The Penn State Research Foundation

Research, Incorporated

Other

Massachusetts Institute of Technology

USA as Represented by Secretary of the Navy

The Firestone Tire & Rubber Company

The United States of America as Represented by the Department of Health

University of Pennsylvania

The United States of America as Represented by the Administrator of the

Exxonmobil Research and Engineering Company

Ethyl Corporation

University of Toronto

Research Corporation Technologies, Inc.

Virus Research Institute

Harry R Allcock

Robert Samuel Langer

Karyn B Visscher

Smadar Cohen

John P O'Brien

Paul E Austin

Ian Manners

Thomas X Neenan

Walter R Laredo

Alexander K Andrianov

Carmen Bano

Paul J Harris

Angelo G Scopelianos

Robert A Frosch

James M Nelson

Oskar Nuyken

Cato T Laurencin

Margaret Alison Wheatley

Timothy J Fuller

Charles H Honeyman

Marie B Chow

Robbyn Prange

Scott D Reeves

Robert W Allen

Christopher T Morrissey

Thomas J Hartle

Archel M Ambrosio

Larry L Fewell

Jared D Bender

Sukky Kwon

Gerhard Renner

Charles G Cameron

Michael A Hofmann

Chester A Crane

David Joseph Baillargeon

Thomas L Evans

Alan Mark Schilowitz

Man Kit Ng

Paul W Brown

Andrew Tsourkas

Roy H Hammerstedt

J Robert Adams, Jr

Lakshmi Sreedharan Nair

David Cormode

Joseph B Tedder, Jr

Stephen S Schwartz

Cato Laurencin

Serguei N Lvov

David Olmeijer

Mark E Napierala

Stephen J O'Connor

Eric H Klingenberg

Maher E Andrew

Nicolas J Sunderland

Young Baek Kim

Carey S Reed

Michael M Coleman

R Prange

Constance J Nelson

Christine R deDenus

Catherine M Ambler

Mark P Weller

A Paul Primrose

Peter Chhour

Daniel T Welna

James Earl Gardner, Deceased

Karen M Smeltz

Kevin S Guigley

Michael B McIntosh

Richard M Wood

Jonathan P Taylor

Karen M Kosydar

Sarah D Wright

Kiyotoshi Matsumura

Robert J Ritchie

Shawn R Pucher

Archel M A Ambrosio

Walter C Kossa

Saadiq El-Amin

Rabe'e Cheheltani

Chen Chen

Subhabrata Bhattacharyya

Jonathan R Taylor

S James Stinnett

Sobrasua Ibim

Andrew R Hess

Yaser E Greish

Michael Kwon

Digby McDonald

Xiang Y Zhou

E Clay Kellam, Iii

Jeffrey A Dodge

Robert V Morford

Dawn E Smith

William D Coggio

Nanoclusters comprising inorganic nanocrystals and a biodegradable polymer are disclosed. The inorganic nanocrystals have a mean particle size of 1 to 500 nm. The inorganic nanocrystals are contained within a core of the nanoclusters, on the surface of the nanoclusters, contained within a core of the nanoclusters, dispersed throughout the nanoclusters, or a combination thereof. The biodegradable polymer allows the inorganic nanocrystals to be excreted renally over a period of time. The nanoclusters can be used for medical imaging or other biomedical applications.

Polyphosphazene delivery system for inorganic nanocrystals

A method for improving wear control in an engine or other mechanical component lubricated with a lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition that includes a lubricating oil base stock as a major component; and at least one phosphazene represented by the formula as a minor component. In the above formula, Q is nitrogen, sulfur or oxygen; a is a value from about 2 to about 6, c is a value from about 2 to about 6, e is a value from about 2 to about 6, g is a value from about 2 to about 6, i is a value from about 2 to about 6, and k is a value from about 2 to about 6; b is a value of 2a+q, d is a value of 2c+r, f is a value of 2e+s, h is a value of 2g+t, j is a value of 2i+u, and l is a value of 2k+v; q, r, s, t, u and v are independently a value of 0 or &#x2212;2; with the proviso that not all of a, c, e, g, i and k are the same value. A lubricating oil having a composition that includes a lubricating oil base stock as a major component; and at least one phosphazene represented by the above formula as a minor component. The lubricating oil is useful in internal combustion engines.

Lubricating oil compositions with engine wear protection and solubility

The invention relates to sulfonimide bearing phenolic compounds and the use of those compounds to produce polyphosphazenes functionalized by one or more of those compounds alone, or in combination with cosubstituents. The invention also relates to blends of sulfonimide functionalized phosphazene polymers with other polymers, membranes formed of the functionalized polymers, and the use of those membranes in devices such as fuel cells.

Synthesis of polyphosphazenes with sulfonimide side groups

Polymeric nanofibers have been developed which are useful in a variety of medical and other applications, such as filtration devices, medical prosthesis, scaffolds for tissue engineering, wound dressings, controlled drug delivery systems, cosmetic skin masks, and protective clothing. These can be formed of any of a variety of different polymers, either non-degradable or degradable. In a preferred embodiment demonstrated in the following examples, nanofibers are formed of biodegradable and non biodegradable polyphosphazenes, their blends with other polyphosphazenes or with organic, inorganic/organometallic polymers as well as composite nanofibers of polyphosphazenes with nanosized particles such as hydroxyapatites.

Polymeric nanofibers for tissue engineering and drug delivery

Proton conducting membranes having improved resistance to methanol crossover are provided, along with methods for their manufacture. In a preferred embodiment, the polymeric membranes are formed by (a) dissolving a polymer, preferably a polyphosphazene, in an organic solvent to form a polymer solution; (b) adding an oxyacid to the polymer solution; (c) optionally, adding water to the polymer solution, preferably in a molar ratio equivalent to the oxyacid; (d) optionally, concentrating the polymer solution; (e) casting the polymer solution on a casting surface, such as one formed of or coated with TEFLON&trade;; and (f) removing the organic solvent, so as to form the polymeric membrane. A particularly useful application for these polymeric membranes is in fuel cells, such as those wherein methanol and oxygen are converted into electrical energy.

Proton conducting polymer membranes

Co-subsituted linear polyphosphazene polymers that useful in gel polymer electrolytes having an ion conductivity at room temperature of at least about 10 S/cm and comprising (i) a polyphosphazene having controlled ratios of side chains that promote ionic conductivity and hydrophobic, non-conductive side chains that promote mechanical stability, (ii) a small molecule additive, such as propylene carbonate, that influences the ionic conductivity and physical properties of the gel polymer electrolytes, and (iii) a metal salt, such as lithium trifluoromethanesulfonate, that influences the ionic conductivity of the gel polymer electrolytes, and methods of preparing the polyphosphazene polymers and the gel polymer electrolytes are disclosed.

Polyphosphazenes as gel polymer electrolytes

A pore plugging material, for pH dependent membrane diffusion, in which cyclic olefins having phosphazene-functional moieties provide predictable erosion properties when used to plug pores in separation barriers and other porous membranes. Specific properties of the polymers are dependent on several factors, including molecular weight and identity of side groups attached to the phosphazene moiety. However, as a class, phosphazene-functional cyclic olefins provide both predictable erodibility and uniformly benign hydrolysis products and are, therefore, uniquely suitable as pore plugging polymers for separation barriers and membranes of all kinds. The invention, therefore, embraces the provision of a pH-sensitive erodible pore plugging material for pores in separation barriers and membranes of all kinds.

pH dependent membrane diffusion

A polymer composition comprising a polynorbonene backbone and pendant cyclotriphosphazene groups has been developed. The pendant cyclotriphosphazene group can have various substituents such as C1-C10 alkyl, C1-C10 haloalkyl, C3-C6 cycloalkyl, phenyl, substituted phenyl, aryl, &mdash;(CH CH OCH CH ) OCH in which n is a positive integer, aminoalkyl, alkoxyalkyl, phenoxyalkyl, aryloxyalkyl and amidoalkyl. The polynorbonene backbone can have substituents such as H, CH , X which is a halo group, and C2-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkoxy, phenoxy, and aryloxy. In a preferred embodiment, the pendant triphosphazene group can have either &mdash;CH CF , phenyl, 4-ethylcarboxylatophenyl, &mdash;CH CH , or &mdash;CH CH OCH CH OCH while the polynorbonene backbone can have H and low alkyl groups. The polyphosphazene compositions can be prepared readily via ring-opening-metathesis-polymerization of an olefin having norbornene structure with pendant cyclotriphosphazene groups. The polyphosphazene compositions disclosed are useful as elastomers, optical materials, electrically conductive materials, biomedical materials, compatibilizing agents, surfactants, additives for coatings, and as flame retardants.

Polynorbornenes with pendant cyclotriphosphazenes

Compositions of polyphosphazene-containing polymers and methods of preparation thereof are provided. The disclosed compositions encompass telechelic functionalized polyphosphazenes and a variety of block and graft polyphosphazene-polystyrene, polyphosphazene-polysiloxane, and polyphosphazene-ROMP of norbornene copolymers. Methods for the preparation of such compositions generally involve generation of a polydichlorophosphazene species, attachment of a function group to the resultant polyphosphazene compound, and coupling the functionalized polyphosphazene with a corresponding organic or inorganic polymers or polymerizing the functionalized polyphosphazene with corresponding organic molecules.

Polyphosphazene polymers

Methods have been developed to produce phosphazene modified organic or siloxane polymers. The method includes (a) providing an organic or siloxane polymer comprising phosphine units, and (b) reacting the organic or siloxane polymer with a phosphazene azide compound under conditions wherein the phosphazene azide compound is bound to the phosphine unites in the polymer, thereby producing the phosphazene-modified organic or siloxane polymer. The organic polymer of step (a) is produced by reacting a first monomer comprising phosphine with a second monomer via free radical or anionic polymerization techniques to produce the organic polymer comprising phosphine units. The first and second monomers can be identical. A wide variety of organic polymer backbones can be modified using these techniques. The second monomer, for example, can be selected from monomers forming polyolefins, polydienes, polyacrylics, polyethylenes, polyvinyl chlorides, polyisoprenes, polystyrenes, polycaprolactam, poly(methyl)(meth)acrylates, and polypropylenes. Alternatively, the siloxane polymer of step (a) is produced by reacting a monomer comprising phosphine with a hydrosilicone polymer via hydrosilylation polymerization techniques to produce the siloxane polymer comprising phosphine units. These phosphazene modified organic and siloxane polymers are useful in a variety of applications, particularly as a fire retardant material.

Phosphinimine modification of organic polymers and silicones

A highly porous three-dimensional biodegradable poly(organophosphazene) matrix with hydrolytically unstable side chains is prepared and used as a scaffold for the growth of osteoblast cells. In a preferred embodiment, the poly(organophosphazene) includes between 10 and 90% hydrolytically unstable side chains including glucosyl, glyceryl, glyceryl, imidazolyl or ethoxy units, for example, poly&lsqb;(methylphenoxy)(ethyl glycinato) phosphazene&rsqb;. The addition of the glucosyl, glycinyl or glyceryl side chains to the polymer can also be used generally to enhance growth rates of cells adhered to the polymer, presumably through uptake and metabolism of the simple sugar or alcohol units.

Poly(organophosphazene) matrices for bone replacement

Incorporation of phosphate and phosphonate units into the side groups of aryloxyphosphazenes, at both the polymer and cyclic trimer levels, is disclosed. Phosphorylated cyclic trimers are utilized as flame-retardant additives to polystyrene.

Phosphorylation of phosphazenes

Biodegradable polymeric compositions are provided, wherein biodegradable polyphosphazenes are combined with at least one other polymer, either in the form of a blend, a semi-interpenetrating network (semi-IPN), or an interpenetrating network IPN. The side groups and composition of the polyphosphazenes are used to determine the properties of the compositions, for example, the rate and extent of degradation, and mechanical properties. These are useful in biomedical applications, including controlled drug delivery and tissue regeneration, and environmental applications. In the most preferred embodiment, as demonstrated by the examples, the polyphosphazenes contain hydrophobic side groups, such as p-methylphenoxy and other aromatic groups, and groups which impart hydrolytic instability, such as amino acid alkyl esters, and degrade by surface erosion. A preferred example is ethyl glycinato-substituted polyphosphazene (PPHOS) with p-methylphenoxy as co-substituent. These are blended with other polymers, such as PLGA, which have desirable mechanical properties but which degrade by bulk erosion, so that the blend degrades by surface erosion. For the biomedical applications, FDA approved polymers, such as polymers of lactic and glycolic acids and their copolymers, are preferred. Methods for making these compositions also are provided.

Biodegradable mixtures of polyphoshazene and other polymers

Flame-retardant polymer blends of a polyurethane polymer or prepolymer and a poly(organophosphazene) are disclosed. Preferred poly(organophosphazenes) contain functional groups capable of reacting with isocyanate groups present during the curing of the polyurethane. The blends are preferably formulated by reacting the poly(organophosphazene) containing functional groups under conditions where some of the functional groups of the poly(organophosphazene) can react with the isocyanate groups present during the polymerization and curing of the polyurethane. These polymer blends are useful for making flame-retardant foamed articles of manufacture.

Blends of polyurethane and polyphosphazene and their use as

A process for the preparation of polyphosphazenes is provided that includes the cationic solution polymerization reaction of a phosphoranimine, using a main group or transition metal halide, or other appropriate halide salt, including a linear phosphazene salt of any chain length, or a preformed non-phosphazene polymer containing a main or transition metal chloride, as an initiator. In a preferred embodiment, triarmed-star polyphosphazenes having the formula N{RN(H)R'.sub.2 P--(N.dbd.PR'.sub.2).sub.n }.sub.3 are prepared via this method. Also, a methods for synthesis of the monomer Cl.sub.3 P.dbd.NSiMe.sub.3 and cyclic trimer N.sub.3 P.sub.3 X.sub.6 from the reactants N(SiR.sub.3).sub.3 and PX.sub.5 are also described.

Synthesis polyphosphazenes with controlled molecular weight and

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State College, PA, United States of America

Harry R Allcock