CN1867591A - Electrically conductive compositions and method of manufacture thereof - Google Patents

Abstract

A method of making a conductive composition comprising blending a polymer precursor with a single-walled carbon nanotube composition; and polymerizing the polymer precursor to form an organic polymer. The method can be conveniently used to manufacture automotive parts, computer parts and other parts that require electrical conductivity.

Description

Conductive composition and preparation method thereof

Cross References to Related Applications

This application claims the benefit of US Provisional Patent Application Serial No. 60/494,678, filed August 12,2003.

Background technique

The present invention relates to a conductive composition and a preparation method thereof.

Articles made from organic polymers are commonly used in materials handling and electronic equipment, such as packaging films, chip carriers, computer, printer and copier components, where static dissipation or electromagnetic shielding are important requirements. Electrostatic dissipation (hereinafter referred to as ESD) is defined as the transfer of electrostatic charge between objects at different potentials by direct contact or by an induced electrostatic field. Electromagnetic shielding (referred to hereinafter as EM shielding) efficiency is defined as the proportional ratio (in decibels) of the electromagnetic field incident on, ie transmitted through, the shielding. As electronic devices become smaller and faster, their susceptibility to electrostatic charges increases, so it is often desirable to use organic polymers that have been modified to provide improved electrostatic discharge performance. In a similar manner, it is desirable to modify organic polymers such that they can provide improved electromagnetic shielding while maintaining some or all of the organic polymer's favorable mechanical properties.

Conductive fillers with diameters greater than 2 microns, such as graphite fibers derived from pitch and polyacrylonitrile, are typically incorporated into organic polymers to improve electrical properties and achieve ESD and EM shielding. However, because of the large size of these graphite fibers, the introduction of such fibers usually results in a reduction in mechanical properties, such as impact properties. There therefore remains a need in the art for conductive polymer compositions that provide adequate ESD and EM shielding while maintaining their mechanical properties.

Brief description of the invention

A method of making a conductive composition comprising blending a polymer precursor with a single-walled carbon nanotube composition; and polymerizing the polymer precursor to form an organic polymer.

Detailed description of the invention

The present invention discloses compositions comprising organic polymers and single-walled carbon nanotube (SWNT) compositions made by adding SWNTs to polymer precursors before or during the polymerization process of the polymer precursors. The present invention discloses compositions comprising an organic polymer and an effective amount of single-walled carbon nanotubes (SWNTs). An effective amount of SWNT means an amount sufficient to provide the composition with a bulk volume resistivity of less than or equal to about ¹⁰¹² ohm-cm, while exhibiting impact properties of greater than or equal to about 5 kJ/square meter and a Class A surface finish. In one embodiment, the composition has a surface resistivity of greater than or equal to about 10 ⁸ ohms/square (ohm/sq) and a bulk volume resistivity of greater than or equal to about 10 ¹² ohm-cm, while exhibiting greater than or equal to about 5 kJ/m² impact performance and Class A surface finish. In another embodiment, the composition has a surface resistivity of less than or equal to about ¹⁰⁸ ohms/square (ohm/sq) and a bulk volume resistivity of greater than or equal to about ¹⁰⁸ ohm-cm, while exhibiting greater than or equal to Impact performance of about 5 kJ/m² and Class A surface finish. In one embodiment, the composition has an impact property of greater than or equal to about 10 kJ/square, while in another embodiment, the composition has an impact property of greater than or equal to about 15 kJ/square.

In one embodiment, the composition has a bulk volume resistivity of less than or equal to about ¹⁰¹⁰ ohm-cm while exhibiting impact performance of greater than or equal to about 5 kJ/square meter and a Class A surface finish. In another embodiment, the composition has a bulk volume resistivity of less than or equal to about ¹⁰⁸ ohm-cm while exhibiting an impact performance of greater than or equal to about 5 kJ/square meter and a Class A surface finish. In another embodiment, the composition has a bulk volume resistivity of less than or equal to about ¹⁰⁵ ohm-cm while exhibiting an impact performance of greater than or equal to about 5 kJ/square meter and a Class A surface finish.

This composition can be conveniently used in computers, electronic products, semiconductor parts, circuit boards, etc. that require protection from static charges. They can also be conveniently used in automotive body panels for automotive interior and exterior components, which can be electrostatically painted if desired.

In one embodiment, SWNTs are added to the polymer precursor prior to the polymerization process. In another embodiment, the SWNTs are added to the polymer precursor during the polymerization process of the polymer precursor. In another embodiment, a certain proportion of SWNTs is added to the polymer precursor prior to the polymerization process and another proportion of SWNTs is added to the polymer precursor during the polymerization process. As defined herein, polymer precursors include monomeric, oligomeric or polymeric reactive species that can undergo polyaddition polymerization.

Organic polymers obtainable from the polymerization of polymer precursors are thermoplastic polymers, blends of thermoplastic polymers or blends of thermoplastic polymers and thermosetting polymers. The organic polymer can also be a blend of polymers, copolymers, terpolymers, interpenetrating network polymers, or a combination comprising at least one of the foregoing organic polymers. Examples of thermoplastic polymers include polyacetals, polyacrylics, polycarbonates, polyalkyds, polystyrenes, polyesters, polyamides, polyaramides, polyamideimides, polyarylates, polyarylsulfones, Polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketoneketone, polybenzoxazole, Polyoxadiazole, polybenzothiazizophenothiazine, polybenzothiazole, polypyrazinoquinoxaline, polypyromellitimide, polyquinoxaline, polybenzimidazole, polyoxindole , polyoxyisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polycarborane, Polyoxabicyclononane, polydibenzofuran, polybenzofuranone, polyacetal, polyanhydride, polyvinyl ether, polyvinyl sulfide, polyvinyl alcohol, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile , polyvinyl ester, polysulfonate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, etc., or a combination comprising at least one of the above organic polymers .

Specific examples of blends of thermoplastic polymers include acrylonitrile-butadiene-styrene/nylon, polycarbonate/acrylonitrile-butadiene-styrene, polyphenylene ether/polystyrene, polyphenylene ether/poly Amides, polycarbonates/polyesters, polyphenylene ethers/polyolefins, and combinations comprising at least one of the foregoing thermoplastic polymer blends.

In one embodiment, the organic polymer that may be used in the composition is polyarylene ether. The term poly(arylene ether) polymer includes polyphenylene ether (PPE) and poly(arylene ether) copolymers; graft copolymers; poly(arylene ether) ether ionomers; and alkenyl aromatic aromatic compounds and poly(arylene ether), block copolymers of vinyl aromatic compounds and poly(arylene ether), and the like; and combinations comprising at least one of the foregoing. Poly(arylene ether) polymers are themselves polymers comprising a plurality of structural units of formula (I):

Wherein for each structural unit, ^each Q is independently hydrogen, halogen, primary or secondary lower alkyl (for example, alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, alkoxy , wherein at least two carbon atoms separate halogen and oxygen atom haloalkoxy and the like; each ^Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, alkoxy, wherein At least two carbon atoms separating the halogen and oxygen atoms, such as halohydrocarbyloxy. Preferably each Q ¹ is alkyl or phenyl, especially C _1-4 alkyl, and each Q ² may be hydrogen.

Both homopolymer and copolymer poly(arylene ether)s are included. Exemplary homopolymers are those containing 2,6-dimethylphenylene ether units. Suitable copolymers include random copolymers containing, for example, such units in combination with 2,3,6-trimethyl-1,4-phenylene ether units or derived from 2,6-dimethylphenol with 2 , 3,6-trimethylphenol copolymerized copolymer. Also included are poly(arylene ethers) containing moieties prepared from grafted vinyl monomers or polymers, such as polystyrene, and coupled poly(arylene ethers), wherein the coupling agent is, for example, low Molecular weight polycarbonates, quinones, heterocycles, and methylals react with the hydroxyl groups of two poly(arylene ether) chains to produce high molecular weight polymers. Poly(arylene ether)s additionally include combinations comprising at least one of the above.

The poly(arylene ether) has a number average molecular weight of about 10,000 to about 30,000 grams per mole (g/mol) and a weight average molecular weight of about 30,000 to about 60,000 g/mol, as determined by gel permeation chromatography. The poly(arylene ether) can have an intrinsic viscosity of about 0.10 to about 0.60 deciliters per gram (dl/g), as measured in chloroform at 25°C. It is also possible to use high intrinsic viscosity poly(arylene ether) and low intrinsic viscosity poly(arylene ether) in the composition. When using two intrinsic viscosities, determining the precise ratio will depend somewhat on the precise intrinsic viscosity of the poly(arylene ether) used and the desired final physical properties.

The poly(arylene ether) is generally prepared by the oxidative coupling of at least one monohydroxyaromatic compound, such as 2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are often used for this coupling; they usually contain at least one heavy metal compound, such as copper, manganese or cobalt compounds, usually in combination with various other materials.

Particularly useful poly(arylene ethers) for many purposes are those poly(arylene ethers) comprising molecules having at least one aminoalkyl-containing end group. The aminoalkyl group is usually located ortho to the hydroxyl group. Products containing such end groups can be obtained by introducing a suitable primary or secondary monoamine such as di-n-butylamine or dimethylamine as one of the components of the oxidative coupling reaction mixture. Also frequently present are 4-phenylphenol end groups, which are generally obtained from reaction mixtures in which the by-product diphenoquinone is present, inter alia, in copper-halide-secondary or tertiary amine systems. A substantial proportion of the polymer molecules, typically up to about 90% by weight of the polymer, may contain at least one of aminoalkyl-containing end groups and 4-phenylphenol end groups.

In another embodiment, the organic polymer used in the composition may be polycarbonate. Polycarbonates comprising aromatic carbonate chain units, compositions comprising structural units having the formula (II):

Wherein the R ¹ group is an aromatic, aliphatic or alicyclic group. R ¹ is an aromatic organic group, and more ideally a group of structural formula (III):

-A ¹ -Y ¹ -A ² - (III)

Wherein A ¹ and A ² are both monocyclic divalent aryl groups, Y ¹ is a bridging group with zero, one or two atoms separating A ¹ and A ² . In an exemplary embodiment, one atom separates A ¹ and A ² . Illustrative examples of groups of this type are -O-, -S-, -S(O)-, -S( _O2 )-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2,2,1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadelidene, cyclododecylidene, adamantylidene wait. The bridging group ^Y1 may be a hydrocarbon group or a saturated hydrocarbon group, such as methylene, cyclohexylidene or isopropylidene.

Polycarbonates can be produced by the Schotten-Bauman interfacial reaction of carbonate precursors with dihydroxy compounds. Typically an aqueous base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. is mixed with an organic water immiscible solvent containing dihydroxy compounds such as benzene, toluene, carbon disulfide or methylene chloride. Phase transfer agents are often used to facilitate the reaction. The molecular weight regulators can be added to the reaction mixture individually or in the form of a mixture. It is also possible to add the branching agents mentioned immediately, individually or in the form of a mixture.

Aromatic dihydroxy compound comonomers that may be used in the present invention include those of general formula (IV):

HO-A ² -OH (IV)

wherein ^A is selected from divalent substituted and unsubstituted aromatic groups.

In some embodiments, ^A has the structure of formula (V):

Wherein G represents ^aryl , such as phenylene, biphenylene, naphthylene and the like. E can be alkylene or alkylidene, such as methylene, ethylene, ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, Pentyl, pentylidene, isopentylidene, etc., and may consist of two or more alkylene or alkylidene groups linked by moieties other than alkylene or alkylidene, such as aromatic linkages; tertiary Amino bond; ether bond; carbonyl bond; silicon-containing bond; or sulfur-containing bond, such as sulfide, sulfoxide, sulfone, etc.; or phosphorus-containing bond, such as phosphinyl group, phosphono group, etc. In addition, E may be an alicyclic group. R ¹ represents hydrogen or a monovalent hydrocarbon group such as alkyl, aryl, aralkyl, alkaryl or cycloalkyl. Y ¹ can be an inorganic atom such as halogen (fluorine, bromine, chlorine, iodine); an inorganic group such as nitro; an organic group such as alkenyl, allyl, or the above R ¹ , or an oxy group , eg OR; it is only necessary that ^Y be inert to and unaffected by the reactants and reaction conditions used to prepare the polymer. The letter m represents any integer, including zero, of the number of positions that may be substituted on ^G1 ; p represents an integer, including zero, of the number of positions that may be substituted on E; "t" represents an integer equal to at least one; "s" is zero or one; and "u" means any integer including zero.

Suitable examples of E include cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, methylcyclohexylidene, 2-[2.2.1]-bicyclohexylidene, neo Pentylene, cyclopentadelidene, cyclododedecyl, adamantyl, etc.; sulfur-containing bonds, such as sulfide, sulfoxide or sulfone; phosphorus-containing bonds, such as phosphinyl, phosphono; ether bonds; a carbonyl group; a tertiary nitrogen group; or a silicon-containing bond such as a silane or siloxy group. In the aromatic dihydroxy comonomer compound (III), wherein A ² is represented by the above structural formula (IV), when more than one Y ¹ substituent is present, they may be the same or different. This also applies to ^R substituents. When s is zero and u is not zero in the structural formula (IV), the aromatic rings are directly connected without insertion of an alkylidene group or other bridges. The positions of hydroxyl and ^Y on the aromatic core residue ^G can vary in the ortho, meta or para position, and the group can be in an ortho, asymmetric or symmetrical relationship, where two or more rings of the hydrocarbon residue Carbon atoms are substituted with Y ¹ and hydroxyl. In some embodiments, the parameters "t,""s," and "u" are all one; the two G1 groups are unsubstituted phenylene; and E is an alkylidene group, such as isopropylidene. In a particular embodiment, two G ^groups are p-phenylene, but two may be ortho- or m-phenylene or one is ortho- or m-phenylene and the other is p-phenylene. Suitable examples of aromatic dihydroxy compounds of formula (IV) are illustrated by: 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,2-bis-(3-chloro-4 -Hydroxyphenyl)propane; 2,2-bis-(3-bromo-4-hydroxyphenyl)propane; 2,2-bis-(4-hydroxy-3-methylphenyl)propane; 2,2- Bis-(4-hydroxy-3-isopropylphenyl)propane; 2,2-bis-(3-tert-butyl-4-hydroxyphenyl)propane; 2,2-bis-(3-phenyl- 4-hydroxyphenyl)propane; 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane; 2,2-bis-(3,5-dibromo-4-hydroxyphenyl) Propane; 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)propane; 2,2-bis-(3-chloro-4-hydroxy-5-methylphenyl)propane; 2 , 2-bis-(3-bromo-4-hydroxyl-5-methylphenyl)propane; 2,2-bis-(3-chloro-4-hydroxyl-5-isopropylphenyl)propane; 2, 2-bis-(3-bromo-4-hydroxy-5-isopropylphenyl)propane; 2,2-bis-(3-tert-butyl-5-chloro-4-hydroxyphenyl)propane; 2, 2-bis-(3-bromo-5-tert-butyl-4-hydroxyphenyl)propane; 2,2-bis-(3-chloro-5-phenyl-4-hydroxyphenyl)propane; 2,2 -bis-(3-bromo-5-phenyl-4-hydroxyphenyl)propane; 2,2-bis-(3,5-diisopropyl-4-hydroxyphenyl)propane; 2,2-bis -(3,5-di-tert-butyl-4-hydroxyphenyl)propane; 2,2-bis-(3,5-diphenyl-4-hydroxyphenyl)propane; 2,2-bis-(4 -Hydroxy-2,3,5,6-tetrachlorophenyl)propane; 2,2-bis-(4-hydroxy-2,3,5,6-tetrabromophenyl)propane; 2,2-bis- (4-Hydroxy-2,3,5,6-tetramethylphenyl)propane; 2,2-bis-(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)propane ; 2,2-bis-(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclohexane; 1,1 -bis(3-chloro-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-4-hydroxyphenyl)cyclohexane; 1,1-bis-(4-hydroxy-3- Methylphenyl)cyclohexane; 1,1-bis-(4-hydroxy-3-isopropylphenyl)cyclohexane; 1,1-bis(3-tert-butyl-4-hydroxyphenyl) Cyclohexane; 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane; 1, 1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis -(3-chloro-4-hydroxy-5-methylphenyl)cyclohexane; 1,1-bis-(3-bromo-4-hydroxy-5-methylphenyl)cyclohexane; 1,1 - Bis-(3-chloro-4-hydroxy-5-isopropylphenyl)cyclohexane; 1,1-bis-(3-bromo-4-hydroxy-5-isopropylphenyl)cyclohexane ; 1,1-bis(3-tert-butyl-5-chloro-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-5-tert-butyl-4-hydroxyphenyl)cyclohexane Hexane; 1,1-bis(3-chloro-5-phenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-5-phenyl-4-hydroxyphenyl)cyclohexane Hexane; 1,1-bis(3,5-diisopropyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-di-tert-butyl-4-hydroxyphenyl)cyclohexane Hexane; 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis-(4-hydroxy-2,3,5,6-tetrachlorophenyl ) cyclohexane; 1,1-bis-(4-hydroxyl-2,3,5,6-tetrabromophenyl)cyclohexane; 1,1-bis-(4-hydroxyl-2,3,5, 6-tetramethylphenyl)cyclohexane; 1,1-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(2 , 6-dibromo-3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-4-hydroxyphenyl)-3,3 , 5-trimethylcyclohexane; 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy -3-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-tert-butyl-4-hydroxyphenyl)-3,3,5-trimethyl 1,1-bis(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-dichloro-4 -Hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane Alkane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-4-hydroxy- 5-methylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-4-hydroxy-5-methylphenyl)-3,3,5-tri Methylcyclohexane; 1,1-bis(3-chloro-4-hydroxy-5-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3- Bromo-4-hydroxy-5-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-tert-butyl-5-chloro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-5-tert-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-5-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-5-phenyl- 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-diisopropyl-4-hydroxyphenyl)-3,3,5-trimethyl 1,1-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5- Diphenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)-3, 3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)-3,3,5-trimethylcyclohexane; 1, 1-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(2,6-dichloro-3 , 5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(2,6-dibromo-3,5-dimethyl-4- hydroxyphenyl)-3,3,5-trimethylcyclohexane; 4,4′-dihydroxy-1,1-biphenyl; 4,4′-dihydroxy-3,3′-dimethyl- 1,1-biphenyl; 4,4'-dihydroxy-3,3'-dioctyl-1,1-biphenyl;4,4'-dihydroxydiphenylether;4,4'-dihydroxydiphenylPhenylsulfide;1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene; 1,3-bis(2-(4-hydroxy-3-methylphenyl)-2 -propyl)benzene; 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene and 1,4-bis(2-(4-hydroxy-3-methylphenyl)- 2-propyl)benzene. A preferred aromatic dihydroxy compound is bisphenol A (BPA).

Other bisphenol A compounds that may be represented by structural formula (IV) include those wherein X is -O-, -S-, -SO- or _-SO2- . Some examples of such bisphenol A compounds are bis(hydroxyaryl) ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, and the like; Bis(hydroxydiaryl)sulfides, such as 4,4'-dihydroxydiphenylthio, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, etc.; bis(hydroxydiaryl ) sulfoxide, such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, etc.; bis(hydroxydiaryl)sulfone, such as 4 , 4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, etc.; or a combination comprising at least one of the above bisphenol A compounds.

Other bisphenol A compounds that can be used for polycondensation of polycarbonate are represented by structural formula (VI)

wherein R ^f is a halogen atom or a halogen-substituted hydrocarbon group of a hydrocarbon group having 1 to 10 carbon atoms; n is a value of 0 to 4. When n is at least 2, R ^f may be the same or different. Examples of bisphenol A compounds which may be represented by structural formula (V) are resorcinol, substituted resorcinol compounds such as 3-methylresorcinol, 3-ethylresorcinol, 3-propane Resorcinol, 3-butylresorcinol, 3-tert-butylresorcinol, 3-phenylresorcinol, 3-cumylresorcinol, 2,3,4 , 6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, etc.; catechol, hydroquinone, substituted hydroquinones, such as 3-methylhydroquinone, 3-ethyl Hydroquinone, 3-Propylhydroquinone, 3-Butylhydroquinone, 3-tert-Butylhydroquinone, 3-Phenylhydroquinone, 3-Isopropylphenylhydroquinone, 2,3,5,6-Tetramethylhydroquinone , 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc., or at least one of the above bisphenol compounds combination of species.

For example, 2,2,2',2'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobis[IH-indene represented by the following structural formula (VII) can also be used ]-6,6'-diol bisphenol compounds.

A preferred bisphenol compound is bisphenol A.

Typical carbonate precursors include carbonyl halides such as carbonyl chloride (phosgene) and carbonyl bromide; dihaloformates such as those of dihydric phenols such as bisphenol A, hydroquinone, etc., and dihydric alcohols such as dihaloformates of ethylene glycol and neopentyl glycol; and diaryl carbonates such as diphenyl carbonate, bis(cresyl)carbonate and bis(naphthyl)carbonate. A preferred carbonate precursor for interfacial reactions is phosgene.

It is also possible to use polymers produced by the polymerization of two or more different dihydric phenols or copolymers of dihydric phenols with diols or with hydroxyl or acid terminated polyesters or with diacids or with hydroxy acids or with aliphatic diacids Polycarbonates, in which case it is desirable to use carbonate copolymers rather than homopolymers. Generally, useful aliphatic diacids have from about 2 to about 40 carbons. A preferred aliphatic diacid is dodecanedioic acid.

Branched polycarbonates and blends of linear and branched polycarbonates can also be used in the composition. The branched polycarbonates can be prepared by adding branching agents during polymerization. These branching agents may include polyfunctional organic compounds containing at least three functional groups, which may be hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and combinations including at least one of the above branching agents. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic chloride, tris-p-hydroxyphenylethane, isatin-diphenol, trisphenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl base) benzene), trisphenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)α,α-dimethylbenzyl)phenol), 4-chloroformylphthalene Formic anhydride, trimesic acid, benzophenone tetracarboxylic acid, etc., or a combination comprising at least one of the above branching agents. The branching agent can be added at a level of about 0.05 to about 2.0 weight percent (wt %) based on the total weight of polycarbonate in a given layer.

In one embodiment, polycarbonates can be produced by melt polycondensation reactions between dihydroxy compounds and diester carbonates. Examples of such carbonic diesters that can be used to produce polycarbonates are diphenyl carbonate, bis(2,4-dichlorophenyl)carbonate, bis(2,4,6-trichlorophenyl)carbonate, Bis(2-cyanophenyl)carbonate, bis(o-nitrophenyl)carbonate, xylyl carbonate, m-cresol carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, bis(diphenyl)carbonate (methyl salicyl) ester, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc., or a combination comprising at least one of the above carbonic acid diesters. Exemplary carbonic diesters are diphenyl carbonate or bis(methylsalicyl) carbonate.

Preferably, the polycarbonate has a number average molecular weight of from about 3,000 to about 1,000,000 grams per mole (g/mole). Within this range, it is desirable to have a number average molecular weight of greater than or equal to about 10,000, preferably greater than or equal to about 20,000, and more preferably greater than or equal to about 25,000 g/mole. Also desirable is a number average molecular weight of less than or equal to about 100,000, preferably less than or equal to about 75,000, more preferably less than or equal to about 50,000, and most preferably less than or equal to about 35,000 g/mole.

Cycloaliphatic polyesters are usually prepared by reacting diols with dibasic acids or derivatives. The diols used in the preparation of cycloaliphatic polyester polymers are linear, branched or cycloaliphatic alkanediols, preferably linear or branched alkanediols, which may contain 2 to 12 carbon atoms.

Suitable examples of diols include ethylene glycol, propylene glycol, i.e. 1,2-propanediol and 1,3-propanediol; butanediol, i.e. 1,3-butanediol and 1,4-butanediol; diethylene glycol, 2 , 2-Dimethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,3-pentanediol and 1,5-pentanediol, dipropylene glycol, 2-methyl 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and especially its cis and trans isomers, triethylene glycol, 1,10-decanediol Alcohols, and mixtures of any of the above. Particularly desirable are dimethanol dicyclooctane, dimethanol decalin, cycloaliphatic diols or their chemical equivalents and especially 1,4-cyclohexanedimethanol or their chemical equivalents. If 1,4-cyclohexanedimethanol is used as the diol component, it is generally desirable to use a mixture of cis to trans isomers in a molar ratio of from about 1:4 to about 4:1. Within this range, it is generally desirable to use a molar ratio of cis to trans isomers of about 1:3.

The diacid used to prepare the cycloaliphatic polyester polymer is an aliphatic diacid comprising a carboxylic acid having two carboxyl groups, each of which is attached to a saturated carbon in a saturated ring. Suitable examples of cycloaliphatic acids include decalin dicarboxylic acid, norbornene dicarboxylic acid, bicyclooctane dicarboxylic acid. Preferred cycloaliphatic diacids are 1,4-cyclohexanedicarboxylic acid and trans-1,4-cyclohexanedicarboxylic acid. Linear aliphatic diacids can also be used when the polyester has at least one cycloaliphatic ring-containing monomer. Illustrative examples of linear aliphatic diacids are succinic acid, adipic acid, dimethylsuccinic acid and azelaic acid. Mixtures of diacids and diols can also be used to prepare the cycloaliphatic polyesters.

Cyclohexanedicarboxylic acids and their chemical equivalents can be obtained, for example, by reacting ring aromatic diacids and corresponding derivatives, such as isophthalic acid, terephthalic acid or naphthalene dicarboxylic acid, in a suitable solvent, water or acetic acid, at room temperature and hydrogenation at atmospheric pressure using a suitable catalyst such as rhodium on a suitable support of carbon or alumina. They can also be prepared by using an inert liquid medium in which the acid is at least partially soluble under the reaction conditions and using palladium or ruthenium catalysts on carbon or silica.

Typically, two or more isomers in which the carboxylic acid group is in the cis or trans position are obtained during hydrogenation. The cis and trans isomers can be separated by crystallization with or without a solvent such as n-heptane, or by distillation. While the cis isomer tends to mix better, the trans isomer has higher melting and crystallization temperatures and is generally preferred. Mixtures of the cis and trans isomers may also be used, and preferably when such mixtures are used, the trans isomer will preferably comprise at least about 75% by weight, and the cis isomer will be the balance, based on Based on the combined weight of the cis and trans isomers mixed. When a mixture of isomers of more than one diacid is used, a copolyester or a mixture of two polyesters can be used as the cycloaliphatic polyester resin.

Chemical equivalents of these diacids including esters can also be used to prepare the cycloaliphatic polyesters. Suitable examples of chemical equivalents of the diacid are alkyl esters such as dialkyl esters, diaryl esters, acid anhydrides, acid chlorides, acid bromides, etc., or combinations comprising at least one of the foregoing chemical equivalents. Exemplary chemical equivalents include the dialkyl esters of the cycloaliphatic diacids, and most preferred chemical equivalents include the dimethyl esters of the acids, especially dimethyl trans-1,4-cyclohexanedicarboxylate.

Dimethyl 1,4-cyclohexanedicarboxylate can be obtained by ring hydrogenation of dimethyl terephthalate, in which two isomers with carboxylic acid groups in the cis and trans positions are obtained. The isomers can be separated, the trans isomer being particularly desirable. Mixtures of such isomers may also be used as detailed above.

The polyester polymer is typically obtained via condensation or transesterification of a diol or diol chemical equivalent component with a diacid or diacid chemical equivalent component and has a repeating unit of formula (VIII):

wherein ^R3 represents an aryl, alkyl or cycloalkyl group which is the residue of a straight chain, branched or cycloaliphatic alkane diol or its chemical equivalent; and ^R4 is an aryl, alkyl or cycloaliphatic group A group which is a decarboxylated residue derived from a diacid, with the proviso that at least one of ^R3 or ^R4 is cycloalkyl. The aryl group may be a substituted aryl group if desired.

A preferred cycloaliphatic polyester is poly(1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate) having repeating units of formula (IX)

wherein in structural formula (VIII), ^R3 is a cyclohexane ring, and wherein ^R4 is a cyclohexane ring derived from cyclohexanedicarboxylate or its chemical equivalent and is selected from its cis or trans isomerism isomers or a mixture of cis and trans isomers. Cycloaliphatic polyester polymers can generally be prepared in the presence of a suitable catalyst, such as tetra(2-ethylhexyl) titanate, in a suitable amount, usually about 50 to 400 ppm titanium, based on the total final product. weighing scale. Poly(1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate) generally forms suitable blends with polycarbonates.

Preferably the copolyestercarbonate or the polyester has a number average molecular weight of from about 3,000 to about 1,000,000 g/mole. Within this range, it is desirable to have a number average molecular weight of greater than or equal to about 10,000, preferably greater than or equal to about 20,000, and more preferably greater than or equal to about 25,000 g/mole. Also desirable is a number average molecular weight of less than or equal to about 100,000, preferably less than or equal to about 75,000, more preferably less than or equal to about 50,000, and most preferably less than or equal to about 35,000 g/mole.

Another preferred polyester is polyarylate. Polyarylate generally denotes polyesters of aromatic dicarboxylic acids and bisphenols. Polyarylate copolymers comprising carbonate linkages in addition to aryl ester linkages are known as polyester-carbonates, and may also conveniently be used in the form of mixtures. The polyarylates can be prepared by solution or melt polymerization of aromatic dicarboxylic acids or their ester-forming derivatives and bisphenols or their derivatives.

In general, it is desirable for polyarylates to include at least one diphenol residue in combination with at least one aromatic dicarboxylic acid residue. Exemplary diphenolic residues illustrated in formula (X) are derived from 1,3-dihydroxybenzene moieties, referred to throughout this specification as resorcinol or resorcinol moieties. Resorcinol or resorcinol moieties include unsubstituted 1,3-dihydroxybenzene and substituted 1,3-dihydroxybenzene.

In the structural formula (X), R is at least one of C _1-12 alkyl or halogen, and n is 0 to 3. Suitable dicarboxylic acid residues include those derived from monocyclic moieties, preferably isophthalic acid, terephthalic acid or a mixture of isophthalic and terephthalic acids, or from polycyclic moieties, such as diphenyldicarboxylate acid, diphenyl ether dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, etc., and aromatic dicarboxylic acid residues comprising combinations of at least one of the above polycyclic moieties. A preferred polycyclic moiety is naphthalene-2,6-dicarboxylic acid.

Preferably the aromatic dicarboxylic acid residue is derived from a mixture of isophthalic and/or terephthalic acids as generally illustrated in formula (XI).

Thus, in one embodiment the polyarylate comprises a resorcinol arylate polyester as illustrated in structural formula (XII).

wherein R is at least one of C _1-12 alkyl or halogen, n is 0 to 3, and m is at least about 8. Preferably R is hydrogen. Preferably n is zero and m is about 10 and about 300. The molar ratio of isophthalate to terephthalate is from about 0.25:1 to about 4.0:1.

In another embodiment, the polyarylate comprises a thermally stable resorcinol arylate polyester having polycyclic aromatic groups as shown in formula (XIII).

wherein R is at least one of C _1-12 alkyl or halogen, n is 0 to 3, and m is at least about 8.

In another embodiment, the polyarylate is copolymerized to form a block copolyestercarbonate comprising a carbonate and an arylate block. They include polymers comprising structural units of formula (XIV).

wherein each R ¹ is independently halogen or C _1-12 alkyl, m is at least 1, p is from about 0 to about 3, each R ² is independently a divalent organic group, and n is at least about 4. Preferably n is at least about 10, more preferably at least about 20 and most preferably from about 30 to about 150. Preferably m is at least about 3, more preferably at least about 10 and most preferably from about 20 to about 200. In an exemplary embodiment, m is present at a value of about 20 and 50.

It is generally desirable that the polyarylate has a weight average molecular weight of from about 500 to about 1,000,000 grams per mole (g/mol). In one embodiment, the polyarylate has a weight average molecular weight of from about 10,000 to about 200,000 g/mol. In another embodiment, the polyarylate has a weight average molecular weight of from about 30,000 to about 150,000 g/mol. In yet another embodiment, the polyarylate has a weight average molecular weight of from about 50,000 to about 120,000 g/mol. Exemplary molecular weights of polyarylates for the cap layer are 60,000 and 120,000 g/mol.

In one embodiment, the polymer precursor includes ethylenically unsaturated groups. The ethylenically unsaturated group used may be any ethylenically unsaturated functional group capable of polymerisation. Suitable ethylenically unsaturated functional groups include functional groups that can be polymerized via radical polymerization or cationic polymerization. Specific examples of suitable ethylenically unsaturated groups are acrylates, methacrylates, vinyl aromatic polymers such as styrene; vinyl ethers, vinyl esters, N-substituted acrylamides, N- Groups of vinylamide, maleate, fumarate, etc. Preferably the ethylenic unsaturation is provided by groups containing acrylate, methacrylate or styrene functionality, and most preferably styrene.

The vinyl aromatic resin is preferably derived from a polymer precursor containing at least 25% by weight of structural units derived from monomers of formula (XV):

wherein R is ^hydrogen , lower alkyl or halogen; ^Z is vinyl, halogen or lower alkyl; and p is 0 to about 5. These polymers include styrene, homopolymers of chlorostyrene and vinyltoluene, styrene with one or more compounds composed of acrylonitrile, butadiene, alpha-methylstyrene, ethylvinylbenzene, divinyl Random copolymers of monomers such as benzene and maleic anhydride, and rubber-modified polystyrene, including blends and grafts, wherein the rubber is polybutadiene or about 98-70% styrene Rubbery copolymer with about 2-30% diene monomer. Polystyrene is miscible with polyphenylene ether in any proportion, and any such blend may contain from about 5 to about 95 wt%, and most often from about 25 to 75 wt%, polystyrene, based on the total weight of the polymer .

In another embodiment, polyimides can be used as the organic polymer in the composition. Useful thermoplastic polyimides have the general formula (XVI)

wherein "a" is greater than or equal to about 1, desirably greater than or equal to about 10, and more desirably greater than or equal to about 1000; and wherein V is a tetravalent linking group without limitation, so long as the linking group is not Synthesis or use of the polyimide is hindered. Suitable linking groups include (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having from about 5 to about 50 carbon atoms, (b) having from 1 to about 30 carbon atoms A substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl group; or a combination thereof. Suitable replacement and/or linking groups include, but are not limited to, ethers, epoxies, amides, esters, and combinations thereof. Preferred linking groups include, but are not limited to, tetravalent aromatic groups of formula (XVII), such as:

Wherein W is a divalent moiety selected from -O-, -S-, -C(O)-, -SO ₂ -, -SO-, -C _y H _2y - (y is an integer from 1 to 5) and other Halogenated derivatives, including perfluoroalkylene, or a group of structural formula -OZO-, wherein the divalent bond of the -O- or the -OZO- group is located at 3,3', 3,4', 4 , 3' or 4, 4' positions, and wherein Z includes, but is not limited to, divalent groups of structural formula (XVIII).

R in the structural formula (XVI) includes substituted or unsubstituted divalent organic groups, such as (a) aromatic hydrocarbon groups and halogenated derivatives thereof with about 6 to about 20 carbon atoms; (b) having about 2 to about A linear or branched chain alkylene group of 20 carbon atoms; (c) a cycloalkylene group having from about 3 to about 20 carbon atoms, or (d) a divalent group of general formula (XIX).

Wherein Q includes a divalent moiety selected from -O-, -S-, -C(O)-, -SO ₂ -, -SO-, -C _y H _2y - (y is an integer from 1 to 5) and other Halogenated derivatives, including perfluoroalkylene.

Preferred classes of polyimides include polyamideimides and polyetherimides, especially those that are melt processable.

Preferred polyetherimide polymers comprise more than one, typically about 10 to about 1000 or more, and more preferably about 10 to about 500 structural units of formula (XX).

Wherein T is -O- or the group of structural formula -O-Z-O-, wherein the divalent bond of the -O- or the -O-Z-O- group is at 3,3', 3,4', 4,3' or 4,4 ' position, and wherein Z includes, but is not limited to, divalent radicals of formula (XVIII) as defined above.

In one embodiment, the polyetherimide may be a copolymer, which further contains polyimide structural units of formula (XXI) in addition to etherimide units as described above.

wherein R is as defined above for formula (XVI) and M includes, but is not limited to, groups of formula (XXII).

The polyetherimide can be prepared by any method comprising reacting an aromatic bis(ether anhydride) of formula (XXIII) with an organic diamine of formula (XIV).

H ₂ NR-NH ₂ (XXIV)

wherein T and R are as defined above in structural formulas (XVI) and (XX).

Illustrative examples of aromatic bis(ether anhydrides) of formula (XXIII) include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis( 3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylthiodianhydride; 4,4'-bis(3,4- Dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride; 2,2-bis[4-(2,3- Dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxybenzene oxy)diphenylthiodianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy) Diphenylsulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-( 2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3 , 4-dicarboxyphenoxy)diphenylthiodianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride and 4-(2,3-Dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, and various mixtures thereof.

The bis(ether anhydride) can be prepared by hydrolyzing the reaction product of a nitro-substituted phenyl dinitrile and a metal salt of a dihydric phenol compound in the presence of a bipolar aprotic solvent, followed by dehydration. Preferred classes of aromatic bis(ether anhydrides) encompassed by formula (XXIII) above include, but are not limited to, wherein T is of formula (XXV)

And the ether bond is for example preferably in the 3,3', 3,4', 4,3' or 4,4' position compounds and mixtures thereof, and wherein Q is as defined above.

Any diamino compound can be used to prepare the polyimide and/or polyetherimide. Examples of suitable compounds are ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine , octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylene Diamine, 4,4-Dimethylheptamethylenediamine, 4-Methylnonamethylenediamine, 5-Methylnonamethylenediamine, 2,5-Dimethylhexamethylenediamine Diamine, 2,5-Dimethylheptamethylenediamine, 2,2-Dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxy Hexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexyldiamine, bis(4-aminocyclohexyl) ) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6- Diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethyl Benzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis-(2-chloro-4-amino-3,5-diethyl phenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(b-amino-tert-butyl)toluene, bis(p-b-amino-tert-butylphenyl)ether, bis( p-b-methyl-o-aminophenyl)benzene, bis(p-b-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4- Aminophenyl)sulfide, bis(4-aminophenyl)sulfone, bis(4-aminophenyl)ether and 1,3-bis(3-aminopropyl)tetramethyldisiloxane. Mixtures of these compounds may also be present. Preferred diamino compounds are aromatic diamines, especially m- and p-phenylenediamine and mixtures thereof.

In an exemplary embodiment, the polyetherimide resin comprises structural units of formula (XX), wherein each R is independently p-phenylene or m-phenylene or a mixture thereof, and T is structural formula (XXVI ) of the divalent group.

Usually, the reaction can be carried out using a solvent such as o-dichlorobenzene, m-cresol/toluene, etc., between the anhydride of structural formula (XVIII) and the diamine of structural formula (XIX), at a temperature of about 100° C. to about 250° C. reaction. Alternatively, the polyetherimide can be prepared by melt polymerization of an aromatic bis(ether anhydride) of formula (XVIII) and a diamine of formula (XIX) by heating the mixture of raw materials to high temperature while stirring. Typically, melt polymerization uses temperatures from about 200°C to about 400°C. Chain terminators and branching agents can also be used in this reaction. When a polyetherimide/polyimide copolymer is used, a dianhydride such as pyromellitic anhydride is used in combination with the bis(ether anhydride). The polyetherimide polymer can optionally be prepared by the reaction of an aromatic bis(ether anhydride) with an organic diamine, wherein the diamine is present in the reaction mixture in an excess of up to about 0.2 molar, and preferably in an excess of less than about 0.2 . Under such conditions, the polyetherimide resin has less than about 15 microequivalents per gram (μeq/g) of acid titratable groups, and preferably has less than about 10 μeq/g of acid titratable groups, such as with chloroform solution Shown by titration of 33 weight percent (wt%) hydrobromic acid in glacial acetic acid. The acid titratable groups are essentially due to the amine end groups in the polyetherimide resin.

Typically, useful polyetherimides have a melt index of from about 0.1 to about 10 grams per minute (g/min), as determined by American Society for Testing and Materials (ASTM) D1238 at 295°C using a 6.6 kilogram (kg) weight . In an exemplary embodiment, the polyetherimide resin has a weight average molecular weight (Mw) of about 10,000 to about 150,000 grams per mole (g/mol), as determined by gel permeation chromatography using polystyrene Standard determination. Such polyetherimide polymers typically have an intrinsic viscosity greater than about 0.2 deciliters per gram (dl/g), and preferably from about 0.35 to about 0.7 dl/g, as measured in m-cresol at 25°C.

In another embodiment, polyamides can be used as the organic polymer in the composition. Polyamides are generally derived from the polymerization of organic lactams having 4 to 12 carbon atoms. An exemplary lactam is represented by structural formula (XXVII).

wherein n is from about 3 to about 11. A highly preferred lactam is ε-caprolactam with n equal to 5.

Polyamides can also be synthesized from amino acids with 4 to 12 carbon atoms. A preferred amino acid is represented by structural formula (XXVIII).

wherein n is from about 3 to about 11. A highly preferred amino acid is ε-aminocaproic acid with n equal to 5.

Polyamides can also be polymerized from aliphatic dicarboxylic acids having 4 to 12 carbon atoms and aliphatic diamines having 2 to 12 carbon atoms.

Suitable and preferred aliphatic dicarboxylic acids are the same as those mentioned above for the synthesis of polyesters. Exemplary aliphatic diamines are represented by the formula (XXIX)

H ₂ N-(CH ₂ ) _n -NH ₂ (XXIX)

wherein n is from about 2 to about 12. A highly preferred aliphatic diamine is hexamethylene diamine (H ₂ N(CH ₂ ) ₆ NH ₂ ). It is preferred that the molar ratio of dicarboxylic acid to diamine is from about 0.66 to about 1.5. Within this range, it is generally desirable to have a molar ratio of greater than or equal to about 0.81, preferably greater than or equal to about 0.96. Also desirable within this range is an amount less than or equal to about 1.22, preferably less than or equal to about 1.04. Preferred polyamides are Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 6,12, Nylon 10, etc., or a combination comprising at least one of the above nylons.

Polyamide esters can also be synthesized from aliphatic lactones having 4 to 12 carbon atoms and aliphatic lactams having 4 to 12 carbon atoms. The aliphatic lactams are the same as those described above for polyester synthesis, and the aliphatic lactams are the same as those described above for polyamide synthesis. The ratio of aliphatic lactone to aliphatic lactam can vary widely, depending on the desired composition of the final copolymer, and the relative reaction rates of the lactone and the lactam. The presently preferred initial molar ratio of aliphatic lactam to aliphatic lactone is from about 0.5 to about 4. Within this range, a molar ratio of greater than or equal to about 1 is desirable. It is also desirable that the molar ratio is less than or equal to about 2.

The composition may further include a catalyst or initiator. In general, any known catalyst or initiator suitable for the corresponding thermal polymerization can be used. Additionally, the polymerization can be carried out without a catalyst or initiator. For example, in the synthesis of polyamides from aliphatic dicarboxylic acids and aliphatic diamines, no catalyst is required.

For the synthesis of polyamides from lactams, suitable catalysts include water and the ω-amino acid corresponding to the ring-opened (hydrolyzed) lactam used for the synthesis. Other suitable catalysts include metal aluminum alkyl compounds (MAl(OR) ₃ H; where M is an alkali or alkaline earth metal and R is a C ₁ -C ₁₂ alkyl), dihydrobis(2-methoxyethoxy ) sodium aluminate, dihydrobis(tert-butoxy) lithium aluminate, aluminum alkyl compound (Al(OR) ₂ R; where R is C ₁ -C ₁₂ alkyl), sodium N-caprolactam, ε-caprolactam Magnesium chloride or magnesium bromide salt (MgXC ₆ H ₁₀ NO, X=Br or Cl), dialkoxyaluminum hydride. Suitable initiators include isophthaloyl biscaprolactam, N-acetal caprolactam, isocyanate ε-caprolactam adducts, alcohols (ROH; where R is C ₁ -C ₁₂ alkyl), diols (HO-R-OH ; wherein R is C ₁ -C ₁₂ alkylene), ω-aminocaproic acid and sodium methoxide.

For the synthesis of polyamide esters from lactones and lactams, suitable catalysts include metal hydride compounds such as lithium aluminum hydride catalysts of the formula LiAl(H) _x (R ¹ ) _y , where x is from about 1 to about 4, y is from about 0 to about 3, x+y is equal to 4, and R ¹ is selected from C ₁ -C ₁₂ alkyl and C ₁ -C ₁₂ alkoxy; highly preferred catalysts include LiAl(H)(OR ² ) ₃ , wherein R ² is selected from C ₁ -C ₈ alkyl groups; a particularly preferred catalyst is LiAl(H)(OC(CH ₃ ) ₃ ) ₃ . Other suitable catalysts and initiators include those described above for the polymerization of poly(ε-caprolactam) and poly(ε-caprolactone).

Preferred types of polyamides are those obtained by the reaction of a first polyamide and a polymeric material selected from the group consisting of a second polyamide, poly(arylene ether), poly(alkenyl aromatic) homopolymer Compounds, rubber-modified poly(alkenyl aromatic) resins, acrylonitrile-butadiene-styrene (ABS) graft copolymers, block copolymers, and combinations comprising two or more of the above. The first polyamide comprises repeating units of formula (XXX):

wherein ^R is a branched or unbranched alkyl group having nine carbons. R ¹ is preferably 1,9-nonane and/or 2-methyl-1,8-octane. Polyamide resins are characterized by the presence of amide groups (-C(O)NH-) which are condensation products of carboxylic acids and amines. The first polyamide is generally prepared by the reaction of one or more diamines comprising nine carbon alkyl moieties with terephthalic acid (1,4-dicarboxybenzene). When more than one diamine is used, the ratio of the diamines may affect some physical properties of the resulting polymer, such as melting temperature. The ratio of diamine to dicarboxylic acid is usually equimolar, but an excess of one or the other can be used to determine the terminal functionality. Additionally, the reaction may further include monoamines and monocarboxylic acids that act as chain terminators and at least to some extent determine the end group functionality. In some embodiments, it is preferred to have an amine end group content of greater than or equal to about 30 meq/g, and more preferably greater than or equal to about 40 meq/g.

The second polyamide comprises repeating units of formula (XXXI) and/or formula (XXXII)

wherein ^R is a branched or unbranched alkyl group having four to seven carbons, and ^R is an aromatic group having six carbons or a branched or unbranched alkyl group having four to seven carbons . R ² is preferably 1,6-hexane in formula XXXI and 1,5-pentane in formula XXXII. ^R3 is preferably 1,4-butane.

The first polyamide has better dimensional stability, heat resistance, moisture absorption resistance, abrasion resistance and chemical resistance than other polyamides. Thus, compositions comprising the first polyamide exhibit these same improved properties when compared to similar compositions comprising other polyamides in place of the first polyamide. In some embodiments, the combination of the first and second polyamides improves the compatibility of the polyamide phase with other phases, such as poly(arylene ether), in the multiphase composition, thereby improving impact resistance . Without being bound by theory, it is believed that the second polyamide increases the amount of available terminal amino groups. In some cases, the terminal amino groups may react with or be functionalized to react with other phase components, thereby improving compatibility.

The organic polymer is generally present in the composition in an amount from about 5 to about 99.999 weight percent (wt %). Within this range, it is generally desirable to use the organic polymer or polymer blend in an amount greater than or equal to about 10 wt%, preferably greater than or equal to about 30 wt%, and more preferably greater than or equal to about 50 wt%, based on the total weight of the composition. thing. The organic polymer or polymer blend is additionally typically used in an amount less than or equal to about 99.99 wt%, preferably less than or equal to about 99.5 wt%, more preferably less than or equal to about 99.3 wt%, based on the total weight of the composition.

SWNTs for the composition can be produced by laser volatilization of graphite, carbon arc synthesis or high pressure carbon monoxide conversion process (HIPCO). These SWNTs typically have a single wall comprising graphite flakes, with an outer diameter of about 0.7 to about 2.4 nanometers (nm). Typically SWNTs having an aspect ratio of about 5 or greater, preferably about 100 or greater, and more preferably about 1000 or greater are used in the composition. While SWNTs are generally closed structures with hemispherical caps at each end of the respective tube, it is contemplated that SWNTs with a single open end or two open ends could also be used. SWNTs typically include a central portion, which is hollow, but can be filled with amorphous carbon.

In an exemplary embodiment, the purpose of dispersing SWNTs in an organic polymer is to disentangle the SWNTs in order to obtain an effective aspect ratio as close as possible to that of the SWNTs. The ratio of effective aspect ratio to aspect ratio is a measure of dispersion effectiveness. The effective aspect ratio is twice the value of the radius of rotation of an individual SWNT divided by the outer diameter of the corresponding individual nanotube. It is generally desirable that the average effective aspect ratio to aspect ratio ratio be greater than or equal to about 0.5, preferably greater than or equal to about 0.75, and more preferably greater than or equal to about 0.90, as in an electron microscope having a magnification of greater than or equal to about 10,000 Measured in photographs.

In one embodiment, SWNTs may exist in the form of rope-like aggregates. These aggregates are commonly referred to as "ropes" and form as a result of van der Waals forces between individual SWNTs. Individual nanotubes in the rope can slide relative to each other and rearrange themselves within the rope to minimize free energy. Typically ropes with 10 to ¹⁰⁵ nanotubes can be used for this composition. Within this range, it is generally desirable for the cord to have greater than or equal to about 100, preferably greater than or equal to about 500 nanotubes. It is also desirable that the rope has less than or equal to about ¹⁰⁴ nanotubes, preferably less than or equal to about 5,000 nanotubes.

In another embodiment, it is desirable that the SWNT ropes are connected to each other in a branched form after dispersion. This results in shared ropes between branches of the SWNT network to form a three-dimensional network in the organic polymer matrix. Branch points may be separated by a distance of about 10 nanometers to about 10 microns in this network type. It is generally desirable for SWNTs to have an intrinsic thermal conductivity of at least 2000 Watts per meter Kelvin (W/mK), and for SWNT ropes to have an intrinsic conductivity of ¹⁰⁴ Siemens/centimeter (S/cm). It is also generally desirable that the SWNT have a tensile strength of at least 80 gigapascals (GPa) and a stiffness of at least about 0.5 terapascals (TPa).

In another embodiment, SWNTs may comprise a mixture of metallic nanotubes and semiconducting nanotubes. Metallic nanotubes are those nanotubes that exhibit electrical properties similar to metals, while semiconducting nanotubes are those nanotubes that are electrically semiconducting. The usual way of rolling graphite sheets produces nanotubes of various helical structures. Two that were still identified were zigzag and armchair nanotubes. In order to minimize the number of SWNTs used in the composition, it is generally desirable for the composition to include a larger fraction of metallic SWNTs. It is generally desirable that the SWNTs used in the composition comprise an amount greater than or equal to about 1 wt%, preferably greater than or equal to about 20 wt%, more preferably greater than or equal to about 30 wt%, more preferably greater than or equal to about 50 wt%, based on the total weight of the SWNT, and Most preferred are greater than or equal to about 99.9 wt% metallic nanotubes. In some cases, it is generally desirable that the SWNTs used in the composition comprise greater than or equal to about 1 wt%, preferably greater than or equal to about 20 wt%, more preferably greater than or equal to about 30 wt%, more preferably greater than or equal to About 50 wt%, and most preferably greater than or equal to about 99.9 wt%, semiconducting nanotubes.

When desired, SWNTs are generally used in amounts of from about 0.001 to about 80 weight percent of the total composition. Within this range, SWNTs are generally employed in an amount greater than or equal to about 0.25 wt%, preferably greater than or equal to about 0.5 wt%, more preferably greater than or equal to about 1 wt%, of the total weight of the composition. Additionally SWNTs are generally used in amounts of less than or equal to about 30 wt%, preferably less than or equal to about 10 wt%, more preferably less than or equal to about 5 wt% of the total weight of the composition.

In one embodiment, SWNTs may contain production-related impurities. Production-related impurities present in SWNTs are defined herein as those produced during processes substantially associated with SWNT production. As noted above, SWNTs are produced in processes such as laser ablation, chemical vapor deposition, carbon arc, high pressure carbon monoxide conversion, and the like. Production-related impurities are those impurities that occur naturally or intentionally during the production of SWNTs in the above-mentioned process or similar manufacturing processes. A suitable example of a naturally occurring production-related impurity is catalyst particles for the production of SWNTs. A suitable example of an intentionally formed production-related impurity is dangling bonds formed on the surface of SWNTs by the intentional addition of small amounts of oxidizing agents during the fabrication process.

Production involves impurities including, for example, carbonaceous reaction by-products such as defective SWNTs, multi-walled carbon nanotubes, branched or coiled multi-walled carbon nanotubes, amorphous carbon, soot, nona-onions, nano Nanohorns, coke, etc.; catalyst residues from catalysts used in the production process, such as metals, metal oxides, metal carbides, metal nitrides, etc., or combinations comprising at least one of the above reaction by-products. A process substantially related to the production of carbon nanotubes is one in which the fraction of SWNTs is greater when compared to the production of any other fraction involving impurities. In order for the process to be substantially related to SWNT production, the SWNT fraction will have to be greater than the fraction of any of the reaction by-products or catalyst residues listed above. For example, the SWNT fraction will have to be greater than the multi-walled nanotube fraction, or the soot or carbon black fraction. The SWNT fraction will not have to be greater than the sum of the fractions of any combination of impurities involved in the production of the process to be considered substantially involved in SWNT production.

Impurities involved in production include, for example, carbon-containing reaction by-products, such as defective SWNT, multi-walled carbon nanotubes, branched or curled multi-walled carbon nanotubes, amorphous carbon, carbon black, nano-onions, nano-horns, coke, etc. ; catalytic residues from catalysts used in the production process, such as metals, metal oxides, metal carbides, metal nitrides, etc., or combinations comprising at least one of the above-mentioned reaction by-products. A process substantially related to the production of SWNTs is one in which the fraction of SWNTs is greater when compared to the production of any other fraction involving impurities. For use in processes substantially related to SWNT production, the SWNT fraction will have to be greater than the fraction of any of the reaction by-products or catalytic residues listed above. For example, the SWNT fraction will have to be greater than the multi-walled nanotube fraction or the soot fraction or the carbon black fraction. The SWNT fraction will not have to be greater than the sum of the fractions for any combination of production-related impurities of the process to be considered substantially related to SWNT production.

Typically, the SWNTs used in the composition may include impurities in an amount from about 0.1 to about 80 wt%. Within this range, the SWNTs can have an impurity content of greater than or equal to about 3 wt%, preferably greater than or equal to about 7 wt%, and more preferably greater than or equal to about 8 wt% of the total SWNT weight. Also desirable within this range is an impurity level of less than or equal to about 50 wt%, preferably less than or equal to about 45 wt%, and more preferably less than or equal to about 40 wt% of the total SWNT weight.

In one embodiment, the SWNTs used in the composition may include catalytic residues in an amount from about 0.1 to about 50 wt%. Within this range, the SWNT can have a catalytic residue of greater than or equal to about 3 wt%, preferably greater than or equal to about 7 wt%, and more preferably greater than or equal to about 8 wt% of the total SWNT weight. Also desirable within this range is a catalytic residue content of less than or equal to about 50 wt%, preferably less than or equal to about 45 wt%, and more preferably less than or equal to about 40 wt% of the total SWNT weight.

Other carbon nanotubes such as multi-walled carbon nanotubes (MWNTs) and VGCFs may also be added to the composition during the polymerization of the polymeric precursors. MWNTs and VGCFs added to the composition were not considered impurities since they were not produced during SWNT production. MWNTs derived from processes not involving SWNT production, such as laser ablation and carbon arc synthesis, can also be used in the composition. MWNTs have at least two graphitic layers connected around an inner hollow core. Hemispherical caps usually close both ends of the MWNT, but it is desirable to use MWNTs with only one hemispherical cap or MWNTs without both caps. MWNTs typically have a diameter of about 2 to about 50 nm. Within this range, it is generally desirable to use MWNTs with a diameter of less than or equal to about 40 nm, preferably less than or equal to about 30 nm, and more preferably less than or equal to about 20 nm. When using MWNTs, it is preferred to have an average aspect ratio of about 5 or greater, preferably about 100 or greater, more preferably about 1000 or greater.

When desired, MWNTs are typically used in amounts of from about 0.001 to about 50 weight percent of the total weight of the composition. Within this range, the MWNTs are typically employed in an amount greater than or equal to about 0.25 wt%, preferably greater than or equal to about 0.5 wt%, more preferably greater than or equal to about 1 wt%, by weight of the total composition. In addition, MWNTs are generally used in amounts of less than or equal to about 30 wt%, preferably less than or equal to about 10 wt%, more preferably less than or equal to about 5 wt%, of the total weight of the composition.

Other conductive fillers, such as vapor-grown carbon fibers, carbon black, conductive metal fillers, solid non-metallic conductive fillers, etc., or a combination comprising at least one of the foregoing may optionally be used in the composition. Vapor-grown carbon fibers or microscopic graphitic or partially graphitic carbon fibers having a diameter of about 3.5 to about 2000 nanometers (nm) and an aspect ratio greater than or equal to about 5, also known as vapor-grown carbon fibers (VGCF), may also be used. When VGCF is used, a diameter of about 3.5 to about 500 nm is preferred, a diameter of about 3.5 to about 100 nm is more preferred, and a diameter of about 3.5 to about 50 nm is most preferred. It is also preferred to have an average aspect ratio of greater than or equal to about 100 and more preferably greater than or equal to about 1000.

When desired, VGCF is generally used in an amount of from about 0.001 to about 50 weight percent of the total composition. Within this range, VGCF is generally used in an amount greater than or equal to about 0.25 wt%, preferably greater than or equal to about 0.5 wt%, more preferably greater than or equal to about 1 wt%, by weight of the total composition. Additionally VGCF is typically used in an amount of less than or equal to about 30 wt%, preferably less than or equal to about 10 wt%, more preferably less than or equal to about 5 wt% of the total weight of the composition.

SWNTs and other carbon nanotubes used in the composition can also be derivatized with functional groups to improve compatibility and facilitate incorporation with organic polymers. SWNTs and other carbon nanotubes can be functionalized on graphite sheets constituting sidewalls, hemispherical caps or on sidewalls and hemispherical end caps. Functionalized SWNTs and other carbon nanotubes are those having the structural formula (XXXIII)

wherein n is an integer, L is a number less than 0.1n, m is a number less than 0.5n, and wherein each R is the same and is selected from _-SO3H , _-NH2 , -OH, -C(OH)R' , -CHO, -CN, -C(O)Cl, -C(O)SH, -C(O)OR', -SR', -SiR ₃ ', -Si(OR') _y R' _{(3- y)} , -R", -AlR ₂ ', halides, ethylenically unsaturated functional groups, epoxy functional groups, etc., wherein y is an integer equal to or less than 3, and R' is hydrogen, alkyl, aryl, ring Alkyl, aralkyl, cycloaryl, poly(alkyl ether), etc. and R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl, cycloaryl, and the like. The carbon atom C _n is the surface carbon of the carbon nanotube. In uniformly and heterogeneously substituted SWNTs and other carbon nanotubes, surface atoms _Cn react.

Heterogeneously substituted SWNTs and other carbon nanotubes can also be used in the composition. These include compositions of formula (I) shown above, wherein n, L, m, R and the carbon nanotubes themselves are as defined above, provided that each R is free of oxygen, or if each R is an oxygen-containing group, Well no COOH.

Also included are SWNTs and other functionalized carbon nanotubes having the formula (XXXIV):

wherein n, L, m, R' and R have the same meanings as above. Most of the carbon atoms in the surface layer of carbon nanotubes are basal carbons. Basal carbon is relatively inert to chemical attack. At defect sites, eg, where the graphitic planes do not fully expand around the carbon nanotubes, there are carbon atoms similar to the carbon atoms at the edges of the graphitic planes. The edge carbon is reactive and must contain some heteroatom or group that saturates the valency of the carbon atom.

The substituted SWNTs and other carbon nanotubes described above can be conveniently further functionalized. These compositions include compositions of structural formula (XXXV):

Where n, L and m are as described above, and A is selected from -OY, -NHY, -CR' ₂ -OY, -C(O)OY, -C(O)NR'Y, -C(O)SY or - C(O)Y, where Y is a suitable functional group, such as a protein, peptide, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of an enzyme substrate or selected from -R'OH, -R'NH ₂ , -R'SH, -R'CHO, -R'CN, -R'X, -R'SiR' ₃ , -RSi-(OR') _y -R ′ _(3-y) , -R′Si-(O-SiR′ ₂ )-OR′, -R′-R″, -R′-NCO, (C ₂ H ₄ O) _w Y, -(C ₃ H ₆ O) _w H, -(C ₂ H ₄ O) _w R', -(C ₃ H ₆ O) _w R' and R", wherein w is an integer greater than 1 and less than 200.

Functionalized SWNTs and other carbon nanotubes of structure (XXXIV) can also be functionalized to produce compositions of structure (XXXVI):

wherein n, L, m, R' and A are as defined above.

Compositions also include SWNTs and other carbon nanotubes on which certain cyclic compounds are adsorbed. These include compositions of matter of formula (XXXVII):

Wherein n is an integer, L is a number less than 0.1n, m is a number less than 0.5n, a is zero or a number less than 10, X is a polynuclear aromatic, polyheteronuclear aromatic or metal polyheteronuclear aromatic moiety and R such as as above. Preferred cyclic compounds are planar macrocycles such as porphyrins and phthalocyanines.

The adsorbed cyclic compound can be functionalized. This composition comprises the compound of structural formula (XXXVIII)

where m, n, L, a, X and A are as defined above and the carbon is on SWNT or on other carbon nanotubes such as MWNT, VGCF, etc.

Without being bound to a particular theory, functionalized SWNTs and other carbon nanotubes are better dispersed into organic polymers because the modified surface properties can make the carbon nanotubes more compatible with the organic polymer, or because The modified functional groups (in particular hydroxyl or amine groups) are directly attached to the organic polymer as end groups. In this way, organic polymers, such as polycarbonate, polyamide, polyester, polyetherimide, etc., are directly attached to the carbon nanotubes, thereby making the carbon nanotubes easier to disperse, having a improved adhesion.

Functional groups can generally be introduced to SWNTs and other carbon nanotubes by contacting the corresponding outer surface with a strong oxidizing agent for a period of time sufficient to oxidize the surface of SWNTs and other carbon nanotubes, and further contacting the corresponding outer surface with a reactant suitable for adding functional groups to the oxidized surface. on the outer surface of other carbon nanotubes. A preferred oxidizing agent consists of a solution of an alkali metal chlorate in a strong acid. Preferred alkali metal chlorates are sodium chlorate or potassium chlorate. An exemplary strong acid used is sulfuric acid. The period of time sufficient for oxidation is from about 0.5 hour to about 24 hours.

Carbon black may also optionally be used in the composition. Preferred carbon blacks are those having an average particle size below about 200 nm, preferably below about 100 nm, more preferably below about 50 nm. Preferred conductive carbon blacks may also have a surface area greater than about 200 square meters per gram ( ^m2 /g), preferably greater than about 400 ^m2 /g, more preferably greater than about 1000 ^m2 /g. Preferred conductive carbon blacks may have a pore volume greater than about 40 cubic centimeters per hundred grams (cm ³ /100 g), preferably greater than about 100 cm ³ /100 g, more preferably greater than about 150 cm ³ /100 g (dibutyl phthalate absorb). Exemplary carbon blacks include carbon black commercially available from Columbian Chemicals under the trademark Conductex ^(R) ; acetylene carbon black available from Chevron Chemical under the trademarks SCF (SuperConductive Furnace) and ECF (Electric Conductive Furnace); Carbon blacks are Vulcan XC72 and Black Pearls; and carbon blacks commercially available from Akzo Co. Ltd under the trademark Ketjen Black EC 300 and EC 600. Preferred conductive carbon blacks can be used in amounts of about 2 wt% to about 25 wt%, based on the total weight of the composition.

Solid conductive metal fillers may also optionally be used in the conductive composition. These may be conductive metals or alloys that do not melt under the conditions used to incorporate them into organic polymers and manufacture finished products therefrom. Metals such as aluminum, copper, magnesium, chromium, tin, nickel, silver, iron, titanium, and mixtures including any of the foregoing can be incorporated into organic polymers as conductive fillers. Physical mixtures as well as true alloys such as stainless steel, bronze, etc. can also be used as conductive filler particles. In addition, some intermetallic compounds of these metals, such as borides, carbides, etc. (such as titanium diboride) can also be used as conductive filler particles. Solid non-metallic conductive filler particles such as tin oxide, indium tin oxide, etc. may also optionally be added to render the organic polymer conductive. The solid metallic and non-metallic conductive fillers can be in the form of powders, strands, strands, fibers, tubes, nanotubes, flakes, laminates, sheets, ellipsoids, discs, and other commercially available geometries exist.

Non-conductive non-metallic fillers whose surface is already coated in substantial part with an adherent layer of solid conductive metal may also optionally be used in the conductive composition. The non-conductive, non-metallic filler is often referred to as a substrate, and a substrate coated with a layer of a solid conductive metal may be referred to as a "metallized filler". Typical conductive metals such as aluminum, copper, magnesium, chromium, tin, nickel, silver, iron, titanium, and mixtures comprising any of the foregoing can be used to coat the substrate. Examples of substrates include those described in "Plastic Additives Handboot", Fifth Edition, edited by Hans Zweifel, Carl Hanser Verlag Verlag, Munich, 2001. Examples of such substrates include silica powders such as fused silica and crystalline silica, boron nitride powder, borosilicate powder, alumina, magnesia (or magnesia), wollastonite, including Surface-treated wollastonite, calcium sulfate (in the form of its anhydride, dihydrate or trihydrate), calcium carbonate, including chalk, limestone, marble and synthetic precipitated calcium carbonate usually in the form of ground particles, talc, including Fibrous, building blocks, acicular and layered talc, hollow and solid glass spheres, kaolin, including hard, soft, calcined kaolin and including various resins known in the art to promote phase formation with polymer matrix resins Capacitive coatings of kaolin, mica, feldspar, silicate spheres, soot, cenospheres, inert silicate microspheres, aluminosilicates (armospheres), natural silica, quartz, quartzite , perlite, diatomite, diatomaceous earth, synthetic silica, and mixtures including any of the foregoing. All of the substrates mentioned above can be coated with a layer of metallic material for the conductive composition.

Regardless of the exact size, shape and composition of the solid metallic and non-metallic conductive filler particles, they can be dispersed into the organic polymer at levels of from about 0.001 to about 50 weight percent of the total weight of the composition, if desired. Within this range, it is generally desirable to have greater than or equal to about 1 wt%, preferably greater than or equal to about 1.5 wt%, and more preferably greater than or equal to about 2 wt% solid metallic and non-metallic conductive filler particles by weight of the total composition. Solid metallic and non-metallic conductive filler particles may be added in an amount of less than or equal to 40 wt%, preferably less than or equal to about 30 wt%, more preferably less than or equal to about 25 wt%, based on the total weight of the composition.

In one embodiment, in the process of making the composition, a polymer precursor in monomeric, oligomeric or polymeric form is added to a reaction vessel. Suitable examples of reaction vessels are pots, thin film evaporators, single or multi-screw extruders, Booth kneaders, Henschel mixers, helicones, Ross mixers, Banbury mixers, roll mills, molding Equipment, such as injection molding machine, vacuum forming machine, blow molding machine, etc., or a combination comprising at least one of the above equipment. The conductive composition comprising SWNTs and optionally other carbon nanotubes and conductive fillers can then be added to the reaction vessel during polymerization of the polymer precursors.

In one embodiment, SWNTs can be added to the reaction vessel prior to polymerization of the polymer precursor. The polymerisation of the polymer precursors can be carried out in a solvent or, if desired, in the melt without the presence of a solvent. In another embodiment, SWNTs can be added to the reaction vessel during the polymerization of the polymer precursor. In another embodiment, SWNTs can be added to the reaction vessel prior to polymerization of the polymer precursor, while other conductive and non-conductive fillers can be added to the reaction vessel after substantially complete polymerization of the organic precursor. In another embodiment, the reaction vessel may contain a high proportion of SWNTs and other conductive and non-conductive fillers during the early stages of the polymerization process in order to adjust the viscosity of the reaction in the vessel to effectively promote disentanglement of SWNTs and other fillers. After stirring the reaction solution for a desired period of time, additional polymer precursor is added to the reaction vessel to continue the polymerization process.

In one embodiment, SWNTs and other conductive and non-conductive fillers can be added to the reaction vessel in masterbatch form. In another embodiment involving the use of masterbatches, a first masterbatch comprising SWNTs is added to the reaction vessel at a first time, while a second masterbatch comprising other non-conductive fillers can be added during the polymer precursor polymerization process. The second time to add to the reaction vessel.

As mentioned above, the composition can be produced in the melt or in solution including a solvent. The melting reaction of the composition involves the use of shear force, tensile force, pressure, ultrasonic energy, electromagnetic energy, thermal energy, or a combination comprising at least one of the foregoing forms of force or energy, and is carried out in a processing device wherein a single screw, Multi-screw, intermeshing co-rotating or counter-rotating screws, non-intermeshing co-rotating or counter-rotating screws, reciprocating screws, pinned screws, screened screws, pinned barrels, rollers, rams, helical rotors, baffles Or a combination comprising at least one of the above applies the above forces.

In one embodiment, ultrasonic energy can be used to disperse SWNTs. The polymer precursors and SWNTs and other optional conductive or non-conductive fillers are first sonicated in a sonicator to disperse the SWNTs. After sonication, the polymer precursors are polymerized. Sonication can be continued during the polymerization process if desired. Ultrasonic energy can be applied to different reactors where polymerization can take place, such as pots, extruders, etc.

Melt reactions involving the aforementioned forces can be carried out in equipment such as but not limited to single or multi-screw extruders, Booth kneaders, Henschel mixers, helicones, Ross mixers, Banbury mixers, rolls Mill, molding equipment, such as injection molding machine, vacuum forming machine, blow molding machine, etc., or a combination comprising at least one of the above equipment. Solution reactions are usually carried out in vessels such as pots.

In one embodiment, the polymer precursors in the form of powders, granules, flakes, etc. may first be mixed with SWNTs and, if desired, other optional fillers before being fed into a reactor, such as an extruder or a Booth kneader. Dry blend in a Henschel mixer or roll mill. While it is generally desirable that the shear forces in the reactor generally cause the SWNTs to disperse in the polymer precursor, it is also desirable to maintain the aspect ratio of the SWNTs during the reaction. In order to do this, it may be desirable to introduce the SWNTs into the reactor in the form of a masterbatch. In such a process, the masterbatch can be introduced into the reactor downstream of the polymer precursor.

A masterbatch may include an organic polymer or polymer precursor and SWNTs. When a masterbatch is used, the SWNTs may be present in the masterbatch in an amount from about 0.01 to about 50 wt%. Within this range, it is generally desirable to use greater than or equal to about 0.1 wt%, preferably greater than or equal to about 0.2 wt%, more preferably greater than or equal to about 0.5 wt% SWNTs by weight of the total masterbatch. It is also desirable that the amount of SWNT is less than or equal to about 30 wt%, preferably less than or equal to about 10 wt%, more preferably less than or equal to about 5 wt%, based on the total weight of the masterbatch. In one embodiment involving the use of a masterbatch, although the SWNT-containing masterbatch may not have measurable bulk or surface resistivity when extruded in strand form or molded into a dumbbell shape, the resulting The composition of the masterbatch has measurable bulk or surface resistivity even though the weight fraction of SWNTs in the composition is lower than the weight fraction of SWNTs in the masterbatch. Preferably the organic polymer in such a masterbatch is semi-crystalline. Examples of semi-crystalline organic polymers which exhibit these properties and which can be used in the masterbatch are polypropylene, polyamide, polyester, etc., or a combination comprising at least one of the aforementioned semi-crystalline organic polymers.

The composition can also be used as a masterbatch if desired. When the composition is used as a masterbatch, the SWNTs may be present in the masterbatch in an amount from about 0.01 to about 50 wt%. Within this range, it is generally desirable to use greater than or equal to about 0.1 wt%, preferably greater than or equal to about 0.2 wt%, more preferably greater than or equal to about 0.5 wt% SWNTs by weight of the total masterbatch. It is also desirable that the amount of SWNT is less than or equal to about 30 wt%, preferably less than or equal to about 10 wt%, more preferably less than or equal to about 5 wt%, based on the total weight of the masterbatch.

In another embodiment involving the use of a masterbatch in the manufacture of a composition comprising a blend of organic polymers, it is often desirable to have a masterbatch comprising the same organic polymer as the organic polymer derived from the polymerization of the polymer precursor. material. This feature allows the use of a significantly smaller proportion of SWNTs, since only the continuous phase of the organic polymer has SWNTs, providing the required volume and surface resistivities of the composition. In another embodiment involving the use of a masterbatch in a polymeric blend, it may be desirable to have a masterbatch that includes an organic polymer that is chemically different from the other polymers used in the composition. In this case, the organic polymer of the masterbatch will form the continuous phase in the blend. In another embodiment, it may be desirable to use a separate masterbatch comprising multi-walled nanotubes, vapor-grown carbon fibers, carbon black, conductive metallic fillers, solid non-metallic conductive fillers, etc., or to include A combination of at least one.

Compositions comprising organic polymers and SWNTs can be subjected to multiple blending and shaping steps if desired. For example, the composition can first be extruded and formed into pellets. The pellets can then be fed into molding equipment where they can be shaped into desired shapes such as computer housings, car panels that can be electrostatically painted, and the like. Additionally, the conductive composition flowing from a separate melt blender can be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

In one embodiment, the organic polymer precursor may first be mixed with SWNTs in a reactor, such as a pot, and subsequently polymerized in a device that uses a combination of shear, stretching, and/or elongation forces during polymerization. Suitable equipment for carrying out the polymerizations are those with single screw, multiple screws, intermeshing co-rotating or counter-rotating screws, non-intermeshing co-rotating or counter-rotating screws, reciprocating screws, pinned screws, pinned screws, pinned barrels , rollers, rams, helical rotors, baffles, or a combination of at least one of the above.

Solution blending can also be used to prepare the composition. Solution blending can also use auxiliary energy, such as shearing, compression, ultrasonic vibration, etc., to promote the homogenization of SWNTs and organic polymers. In one embodiment, a polymer precursor can be introduced into a sonotrode along with SWNTs. The mixture can be solution blended by sonication for a time effective to disperse the SWNTs onto the organic polymer particles before or during the synthesis of the polymer precursors. The organic polymer can then be dried, extruded and molded together with the SWNTs if desired.

A fluid such as a solvent may optionally be introduced into the sonotrode along with the SWNT and organic polymer precursors. The time period of sonication is generally an amount effective to promote dispersion and/or capping of SWNTs by the organic polymer precursor. After capping, the organic polymer precursor is then polymerized to form an organic polymer with SWNTs dispersed therein. This method of dispersing SWNTs in an organic polymer promotes the maintenance of the aspect ratio of the SWNTs, which thus allows the composition to increase conductivity at lower SWNT loadings.

Generally, it is desirable to sonicate the mixture of organic polymer, organic polymer precursor, fluid, and/or SWNT for about 1 minute to about 24 hours. Within this range, it is desirable to sonicate the mixture for greater than or equal to about 5 minutes, preferably greater than or equal to about 10 minutes, and more preferably greater than or equal to about 15 minutes. Also desirable within this range is a time period of less than or equal to about 15 hours, preferably less than or equal to about 10 hours, and more preferably less than or equal to about 5 hours.

In one embodiment involving dispersing SWNTs with production-related impurities, a SWNT composition with a higher impurity fraction may use less energy to disperse than a SWNT composition with a lower impurity fraction. Without being bound by theory, it is believed that in certain organic polymers, impurity interactions promote a reduction in van der Waals forces, thereby facilitating easier dispersion of the nanotubes within the organic polymer.

In another embodiment involving dispersing SWNTs with production-related impurities, SWNT compositions with higher impurity fractions may require greater mixing amounts than those compositions with lower impurity fractions. However, compositions with lower impurity fractions of SWNTs generally lose conductivity upon additional mixing, while compositions with higher SWNT impurity fractions generally increase conductivity with increasing amounts of incorporation. These compositions can be used in applications where an excellent balance of flow, impact and conductivity is required. They can also be used in applications where conductive materials are used and where the conductive materials have very low levels of conductive fillers, such as fuel cells, electrostatic coating applications, and the like.

Compositions as described above can be used in various industrial applications. They can be conveniently used as films for packaging electronic components that need to be protected from static dissipation, such as computers, electronic products, semiconductor components, circuit boards, and the like. They can also be used internally in computers and other electronic products to provide electromagnetic shielding for personnel and other electronic equipment located outside the computer, and to protect internal computer components from other external electromagnetic interference. They can also be conveniently used in automotive body panels for automotive interior and exterior components, which can be electrostatically painted if desired.

The following examples are intended to be illustrative, not limiting, and illustrate the compositions described herein and the preparation of some of the various embodiments of the conductive compositions.

Example 1

This example was carried out with SWNTs dispersed in polycarbonate (PC), and a masterbatch of SWNTs formed in PC. First, 250 milligrams (mg) of SWNT purchased from Carbon Nanotechnologies Incorporated were dispersed in 120 milliliters (ml) of 1,2-dichloroethane by sonicating the buzzer for 30 minutes. The ultrasonic buzzer uses an ultrasonic processor (600 watts, 13 mm probe diameter, available from Sonics & Materials Incorporated) at 80% amplitude. 30 gms of bis(methylsalicyl)carbonate (BMSC) and 20.3467 gms of bisphenol A (BPA) (BMSC moles/BPA moles = 1.02) were added to the dispersion and SWNTs, and the reaction mixture was sonicated for 30 minutes . The sonicated material was transferred to a glass reactor, which was first passivated by soaking in a bath containing 1 molar aqueous hydrochloric acid for 24 hours, followed by a thorough rinse with deionized water. The solvent was dried by heating the glass reactor to 100°C in the presence of flowing nitrogen at low pressure. The appropriate amount of catalyst solution is then injected into the reactor using a syringe. The amount of catalyst included 4.5×10 ⁻⁶ moles of NaOH per mole of BPA and 3.0×10 ⁻⁴ moles of TBPA (tetrabutylphosphonium acetate) per mole of BPA (bisphenol A).

The reactor was then evacuated and purged with nitrogen using a vacuum source. This cycle was repeated 3 times, after which the reactor contents were heated to melt the monomer mixture (bis(methylsalicyl)carbonate (BMSC) and bisphenol A (BPA)). When the temperature of the mixture reaches about 180° C., the stirrer in the reactor is turned on and adjusted to about 60 revolutions per minute (rpm) to ensure complete melting of all solid matter, which usually takes about 15 to about 20 minutes. The reaction mixture was then heated to about 220°C while the pressure in the reactor was slowly adjusted to about 100 mbar using a vacuum source. After stirring the reaction mass under these conditions for about 15 minutes, the reaction temperature was raised to about 280° C. while the pressure was again adjusted to about 20 mbar. After about 10 minutes at these conditions, the temperature of the reaction mixture was raised to 300° C. while the pressure was lowered to about 1.5 mbar. After allowing the reaction to proceed under these conditions for about 2 to about 5 minutes, the pressure in the reactor is brought to atmospheric pressure and the reactor is vented to release any excess pressure. Product isolation was performed by opening glass tube fittings at the bottom of the reactor and collecting material. The glass reactor was dismantled and the remaining polymer was removed from the reaction tube.

For the determination of molecular weight, the resulting polycarbonate was dissolved in dichloromethane, followed by reprecipitation of the polymer from methanol. Polymer molecular weights were determined by gel permeation chromatography relative to polystyrene standards. The weight average molecular weight was 55756 g/mole, while the number average molecular weight was 23,938 g/mole, and the polydispersity index was 2.32.

Example 2

This example was carried out to disperse SWNTs in PCCD (poly(1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate) polymer and form a masterbatch of SWNTs in PCCD. The PCCD The polymer was synthesized by melt polycondensation in the presence of SWNTs purchased from Carbon Nanotechnologies Incorporated. By combining SWNTs with 1,4-dimethylcyclohexane dicarboxylate (14.01 gm, 0.07 moles) (DMCD), 1,4 - Cyclohexanedimethanol (10.09gm, 0.07mol) (CHDM) and 1,2-dichloroethane (50mL) were mixed under high speed stirring to prepare SWNT slurry (0.24gm, 1wt%). The slurry was transferred to into a glass reaction tube. The reaction tube was assembled into a melt polycondensation reactor equipped with a side arm, a mechanical stirrer driven by a top stirring motor, and a side arm with a rotary valve. The side arm was used for purging Nitrogen was used to apply the vacuum. Initially, the reaction tube was heated under nitrogen to remove 1,2-dichloroethane, and cooled to room temperature. Evacuated and purged the contents of the reactor three times with nitrogen to remove any traces of oxygen The reactor was purged with nitrogen and brought to atmospheric pressure, and the contents of the reaction mixture were heated to 200° C. with constant stirring (100 rpm). 400 parts per million (ppm) of isopropoxide was added as catalyst via a sidearm Titanium(IV), and the transesterification reaction proceeds with distillation of methanol, which is collected in a graduated cylinder (receiver) via a side arm. The temperature of the melt is raised to 250° C. and stirred for 1 hour under nitrogen. The pressure was reduced from 900mm Hg to 700, 500, 300, 100, 50, 25, and 10 millimeters of mercury (mmHg) for polycondensation. Finally, a full vacuum of 0.5 to 0.1 mbar was applied to the reactor and polymerization was continued for 30 minutes. Polymerization After completion, the pressure in the reactor was brought to atmospheric pressure by purging with nitrogen, and the polymer composition was removed from the reaction tube. The polymer was dissolved in methylene chloride and the molecular weight was determined using the intrinsic viscosity method. Measured in phenol/tetrachloro The solution viscosity in ethane (2:3 by volume at 25° C.) solution was 0.58 deciliters/gram (dL/g), which corresponds to a viscosity average molecular weight of 50,000 g/mole.

The masterbatches prepared in Examples 1 and 2 were then melt blended with the polymers in a small laboratory mixing and molding machine to reduce the amount of SWNT added. Wires from the molding machine were broken under liquid nitrogen and the exposed ends were painted with conductive silver paint for conductivity measurements. Conductivity values are shown in Table 1 below.

Table 1 sample number final composition Resistivity (kOhm-cm) 1 1.1wt% SWNT in PC 3.5 2 0.5wt% SWNT in PC 49 3 0.3wt% SWNT in PC 119 4 0.2wt% SWNT in PC 18,500 5 1.1wt% SWNT in PCCD 17.5 6 0.5wt% SWNT in PCCD 76 7 0.3wt% SWNT in PCCD 1,100 8 0.5 wt% SWNT (50/50 by weight) in PCCD/PC 10.0 9 0.3 wt% SWNT (30/70 by weight) in PCCD/PC 275

As can be seen from the table above, Samples 2-4 were made from the PC masterbatch of Example 1 (Sample 1), while Samples 6-9 were made from the masterbatch of Example 2 (Sample 5). From the examples it is clear that as the SWNT level increases, the resistivity decreases. Furthermore, it can be seen that masterbatches can be conveniently used to disperse SWNTs in polymers.

Example 3

This example was used to prepare a masterbatch of SWNTs in nylon 6 during polyamide polymerization. Take 24.8 gm of ε-caprolactam in a beaker and heat to 90°C. After the compound was melted, 250 milligrams (mg) of SWNT (commercially available from Carbon Nanotechnologies Incorporated) containing about 10 wt% impurity was added to the ε-caprolactam. The mixture was sonicated at the same temperature for half an hour using a sonicator (600 watts, 13 mm probe diameter, purchased from Sonics & Materials Incorporated) at 80% amplitude. The SWNT dispersion in molten ε-caprolactam was then transferred to a reaction tube and left overnight to allow the SWNT ropes to gel (form a network). 1.5 gm of aminocaproic acid was then added to the reactor, and the caprolactam was polymerized to nylon-6 by ring-opening polymerization at 260° C. for 9 hours under nitrogen with slow stirring.

Example 4

This experiment was performed to prepare SWNT composites in PCCD by solvent-free in situ polymerization. In this example, 17.29 gm of 1,4-cyclohexanedicarboxylate and 24.03 gms of 1,4-cyclohexanedimethanol were mixed in a beaker and melted at 80°C. 33 mg of SWNTs (commercially available from Carbon Nanotechnologies Incorporated) containing about 10 wt% impurities were added to the beaker. The mixture was sonicated at the same temperature for half an hour using a sonicator (600 watts, 13 mm probe diameter, Sonics & Materials Incorporated, USA) at 80% amplitude. The SWNT dispersion in the molten monomer mixture was then transferred to a reaction tube and left overnight to allow the SWNT ropes to gel (form a network). The monomer was then polymerized into PCCD using the same method as in Example 2.

A portion of the composite prepared above was heated to 240°C (above the melting point of nylon 6) for the nylon 6 composite of Example 3 and 230°C for the PCCD composite of Example 4 for one hour, respectively. The composite was then cooled slowly to room temperature and the electrical conductivity was measured as shown in Table 2. Similarly, the composites of Examples 3 and 4 were melt blended with additional polymers and pressed through a small laboratory mixing and molding machine to form of thread. These results are also shown in Table 4.

Table 4 sample number final composition Resistivity (kOhm-cm) (SD ^* ) 10 0.1wt% SWNT in the PCCD of embodiment 4 --- 11 0.1wt% SWNT (annealed) in the PCCD of embodiment 4 10,030 12 1wt% SWNT in the nylon 6 of embodiment 3 33(13) 13 1 wt% SWNT (annealed) in nylon 6 of embodiment 3 24(14) 14 0.5 wt% SWNT in Nylon 6 (melt blended; sample 12 used as masterbatch) 14715(3986) 15 0.5 wt% SWNT in Nylon 6 (melt blended and using sample 13 as masterbatch) 4075(2390) 16 0.5wt% SWNT in Nylon 6 (melt mixed and annealed in mold) 702

^* SD indicates that the values in parentheses are standard deviations.

From the above data, it can be seen that the annealed samples showed superior electrical properties compared to those annealed samples. Annealing enables the rearrangement of SWNT ropes in the polymer matrix and enhances the reunion/distribution of SWNT rope branches, forming an extensive long-range network morphology, which in turn leads to higher conductivity of the composite.

While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the invention.

Claims (17)

1. method for preparing conductive composition comprises:

Make the single wall carbon nanotube composition blend of polymer precursor and significant quantity; And

The polymer, polymer precursor is formed with organic polymer;

Wherein composition has and is less than or equal to about 10 ¹²The overall volume resistivity of ohm-cm, and more than or equal to about 5 kilojoules/square metre notched izod intensity.

2. the process of claim 1 wherein that the significant quantity of single wall carbon nanotube composition comprises 1 to about 99wt% metal carbon nanotube.

3. each method of claim 1-3, wherein the significant quantity of single wall carbon nanotube composition comprises 1 to about 99wt% semiconductor carbon nanometer tube.

4. each method of claim 1-3, wherein composition has and is less than or equal to about 10 ¹²The surface resistivity of ohm-sq.

5. each method of claim 1-4, wherein composition comprises and is selected from following group polymer precursor:

A) polymer precursor of structure (I):

Wherein for each structural unit, each Q ¹Independently for hydrogen, halogen, uncle or secondary low alkyl group, phenyl, haloalkyl, aminoalkyl group,-oxyl, wherein at least two carbon atoms separate the halo-oxyl of halogen and Sauerstoffatom; Each Q ²Independently for hydrogen, halogen, uncle or secondary low alkyl group, phenyl, haloalkyl,-oxyl, wherein at least two carbon atoms separate the halo-oxyl of halogen and Sauerstoffatom;

B) 2,6-xylenol and 2,3,6-pseudocuminol; And

C) ethylenically unsaturated monomers.

6. each method of claim 1-5, wherein composition comprises and is selected from following group polymer precursor:

A) polymerisate of carbonyl compound and dihydroxy compound, wherein dihydroxy compound has general formula (IV)

HO-A ²-OH (IV)

A wherein ²Structure with structure formula V:

G wherein ¹The expression aryl, E represents alkylidene group, alkylidene or cycloaliphatic radical, R ¹Expression hydrogen or univalence hydrocarbyl, Y ¹Be inorganic atoms, m represents from zero to G ¹On the positional number purpose integer that can replace and comprise zero; P represents to go up the positional number purpose integer that can replace and comprise zero from zero to E; T represents to equal at least one integer; S is zero or one; And u represents to comprise any integer of zero;

B) have the polyester polymers of the repeating unit of structural formula (VIII):

R wherein ³Expression has aryl, the alkyl or cycloalkyl group more than or equal to about 2 carbon atoms, and it is the residue of straight chain, branching or cyclic aliphatic alkane diol; And R ⁴Be aryl, alkyl or cycloaliphatic groups;

C) polymerisate of dibasic alcohol or dibasic alcohol chemical equivalence thing and diprotic acid or diprotic acid chemical equivalence thing;

D) has poly-(1,4-hexanaphthene-dimethanol-1,4 cyclohexanedicarboxylic acid ester) of the repeating unit of structural formula (IX);

E) polymerisate of aromatic dicarboxylic acid and bis-phenol;

F) comprise the organic polymer of the structural unit of structural formula (XIV)

Each R wherein ¹Be halogen or C independently _1-12Alkyl, m is at least 1, and p is for about 3 at the most, each R ²Be divalent organic base independently, and n is at least about 4;

G) polymerisate of the polymer precursor of structural formula (XV):

R wherein ⁵Be hydrogen, low alkyl group or halogen; Z ¹Be vinyl, halogen or low alkyl group; And p is 0 to about 5;

H) styrol copolymer;

I) has the polyimide of general formula (XVI)

Wherein a is more than or equal to about 1; And wherein V is the tetravalence connector, comprise that (a) has about 5 replacement or unsubstituted, saturated, unsaturated or aromatic series monocycle and many cyclic groups to about 50 carbon atoms, (b) has 1 replacement or unsubstituted, linear or branching, saturated or unsaturated alkyl to about 30 carbon atoms; The combination of perhaps above-mentioned tetravalence connector; R has about 6 replacement or unsubstituted divalent aromatic hydrocarbyl groups to about 20 carbon atoms, has the about 2 straight or branched alkylidene groups to about 20 carbon atoms, has about 3 to the ring alkylidene group of about 20 carbon atoms or the divalent group of general formula (XIX)

Wherein Q comprises divalent moiety, be selected from-O-,-S-,-C (O)-,-SO ₂-,-SO-,-C _yH _2y-or its halo derivatives, and y is about 1 to about 5;

J) polymeric amide, also promptly by organic lactan of structural formula (XXVII) expression and the amino acid whose polymerisate of representing by structural formula (XXVIII):

Wherein n is about 3 to about 11,

Wherein n is about 3 to about 11;

K) polymeric amide, aliphatic dicarboxylic acid that also promptly has 4 to 12 carbon atoms and polymerisate with aliphatie diamine of 2 to 12 carbon atoms;

L) polymeric amide also is the polymerisate of first polymeric amide and second polymeric amide; Wherein first polymeric amide comprises the repeating unit of structural formula (XXX)

R wherein ¹Be branching or nonbranched alkyl with nine carbon; And wherein second polymeric amide comprises the repeating unit of structural formula (XXXI) and/or structural formula (XXXII)

R wherein ²Be branching or nonbranched alkyl with four to seven carbon, and R ³Be aryl or branching with four to seven carbon or nonbranched alkyl with six carbon.

7. each method of claim 1-6, wherein composition includes organic polymer, and this organic polymer comprises the have general formula polyimide of (XVI), and wherein the tetravalence connector comprises the aromatic group of structural formula (XVII),

With

Wherein W be-O-,-S-,-C (O)-,-SO ₂-,-SO-,-C _yH _2y-or its halo derivatives, wherein y is 1 to 5, or the group of structural formula-O-Z-O-, wherein-O-or-two valence links of O-Z-O-group are positioned at 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position, and wherein Z is the divalent group of structural formula (XVIII):

With

8. each method of claim 1-7, wherein composition includes organic polymer, and wherein this organic polymer is a polyacetal, polyacrylic, polyalcohols acid, polyacrylic ester, polycarbonate, polystyrene, polyester, polymeric amide, polyaramide, polyamidoimide, polyarylester, polyarylsulphone, polyethersulfone, polyphenylene sulfide, polysulfones, polyimide, polyetherimide, tetrafluoroethylene, polyetherketone, polyether-ether-ketone, PEKK, poly-benzoxazol, polyoxadiazole, polyphenyl and thiazine and thiodiphenylamine, polybenzothiozole, polypyrazine and quinoxaline, polypyromellitimide, polyquinoxaline, polybenzimidazole, poly-oxindole, polyoxy is for isoindoline, poly-dioxoisoindolin, poly-triazine, poly-pyridazine, poly-piperazine, poly-pyrimidine, poly-piperidines, polytriazoles, poly-pyrazoles, poly-carborane, the polyoxy bicyclic nonane of mixing, poly-diphenylene-oxide, paracoumarone ketone, polyacetal, polyanhydride, polyvinyl ether, EOT, polyvinyl alcohol, polyethylene ketone, polyvinyl halides, polyethylene nitrile, polyvinyl ester, polysulfonate, polysulphide, polythioester, polysulfones, polysulphonamide, polyureas, polyphosphonitrile, polysilazane, or comprise at least a combination of above-mentioned thermoplastic polymer.

9. each method of claim 1-8 further comprises carbon nanotube, and wherein this carbon nanotube is multi-walled carbon nano-tubes, vapor-grown carbon fibers or at least a combination that comprises above-mentioned carbon nanotube type.

10. each method of claim 1-10, wherein Single Walled Carbon Nanotube has about 10 ⁴The intrinsic conductivity of Siemens/cm.

11. each method of claim 1-10, wherein single wall carbon nanotube composition comprises and is selected from following group Single Walled Carbon Nanotube:

A) in the Single Walled Carbon Nanotube of first being processed rope form, and described Single Walled Carbon Nanotube is three-dimensional Single Walled Carbon Nanotube latticed form after processing;

B) metal carbon nanotube, semiconductor carbon nanometer tube, or comprise at least a combination of above-mentioned Single Walled Carbon Nanotube;

C) armchair shape nanotube, zig-zag nanotube or comprise at least a combination of above-mentioned carbon nanotube;

D) with functional group's deutero-Single Walled Carbon Nanotube;

E) in sidewall or hemispherical head functional group's deutero-Single Walled Carbon Nanotube;

F) be not connected with hemispherical head or be connected with the Single Walled Carbon Nanotube of at least one hemispherical head; With

G) comprise at least a combination of above-mentioned nanotube.

12. each method of claim 1-11, wherein blend is finished via one of following:

A) ultrasonication;

B) in comprising the solution of solvent;

C) with melt form;

D) use shearing force, drawing force, pressure, ultrasonic energy, electromagnetic energy, heat energy or comprise at least a combination of above-mentioned power and energy, and in processing units, carry out, wherein by single screw rod, multiscrew, engagement in the same way rotation or contra rotating screw, non-engagement in the same way rotation or contra rotating screw, reciprocating screw, the pin screw rod is arranged, the pin machine barrel is arranged, filtering net combination, roller, percussion hammer, helical rotor, retaining are pulled, ultrasonic generator applies above-mentioned power; And

E) comprise above-mentioned at least a combination.

13. each method of claim 1-12, wherein composition further with other organic polymer blend.

14. the method for claim 13 is a hypocrystalline or unbodied with the organic polymer of composition blend further wherein, and has about 100g/mole to about 1,000, the molecular weight of 000g/mole.

15. each method of claim 1-14, wherein the blend of composition is carried out in pot, carry out in a kind of equipment and be aggregated in, described equipment have single screw rod, multiscrew, engagement in the same way rotation or contra rotating screw, non-engagement in the same way rotation or contra rotating screw, reciprocating screw, the pin screw rod is arranged, the sieve screw rod is arranged, have pin machine barrel, roller, percussion hammer, helical rotor, retaining to pull or comprises above-mentioned at least a combination.

16. a conductive composition of being made by each method of claim 1-15, wherein said composition is as masterbatch.

17. goods, it comprises the composition of being made by each method of claim 1-16.