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

Abstract

The invention relates to unique applications for the novel high melt flow, low viscosity, selectively hydrogenated styrene-butadiene-styrene (hSBS) or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene (hSBSS) block copolymers, wherein the melt flow rate of said block copolymer is at least 100 g/10 min at 230° C. under 2.16 kg mass according to ASTM D1238. These block copolymers are novel and have the highest melt flow rate of any styrenic block copolymer also possessing high strength and elasticity. It has applications that prior to the present invention were not normally possible due to the normal low melt flow rate of styrenic block copolymers. The present invention also encompasses various fields of use such as a fiberglass hSBS or hSBSS reinforced mat, low viscosity hSBS or hSBSS coatings for industrial uses, hot melt adhesives prepared from hSBS or hSBSS blended with polyalpha-olefins, and elastic film, fiber, and nonwoven constructions using hSBS or hSBSS.

1 . A fibrous reinforced mat, comprising polymer or ceramic fibers or bundles of fibers in a mat or scrim and styrenic block copolymer bonded to said mat, said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being selectively hydrogenated styrene-diene-styrene or a selectively hydrogenated controlled distribution styrene-diene/styrene-styrene, where diene can be butadiene, isoprene, or mixtures thereof. 
     
     
         2 . The fibrous reinforced mat of  claim 1 , wherein 50-1000 g/m 2  of said styrenic block copolymer increases the average impact energy of said mat by at least 2 times, than without said styrenic block copolymer. 
     
     
         3 . The fibrous reinforced mat of  claim 2 , wherein said amount of styrenic block copolymer is 50 to 500 g/m 2 . 
     
     
         4 . The fibrous reinforced mat of  claim 2 , wherein said amount of styrenic block copolymer is 50 to 200 g/m 2 . 
     
     
         5 . The fibrous reinforced mat of  claim 1 , wherein said styrenic block copolymer has a minimum true molecular weight of 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%. 
     
     
         6 . The fibrous reinforced mat of  claim 1 , wherein said styrenic block copolymer is a selectively hydrogenated linear or coupled block copolymer structure of SDS or (SD) n X, respectively, where S=styrene, D=diene or diene/styrene, n=2 or 3, and X is a coupling agent residue. 
     
     
         7 . The fibrous reinforced mat of  claim 1 , where said mat is a fiberglass mat, combined with bitumen, fillers and surfacing materials, to form a roofing shingle, roofing membrane, insulation, sound mitigating article, vibration damping article, wind resistant article, or a geo-membrane having vegetative root growth resistance. 
     
     
         8 . A thermoset composite containing the fibrous reinforced mat of  claim 1 , wherein said thermoset is epoxy, urethane, polyester, acrylics, or a vinyl ester resin, to form a composite article intended for industrial, automotive, aerospace, or consumer applications such as boat hulls, car body panels, turbine blades, hulls, or sound mitigating articles, vibration damping articles, wind resistant articles, a geo-membrane having root growth resistance, or a molding sheet. 
     
     
         9 . Low viscosity polymer coating, comprising: a blend of solvent and styrenic block copolymer, said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being a selectively hydrogenated styrene-diene-styrene or selectively hydrogenated controlled distribution styrene-diene/styrene-styrene. 
     
     
         10 . The low viscosity polymer coating of  claim 9 , wherein said solvent includes a non-exempt hydrocarbon solvent or plasticizer from the class of Aromatic 100, Aromatic 200, xylene, toluene and the like, wherein said blend is at least 40 wt. % solids, with a formulated solution VOC content of <450 grams/liter. 
     
     
         11 . The low viscosity polymer coating of  claim 10 , wherein said VOC content is <350 g/liter. 
     
     
         12 . The low viscosity polymer coating of  claim 10 , containing an additional exempt solvent selected from the class of methyl acetate, para-chlorobenzotriflouride, tert-butyl acetate, or acetone, wherein said VOC content is <350 g/l. 
     
     
         13 . The low viscosity polymer coating of  claim 9 , wherein said solvent is exempt and selected from the class of methyl acetate, para-chlorobenzotriflouride, tert-butyl acetate, or acetone, wherein said blend is at least 40 wt. % solids and said VOC content is <350 g/l. 
     
     
         14 . The low viscosity polymer coating of  claim 13 , containing one or more components of low molecular weight, low softening point end block resins; polyisobutylene; low molecular polyphenylene ether; and/or one or more fillers such as TiO 2 , CaCO 3 , carbon black, other pigments, and said coating having a Brookfield viscosity <150,000 cps as measured by ASTM D2196A. 
     
     
         15 . The low viscosity polymer coating of  claim 9 , wherein said styrenic block copolymer is functionalized with maleic anhydride. 
     
     
         16 . The low viscosity polymer coating of  claim 9 , further including reactive monomers such as epoxy, acrylic, styrenic, vinyl-ester, or polyester resin. 
     
     
         17 . The low viscosity polymer coating of  claim 9 , wherein said styrenic block copolymer is a selectively hydrogenated linear or coupled block copolymer structure of SDS or (SD) n X, respectively, where S=styrene, D=diene or diene/styrene, n=2 or 3, and X is a coupling agent residue, said block copolymer has a minimum linear true molecular weight 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%. 
     
     
         18 . The low viscosity polymer coating of  claim 9 , further containing a slip-resistant additive; a component making said coating removable, such as a protective coating; a corrosion resistant additive; a shatter-proof additive; or a primer additive 
     
     
         19 . The low viscosity polymer coating of  claim 18 , further including at least one unsaturated styrenic block copolymer such as SBS or SIS. 
     
     
         20 . A non-pressure sensitive adhesive composition intended for us as a personal hygiene construction adhesive, elastic attachment adhesive, and hot-melt adhesive comprising: a blend of poly-alpha-olefin, styrenic block copolymer, and tackifying resin, said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being selectively hydrogenated styrene-diene-styrene or selectively hydrogenated controlled distribution styrene-diene/styrene-styrene, where the diene is butadiene, isoprene, or mixtures thereof. 
     
     
         21 . The adhesive composition of  claim 20 , wherein said poly-alpha-olefin is present from about 30 to about 80 wt. % of said composition, said styrenic block copolymer is present from about 10 to about 35 wt. % of said composition, and said tackifying resin is present from about 20 to about 60 wt. % of said composition. 
     
     
         22 . The adhesive composition of  claim 20 , wherein said poly-alpha-olefin is amorphous. 
     
     
         23 . The adhesion composition of  claim 20 , wherein said styrenic block copolymer is a selectively hydrogenated linear or coupled block copolymer having the structure of SDS or (SD) n X, respectively, wherein S is styrene, D is diene or diene/styrene, where n=2 or 3; and X is a coupling agent residue. 
     
     
         24 . The adhesive composition of  claim 23 , has a minimum true linear molecular weight of about 45,000; a PSC of between about 18 to about 33%, a vinyl content of about 65 to 80%, and a coupling efficiency of about 60 to about 97%. 
     
     
         25 . A melt blown elastic non-woven fabric, said fabric including styrenic block copolymer fiber having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, wherein said fabric at 50 g/m 2  exhibits an elongation >200% with a hysteresis recovered energy >70%, and a permanent set <20%. 
     
     
         26 . The melt blown elastic fabric of  claim 25 , wherein said styrenic block copolymer is a selectively hydrogenated linear or coupled block copolymer having the structure of SDS or (SD) n X, respectively, wherein S is styrene, D is diene or diene/styrene, where n=2 or 3; and X is a coupling agent residue. 
     
     
         27 . The melt blown elastic fabric of  claim 26 , wherein said styrenic block copolymer has 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 or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene. 
     
     
         28 . A nonwoven laminate construction comprising the fabric of  claim 25 , and further including at least one additional nonwoven layer comprised of thermoplastic polymer—including spunbond, bicomponent spunbond, melt blown, or a bonded-carded-web layer used in the construction of an absorbent personal hygiene product such as a baby diaper article, adult incontinence article, or feminine napkin article. 
     
     
         29 . A slush molded, rotational molded, injection molded, or calendared article comprising styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being hydrogenated styrene-butadiene-styrene or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene. 
     
     
         30 . The molded or calendared article of  claim 29 , containing an additional component of high flow polyolefin having a melt flow rate >40 g/10 min at 210° C. and 2.16 kg mass, 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. 
     
     
         31 . A slush or rotational molding composition comprising: a styrenic block copolymer, poly-1-butene, polypropylene and mineral oil, wherein said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being hydrogenated styrene-butadiene-styrene or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene. 
     
     
         32 . The molding composition of  claim 31 , wherein said styrenic block copolymer is present in a range from 50 to 70 wt. %; said poly-1-butene is present in a range of 10-15 wt. %; said polypropylene is present in a range of 8 to 11 wt. %; and said mineral oil is present in a range of 7-10 wt. %, all percentages based on 100 wt. % of the composition. 
     
     
         33 . A aqueous based emulsion of styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being hydrogenated styrene-butadiene-styrene or selectively hydrogenated controlled distribution styrene -butadiene/styrene-styrene. 
     
     
         34 . The aqueous based emulsion of  claim 33 , wherein said styrenic block copolymer includes grafted maleic anhydride. 
     
     
         35 . The aqueous based emulsion of  claim 33 , containing less than 20 wt. % organic solvent. 
     
     
         36 . The aqueous based emulsion of  claim 33 , where said emulsion includes a tackifier and is employed as a coating. 
     
     
         37 . A reinforced fabric comprising a fabric layer impregnated with a styrenic block copolymer, said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being a selectively hydrogenated styrene-butadiene-styrene or selectively hydrogenated controlled distribution styrene-butadiene/styrene-styrene. 
     
     
         38 . The reinforced fabric of  claim 37 , wherein said fabric is nonwoven. 
     
     
         39 . The reinforced fabric of  claim 37 , wherein said fabric is felt. 
     
     
         40 . A low viscosity coating of  claim 9 , wherein said coating contains a foaming agent and is incorporated in foamed articles. 
     
     
         41 . A fibrous reinforced mat of  claim 1 , where a maleated selectively hydrogenated styrene-diene-styrene or a maleated selectively hydrogenated controlled distribution styrene-diene/styrene-styrene is bonded to the surface of the individual fibers or bundles of fibers. 
     
     
         42 . A low viscosity modified wax comprising styrenic block copolymers comprising up to about 20 wt. % hSBS polymer with melt flow rate >100 g/10 min at 230° C. and 2.16 kg mass;
 about 10-15% wax; 30-35% midblock resin; about 5% other additives such as EVA or/and PE wax, about 30-40% of organic fillers to control shrinkage and provide less cavitation 
 
     
     
         43 . A low viscosity modified wax of  claim 42 , wherein the viscosity is 2,000-10,000 cps as measured via cone and plate rheometry at 140° F. and 50 sec −1 . 
     
     
         44 . A low viscosity modified wax of  claim 43 , wherein the viscosity is 3,000-5,000 cps as measured via cone and plate rheometry at 140° F. and 50 sec −1 . 
     
     
         45 . A low viscosity modified wax of  claim 42 , wherein the wax is a microcrystalline wax, polyethylene wax, paraffin wax, naphthalene wax, or less refined wax. 
     
     
         46 . A low viscosity modified wax of  claim 42 , wherein the midblock resin is a C 5  resin, hydrogenated C 5  resin, terpene resin, rosin ester resin, or combinations thereof 
     
     
         47 . A low viscosity modified wax of  claim 42 , wherein the organic filler comprises crosslinked polystyrene, bisphenol acid, terephthalic acid or combinations thereof and has a particle size of less than 200 microns. 
     
     
         48 . A fibrous reinforced mat of  claim 1 , wherein said fibers or bundles of fibers are glass, carbon or aramid fibers. 
     
     
         49 . Fibers or bundles of fibers coated with styrenic block copolymer bonded thereto, said styrenic block copolymer having a melt flow rate greater than 100 g/10 min at 230° C., and 2.16 kg mass, said styrenic block copolymer being selectively hydrogenated styrene-diene-styrene or a selectively hydrogenated controlled distribution styrene-diene/styrene-styrene, where diene is butadiene, isoprene, or mixtures thereof, and where said fibers or bundles of fibers are glass, carbon or aramid fibers, and optionally where said selectively hydrogenated styrene-diene-styrene or selectively hydrogenated controlled distribution styrene-diene/styrene-styrene are maleated.