US008524796B2

(12) United States Patent (10) Patent No.: US 8,524,796 B2 Kim et al. (45) Date of Patent: *Sep. 3, 2013

(54) ACTIVE POLYMER COMPOSITIONS WO 20060967.91 9, 2006 WO 2007024.125 3, 2007 (75) Inventors: Young-Sam Kim, Midland, MI (US); WO 20070307912007078568 3,7/2007 2007 Leonardo C. Lopez, Midland, MI (US); WO 2007099397 9, 2007 Scott T. Matteucci, Midland, MI (US); WO 2007121458 10/2007 Steven R. Lakso, Sanford, MI (US) WO 2008101051 8, 2008 WO 2008112833 9, 2008 (73) Assignee: Dow Global Technologies LLC WO 2008.150970 12/2008 WO 2009 134824 11, 2009 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 U.S.C. 154(b) by 457 days. Ciferri, Alberto, “Supramolecular Polymers'. Second Edition, 2005, pp. 157-158, CRC Press. This patent is Subject to a terminal dis Corbin et al., “Chapter 6 Hydrogen-Bonded Supramolecular Poly claimer. mers: Linear and Network Polymers and Self-Assembling Discotic Polymers'. Supramolecular Polymers, 2nd edition, CRC Press, (21) Appl. No.: 12/539,793 2005, pp. 153-185. Duan et al., “Preparation of Antimicrobial Poly (e-caprolactone) (22) Filed: Aug. 12, 2009 Electrospun Nanofibers Containing Silver-Loaded Zirconium Phos phate Nanoparticles”, Journal of Applied Polymer Sciences, 2007. (65) Prior Publication Data vol. 106, pp. 1208-1214, Wiley Periodicals, Inc. US 201O/OO41292 A1 Feb. 18, 2010 Hagewood, "Potential of Polymeric Nanofibers for Nonwovens and Medical Applications'. Fiberjournal.com, Feb. 26, 2008, 4 Pages, Related U.S. Application Data J.Hagewood, LLC and Ben Shuler, Hills, Inc. Khil et al., “Electrospun Nanofibrous Polyurethane Membrane as (60) Provisional application No. 61/088,537, filed on Aug. Wound Dressing”, Wiley Periodicals, Inc., 2003, pp. 675-679. 13, 2008. Koevoets et al., “Molecular Recognition in a Thermoplastic Elastomer'. Journal of the American Chemical Society, 2005, pp. (51) Int. Cl. 2999-3003, vol. 127. A6IL 9/04 (2006.01) Krook et al., “Barrier and mechanical properties of injection molded COSL 77/00 (2006.01) montmorillonite/polyesteramide nanocomposites'. Polymer Engi C08G 69/00 (2006.01) neering and Science, 2005, pp. 135-141, vol. 45 No. 1. (52) U.S. Cl. Lips et al., “Incorporation of different crystallizable amide blocks in USPC ...... 523/102:523/105:523/122:524/602; segmented poly(ester amide)s'. Polymer, 2005, pp. 7834-7842, vol. 46, Elsevier Ltd. 528/291; 106/15.05 Lips et al., “Synthesis and characterization of poly(ester amide)S (58) Field of Classification Search containing crystallizable amide segments'. Polymer, 2005, pp. 7823 USPC ...... 523/102,105, 122; 524/602; 528/291; 7833, vol. 46, Elsevier Ltd. 106/15.05 Liu et al., “The preparation and properties of biodegradable See application file for complete search history. polyesteramide composites reinforced with nano-CaCO3 and nano SiO2, Materials Letters, 2007, pp. 4216-4221, vol. 61, Elsevier Ltd. (56) References Cited Zou et al., "Stabilization and mechanical properties of biodegradable aliphatic polyesteramide and its filled composites'. Polymer Degra U.S. PATENT DOCUMENTS dation and Stability, 2004, pp. 87-92, vol. 83, Elsevier Ltd. 6,034,163 A 3, 2000 Barbee et al. 6,172,167 B1 1/2001 Stapert et al. * cited by examiner 6,821.479 B1 1 1/2004 Smith et al. 6,833,104 B2 12/2004 Berger 6,852,410 B2 2/2005 Veedu et al. Primary Examiner — Tae HYoon 6,897,349 B2 5, 2005 Gibbins et al. 6,967.261 B1 1 1/2005 Soerens et al. (57) ABSTRACT 7,235,295 B2 6/2007 Laurencin et al. 8,268,042 B2* 9/2012 Lopez et al...... 95/52 The instant invention generally provides an activated polymer 8,343,257 B2 * 1/2013 Matteucci et al...... 95/45 composition containing an active agent (i.e., a chemically- or 2004/0180201 A1 9, 2004 Veedu et al. biologically-active agent), an activated fiber comprising the 2005, 0100501 A1 5, 2005 Veedu et al. activated polymer composition, an activated-fiber composite 2005/01701.92 A1 8, 2005 Kambe et al. comprising the activated fiber and a fiberweb support, pro 2006.0034907 A1 2/2006 Nagaike et al. 2008.OOO8739 A1* 1/2008 Hossainy et al...... 424/426 cesses of fabricating the activated fiber and activated-fiber 2008.009 1233 A1 4/2008 Ellis-Behnke et al. composition, and an article comprising the activated polymer 2008, 0214743 A1 9, 2008 Broos et al. composition. The instant invention also generally provides a 2010.0041857 A1 2/2010 Harris et al. highly filled polymer filler composite comprising a molecu 2010/0179284 A1* 7, 2010 Ward et al...... 525,542 larly self-assembling (MSA) material and a mineral filler or 2010/0200494 A1* 8, 2010 Storer et al...... 210,510.1 conductive filler dispersed in the MSA material, and a process FOREIGN PATENT DOCUMENTS of making and article comprising the highly filled polymer EP O376323 7, 1990 filler composite. WO 0042105 T 2000 WO O3O28O39 4/2003 8 Claims, 8 Drawing Sheets U.S. Patent Sep. 3, 2013 Sheet 1 of 8 US 8,524,796 B2

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U.S. Patent Sep. 3, 2013 Sheet 7 of 8 US 8,524,796 B2

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Fig. 7 U.S. Patent Sep. 3, 2013 Sheet 8 of 8 US 8,524,796 B2

Fig. 8 US 8,524,796 B2 1. 2 ACTIVE POLYMER COMPOSITIONS the process comprising the steps of elongating under fiber forming conditions either a melt comprising the MSA mate CROSS-REFERENCE TO RELATED rial or a solution comprising a solvent and the MSA material; APPLICATION(S) and contacting one or more active agents to the MSA material to produce one or more activated fibers of the second embodi This application claims benefit of priority from U.S. Pro ment. visional Patent Application No. 61/088,537, filed Aug. 13, In a fifth embodiment, the instant invention is a process of 2008, which application is incorporated by reference herein making the activated-fiber composite of the third embodi in its entirety. ment, the process comprising the steps of elongating under The present invention is in the field of polymer composi 10 fiber-forming conditions either a melt comprising the MSA tions and fibers comprising the polymer compositions. material or a solution comprising a solvent and the MSA material; contacting one or more active agents to the MSA BACKGROUND OF THE INVENTION material to produce one or more activated fibers of the second embodiment; and operatively contacting the one or more U.S. Pat. No. 6,852,410 B2 and its divisional USPAPN US 15 activated fibers to a fiberweb support to make the activated 2005/0100501 A1 mention single-wall carbon nanotube fiber composite of the third embodiment. (SWNT)-PAN composites and SWNT-PAN composite fibers In a sixth embodiment, the instant invention is an article fabricated therefrom. comprising the activated polymer composition of the first There is a need in the polymer art for polymer composi embodiment. Preferably, the activated polymer composition tions containing chemically- and biologically-active agents, comprises the activated fiber or activated-fiber composite of fibers comprising the polymer compositions, processes of the second or third embodiments, respectively. Preferably, the fabricating Such fibers, and articles comprising Such polymer article comprises abandage, medical gown, medical scaffold, compositions and fibers. cosmetic, Sound insulation, barrier material, diaper cover stock, adult incontinence pants, training pants, underpad, SUMMARY OF THE INVENTION 25 feminine hygiene pad, wiping cloth, porous filter medium (e.g., for filtering air, gasses, or liquids), durable paper, fabric The instant invention generally provides an activated poly softener, home furnishing, floor covering backing, geotextile, mer composition comprising a molecularly self-assembling apparel, apparel interfacing, apparel lining, shoe, industrial material and an active agent (i.e., a chemically- or biologi garment, protective garments and fabrics, agricultural fabric, cally-active agent), an activated fiber comprising the acti 30 automotive fabric, coating Substrate, laminating Substrate, vated polymer composition, an activated-fiber composition leather, or electronic component. comprising the activated fiber and a fiberweb support, pro In a seventh embodiment, the article of the sixth embodi cesses of fabricating the activated fiber and activated-fiber ment comprises an activated woven or co-woven fabric. composition, and an article comprising the activated polymer Accordingly, the instant invention also comprises a woven composition. 35 fabric comprising one or more activated fibers (e.g., activated In a first embodiment, the instant invention is an activated filament(s)) of the second embodiment. The woven fabric is polymer composition comprising a molecularly self-assem prepared by a process comprising a step of weaving an MSA bling (MSA) material and one or more active agents, wherein fiber (e.g., MSA filament) useful in the second embodiment each active agent independently comprises odor control or the activated fiber of the second embodiment to provide the material, polyelectrolyte, chelating agent, microspheres, 40 woven fabric. The active agent is contacted to the MSA fiber non-peptidic antimicrobial Substance, an anti-clotting com useful in the second embodiment during or after the weaving pound, a clotting compound, or a wound healing promoter. step employing the same. Preferably, the one or more active agents comprise a total of In an eighth embodiment, the instant invention is a highly from 0.0001 weight percent (wt %) to 75 wt %, and more filled polymer filler composite comprising a molecularly self preferably from 0.01 wt % to 50 wt %, of the activated 45 assembling (MSA) material and a mineral filler or conductive polymer composition based on total weight of the activated filler dispersed in the MSA material, wherein the mineral polymer composition. The one or more active agents are in filler comprises a finely divided metal, metal carbonate, metal operative contact with a surface of the MSA material (e.g., the oxide, silica, or talc; the conductive filler comprises an acti MSA material has a surface and the active agent(s) are in vated carbon, carbon black, carbon nanotube (e.g., single wall coating operative contact with the surface of the MSA mate 50 and multiwall), or fullerene and the conductive filler is in the rial), are dispersed within the MSA material, or both. form of a particle having an average size of 30 micrometers or In a second embodiment, the activated polymer composi smaller; the mineral filler or conductive filler comprising tion of the first embodiment comprises an activated fiber. from 76 weight percent (wt %) to 90 wt % of the highly filled Accordingly, instant invention also is an activated fiber com polymer filler composite based on total weight of the highly prising a fiber of a molecularly self-assembling (MSA) mate 55 filled polymer filler composite. Preferably, the mineral filler rial and one or more active agents, wherein the active agents or conductive filler comprises 85 wt % or less, or 80 wt % or are as described in the first embodiment. Preferably, the acti more of the highly filled polymer filler composite. Also pref vated fiber comprises a woven or, more preferably, nonwoven erably, the mineral filler is in the form of a particle having an web. average size of 1.0 micrometer or larger or a fiber having an In a third embodiment, the instant invention is an activated 60 average diameter of 1.0 micrometer or larger. fiber composite comprising an activated fiber of the second In a ninth embodiment, the instant invention is a process for embodiment and a fiberweb support, wherein the fiberweb making the highly filled polymer filler composite of the Support is in Supporting operative contact with the activated eighth embodiment, the process comprising the step of dis fiber of the second embodiment. In some embodiments, the persing a highly filling amount of the mineral filler or con fiberweb support is porous. 65 ductive filler in either a melt comprising the MSA material or In a fourth embodiment, the instant invention is a process a solution comprising a solvent and the MSA material to for fabricating the activated fiber of the second embodiment, produce the highly filled polymer filler composite of the US 8,524,796 B2 3 4 eighth embodiment. Preferably the process employs the melt prises.” and the like (which are synonymous with “including.” comprising the MSA material. “having and “characterized by’’) may be replaced by the In a tenth embodiment, the instant invention is an article respective partially closed phrases "consisting essentially of comprising the highly filled polymer filler composite of the consists essentially of” and the like or the respective closed eighth embodiment. Preferably, the highly filled polymer 5 phrases "consisting of “consists of and the like. filler composite of the eighth embodiment is extruded, For purposes of United States patent practice and other molded, blow molded, or cast to form the article. patent practices allowing incorporation of Subject matter by The highly filled polymer filler composite of the eighth reference, and the entire contents—unless otherwise indi embodiment is melt processable even at high filler concen cated—of each U.S. patent, U.S. patent application, U.S. trations (e.g., greater than or equal to 50 wt % filler). 10 patent application publication, PCT international patent The instant invention also comprises a co-woven fabric application and WO publication equivalent thereof, refer comprising one or more non-MSA fibers and one or more enced in the instant Detailed Description of the Invention are activated fibers of the second embodiment, the one or more hereby incorporated by reference, especially with respect to activated fibers and the one or more non-MSA fibers being the disclosure of synthetic techniques, reaction conditions, co-woven to provide the co-woven fabric. Preferred non- 15 and compounds. When available, a U.S. patent or U.S. patent MSA fibers are fibers comprising cotton, silk, rayon, wool, application publication family member thereof may be incor olefinic fibers, nylon, polyester, other textile fibers, and com porated by reference instead of the PCT international patent binations thereof. The co-woven fabric is prepared by a pro application or WO publication equivalent. In an event where cess comprising a step of co-weaving the non-MSA fiber(s) there is a conflict between what is written in the present with either the MSA fiber (e.g., MSA filament) useful in the 20 specification and what is written in a patent, patent applica second embodiment or the activated fiber of the second tion, or patent application publication, or a portion thereof embodiment to provide the co-woven fabric. The active agent that is incorporated by reference, what is written in the is contacted to the MSA fiber (e.g., MSA filament) useful in present specification controls. the second embodiment during or after the co-weaving step In the present application, any lower limit of a range, or any employing the same. 25 preferred lower limit of the range, may be combined with any Additional embodiments of the present invention are illus upper limit of the range, or any preferred upper limit of the trated in the accompanying drawings and are described in the range, to define a preferred embodiment of the range. following detailed description and claims. In an event where there is a conflict between a value given in a U.S. unit (e.g., inches) and a value given in a standard BRIEF DESCRIPTION OF THE DRAWINGS 30 international unit (e.g., centimeters), the U.S. unit value con trols. FIG. 1 is a scanning electron microscope (SEM) image of In the present application, when referring to a preceding the in situ silver chloride-treated nonwoven web comprising list of elements (e.g., ingredients), the phrases “mixture MSA fibers of Example 3 at 500x magnification. thereof.” “combination thereof.” and the like mean any two or FIG. 2 is a scanning electron microscope (SEM) image of 35 more of the listed elements. the in situ silver chloride-treated nonwoven web comprising Definitions MSA fibers of Example 3 at 2500x magnification. As used herein, the term “active agent’ means an effica FIG. 3 is a scanning electron microscope (SEM) image of cious Substance that is capable of chemical or biological the in situ silver chloride-treated nonwoven web comprising function, or both. The efficacious substance is not a MSA MSA fibers of Example 3 at 20,010x magnification. 40 material. In some embodiments, the efficacious Substance is FIG. 4 graphically depicts thermogravimetric analysis capable of one such function or more than one Such function. (TGA) for the MSA material of Comparative Example 1 and The term “activated fiber’ means the activated fiber of the talc composites of Examples 5A to 5F. second embodiment of the present invention and preferred FIG. 5 graphically depicts dynamic mechanical spectros embodiments thereof except as otherwise noted. copy (DMS) results for the MSA material of Comparative 45 The term “activated-fiber composite' means the activated Example 2 and the talc composites of Examples 5A and 5C to fiber composite of the third embodiment of the present inven 5F. tion and preferred embodiments thereof except as otherwise FIG. 6 graphically depicts melt viscosity results for the noted. MSA material of Comparative Example 1 and the talc com The term “activated polymer composition” means the acti posites of Examples 5A, 5B, and 5D to 5F. 50 vated polymer composition of the first embodiment of the FIG. 7 graphically depicts melt viscosity results for the present invention and preferred embodiments thereof except MSA material of Comparative Example 1 and the silica com as otherwise noted. posite of Example 6. The term “anti-clotting compound' means an antithrom FIG. 8 is a TEM image at 1000 times magnification of the botic substance. Preferred antithrombotic substances are anti silica composite of Example 6. 55 coagulants, antiplatelets, and thrombolytic drugs. More pre ferred antithrombotic Substances are vitamin Kantagonists, DETAILED DESCRIPTION OF THE INVENTION aspirin, clopidogrel, dipyrimadole, propanolol, Sulfinpyra Zone, ticlopidine, warfarin, and heparin. The instant invention generally provides an activated poly The term “antimicrobial substance” means an antibiotic, mer composition containing an active agent (i.e., a chemi- 60 antiviral, antiparasitic, antiamoebic, or antifungal material, cally- or biologically-active agent), an activated fiber com preferably an antibiotic, antiviral, antiparasitic, antiproto prising the activated polymer composition, an activated-fiber Zoal, orantifungal compound. Preferred non-peptidic antimi composite comprising the activated fiber and a fiberweb Sup crobial substances (abbreviations) are: N-trichlorometh port, processes of fabricating the activated fiberand activated ylthio-4-cyclohexene-1,2-dicarboximide (Captan); tri/ fiber composite, and an article comprising the activated poly 65 dibromo salicylanilide (TBS); N-fluorodichloromethylthio mer composition. In any embodiment of the instant invention phthalamide (fluorofolpet); 3-iodo-2-propynyl-butyl described herein, the open-ended terms "comprising.” “com carbamate (IPBC): 2-(4-thiazolyl)-benzimidazole (TBZ); US 8,524,796 B2 5 6 quaternary ammonium compounds (e.g., tetrabutylammo critical and in some embodiments is characterized as being nium chloride); phenyl mercuric acetate (PMA); bis(tributyl monodispersed, Gaussian, or random. Also preferably, the tin) oxide (TBTO); tributyltin esters (TBT ester such as tribu particulate Solid is characterized as having a Braunauer-Em tyltin acetate); zinc pyrithione (ZPT); N-butyl-1,2- mett–Teller (BET) surface area of about 1 meter squared per benzisothiazolin-3-one (BBIT); N-trichloromethylthio gram (m/g) to about 1000 m/g, more preferably from about phthalamide (Folpet); and silver containing glass, Zeolite, 10 m/g to about 700 m/g, and still more preferably from ceramic, and inorganic carriers. Especially preferred non about 50 m/g to about 500 m/g. peptidic antimicrobial substances (abbreviations) are: 10,10'- Preferably, the finely-divided metal consists essentially of oxybisphenoxarsine (OBPA): 2-(normal-octyl)-4-isothiazo titanium (Ti), Zirconium (Zr), chromium (Cr), molybdenum lin-3-one (OIT): 4,5-dichloro-2-(normal-octyl)-4- 10 isothiazolin-3-one (DCOIT); and 2,4,4-trichloro-2'- (Mo), tungsten (W), iron (Fe), ruthenium (Ru), cobalt (Co), hydroydiphenyl ether (TCPP). Other especially preferred rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), non-peptidic antimicrobial substances are AEM 5700 (con copper (Cu), silver (Ag), gold (Au), Zinc (Zn), cadmium (Cd), taining components having Chemical Abstracts Registry aluminum (Al), gallium (Ga), carbon (C), silicon (Si), ger Numbers (CAS RegNos)67-56-1,27668-52-6), and 2530 15 manium (Ge), tin (Sn), lead (Pb), or an alloy of two or more 87-2 and commercially available from Aegis Environments); thereof. More preferably, the finely-divided metal consists X-Static (a 17% silver coated polyamide and commercially essentially of Pd, Pt, Cu, Ag, Au, or Zn. Still more preferably, available from Noble Fiber Technologies); Alphasan RC the finely-divided metal consists essentially of Cu, Ag, Au, or 5000 or Alphasan RC 2000 (a silver zirconium phosphate Zn. having CAS RegNo. 265647-11-8 and commercially avail The term “highly filling amount’ means a weight sufficient able from Miliken Chemical); SmartSilver (a nanocrystalline to prepare a highly filled composite. silver having CAS RegNos. 7440-22-4 and 9003-07-0 and The term “metal carbonate’ means an organic particulate commercially available from NanoHorizons); and Microban consisting of carbonate (i.e., CO) or bicarbonate (i.e., Additive b (having CAS RegNo. 3380-34-5 and commer HCO,') and one or more cationic elements of any one of cially available from Microban Products Company). Other 25 Groups 3 to 14 of the periodic table of the chemical elements preferred antibiotic, antiviral, antiparasitic, antifungal and and having an average diameter of 1000 um or lower. Prefer antiprotozoal materials are described later. ably, the organic particulates have an average diameter of The term “chelating agent’ means abidentate or multiden 1000 nm or lower. tate ligand capable of coordinatively or ionically bonding, or Preferably, average particle size of the organic particulates a combination thereof, to a metalion. Preferably, the ligand is 30 is from about 0.001 um to about 1000 um, more preferably non-peptidic. Also, the metal ion preferably is a so-called from about 0.05 um to about 500 um, still more preferably heavy metal cation such as, for example, an arsenic cation, from about 0.1 um to about 300 um, and even more preferably mercury cation, or lead cation. Examples of Such ligands are from about 0.5um to about 150 um. The particle size distri ethylenediaminetetraacetic acid (EDTA), citric acid, and bution is not critical and in some embodiments is character polyphosphonic acids. 35 ized as being monodispersed, Gaussian, or random. The BET The term "clotting compound' means a thrombus forma Surface area of the organic particulates preferably is from tion-promoting Substance. about 1 m/g to about 1000 m/g, preferably is from about 10 The phrase "elongating under fiber-forming conditions' m?g.to about 700 m/g, and more preferably is from about 50 means Subjecting a material to a means for increasing the m/g to about 500 m/g. materials aspect ratio until the material at least becomes 40 Preferred metal carbonates are sodium carbonate, sodium thread-, filament-, or fibril-like. Examples of the means for bicarbonate, lithium carbonate, lithium bicarbonate, potas increasing the materials aspect ratio are extruding, fiber sium carbonate, potassium bicarbonate, magnesium carbon drawing, textile spinning, spunbonding, Solution electrospin ate, and calcium carbonate. More preferred organic particu ning, melt electrospinning, Solution electroblowing, melt lates are sodium carbonate, Sodium bicarbonate, and electroblowing, and melt blowing. The means for increasing 45 potassium bicarbonate. the materials aspect ratio are known and preferably employ The term “metal oxide” means an inorganic particulate conventional processing parameters such as temperature, consisting of oxygen and one or more cationic elements of Voltage, gas flow, pressure, collector distance, atmosphere, any one of Groups 3 to 14 of the periodic table of the chemical and the like that are useful for extruding, fiber drawing, textile elements. Preferably, the average particle size of the inor spinning, spunbonding, solution electrospinning, melt elec 50 ganic particulate is from about 0.001 um to about 1000 um, trospinning, Solution electroblowing, melt electroblowing, or more preferably from about 0.05 um to about 500 um, still melt blowing a melt of a polymer. more preferably from about 0.1 um to about 300 um, and even The term “finely-divided metal' means a particulate solid more preferably from about 0.5 um to about 150 lum. The consisting essentially of (i.e., at least 95 percent by weight) particle size distribution is not critical and in some embodi one or more neutral elements of Groups 3 to 14 of the periodic 55 ments is characterized as being monodispersed, Gaussian, or table of the chemical elements and having an average diam random. The BET surface area of the inorganic particulates eter of 1000 um or lower. Preferably, the average diameter is preferably is from about 1 m/g to about 1800 m/g, more 1000 nm or lower. Preferably, the particulate solid will have preferably from about 100 m/g to about 1600 m/g, and still an average particle size in the range of from about 0.001 um more preferably from about 200 m/g to about 1400 m/g. to about 1000 um, more preferably from about 0.05 um to 60 Preferred metal oxides are aluminum oxide, silicon diox about 500 um, still more preferably from about 0.1 um to ide, titanium dioxide, and zinc oxide. More preferred metal about 300m, and even more preferably from about 0.5um to oxides are titanium dioxide and Zinc oxide. about 150 um. Particle size analysis methods and instruments The term “microsphere” means an approximately round are well known to the skilled person in the art. Preferably, particle having an average diameter of 1000 micrometers particle size is determined using a Beckman Coulter RAPID 65 (Lm) or lower and being characterized as having or lacking VUETM instrument (Beckman Coulter Particle Characteriza interior (i.e., closed) pores. Preferably, the average diameter tion, Miami, Fla., USA). The particle size distribution is not preferably is 1000 nanometers (nm) or lower. US 8,524,796 B2 7 8 Preferably, the majority of the approximately round par especially actinium (Ac), thorium (Th), protactinium (Pa), ticles have an average particle size of from about 0.001 um to uranium (U), neptunium (Np), plutonium (Pu), americium about 1000 um, more preferably from about 0.05um to about (Am), curium (Cu), berkelium (Bk), californium (Cf), ein 500 um, still more preferably from about 0.1 um to about 300 steinium (Es) fermium (Fm), mendelevium (Md), nobelium um, and even more preferably from about 0.5um to about 150 (No), and lawrencium (Lr). um. The particle size distribution is not critical and in some Preferred Group 3 elements are Sc and Y. In addition to embodiments is characterized as being monodispersed, titanium (Ti), Zirconium (Zr), and hafnium (Hf), another Gaussian, or random. The BET surface area of the approxi Group 4 element useful in the present invention is rutherfor mately round particles is preferably from about 1 m/g to dium (Rf). Group 5 elements useful in the present invention about 1800 m/g, more preferably from about 100 m/g to 10 are vanadium (V), niobium (Nb), tantalum (Ta), and dubnium about 1600 m/g, and still preferably from about 200 m/g to (Db). Preferred Group 5 elements are V, Nb, and Ta. Group 6 about 1400 m/g. elements useful in the present invention are chromium (Cr), Preferably, the approximately round particle comprises a molybdenum (Mo), tungsten (W), and seaborgium (Sg). Pre thermoplastic polymer, thermoset polymer, cross-linked ferred Group 6 elements are Cr, Mo, and W. polymer (e.g., cross-linked polymer beads with or without 15 The term “polyelectrolyte’ means an ionizable organic ion-exchangeable functional groups), metal, ceramic or polymer comprising at least one repeat unit bearing an acid or glass. Also preferably, the microspheres are characterized as base functionality, or a respective conjugate base or acid having a microporosity of from about 0.2 cubic centimeters thereof, that is capable of disassociating in pH 7 water. Ion per gram (cc/g) to about 0.4 cc/g; a mesoporosity of at least izable organic polymers include polycations, polyanions, and about 0.3 cc/g, more preferably at least about 0.5 cc/g; and a polyampholytes. Examples of polycations are polyethylene total porosity of at least about 0.8 cc/g, more preferably at imine, poly(2-(dimethylamino)ethyl methacrylate), poly(2- least about 1.5 cc/g, and the microporosity comprises less dimethylamino ethyl methacrylate), poly(N-3-(dimethy than about 40 percent, more preferably less than about 20 lamino)propylmethacrylamide), percent, of the total porosity. polydiallyldimethylammonium chlorides, polyvinylpy BET Surface area, pore size and porosity are determined on 25 ridines, poly(4-vinylaniline), polyvinylamine, cationic a Quantachrome Model Autosorb-1 nitrogen adsorption ana hydroxyethyl cellulose, (for example, UCARE JR-09, lyZerby measuring the Volume of gaseous nitrogen adsorbed JR-400, LR-400 and JR-30M from Amerchol Corporation, by a sample at a given nitrogen partial pressure and by con USA), a chiosonium pyrrolidone carboxylate (available com ducting the appropriate calculations according to the BET mercially as KYTAMERTM PC from Amerchol Corporation), model. Micropores are defined as pores of less than 2 nm in 30 and their conjugate acids. Examples of polyanions are poly diameter. (sodium styrene Sulfonate), poly(acrylic acid), poly(meth Mesopores are defined as pores ranging from 2 to 20 nm in acrylic acid), and salts thereof. Examples of polyampholytes diameter. Macropores are defined as pores of greater than 20 are a copolymer derived from vinyl pyridine and methacrylic nm in diameter. The terms microporosity, mesoporosity and acid. Examples of acid functionalities are carboxylic and macroporosity refer to the pore Volume per gram of sample 35 Sulfonic acids. Conjugate bases of carboxylic and Sulfonic for each type of respective pore and are reported in units of acids include Sodium carboxylates and Sulfonates, respec cc/g. These porosities, as well as BET Surface area and aver tively. Examples of base functionalities are primary, second age pore size, are determined by the nitrogen adsorption ary, and tertiary alkyl amines and pyridines. Conjugate acids method in which dried and degassed samples are analyzed on of primary, secondary, and tertiary alkylamines and pyridines an automatic Volumetric sorption analyzer, Quantachrome 40 include protonated and methylated primary, secondary, and Model Autosorb-1 nitrogen adsorption analyzer. The instru tertiary ammonium and pyridinium salts, respectively. ment works on the principle of measuring the Volume of The term “T” means glass transition temperature as deter gaseous nitrogen adsorbed by a sample at a given nitrogen mined by techniques known in the art Such as differential partial pressure. The Volumes of gas adsorbed at various scanning calorimetry (DSC). pressures are used in the BET model for the calculation of the 45 The term “T” means melting temperature (i.e., melting BET surface area of the sample. The average pore radius is point) as determined by techniques known in the art, prefer calculated from the relationship between the BET surface ably by differential scanning calorimetry (DSC). If a MSA area and the pore Volume of the sample, assuming cylindrical material has one or more T, preferably at least one T is 25 pore geometry. degrees Celsius (°C.) or higher. The term “non-peptidic' means lacking an oligomer or 50 The term “viscosity” means Zero shear viscosity unless polymer comprising two or more alpha-amino acids (includ specified otherwise. ing naturally occurring and man-made alpha-amino acids). The term “wound healing promoter” means a dermal and The term "odor control material' means a deodorant sub epidermal tissue-regenerating stimulant. Preferably, the der stance that absorbs, adsorbs, sequesters, masks, or reacts with mal and epidermal tissue-regenerating stimulant comprises an odorant, or inhibits production of the odorant. Preferred 55 one or more of platelet-enriched plasma, a debriding agent, odor controlling materials absorb, adsorb, sequester, mask, or Vitamin A, vitamin C, collagen, estrogen, dihydroepiandros react with the odorant. terone (DHEA), and finely-divided titanium dioxide (prefer Unless otherwise noted, the phrase “Periodic Table of the ably with ultraviolet light therapy). A "debriding agent' Elements' refers to the official periodic table, version dated means a dead tissue removing Substance. Preferred dead tis Jun. 22, 2007, published by the International Union of Pure 60 Sue removing (e.g., by reaction therewith Such as reaction and Applied Chemistry (IUPAC). Group 3 elements (symbol) leading to degradation of dead tissue) Substances are a colla useful in the present invention are scandium (Sc), yttrium (Y), genase enzyme, a papain-urea enzyme, polyacrylate particles the lanthanides, especially lanthanum (La), cerium (Ce), (e.g., TenderWetTM, IVF Hartman AG) praseodymium (Pr), neodymium (Nd), promethium (Pm), Active Agents Samarium (Sm), europium (Eu), gadolinium (Gd), terbium 65 Preferred antibiotic substances are silver compounds and (Tb), dysprosium (Dy), holium (Ho), erbium (Er), thulium compounds selected from the following structural classes of (Tm), ytterbium (Yb), and lutetium (Lu), and the actinoids, antibiotics: aminoglycosides, beta-lactams, cephalosporins, US 8,524,796 B2 10 macrollides, penicillins, fluoroquinolones, Sulfonamides, and lar associations do not increase the molecular weight (Mn tetracyclines. More preferably, antibiotic substances are sil Number Average molecular weight) or chain length of the Vercompounds Such as, for example, silver salts, silver com self-assembling material and covalent bonds between said plex ions, colloidal silver, silver/Zeolite composites, silver/ materials do not form. This combining or assembling occurs phosphate, silver/glass particles (antimicrobial, controlled spontaneously upon a triggering event such as cooling to form release), and mixtures thereof. Preferred silver salts are silver the larger associated or assembled oligomer or polymer struc chloride, silver nitrate, silver acetate, silver benzoate, silver tures. Examples of other triggering events are the shear-in bromate, silver chlorate, silver lactate, silver molybdate, sil duced crystallizing of, and contacting a nucleating agent to, a ver nitrite, silver(I) oxide, silver perchlorate, silver perman molecularly self-assembling material. Accordingly, in pre ganate, silver selenate, silver selenite, silver Sulfadiazine, 10 ferred embodiments MSAs exhibit mechanical properties silver sulfate, and mixtures thereof. Preferred silver complex similar to some higher molecular weight synthetic polymers ions are silver chloro complex ions, silver thiosulfato com and Viscosities like very low molecular weight compounds. plex ions, or mixtures thereof. Preferred colloidal silver par MSA organization (self-assembly) is caused by non-covalent ticles are silver nanoparticles, including nanocrystalline sil bonding interactions, often directional, between molecular versuch as, for example, SICRYSTTM nanocrystals (Nucryst 15 functional groups or moieties located on individual molecular Pharmaceuticals Corporation). (i.e. oligomer or polymer) repeat units (e.g. hydrogen-bonded Preferred antifungal substances are from the following arrays). Non-covalent bonding interactions include: electro structural classes: allylamines, echinocandins, imidazoles, static interactions (ion-ion, ion-dipole or dipole-dipole), polyenes, and triazoles. coordinative metal-ligand bonding, hydrogen bonding, JU-T- Preferred antiviral substances are from the following activ structure stacking interactions, donor-acceptor, and/or van ity classes: anti-hepatitis virus, anti-herpesvirus, anti-human der Waals forces and can occur intra- and intermolecularly to immunodeficiency virus (HIV), and anti-influenza virus, impart structural order. One preferred mode of self-assembly including anti-avian influenza virus. is hydrogen-bonding and this non-covalent bonding interac Preferred antiparasitic substances are from the following tions is defined by a mathematical Association constant. activity classes: antinematodes, anticestodes, antitrematodes, 25 K(assoc) constant describing the relative energetic interac antiamoebics, and antiprotozoals. tion strength of a chemical complex or group of complexes Preferred antiprotozoal substances are from the following having multiple hydrogen bonds. Such complexes give rise to activity classes: antimalarials (e.g., chloroquine and artemisi the higher-ordered structures in a mass of MSA materials. A nin) and agents against leishmaniasis or trpanosomiasis. description of self assembling multiple H-bonding arrays can Preferred odor control agents are finely-divided metals, 30 be found in “Supramolecular Polymers’, Alberto Ciferri Ed., metal carbonates, metal oxides, microspheres, magadiite, 2nd Edition, pages (pp) 157-158. A “hydrogen bonding silica, talc, extracts from quillaja, yucca, and aloe plants, array is a purposely synthesized set (or group) of chemical fragrances, cyclodextrins, chitosan, activated carbon, carbon moieties (e.g. carbonyl, amine, amide, hydroxyl. etc.) nanotubes, and Zeolites. A preferred silica is fumed silica. A covalently bonded on repeating structures or units to prepare preferred metal oxide is silicon dioxide, titanium dioxide, 35 a self assembling molecule so that the individual chemical aluminum oxide, magnesium oxide, or Zinc oxide. A pre moieties preferably form self assembling donor-acceptor ferred metal carbonate or metal bicarbonate is sodium bicar pairs with other donors and acceptors on the same, or differ bonate, sodium carbonate, lithium bicarbonate, lithium car ent, molecule. A “hydrogen bonded complex' is a chemical bonate, potassium carbonate, or potassium bicarbonate. A complex formed between hydrogen bonding arrays. Hydro preferred finely-divided metal is finely divided gold, silver, 40 gen bonded arrays can have association constants K (assoc) copper, or Zinc. between 10 and 10 M' (reciprocal molarities), generally In some embodiments, the active agent is in the form of a greater than 10 M'. In preferred embodiments, the arrays particulate solid. Preferred particulate solids are character are chemically the same or different and form complexes. ized as having morphology of platelets, tubes (e.g., carbon Accordingly, the molecularly self-assembling materials nanotubes, including single-wall carbon nanotubes 45 (MSA) presently include: molecularly self-assembling poly (SWNT)), cylinders, polycylinders, spheres, balls (e.g., esteramides, copolyesteramide, copolyetheramide, copoly fullerene types), polyhedrals, discs, needles, polyneedles, etherester-amide, copolyetherester-urethane, copolyether cubes, irregular shapes, ellipsoids, wiskers, or mixtures of urethane, copolyester-urethane, copolyester-urea, two or more thereof. copolyetherester-urea and their mixtures. Preferred MSA Preferably, the one or more active agents comprise a total 50 include copolyesteramide, copolyether-amide, copolyester of at least about 0.0001 weight percent (wt %), more prefer urethane, and copolyether-urethanes. The MSA preferably ably at least 0.01 wt %, still more preferably at least 0.1 wt %, has number average molecular weights, MW, (interchange and even more preferably at least 1.0 wt % of the activated ably referred to as M) (as is preferably determined by NMR polymer composition of the first embodiment based on total spectroscopy) of 2000 grams per mole or more, more prefer weight of the activated polymer composition. Also prefer 55 ably at least about 3000 g/mol, and even more preferably at ably, the one or more active agents comprise a total of about least about 5000 g/mol. The MSA preferably has MW, 75 wt % or less, more preferably 50 wt % or less, still more 50,000 g/mol or less, more preferably about 20,000 g/mol or preferably 30 wt % or less, and even more preferably about 20 less, yet more preferably about 15,000 g/mol or less, and even wt % or less of the activated polymer composition of the first more preferably about 12,000 g/mol or less. The MSA mate embodiment based on total weight of the activated polymer 60 rial preferably comprises molecularly self-assembling repeat composition. units, more preferably comprising (multiple) hydrogen bond Molecularly Self-Assembling Material ing arrays, wherein the arrays have an association constant K As used herein a MSA material means an oligomer or (assoc) preferably from 10° to 10 reciprocal molarity (M'.) polymer that effectively forms larger associated or assembled and still more preferably greater than 10 M'; association of oligomers and/or polymers through the physical intermolecu 65 multiple-hydrogen-bonding arrays comprising donor-accep lar associations of chemical functional groups. Without wish tor hydrogen bonding moieties is the preferred mode of self ing to be bound by theory, it is believed that the intermolecu assembly. The multiple H-bonding arrays preferably com US 8,524,796 B2 11 12 prise an average of 2 to 8, more preferably 4-6, and still more diethylene glycol), groups derived from branched diols such preferably at least 4 donor-acceptor hydrogen bonding moi as neopentyl glycol or derived from cyclo-hydrocarbylene eties per molecularly self-assembling unit. Molecularly self diols such as Dow Chemical's UNOXOL(R) isomer mixture of assembling units in preferred MSA materials include bis 1.3- and 1.4-cyclohexanedimethanol, and other non-limiting amide groups, and bis-urethane group repeat units and their groups, such -methylcylohexyl-, -methyl-cyclohexyl-me higher oligomers. thyl-, and the like. “Heterocycloalkyl is one or more cyclic Preferred self-assembling units in the MSA material useful ring systems having 4 to 12 atoms and, containing carbon in the present invention are bis-amides, bis-urethanes and atoms and at least one and up to four heteroatoms selected bis-urea units or their higher oligomers. A more preferred from nitrogen, oxygen, or Sulfur. Heterocycloalkyl includes self-assembling unit comprises a poly(ester-amide), poly 10 fused ring structures. Preferred heterocyclic groups contain (ether-amide), poly(ester-urea), poly(ether-urea), poly(ester two ring nitrogen atoms, such as piperazinyl. In some urethane), or poly(ether-urethane), or a mixture thereof. For embodiments, the heterocycloalkyl groups herein are option convenience and unless stated otherwise, oligomers or poly ally substituted in one or more substitutable positions. For mers comprising the MSA materials may simply be referred example in some embodiments, heterocycloalkyl groups are to herein as polymers, which includes homopolymers and 15 optionally Substituted with halides, alkoxy groups, hydroxy interpolymers such as co-polymers, terpolymers, etc. groups, thiol groups, ester groups, ketone groups, carboxylic In some embodiments, the MSA materials include “non acid groups, amines, and amides. aromatic hydrocarbylene groups' and this term means spe Examples of MSA materials useful in the present invention cifically herein hydrocarbylene groups (a divalent radical are poly(ester-amides), poly(ether-amides), poly(ester formed by removing two hydrogen atoms from a hydrocar ureas), poly(ether-ureas), poly(ester-urethanes), and poly bon) not having or including any aromatic structures such as (ether-urethanes), and mixtures thereof that are described, aromatic rings (e.g. phenyl) in the backbone of the oligomer with preparations thereof, in United States Patent Number or polymer repeating units. In some embodiments, non-aro (USPN) U.S. Pat. No. 6,172,167; and applicants co-pending matic hydrocarbylene groups are optionally Substituted with PCT application numbers PCT/US2006/023450, which was various Substituents, or functional groups, including but not 25 renumbered as PCT/US2006/004005 and published under limited to: halides, alkoxy groups, hydroxy groups, thiol PCT International Patent Application Number (PCT-IPAPN) groups, ester groups, ketone groups, carboxylic acid groups, WO 2007/099397; PCT/US2006/035201, which published amines, and amides. A “non-aromatic heterohydrocarbylene’ under PCT-IPAPN WO 2007/030791; PCT/US08/053,917; is a hydrocarbylene that includes at least one non-carbon PCT/US08/056,754; and PCT/US08/065,242. Preferred said atom (e.g. N, O, S, P or other heteroatom) in the backbone of 30 MSA materials are described below. the polymer or oligomer chain, and that does not have or In a set of preferred embodiments, the molecularly self include aromatic structures (e.g., aromatic rings) in the back assembling material comprises ester repeat units of Formula bone of the polymer or oligomer chain. In some embodi I: ments, non-aromatic heterohydrocarbylene groups are optionally substituted with various substituents, or functional 35 groups, including but not limited to: halides, alkoxy groups, Formula I hydroxy groups, thiol groups, ester groups, ketone groups, carboxylic acid groups, amines, and amides. Heteroalkylene --O-R-O-Ö-R-6-- is an alkylene group having at least one non-carbonatom (e.g. N, O, S or other heteroatom) that, in some embodiments, is 40 optionally substituted with various substituents, or functional and at least one second repeat unit selected from the estera groups, including but not limited to: halides, alkoxy groups, mide units of Formula II and III: hydroxy groups, thiol groups, ester groups, ketone groups, carboxylic acid groups, amines, and amides. For the purpose of this disclosure, a “cycloalkyl group is a saturated carbocy 45 Formula II clic radical having three to twelve carbon atoms, preferably O O O O three to seven. A “cycloalkylene' group is an unsaturated | carbocyclic radical having three to twelve carbonatoms, pref --O-R-C-RN-C-R2-O-O-R-C-i- erably three to seven. Cycloalkyl and cycloalkylene groups Formula III independently are monocyclic or polycyclic fused systems as 50 long as no aromatics are included. Examples of carbocyclic O O O O radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclo hexyl and cycloheptyl. In some embodiments, the groups --O-R-O--R-8-FR-8-R-8 -y herein are optionally substituted in one or more substitutable positions as would be known in the art. For example in some 55 and the ester-urethane units of Formula IV: embodiments, cycloalkyl and cycloalkylene groups are optionally Substituted with, among others, halides, alkoxy groups, hydroxy groups, thiol groups, ester groups, ketone Formula IV groups, carboxylic acid groups, amines, and amides. In some O O O O embodiments, cycloalkyl and cycloalkene groups are option 60 ally incorporated into combinations with other groups to form | | additional Substituent groups, for example: “-Alkylene-cy --O-R-O-C-RN-C-O-R-O-O-R-C-i- cloalkylene-, "-alkylene-cycloalkylene-alkylene-”, “-het eroalkylene-cycloalkylene-, and "-heteroalkylene-cy wherein cloalkyl-heteroalkylene' which refer to various non-limiting 65 R is at each occurrence, independently a C-Co non-aro combinations of alkyl, heteroalkyl, and cycloalkyl. These matic hydrocarbylene group, a C-Co non-aromatic hetero combinations include groups such as OXydialkylenes (e.g., hydrocarbylene group, or a polyalkylene oxide group having US 8,524,796 B2 13 14 a group molecular weight of from about 100 to about 5000 more than about 20,000. More preferably, the molecular g/mol. In preferred embodiments, the C-C non-aromatic weight is no more than about 12,000. hydrocarbylene at each occurrence is independently specific For convenience the chemical repeat units for various groups: alkylene-, -cycloalkylene-, -alkylene-cycloalkylene-, embodiments are shown independently. The invention -alkylene-cycloalkylene-alkylene-(including dimethylene encompasses all possible distributions of the w, x, y, and Z cyclohexyl groups). Preferably, these aforementioned spe units in the copolymers, including randomly distributed W, X, cific groups are from 2 to 12 carbon atoms, more preferably y and Zunits, alternatingly distributed w, x, y and Zunits, as from 3 to 7 carbon atoms. The C-C non-aromatic hetero well as partially, and block or segmented copolymers, the hydrocarbylene groups are at each occurrence, independently definition of these kinds of copolymers being used in the specifically groups, non-limiting examples including: -het 10 conventional manner as known in the art. Additionally, there ereoalkylene-, -heteroalkylene-cycloalkylene-, -cycloalky are no particular limitations in the invention on the fraction of lene-heteroalkylene-, or -heteroalkylene-cycloalkylene-het the various units, provided that the copolymer contains at eroalkylene-, each aforementioned specific group preferably least one w and at least one X, y, or Z unit. In some embodi comprising from 2 to 12 carbon atoms, more preferably from 15 ments, the mole fraction of w to (x+y+Z) units is between 3 to 7 carbon atoms. Preferred heteroalkylene groups include about 0.1:0.9 and about 0.9.0.1. In some preferred embodi oxydialkylenes, for example diethylene glycol ments, the copolymer comprises at least 15 mole percent w ( CHCHOCHCH O—). When R is a polyalkylene units, at least 25 mole percent w units, or at least 50 mole oxide group it preferably is a polytetramethylene ether, percent w units polypropylene oxide, polyethylene oxide, or their combina In some embodiments, the number average molecular tions in random or block configuration wherein the molecular weight (M) of the MSA material useful in the present inven weight (Mn-average molecular weight, or conventional tion is between 1000 g/mol and 30,000 g/mol, inclusive. In molecular weight) is preferably about 250 g/ml to 5000, some embodiments, M., of the MSA material is between g/mol, more preferably more than 280 g/mol, and still more 2,000 g/mol and 20,000 g/mol, inclusive, preferably 5,000 preferably more than 500 g/mol, and is preferably less than 25 g/mol to 12,000 g/mol. In more preferred embodiments, M. 3000 g/mol; in some embodiments, mixed length alkylene of the MSA material is less than 5,000 g/mol. Thus, in some oxides are included. Other preferred embodiments include more preferred embodiments, M, of the MSA material is at species where R is the same C-C alkylene group at each least about 1000 g/mol and 4,900 g/mol or less, more prefer occurrence, and most preferably it is —(CH2) . ably 4,500 g/mol or less. R" is at each occurrence, independently, a bond, or a 30 C-Co non-aromatic hydrocarbylene group. In some pre For preparing fibers comprising the MSA material useful ferred embodiments, R' is the same C-C alkylene group at in the present invention, including the activated fibers, vis each occurrence, most preferably —(CH) -. cosity of a melt of a preferred MSA material is characterized R" is at each occurrence, independently, a C-Co non as being Newtonian over the frequency range of 10' to 10° aromatic hydrocarbylene group. According to another 35 radians per second (rad./S.) at a temperature from above a embodiment, R' is the same at each occurrence, preferably melting temperature T, up to about 40°C. above T, prefer C-C alkylene, and even more preferably R is -(CH2). , ably as determined by differential scanning calorimetry (CH2). , —(CH) , or —(CH2)5 -. (DSC). Depending upon the polymer or oligomer, preferred R is at each occurrence - N(R)-Ra N(R) , where MSA materials exhibit Newtonian viscosity in the test range R is independently H or a C-C alkyl, preferably C-C, 40 frequency at temperatures above 100° C., more preferably alkyl, or R' is a C-Coheterocycloalkylenegroup containing above 120° C. and more preferably still at or above 140° C. the two nitrogen atoms, wherein each nitrogen atom is and preferably less than 300° C., more preferably less than bonded to a carbonyl group according to Formula II or III 250° C. and more preferably still less than 200° C. For the above; w represents the ester mol fraction, and X, y and Z purposes of the present disclosure, the term Newtonian has its represent the amide or urethane mole fractions where w-X+ 45 conventional meaning; that is, approximately a constant vis y+Z-1, 0solvents are used in the Solution electrospinning activated polymer composition dissolved in a solvent is fed process. A preferred solution-electroSpinning solvent is into or onto the spinneret from, for example, a Syringe at a (monohalo to perhalo)(C-C)alkyl; RC(O)OR: RC(O) constant and controlled rate using a metering pump. A high 25 NRR: ROR: RC(O)R: or a mixture thereof, wherein voltage (1 kilovolt (kV) to 120 kV, preferably 1 kV to 100 kV. each halo independently is fluoro or chloro, each R" and R' and more preferably 1 kV to 50 kV) is applied and a portion independently is Hor (C-C)alkyl, each RandR' indepen of the activated polymer composition, preferably in the form dently is Hor (C-C)alkyl or Rand R taken together form of a droplet, at the nozzle (e.g., needle) of the Syringe a (C-C)alkylene, and each RandR independently is (C- becomes highly electrified. At a characteristic Voltage the 30 C.)alkyl or RandR taken together forma (C-C)alkylene. portion (e.g., droplet) forms one or more Taylor cones, and a A more preferred solvent is chloroform, methanol, water, fine jet, in some embodiments of the present invention two or formic acid, alcohols (e.g., ROR wherein R is (C-C)alkyl more Such jets, of the activated polymer composition devel and R is H), N,N-dimethylformamide, tetrahydrofuran, 1.2- ops. The fine jet of activated polymer composition is drawn dichloroethane, ethylacetate, methylethylketone, or mixtures towards the grounded conductor which is placed opposing the 35 thereof. Still more preferred are chloroform and formic acid. spinneret. For electrospinning solvents, the term “(C-C)alkyl While being drawn towards the grounded conductor, the means methyl, ethyl, 1-propyl, or 2-propyl. The term “(C- Solution-electrospinning solvent at least partially dissipates C.)alkylene' means a straight or branched hydrocarbon (e.g., at least partially phase separates, evaporates, or a com diradical of 2 to 6 carbon atoms. The (C-C)alkyl and (C- bination thereof) and the jet solidifies into activated fibers. 40 C.)alkylene independently are unsubstituted or substituted Preferably, the solution-electrospinning solvent is substan with one or more Substituents halides, alkoxy groups (e.g., tially completely dissipated (i.e., lost) from the activated (C-C)alkoxy), hydroxy, thiol (i.e., -SH), carboxylic ester fibers. Substantially complete dissipation of the solvent from groups (e.g., —C(O)OR), ketone groups (e.g., -C(O)R’), the activated fibers (e.g., loss of at least 95 wt %, more carboxylic acid (i.e., -COOH), amines (e.g., NRR), and preferably at least 99 wt % of the solvent from the fibers) may 45 amides (e.g., C(O)NR'R''), wherein R. R. R', and Rare occur before, during, or after the activated fibers are deposited unsubstituted versions of the groups as defined herein for the and may comprise part of a solution electroSpinning unit electrospinning solvents. operation or a separate unit operation (e.g., a drying operation In some embodiments, a surfactant, salt, and other material that may or may not be in direct communication with the is added to the electrospinning solution to modify one or more Solution electrospinning unit operation). Preferably, the acti 50 of the operating characteristics (e.g., viscosity, conductivity vated fibers are deposited on a collector that is placed in front (or resistivity), and surface tension) of the solution. These of the conductor. In some embodiments, the activated fibers additives include, but are not limited to, sodium dodecyl are deposited on the collector as a randomly oriented, non Sulfate, pyridinium formate, inorganic salt, poly(ethylene woven mat. The activated fibers are subsequently stripped glycol), triethylbenzyl ammonium chloride, poly(propylene from the collector if desired. In other embodiments, a charged 55 oxide)- and poly(ethylene oxide)- ethers, nanoclay (laponite) conductor (opposite polarity to that of electrode) is employed and combinations thereof. instead of the grounded conductor. Producing Activated Fibers by Melt Electrospinning The parameters for operating the electrospinning apparatus In a typical melt electrospinning process for producing may be readily determined by a person of ordinary skill in the activated fibers, the melt of the activated polymer composi art without undue experimentation. By way of example, the 60 tion is fed into or onto the spinneret from, for example, the spinneret is operated at about 20° C. or ambient temperature, Syringe at a constant and controlled rate using a metering the spin electrode is maintained at the same temperature or pump. A high Voltage (e.g., 1 kV to 120kV) is applied and the temperature at which the MSA material has sufficiently low drop of composition at the nozzle of the Syringe becomes viscosity to allow thin (e.g., average diameter below 1000 highly electrified. At a characteristic voltage the droplet nm) fiber formation. If desired, the spinneret is generally 65 forms a Taylor cone, and a fine jet of activated polymer heated up to about 300° C. and the surrounding environmen composition develops. The fine jet is drawn to the conductor tal temperature optionally is maintained at about similar tem (e.g., a grounded conductor), which is placed opposite the US 8,524,796 B2 19 20 spinneret. While being drawn to the conductor, the jet cools preferably the stretch gas is air. An example of a melt blowing and hardens into activated fibers. Preferably, the activated device is an Oerlikon Neumag Meltblown TechnologyTM sys fibers are deposited on a collector that is placed in front of the tem (Oerlikon Heberlein Wattwil AG, Switzerland). conductor. In some embodiments, the activated fibers are The invention herein may use any melt blowing system but deposited on the collector as a randomly oriented, nonwoven 5 preferably uses specialized process melt-blowing systems mat or individually captured and wound-up on a roll. The produced by Hills, Inc. of West Melbourne, Fla. 32904. See activated fibers are subsequently stripped from the collector if e.g. U.S. Pat. No. 6,833,104 B2, and WO 2007/121458A2 the desired. In other embodiments, a charged conductor (oppo teachings of each of which are hereby incorporated by refer site polarity to that of electrode) is employed instead of the ence. See also www.hillsinc.net/technology.shtml and grounded conductor. 10 www.hillsinc.net/nanomeltblownfabric.shtml and the article The parameters for operating the electrospinning apparatus “Potential of Polymeric Nanofibers for Nonwovens and for effective melt spinning of the activated polymer compo Medical Applications” by Dr John Hagewood, J. Hagewood, sition are readily determined by a person of ordinary skill in LLC, and Ben Shuler, Hills, Inc, published in the 26 Feb. 2008 the art without undue experimentation. By way of example, Volume of Fiberjournal.com. Preferred dies have very large the spinneret is generally heated up to about 300°C., the spin 15 Length/Diameter flow channel ratios (L/D) in the range of electrode temperature is maintained at about 10°C. or higher greater than 20/1 to 1000/1, preferably greater than 100/1 to (e.g., up to just below a decomposition temperature of the 1000/1, including for example, but not limited to, L/D values composition or up to about 150° C. higher) above the melting 150/1, 200/1, 250/1, 300/1 and the like so long as there is point or temperature at which the activated polymer compo sufficient polymer back pressure for even polymer flow dis sition has sufficiently low viscosity to allow thin fiber forma tribution. Additionally, the die spinholes (“holes') are typi tion, and the Surrounding environmental temperature is cally on the order of 0.05 to 0.2 mm in diameter. unregulated or, optionally, heated (e.g., maintained at about In an alternative process, the Solution electrospinning, melt similar temperatures using hot air). electrospinning, or melt blowing process for producing acti Alternatively, the spinneret is generally heated up to about vated fibers described above is repeated except a MSA mate 300° C. and the surrounding environmental temperature 25 rial is used instead of the activated polymer composition to optionally is maintained at about room temperature (i.e., from produce MSA fibers, which are then contacted with one or about 20°C. to 30°C.). The applied voltage is generally about more active agents useful in the present invention to give the 1 kV to 120 kV, preferably 1 kV to 80 kV. The electrode gap activated fibers wherein the one or more active agents are in (the gap between spin electrode and collector) is generally coating operative contact with the MSA fibers. between about 3 cm and about 50 cm, preferably about 3 cm 30 The Highly Filled Polymer Filler Composite and about 19 cm. Preferably, the activated fibers are fabri A preferred highly filled polymer filler composite is char cated at about ambient pressure (e.g., 1.0 atmosphere) acterized, when a melt, as having a Zero shear Viscosity of less although the pressure may be higher or lower. than 10,000 Pa's. at from above T. up to about 40°C. above Preferred electrospinning devices are those that are mar T. The viscosity of a melt of one of the preferred highly filled keted commercially as being useful for melt electrospinning. 35 polymer filler composites is less than 90 Pas. at 180°C., and Use of commercially available melt electrospinning device more preferably in the range of from 1 Pas. to 100 Pas. at such as NS Lab M device, Elmarco S.r.o., Liberec, Czech 150° C. to 170° C. Republic (e.g., using NanoSpiderTM technology), are more Another preferred highly filled polymer filler composite is preferred. characterized as having a storage modulus (G) compared to The activated fibers that are prepared by a melt electrospin 40 G' of the MSA material alone (i.e., unfilled), of 2 times or ning process described herein generally have an average higher, more preferably 3 times or higher, and still more diameter of about 1000 nm or less, more preferably about 800 preferably 6 times or higher. In some embodiments, G' of the nm or less, and more preferably about 600 nm or less. Pref highly filled polymer filler composite at room temperature erably, the average diameter is at least 100 nm, more prefer (i.e., 25°C.) is 200 megaPascals (MPa) or higher than G' of ably at least 200 nm. In other aspects, the average diameter is 45 the MSA material alone. In other embodiments, G' of the from about 30 nm to about 1000 nm, more preferably about highly filled polymer filler composite is 400 MPa or higher, 200 nm to about 600 nm. In other aspects, the average diam more preferably 600 MPa or higher, and still more preferably eter is from about 50 nm to about 1000 nm. In some embodi 700 MPa or higher. Storage modulus G' is measured by ments, activated fibers are fabricated with diameters as low as dynamic mechanical spectroscopy (DMS) according to the about 30 nm. Particularly preferred are activated fibers with 50 method described later. average diameters of about 200 nm to 300 nm. A melt electrospinning process described above produces Materials and Methods the activated fibers without beading. Producing Activated Fibers by Melt Blowing Compounding Procedures for Preparing Filled MSA Com A melt blowing device typically comprises at least one die 55 positions and Composites block having a portion that functions as a die tip; at least one Prior to compounding, all MSA materials and filler mate gas knife assembly; a source of a stretch gas stream; and a rials are pre-weighed and stored separately. collector, wherein the Source of a stretch gas stream indepen Compounding Procedure 1: any filler (e.g., talc). A Haake dently is in operative fluid communication with the gas knife PolyLab Rheocord blender (Haake) is outfitted with a 20 assembly and the die tip. The die tip defines at least one, 60 milliliter (mL) bowl. Temperatures of all Zones of the Haake preferably a plurality of apertures through which a melt of a mixer are set to 160°C. An air cooling hose is attached to the material to be melt blown (i.e., MSA material or activated central one of the Zones in order to maintain temperature polymer composition) passes. A source of the melt is in control. The MSA material is loaded into the 20 uL bowl and operative fluid communication with the apertures of the die allowed to melt. Filler material is added directly to the MSA tip. Examples of useful stretch gases are air, nitrogen, argon, 65 material melt. Then, a plunger is lowered into the Haake, and helium, and a mixture of any two or more thereof. Preferably, the melt of the MSA material and filler is compounded at a the stretch gas is air, nitrogen, or a mixture thereof more rotor speed of 200 revolutions per minute (rpm), and a resi US 8,524,796 B2 21 22 dence time of approximately 2.5 minutes. The residence time TABLE B-continued begins with the lowering of the plunger, and ends with the raising a stopper. Table A presents the timing for the talc Summary of compression molding parameters for compounding. composites Examples 5A to SF Load ramp TABLE A Temperature rate, Temperature ramp rate Load, kg/minute Time Summary of tale composite compounding procedure Step (° C.) (C. minute) kg (klb) (klb/min) (minutes)

Time rpm Comment 3 140 93 18143 (4.0) 317 x 10 3 10 (1200) O second 200 4 37.8 93 450 (1) 317 x 103 5 10 seconds 50 Add MSA material (1200) 1 minute 200 Allow MSA material to 5 End 10 seconds melt 1 minute 200 Add filler (e.g., talc) 30 seconds 15 Compression Molding Procedure 3 (used for composite of 2 minutes 200 Compound to give filler Example 6 of the Present Invention below): 30 seconds composite Samples containing silica are compression molded into 5 5 minutes O Recover filler composite cm by 5 cm by 0.3 cm plaques at 90° C. and 5000 psi. Cool composites under pressure in molder to room temperature or Compounding Procedure 2: preferred for when filler is less to allow clean removal of the plaques from the mold silica. The Haake is fitted with a 60 uL bowl and run at 170° chase. C. and 50 rpm. The MSA material is added to the Haake bowl Testing: first and allowed to melt. Then the silica is added and blended Ultimate Tensile: procedure of ASTM D-638 into the MSA material for 10 minutes after all the silica is Flexural modulus: procedure of ASTM D-790 added. The resulting composites are removed from the Haake 25 Imaging: and pressed into flat pieces while still warm. After cooling at Transmission electron microscope (TEM) imaging: room temperature, the pressed composite material is cut into Samples, approximately 0.5 mm in thickness, from the com pieces for compression molding. pression molded plaques and mounted in a chuck for Compression Molding: ultracryomicrotomy. Cross-sectional to the thickness, the Prior to molding, all samples are allowed to dry overnight 30 samples are trimmed into a trapezoid and cooled to -100° C. (at least 16 hours) at 65°C. in a vacuum of approximately 36 in the microtome. Thin-sections, approximately 80 nm are cmHg (48 kiloPascals (kPa)). Samples are compression obtained with a Leica UC6:FC6 cryo-microtome and exam molded into 10 cmx10 cm x0.05 cm plaques and 5 cm x 1.25 ined in a JEOL 1230 operating at an accelerating Voltage of cmx0.32 cm bars unless otherwise noted. Compression mold 120 kilovolts (kV). Digital TEM images of the microstructure ing is done using a MPT-14 compression/lamination press 35 are recorded at various magnifications (typically 1,000 times; (Tetrahedron Associates, Inc., San Diego, Calif., USA) hav 10,000 times; and 50,000 times magnification) using a Gatan ing a molder and mold chase. Multiscan CCD camera. Compression Molding Procedure 1 (used for composites of Thermogravimetric Analysis (TGA) Procedure Comparative Example(s) below): Samples weighing between 5 milligrams (mg) and 10 mg 40 are loaded into an aluminum TGA pan and heated to 500° C. at a rate of 10°C/minute in a TA Instruments Q5000 TGA in a nitrogen gas atmosphere. TGA is used to determine actual Procedure 1: 170° C.f4 minutes 1000 pounds per square inch (psi) (7000 concentration of inorganics in a composite. kiloPascals (kPa)) 170° C.1 minutes/35000 psi (240,000 kPa) Dynamic Mechanical Spectroscopy (DMS) Procedure Cool/3:30 minutes/35000 psi (240,000 kPa) 45 Prior to conducting DMS experiments, all samples are Repack: 170° C./5 minutes/1000 psi (7000 kPa) exposed to laboratory atmosphere for at least 40 hours to 170° C./2 minutes/40000 psi (300,000 kPa) allow for sample equilibration to the test environment. 170° C./2 minutes/1000 psi (7000 kPa) 170° C./2 minutes/40000 psi (300,000 kPa) Samples are in the form of the 5 cm x 1.25 cmx0.32 cm com Cool/5 minutes/40000 psi (300,000 kPa) pression molded bars, which are loaded into torsional rectan 50 gular holders of an Ares Rheometer from TA Instruments. Initially, a dynamic strain sweep is conducted at 1 Hz and 25° Compression Molding Procedure 2 (used for composites of C. beginning at a strain of 0.001%. For each sample a strain Examples 5A to 5F of the Present Invention below) are sum value is obtained from a region where storage modulus (G) is marized in Table B: linear over a range of Strain values. This strain value is used 55 for Subsequent dynamic frequency Sweeps and dynamic tem TABLE B perature ramps. Using the Strain value obtained during the Summary of compression molding parameters for strain Sweep, a frequency Sweep is conducted at 25°C. The composites Examples 5A to SF frequency ranged from 100 radians per second (rad/s.) to 0.01 rad/s. Finally, a temperature ramp is conducted from -80° C. Load ramp 60 Temperature rate, to 100° C. at a heating rate of 5°C/minute. The frequency is Temperature ramp rate Load, kg/minute Time held constant at 1 Hz. Step (° C.) (C. minute) kg (klb) (klb/min) (minutes) Melt Viscosity Measurement Procedure Samples are die cut from a plaque of composite. Parallel 1 140 93 608 (1.5) 317 x 10 5 (1200) plate geometry holders in an Ares Rheometer (TA Instru 2 140 93 4536 (10) 317 x 10 4 65 ments) are heated to 170° C. The holders are zeroed at tem (1200) perature. A sample is loaded onto the holders, and the top holder is lowered into that sample so that there is significant US 8,524,796 B2 23 24 normal force on the sample. The sample is allowed to melt, Step (b): preparation of a MSA copolyesteramide with 50 and any melted sample that extends beyond the holders is mole percent amide content (PEA-C2C50%) removed. Initially, a dynamic strain Sweep is conducted at 1 Loading a Reactor HZ and 170° C. beginning at a strain of 0.1%. For each A 100 L single-shaft Kneader-Devolatizer reactor sample, a strain value is obtained from a region where 5 equipped with a distillation column and a powerful vacuum dynamic loss shear modulus (G") is linear over a range of pump system is nitrogen purged and heated to 80° C. (ther strain values. This strain value is used for Subsequent mostat oil). Dimethyl adipate (DMA), 38.324 kilograms (kg) dynamic frequency Sweeps. Using the strain value obtained and granulated C2C monomer (31.724 kg, prepared as during the strain Sweep, a frequency sweep is conducted at described above in Step (a)) are fed into the kneader. The 170° C. The frequency ranged from 100 rad/s. to 0.1 rad/s. 10 slurry is stirred at 50 revolutions perminute (rpm). 1,4-butane Determining Copolymer Number Average Molecular Weight diol (1,4-BD: 18.436 kg) is added to the slurry at a tempera ture of about 60° C. The reactor temperature is further (M) increased to 145° C. to obtain a homogeneous Solution. Proton nuclear magnetic resonance spectroscopy (proton Step (c): Distilling Methanol and Transesterification NMR or "H-NMR) is used to determine monomer purity, 15 Still under nitrogen atmosphere, titanium(IV) tetrabutox copolymer composition, and copolymer number average ide catalyst, 153 grams (g) in 1.380 kg 1,4-BD is injected at a molecular weight M, utilizing the CH-OH end groups. Pro temperature of 145° C. in the reactor; methanol evolution ton NMR assignments are dependent on the specific structure starts. The temperature in reactor is slowly increased to 180° being analyzed as well as the solvent, concentration, and C. in 1.75 hours and is held for 45 additional minutes to temperatures utilized for measurement. For ester amide complete the methanol distillation at ambient pressure. monomers and co-polyesteramides, d4-acetic acid is a con Methanol (12.664 kg) is collected. venient solvent and is the solvent used unless otherwise Step (d): Distilling 1,4-butanediol and Polycondensation to noted. For ester amide monomers of the type called DD that Give PEA-C2C50% are methyl esters typical peak assignments are about 3.6 to 3.7 The reactor dome temperature is increased to 130° C. and ppm for C(=O)—OCH; about 3.2 to 3.3 ppm for 25 the vacuum system activated stepwise to a reactor pressure of N—CH2—, about 2.2 to 2.4 ppm for C(=O)—CH2—, and 7 millibars (mbar) in 1 hour. Temperature in the kneader/ about 1.2 to 1.7 ppm for C CH. C. For co-polyesteram devolatizer reactor is kept at 180° C. Then the vacuum is ides that are based on DD with 1,4-butanediol, typical peak increased to 0.7 mbar for 7 hours while the temperature is assignments are about 4.1 to 4.2 ppm for C(=O)—OCH -: increased to 190° C. The reactor is kept for 3 additional hours about 3.2 to 3.4 ppm for N CH ; about 2.2 to 2.5 ppm for 30 at 191° C. and with vacuum ranging from 0.87 mbar to 0.75 C(=O)—CH ; about 1.2 to 1.8 ppm for C CH, C, and mbar. At this point a sample of the reactor contents is taken about 3.6 to 3.75 - CH-OH end groups. (Sample Number 1); melt viscosities are 6575 megaPascals (mPa.) at 180° C. and 5300 mPa. at 190° C. The reaction is PREPARATIONS continued for another 1.5 hours until a sample (Sample Num 35 ber 2) shows final melt viscosities are 8400 mPa. at 180° C. Preparation 1 and 6575 mPa. at 190° C. Then the liquid Kneader/Devola tizer reactor contents are discharged at high temperature of Preparation of MSA Material that is a about 190° C. into collecting trays, the resulting MSA mate Polyesteramide (PEA) Comprising 50 Mole Percent rial is cooled to room temperature and grinded. Weight of of Ethylene-N,N'-dihydroxyhexanamide (C2C) 40 final product PEA-C2C50% of Preparation 1 is 57.95 kg Monomer (the MSA Material is Generally (87.8% yield). A sample (Sample Number 3) of the PEA Designated as a PEA-C2C50%) C2C50% of Preparation 1 has melt viscosities of 8625 mPa. at 180° C. and 6725 mPa. at 190° C. Viscosities are determined Step (a) Preparation of the Diamide Diol, Ethylene-N,N'- using a Brookfield DV-II+ Vicosimeter with spindle number dihydroxyhexanamide (C2C) 45 28 at 20 revolutions per minute (rpm). Proton NMR deter A 10-liter (L) stainless steel reactor equipped with an agi mines that Sample Numbers 1 to 3 have M, of 6450grams per tator and a cooling water jacket is charged with e-caprolac mole (g/mol); 6900 g/mol; and 7200 g/mol, respectively. tone (5.707 kilograms (kg), 50 moles) and purged with nitro gen. Under rapid stirring, ethylene diamine (EDA, 1.502 kg, Preparation 2 25 moles) is added at once. After an induction period a slow 50 exothermic reaction starts. The reactor temperature gradually Formation of Nonwoven Webs Comprising MSA rises to 90° C. under maximum cooling applied. A white Fibers by Melt Blowing deposit forms and the reactor contents solidify, at which point stirring is stopped. The reactor contents are then cooled to 20° The nonwoven web of Preparation 2 is prepared by melt C. and are then allowed to rest for 15 hours. The reactor 55 blowing the MSA material of Sample 3 (M 7200 g/mol) of contents are then heated to 140°C. (at which temperature the Preparation 1. An Oerlikon Neumag Melt-blown Technol solidified reactor contents melt), and heated then further to ogyTM (M&J technology) system comprising a die block is 160° C. under continued stirring for at least 2 hours. The used to prepare fibers and nonwoven webs. The die block resulting liquid product is then discharged from the reactor comprises a beam defining spinholes, the beam having a into a collecting tray. A nuclear magnetic resonance study of 60 spinhole density of 55 spinholes per inch (i.e., 22 spinholes the resulting product shows that the molar concentration of per centimeter). AS is known in the art, the spinhole density C2C in the product exceeds 80 percent. The procedure is may be higher or lower depending on the particular nonwoven repeated four more times resulting in five product lots. The web desired. Each spinhole has a diameter of 0.3 mm and a melting point of the product is determined to be 130-140°C. length-to-depth (L/D) ratio of 10. Length of the beam defines (main melting point) by differential scanning calorimetry 65 width of the nonwoven web. A 100 mesh screen pack is used (DSC) (peak maximum). The solid material is granulated and in the die block for filtering materials to be melt blown. MSA used without further purification. materials preferably are dried at 80° C. for 2 hours in a US 8,524,796 B2 25 26 ventilating silo/dryer to remove any residual water before COMPARATIVE (NON-INVENTION) being melt blown. The MSA material or activated polymer EXAMPLE(S) composition of the first embodiment is melt-blown at 170° C. melt temperature and 170° C. stretch gas temperature (pref Comparative Example 1 erably, the stretch gas is air sourced from a compressed air 5 chamber and the temperature of the stretch gas is measured in the compressed air chamber). Melt blowing the PEA Unfilled PEA-C2C50% of Preparation 1 C2C50% of Preparation 1 yields a nonwoven web comprising MSA fibers of Preparation 2, the nonwoven web having a Separate samples of the PEA-C2C50% of Preparation 1 are basis weight of 25 GSM (grams per meter squared). 10 compression molded, prepared as plaques, or prepared as flat sheets, and subjected to TGA, DMS, and melt viscosity mea Preparation 3 Surements according to the procedures described previously. TGA results are shown as parts of FIG. 9. DMS results are Formation of a Fiber Composite Comprising MSA shown as part of FIG. 10. The TGA and DMS results are Fibers Prepared by Melt Electrospinning and Porous 15 discussed later. Polypropylene Support Melt viscosity results are shown as parts of FIGS. 11 and 12. In the figures, the unfilled PEA-C2C50% of Preparation 1 The fiber composite of Preparation 3 is prepared by melt is referred to as “C2C-50,” “C2C-50 (unfilled), or “unfilled electrospinning the MSA material of Sample 3 of Preparation PEA-C2C50%. 2 utilizing a NS Lab-M device manufactured by Elmarco s.r.o., Liberec, Czech Republic. A voltage of 100 kV is EXAMPLES OF THE PRESENT INVENTION applied across 20 cm distance. The polymer melt temperature is 190° C. and the rotating electrode (20 rpm) is heated by In all case for the Examples 1 to 5 below, specimens of applying 150 volts across it. 25 nonwoven webs comprising MSA fibers are prepared by cut The generated fibers are deposited on a spunbonded porous ting the nonwoven web comprising the MSA fibers of Prepa polypropylene Support to give the fiber composite of Prepa ration 2 into 50 square-centimeter (cm) circles using a die ration3. The porous polypropylene Support has a basis weight and clicker press. The weight of each specimen is recorded. of about 20 GSM and travels at a speed of about 1 meter per minute. 30 Pore size distribution of the fiber composite of Preparation Example 1 3 is characterized by the method of capillary flow porometry ASTM E-1294-89 (1999), where 99.5% of the pores of the Silver Acetate Treated Nonwoven Web Comprising fiber composite of Preparation 3 have mean flow pore sizes MSA Fibers within +0.05 um of a mode pore size of 3.19 Lim. The mode 35 pore size of 3.19 um contains 85.9% of the pores. A stock 1 wt % silver acetate solution (50 grams (g)) is prepared using deionized water (49.5 g) and silver acetate Preparation 4 (0.5 g; Alfa Aesar stock #11660). To speed up dissolution, the silver acetate solution is heated to 65° C. for 15 minutes and Preparation of MSA Material that is a 40 Polyesteramide (PEA) Comprising 6.9 Mole Percent allowed to cool to room temperature. of Ethylene-N,N'-dihydroxyhexanamide (C2C) The solution is then poured into a 100 millimeter (mm)x20 Monomer (the MSA Material is Generally mm Petri culture dish (from VWR catalogue #8900-324). Designated as a PEA-C2C6.9%) Individual specimens of the nonwoven web comprising the 45 MSA fibers of Preparation2 are submerged in the solution for In a nitrogen atmosphere, load titanium (IV) butoxide 2 minutes, removed, allowed to drip for 30 seconds, and then (0.58 g, 1.7 mmol), recrystallized N,N'-1,2-ethanediylbis(6- laid flat on an oven rack. When the rack is full, it is placed in hydroxyhexanamide) (C2C) (22.63 g, 78.47 mmol), dimethyl an oven at 65° C. for 4 hours to dry to a constant weight. The adipate (195.27g, 1.1210 mol), and 1,4-butanediol (144.46g, specimen weight is recorded again to determine the weight 1.603 mol) into a 500 mL roundbottom flask. Into the flask 50 gain. The procedure is repeated five more times and the insert a stir-shaft and blade, Claisen style distillation head results for the three runs (1 to 6) are shown below in Table 1. with Vigreux column, and stir-bearing, and attacha collection receiver. Degas the resulting apparatus with three vacuum/ Example 2 nitrogen gas cycles before leaving under nitrogen. Heat-trace distillation head and immerse flask into 160° C. bath, and 55 raise bath setpoint to 175°C. with a total of 2 hours from 160° Chelated Silver Acetate-Treated Nonwoven Web C. to 175°C. Over a period of about 2.25 hours, lower pres Comprising MSA Fibers Sure stepwise and hold pressure at 10 Torr. Keep apparatus under full vacuum (about 0.4 Torr to 0.6 Torr) for a total of A stock of a 1 wt % silver acetate and 2.5 wt % of ethyl about 5 hours. Increase the bath temperature after about 2 60 enediaminetetracetic acid disodium salt (VERSENETMNa, hours to 190° C., and subsequently increase after about 2 The Dow Chemical Company) solution (50 g) is prepared hours to 210° C. Holdbath temperature at 210°C. for about 1 from silver acetate (0.5 g), VERSENETM Na (1.25 g), and hour. Collect the resulting PEA-C2C6.9% product. PEA deionized water (48.25 g). To speed up dissolving, the solu C2C6.9% has inherent viscosity=0.229 dL/g (0.5 g/dL, 30.0° tion is heated to 65° C. for 15 minutes and allowed to cool to C., chloroform/methanol (1/1, w/w)). By DSC, T=65° C. 65 room temperature. Three specimens of the nonwoven web (60 J/g). By proton NMR, M, is 7900 grams per mole and comprising the MSA fibers of Preparation 2 are separately C2C content is 6.9 mol%. treated with the solution in a manner analogous to that US 8,524,796 B2 27 28 described above for Example 1, and the results for the three Example 5A to 5F runs (7 to 9) are also shown below in Table 1. Composites of talc and PEA-C2C50% of Example 3 Preparation 1 In Situ Silver Chloride-Treated Nonwoven Web Following Compounding Procedure 1, Haake blending of Comprising MSA Fibers separate weighed samples of the PEA-C2C50% of Prepara tion 1 and weighed amounts of the Jetfil 625C talc are sepa In a first container, a stock 1 wt % silver acetate solution (50 rately carried out as described previously to give talc com grams (g)) is prepared as described above in Example 1. In a 10 posites having 5 wt %, 10 wt %, 20 wt %, 30 wt %, 40 wt %, second container, 300 grams of a 0.9 wt % NaCl solution is or 50 wt % of the Jetfil 625C talc as shown in Table 6. prepared using deionized water (297.3 g) and sodium chlo ride (2.7 g; reagent grade: 299% purity). The 1 wt % silver TABLE 6 acetate solution is then poured into a 100 millimeter (mm)x20 mm Petriculture dish.30grams of the 0.9 wt % NaCl solution 15 tale composites of Examples 5A to SF: is poured into a second 100 millimeter (mm)x20 mm Petri Example Number. culture dish. Three specimens of the nonwoven web compris ing the MSA fibers of Preparation 2 are separately first sub merged in the 1 wt % silver acetate solution for 1 minute, Amount of 5 10 2O 30 40 50 removed, and then placed in the 0.9 wt % NaCl solution for 30 Jetfi 62SC seconds. The specimens are then removed from the 0.9 wt % talc (wt %) NaCl solution, allowed to drip for 30 seconds, then laid flat on an oven rack. When the rack is full, it is placed in an oven at Separate samples of the talc composites of Examples 5A to 65° C. for 4 hours to dry as described in Example 1. The 25 5F are compression molded, prepared as plaques, or prepared treated specimen weights from the three runs (10 to 12) are as flat sheets, and subjected to TGA, TEM imaging, DMS, recorded again to determine the weight gain, and the results and melt viscosity measurements according to the procedures described above. Results are shown in FIGS. 4-6. In FIGS. for the three runs (10 to 12) are also shown below in Table 1. 4-6, the talc composites of Examples 5A to 5F are referred to 30 by their respective weight percents of Jetfil 625C talc. TABLE 1. TGA results are shown as parts of FIG. 4. The TGA results Weight of in FIG. 4 demonstrates that the talc is dispersed in the talc treated MSA composites of Examples 5A to 5F after compounding. DMS Wt. (g) Wt. (g) fiber minus Percent results for the talc composites of Examples 5A and 5C to 5F untreated treated untreated of Weight are shown as parts of FIG.5. Comparing the DMS results with Run MSA MSA MSA fiber Increase 35 those of the unfilled PEA-C2C50% of Comparative Example Number fiber fiber (g) (%) 1 in FIG. 5 demonstrates that storage modulus G' increases 1 O.1147 O.1251 O.O104 9.1 with increasing concentration of talc in the talc composites of 2 0.1175 O.1253 O.OO78 6.6 Examples 5A and 5C to 5F. For these examples, G' increases 3 O-116 O.1232 O.OO72 6.2 from about 200 MPa for the unfilled PEA-C2C50% at 20° C. 4 O. 1148 O.1245 O.OO97 8.5 40 5 O-110 O.1184 O.OO84 7.6 ultimately to about 1000 MPa in the talc composite of 6 O.1127 O.122 O.OO93 8.3 Example 5F at 20° C. FIG. 5 also shows that the (dynamic) 7 O.1213 0.1553 O.O34 28.0 storage modulus (G) of the talc composites of Examples 5A 8 O.1172 O.1453 O.O281 24.0 and 5C to 5F is increased up to six times that of the unfilled 9 O.1317 O.178 O.O463 35.2 10 O.1337 O.145 O.O113 8.5 PEA-C2C50% of Comparative Example 1. 11 O.1323 O.1421 O.OO98 7.4 45 Melt viscosity results are shown as part of FIG. 6. FIG. 6 12 O.1343 O.1455 O.O112 8.3 shows that the melt dynamic viscosities of the talc composites of Examples 5A, 5B, and 5D to 5F are within the range for processing by conventional melt processing techniques (i.e., The results in Table 1 show that each specimen of the silver materials maintain their processability when highly filled). salt-treated nonwoven web comprising the MSA fibers of 50 Even at relatively high talc loadings, such as 40 wt % and 50 Preparation 2 contains silver salt (i.e., silver acetate for Runs wt % talc in FIG. 6, the talc composites of Examples 5A, 5B, 1-6, chelated silver acetate for runs 7-9, and in situ silver and 5D to 5F exhibit melt viscosities at or below 10,000 Pa-S. chloride for runs 10-12). Example 6 Example 4 55 Composite of Silica and PEA-C2C6.9% of SEM Imaging of In Situ Silver Chloride-Treated Preparation 1 Nonwoven Web Comprising MSA Fibers Haake blending of 34 wt % PEA-C2C6.9% of Preparation 4 and 66 wt % of the Min-U-SiTM 5 silica is carried out as The in situ silver chloride-treated nonwoven web compris 60 described previously to give a silica composite having 66 wit ing MSA fibers of Example 3 are studied at different magni % of the Min-U-SilTM 5 silica. Melt viscosity results are fications (500x, 2500x, and 20,010x) using SEM, and the shown as part of FIG. 7. TEM imaging results are shown in images are shown in FIGS. 1 to 3, respectively. FIGS. 1 to 3 FIG. 8. In FIG. 7, the Min-U-SilTM 5 silica composite of showed fiber surfaces coated with evenly distributed silver Example 6 is referred as “PEA+66 wt % Min-U-Sil.” FIG. 7 chloride crystals in the forms of particles or agglomerates of 65 shows that the melt dynamic viscosity if the Min-U-SiltM 5 a few micrometers size to single particles of a few hundred silica composite of Example 6 is within an acceptable range nanometers size. for processing by conventional melt processing techniques US 8,524,796 B2 29 30 (i.e., materials maintain their processability when highly wherein: filled). FIG.8 shows dispersion of Min-U-SilTM5 silica in the Min-U-SilTM5 silica composite of Example 6. R is at each occurrence, independently a C-C non While the invention has been described above according to aromatic hydrocarbylene group, a C-Co non-aro its preferred embodiments of the present invention and matic heterohydrocarbylene group, or a polyalkylene examples of steps and elements thereof, it may be modified oxide group having a group molecular weight of from within the spirit and scope of this disclosure. This application about 100 grams per mole to about 5000 grams per is therefore intended to cover any variations, uses, or adapta mole; tions of the instant invention using the general principles R" at each occurrence independently is a bond or a disclosed herein. Further, this application is intended to cover 10 C-Co non-aromatic hydrocarbylene group; Such departures from the present disclosure as come within the known or customary practice in the art to which this R at each occurrence independently is a C-Co non invention pertains and which fall within the limits of the aromatic hydrocarbylene group; following claims. RY is N(R) Ra N(R)-, where Rat each occur What is claimed is: 15 rence independently is H or a C-C alkylene and Ra 1. An activated polymer composition comprising a is a C-Co non-aromatic hydrocarbylene group, or molecularly self-assembling material and one or more active R’ is a C-Coheterocycloalkyl group containing the agents, wherein each active agent independently comprises two nitrogen atoms, wherein each nitrogen atom is an odor control material, polyelectrolyte, chelating agent, bonded to a carbonyl group according to formula (III) microspheres, non-peptidic antimicrobial Substance selected above; from the group consisting of 10,10'-oxybisphenoxarsine; n is at least 1 and has a mean value less than 2; and 2-(normal-octyl)-4-isothiazolin-3-one; 4.5-dichloro-2-(nor mal-octyl)-4-isothiazolin-3-one; 2,4,4'-trichloro-2'-hydroy w represents the ester mol fraction of Formula I, and x,y and Z represent the amide or urethane mole fractions of diphenyl ether, an anti-clotting compound, a clotting com Formulas II, III, and IV, respectively, where w-X-y+ pound, or a woundhealing promoter, wherein the molecularly 25 self-assembling material comprises repeat units of formula I: ZF1. 2. An activated polymer composition of claim 1, wherein Formula I the molecularly self-assembling material comprises self-as sembling units comprising multiple hydrogen bonding --O-R-O-Ö-R-6-- 30 arrays. 3. An activated polymer composition of claim 1, wherein and at least one second repeat unit selected from the ester the number average molecular weight (Mn) of the molecu amide units of Formula II and III: larly self-assembling material is between about 1000 grams per mole (g/mol) and about 50,000 g/mol, inclusive. 35 4. An activated polymer composition of claim 3, wherein Formula II the M of the molecularly self-assembling material is less O O O than 5,000 g/mol. --O-R-C-RN-Ö-R-O-Ö-R-Ö--; 5. An activated polymer composition of claim 1, wherein Formula III each active agent independently comprises the odor control 40 material. O O O O 6. An activated polymer composition of claim 1, wherein each active agent independently comprises the non-peptidic --O-R-O-O-R-C-E-R-O-R-C++, antimicrobial Substance, anti-clotting compound, clotting 45 compound, or wound healing promoter. and the ester-urethane units of Formula IV: 7. An activated polymer composition of claim 1, wherein the one or more active agents comprises a total of from 0.0001 weight percent (wt %) to 75 wt % of the activated polymer Formula IV composition based on total weight of the activated polymer O O O 50 composition. 8. An article comprising the activated polymer composi --O-R-O-C-RN-C-O-R-O-O-R-C-i- tion of claim 1.