain stabilization.
  • bitumen-soluble elastomeric copolymer containing a styrene segment serves a dual function, namely (1) effects a uniform dispersion of polystyrene- based rigid polymers normally incompatible with bitumen and (2) provides a styrene domain as a receiving unit for stabilization of the dispersed polystyrene-based rigid polymer against separation from the bitumen.
  • the polystyrene domains which are dispersed throughout the bitumen by reason of the stabilization or compatibilization of the elastomeric triblock copolymer in the bitumen enable the normally-incompatible rigid polystyrene macromolecules to be incorporated into the bitumen by receiving the polystyrene particulates into the domains.
  • the domains in the rubberized bitumen continuous phase become larger once the rigid polystyrene macromolecules are blended in and increase in dimension with increasing levels of dispersed rigid polystyrene.
  • Elastomeric triblock copolymers may comprise about 20 to about 80% of terminal styrene blocks, preferably about 24 to about 45%.
  • block copolymers examples include styrene-butadiene-styrene triblock copolymers (SBS) , styrene-ethylene/butylene-styrene triblock copolymers (SEBS) and styrene-isoprene-styrene block copolymers (SIS) .
  • SBS styrene-butadiene-styrene triblock copolymers
  • SEBS styrene-ethylene/butylene-styrene triblock copolymers
  • SIS styrene-isoprene-styrene block copolymers
  • Elastomeric block copolymers which may be used in the composition of the present invention may have a molecular weight (Mn) of from about 30,000 to about 375,000, preferably about 75,000 to about 275,000.
  • the rigid styrenic polymeric which are stably dispersed in bitumen according to the invention may be polystyrene homopolymers, such as crystal polystyrene and polystyrene foam, or may be grafted copolymers and physical blends/alloys with various rubbers, or may be polymer of styrene derivatives, such as poly(alpha- methylstyrene) , poly (p-tert-butylstyrene) and polychlorostyrene .
  • the rigid styrenic polymers also may be comprise styrene based rigid copolymers, such as poly (styrene-co-vinylacetate) and poly (styrene-co- vinylthiophene) .
  • the styrenic polymers may be natural or recycled polymer, including comingled blends of styrenic polymers.
  • the SEBS, SBS or SIS triblock copolymers also may be used to disperse and form stable dispersions of other polymers in place of polystyrene, provided that the polymer is miscible with polystyrene in the molten state and hence particulates can be received by the polystyrene domains.
  • One such polymer is polyphenylene oxide (PPO) , which is difficult to disperse in bitumen but which is miscible with polystyrene in a molten state at any ratio and may be dispersed and incorporated into the bitumen by the domain effect.
  • PPO polyphenylene oxide
  • Such styrenic polymers may have a molecular weight of from about 40,000 to about 1,400,000, preferably about 100,000 to about 300,000.
  • the present invention also is applicable to other systems of stabilization of crystalline or rigid polymers in bitumen utilizing the procedures described herein.
  • the incorporation of the chemically-reactive blend of the above described multi-polymer components into bitumen generally is carried out in a two-step reaction procedure to prepare a polymer-stabilized asphalt composition which is capable of being granulated or otherwise processed to a desired physical form.
  • the procedure which may be employed according to the invention involves 1) reactively blending the polymeric components in bitumen and 2) then chemically incorporating the polymers into bitumen by the incremental addition of a cross-linking agent, such as sulfur, to the mixture.
  • a cross-linking agent such as sulfur
  • the polymer is heated above the crystallization temperature of the polymer used to produce a profusion of dispersed microscopic particles of molten polyolefin.
  • the polyolefin (s) stably incorporated in the bitumen matrix do not lose the ability to crystallize once cooled below their melting temperature.
  • the small size of the crystalline or rigid polymer particles incorporated into the bitumen and the loading levels of the crystalline or rigid polymer in the compositions ensure that the compositions have a stiffness and cohesion high enough to be granulated or pelletized and permit their granular nature to be maintained over a considerable length of storage time at ambient temperatures.
  • compositions provided according to the present invention may be granulated or pelletized by any conventional or appropriate granulation process. Alternatively, the compositions may be processed to any desired physical shape.
  • the pelletized or granulate material which retains a free-flowing condition, may be shipped in bulk to the user in any convenient form of packaging, such as bags, boxes or bulk containers.
  • the pellets can be diluted and let down with molten asphalt under low shear stirring, providing a polymer-modified asphalt in which the dispersed polymer, usually polyethylene or polystyrene, remains stable and is able to impart beneficial characteristics to the bitumen, as a result of elastic stabilization by the techniques described above.
  • pellets or granules may be blended directly into the pug mill of an asphalt hot mix plant to produce polymer modified asphalt hot mix.
  • Different formulations may be prepared for different commercial end uses, for example pelletized composition for use in stone mastic asphalts (SMA) to which cellulosic fibres are added to minimize run off of the asphalt binder from the aggregate.
  • SMA stone mastic asphalts
  • the dilution of the pellets with asphalt may be effected to any desired level of polymer modification of the final composition consistent with the end use contemplated, so that the bitumen granulate compositions provided herein are versatile in end use while the polymer remains stably dispersed in the final composition.
  • the provision of the free-flowing polymer-modified bitumen pellets or granules herein results in an improved production capacity from a polymer modified aspahlt manufacturing facility, since the production of materials in the pelletized form may be effected during what normally may be an off season for the plant. Since the pellets are free flowing at ambient temperature, no special tankage or heating is required to be associated with storage or use of the pellets.
  • the free-flowing polymer-modified bitumen pellets may be stored at ambient temperature in any suitable packaging, resulting in a reduced energy consumption resulting from the elimination of heated tanks.
  • Bituminous compositions produced herein from the pellets or other physical form of the concentration may be used as a paving material for all types of paving as well as finding applications in roofing membranes, shingles, waterproofing membranes, sealants, caulks, potting resins and protective finishes.
  • Paving materials generally include aggregate, such as crushed stone, pebbles, sand etc., along with the bitumen composition.
  • other additives to the bitumen composition are employed, depending on the end use to which the invention is put.
  • a roofing material may be obtained by the addition of suitable filler, such as asbestos, carbonates, silicas, cellulosic fibers, mica, sulfates, clays, pigments and/or fire retardants, such as chlorinated waxes.
  • suitable filler such as asbestos, carbonates, silicas, cellulosic fibers, mica, sulfates, clays, pigments and/or fire retardants, such as chlorinated waxes.
  • an oxide may advantageously be added
  • compositions prepared according to the Examples had a viscosity range from 100 poise to 10 poise at temperature around 200°C.
  • the resultant compositions were pelletized in solid form at room temperature with conventional granulators.
  • the resulting pellets were stored at normal ambient temperature over a considerable length of time without losing their free-flowing property.
  • the storage stability of the pellets was tested when blended with asphalt to about 2% polymer loading level and during hot storage at 320°F for 48 hours, using the ASTM 5892- 96 test method. In accordance with this method, stability is considered satisfactory if the difference in softening temperature between top and bottom of the sample after hot storage is no greater than 4°F.
  • Example 1 Example 1:
  • Example 2 The resulting composition was poured out of the vessel to cool down at room temperature to form a solidified mass. A conventional granulator was used to pelletize the solid to small free flowing pellets sized about to inch. The pellets were packaged in a plastic bottle container and were stored at room temperature for 30 months without loosing their free- flowing property.
  • Example 2 Example 2 :
  • Example 1 The method of Example 1 was repeated with a recycled low density polyethylene having a high melt flow index (MI: 100).
  • MI melt flow index
  • the viscosity of the resulting composition was 25 poise at 200°C, which was significantly lower than that of the composition in Example 1.
  • Pellets made from the composition have retained their free flowing property over the same 30 months storage time and conditions as in the samples from Example 1.
  • Example 3
  • Example 1 The method of Example 1 was again repeated using the same polyethylene as used in Example 2 except for using llOg of polyethylene instead of 139g to make a final granulate asphalt composition containing 30% of stabilized polymers, rather than 35% of the polymers as in Examples 1 and 2.
  • the viscosity of this composition was about 18 poises at 200°C.
  • the granulates obtained from this formulation also exhibited a good free flowing property after 30 month storage under the same condition as those set forth in Example 1.
  • Example 1 The procedure of Example 1 was repeated again using the polyethylene of Example 1 and further incorporating a composition prepared according to WO 94/14896, comprising a 40/20/40 blend of devulcanized crumb rubber, oil and bitumen, rather than the styrene- butadiene rubber.
  • the viscosity of the resulting composition was about 75 poises at 200°C.
  • Pellets made from the composition have retained their free-flowing property over 30 months storage time and conditions as set forth in Example 1.
  • Example 5 The procedure of Example 1 was repeated using the polyethylene of Example 1 but employing a harder bitumen, namely AC-20. The stability of the composition prior to pelletizing was tested by diluting the composition to a 2% polymer load level. The difference in softening point between top and bottom was 2°F, showing acceptable stability. Pellets were made from the composition and have retained their free-flowing property over 3 months storage time and conditions as set forth in Example 1.
  • Table summarizes the compositions used in the Examples:
  • the present invention provides a novel bitumen granulate in which crystalline or rigid polymer is stably dispersed and which retains a free-flowing homogeneous condition over many months of storage and yet is able to be readily dispersed in hot bitumen and retain stable dispersion of the polymer modifier, so that the beneficial properties of the polymer modifier are retained. Modifications are possible within the scope of the invention.

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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)
  • Road Paving Structures (AREA)

Abstract

Ces compositions d'asphalte granulaire contiennent du bitume à raison d'environ 45 à environ 80 % en poids et un polymère cristallin et/ou rigide à raison d'environ 15 à environ 50 % en poids, une telle composition ayant été stabilisée ou incorporée au bitume avec du caoutchouc synthétique selon une quantité allant de 3 à 25 % en poids. Le bitume, utilisé dans les compositions susmentionnées, qui est susceptible d'être doté d'un large pouvoir de pénétration compris dans une gamme allant du pouvoir de pénétration d'une base molle à celui d'une base dure, constitue le composant principal de la composition et ce, jusqu'à 80 % en poids. Les compositions résultantes peuvent être converties en granules et les granules être stockées très longtemps sans s'agglutiner. Ces granules peuvent être facilement et rapidement dispersées dans le bitume pour étendre le contenu polymère, lequel polymère demeure dispersé, de manière stable, dans le bitume. Ces granules, qui sont des plus utiles dans le cadre de nombreuses applications, au nombre desquelles le revêtement de sol, la couverture et d'autres industries de la construction, se transportent facilement sur les sites et se présentent prêtes à l'emploi.
EP98903960A 1997-02-18 1998-02-18 Granules de bitume stabilises par adjonction de polymere Withdrawn EP0961812A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US3820097P 1997-02-18 1997-02-18
US38200P 1997-02-18
PCT/CA1998/000122 WO1998037146A1 (fr) 1997-02-18 1998-02-18 Granules de bitume stabilises par adjonction de polymere

Publications (1)

Publication Number Publication Date
EP0961812A1 true EP0961812A1 (fr) 1999-12-08

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EP98903960A Withdrawn EP0961812A1 (fr) 1997-02-18 1998-02-18 Granules de bitume stabilises par adjonction de polymere

Country Status (11)

Country Link
EP (1) EP0961812A1 (fr)
JP (1) JP2000510193A (fr)
KR (1) KR20000071224A (fr)
CN (1) CN1252826A (fr)
AU (1) AU6201798A (fr)
BR (1) BR9807421A (fr)
CA (1) CA2281590A1 (fr)
HU (1) HUP0000539A3 (fr)
IL (1) IL131405A0 (fr)
PL (1) PL335164A1 (fr)
WO (1) WO1998037146A1 (fr)

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WO2004060827A1 (fr) * 2003-01-07 2004-07-22 Brian William Doyle Composition, procede de fabrication d'un element de construction, moule et element de construction
NL1023333C2 (nl) * 2003-05-02 2004-11-03 Dsm Nv De uitvinding heeft betrekking op een samenstelling welke bitumen en polyetheen bevat.
CN100392019C (zh) * 2006-02-27 2008-06-04 广州金邦橡胶沥青有限公司 干法与湿法相结合制备复合改性橡胶沥青混合料的方法
WO2009074348A1 (fr) * 2007-12-12 2009-06-18 Taieb Marzouki Procédé pour transporter du bitume pur et mélange bitumineux
CN101817659B (zh) * 2010-02-01 2012-10-17 北京天成垦特莱科技有限公司 一种复合路面增强剂及其生产方法
CN102408729A (zh) * 2011-08-17 2012-04-11 交通运输部公路科学研究所 一种储存稳定的聚乙烯复合改性沥青及其制备方法
ITAN20110150A1 (it) * 2011-11-03 2013-05-04 Tecnofilm Spa Bitume modificato e compound.
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
CN102766337A (zh) * 2012-06-06 2012-11-07 谷忠武 非沉淀橡胶改性沥青
US9493655B2 (en) 2013-04-22 2016-11-15 Denso-Holding Gmbh & Co. Composition for filling joints and/or cracks
CN105623280B (zh) * 2014-11-03 2017-10-27 中国石油化工股份有限公司 一种沥青组合物颗粒及其制备方法和应用
CN105623281B (zh) * 2014-11-03 2017-10-27 中国石油化工股份有限公司 一种高软化点沥青组合物颗粒的制备方法
CN115557277A (zh) * 2016-03-07 2023-01-03 加拿大国家铁路公司 干散装运输沥青材料的方法和球粒，获得沥青球粒的方法和运输容器
CN106700573B (zh) * 2016-11-22 2019-03-26 西藏宝利沥青有限公司 一种降温聚合物改性沥青的制备方法及其包装方法
US10308551B2 (en) * 2017-04-18 2019-06-04 Jorge B. Sousa Rubber composite and process for obtaining same

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GB1468215A (en) * 1974-05-23 1977-03-23 Permanite Ltd Sheet material
FR2436160A1 (fr) * 1978-09-13 1980-04-11 Cib Composition bitumineuse contenant des polymeres et ses applications
GB9306517D0 (en) * 1993-03-29 1993-05-19 Polyphalt Inc Stabilized bitumen compositions

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Also Published As

Publication number Publication date
PL335164A1 (en) 2000-04-10
HUP0000539A3 (en) 2000-09-28
IL131405A0 (en) 2001-01-28
CA2281590A1 (fr) 1998-08-27
HUP0000539A2 (en) 2000-07-28
CN1252826A (zh) 2000-05-10
JP2000510193A (ja) 2000-08-08
BR9807421A (pt) 2002-01-15
KR20000071224A (ko) 2000-11-25
AU6201798A (en) 1998-09-09
WO1998037146A1 (fr) 1998-08-27

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