Nanocomposites of dendritic polymers

Abstract

In the present invention, an inorganic reactant is, or reactants are, localized with respect to a dendritic polymer by physical constraint within or by a non-covalent conjugation to the dendritic polymer. The localized inorganic reactant or reactants is/are subsequently transformed to form a reaction product which is immobilized with respect to the dendritic polymer. This immobilization occurs on a nanoscopic scale as a consequence of the combined effects of structural, chemical and physical changes without having covalent bonds between the product(s) and the dendritic container and results in new compositions of matter called dendritic nanocomposites. The resulting nanocomposite material can be used to produce revolutionary products such as water soluble elemental metals, with specific applications including magnetic resonance imaging, catalytic, magnetic, optical, photolytic and electroactive applications.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:  
     
         1 . A method of forming a composite composition comprising: 
 localizing at least one inorganic or organic reactant with respect to a dendritic polymer by physical constraint, by non-covalent interaction, or by both physical constraint and non-covalent interaction; and    transforming the reactant or reactants into a reaction product which is dispersed at a nanoscale level in the composite as a discrete entity having a size and size-distribution which is determined and controlled by the dendritic polymer, and in which the reaction product is constrained with respect to the dendritic polymer, non-covalently conjugated to the dendritic polymer or both.    
     
     
         2 . The method of    claim 1    further comprising the step of distributing the composite composition into a polymeric matrix material, after transforming the reactant or reactants.  
     
     
         3 . The method of    claim 1   , in which the dendritic polymer is distributed in a polymeric matrix before the inorganic reactant is or reactants are, localized and transformed.  
     
     
         4 . The method of    claim 2   , in which the dendritic polymer is decomposed within the polymeric matrix after the reactant is, or reactants are, localized and transformed.  
     
     
         5 . The method of    claim 3   , in which the dendritic polymer is decomposed within the polymeric matrix after the reactant is, or reactants are, localized and transformed.  
     
     
         6 . The method of    claim 1   , in which the dendritic polymer is a dendrimer, a hyperbranched dendritic polymer, a dendrigraft, a dendritic copolymer, a crosslinked dendrimer, a covalently linked dendrimer cluster, or a combination thereof.  
     
     
         7 . The method of    claim 1   , wherein the first reactant is localized within the interior of the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         8 . The method of    claim 7   , wherein the non-covalent bonding of the first reactant with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, donor-acceptor bond, a coordinative bond, Van der Waal interactions, or London dispersion forces.  
     
     
         9 . The method of    claim 1   , wherein the reaction product is constrained within the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         10 . The method of    claim 9   , wherein the non-covalent bonding of the reaction product with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, Van der Waal interactions, or London dispersion forces.  
     
     
         11 . The method of    claim 1   , wherein the reaction product is physically constrained within the interior of the dendritic polymer molecule.  
     
     
         12 . The method of    claim 1    in which the dendritic polymer has a diameter of from about 10 to about 1,000 Angstroms.  
     
     
         13 . The method of    claim 1    in which the dendritic polymer has a diameter of from about 10 to about 600 Angstroms.  
     
     
         14 . The method of    claim 1    in which the dendritic polymer is a dense star polymer.  
     
     
         15 . The method of    claim 14    in which the dense star polymer has a spheroid shape, an ellipsoid shape, or a rod shape.  
     
     
         16 . The method of    claim 14    in which the dense star polymer is a poly(amidoamine) dendrimer.  
     
     
         17 . The method of    claim 16    in which the poly(amidoamine) dense star polymer has a diameter of from about 40 to about 130 Angstroms.  
     
     
         18 . The method of    claim 1    in which the dendritic polymer molecule includes at least two dense star polymer molecules ionically, physically or covalently bonded to each other.  
     
     
         19 . The method of    claim 1    in which the dendritic polymer is a poly(propylenamine) dendrimer.  
     
     
         20 . The method of    claim 1    in which the dendritic polymer includes asymmetric branch cells.  
     
     
         21 . The method of    claim 1    in which the dendritic polymer is a polyester dendrimer.  
     
     
         22 . The method of    claim 1    in which the product of the first and second reactants is insoluble in a solvent in which the dendritic polymer is soluble.  
     
     
         23 . The method of    claim 1    in which the dendritic polymer molecule and the reactant or reactants are all soluble in a selected solvent, the method including solubilizing the dendritic polymer molecule and the first and second reactants in the selected solvent and reacting the first and second reactants in solution phase.  
     
     
         24 . The method of    claim 1    in which reactant or reactants are soluble in a selected solvent in which the dendritic polymer molecule is insoluble, the method including solubilizing the reactants in the selected solvent and reacting the first and second reactants in a solution or gas phase.  
     
     
         25 . The method of    claim 1    in which the dendritic polymer molecule is soluble in a first phase and insoluble in a second phase in which the reactant or reactants are soluble, and wherein the reactants pass through an interphase between the phases into the interior of the dendritic polymer molecule.  
     
     
         26 . A composite composition prepared by localizing at least one organic or inorganic reactant with respect to a dendritic polymer by physical constraint, by non-covalent interaction, or by both physical constraint and non-covalent interaction; and 
 transforming the reactant or reactants into a reaction product which is dispersed at a nanoscale level in the composite as a discrete entity having a size and size-distribution which is determined and controlled by the dendritic polymer, and in which the reaction product is constrained with respect to the dendritic polymer, non-covalently conjugated to the dendritic polymer or both.    
     
     
         27 . The method of    claim 26    further comprising the step of distributing the composite composition into a polymeric matrix material, after transforming the reactant or reactants.  
     
     
         28 . The method of    claim 26   , in which the dendritic polymer is distributed in a polymeric matrix before the inorganic reactant is, or reactants are, localized and transformed.  
     
     
         29 . The method of    claim 27   , in which the dendritic polymer is decomposed within the polymeric matrix after the reactants is, or reactants are, localized and transformed.  
     
     
         30 . The method of    claim 28   , in which the dendritic polymer is decomposed within the polymeric matrix after the reactant is, or reactants are, localized and transformed.  
     
     
         31 . The method of    claim 26   , in which the dendritic polymer is a dendrimer, a hyperbranched dendritic polymer, a dendrigraft, a dendritic copolymer, a crosslinked dendrimer, a covalently linked dendrimer cluster, or a combination thereof.  
     
     
         32 . The method of    claim 26   , wherein the first reactant is localized within the interior of the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         33 . The method of    claim 32   , wherein the non-covalent bonding of the first reactant with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, donor-acceptor or coordination bond, Van der Waal interactions, or London dispersion forces.  
     
     
         34 . The method of    claim 26   , wherein the reaction product is constrained within the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         35 . The method of    claim 34   , wherein the non-covalent bonding of the reaction product with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, a donor-acceptor or coordination bond, Van der Waal interactions, or London dispersion forces.  
     
     
         36 . The method of    claim 26   , wherein the reaction product is physically constrained within the interior of the dendritic polymer molecule.  
     
     
         37 . The method of    claim 26   , in which the dendritic polymer has a diameter of from about 10 to about 1,000 Angstroms.  
     
     
         38 . The method of    claim 26   , in which the dendritic polymer has a diameter of from about 10 to about 600 Angstroms.  
     
     
         39 . The method of    claim 26   , in which the dendritic polymer is a dense star polymer.  
     
     
         40 . The method of    claim 39   , in which the dense star polymer has a spheroid shape, an ellipsoid shape, or a rod shape.  
     
     
         41 . The method of    claim 39   , in which the dense star polymer is a poly(amidoamine) dendrimer.  
     
     
         42 . The method of    claim 41   , in which the poly(amidoamine) dense star polymer has a diameter of from about 40 to about 130 Angstroms.  
     
     
         43 . The method of    claim 26   , in which the dendritic polymer molecule includes at least two dense star polymer molecules ionically, physically or covalently bonded to each other.  
     
     
         44 . The method of    claim 26   , in which the dendritic polymer is a poly(polypropylenamine) dendrimer.  
     
     
         45 . The method of    claim 26   , in which the dendritic polymer includes asymmetric branch cells.  
     
     
         46 . The method of    claim 26   , in which the dendritic polymer is a polyester dendrimer.  
     
     
         47 . The method of    claim 26   , in which the product of the first and second reactants is insoluble in a solvent in which the dendritic polymer is soluble.  
     
     
         48 . The method of    claim 26   , in which the dendritic polymer molecule,and the reactant or reactants are all soluble in a selected solvent, the method including solubilizing the dendritic polymer molecule and the first and second reactants in the selected solvent and reacting the first and second reactants in solution phase.  
     
     
         49 . The method of    claim 26   , in which reactant or reactants are soluble in a selected solvent in which the dendritic polymer molecule is insoluble, the method including solubilizing the reactants in the selected solvent and reacting the first and second reactants in a solution or gas phase.  
     
     
         50 . The method of    claim 26   , in which the dendritic polymer molecule is soluble in a first phase and insoluble in a second phase in which the reactant or reactants are soluble, and wherein the reactants pass through an interphase between the phases into the interior of the dendritic polymer molecule.  
     
     
         51 . A method of forming a composite composition comprising: 
 providing a dendritic polymer having an interior and a surface which is sufficiently permeable to allow at least one molecule of at least one reactant to enter the interior;    introducing the reactant or reactants into the interior of the dendritic polymer; and    reacting the reactant or reactants to form a product which is constrained within the interior of the dendritic polymer, without forming a covalent bond between the dendritic polymer and the reactant or reactants or their reaction product.    
     
     
         52 . The method of    claim 51   , wherein the first reactant is localized within the interior of the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         53 . The method of    claim 52   , wherein the non-covalent bonding of the reactant or reactants with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, a donor-acceptor interaction, coordination bond, Van der Waal interactions, or London dispersion forces.  
     
     
         54 . The method of    claim 51   , wherein the reaction product is constrained within the dendritic polymer molecule by non-covalent bonding with the dendritic polymer molecule.  
     
     
         55 . The method of    claim 54   , wherein the non-covalent bonding of the reaction product with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, a donor-acceptor interaction, a coordinative bond, Van der Waal interactions, or London dispersion forces.  
     
     
         56 . The method of    claim 51   , wherein the reaction product is physically constrained within the interior of the dendritic polymer molecule.  
     
     
         57 . The method of    claim 51    in which the dendritic polymer has a diameter of from about 10 to about 1,000 Angstroms.  
     
     
         58 . The method of    claim 51    in which the dendritic polymer has a diameter of from about 10 to about 600 Angstroms.  
     
     
         59 . The method of    claim 51    in which the dendritic polymer is a dense star polymer.  
     
     
         60 . The method of    claim 59    in which the dense star polymer has a spheroid shape, an ellipsoid shape, or a rod shape.  
     
     
         61 . The method of    claim 59    in which the dense star polymer is a poly(amidoamine) dendrimer.  
     
     
         62 . The method of    claim 61    in which the poly(amidoamine) dense star polymer has a diameter of from about 40 to about 130 Angstroms.  
     
     
         63 . The method of    claim 51    in which the dendritic polymer molecule includes at least two dense star polymer molecules ionically, physically or covalently bonded to each other.  
     
     
         64 . The method of    claim 51    in which the dendritic polymer is a poly(propylenamine) dendrimer.  
     
     
         65 . The method of    claim 51    in which the dendritic polymer includes asymmetric branch cells.  
     
     
         66 . The method of    claim 51    in which the dendritic polymer is a dendrigraft.  
     
     
         67 . The method of    claim 51    in which the dendritic polymer is a hyperbranched polymer.  
     
     
         68 . The method of    claim 51    in which the dendritic polymer is a polyester dendrimer.  
     
     
         69 . The method of    claim 51    in which the product of the first and second reactants is insoluble in a solvent in which the dendritic polymer is soluble.  
     
     
         70 . The method of    claim 51    in the dendritic polymer molecule, and the reactant or reactants are all soluble in a selected solvent, the method including solubilizing the dendritic polymer molecule and the first and second reactants in the selected solvent and reacting the first and second reactants in solution phase.  
     
     
         71 . The method of    claim 51    in which reactant or reactants are soluble in a selected solvent in which the dendritic polymer molecule is insoluble, the method including solubilizing the reactants in the selected solvent and reacting the first and second reactants in a solution or gas phase.  
     
     
         72 . The method of    claim 51    in which the dendritic polymer molecule is soluble in a first phase and insoluble in a second phase in which the reactant or reactants are soluble, and wherein the reactants pass through an interphase between the phases into the interior of the dendritic polymer molecule.  
     
     
         73 . A composite composition comprising: 
 a dendritic polymer molecule having an interior, and a reaction product constrained within the interior of the dendritic polymer molecule, the reaction product being formed by reaction between first and second reactants which are capable of entering the interior of the dendritic polymer molecule, without forming a covalent bond between the dendritic polymer and either the first or second reactants or their reaction product.    
     
     
         74 . The composite composition of    claim 73   , wherein the first reactant is localized within the interior of the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         75 . The composite composition of    claim 74   , wherein the non-covalent bonding of the first reactant with the interior of the dendritic polymer molecule comprises an ionic bond, a hydrogen bond, a donor-acceptor bond, a coordination bond, Van der Waal interactions, or London dispersion forces.  
     
     
         76 . The composite composition of    claim 73   , wherein the reaction product is constrained within the dendritic polymer molecule by non-covalent bonding with the interior of the dendritic polymer molecule.  
     
     
         77 . The composite composition of    claim 76   , wherein the non-covalent bonding of the reaction product with the dendritic polymer molecule comprises an ionic bonding, a hydrogen bond, a donor-acceptor bond, a coordination bond, Van der Waal interactions, or London dispersion forces.  
     
     
         78 . The composite composition of    claim 73   , wherein the reaction product is physically constrained within the interior of the dendritic polymer molecule.  
     
     
         79 . The composite composition of    claim 73    in which the dendritic polymer has a diameter of from about 10 to about 1,000 Angstroms.  
     
     
         80 . The composite composition of    claim 73    in which the dendritic polymer has a diameter of from about 10 to about 600 Angstroms.  
     
     
         81 . The composite composition of    claim 73    in which the dendritic polymer is a dense star polymer.  
     
     
         82 . The composite composition of    claim 81    in which the dense star polymer is a poly(amidoamine) dendrimer.  
     
     
         83 . The composite composition of    claim 82    in which the dense star poly(amidoamine) dendrimer has a diameter of from about 40 to about 130 Angstroms.  
     
     
         84 . The composite composition of    claim 83    in which the dendritic polymer molecule includes at least two dense star polymer molecules which have been ionically, physically or covalently bonded to each other.  
     
     
         85 . A composite composition of    claim 83    in which the dendritic polymer is a poly(propylenamine) dendrimer.  
     
     
         86 . A composite composition of    claim 83    in which the dendritic polymer includes asymmetric branch cells.  
     
     
         87 . A composite composition of    claim 83    in which the dendritic polymer is a dendrigraft.  
     
     
         88 . A composite composition of    claim 83    in which the dendritic polymer is a hyperbranched polymer.  
     
     
         89 . A composite composition of    claim 83    in which the dendritic polymer is a poly(ester) dendrimer.  
     
     
         90 . A composite composition of    claim 83    in which the product of the first and second reactants is insoluble in a solvent in which the dendritic polymer is soluble.  
     
     
         91 . The composite composition of    claim 73    in which at least one of the reactants contains at least one metal atom which is responsive to a magnetic field.  
     
     
         92 . The method of    claim 91   , wherein the reagent which reacts with the metal-dendritic polymer complex is an oxalate, and the solvent dispersible complex is a metal oxalate/dendritic polymer complex.  
     
     
         93 . The method of    claim 92   , wherein the reagent which reacts with the metal-dendritic polymer complex is a phosphate, and the solvent dispersible complex is a metal phosphate/dendritic polymer complex.  
     
     
         94 . The method of    claim 91   , wherein the reagent which reacts with the metal-dendritic polymer complex is a reducing agent, and the solvent dispersible complex is a metal/dendritic polymer complex.  
     
     
         95 . A method of immobilizing a compound which is substantially insoluble in a solvent in a soluble molecular scaffold, comprising contacting a solution of reactants with a dendritic polymer to form a dendritic polymer complex, and subsequently contacting the dendritic polymer complex with a reagent which reacts with the complex compound to form a solvent dispersible complex.  
     
     
         96 . The method of    claim 95   , wherein the reactant solution is a solution metal containing an acetate.  
     
     
         97 . The method of    claim 96   , wherein the metal of the metal acetate is cadmium, copper, zinc, lead, bismuth or manganese.  
     
     
         98 . The method of    claim 95   , wherein the reactant solution is a solution containing a metal sulfate.  
     
     
         99 . The method of    claim 98   , wherein the metal ion of the metal sulfate solution is iron.  
     
     
         100 . The method of    claim 95   , wherein the reactant solution is a solution containing a metal trifluorosulfonate solution.  
     
     
         101 . The method of    claim 90   , wherein the metal ion of the metal trifluorosulfonate solution is silver.  
     
     
         102 . The method of    claim 95   , wherein the reagent which is reacted with the metal-dendritic polymer complex is hydrogen sulfide gas, and the solvent dispersible complex is a metal sulfide-dendritic polymer complex.  
     
     
         103 . The method of    claim 95   , wherein the reagent which reacts with the metal-dendritic polymer complex is a halide ion, and the solvent dispersible complex is a metal halide/dendritic polymer complex.  
     
     
         104 . The method of    claim 95   , wherein the reagent which reacts with the metal-dendritic polymer complex is a hydroxyl ion, and the solvent dispersible complex is a metal hydroxide/dendritic polymer complex.  
     
     
         105 . The method of    claim 95   , wherein the dendritic polymer is a dendrimer.  
     
     
         106 . The method of    claim 95   , wherein the dendritic polymer is a dense star poly(amidoamine) dendrimer.  
     
     
         107 . The method of    claim 95   , wherein the dendritic polymer is at least a fourth generation polyamidoamine dendrimer.  
     
     
         108 . The method of    claim 96   , wherein the polyamidoamine dendrimer is modified to provide a hydrophobic surface which facilitates solubility of the solvent-dispersible complex in a non-polar solvent.  
     
     
         109 . The method of    claim 97   , wherein the dendrimer is surface modified by reaction with 1,2-epoxyalkane to provide a hydrophobic surface which facilitates solubility of the solvent dispersible complex in a non-polar solvent.  
     
     
         110 . A metal-containing complex exhibiting improved solvent dispersibility, comprising a metal compound, which is substantially insoluble in a solvent, complexed with a dendritic polymer which is soluble in the solvent.  
     
     
         111 . The complex of    claim 110   , wherein the metal compound is a metal sulfide.  
     
     
         112 . The complex of    claim 111   , wherein the metal of the metal sulfide is cadmium, copper, zinc, lead, iron, silver, cobalt, mercury, bismouth or nickel.  
     
     
         113 . The complex of    claim 110   , wherein the metal compound is a metal halogenide.  
     
     
         114 . The complex of    claim 113   , wherein the metal of the metal halogenide is silver.  
     
     
         115 . The complex of    claim 110   , wherein the metal compound is a metal hydroxide.  
     
     
         116 . The complex of    claim 115   , wherein the metal of the metal hydroxide is silver, aluminum, copper or cobalt.  
     
     
         117 . The complex of    claim 110   , wherein the metal compound is elemental metal.  
     
     
         118 . The complex of    claim 117   , wherein the elemental metal is silver, copper, gold, iron, cobalt or nickel.  
     
     
         119 . The complex of    claim 110   , wherein the dendritic polymer is a dendrimer.  
     
     
         120 . The complex of    claim 110   , wherein the dendritic polymer is a polyamidoamine dendrimer.  
     
     
         121 . The complex of    claim 110   , wherein the dendritic polymer is at least a fourth generation polyamidoamine dendrimer.  
     
     
         122 . The complex of    claim 110   , wherein the metal is a copper oxide.  
     
     
         123 . The complex of    claim 110   , wherein the metal compound is uranyl phosphate.  
     
     
         124 . The complex of    claim 110   , wherein the dendritic polymer is hydrophobically modified.  
     
     
         125 . The complex of    claim 124   , wherein the dendritic polymer is hydrophobically modified by reaction with an epoxy alkane.  
     
     
         126 . The complex of    claim 125   , wherein the metal compound is a metal sulfide, and wherein the metal is copper, silver, cadmium, iron, nickel, manganese, calcium, gadolinium, or aluminum.  
     
     
         127 . A method of forming a composite composition comprising: 
 contacting a first reactant with a dendritic polymer molecule having an interior which is accessible to the first reactant, the first reactant being capable of entering the interior of the dendritic polymer molecule and being localized within the interior of the dendritic polymer molecule; and    contacting the dendritic polymer and the first reactant localized within the interior of the dendritic polymer with a second reactant which is capable of entering the interior of the dendritic polymer molecule and reacting with the first reactant localized within the interior of the dendritic polymer molecule to form a composite material comprising the dendritic polymer molecule and a reaction product constrained within the interior of the dendritic polymer molecule, without forming a covalent bond between the dendritic polymer and either the first or second reactants or their reaction product.