WO1997030121A1 - Compositions bitumineuses stabilisees a base de polymeres melanges in-situ - Google Patents

Compositions bitumineuses stabilisees a base de polymeres melanges in-situ Download PDF

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Publication number
WO1997030121A1
WO1997030121A1 PCT/CA1997/000102 CA9700102W WO9730121A1 WO 1997030121 A1 WO1997030121 A1 WO 1997030121A1 CA 9700102 W CA9700102 W CA 9700102W WO 9730121 A1 WO9730121 A1 WO 9730121A1
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WO
WIPO (PCT)
Prior art keywords
bitumen
polystyrene
composition
polymer
styrene
Prior art date
Application number
PCT/CA1997/000102
Other languages
English (en)
Inventor
Zhi-Zhong Liang
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.
Priority to AU15870/97A priority Critical patent/AU1587097A/en
Priority to CA002246415A priority patent/CA2246415C/fr
Priority to US09/117,956 priority patent/US6174939B1/en
Publication of WO1997030121A1 publication Critical patent/WO1997030121A1/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

Definitions

  • the present invention is related to a process of combining polystyrene (PS) or PS-based plastics with an elastomer or rubber as a dispersion agent to form a novel stabilized bituminous composition, which comprises: a) bitumen, b) a PS-based plastic (PS homopolymer or PS blend or graft copoiymer) which is itself not compatible with bitumen, and c) an elastomeric triblock copoiymer containing styrene which is compatible with bitumen.
  • PS polystyrene
  • PS-based plastic PS homopolymer or PS blend or graft copoiymer
  • PS or PS based plastics are among the most commonly used thermoplastic polymers and generate a considerable amount cf recoverable scrap material. Like other polymeric materials, such as polyethylene (PE) , polypropylene (PP) and ethylene-vinyl acetate (EVA) , due to their high stiffness over a range of service temperatures, PS would also seem very suitable for addition to bitumen and could thereby contribute effectively to the stiffness and strength of bitumen. Unfortunately, PS has problems similar to those of other polymeric materials, in that it does not significantly increase the elasticity of the asphalt binder and blends or dispersions with a range of different type of bitumens demix quite rapidly during hot storage.
  • PE polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate
  • PS has been found to be very difficult to disperse into bitumen even using high shear, because of its intrinsic structural features of rigid molecular chains with high melt strength. Although it is economically attractive to consider PS based scrap thermoplastics as a modifier for asphalt, the above discussed obstacles have limited such an application.
  • Polystyrene (PS) plastics represents a line of rigid polystyrene based products from crystal homopolymer, toughened graft copolymers, to blends or alloys with various rubbers. The rigidity and high melt strength of PS plastics causes them to be very difficult to disperse into hot liquid bitumen.
  • thermoplastic rubbers commonly called thermoplastic rubbers (TR) , which are produced by a sequential chemical operation of successive polymerisations of styrene-butadiene-styrene (SBS), styrene-ethylene/butylene-styrene (SEBS) and of styrene-isoprene-styrene (SIS) systems.
  • SBS styrene-butadiene-styrene
  • SEBS styrene-ethylene/butylene-styrene
  • SIS styrene-isoprene-styrene
  • TR dispersions can render their strength and elasticity to bitumen from a physical crosslinking of styrene segments into a three-dimensional network as disclosed by Holden et al. in the Proceedings of International Rubber Conference, 1967 Maclaren. This result can be achieved by the agglomeration of the styrene polymerized block (or polystyrene segments of triblock copolymers) , forming very fine domains (down to the nm scale) , which provide the physical cross-linkage for a three-dimensional butadiene, ethylene/butylene or isoprene polymerized rubbery matrix.
  • homopolymers or copolymers of styrene and styrene derivatives can be stably dispersed in bitumen by employing a triblock copoiymer which is readily dispersed or dissolved in the bitumen and which comprises an elastomeric copoiymer containing styrene which is compatible with bitumen.
  • a stable bituminous composition comprising: a continuous bitumen phase, an elastomeric triblock copoiymer comprising polystyrene segments and stabilized and compatibilized in said bituminous phase, and a dispersed particulate polymer phase miscible in the molten state with polystyrene dispersed in said bituminous phase and normally incompatible with said bituminous phase and stabilized against separation from said bituminous phase by said triblock copoiymer.
  • bitumen-soluble elastomeric copoiymer 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 with bitumen.
  • the polystyrene domains which are dispersed throughout the bitumen by reason of the stabilization or compatibilization of the elastomeric triblock copoiymer in the bitumen enable the normally-incompatible 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 polystyrene macromolecules are blended in and increase in dimension with increasing levels of dispersed polystyrene.
  • 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.
  • asphalts, tars, pitches and asphaltites are typical.
  • asphaltitious material 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.
  • Elastomeric triblock copoiymer in which the butadiene rubber segments are compatible with or soluble in or are able to be compatibilized with or solubilized in bitumen.
  • 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 polymers 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 polymers of styrene derivatives, such as poly(alpha- methylstyrene) , poly(p-tert-butylstyrene) and polychlorostyrene.
  • the rigid styrenic polymers also may 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 bitumen-compatible elastomeric triblock copoiymer may be provided in any desired amount in the bitumen consistent with the amount of normally non- dispersible polymer to be dispersed and the properties desired to be imparted to the bitumen by the dispersed polymer.
  • the quantity of elastomeric triblock copoiymer dispersed in bitumen may range from about 1 to about 20 wt%, preferably about 3 to about 15 wt%, of the bituminous composition.
  • the quantity of styrenic polymer dispersed in the bitumen may vary from about 1 to about 35 wt%, preferably about 3 to about 15 wt%, of the bituminous composition.
  • the stabilized bituminous compositions of the invention show no tendency to phase separate at elevated temperatures in the range of about 100° to about 200°C and remain stable in the absence of stirring, i.e. the compositions exhibit no tendency for the dispersed particulate phase to separate from the continuous bituminous phase.
  • the stabilized bituminous compositions of the invention also may be cooled to ambient temperature, may be reheated up to about 160°C or more up to about 200°C, several times, and may be maintained at such high temperatures for several days, without any tendency to phase separation of the dispersed particulate phase.
  • the stable dispersions of rigid styrene polymers or other rigid polymer miscible in the molten state with the polystyrene in the continuous bituminous phase may be produced in any convenient manner.
  • the elastomeric triblock copoiymer first is uniformly incorporated into the bitumen, usually by dissolving the elastomeric triblock copoiymer in the bitumen as to establish very fine polystyrene domains (sized down to the nm scale) and a cross-linked rubbery matrix in the continuous bituminous phase.
  • the polystyrene or other polymer then is added to the composition for dispersion therein, at a temperature of about 150° to about 200°C, preferably about 170° to about 180°C, which may be effected under high shear conditions.
  • the styrene component of the elastomeric triblock copoiymer provides domains which assist first in the dispersion of the styrene polymer in the continuous bituminous phase and then in stabilizing the dispersed styrene polymer against phase separation from the continuous bituminous phase.
  • the elastomeric triblock copoiymer and rigid styrene polymer may be blended into the bitumen simultaneously to provide the stable composition.
  • the stabilized bituminous compositions provided herein 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 composition of the invention is put.
  • a roofing material may be obtained by the addition of suitable fillers, such as asbestos, carbonates, silicas, wood fibers, mica, sulfates, clays, pigments and/or fire retardants, such as chlorinated waxes.
  • suitable fillers such as asbestos, carbonates, silicas, wood fibers, mica, sulfates, clays, pigments and/or fire retardants, such as chlorinated waxes.
  • an oxide may advantageously be added.
  • Polystyrene employed in the experiments was a crystal polystyrene plastic in pellet form (PS, melt index: 5 gram/10 min and supplied by Poiysar limited) and the two triblock copolymers were styrene-butadiene- styrene (SBS) thermoplastics rubber (Europrene sol T 161 B, 30% bound styrene, 70% bound butadiene, manufactured by Enichem Elastomers America Inc.) and styrene- ethylene/butylene-styrene (SEBS) thermoplastics rubber ( raton G 1652, 30% bound styrene, 70% bound ethylene/butylene, manufactured by Shell Chemicals Inc.) .
  • SBS styrene-butadiene- styrene
  • SEBS styrene- ethylene/butylene-styrene
  • Asphalt 1 used for runs 1, 2, 4, 7 and 8 has 167 dmm cf penetration at 25°C, 40°C softening point and 195 cp.
  • cf brookfield viscosity at 135°C and Asphalt 2 used for run 3, 5 and 6 has 148 dmm of penetration at 25°C, 45°C softening point and 233 cp. of Brookfield viscosity at 135°C.
  • the present invention provides a novel system for stably dispersing normally-incompatible styrenic polymers, particularly rigid styrenic polymers, in bitumen by providing dispersed in the bitumen an elastomeric triblock copoiymer normally compatible with the bitumen and which is an elastomeric copoiymer of styrene. Modifications are possible within the scope of this invention.

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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

Il est possible d'incorporer de manière stable au bitume des polymères styréniques normalement incompatibles en recourant à un copolymère élastomère à trois blocs solubilisé ou compatibilisé dans la phase bitumineuse. Ledit copolymère, une fois incorporé à la phase bitumineuse continue présente des domaines polystyréniques dispersés dans le bitume, ou une unité réceptrice qui stabilise le polystyrène particulaire et l'empêche de se dissocier du bitume.
PCT/CA1997/000102 1996-02-16 1997-02-14 Compositions bitumineuses stabilisees a base de polymeres melanges in-situ WO1997030121A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU15870/97A AU1587097A (en) 1996-02-16 1997-02-14 Stabilized bituminous composition based on polymer in-situ blend
CA002246415A CA2246415C (fr) 1996-02-16 1997-02-14 Compositions bitumineuses stabilisees a base de polymeres melanges in-situ
US09/117,956 US6174939B1 (en) 1997-02-14 1997-02-14 Stabilized bituminous composition based on polymer in-situ blend

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1182696P 1996-02-16 1996-02-16
US60/011,826 1996-02-16

Publications (1)

Publication Number Publication Date
WO1997030121A1 true WO1997030121A1 (fr) 1997-08-21

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PCT/CA1997/000102 WO1997030121A1 (fr) 1996-02-16 1997-02-14 Compositions bitumineuses stabilisees a base de polymeres melanges in-situ

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CN (1) CN1119382C (fr)
AU (1) AU1587097A (fr)
CA (1) CA2246415C (fr)
WO (1) WO1997030121A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197852B1 (en) 2000-02-28 2001-03-06 Equistar Chemicals, Lp Polyolefin concentrates and composition having improved carbon black dispersion
WO2002042377A1 (fr) * 2000-11-23 2002-05-30 Atofina Research Composition de bitume comprenant du sbs/ppe

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629387B (zh) * 2015-01-09 2016-08-24 山西省交通科学研究院 一种用于铺筑应力吸收带的高强度路面功能材料
FR3119170B1 (fr) * 2021-01-28 2023-02-10 Total Marketing Services Compositions pour la réalisation de membranes d’étanchéité, procédés et membranes associés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2283179A1 (fr) * 1974-08-27 1976-03-26 Shell Int Research Compositions bitumineuses contenant au moins deux constituants polymeres
EP0146163A2 (fr) * 1983-12-16 1985-06-26 Shell Internationale Researchmaatschappij B.V. Composition bitumineuse contenant des polymères
WO1993007219A1 (fr) * 1991-09-30 1993-04-15 The University Of Toronto Innovations Foundation Compositions stabilisees in-situ
US5280064A (en) * 1991-09-30 1994-01-18 Simon Hesp Bitumen-polymer stabilizer, stabilized bitumen-polymer compositions and methods for the preparation thereof
WO1994022957A1 (fr) * 1993-03-29 1994-10-13 Polyphalt Inc. Compositions stabilisees de bitume

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2283179A1 (fr) * 1974-08-27 1976-03-26 Shell Int Research Compositions bitumineuses contenant au moins deux constituants polymeres
EP0146163A2 (fr) * 1983-12-16 1985-06-26 Shell Internationale Researchmaatschappij B.V. Composition bitumineuse contenant des polymères
WO1993007219A1 (fr) * 1991-09-30 1993-04-15 The University Of Toronto Innovations Foundation Compositions stabilisees in-situ
US5280064A (en) * 1991-09-30 1994-01-18 Simon Hesp Bitumen-polymer stabilizer, stabilized bitumen-polymer compositions and methods for the preparation thereof
WO1994022957A1 (fr) * 1993-03-29 1994-10-13 Polyphalt Inc. Compositions stabilisees de bitume

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197852B1 (en) 2000-02-28 2001-03-06 Equistar Chemicals, Lp Polyolefin concentrates and composition having improved carbon black dispersion
WO2002042377A1 (fr) * 2000-11-23 2002-05-30 Atofina Research Composition de bitume comprenant du sbs/ppe
EP1211291A1 (fr) * 2000-11-23 2002-06-05 ATOFINA Research Composition à base de SBS, PPE et bitume

Also Published As

Publication number Publication date
AU1587097A (en) 1997-09-02
CA2246415A1 (fr) 1997-08-21
CN1216056A (zh) 1999-05-05
CN1119382C (zh) 2003-08-27
CA2246415C (fr) 2005-01-25

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