Polycrystalline conducting polymers and precursors thereof having adjustable morphology and properties

Abstract

Polycrystalline materials containing crystallies of precursors to electrically conductive polymers and electrically conductive polymers are described which have an adjustable high degree of crystallinity. The intersticial regions between the crystallites contains amorphous material containing precursors to electrically conductive polymers and/or electrically conductive polymers. The degree of crystallinity is achieved by preparing the materials under conditions which provide a high degree of mobility to the polymer molecules permitting them to associate with one another to form a crystalline state. This is preferable achieved by including additives, such as plasticizers and diluents, to the solution from which the polycrystalline material is formed. The morphology of the polycrystalline material is adjustable to modify the properties of the material such as the degree of crystallinity, crystal grain size, glass transition temperature, thermal coefficient of expansion and degree of electrical conductivity. High levels of electrical conductivity are achieved in in the electrically conductive polycrystalline materials without stretch orienting the material. The enhanced electrical conductivity is isotropic as compared to a stretch oriented film which has isotropic electrical conductivity.

1 . A composition of matter comprising:
 a polycrystalline material comprising crystallites of polymers with intersticial regions therebetween;   wherein said polymer is a precursor to an electrically conductive polymer;   said intersticial regions between said crystallites comprising amorphous material comprising an additive;   said additive provides mobility to said polymer to allow said polymer to associate with one another to achieve said crystallites;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       2 . A composition of matter according to  claim 1 , wherein said structure is electrically conductive and has an isotropic electrical conductivity. 
   
   
       3 . A composition of matter according to  claim 1 , wherein said polymer is selected from the group consisting of substituted and unsubstituted polyparaphenylene vinylenes, polyparaphenylenes, polyanilines, polythiophenes, polyazines, polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers and copolymers of the monomers thereof. 
   
   
       4 . A composition of matter according to  claim 1 , wherein said structure has crystallinity greater than about 25%. 
   
   
       5 . A composition of matter comprising:
 a polycrystalline material comprising crystallites of polymers with intersticial regions therebetween;   said polymer is a precursor to an electrically conductive polymer;   said intersticial regions comprise an amorphous material selected from the group consisting of said polymers;   said amorphous material includes an additive;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       6 . A composition of matter according to  claim 5 , wherein said polymer is an electrically conductive polymer and said polycrystalline material has a conductivity which is isotropic. 
   
   
       7 . A composition of matter according to  claim 5 , wherein said polymer is selected from the group consisting of substituted and unsubstituted polyparaphenylene vinylenes, polythianophthenes, polyparaphenylenes, polyanilines, polythiophenes, polyazines, polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers and copolymers of the monomers thereof. 
   
   
       8 . A composition of matter according to  claim 1 , wherein the amount of said additive is adjustable. 
   
   
       9 . A composition of matter according to  claim 8 , wherein said amount is controlled to modify physical properties of said structure. 
   
   
       10 . A composition of matter according to  claim 9 , wherein said physical properties are selected from the group consisting of glass transition temperature, compliance, thermal coefficient of expansion, modulus, yield and tensile strength, hardness, density. 
   
   
       11 . A composition of matter according to  claim 1 , wherein said crystallites have a size greater than about 80 Å. 
   
   
       12 . A composition of matter according to  claim 5 , wherein said crystallites have a size greater than about 80 Å. 
   
   
       13 . A composition of matter comprising:
 a polycrystalline material comprising crystallites of polyaniline with intersticial regions therebetween;   said polyaniline is a precursor to an electrically conductive polyaniline;   said intersticial regions comprise an amorphous material selected from the group consisting of polyaniline;   said amorphous material includes an additive in an amount from about 0.001% to about 90% by weight;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       14 . A composition of matter according to  claim 1 , wherein the amorphous material in the intersticial regions contains crosslinks. 
   
   
       15 . A composition of matter according to  claim 1 , wherein the amorphous material in the intersticial regions are deaggregated. 
   
   
       16 . A composition of matter according to  claim 1 , wherein the additive is in an amount for about 0.001% to about 90% by weight. 
   
   
       17 . A structure according to  claim 1 , wherein said amorphous regions have crystalline order. 
   
   
       18 . A structure according to  claim 1 , wherein said additive has a different material composition from said polycrystalline material. 
   
   
       19 . A structure comprising:
 a surface of a structure selected from the group consisting of an electrostatic discharge shield, a wire, a solder, around an electromagnetic interference shield, a semiconductor device, and a corrodible material;   said surface has disposed thereon a composition of matter comprising crystalline material comprising crystallites of polymers with intersticial regions therebetween;   wherein said polymer is a precursor to an electrically conductive polymer;   said intersticial regions between said crystallites comprising amorphous material comprising an additive;   said additive provides mobility to said polymer to allow said polymer to associate with one another to achieve said crystallites;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       20 . A structure according to  claim 19 , wherein said structure is electrically conductive and has an isotropic electrical conductivity. 
   
   
       21 . A structure according to  claim 19 , wherein said polymer is selected from the group consisting of substituted and unsubstituted polyparaphenylene vinylenes, polyparaphenylenes, polyanilines, polythiophenes, polyazines, polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers and copolymers of the monomers thereof. 
   
   
       22 . A structure according to  claim 21 , wherein said structure has crystallinity greater than about 25%. 
   
   
       23 . A structure comprising:
 a polycrystalline material comprising crystallites of polymers with intersticial regions therebetween;   said polymer is a precursor to an electrically conductive polymer;   said intersticial regions comprise an amorphous material selected from the group consisting of said polymers;   said amorphous material includes an additive;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       24 . A structure according to  claim 23 , wherein said polymer is an electrically conductive polymer and said polycrystalline material has a conductivity which is isotropic. 
   
   
       25 . A structure according to  claim 23 , wherein said polymer is selected from the group consisting of substituted and unsubstituted polyparaphenylene vinylenes, polythianophthenes, polyparaphenylenes, polyanilines, polythiophenes, polyazines, polyfuranes, polypyrroles, polyselenophenes, poly-p-phenylene sulfides, polyacetylenes formed from soluble precursors, combinations thereof and blends thereof with other polymers and copolymers of the monomers thereof. 
   
   
       26 . A structure according to  claim 23 , wherein the amount of said additive is adjustable. 
   
   
       27 . A structure according to  claim 26 , wherein said amount is controlled to modify physical properties of said structure. 
   
   
       28 . A structure according to  claim 27 , wherein said physical properties are selected from the group consisting of glass transition temperature, compliance, thermal coefficient of expansion, modulus, yield and tensile strength, hardness, density. 
   
   
       29 . A structure according to  claim 23 , wherein said crystallites have a size greater than about 80 Å. 
   
   
       30 . A structure according to  claim 23 , wherein said crystallites have a size greater than about 80 Å. 
   
   
       31 . A structure comprising:
 a polycrystalline material comprising crystallites of polyaniline with intersticial regions therebetween;   said polyaniline is a precursor to an electrically conductive polyaniline;   said intersticial regions comprise an amorphous material selected from the group consisting of polyaniline;   said amorphous material includes an additive in an amount from about 0.001% to about 90% by weight;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.   
   
   
       32 . A structure according to  claim 23 , wherein the amorphous material in the intersticial regions contains crosslinks. 
   
   
       33 . A structure according to  claim 23 , wherein the amorphous material in the intersticial regions are deaggregated. 
   
   
       34 . A structure according to  claim 23 , wherein the additive is in an amount for about 0.001% to about 90% by weight. 
   
   
       35 . A structure comprising:
 a polycrystalline material comprising crystallites of polymers with intersticial regions therebetween;   wherein said polymer is a precursor to an electrically conductive polymer;   said intersticial regions between said crystallites comprising amorphous material comprising an additive;   said additive provides mobility to said polymer to allow said polymer to associate with one another to achieve said crystallites;   said polycrystalline material is characterized by a degree of crystallinity and a degree of amorphous regions, said degree of polycrystallinity and said degree of amorphous regions are selected by selecting the composition of said additive and the amount of said additive; and   wherein said additive is a plasticizer selected from the group consisting of:   Adipic acid derivatives Sebacic acid derivatives   Azelaic acid derivatives Stearic acid derivatives   Benzoic acid derivatives Diethyl succinate   Citric acid derivatives N-Ethyl o,p-tolusnesulfonamide   Dimer acid derivatives o,p-toluenesulfonanamide   Epoxy derivatives Terpentines   Fumaric acid derivatives Terpentine derivatives   Glycerol triacetate Siloxanes   Isobutyrate derivatives Polysiloxanes   Isophthalic acid derivatives Ethylene glycols   Lauric acid derivatives Polyethylene glycols   Linoleic acid derivative Polyesters   Maleic acid derivative Sucrose derivatives   Mellitates Tartaric acid derivative   Myristic acid derivatives Terephthalic acid derivative   Oleic acid derivatives Trimellitic acid derivatives   Palmitic acid derivatives Glycol derivatives   Paraffin derivatives Glycolates   Phosphoric acid derivatives poly(alkyl naphthalene)s   Phthalic acid derivatives aliphatic aromatics Leromoll   Ricinoleic acid derivatives Phosphonic acid derivatives   Polysilanes.