US20130225020A1 - High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications - Google Patents

High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications Download PDF

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Publication number
US20130225020A1
US20130225020A1 US13/404,150 US201213404150A US2013225020A1 US 20130225020 A1 US20130225020 A1 US 20130225020A1 US 201213404150 A US201213404150 A US 201213404150A US 2013225020 A1 US2013225020 A1 US 2013225020A1
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United States
Prior art keywords
styrene
block copolymer
styrenic block
diene
selectively hydrogenated
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Abandoned
Application number
US13/404,150
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English (en)
Inventor
John Flood
Kathryn Wright
Lydia Salazar
Robert Q. Kluttz
Donn DuBois
Troy Wiegand
Norio Masuko
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Kraton Polymers US LLC
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Kraton Polymers US LLC
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.)
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Publication date
Application filed by Kraton Polymers US LLC filed Critical Kraton Polymers US LLC
Priority to US13/404,150 priority Critical patent/US20130225020A1/en
Assigned to KRATON POLYMERS U.S. LLC reassignment KRATON POLYMERS U.S. LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUBOIS, DONN, MASUKO, NORIO, FLOOD, JOHN, KLUTTZ, ROBERT Q., SALAZAR, LYDIA, WIEGAND, TROY, WRIGHT, KATHRYN
Priority to TW104132881A priority patent/TWI595061B/zh
Priority to TW102101683A priority patent/TWI561602B/zh
Priority to PCT/US2013/027009 priority patent/WO2013148024A1/en
Priority to CN201611230886.4A priority patent/CN107057260B/zh
Priority to BR112014020022A priority patent/BR112014020022A8/pt
Priority to EP18172919.5A priority patent/EP3381953B1/en
Priority to JP2014558810A priority patent/JP6001685B2/ja
Priority to CN201380010772.7A priority patent/CN104379667B/zh
Priority to EP13769284.4A priority patent/EP2817371B1/en
Priority to KR1020147026808A priority patent/KR101680441B1/ko
Priority to US13/940,663 priority patent/US9771473B2/en
Publication of US20130225020A1 publication Critical patent/US20130225020A1/en
Priority to US14/469,716 priority patent/US9359523B2/en
Priority to US14/469,695 priority patent/US9243163B2/en
Priority to US14/469,732 priority patent/US9249335B2/en
Priority to US14/972,188 priority patent/US9637660B2/en
Priority to JP2016004995A priority patent/JP6321055B2/ja
Priority to JP2017156467A priority patent/JP6702917B2/ja
Abandoned legal-status Critical Current

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Definitions

  • the invention relates to high melt flow, low viscosity selectively hydrogenated styrene-butadiene-styrene (hSBS, also known as SEBS) or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene (hSBSS, also known as styrene-ethylene butadiene/styrene-styrene (S-EB/S-S)) block copolymers and applications therefore, wherein the melt flow rate is at least 100 g/10 min at 230° C. under a 2.16 kg mass according to ASTM D1238.
  • block copolymers are novel and have significantly higher melt flow rates than other known styrenic block copolymers and also exhibit surprising high strength and elasticity. They have applications that, prior to the present invention, were not possible due to the normally low melt flow rate of styrenic block copolymers.
  • Melt flow rate is inversely correlated to viscosity of the polymer.
  • a high melt flow rate means that the polymer has a low viscosity and vice versa. While a few styrenic block copolymers have high melt flow rates, they achieve that with a high (>60 wt. %) diblock content and therefore have comparatively poor mechanical properties.
  • U.S. Pat. No. 7,439,301 to Handlin, Jr. relates to coupled block copolymers having high melt flow and high elasticity.
  • the true molecular weight for the block copolymer is between 40,000 to 70,000; the polystyrene content (PSC) is between 13 to 25%, the vinyl content is between 60 to 85%, and a coupling efficiency of 89 to 97%.
  • PSC polystyrene content
  • composite systems have been based on fiberglass mat plies or layers in addition to a binder.
  • the binder could include non-reactive or reactive polymeric binder such as polyester, vinyl ester or epoxy resins, or a non-reactive resin such as asphalt or bitumen.
  • the fiberglass mat plies are commonly used as structural support components for the composite.
  • Composites are often designed to have maximum impact resistance while maintaining low density so that weight can be minimized.
  • Traditional composite designs achieve toughness either through toughening of the reactive resin through the addition of dispersed rubber particles that arrest crack growth or through the use of optimized sizings on the glass fibers in order to improve adhesion between the glass fibers and the reactive resin binder. Both toughening mechanisms can also be used simultaneously.
  • Low viscosity coatings using styrenic block copolymers are virtually unknown because the copolymers normally have such high viscosity. Often a balance must be achieved between low volatile organic compounds (VOC), high solids content, and low viscosity.
  • VOC low volatile organic compounds
  • Styrenic block copolymers have been employed in the adhesive market for hot melt, quick release covering, and pressure sensitive adhesives.
  • Adhesives made with traditional hSBS SEBS
  • SEBS Styrenic block copolymers
  • SEBS Styrenic block copolymers
  • SEBS Styrenic block copolymers
  • SEBS Styrenic block copolymers
  • SBS Styrenic block copolymers
  • SEBS Styrenic block copolymers
  • SEBS Styrenic block copolymers
  • APO amorphous poly alpha olefins
  • U.S. Pat. No. 7,348,376 to Gelles describes the combination of low melt flow rate hSBS polymers with APOs. However, these formulations lack the viscosity needed for application at low spray temperatures of ⁇ 325° F.
  • the novel compound of the present invention is different than more conventional hSBS or controlled distribution hSBSS because it has a very high melt flow rate, a corresponding low viscosity, and good tensile strength and elasticity. This also makes it possible for such polymers to participate in markets not typically considered, such as toughening fiberglass, low viscosity—low VOC polymer coatings, adhesives based on blended systems requiring low viscosity for improved processability, and film and non-woven personal hygiene applications. Thus there is a need for high melt flow rate hSBC products that have good performance characteristics such as strength and elasticity.
  • ranges set forth in the specification and claims include not only the end point of the ranges, but also every conceivable number between the end point of the ranges, since that is the very definition of a range.
  • ranges specifying the molecular weight, polystyrene content, vinyl content, coupling efficiency, etc. are intended to include this definition of a range.
  • the present invention encompasses a novel hSBS (S-EB-S) or hSBSS (S-EB/S-S) that possess a high melt flow rate, low viscosity, high strength, and good elastic properties.
  • the styrenic block copolymer comprises a melt flow rate equal to or greater than 100 g/10 min, a minimum linear true peak molecular weight (Mp) of about 45,000, a PSC of between about 18 to about 45%, a vinyl content of about 65 to 80%, and a coupling efficiency of about 60 to about 97%, said styrenic block copolymer having a structure consistent with selectively hydrogenated poly(monoalkenylarene-diene-monoalkenylarene), or poly(mono-alkenylarene-diene) n X, or controlled distribution poly(monoalkenylarene-diene/monoalkenyl-arene-monoalkenylarene) or poly(mono
  • the mono-alkenylarene monomer is preferably selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, tertiary-butyl styrene, vinyl toluene and the like or mixtures thereof; of these, styrene is the most preferred.
  • the diene monomer can be any aliphatic conjugated diene including 1,3-butadiene or substituted butadienes such as isoprene or mixtures thereof; of these, 1,3-butadiene is the most preferred.
  • butadiene refers specifically to “1,3-butadiene”.
  • An hSBS of selectively hydrogenated poly(styrene-butadiene-styrene) is also known as S-EB-S
  • an hSBSS of selectively hydrogenated controlled distribution poly(styrene-butadiene/styrene-styrene) is also known as S-EB/S-S.
  • These styrenic block copolymers may be functionalized in a number of ways to include reactive groups such as carboxylic acids and their salts, anhydrides, esters, imides, amides, amide and acid chloride groups.
  • the present invention also encompasses various fields of use, such as toughened fiberglass hSBS or hSBSS reinforced mats for composite applications, low viscosity hSBS or hSBSS coatings for industrial uses, hot melt adhesives prepared from hSBS or hSBSS blends with APOs, elastic films, melt blown fibers and articles, and low viscosity molding applications, such as slush molding, rotational molding, or injection molding.
  • Fiber-reinforced polymers can be of the thermoset or thermoplastic type.
  • the fiber reinforcement is typically in the form of a chopped, non-woven, or wet-laid mat or woven scrim.
  • the fiber reinforcement is typically in the form of chopped fibers either short or long in dimension.
  • a sizing or coating is sometimes applied to the surface of the fibers or bundles of fibers. Many different techniques have been developed to coat ceramic or polymeric fibers or bundles of fibers.
  • hSBS or hSBSS or maleated hSBS or hSBSS finds utility as a sizing agent or coating when bonded to the surface of individual ceramic or polymeric fibers or bundles of fibers.
  • ceramic and polymeric fibers include but are not limited to glass fiber (or fiberglass), carbon fiber, aramid fiber, and polyester fiber.
  • a fiberglass reinforced mat comprising: a woven, nonwoven, chopped, or wet laid fiberglass mat or scrim (herein referred to as mat) and an hSBS or hSBSS block copolymer article bonded to said mat; said hSBS or hSBSS block copolymer having a melt flow rate equal to or greater than 100 g/10 min, wherein when 140 g/m 2 (grams per square meter) of said styrenic block copolymer is applied to said mat, the average impact energy is at least 3 times larger than without said styrenic block copolymer.
  • the amount of styrenic block copolymer of the present invention in a reinforced mat or scrim is about 50 to about 500 g/m 2 .
  • the amount of styrenic block copolymer of the present invention in a reinforced mat or scrim is about 50 to about 200 g/m 2 .
  • Such reinforced mats possess an average impact energy of at least 2 times, and preferably at least 3 times (or more), than mats without the hSBS or hSBSS block copolymer of the present invention.
  • Maleated hSBS or hSBSS finds utility as a sizing agent when bonded to the surface of individual glass fibers.
  • other rigid fibers routinely used in composite articles, such as carbon fibers may be used in place of fiberglass.
  • Low viscosity coatings containing solvent and styrenic block copolymers of the present invention are primarily used in industrial and marine applications, in coating metal to prevent corrosion, or concrete to protect against certain chemical attack, such as oil.
  • Such coatings may further contain a slip-resistant additive, a component making said coating removable, such as a protective coating; a corrosion resistant additive, a shatter-proof additive, a primer additive, or a maintenance corrosion resistance additive such as iron oxide.
  • a low viscosity hSBS or hSBSS polymer coating formulation comprising: a blend of solvent and hSBS or hSBSS block copolymer; said block copolymer having a melt flow rate equal to or greater than 100 g/10 min, wherein said solvent is selected from the class of non-exempt organic solvents or exempt solvents or mixtures thereof.
  • Exempt solvents include: methyl acetate, para-chlorobenzotriflouride, tertiary-butyl acetate, or acetone, wherein said blend is at least 50 wt. % solids.
  • the blend may also contain at least one other ingredient selected from the group of endblock resin, midblock resin, polyisobutylene polymers, polyphenylene ether, and/or one or more fillers such as TiO 2 , CaCO 3 , carbon black, or other pigments, and said coating having a Brookfield viscosity ⁇ 150,000 cps as measured by ASTM D2196A.
  • These low viscosity polymer coating formulations may also include reactive monomers such as epoxy, acrylic, styrenic, vinyl-ester, or polyester resin. Such coatings find utility in industrial and marine applications.
  • Functionalized polymers of the present invention such as maleic anhydride grafted onto the backbone of hSBS or hSBSS polymers also find utility in low viscosity polymer coatings.
  • modified wax compositions comprising the addition of midblock resin(s), additives such as EVA or/and PE wax, organic fillers, and hydrogenated styrenic block copolymers have utility in applications such as investment casting, flexible packaging wax (paper/film/foil-based, in-mold labeling, confectionery wrap, cheese & butter wrap, coffee packaging), hot melt adhesive wax, general industrial wax, cosmetic and pharmaceutical wax (crèmes and ointments, decorative cosmetics, depilatory wax, medical wax) paper and board converting (board & sheet laminating, multi wall paper bags & sacks, envelopes, security & document bags, tube winding, case & carton, labeling) , construction (roof insulation, roofing membranes, sandwich panels), product assembly (strapping, air filters), emulsions, wax coatings, food (chewing gum and dairy), wax extrusion, tire & rubber (tires, technical rubber
  • Suitable midblock resins are C 5 resin (pentadiene resin, pentene, etc.), hydrogenated C 5 resin, terpene resin, rosin ester resin, or combinations thereof.
  • Suitable organic fillers are crosslinked polystyrene, bisphenol acid, terephthalic acid or combinations thereof and have a particle size of less than 200 microns.
  • High melt flow hSBS polymers of the present invention in blends containing microcrystalline wax, polyethylene wax, naphthalene wax, paraffin wax, and less refined wax or combinations thereof are of interest in modified wax applications to improve strength, toughness, and elasticity, yet remain sufficiently ridged while maintaining a formulated viscosity of about 2,000-10,000 cps, more preferably 3,000-5,000 cps measured via cone and plate rheometry at 140° F. and 50 sec ⁇ 1 .
  • Low temperature, impact resistance, lower moisture vapor transmission rate, and improved flex crack resistance are also beneficial features that the low viscosity polymers bring to modified wax applications. Examples of applications are investment casting where wax is brittle for large molds or very thin parts. High margin investment casting molds are used in automotive, aerospace, medical body prosthetic replacement (e.g. knee and hip parts), and leisure sports (e.g. golf parts) industries.
  • High melt flow (low viscosity) hSBS polymers are also of interest to modify less refined wax where oil bleed out must be controlled such as scale wax.
  • the use of high melt flow hSBS polymers to improve strength, toughness, and elasticity of less refined wax adds value to the system economics as less refined wax is less expensive and more plentiful.
  • an adhesive composition comprising: a blend of amorphous poly-alpha-olefin, hSBS or hSBSS block copolymer, and tackifier; said block copolymer having a melt flow rate equal to or greater than 100 g/10 min, said amorphous poly-alpha-olefin is present from about 30 to about 80 wt. % of said composition, said block copolymer is present from about 10 to about 35 wt. % of said composition, and said tackifier is present from about 20 to about 60 wt. % of said composition.
  • a film or melt blown article containing hSBS or hSBSS having a low molecular weight in a range between 45,000 to 65,000, with a melt flow rate equal to or greater than 100 g/10 min has excellent strength and elasticity, as defined by a film article having a tensile strength >10MPa and elongation >500% in addition to a hysteresis set after 100% elongation of about 5%.
  • the melt blown elastic article at 50 g/m 2 (grams per square meter) has excellent elasticity, defined by having an ultimate tensile elongation >400%, with 100% hysteresis recovered energy >80%, and permanent set ⁇ 10%.
  • a melt blown fabric may further include at least one additional nonwoven layer comprised of thermoplastic polymer comprising spunbond, bicomponent spunbond, melt blown, or a bonded-carded-web layer used in the construction of an adsorbent personal hygiene product such as a baby diaper article, adult incontinence article, or feminine napkin article.
  • the non-woven laminate can be made more elastic via an activation process such as tentering, drawing and ring rolls.
  • Melt blown articles may contain an additional component of high flow polyolefin having a melt flow rate >40 g/10 min, polyisobutylene, polybutene, thermoplastic polyurethane, thermoplastic copolyester, oil, styrenic block copolymer with melt flow rate ⁇ 100 g/10 min, and/or mid-block or end block resins, such as Oppera 100A, Regalrez 1126, or Kristalex 5140.
  • a slush molding or rotational molding composition such as is disclosed in EP Pat. No. 0733677 or WO Pat. No. 2011/092071 employs, styrenic block copolymer, wherein the molding composition has a melt index in the range from 5 to 75, but examples disclose 40 to 89 g/10 min at 190° C. with 2.16 kg mass.
  • an aqueous based emulsion of the styrenic block copolymer of the present invention (hSBS and or hSBSS) having the low melt flow rate and molecular weight described previously may be employed as a coating.
  • the coating may optionally include functionalized styrenic block copolymers of the invention, less than 20 wt. % organic solvent, and/ or tackifying resin.
  • Either the solvent based or aqueous based coating may find utility by impregnating a fabric (woven or nonwoven) or felt.
  • the coating may include a foaming agent and be incorporated in foamed articles.
  • FIG. 1 is a graph of chopped fiberglass mat toughening shown by Total Impact Energy in inch—pound force vs. hSBS basis weight in grams per square meter, as tabulated in Table 1.
  • FIG. 2 is a photo of the test specimens associated with Tables 10 and 11.
  • the term “molecular weights” refers to the true molecular weight in g/mol of the polymer or block of the copolymer.
  • the molecular weights referred to in this specification and claims can be measured with gel permeation chromatography (GPC) using polystyrene calibration standards, such as is done according to ASTM 3536.
  • GPC gel permeation chromatography
  • polystyrene calibration standards such as is done according to ASTM 3536.
  • GPC is a well-known method wherein polymers are separated according to molecular size, the largest molecule eluting first.
  • the chromatograph is calibrated using commercially available polystyrene molecular weight standards.
  • the molecular weight of polymers measured using GPC so calibrated are styrene equivalent molecular weights, also known as apparent molecular weights.
  • the styrene equivalent molecular weight may be converted to true molecular weight when the styrene content of the polymer and the vinyl content of the diene segments are known.
  • the detector used is preferably a combination ultraviolet and refractive index detector.
  • the molecular weights expressed herein are measured at the peak of the GPC trace, converted to true molecular weights, and are commonly referred to as “peak molecular weights”. When expressed as apparent molecular weights they are similarly determined with the exception that consideration of the block copolymer composition and the subsequent conversion to true molecular weights is not done.
  • Starting materials for preparing the block copolymers of the present invention include the initial monomers.
  • the alkenyl arene can be selected from styrene, alpha-methylstyrene, para-methylstyrene, vinyl toluene, vinylnaphthalene, and para-butyl styrene or mixtures thereof. Of these, styrene is most preferred and is commercially available, and relatively inexpensive, from a variety of manufacturers.
  • the conjugated dienes for use herein are 1,3-butadiene and substituted butadienes such as isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, and 1-phenyl-1,3-butadiene, or mixtures thereof. Of these, 1,3-butadiene is most preferred. As used herein, and in the claims, “butadiene” refers specifically to “1,3-butadiene”.
  • polymerization initiators include, for example, alkyl lithium compounds and other organolithium compounds such as s-butyllithium, n-butyllithium, t-butyllithium, amyllithium and the like, including di-initiators such as the di-sec-butyl lithium adduct of m-diisopropenyl benzene.
  • di-initiators are disclosed in U.S. Pat. No. 6,492,469.
  • s-butyllithium is preferred.
  • the initiator can be used in the polymerization mixture (including monomers and solvent) in an amount calculated on the basis of one initiator molecule per desired polymer chain.
  • the lithium initiator process is well known and is described in, for example, U.S. Pat. Nos. 4,039,593 and Re. 27,145, which descriptions are incorporated herein by reference.
  • the solvent used as the polymerization vehicle may be any hydrocarbon that does not react with the living anionic chain end of the forming polymer, is easily handled in commercial polymerization units, and offers the appropriate solubility characteristics for the product polymer.
  • non-polar aliphatic hydrocarbons which are generally lacking in ionizable hydrogens make particularly suitable solvents.
  • cyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, all of which are relatively non-polar.
  • Other suitable solvents will be known to one skilled in the art and can be selected to perform effectively in a given set of process conditions, with temperature being one of the major factors taken into consideration.
  • radial (branched) polymers require a post-polymerization step called “coupling”. It is possible to have either a branched selectively hydrogenated block copolymer and/or a branched tailored softening modifier.
  • n is an integer of from 2 to about 30, preferably from about 2 to about 15, and X is the remnant or residue of a coupling agent.
  • a variety of coupling agents are known in the art and include, for example, dihalo alkanes, silicon halides, siloxanes, multifunctional epoxides, silica compounds, esters of monohydric alcohols with carboxylic acids, (e.g., dimethyl adipate) and epoxidized oils.
  • Star-shaped polymers are prepared with polyalkenyl coupling agents as disclosed in, for example, U.S. Pat. Nos. 3,985,830; 4,391,949; and 4,444,953; Canadian Pat. No. 716,645.
  • Suitable polyalkenyl coupling agents include divinylbenzene, and preferably m-divinylbenzene.
  • tetra-alkoxysilanes such as tetra-ethoxysilane (TEOS) and tetra-methoxysilane
  • alkyl-trialkoxysilanes such as methyl-trimethoxy silane (MTMS)
  • MTMS methyl-trimethoxy silane
  • aliphatic diesters such as dimethyl adipate and diethyl adipate
  • diglycidyl aromatic epoxy compounds such as diglycidyl ethers deriving from the reaction of bis-phenol A and epichlorohydrin.
  • Coupling efficiency is of critical importance in the synthesis of block copolymers, which copolymers are prepared by a linking technology.
  • the unlinked arm has only one hard segment (typically polystyrene). Two hard segments are required in the block copolymer if it is to contribute to the strength mechanism of the material. Uncoupled arms dilute the strength forming network of a block copolymer that weakens the material.
  • the very high coupling efficiency realized in the present invention is key to making high strength, coupled, block copolymers.
  • Another important aspect of the present invention is to control the microstructure or vinyl content of the conjugated diene in the B block.
  • the term “vinyl” has been used to describe the polymer product that is made when 1,3-butadiene is polymerized via a 1,2-addition mechanism. The result is a monosubstituted olefin group pendant to the polymer backbone, a vinyl group.
  • insertion of the isoprene via a 3,4-addition mechanism affords a geminal dialkyl C ⁇ C moiety pendant to the polymer backbone.
  • Polymer microstructure (mode of addition of the conjugated diene) is effectively controlled by addition of an ether, such as diethyl ether, a diether such as 1,2-diethoxypropane, or an amine as a microstructure modifier to the diluent.
  • an ether such as diethyl ether
  • a diether such as 1,2-diethoxypropane
  • an amine as a microstructure modifier to the diluent.
  • Suitable ratios of microstructure modifier to lithium polymer chain end are disclosed and taught in U.S. Pat. No. Re. 27,145.
  • chelating ether means an ether having more than one oxygen as exemplified by the formula R(OR′).sub.m (OR′′).sub.o OR where each R is individually selected from 1 to 8, preferably 2 to 3, carbon atom alkyl radicals; R′ and R′′ are individually selected from 1 to 6, preferably 2 to 3, carbon atom alkylene radicals; and m and o are independently selected integers of 1-3, preferably 1-2.
  • preferred ethers include diethoxypropane, 1,2-dioxyethane (dioxo) and 1,2-dimethyoxyethane (glyme).
  • Suitable materials include CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 3 (C 6 H 14 O 3 —diglyme) and CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 —OCH 2 CH 3 .
  • “Chelating amine” means an amine having more than one nitrogen such as N,N,N′,N′-tetramethylethylene diamine.
  • the amount of polar modifier is controlled in order to obtain the desired vinyl content in the conjugated diene block.
  • the polar modifier is used in an amount of at least 0.1 moles per mole of lithium compound, preferably 1-50, more preferably 2-25, moles of promoter per mole of the lithium compound.
  • the concentration can be expressed in parts per million by weight based on the total weight of solvent and monomer. Based on this criteria from 10 parts per million to about 1 weight percent, preferably 100 parts per million to 2000 parts per million are used. This can vary widely, however, since extremely small amounts of some of the preferred modifiers are very effective. At the other extreme, particularly with less effective modifiers, the modifier itself can be the solvent. Again, these techniques are well known in the art, disclosed for instance in Winkler, U.S.
  • Hydrogenation can be carried out via any of the several hydrogenation or selective hydrogenation processes known in the prior art.
  • such hydrogenation has been accomplished using methods such as those taught in, for example, U.S. Pat. Nos. 3,595,942; 3,634,549; 3,670,054; 3,700,633; and Re. 27,145, the disclosures of which are incorporated herein by reference. These methods operate to hydrogenate polymers containing aromatic or ethylenic unsaturation and are based upon operation of a suitable catalyst.
  • Such catalyst, or catalyst precursor preferably comprises a Group VIII metal such as nickel or cobalt which is combined with a suitable reducing agent such as an aluminum alkyl or hydride of a metal selected from Groups I-A, II-A and III-B of the Periodic Table of the Elements, particularly lithium, magnesium or aluminum.
  • a suitable reducing agent such as an aluminum alkyl or hydride of a metal selected from Groups I-A, II-A and III-B of the Periodic Table of the Elements, particularly lithium, magnesium or aluminum.
  • This preparation can be accomplished in a suitable solvent or diluent at a temperature from about 20° C. to about 80° C.
  • Other catalysts that are useful include titanium based catalyst systems.
  • controlled distribution is defined as referring to a molecular structure having the following attributes: (1) terminal regions adjacent to the mono alkenyl arene homopolymer (“A”) blocks that are rich in (i.e., having a greater than average amount of) conjugated diene units; (2) one or more regions not adjacent to the A blocks that are rich in (i.e., having a greater than average amount of) mono alkenyl arene units; and (3) an overall structure having relatively low blockiness.
  • “rich in” is defined as greater than the average amount, preferably greater than 5% the average amount.
  • This relatively low blockiness can be shown by either the presence of only a single glass transition temperature (“Tg,”) intermediate between the Tg's of either monomer alone, when analyzed using differential scanning calorimetry (“DSC”) thermal methods or via mechanical methods, or as shown via proton nuclear magnetic resonance (“H-NMR”) methods.
  • Tg glass transition temperature
  • DSC differential scanning calorimetry
  • H-NMR proton nuclear magnetic resonance
  • the potential for blockiness can also be inferred from measurement of the UV-visible absorbance in a wavelength range suitable for the detection of polystyryllithium end groups during the polymerization of the B block. A sharp and substantial increase in this value is indicative of a substantial increase in polystyryllithium chain ends. In this process, this will only occur if the conjugated diene concentration drops below the critical level to maintain controlled distribution polymerization.
  • styrene blockiness as measured by those skilled in the art using proton NMR, is defined to be the proportion of S units in the polymer having two S nearest neighbors on the polymer chain. The styrene blockiness is determined after using H-1 NMR to measure two experimental quantities as follows:
  • the total number of styrene units is determined by integrating the total styrene aromatic signal in the H-1 NMR spectrum from 7.5 to 6.2 ppm and dividing this quantity by 5 to account for the 5 aromatic hydrogens on each styrene aromatic ring.
  • the blocky styrene units are determined by integrating that portion of the aromatic signal in the H-1 NMR spectrum from the signal minimum between 6.88 and 6.80 to 6.2 ppm and dividing this quantity by 2 to account for the two ortho hydrogens on each blocky styrene aromatic ring.
  • the assignment of this signal to the two ortho hydrogens on the rings of those styrene units which have two styrene nearest neighbors was reported in F. A. Bovey, High Resolution NMR of Macromolecules (Academic Press, New York and London, 1972), Chapter 6.
  • the styrene blockiness is simply the percentage of blocky styrene to total styrene units:
  • Blocky % 100 times(Blocky Styrene Units/Total Styrene Units)
  • Polymer-Bd-S—(S) n —S-Bd-Polymer where n is greater than zero is defined to be blocky styrene.
  • n 8 in the example above, then the blockiness index would be 80%. It is preferred that the blockiness index be less than about 40. For some polymers, having styrene contents of ten weight percent to forty weight percent, it is preferred that the blockiness index be less than about 10.
  • Hydrogenation can be carried out under such conditions that at least about 90% of the conjugated diene double bonds have been reduced, and between zero and 10% of the arene double bonds have been reduced. Preferred ranges are at least about 95% of the conjugated diene double bonds reduced, and more preferably about 98% of the conjugated diene double bonds are reduced.
  • aqueous acid preferably 20-30 percent by weight
  • Suitable acids include phosphoric acid, sulfuric acid and organic acids. This stirring is continued at about 50° C. for about 30 to about 60 minutes while sparging with a mixture of oxygen in nitrogen. Care must be exercised in this step to avoid forming an explosive mixture of oxygen and hydrocarbons.
  • a reinforcement may be defined simply as the material that is added to a resinous matrix to improve the strength of the polymer. Most of these reinforcing materials are inorganic or organic products of high molecular weight. Various examples include calcium carbonate, talc, silica, clays, glass fibers, asbestos, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers. Especially preferred are reinforced polymer blends of the instant invention containing about 2 to about 80 percent by weight calcium carbonate, based on the total weight of the resulting reinforced blend.
  • polymer blends of the present invention may be compounded further with other polymers, oils, fillers, reinforcements, antioxidants, stabilizers, fire retardants, antiblocking agents, lubricants and other rubber and plastic compounding ingredients without departing from the scope of this invention.
  • Tackifying resins include polystyrene block compatible resins and midblock compatible resins.
  • the polystyrene block compatible resin may be selected from the group of coumarone-indene resin, polyindene resin, poly(methyl indene) resin, polystyrene resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin and polyphenylene ether, in particular poly(2,6-dimethyl-1,4-phenylene ether).
  • Such resins are e.g. sold under the trademarks “HERCURES”, “ENDEX”, “KRISTALEX”, “NEVCHEM” and “PICCOTEX”.
  • Resins compatible with the hydrogenated (mid) block may be selected from the group consisting of compatible C 5 hydrocarbon resins, hydrogenated C 5 hydrocarbon resins, styrenated C 5 resins, C 5 /C 9 resins, styrenated terpene resins, fully hydrogenated or partially hydrogenated C 9 hydrocarbon resins, rosins esters, rosins derivatives and mixtures thereof. These resins are e.g. sold under the trademarks “REGALITE”, “REGALREZ”, “ESCOREZ” and “ARKON.
  • the amount of tackifying resin employed varies from about 5 to about 100 parts by weight per hundred parts by weight rubber, or block copolymer, preferably about 20 to about 50 parts by weight. Also, one may use both a polystyrene block compatible resin and a midblock compatible resin.
  • the novel hSBS or hSBSS block copolymer has a melt flow rate >100 g/10 min at 230° C., and 2.16 kg mass (ASTM D-1238), a minimum linear molecular weight of about 45,000 to about 65,000, a PSC of between about 18 to about 45%, a vinyl content of about 65 to 80%, and a coupling efficiency of about 60 to about 97%, said styrenic block copolymer being selectively hydrogenated styrene-butadiene-styrene (hSBS) or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene (hSBSS).
  • hSBS selectively hydrogenated styrene-butadiene-styrene
  • hSBSS selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene
  • the novel hSBS or hSBSS is a styrenic block copolymer having a structure consistent with selectively hydrogenated poly(monoalkenylarene-diene-monoalkenylarene), poly(monoalkenylarene-diene) n X, controlled distribution poly(monoalkenylarene-diene/monoalkenylarene-monoalkenylarene), or poly(monoalkenylarene-diene/monoalkenylarene) n X.
  • the monoalkenylarene monomer is preferably selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, tertiary-butyl styrene, vinyl toluene and the like or mixtures thereof; of these styrene is the most preferred.
  • the diene monomer can be any aliphatic conjugated diene including 1,3-butadiene or substituted butadienes such as isoprene or mixtures thereof; of these 1,3-butadiene is the most preferred.
  • butadiene refers specifically to “1,3-butadiene”.
  • the melt flow rate is achieved by hSBS or hSBSS wherein each styrene block has a peak molecular weight of between 5000 and 7000, and the total peak weight for either block copolymer is between 45,000 to 65,000.
  • the polymer, before hydrogenation, can be linear or radial having the respective S-D-S or (S-D) n X structure where n is 2-3, S is styrene, D is diene or diene/styrene, and X is the coupling agent residue.
  • the diene can be butadiene, isoprene, or mixtures thereof.
  • the coupling agent could include but is not limited to Epon 825, 862, 826, silanes like methyltrimethoxy silane, tetramethoxy silane, dimethyldimethoxy silane, and chlorosilanes.
  • the styrenic block copolymers of the present invention can also be functionalized by the incorporation of grafted maleic anhydride, for example, onto the back bone of the block copolymer.
  • the block copolymers of the present invention can be functionalized in a number of ways.
  • One way is by treatment with an unsaturated monomer having one or more saturated groups or their derivatives such as carboxylic acid groups and their salts, anhydrides, esters, imides, amides, or acid chloride groups.
  • the preferred monomers to be grafted onto the block copolymers are maleic anhydride, maleic acid, fumaric acid, or their derivatives. See, U.S. Pat. Nos. 4,578,429 and 5,506,299.
  • the selectively hydrogenated block copolymer of the present invention may be functionalized by grafting silicon or boron containing compounds to the polymer as taught by U.S. Pat. No. 4,882,384.
  • the block copolymer of the present invention may be reacted with an alkoxy-silane compound to form silane-modified block copolymer.
  • the block copolymers of the present invention may be functionalized by grafting at least one ethylene oxide molecule to the polymer as taught by U.S. Pat. No. 4,898,914, or reacting the polymer with carbon dioxide as taught by U.S. Pat. No. 4,970,265.
  • hSBS 201 kg Cyclohexane and 9.1 kg styrene were charged to an 80 gal stainless steel reactor at about 50° C. 2428 mL of about 12 wt. % s-butyllithium were then charged to the reactor to initiate polymerization. The styrene polymerization was allowed to proceed at about 50° C. until completion and a sample was collected for GPC. The molecular weight at this step was determined to be 4.8 kg/mole. An additional 0.38 kg of styrene was added and allowed to polymerize. GPC analysis of this polymer indicated that the molecular weight was 5.0 kg/mole. Butadiene was added at a rate of about 1 kg/min.
  • the S-B diblock polymer was then coupled by the addition of 114 mL of methyl trimethoxysilane, resulting in a polymer in which 94% of the diblock chains are coupled, the majority (82%) being linear, and the remainder being primarily 3-arm radial species. 55 ml of methanol were added to ensure termination.
  • This polymer was then hydrogenated to a residual unsaturation of 0.12 meq olefin/g using a Co/Al catalyst (1.7:1 Al:Co (mole/mole), about 22 PPM Co) at 700 psi hydrogen, 85° C.
  • a selectively hydrogenated styrene-butadiene-styrene polymer about 60 kg of the total 125 kg of polymer solution was added in the initial batch charge and the remainder was added at a rate as required to maintain the reaction temperature in the desired range.
  • the catalyst was oxidized and extracted by contacting the cement with aqueous phosphoric acid while sparging with an N 2 /O 2 gas blend; in addition, about 100 mL of caprylic acid was added.
  • the cement was then neutralized by sparging with ammonia, washed with deionized water and stabilized by the addition of Ethanox 330 (0.2 wt. % polymer basis) and Irgafos 168 (0.3 wt. % polymer basis).
  • Ethanox 330 0.2 wt. % polymer basis
  • Irgafos 168 0.3 wt. % polymer basis.
  • the resulting Inventive hSBS polymer had a melt flow rate of 2
  • the technology of the present invention is expected to provide impact resistance and enhanced toughness to composites containing fiberglass mats and scrims with significantly improved manufacturing and health, safety, and environmental aspects.
  • the hSBS or hSBSS of the present invention having a melt flow rate >100 g/10 min has sufficiently high molecular weight that it is not volatile and exhibits excellent elasticity and toughness while its high flow characteristics enable application as a melt blown fiber, fabric, or low basis weight film.
  • At least 3 different processes can be envisioned to combine a tough, elastic high flow hSBS or hSBSS with a fiberglass mat or scrim.
  • roofing materials are composites comprising at least one fiber glass mat and asphalt as the binder.
  • the hSBS or hSBSS was produced as a low basis weight film which was then laminated to a fiberglass mat.
  • a surprisingly low basis weight of the styrenic block copolymer was required in order to achieve a significant increase in the fiberglass mat's impact resistance. The following materials were used in this example.
  • HSBS film was extruded on a Killion film extruder with temperature settings of 300-330-360-370° F. with the die set to 370° F.
  • Fiberglass mat samples were cut into 15 inch-wide sections. HSBS film thicknesses having 140, 280, and 560 grams per square meter were overlaid on top of the fiberglass mat sections. The multi-layer construction was passed through a two roll laminator with the roll temperature set to 350° F. 10 cm ⁇ 10 cm squares were cut out of the laminated fiberglass mat sections and baked at 450° F. for 90 seconds with no applied pressure.
  • the 10 cm ⁇ 10 cm laminated fiberglass mat sections were tested in a Dynatup Instrumented Impact Tester Model 8250 where a weight of 4.2 lbs was impacted into the sample at a velocity of ⁇ 8400 in/min. The total impact force was measured by a load cell and the total impact energy was reported in in-lbf. The impact test temperature was 23° C.
  • a melt coating of hSBS applied at only 140 gsm results in an increase in the total impact energy by an order of magnitude from 2 in-lbf to 20 in-lbf, see Table 1 and FIG. 1 .
  • This basis weight is significantly lower than that of a reactive resin reported to provide sufficient toughening.
  • the total impact energy continued to increase such that the combination of basis weight and impact resistance could be tailored for specific applications.
  • laminated fiberglass mats of the present invention containing 50 to 1000 g/m 2 of the hSBS have an average impact energy of at least 2 times, preferably at least 3 times more compared to mats having no hSBS.
  • Fiberglass reinforced mats combined with bitumen, fillers and surfacing materials, find employment in forming roofing shingles, roofing membranes, insulation, sound mitigating articles, vibration damping articles, wind resistant articles, and geo-membranes having vegetative root growth resistance.
  • thermoset is epoxy, urethane, polyester, acrylic, or a vinyl ester resin
  • hSBS Low viscosity polymers
  • VOC volatile organic carbon
  • hSBSS Low viscosity polymers
  • hSBS has a high melt flow rate (low viscosity) and was compared to other low viscosity polymers. It has been determined that only 4 VOC exempt solvents can be considered with hSBS, namely methyl acetate, p-chlorobenzotriflouride, t-butyl acetate, and acetone. In areas where non-VOC restrictions are acceptable, any non-exempt solvent (organic solvents that are not exempt) compatible with the low viscosity polymer may be employed.
  • non-exempt solvents are Aromatic 100 (a light aromatic naphtha), Aromatic 200 (a heavy aromatic naphtha), xylene, toluene, and the like.
  • Coatings comprising a blend of solvent (exempt, non-exempt, or a mixture thereof) and at least 40 wt. % of the styrenic block copolymer of the present invention of hSBS or hSBSS have a VOC content of ⁇ 450 grams/liter, preferably ⁇ 350 grams/liter, and more preferably ⁇ 250 grams/liter.
  • PCBTF solvent p-chlorobenzotriflouride
  • Elastomeric white roof coatings have more stringent requirements such as the VOC must not be more than 250 g/liter.
  • Elastomeric white roof coating formulations were made to compare solution viscosities of G1643 and hSBS polymers. Formulations were targeted to meet a VOC of 250 grams/liter and all ingredient concentrations are listed in wt. %. Reduced viscosity has a significant effect on the application basis weight and drying time of the coating.
  • HSBS resulted in a coating formulation with suitable properties and lower viscosity than G1643. See Table 4.
  • the requirements for elastomeric roof coatings are listed in ASTM D6083. The viscosity requirement is 85-141 cps as measured by ASTM D562 Method A, Procedure A.
  • Aromatic 100 is the only solvent approved in Europe for white roof applications.
  • APO based adhesive formulations are low cost and low performance. They are, however, sprayable which enables applicability to a wide range of articles.
  • the performance of APO adhesive formulations can be upgraded to at least a mid-range performance by blending with hSBS of the present invention.
  • the formulation is still sprayable, unlike many mid-range performance polymers, including traditional SEBS based formulations based on SEBS polymer with melt flow rates less than 100 g/10 min.
  • Adhesive formulations find utility in pressure sensitive adhesives, hot melt adhesives, construction adhesives, elastic adhesives, and the like.
  • these formulations contain styrenic block copolymers of the present invention, poly-alpha-olefin resins, tackifying resins, and optional ingredients such as mineral oil, antioxidants, etc.
  • these compositions include poly-alpha-olefin present from about 30 to about 80 wt. % of said composition, styrenic block copolymer hSBS and/or hSBSS present from about 10 to about 35 wt. % of said composition, and said tackifying resin present from about 20 to about 60 wt. % of said composition.
  • Standard peel, tack, cohesion, and viscosity tests were carried out on these formulations as described in the Test method manual for Pressure Sensitive Tapes from the Pressure Sensitive Tape Council (PSTC), the standard FINAT test method for Pressure sensitive materials, the AFERA test methods for Pressure Sensitive Adhesive Tapes, and the ASTM related methods.
  • PSTC Pressure Sensitive Tape Council
  • FINAT test method for Pressure sensitive materials
  • AFERA test methods for Pressure Sensitive Adhesive Tapes and the ASTM related methods.
  • Different testing surfaces have been used in determining the formulations' function in the application: chromed stainless steel plates (No. 304 “ss”) as recommended by the FINAT and Kraft paper.
  • Rolling Ball Tack is the distance, expressed in centimeters, a steel ball rolls on the adhesive film with a standard initial velocity (Pressure Sensitive Tape Council Test No. 6; ASTM D3121-73). Small numbers indicate aggressive tack.
  • Loop Tack was determined using PSTC-5 and FTM 9 loop tack method. High numbers LT indicate aggressive tack.
  • the SAFT shear adhesion failure temperature
  • any process such as, a mechanical mixing process making use of rolls, a Banbury mixer or a Dalton kneader, a hot-melt process characterized in that heating and mixing are conducted by using a melting kettle equipped with a stirrer, a high shear Z-blade mixer, a single- or twin-screw extruder, a solvent process in which the compounding components are poured in a suitable solvent and stirred, thereby obtaining an intimate solution of the pressure sensitive adhesive composition may be used.
  • test formulations shown in Table 5 were hot melt mixed in a high shear sigma blade mixer that was blanketed with nitrogen. Typical order of addition was polymer combined with stabilizer, then resin followed by addition of oil. Mixing time averaged about one hour for the preparation of the homogeneous adhesive. Samples were then coated on 4 mil Mylar® film as a hot melt drawn down with a heated doctor blade to the average film thicknesses give in Table 5. General test results are reported in Table 6. Hot melt test results are reported in Table 7.
  • HMA4 hot melt viscosity under 10,000 cps at 350° F. (typical spray application temperature) that enables acceptable spray performance.
  • the control formulation consisting of the APO only (HMA4) has desirable low viscosity, and a saturated backbone but exhibits unacceptably poor adhesion properties, i.e. almost no measureable tack or peel.
  • the adhesive formulation of HMA4 adhered poorly to both the Mylar® (polyester) and stainless steel substrates.
  • the comparison formulation using SBS in HMA5 has the issue of color stability and long term aging due to the unsaturated polybutadiene rubber phase.
  • This type of industry standard formulation using SBS in HMA5 (20% polymer, 60% resin, 20% oil) has low polymer content (for economy and low melt viscosity) and this negatively affects the failure mechanism of the adhesive.
  • Table 8 demonstrates that film made from the high melt flow SEBS (Inventive hSBS) has equivalent or better mechanical properties to film made from lower melt flow hSBS polymer formulations (Comparative 1 and 2). Melt flow rates measured at 230° C. and 2.16 kg for MD6705 and MD6717 were 48 g/10 min and 55 g/10 min respectively. The recovered energy for Example 3 is 90% and the tensile set is 5%, indicating exceptional elasticity for such a low molecular weight polymer.
  • Table 8 shows that the high melt flow SEBS has excellent elasticity, up to 300% elongation at break. Good elasticity at high elongation, or strain, is also an indicator that the stress relaxation should be low. Low stress relaxation results in a better fit versus time for the elastic components in an absorbent personal hygiene garment or article such as a diaper.
  • Table 9 is a comparison of mechanical properties for a melt blown fabric made from the high melt flow polymer (Inventive hSBS) to typical films used in personal hygiene applications at similar basis weights (Comparative 3 and 4). Because the basis weights are similar and all of the tested samples were the same width, force can be used as an indicator of strength and modulus at various strains. Table 9 demonstrates that the Inventive hSBS fabric, in the machine direction, has equivalent or better 100% and 300% modulus and 100% and 300% hysteresis performance to Comparative 3 and 4 in the cross direction. In addition, the inventive hSBS fabric has equivalent or better performance (modulus and hysteresis) than Comparative 4 in machine direction.
  • the elongation at break and tensile strength at break are significantly lower for the Inventive hSBS fabric when compared to the film comparatives because the films can strain harden while the melt blown fabric is inherently limited by its structure. Consequently, since most commercial personal hygiene applications do not require strains much higher than 300%, the Inventive hSBS fabric demonstrates that an ultra-high melt flow hSBS could perform well in personal hygiene elastic components.
  • Comparative 1 is a compound made with an 18 MFR high vinyl SEBS.
  • Comparative 2 is also a compound made with the same 18 MFR SEBS but it also contains a high melt flow polyolefin.
  • the inventive hSBS has a melt flow rate of 220 g/10 min.
  • Comparative 3 is a typical personal hygiene elastic film compound made with a relatively high molecular weight and low MFR hSBS (Kraton G).
  • Comparative 4 is a film made from a typical personal hygiene SIS polymer (D1114).
  • Formulation 100 104 Ingredient % lbs % lbs Polymer 2 modified from 60.1 30.0 USSN 13/ 243,533 Inventive hSBS 60.1 30.0 poly-1-butene 13.3 6.7 13.3 6.7 Polypropylene 9.5 4.7 9.5 4.7 Aliphatic Oil 8.5 4.2 8.5 4.2 Plastomer 4.1 2.1 4.1 2.1 Slip Additive 3.9 2.0 3.9 2.0 Antioxidant 0.39 0.20 0.39 0.20 UV absorber 0.20 0.10 0.20 0.10 Total 100.0 50.0 100.0 50.0 Modifed Polymer 2 has a polystyrene end block mol wt. of 7.2 kg/mol and a total apparent mol wt. of 127 kg/mol, with a MFR of about 43 g/10 min at 230° C. and 2.16 kg/mass.

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US13/404,150 US20130225020A1 (en) 2012-02-24 2012-02-24 High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications
TW104132881A TWI595061B (zh) 2012-02-24 2013-01-16 高流動性之氫化苯乙烯-丁二烯-苯乙烯嵌段共聚物之應用
TW102101683A TWI561602B (en) 2012-02-24 2013-01-16 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
CN201380010772.7A CN104379667B (zh) 2012-02-24 2013-02-21 高流动的、氢化的苯乙烯‑丁二烯‑苯乙烯嵌段共聚物和应用
JP2014558810A JP6001685B2 (ja) 2012-02-24 2013-02-21 高流動水素化スチレン−ブタジエン−スチレンブロックコポリマーおよび用途
EP13769284.4A EP2817371B1 (en) 2012-02-24 2013-02-21 High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications
CN201611230886.4A CN107057260B (zh) 2012-02-24 2013-02-21 高流动的、氢化的苯乙烯-丁二烯-苯乙烯嵌段共聚物和应用
BR112014020022A BR112014020022A8 (pt) 2012-02-24 2013-02-21 Composição de adesivo não sensível à pressão, tecido não tecido elástico, artigo, composição de moldagem, emulsão de base aquosa de copolímero em bloco estirênico, e, fibras ou feixes de fibras
EP18172919.5A EP3381953B1 (en) 2012-02-24 2013-02-21 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
PCT/US2013/027009 WO2013148024A1 (en) 2012-02-24 2013-02-21 High flow, hydrogenated styrene-butadiene-styrene block copolymer and applications
KR1020147026808A KR101680441B1 (ko) 2012-02-24 2013-03-15 고 유동성 수소화된 스티렌-부타디엔-스티렌 블록 공중합체 및 이의 이용성
US13/940,663 US9771473B2 (en) 2012-02-24 2013-07-12 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
US14/469,732 US9249335B2 (en) 2012-02-24 2014-08-27 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
US14/469,716 US9359523B2 (en) 2012-02-24 2014-08-27 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
US14/469,695 US9243163B2 (en) 2012-02-24 2014-08-27 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
US14/972,188 US9637660B2 (en) 2012-02-24 2015-12-17 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
JP2016004995A JP6321055B2 (ja) 2012-02-24 2016-01-14 高流動水素化スチレン−ブタジエン−スチレンブロックコポリマーおよび用途
JP2017156467A JP6702917B2 (ja) 2012-02-24 2017-08-14 高流動水素化スチレン−ブタジエン−スチレンブロックコポリマーおよび用途

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US14/469,732 Division US9249335B2 (en) 2012-02-24 2014-08-27 High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
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