WO2002000787A1 - Copolymeres tetrasequences - Google Patents

Copolymeres tetrasequences Download PDF

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Publication number
WO2002000787A1
WO2002000787A1 PCT/US2001/020289 US0120289W WO0200787A1 WO 2002000787 A1 WO2002000787 A1 WO 2002000787A1 US 0120289 W US0120289 W US 0120289W WO 0200787 A1 WO0200787 A1 WO 0200787A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
road
weight
component
residual
Prior art date
Application number
PCT/US2001/020289
Other languages
English (en)
Inventor
Roger Robert Delme
Jacques Bernard Lechat
Chantal Mathilde Martin
Original Assignee
Exxonmobil Chemical Company
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
Priority claimed from US09/605,032 external-priority patent/US6576686B1/en
Application filed by Exxonmobil Chemical Company filed Critical Exxonmobil Chemical Company
Priority to JP2002505905A priority Critical patent/JP2004502013A/ja
Priority to MXPA02012668A priority patent/MXPA02012668A/es
Priority to BR0112354-8A priority patent/BR0112354A/pt
Priority to EP01950485A priority patent/EP1299475A1/fr
Publication of WO2002000787A1 publication Critical patent/WO2002000787A1/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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes

Definitions

  • This invention relates generally to linear tetrablock copolymer compositions and their use in road-marking applications.
  • These tetrablock copolymers contain polystyrene, polyisoprene and polybutadiene components.
  • Road-marking compounds prepared from these copolymers typically further contain hydrocarbon resin, fillers and glass beads.
  • Block copolymers are generally known in the art and have been used in a variety of applications. There are two basic, distinct block copolymer types: linear and radial. Radial block copolymers contain polymer block branches radiating from a central coupling agent. Such polymers are described in, for example, U.S. Patent No. 5,399,627. This patent describes polymers for use in pressure sensitive adhesive compositions and describes radial block copolymers comprised of polystyrene, polyisoprene, and polybutadiene block segments. Linear block copolymers do not have radiating branches; the block components are arranged sequentially. For example, U.S. Patent No. 5,750,623 describes linear styrene-isoprene-styrene and styrene-butadiene-styrene block copolymers useful in hot-melt adhesives.
  • Linear block copolymers are also used to prepare compositions for road or pavement marking.
  • Such compositions typically comprise copolymer elastomer and hydrocarbon resin components as well as color and reflective additives such as pigments and glass beads.
  • U.S. Patent No. 5,213,439 is directed to pavement marking and describes a dry-blended powder containing linear or radial tri-block copolymers with two poly(vinylaromatic) blocks and a conjugated diene block.
  • This copolymer must be ground to a powder before mixing with hydrocarbon resins and other additives. This grinding replaces prolonged melt-blending procedures using expensive high- shear stirring to mix thermoplastic rubbers with hydrocarbon resin.
  • We have discovered that certain linear tetrablock copolymer compositions are readily melted and mixed with hydrocarbon resin thus avoiding both powder grinding and high-shear stirring.
  • Such copolymers have potential value in road- marking applications in addition to their more typical adhesive applications.
  • the present invention relates to a tetrablock copolymer composition
  • a tetrablock copolymer composition comprising a linear SISI of SISB block copolymer.
  • the block copolymers are of styrene and isoprene and/or butadiene.
  • the styrene content of the polymers used in the present invention should be from 10-27 percent by weight, alternatively from 12-20 or 15-18 percent by weight.
  • Molecular weights are measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated for example by using standards of similar known-molecular- weight polymer. Accordingly, the present invention selects polymers that enable good melting when mixed in traditional thermoplastic road-marking mixers. Some polymer embodiments have the following properties: an overall styrene content between 10-27 wt%, alternatively between 12-20 wt%. The preferred rubbers are 100% tetrablock.
  • the styrenic block copolymers used in some invention embodiments have a molecular weight of from 45,000-250,000. The molecular weights of the various copolymer blocks may be varied. Some embodiments select the styrenic - blocks with a molecular weight of from 4,000-35,000, alternatively, 6,000-20,000 or 8,000-20,000.
  • the unsaturated diene blocks should have a molecular weight of from
  • Unsaturated diene blocks with molecular weights of 20,000 or above provide a suitably strong polymer. Unsaturated diene blocks with molecular weights of 200,000 or less are suitably processable. Where SISI, SISB, SBSI, or SBSB polymers are used, the molecular weight of the two unsaturated diene blocks can be varied. DETAILED DESCRIPTION
  • linear tetrablock copolymers are particularly useful in road-marking compounds due to their flowability and quick melting capability. They can easily be melt mixed with hydrocarbon resins and other additives without powdering or high-shear mixing. Each block may be either polystyrene
  • the tetrablock copolymer contains two S blocks plus two B blocks, two I blocks, or one B and one I block, i.e.: S-I-S-I, S-I-S-B, S-B-S-B and S-B-S-I. Each block is present at 10-90 wt% of block copolymer based on the total copolymer weight.
  • an S component exists in a tetrablock copolymer at a minimum of 5 wt%, alternatively, a minimum of 10 wt%.
  • the S component exists at up to 70 wt%, alternatively up to 60 wt%, up to 40 or up to 30 wt% of the copolymer.
  • the weight-average molecular weight of invention tetrablock copolymers varies widely depending on the copolymer's make-up. Generally, the overall peak weight-average molecular weight has a minimum of 10,000, alternatively, a minimum of 50,000, or 100,000. The overall peak weight-average molecular weight maximum is 1,000,000, alternatively not more than 500,000, not more than 300,000, or not more than 200,000.
  • the invention linear tetrablock copolymers are "pure" in the sense that they contain no measurable residual triblock or diblock copolymer. But they may contain up to 1% by weight residual triblock and/or diblock copolymer.
  • these linear tetrablock copolymers are mixed with a hydrocarbon resin, such as a substantially non-aromatic hydrocarbon resin, or with a rosin ester or a blend of both.
  • a hydrocarbon resin such as a substantially non-aromatic hydrocarbon resin, or with a rosin ester or a blend of both.
  • substantially non-aromatic means that if there is aromatic hydrocarbon present, it is at a low enough level to function in these copolymer compositions.
  • Preferred non-aromatic resins are polymerized from a stream of aliphatic petroleum derivatives in the form of dienes and mono- olefins containing 5 to 6 carbon atoms. At room temperature, these hydrocarbons range from materials that are normally liquid to those that are normally solid at room temperature.
  • Commercially available resins such as ESCOREZTM 1102RM (ExxonMobil Chemical), are suitable. Many useful resins have a Ring and Ball softening point (ASTM D 28-96) from 90-110°C, alternatively from 95-105°C, and a melt viscosity at 160°C (ETM-E-31) from 500-3000 mPa sec, alternatively from 1000-2500 mPa sec.
  • Suitable hydrocarbon resins are well known and commercially available, e.g. under the trademarks “ESCOREZTM”, “HERCULESTM”, “QUINTONETM”.
  • Suitable rosin esters are commercially available, e.g. under the trademarks "BEVILLNETM” and “SYLVATACTM”.
  • the relative amounts of tetrablock copolymer and hydrocarbon resin depends on the selected components. Typically, the block copolymer and hydrocarbon resin are present in a weight ratio of from 0.5:99.5 to 20:80, preferably from 2:98 to 15:85.
  • Invention road-marking compositions may further contain additives such as pigments, glass beads, fillers, oils, and viscosity modifiers. Titanium dioxide is a particularly useful pigment, and mineral aggregates are particularly useful fillers.
  • compositions' individual components may be combined in a number of ways, but the invention copolymers are uniquely suited to simple melt mixing with the hydrocarbon resin and any desired additive.
  • the melt-mixing temperature has a minimum of 170°C or 180°C.
  • the maximum melt- mixing temperature is 200°C, but melt-mixing temperatures as high as 210°C are not unusual.
  • the tetrablock copolymers may be prepared by any suitable polymerization technique. Polymerization systems in which the blocks are produced sequentially are preferred to those in which two or more pre-formed blocks are coupled to each other. The preferred, sequential, polymer development enables greater variation in the molecular weight of the blocks.
  • the molecular weights reported here are peak molecular weight as measured by size exclusion chromatography using polystyrene calibration. Commercially available polystyrene standards were used for calibration, and the molecular weights of copolymers corrected according to Runyon et al, Journal of Applied Polymer Science, Vol. 13, Page 359 (1969) and Tung, L. H., Journal of Applied Polymer Science, Vol. 24, Page 953 (1979).
  • the melt-mixing temperature has a minimum of 170 °C or 180 °C.
  • the maximum melt-mixing temperature is usually 200 °C, but melt- mixing temperatures as high as 210 °C are not unusual.
  • Melt flow rate was determined using ASTM D 1238, 200/5.0.
  • Comparative Sample 1 is an S-I-S triblock copolymer, VECTORTM 4111 (commercially available from Dexco Polymers).
  • Comparative Sample 2 is an S-I-S/S-I triblock/diblock copolymer mix,
  • VECTORTM 4113 (commercially available from Dexco Polymers).
  • Comparative Sample 3 is an S-I-S/S-I triblock/diblock copolymer mix, VECTORTM 4114 (commercially available from Dexco Polymers).
  • Comparative Sample 4 is an S-I-S/S-I triblock/diblock copolymer mix, DPX 559TM, (commercially available from Dexco Polymers) having 15% styrene,
  • Comparative Sample 5 is an S-I-S triblock copolymer, DPX 562TM (commercially available from Dexco Polymers). DPX 562TM is a linear SIS with 15% styrene and a Melt Flow Rate (ASTM 1238, 200/5.0) of 25 g/10 min. Comparative Sample 6 is an S-I-S/S-I triblock/diblock copolymer mix,
  • DPX 565TM (commercially available from Dexco Polymers). DPX 565TM has the following properties. Molecular weight SIS: 176000 g/mol; Molecular weight SI: 83000 g/mol; Styrene content SIS: 16.1% (by weight); Styrene content SI: 16.1% (by weight); SI content: 54% of the polymer.
  • Invention Sample 7 is an S-I-S-I tetrablock copolymer in accordance with this invention made at Dexco Polymers by sequential polymerization. It has the following respective molecular weights, in g/mol: 12400, 60000, 12400, 70000, and styrene content of 16% (by weight).
  • Invention Sample 8 is an invention S-I-S-B tetrablock copolymer made at Dexco Polymers by sequential polymerization. It has the following respective molecular weights, in g/mol: 11000, 57000, 11000, 40000, and styrene content of 19% (by weight).
  • Comparative Sample 9 is an S-I-S/S-I triblock/diblock copolymer mix, TR 1107TM (commercially available from Shell Oil Company).
  • Comparative Sample 10 is an S-I-S/S-I triblock/diblock copolymer mix, KRATONTM D 601 P (commercially available from Shell Oil Company).
  • Comparative Sample 11 is an S-I-S/S-I triblock/diblock copolymer mix, KRATONTM D 113 (commercially available from Shell Oil Company).
  • Comparative Sample 12 is an S-I-S/S-I triblock/diblock copolymer mix, QUINTACTM 3433 (commercially available from Nippon Zeon).

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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)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention se rapporte à des compositions de copolymères tétraséquencés linéaires et à leur utilisation dans les applications de marquage de chaussées. Ces copolymères tétraséquencés contiennent des composants polystyrène, polyisoprène et polybutadiène. Les composés de marquage de chaussées préparés à partir de ces copolymères contiennent une résine hydrocarbure ou un ester de colophane ou bien les deux. Ces copolymères tétraséquencés sont facilement mélangés selon des techniques de mélange à l'état fondu, ce qui permet à la fois d'éviter la réduction à l'état de poudre et le mélange à cisaillement élevé.
PCT/US2001/020289 2000-06-27 2001-06-25 Copolymeres tetrasequences WO2002000787A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2002505905A JP2004502013A (ja) 2000-06-27 2001-06-25 テトラブロックコポリマー
MXPA02012668A MXPA02012668A (es) 2000-06-27 2001-06-25 Copolimeros de tetra-bloque.
BR0112354-8A BR0112354A (pt) 2000-06-27 2001-06-25 Copolìmeros de tetrabloco
EP01950485A EP1299475A1 (fr) 2000-06-27 2001-06-25 Copolymeres tetrasequences

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US60353000A 2000-06-27 2000-06-27
US09/605,032 US6576686B1 (en) 2000-06-27 2000-06-27 Road marking compound comprising linear tetrablock copolymers
US09/603,530 2000-06-27
US09/605,032 2000-06-27

Publications (1)

Publication Number Publication Date
WO2002000787A1 true WO2002000787A1 (fr) 2002-01-03

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ID=27084451

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/020289 WO2002000787A1 (fr) 2000-06-27 2001-06-25 Copolymeres tetrasequences

Country Status (6)

Country Link
EP (1) EP1299475A1 (fr)
JP (1) JP2004502013A (fr)
CN (1) CN1219821C (fr)
BR (1) BR0112354A (fr)
MX (1) MXPA02012668A (fr)
WO (1) WO2002000787A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1348737A1 (fr) * 2002-03-28 2003-10-01 KRATON Polymers Research B.V. Coposition bitumineuse
WO2006017776A2 (fr) 2004-08-05 2006-02-16 Firestone Polymers, Llc Synthese en une seule etape d'un polymere fonctionnel multibloc

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2087038B1 (fr) * 2006-11-20 2014-01-01 Trimurti Holding Corporation Copolymeres tetrablocs de styrene et compositions de melange de polymeres a base de ces copolymeres
JP7392642B2 (ja) * 2018-02-27 2023-12-06 日本ゼオン株式会社 テトラブロック共重合体、およびポリマー組成物、ならびにこれらを用いたホットメルト粘接着剤組成物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161472A (en) * 1978-01-23 1979-07-17 The B. F. Goodrich Company Impact modified vinyl chloride polymer composition
US4168286A (en) * 1977-09-23 1979-09-18 Phillips Petroleum Co. Tetrablock polymers and their hydrogenated analogs
GB2226322A (en) * 1988-12-23 1990-06-27 Enichem Elastomers Block polymer compositions
EP0499326A1 (fr) * 1991-02-14 1992-08-19 Shell Internationale Researchmaatschappij B.V. Procédé de marquage de chaussée
GB2289681A (en) * 1994-05-19 1995-11-29 Nissin Kasei Co Limited A binder composition for a colored pavement
WO1997009385A1 (fr) * 1995-09-06 1997-03-13 Exxon Chemical Patents Inc. Compositions de bitume
US5627235A (en) * 1993-11-03 1997-05-06 Shell Oil Company Multiblock hydrogenated polymers for adhesives
WO2000056796A1 (fr) * 1999-03-25 2000-09-28 Bridgestone Firestone Inc Compositions d'adhesif contenant des copolymeres multisequences de polyisoprene-polystyrene et articles contenant ces dernieres

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4168286A (en) * 1977-09-23 1979-09-18 Phillips Petroleum Co. Tetrablock polymers and their hydrogenated analogs
US4161472A (en) * 1978-01-23 1979-07-17 The B. F. Goodrich Company Impact modified vinyl chloride polymer composition
GB2226322A (en) * 1988-12-23 1990-06-27 Enichem Elastomers Block polymer compositions
EP0499326A1 (fr) * 1991-02-14 1992-08-19 Shell Internationale Researchmaatschappij B.V. Procédé de marquage de chaussée
US5627235A (en) * 1993-11-03 1997-05-06 Shell Oil Company Multiblock hydrogenated polymers for adhesives
GB2289681A (en) * 1994-05-19 1995-11-29 Nissin Kasei Co Limited A binder composition for a colored pavement
WO1997009385A1 (fr) * 1995-09-06 1997-03-13 Exxon Chemical Patents Inc. Compositions de bitume
WO2000056796A1 (fr) * 1999-03-25 2000-09-28 Bridgestone Firestone Inc Compositions d'adhesif contenant des copolymeres multisequences de polyisoprene-polystyrene et articles contenant ces dernieres

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1348737A1 (fr) * 2002-03-28 2003-10-01 KRATON Polymers Research B.V. Coposition bitumineuse
WO2003082985A1 (fr) * 2002-03-28 2003-10-09 Kraton Polymers Research B.V. Composition bitumineuse
US7271207B2 (en) 2002-03-28 2007-09-18 Kraton Polymers U.S. Llc Bituminous composition
WO2006017776A2 (fr) 2004-08-05 2006-02-16 Firestone Polymers, Llc Synthese en une seule etape d'un polymere fonctionnel multibloc
WO2006017776A3 (fr) * 2004-08-05 2006-05-18 Firestone Polymers Llc Synthese en une seule etape d'un polymere fonctionnel multibloc
US7902295B2 (en) 2004-08-05 2011-03-08 Firestone Polymers, Llc Single step synthesis of functional multi-block polymer

Also Published As

Publication number Publication date
MXPA02012668A (es) 2004-07-30
CN1441829A (zh) 2003-09-10
JP2004502013A (ja) 2004-01-22
CN1219821C (zh) 2005-09-21
BR0112354A (pt) 2003-05-06
EP1299475A1 (fr) 2003-04-09

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