Abstract: A new polymerization process (atom transfer radical polymerization, or ATRP) based on a redox reaction between a transition metal (e.g., Cu(I)/Cu(II), provides “living” or controlled radical polymerization of styrene, (meth)acrylates, and other radically polymerizable monomers. Using various simple organic halides as model halogen atom transfer precursors (initiators) and transition metal complexes as a model halogen atom transfer promoters (catalysts), a “living” radical polymerization affords (co)polymers having the predetermined number average molecular weight by &Dgr;[M]/[I]0 (up to Mn>105) and a surprisingly narrow molecular weight distribution (Mw/Mn) as low as 1.15. The participation of free radical intermediates in ATRP is supported by end-group analysis and stereochemistry of the polymerization. In addition, polymers with various topologies (e.g.

Abstract: A polymerization process is provided for the preparation of graft (co)polymers. An embodiment of the polymerization process of the present invention comprises copolymerizing macromonomers with (co)monomers utilizing a macroinitiator to form a graft (co)polymer. A further embodiment of a polymerization process of the present invention comprises (co)polymerizing macromonomers and monomers with a graft copolymer macroinitiator to form a block-graft (co)polymer. Another embodiment of the process of the present invention comprises (co)polymerizing macromonomers and monomers with a compatible macroinitiator. The chemical and structural properties of the product graft (co)polymer may be controlled by use of a compatible macroinitiator and the functional group on the macromonomer which effect the relative rates of incorporation of the macromonomer and the monomer. Graft (co)polymers may be prepared with homogeneous or heterogeneous distribution of grafts.

Abstract: The present invention describes catalysts for atom transfer radical polymerization processes. Specifically, a hybrid catalyst system comprising transition metal complexes held in close conjunction with a solid support and of a soluble ligand, or soluble transition metal complex or desorbed catalyst. The hybrid catalyst system may be used in a controlled polymerization process of radically (co)polymerizable monomers in the presence of a system comprising an initiator comprising one or more radically transferable atom(s) or group(s). The catalyst may include a transition metal, one or more counterions, a ligand attached to a solid support, and a soluble ligand. The hybrid catalyst may also be comprised of an attached transition metal complex, and a soluble transition metal complex.

Abstract: The present invention describes preparation of nanocomposite particles and structures by polymerizing monomers onto a functional inorganic colloid comprising a polymerization initiation site. The polymerization process is preferably a controlled/living polymerization process, including but not limited to, atom transfer radical polymerization and stable free radical polymerization. The nanocomposite particles can self-organize in solution, on surfaces or in films forming nanocomposite structures. Tethered AB block nanocomposite particles bring size control, solubility control and control over micro- and macro-functionality to the particles. The process may be catalyzed by a transition metal complex which participates in a reversible redox cycle with at least one of the group and a compound having a radically transferable atom or group, to form a nanocomposite particle with a tethered polymer chain. The process may be continued to form tethered copolymer chain.

Abstract: A new polymerization process (atom transfer radical polymerization, or ATRP) based on a redox reaction between a transition metal (e.g., Cu(I)/Cu(II), provides “living” or controlled radical polymerization of styrene, (meth)acrylates, and other radically polymerizable monomers. Using various simple organic halides as model halogen atom transfer precursors (initiators) and transition metal complexes as a model halogen atom transfer promoters (catalysts), a “living” radical polymerization affords (co)polymers having the predetermined number average molecular weight by &Dgr;[M]/[I]0 (up to Mn>105) and a surprisingly narrow molecular weight distribution (Mw/Mn), as low as 1.15. The participation of free radical intermediates in ATRP is supported by end-group analysis and stereochemistry of the polymerization. In addition, polymers with various topologies (e.g.

Abstract: An improved process for free radical polymerization is produced making it possible to control the growth steps of a polymerization to produce homopolymers and copolymers, including block and graft copolymers. The process uses a long half-life radical initiators and compounds which have the structure of formula I wherein X is a group having at least one carbon atom and is such that the free radical X.

Abstract: The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydipersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand, the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a mac

Abstract: The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a ma

Abstract: A process is provided for the preparation of (co)polymer emulsions or suspensions from a full range of free radically (co)polymerizable monomers, wherein the (co)polymers exhibit the characteristics of "living" polymerization, including one or more of predictable molecular weights, narrow or controllable molecular weight distributions and a variety of polymer architectures, including the roles of surfactants, catalyst and ligands, several initiation methods, and methods for catalyst removal from the emulsions or suspensions made, and the (co)polymer emulsions and suspensions made thereby.

Abstract: The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a ma

Abstract: The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a ma

Abstract: An improved process for free radical polymerization is produced making it possible to control the growth steps of a polymerization to produce homopolymers and copolymers, including block and graft copolymers. The process uses a long half-life radical initiators and compounds which have the structure of formula I ##STR1## wherein X is a group having at least one carbon atom and is such that the free radical X is capable of polymerizing the unsaturated monomer by free radical polymerization, and the radical functionality resides on the or one of the carbon atoms, R.sup.1, R.sup.2, R.sup.5 and R.sup.6 represent the same or different straight chain or branched substituted or unsubstituted alkyl groups of a chain length sufficient to provide steric hindrance and weakening of the O--X bond, and R.sup.3 and R.sup.4 represent the same or different, straight chain or branched, substituted alkyl groups or R.sup.3 CNCR.sup.

Abstract: Improved processes have been developed for atom (or group) transfer radical polymerization (ATRP). In one improvement, the ATRP process involves polymerizing in the presence of a (partially) free radical-deactivating amount of the corresponding reduced or oxidized transition metal compound. In a further improvement, the ATRP process involves polymerizing in a homogeneous system or in the presence of a solubilized initiating/catalytic system. The present invention also concerns end-functional, site-specific functional and telechelic homopolymers and copolymers; block, random, graft, alternating and tapered (or "gradient") copolymers which may have certain properties or a certain novel structure; star, comb and "hyperbranched" polymers and copolymers; multi-functional hyperbranched, end-functional polymers; cross-linked polymers and gels; water-soluble polymers and hydrogels (e.g.

Abstract: The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a ma

Abstract: A new polymerization process (atom transfer radical polymerization, or ATRP) based on a redox reaction between a transition metal (e.g., Cu(I)/Cu(II), provides "living" or controlled radical polymerization of styrene, (meth)acrylates, and other radically polymerizable monomers. Using various simple organic halides as model halogen atom transfer precursors (initiators) and transition metal complexes as a model halogen atom transfer promoters (catalysts), a "living" radical polymerization affords (co)polymers having the predetermined number average molecular weight by .DELTA.?M!/?I!.sub.0 (up to M.sub.n >10.sup.5) and a surprisingly narrow molecular weight distribution (M.sub.w /M.sub.n), as low as 1.15. The participation of free radical intermediates in ATRP is supported by end-group analysis and stereochemistry of the polymerization. In addition, polymers with various topologies (e.g.

Abstract: Organopolysiloxane oils and gums are produced by the condensation of silanol-terminated organosiloxane in the presence of an effective amount of a peralkylated phosphazene base as a catalyst and at reduced pressure.

Abstract: Polyphosphazenes are produced by polymerizing a silylated phosphinimine in the presence of an initiator, preferably an anionic initiator at temperatures below those typically necessary for such polymerization reactions. The polyphosphazenes obtained are suitable for use in the production of elastomeric and thermoplastic materials.

Abstract: This invention concerns a "living" free radical polymerization process for preparing polymers having a narrow distribution of molecular weights.

Abstract: A method of chemically modifying the poly (methyl methacrylate) (hereinafter "PMMA") clad surface of an optical fiber to introduce amino groups. N-butyl lithium in a suitable organic solvent with ethylene diamine is applied to the clad surface of the optical fiber in a substantially oxygen-free atmosphere, such as nitrogen, at approximately 10.degree. C. to 40.degree. C. for about one to two hours. A pH-sensitive dye with isothiocyanate functionality can be bounded to the modified clad surface resulting in a pH sensor based on fiber optics.

Abstract: A method of chemically modifying the poly (methyl methacrylate) (hereinafter "PMMA") clad surface of an optical fiber to introduce amino groups. N-butyl lithium in a suitable organic solvent with ethylene diamine is applied to the clad surface of the optical fiber in a substantially oxygen-free atmosphere, such as nitrogen, at approximately 10.degree. C. to 40.degree. C. for about one to two hours. A pH-sensitive dye with isothiocyanate functionality can be bounded to the modified clad surface resulting in a pH sensor based on fiber optics.