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WO2000056796A1 - Compositions d'adhesif contenant des copolymeres multisequences de polyisoprene-polystyrene et articles contenant ces dernieres - Google Patents

Compositions d'adhesif contenant des copolymeres multisequences de polyisoprene-polystyrene et articles contenant ces dernieres Download PDF

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Publication number
WO2000056796A1
WO2000056796A1 PCT/US2000/008012 US0008012W WO0056796A1 WO 2000056796 A1 WO2000056796 A1 WO 2000056796A1 US 0008012 W US0008012 W US 0008012W WO 0056796 A1 WO0056796 A1 WO 0056796A1
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WO
WIPO (PCT)
Prior art keywords
weight
baba
block copolymer
copolymer
average molecular
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.)
Ceased
Application number
PCT/US2000/008012
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English (en)
Inventor
Inc. Bridgestone/Firestone
David Dougherty
Mark Wollum
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.)
Bridgestone Firestone Inc
Original Assignee
Bridgestone Firestone 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 Bridgestone Firestone Inc filed Critical Bridgestone Firestone Inc
Publication of WO2000056796A1 publication Critical patent/WO2000056796A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • C08F297/046—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 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes

Definitions

  • this invention relates to adhesive compositions constituted of multiblock polyisopre ⁇ e-polystyrene block copolymers.
  • it relates to pressure sensitive adhesives, especially pressure- sensitive, hot-melt adhesives formed from such block copolymers.
  • Increasing tack by known techniques such as, for example, increasing the amounts of plasticizer oil and/or tackifier generally also results in decreased strength and heat resistance.
  • increasing strength or heat resistance by increasing polymer content, or by using endblock-associating resins, generally raises viscosity and/or decreases tack.
  • improving cohesive strength of such adhesives without adversely affecting tack, bonding characteristics, and heat resistance, as well as not increasing adhesive viscosity, remains desirable.
  • the present invention provides a bimodal multiblock BABA copolymer.
  • A represents a polystyrene block having a weight average weight (M «) of from about 7,000 t ⁇ about 30,000
  • B represents a ⁇ olyisoprena block having a M w of from about 48,000 ,o about 120,000.
  • the block copolymer has an overall M» of from about 70,000 t ⁇ about 150,000, an overall styre ⁇ e content of from about 15 to about 50% (by wt.), and a Melt Index G of from 4 to 22 g/s.
  • the bimodal multiblock BABA block copolymer can include one block copolymer having a M w of from 50,000 to 140,000 and a second block copolymer having a M* of
  • the present invention provides an article that includes a backing substrate and an adhesive layer on at least one major surface of the substrate.
  • the adhesive layer is derived from a composition that includes a tackifying resin and the just-described
  • Fig, 1 displays a GPC graph of the BABA block copolymer used in Example 1.
  • the present invention provides multiblock polyisoprene- polystyrene copolymers which, when formulated with tackifier resins, plasticizer oils, and antjoxida ⁇ ts, produces PSAs, particularly pressure 30 sensitive hot-melt adhesives having high cohesive strength. PSAs must rapidly wet the surfaces to which they are to adhere, For good PSA performance, the overall adhesive mass must be soft, i.e., possess high creep compliance or low modulus.
  • the multiblock copolymers of the present invention readily can be formulated to provide PSAs with good tack, adequate cohesive strength, and adequate heat resistance for most applications.
  • improving tack can be accomplished by increasing t e plasticizer oil or liquid resin content of the adhesive mass. However, doing so dilutes the styrene domains of the block copolymer, which leads t ⁇ a loss in cohesive strength and heat resistance.
  • use of bimodal BABA block copolymers can provide improved cohesive strength without adversely affecting tack properties. Styrene content and overall molecular weight of the BABA block copolymer have been found to be key parameters for achieving a desired balance of properties in adhesive applications.
  • the BABA block copolymers of the present invention can be bimodal, having two block copolymers with different molecular weights.
  • One block copolymer typically has a M* of from 50,000 to 140,000, and the other typically has a Mw of from 100,000 to 250,000.
  • These bimodal BABA copolymers provide tack development and low temperature flexibility in the PSA system as well as improved cohesive strength. They also maintain good heat resistance without adversely affecting tack properties.
  • the composition and molecular weight of the BABA block copolymer are important factors.
  • the styrene domains stiffen (or raise the modulus of) the BABA block copolymer, and therefore increase the cohesive strength by providing a hard domain structure in the adhesive system.
  • a monomodal BABA block copolymer often is too stiff (hard) to be used in a PSA system
  • a bimodal BABA block copolymer with its polyj ⁇ oprene blocks contributing flexibility and compatibility, has been found to be optional.
  • Conjugated diene-monovinyl aromatic block copolymers useful in this invention are block copolymers derived from a monovinyl substituted aromatic compound and a conjugated diene. These include block copolymers such as BABA where A represents a polymerized monovinyl aromatic compound, usually styrene, and B represents a polymerized conjugated diene, usually 1.3-butadiene.
  • the rubbery B block could be polybutadiene, a random or tapered styrene/ butadiene copolymer, polyisoprene, a random or tapered styrene-isoprene copolymer, or mixtures thereof.
  • Conjugated diene-monovinyl aromatic block copolymers of the present invention can be bimodal, which means that they have a molecular weight distribution with two peaks that may not be completely separated-
  • Fig. 1 displays a GPC graph of a BABA block copolymer
  • polyisoprene-styrene-polyisoprene-8tyrene such as that used in Example 1.
  • the two peaks between 15 and 20 minutes display the bimodal presence of different block copolymers having number average molecular weights (Mschreib) of 146,372 (first peak) and 77,387 (second peak).
  • These copolymers, having resinous properties contain from about 20 to about 40% (by wt) polymerized styrene based on total weight of the copolymer. The remainder of the block copolymer is polymerized conjugated diene.
  • bimodal block copolymers can be produced in accordance with U.S. Pat. Nos. 3,639,517 and 3,251 ,905. More specifically, they can be prepared by sequential charge copolymerizatjon such as for example, that described in U.S. Pat. Nos, 4,584,346, 4,091 ,053, 4,704,434 and 4,704,435.
  • a PSA composition can be formed by admixing a bimodal BABA block copolymer with compatible primary tackifying resins, a plasticizer oil and/or secondary tackifying resin, and an antioxida ⁇ t.
  • the compatible primary tackifying resins with which the BABA block copolymers are admixed may be the same or different, but generally better results are obtained by the use of different primary tackifying resins in any given formulation.
  • Preferred PSA compositions can include, per 100 parts by weight (pbw) of bimodal BABA block copolymers, from about 80 to about 225 pbw, preferably from about 00 to about 180 pbw, of primary tackifying resins and from about 0 to about 100 pbw, preferably from about 0 to about 50 pbw, of the plasticizer oil and/or secondary tackifying resin.
  • the blend also can contain from about 0.1 to about 2% (by wt), preferably from about 0.5 to about 1.5% (by wt.), of an antioxidant.
  • Useful tackifying resins include hydrocarbon resins, synthetic polyterpenes, rosin esters, and natural terpene ⁇ that are at least somewhat solid at ambient temperatures and that soften or become liquid at temperatures ranging from about 70" to about 135 ⁇ C, preferably from about 85" to about 120"C
  • Exemplary primary tackifying resins include compatible resins such as (1) natural and modified rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin, (2) glycerol and pentae ythritol esters of natural and modified rosins, such, for example, as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the
  • plasticizing oils are useful in the practice of this invention.
  • the plasticizing oil can be used in place of or in combination with the secondary tackifier to reduce viscosity and improve tack properties.
  • Plasticizing oils that have been found useful include olefin oligomers and low molecular weight polymers, as well as vegetable and animal oils and their derivatives.
  • Petroleum-derived oils that can be employed are relatively high boiling materials containing only a minor proportion of aromatic hydrocarbons (preferably less than 30% and, more preferably, less than 15% by weight of the oil).
  • the oligomers may be p ⁇ lypropylenes, polybutenes, hydrogenated polyisoprene, hydrogenated polybutadiene, polypiperylene and copolymers of piperylene and isopre ⁇ e, or the like a having a M w between about 350 and about 10,000.
  • Vegetable and animal oils include glyceryl esters of the usual fatty acids and polymerization products thereof.
  • Stabilizer or antioxidant to be used in accordance with the practice of this invention includes high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-containing phenols.
  • Hindered phenols are known to those skilled in the art and may be characterized as phenolic compounds that also contain sterically bulky radicals In close proximity to the phenolic hydroxyl group thereof.
  • tertiary butyl groups generally are substituted onto the benzene ring in at least one of the ortho positions relative to the phenolic hydroxy group, The presence of these sterically bulky substituted radicals in the vicinity of the hydroxyl group serves to retard its stretching frequency and, correspondingly, its reactivity; this steric hindrance thus providing the phenolic compound with its stabilizing properties.
  • hindered phenols include lAS-trim thyl ⁇ Ae-tris-fS.B-di-tert-butyM- hydroxybenzyl) benzene; pentaerythrityl tetraki3-3-(3 ( 5-di-tert-butyl-4- hydroxypheny
  • the PSA composition can be formed by mixing the required components in molten state, or the components can be dissolved in a suitable hydrocarbon solvent, e.g., an aromatic hydrocarbon such as benzene, toluene, xylene or the like, or an aliphatic hydrocarbon such as hexane, heptane or the like.
  • a suitable hydrocarbon solvent e.g., an aromatic hydrocarbon such as benzene, toluene, xylene or the like, or an aliphatic hydrocarbon such as hexane, heptane or the like.
  • the adhesive composition can be prepared by melt mixing the BABA block polymers with the primary tackifying resin(s), the secondary tackifying resin a ⁇ i'or plasticizing oil and stabilizer, in any order or sequence, or these materials can be added together simultaneously to form the adhesive composition.
  • the primary tackifying resjn(s) and the BABA copolymers can be blended together at a sufficiently elevated temperature to form a fluid melt.
  • the BABA block copolymers can be blended with a solid compatible primary tackifying resin(s) and stabilizer at temperatures of from about 130" to about 200 ⁇ C, preferably at from about 150" to about 180°C, to form a fluid melt.
  • the secondary liquid tackifying resin or plasticizing oil then can be added to the melt.
  • PSAs can be mixed and coated as a hot melt mass, dissolved in and applied from hydrocarbon solvents, and applied to a backing substrate, e.g., paper, cloth, film, metal foil, tape or the like, by coating techniques conventionally used for this purpose in the adhesive tape industry.
  • the adhesive may be coated on one or both sides of the substrate depending upon its intended use. These adhesives are particularly useful in tape and label applications, packaging, bookbinding and disposable applications.
  • the adhesive compositions are particularly useful in, for example, the construction of a disposable articles comprised of polyethylene or polypropylene bonded to a tissue, ⁇ on woven, polyethylene or polypropylene substrate, particularly disposable diapers and feminine hygiene products; or in packaging applications to bond a wide variety of high and low energy surfaces, i.e., paper, plastir., films, metals or the like.
  • the BABA block copolymers are also useful as a component in asphalt applications for sealant products.
  • Styrene content was calculated from the spectra by the method of V.D. Mochel, Rubber Ch ⁇ m. and Tech., 40, 1200 (1967).
  • SAFT Shear Adhesion Failure Temperature
  • a 1 inch y 6 inch (2.5 cm x 15.2 cm) strip of adhesive tape (on a 0 05 mm metallized polyester backing) is applied to a stainless steel (SS), polyethylene (PE) or polypropylene (PP) panel with a 4.5 lb. (2 Kg) rubber roller.
  • the tape is peeled back over itself at 180" in a tensile tester at a constant crosshead speed of 12 in/min (0 51 cm/s). The average force required to peel the tape from the panel is recorded.
  • the 180° peel adhesion value is reported as the average of two or three such determinations.
  • Quick Stick is that property of a PSA that causes it to adhere instantly to a surface, using no external pressure, to secure a thorough bond. This method is described in PSTC-5.
  • Quick stick is measured as the force resisting peeling of a tape at 90" from a standard surface upon which jt has been applied under no other pressure than the weight of the tape itself.
  • Quick Stick is measured using a tens ⁇ meter with a crosshead speed of 12 in/min (0.51 cm/s). The Quick Stick is reported as the average of two or three determinations.
  • This bimodal BABA block copolymer had an overall Mw of 120,000, a styrene content of 20% by weight, and Melt Index G of 13 g/s.
  • the comparative adhesive formulations A-C utilized KratonTM 1107
  • the KratonTM 1107 S-l-S block copolymer had an overall M* of 115,000, a styrene content of 17% by weight, and a Melt Index G of 13 g/s.
  • Table 1 summarizes and identifies the properties of the formulated adhesive compositions.
  • Adhesive compositions having good tack and high cohesive strength are useful in many PSA applications such as tapes and labels.
  • the adhesive compositions can be coated from the melt or from solution onto various substrates such as paper or plastic films such as polyester, polypropylene, polyethylene, etc., or foam such as polyurethane, polystyrene, etc.
  • the adhesive compositions of this invention as exemplified by Examples 1 through 3 clearly are superior to an adhesive composition prepared from ABA block copolymers,
  • polyisoprene-polystyrene-polyisopre ⁇ e-polystyre ⁇ e or BABA block copolymers described herein may be prepared using any of the well-known anionic polymerization synthesis techniques for preparing linear styrenic block copolymers.
  • anionic polymerization synthesis techniques for preparing linear styrenic block copolymers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

On décrit des copolymères multiséquencés de polyisoprène-polystyrène qui peuvent être utilisés avec des résines donnant du collant, de l'huile ramollissante et des antioxydants pour préparer des adhésifs thermofusibles sensibles à la pression se caractérisant par un équilibre amélioré de leurs propriétés de pouvoir collant, de viscosité, de liaison et la température de défaut d'adhérence par cisaillement.
PCT/US2000/008012 1999-03-25 2000-03-24 Compositions d'adhesif contenant des copolymeres multisequences de polyisoprene-polystyrene et articles contenant ces dernieres Ceased WO2000056796A1 (fr)

Applications Claiming Priority (2)

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US27600999A 1999-03-25 1999-03-25
US09/276,00919990325 1999-03-25

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WO2000056796A1 true WO2000056796A1 (fr) 2000-09-28

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002000787A1 (fr) * 2000-06-27 2002-01-03 Exxonmobil Chemical Company Copolymeres tetrasequences
WO2002000806A3 (fr) * 2000-06-27 2002-05-23 Exxonmobil Chem Patents Inc Adhesifs a meilleure performance de decoupage a l'emporte-piece
US6576686B1 (en) 2000-06-27 2003-06-10 Exxonmobil Chemical Patents Inc. Road marking compound comprising linear tetrablock copolymers
EP1348737A1 (fr) * 2002-03-28 2003-10-01 KRATON Polymers Research B.V. Coposition bitumineuse
WO2005075594A1 (fr) * 2004-02-06 2005-08-18 Kraton Polymers Research B.V. Adhesif sensible a la pression et compositions preparees a l'aide de celui-ci
WO2006017776A2 (fr) 2004-08-05 2006-02-16 Firestone Polymers, Llc Synthese en une seule etape d'un polymere fonctionnel multibloc
WO2007012612A1 (fr) * 2005-07-26 2007-02-01 Kraton Polymers Research B.V. Films d'emballage lamines souples comprenant une couche d'un copolymere sequence
US7262248B2 (en) 2004-05-11 2007-08-28 Kraton Polymers U.S. Llc Articles prepared from high molecular weight tetrablock copolymers
CN112210314A (zh) * 2020-09-22 2021-01-12 广东新时代新材料科技有限公司 一种保温毯胶带

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251905A (en) * 1963-08-05 1966-05-17 Phillips Petroleum Co Method of preparing block copolymers of conjugated dienes and vinyl-substituted aromatic compounds using dilithio catalysts and diluent mixture of hydrocarbon and ether
US3639517A (en) * 1969-09-22 1972-02-01 Phillips Petroleum Co Resinous branched block copolymers
US5554697A (en) * 1994-04-11 1996-09-10 Shell Oil Company Linear block copolymers process for their preparation and adhesive composition containing them
US5773506A (en) * 1995-03-03 1998-06-30 Minnesota Mining And Manufacturing Pressure sensitive adhesive comprising a block copolymer having low molecular weight endblocks and endblock-compatible tackifier or oil
US5773521A (en) * 1995-12-19 1998-06-30 Shell Oil Company Coupling to produce inside-out star polymers with expanded cores

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251905A (en) * 1963-08-05 1966-05-17 Phillips Petroleum Co Method of preparing block copolymers of conjugated dienes and vinyl-substituted aromatic compounds using dilithio catalysts and diluent mixture of hydrocarbon and ether
US3639517A (en) * 1969-09-22 1972-02-01 Phillips Petroleum Co Resinous branched block copolymers
US5554697A (en) * 1994-04-11 1996-09-10 Shell Oil Company Linear block copolymers process for their preparation and adhesive composition containing them
US5773506A (en) * 1995-03-03 1998-06-30 Minnesota Mining And Manufacturing Pressure sensitive adhesive comprising a block copolymer having low molecular weight endblocks and endblock-compatible tackifier or oil
US5773521A (en) * 1995-12-19 1998-06-30 Shell Oil Company Coupling to produce inside-out star polymers with expanded cores

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004502020A (ja) * 2000-06-27 2004-01-22 エクソンモービル・ケミカル・パテンツ・インク 改良された打抜き性能を有する接着剤
WO2002000806A3 (fr) * 2000-06-27 2002-05-23 Exxonmobil Chem Patents Inc Adhesifs a meilleure performance de decoupage a l'emporte-piece
US6576686B1 (en) 2000-06-27 2003-06-10 Exxonmobil Chemical Patents Inc. Road marking compound comprising linear tetrablock copolymers
US6627678B2 (en) 2000-06-27 2003-09-30 Exxonmobil Chemical Patents Inc. Road marking compound comprising linear tetrablock copolymers
WO2002000787A1 (fr) * 2000-06-27 2002-01-03 Exxonmobil Chemical Company Copolymeres tetrasequences
US7271207B2 (en) 2002-03-28 2007-09-18 Kraton Polymers U.S. Llc Bituminous composition
WO2003082985A1 (fr) * 2002-03-28 2003-10-09 Kraton Polymers Research B.V. Composition bitumineuse
EP1348737A1 (fr) * 2002-03-28 2003-10-01 KRATON Polymers Research B.V. Coposition bitumineuse
WO2005075594A1 (fr) * 2004-02-06 2005-08-18 Kraton Polymers Research B.V. Adhesif sensible a la pression et compositions preparees a l'aide de celui-ci
US7262248B2 (en) 2004-05-11 2007-08-28 Kraton Polymers U.S. Llc Articles prepared from high molecular weight tetrablock copolymers
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
CN1993395B (zh) * 2004-08-05 2010-12-15 费尔斯通聚合物有限责任公司 多嵌段的功能聚合物
US7902295B2 (en) 2004-08-05 2011-03-08 Firestone Polymers, Llc Single step synthesis of functional multi-block polymer
WO2007012612A1 (fr) * 2005-07-26 2007-02-01 Kraton Polymers Research B.V. Films d'emballage lamines souples comprenant une couche d'un copolymere sequence
CN112210314A (zh) * 2020-09-22 2021-01-12 广东新时代新材料科技有限公司 一种保温毯胶带

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