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

Abstract

A method for manufacturing a conductive composition comprises blending a polymer precursor with a single wall carbon nanotube composition; and polymerizing the polymer precursor to form an organic polymer. The method may be advantageously used for manufacturing automotive components, computer components, and other components where electrical conductivity properties are desirable.

Description

Conductive composition and preparation method thereof

The cross reference of related application

The application requires the rights and interests of the U.S. Provisional Patent Application sequence number 60/494,678 of submission on August 12nd, 2003.

Background technology

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

Goods by the organic polymer manufacturing are generally used for material processing and electronics, for example packaging film, chip carrier, computer, printer and copier part, and electrostatic dissipation or electromagnetic shielding are important requirements therein.Electrostatic dissipation (below be designated as ESD) is defined as shifting by the direct contact or the static charge that will be in by induced electrostatic field between the object of different potentials.Electromagnetic shielding (below be designated as EM shielding) efficient is defined as inciding on the shield, also promptly via the proportion (with decibelmeter) of the electromagnetic field of its transmission.Along with electronics becomes more and more littler and more and more faster, they improve for the susceptibility of static charge, therefore wish usually to use the organic polymer of modification so that the electrostatic discharge performance of improvement to be provided.In a similar manner, wish that they can provide the electromagnetic shielding of improvement to keep the favourable mechanical property of some or all these organic polymers simultaneously like this in addition modification of organic polymer.

Usually with the conductive filler material of diameter, for example introduce organic polymer, to improve electric property and to reach ESD and the EM shielding derived from the graphite fibre of pitch and polyacrylonitrile greater than 2 microns.But, because these graphite fibre sizes are bigger, introduce this fiber and cause mechanical property usually, for example impact property reduces.The conductive polymer compositions that can keep its mechanical property when therefore still needing in this area enough ESD and EM shielding are provided.

The invention summary

A kind of method of making conductive composition comprises polymer precursor and single wall carbon nanotube composition blend; And make this polymer precursor polymerization be formed with organic polymer.

Detailed Description Of The Invention

The present invention openly includes the composition of organic polymer and Single Walled Carbon Nanotube (SWNT) composition, these compositions be by before the polymer precursor polymerization process or during add SWNT to polymer precursor manufacturing.The present invention openly includes the composition of the Single Walled Carbon Nanotube (SWNT) of organic polymer and significant quantity.The significant quantity of SWNT represents that being enough to make composition to have is less than or equal to about 10 ¹²The overall volume resistivity of ohm-cm, show simultaneously more than or equal to about 5 kilojoules/square metre impact property and the amount of A level surface smoothness.In one embodiment, said composition has more than or equal to about 10 ⁸The surface resistivity of ohm-sq (ohm/sq) and more than or equal to about 10 ¹²The overall volume resistivity of ohm-cm, show simultaneously more than or equal to about 5 kilojoules/square metre impact property and A level surface smoothness.In another embodiment, said composition has and is less than or equal to about 10 ⁸The surface resistivity of ohm-sq (ohm/sq) and more than or equal to about 10 ⁸The overall volume resistivity of ohm-cm, show simultaneously more than or equal to about 5 kilojoules/square metre impact property and A level surface smoothness.In one embodiment, said composition have more than or equal to about 10 kilojoules/square metre impact property, and in another embodiment, said composition have more than or equal to about 15 kilojoules/square metre impact property.

In one embodiment, said composition has and is less than or equal to about 10 ¹⁰The overall volume resistivity of ohm-cm show simultaneously more than or equal to about 5 kilojoules/square metre impact property and A level surface smoothness.In another embodiment, said composition has and is less than or equal to about 10 ⁸The overall volume resistivity of ohm-cm show simultaneously more than or equal to about 5 kilojoules/square metre impact property and A level surface smoothness.In another embodiment, said composition has and is less than or equal to about 10 ⁵The overall volume resistivity of ohm-cm show simultaneously more than or equal to about 5 kilojoules/square metre impact property and A level surface smoothness.

This composition can be advantageously used in avoiding computer, electronic product, semiconductor device, circuit card of static charge etc.They also can be used in the car body panel that is used for automotive interior and external component easily, and it can be painted by static if desired.

In one embodiment, SWNT was joined in the polymer precursor before polymerization process.In another embodiment, SWNT is joined in the polymer precursor during the polymer precursor polymerization process.In another embodiment, a certain proportion of SWNT was joined in the polymer precursor before polymerization process, and the SWNT of another certainty ratio is joined in the polymer precursor during polymerization process.As defined herein, polymer precursor comprises that monomeric, oligomeric or polymeric can carry out the reactive behavior material of addition polymerization.

The organic polymer that can be obtained by the polymer precursor polymerization is the blend of thermoplastic polymer, thermoplastic polymer or the blend of thermoplastic polymer and thermosetting polymer.Organic polymer can also be the blend of polymkeric substance, multipolymer, terpolymer, interpenetrating net polymer, or comprises at least a combination of above-mentioned organic polymer.The example of thermoplastic polymer comprises polyacetal, polyacrylic, polycarbonate, polyalcohols acid, 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, polypyridine, 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, polyvinylhalide, polyethylene nitrile, polyvinyl ester, polysulfonate, polysulphide, polythioester, polysulfones, polysulphonamide, polyureas, polyphosphonitrile, polysilazane etc., or comprise at least a combination of above-mentioned organic polymer.

At least a combination that the specific examples of the blend of thermoplastic polymer comprises acrylonitrile-butadiene-styrene (ABS)/nylon, PC, polyphenyl ether/styrene, polyphenylether/polyamide, polycarbonate/polyester, polyphenylene oxide/polyolefine and comprises above-mentioned thermoplastic polymer blend.

In one embodiment, the organic polymer that can be used for said composition is a poly (arylene ether).Poly-(arylene ether) polymkeric substance of term comprises polyphenylene oxide (PPE) and poly-(arylene ether) multipolymer; Graft copolymer; Poly-(arylene ether) ether ionomer; And alkenyl aromatic and poly-(arylene ether), the segmented copolymer of vinyl aromatic compounds and poly-(arylene ether) etc.; And comprise above-mentioned at least a combination.Poly-(arylene ether) polymkeric substance self is the polymkeric substance that comprises the structural unit of a plurality of structural formulas (I):

Wherein for each structural unit, each Q ¹Independently for hydrogen, halogen, uncle or secondary low alkyl group (for example containing the alkyl of 7 carbon atoms at the most), phenyl, haloalkyl, aminoalkyl group,-oxyl, wherein at least two carbon atoms separate the halo-oxyl of halogen and Sauerstoffatom etc.; 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 etc.Preferred each Q ¹Be alkyl or phenyl, be in particular C _1-4Alkyl, and each Q ²Can be hydrogen.

Homopolymer and multipolymer poly-(arylene ether) are all comprised.Exemplary homopolymer contains 2 for those, the homopolymer of 6-dimethylphenylene ether units.Suitable copolymers comprises and for example containing with 2,3,6-trimethylammonium-1, this unitary random copolymers of 4-phenylene ether units bonded or derived from 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol copolymerization.What also comprise is to contain by grafting vinyl monomers or polymkeric substance, polystyrene for example, and poly-(arylene ether) of the part of link coupled poly-(arylene ether) preparation, for example low-molecular polycarbonate, quinones, heterocycle and methylal of coupling agent wherein, react with the hydroxyl of two poly-(arylene ether) chains, produce high molecular polymer.Poly-(arylene ether) comprises above at least a combination in addition.

Should poly-(arylene ether) have about 10,000 number-average molecular weights and about 30,000 to about 30,000 gram/moles (g/mol) and arrive approximately 60, the weight-average molecular weight of 000g/mol is passed through gel permeation chromatography.Should poly-(arylene ether) can have about 0.10 limiting viscosity, in 25 ℃ of following chloroforms, measure to about 0.60 deciliter of every gram (dl/g).Also may in composition, use high intrinsic viscosity poly (arylene ether) and low intrinsic viscosity poly (arylene ether).When using two specific character viscosity, determine that accurate ratio will depend on the precise characteristics viscosity of gathering (arylene ether) of use and required final physical performance in a way.

Should poly-(arylene ether) usually by at least a monohydroxy aromatics, 2 or 2,3 for example, the oxidative coupling preparation of 6-pseudocuminol.Catalyst system is normally used for this coupling; They contain at least a heavy metal compound usually, for example copper, manganese or cobalt compound, its usually with various other combinations of materials.

Comprise poly-(arylene ether) of molecule for many purposes useful especially poly-(arylene ether) for those with at least one end group that contains aminoalkyl group.This aminoalkyl groups is usually located at the ortho position of hydroxyl.The product that contains this end group can be by with suitable uncle or secondary monoamine, and for example Di-n-Butyl Amine or dimethylamine obtain as the introducing of one of the component of oxidative coupling mixture.Same ever-present is 4-phenylphenol end group, it obtains from by product phenoquinone wherein is present in reaction mixture copper-halogenide-second month in a season or the tertiary amine system especially usually.This polymer molecule of sizable ratio, account for usually this polymkeric substance up to about 90wt%, can contain the end group of aminoalkyl group and at least one of 4-phenylphenol end group.

In another embodiment, the organic polymer that is used for said composition can be polycarbonate.The polycarbonate that comprises the aromatic carbonate chain unit comprises the have structural formula composition of structural unit of (II):

R wherein ¹Group is aromatic series, aliphatics or alicyclic group.R ¹Be the aromatic series organic group, and more desirably be the group of structural formula (III):

-A ¹-Y ¹-A ²- (III)

A wherein ¹And A ²Be the monocycle divalent aryl, Y ¹For having zero, one or two atom, separate A ¹And A ²Bridged group.In an exemplary, an atom separates A ¹And A ²The illustrative example of the type group is-O-,-S-,-S (O)-,-S (O ₂)-,-C (O)-, methylene radical, cyclohexyl-methylene radical, 2-[2,2,1]-dicyclo fork in heptan base, ethidine, isopropylidene, new pentylidene base, ring pitched base, ring 15 fork bases, encircled ten y-bend bases, Buddha's warrior attendant alkylidene etc.This bridged group Y ¹Can be alkyl or saturated hydrocarbyl, for example methylene radical, ring have been pitched base or isopropylidene.

Polycarbonate can produce by the Schotten-Bauman surface reaction of carbonate precursor and dihydroxy compound.Usually with aqueous base, for example sodium hydroxide, potassium hydroxide, calcium hydroxide etc. and the immiscible solvent of organic water that contains dihydroxy compound, for example benzene, toluene, dithiocarbonic anhydride or methylene dichloride mix.Consisting of phase-transferring agent is used to promote reaction usually.Can separately or with form of mixtures molecular weight regulator be added reaction mixture.Also can add the branching agent of narration immediately separately or with form of mixtures.

Can be used for aromatic dihydroxy compound comonomer of the present invention and comprise those of general formula (IV):

HO-A ²-OH (IV)

A wherein ²Be selected from bivalent substituted and unsubstituted aromatic group.

In some embodiments, A ²Structure with structure formula V:

G wherein ¹Expression aryl, for example phenylene, biphenylene, naphthylidene etc.E can be alkylidene group or alkylidene, for example methylene radical, ethylidene, ethidine, propylidene, propylidene base, isopropylidene, butylidene, fourth fork base, isobutyl fork base, pentylidene, pentylidene base, isoamyl are pitched base etc., and can form aromatics key for example by two or more alkylidene groups or the alkylidene that connect by the part that is different from alkylidene group or alkylidene; The amino key of uncle; Ehter bond; Ketonic linkage; Linkage containing silicon; Perhaps linkage containing sulfur, for example sulfide, sulfoxide, sulfone etc.; Or phosphorous key, for example phosphinyl, phosphono etc.In addition, E can be alicyclic group.R ¹Expression hydrogen or univalence hydrocarbyl, for example alkyl, aryl, aralkyl, alkaryl or cycloalkyl.Y ¹Can be inorganic atoms, for example halogen (fluorine, bromine, chlorine, iodine); Inorganic group, for example nitro; Organic group, for example alkenyl, allyl group or above R ¹, or oxygen base group, for example OR; Unique essential be Y ¹Be inert and not influenced by it for the reactant and the reaction conditions that are used to prepare this polymkeric substance.Letter m represents G ¹On any integer of positional number purpose that can replace, comprise zero; P represents the positional number purpose integer that can replace on the E, comprises zero; " t " expression equals to be at least one integer; " s " is zero or one; And " u " expression comprises any integer of zero.

The suitable example of E comprises cyclopentylidene base, cyclohexylidene base, 3,3,5-3-methyl cyclohexanol fork base, methyl cyclohexane fork base, 2-[2.2.1]-dicyclo fork in heptan base, new pentylidene base, ring 15 fork bases, ring ten y-bend bases, Buddha's warrior attendant alkylidene etc.; Linkage containing sulfur, for example sulfide, sulfoxide or sulfone; Phosphorous key, for example phosphinyl, phosphono; Ehter bond; Carbonyl; Uncle's nitrogen base; Or linkage containing silicon, for example silane or siloxy-.In aromatic dihydroxy comonomer compounds (III), A wherein ²By above structural formula (IV) expression, when existing more than a Y ¹During substituting group, they can be identical or different.This also is applicable to R ¹Substituting group.S is zero and u when non-vanishing in the structural formula (IV), and aromatic ring directly connects, and does not insert alkylidene or other bridged bond.Hydroxyl and Y ¹At aromatic kernel residue G ¹On the position can adjacent, or contraposition change, and this group can be ortho position, asymmetric or symmetric relation, wherein two or more ring carbon atom Y of hydrocarbon residue ¹Replace with hydroxyl.In some specific embodiments, parameter " t ", " s " and " u " are one; Two G1 bases are unsubstituted phenylene; And E is alkylidene group, for example isopropylidene.In special embodiment, two G ¹Base is to phenylene, but two can be that neighbour or metaphenylene and another are to phenylene for neighbour or metaphenylene or one.The suitable example of the aromatic dihydroxy compound of structural formula (IV) is illustrated by following material: 2, and 2-pair-(4-hydroxyphenyl) propane (dihydroxyphenyl propane); 2,2-pair-(3-chloro-4-hydroxyphenyl) propane; 2,2-pair-(3-bromo-4-hydroxyphenyl) propane; 2,2-pair-(4-hydroxy-3-methyl phenyl) propane; 2,2-pair-(4-hydroxyl-3-isopropyl phenyl) propane; 2,2-pair-(the 3-tertiary butyl-4-hydroxyphenyl) propane; 2,2-pair-(3-phenyl-4-hydroxyphenyl) propane; 2,2-pair-(3,5-two chloro-4-hydroxyphenyl) propane; 2,2-pair-(3,5-two bromo-4-hydroxyphenyl) propane; 2,2-pair-(3,5-dimethyl-4-hydroxyphenyl) propane; 2,2-pair-(3-chloro-4-hydroxy-5-methyl base phenyl) propane; 2,2-pair-(3-bromo-4-hydroxy-5-methyl base phenyl) propane; 2,2-pair-(3-chloro-4-hydroxyl-5-isopropyl phenyl) propane; 2,2-pair-(3-bromo-4-hydroxyl-5-isopropyl phenyl) propane; 2,2-pair-(the 3-tertiary butyl-5-chloro-4-hydroxyphenyl) propane; 2,2-pair-(the 3-bromo-5-tertiary butyl-4-hydroxyphenyl) propane; 2,2-pair-(3-chloro-5-phenyl-4-hydroxyphenyl) propane; 2,2-pair-(3-bromo-5-phenyl-4-hydroxyphenyl) propane; 2,2-pair-(3,5-di-isopropyl-4-hydroxyphenyl) propane; 2,2-pair-(3,5-di-t-butyl-4-hydroxyphenyl) propane; 2,2-pair-(3,5-phenylbenzene-4-hydroxyphenyl) propane; 2,2-pair-(4-hydroxyl-2,3,5,6-tetrachloro phenyl) propane; 2,2-pair-(4-hydroxyl-2,3,5,6-tetrabromo phenyl) propane; 2,2-pair-(4-hydroxyl-2) propane; 2,2-pair-(2,6-two chloro-3,5-dimethyl-4-hydroxyphenyl) propane; 2,2-pair-(2,6-two bromo-3,5-dimethyl-4-hydroxyphenyl) propane; 1, two (4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 3-chloro-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 3-bromo-4-hydroxyphenyl) hexanaphthenes of 1-; 1,1-pair-(4-hydroxy-3-methyl phenyl) hexanaphthene; 1,1-pair-(4-hydroxyl-3-isopropyl phenyl) hexanaphthene; 1, two (the 3-tertiary butyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3-phenyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-two chloro-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-two bromo-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-dimethyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1,1-pair-(3-chloro-4-hydroxy-5-methyl base phenyl) hexanaphthene; 1,1-pair-(3-bromo-4-hydroxy-5-methyl base phenyl) hexanaphthene; 1,1-pair-(3-chloro-4-hydroxyl-5-isopropyl phenyl) hexanaphthene; 1,1-pair-(3-bromo-4-hydroxyl-5-isopropyl phenyl) hexanaphthene; 1, two (the 3-tertiary butyl-5-chloro-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 3-bromo-5-tertiary butyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 3-chloro-5-phenyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 3-bromo-5-phenyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-di-isopropyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-di-t-butyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (3, the 5-phenylbenzene-4-hydroxyphenyl) hexanaphthenes of 1-; 1,1-pair-(4-hydroxyl-2,3,5,6-tetrachloro phenyl) hexanaphthene; 1,1-pair-(4-hydroxyl-2,3,5,6-tetrabromo phenyl) hexanaphthene; 1,1-pair-(4-hydroxyl-2) hexanaphthene; 1, two (2,6-two chloro-3, the 5-dimethyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (2,6-two bromo-3, the 5-dimethyl-4-hydroxyphenyl) hexanaphthenes of 1-; 1, two (the 4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-chloro-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-bromo-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 4-hydroxy-3-methyl phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 4-hydroxyls-3-isopropyl phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-tertiary butyls-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-phenyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-two chloro-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-two bromo-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-dimethyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-chloro-4-hydroxy-5-methyl base phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-bromo-4-hydroxy-5-methyl base phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-chloro-4-hydroxyls-5-isopropyl phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-bromo-4-hydroxyls-5-isopropyl phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-tertiary butyls-5-chloro-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-bromo-5-tertiary butyls-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-chloro-5-phenyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 3-bromo-5-phenyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-di-isopropyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-di-t-butyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (3,5-phenylbenzene-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (4-hydroxyl-2,3,5, the 6-tetrachloro phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (4-hydroxyl-2,3,5, the 6-tetrabromo phenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (the 4-hydroxyl-2)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (2,6-two chloro-3,5-dimethyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 1, two (2,6-two bromo-3,5-dimethyl-4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane; 4,4 '-dihydroxyl-1,1-biphenyl; 4,4 '-dihydroxyl-3,3 '-dimethyl-1,1-biphenyl; 4,4 '-dihydroxyl-3,3 '-dioctyl-1,1-biphenyl; 4,4 '-dihydroxy diphenyl ether; 4,4 '-the dihydroxyl diphenylsulfide; 1, two (2-(4-the hydroxy phenyl)-2-propyl group) benzene of 3-; 1, two (2-(4-hydroxy-3-methyl the phenyl)-2-propyl group) benzene of 3-; 1, two (2-(4-the hydroxy phenyl)-2-propyl group) benzene and 1 of 4-, two (2-(4-hydroxy-3-methyl the phenyl)-2-propyl group) benzene of 4-.Preferred aromatic dihydroxy compound is dihydroxyphenyl propane (BPA).

Can comprise by other dihydroxyphenyl propane compound of structural formula (IV) expression those wherein X for-O-,-S-,-SO-or-SO ₂-compound.Some examples of this dihydroxyphenyl propane compound are two (hydroxyaryl) ethers, for example 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl-3,3 '-the dimethyl phenylate etc.; Two (hydroxyl diaryl) sulfide, for example 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl-3,3 '-the dimethyl diphenyl sulfide or the like; Two (hydroxyl diaryl) sulfoxide, for example 4,4 '-dihydroxyl thionyl benzene, 4,4 '-dihydroxyl-3,3 '-the dimethyl thionyl benzene etc.; Two (hydroxyl diaryl) sulfone, for example 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxyl-3,3 '-diphenylsulfone dimethyl or the like; Or comprise at least a combination of above-mentioned dihydroxyphenyl propane compound.

Other dihydroxyphenyl propane compound that can be used for polycarbonate polycondensation is represented by structural formula (VI)

R wherein ^fThe alkyl that replaces for the halogen atom or the halogen of alkyl with 1 to 10 carbon atom; N is 0 to 4 value.When n is at least 2, R ^fCan be identical or different.The dihydroxyphenyl propane examples for compounds that can be represented by the structure formula V is the resorcinol compound of Resorcinol, replacement, for example 3-methylresorcinol, 3-ethyl resorcinol, 3-propyl group Resorcinol, 3-butyl Resorcinol, 3-tert-butyl resorcin, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,3,4,6-tetrafluoro Resorcinol, 2,3,4,6-tetrabromo Resorcinol etc.; The quinhydrones of catechol, quinhydrones, replacement, for example 3-toluhydroquinone, 3-ethyl quinhydrones, 3-propyl group quinhydrones, 3-butylhydroquinone, 3-tertiary butylated hydroquinone, 3-phenyl quinhydrones, 3-cumyl quinhydrones, 2,3,5,6-duroquinol, 2,3,5,6-tetra-tert quinhydrones, 2,3,5,6-tetrafluoro quinhydrones, 2,3,5,6-tetrabromo quinhydrones etc., or comprise at least a combination of above-mentioned bisphenol cpd.

Also can use by following structural formula (VII) expression for example 2,2,2 ', 2 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two [IH-indenes]-6,6 '-bisphenol cpd of glycol.

Preferred bisphenol cpd is a dihydroxyphenyl propane.

Typical carbonate precursor comprises carbonylic halide, for example carbonyl chloride (phosgene) and carbonyl bromide; Two haloformates, dihydric phenol for example, as two haloformates of dihydroxyphenyl propane, quinhydrones etc., and dibasic alcohol, for example two haloformates of ethylene glycol and neopentyl glycol; And diaryl carbonate, for example diphenyl carbonate, carbonic acid two (tolyl) ester and carbonic acid two (naphthyl) ester.The preferred carbonate precursor that is used for surface reaction is a carbonyl chloride.

Also may use by two or more different dihydric phenols or dihydric phenol multipolymer and dibasic alcohol or with hydroxyl or sour terminated polyester with diprotic acid or with alcohol acid or the polycarbonate that produces with the aliphatic diacid polymerization, it is desirable to use carbonate copolymer rather than homopolymer under this situation.Usually, useful aliphatic diacid has about 2 to about 40 carbon.The preferred aliphat diacid is a dodecanedioic acid.

The blend of branching polycarbonate and linear polycarbonate and branching polycarbonate also can be used for said composition.This branching polycarbonate can be by adding the branching agent preparation in polymerization process.These branching agents can comprise multifunctional organic compound that contains at least three functional groups and at least a combination that comprises above-mentioned branching agent, and described functional group can be hydroxyl, carboxyl, carboxylic acid anhydride, halogen formyl.Specific examples comprises trimellitic acid, trimellitic acid 1,2-anhydride, inclined to one side benzene three acyl chlorides, three-p-hydroxybenzene ethane, isatin-biphenol, trisphenol TC (1,3,5-three ((to hydroxyphenyl) sec.-propyl) benzene), trisphenol PA (4 (4 (1, two (to the hydroxyphenyl)-ethyls of 1-) α, the alpha-alpha-dimethyl phenmethyl) phenol), 4-chloroformyl Tetra hydro Phthalic anhydride, trimesic acid, benzophenone tetracarboxylic acid etc., or comprise at least a combination of above-mentioned branching agent.This branching agent can be to add to the level of about 2.0 weight percents (wt%) based on the polycarbonate gross weight about 0.05 in the given layer.

In one embodiment, polycarbonate can produce by the melt polycondensation reaction between dihydroxy compound and the carbonic diester.The example that can be used to produce this carbonic diester of polycarbonate is diphenyl carbonate, carbonic acid two (2, the 4-dichlorophenyl) ester, carbonic acid two (2,4, the 6-trichlorophenyl) two (2-cyano-phenyl) esters of ester, carbonic acid, two (ortho-nitrophenyl base) esters of carbonic acid, carboxylol ester, carbonic acid meta-cresol ester, carbonic acid dinaphthyl ester, two (phenylbenzene) esters of carbonic acid, two (methyl salicyl) esters of carbonic acid, diethyl carbonate, methylcarbonate, dibutyl carbonate, carbonic acid two cyclohexyls etc., or comprise at least a combination of above-mentioned carbonic diester.Exemplary carbonic diester is two (methyl salicyl) esters of diphenyl carbonate or carbonic acid.

The number-average molecular weight of preferred this polycarbonate is about 3,000 to about 1,000,000 gram/mole (g/mole).In this scope, it is desirable to have more than or equal to about 10,000, be preferably greater than or equal about 20,000, and more preferably greater than or equal about 25, the number-average molecular weight of 000g/mole.It is about 100,000 for being less than or equal to it is desirable to number-average molecular weight equally, preferably is less than or equal to approximately 75,000, be more preferably less than or equal about 50,000, and most preferably be less than or equal to about 35,000g/mole.

Present cycloaliphatic polyesters is usually by glycol and diprotic acid or derivatives reaction preparation.The glycol that is used to prepare the present cycloaliphatic polyesters polymkeric substance is straight chain, branching or alicyclic alkane diol, and preferred straight chain or branched alkane dibasic alcohol can contain 2 to 12 carbon atoms.

The suitable example of glycol comprises ethylene glycol, propylene glycol, promptly 1, and 2-propylene glycol and 1, ammediol; Butyleneglycol, i.e. 1,3 butylene glycol and 1,4-butyleneglycol; Glycol ether, 2,2-dimethyl-1, ammediol, 2-ethyl-2-methyl isophthalic acid, ammediol, 1,3-pentanediol and 1,5-pentanediol, dipropylene glycol, 2-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol and particularly its cis and trans-isomer(ide), triglycol, 1,10-decanediol, and above-mentioned any mixture.It is desirable to dimethanol bicyclooctane, dimethanol naphthane, alicyclic diol or its chemical equivalence thing and particularly 1 especially, 4-cyclohexanedimethanol or its chemical equivalence thing.If use 1,4 cyclohexane dimethanol as diol component, it is desirable to usually to use cis to the mol ratio of trans-isomer(ide) for about 1: 4 to about 4: 1 mixture.In this scope, it is desirable to use the mol ratio of about 1: 3 cis usually to trans-isomer(ide).

The diacid that is used to prepare the present cycloaliphatic polyesters polymkeric substance is the aliphatic diacid that comprises the carboxylic acid with two carboxyls, and wherein each carboxyl is connected to the saturated carbon in the saturated rings.The suitable example of alicyclic acid comprises naphthane dicarboxylic acid, norbornene dicarboxylic acids, bicyclooctane dicarboxylic acids.Preferred alicyclic diacid is 1,4-cyclohexane dicarboxylic acid and anti-form-1,4-cyclohexane dicarboxylic acid.When polyester has at least a monomer that contains alicyclic ring, also can use linear aliphatic family diacid.The illustrative example of linear aliphatic family diacid is succsinic acid, hexanodioic acid, dimethyl succinic acid and nonane diacid.The mixture of diacid and glycol also can be used to prepare this present cycloaliphatic polyesters.

Cyclohexane dicarboxylic acid and their chemical equivalence thing can for example pass through cyclophane family diacid and corresponding derivative, for example m-phthalic acid, terephthalic acid or naphthalic acid are in appropriate solvent, water or acetate, in room temperature with under atmospheric pressure use appropriate catalyst hydrogenation preparation, described catalyzer for example is carried on the rhodium on carbon or the aluminum oxide suitable carrier.They also can be by using the inert liquid medium preparation, and wherein acid is palladium or the ruthenium catalyst in solvable and use carbon or the silicon-dioxide under reaction conditions to small part.

Usually, obtain in the hydrogenation process two or more wherein hydroxy-acid group at the isomer of cis or trans position.This cis and trans-isomer(ide) can by with or the solvent crystallization of normal heptane for example, perhaps pass through fractionation by distillation.Though this cis-isomeride is easy to better mixing, this trans-isomer(ide) has higher fusion and Tc and normally preferred.Also can use the mixture of this cis and trans-isomer(ide), and preferably when this mixture of use, trans-isomer(ide) will account at least about 75wt% preferably, and this cis-isomeride will be surplus, based on blended cis and trans-isomer(ide) gross weight meter.When the mixture of isomers used more than a kind of diacid, the mixture of copolyesters or two kinds of polyester can be used as this cycloaliphatic polyester resin.

The chemical equivalence thing that comprises these diacid of ester also can be used to prepare this present cycloaliphatic polyesters.The suitable example of the chemical equivalence thing of this diacid is an alkyl ester, for example dialkyl, diaryl ester, and acid anhydrides, chloride of acid, acid bromide etc., or comprise at least a combination of above-mentioned chemical equivalence thing.Exemplary chemical equivalence thing comprises the dialkyl of this alicyclic diacid, and most preferably the chemical equivalence thing comprises sour dimethyl ester, particularly anti-form-1,4-dimethyl hexahydrophthalate.

The 1,4 cyclohexanedicarboxylic acid dimethyl ester can obtain by the hydrogenated of dimethyl terephthalate (DMT), wherein obtains having in cis and trans position two kinds of isomer of hydroxy-acid group.This isomer can be separated, and this trans-isomer(ide) is special ideal.As described in detail above also can use this mixture of isomers.

This polyester polymers obtains via the condensation or the ester interchange polymerization of glycol or glycol chemical equivalence thing component and diacid or diacid chemical equivalence thing component usually, and has the repeating unit of structural formula (VIII):

R wherein ³Expression aryl, alkyl or cycloalkyl, it is the residue of straight chain, branching or alicyclic alkanes glycol or its chemical equivalence thing; And R ⁴Be aryl, alkyl or alicyclic group, it is the decarboxylation residue derived from diacid, and condition is R ³Or R ⁴At least one be cycloalkyl.This aryl can be substituted aryl if desired.

Preferred present cycloaliphatic polyesters is poly-(1,4-hexanaphthene-dimethanol-1,4-cyclohexanedicarboxyester ester) with repeating unit of structural formula (IX)

Wherein in structural formula (VIII), R ³Be cyclohexane ring, and R wherein ⁴For derived from the cyclohexane ring of cyclohexanedicarboxyester ester or its chemical equivalence thing and be selected from its cis or the mixture of trans-isomer(ide) or its cis and trans-isomer(ide).The present cycloaliphatic polyesters polymkeric substance usually can be in appropriate catalyst, and for example there is preparation down in metatitanic acid four (the 2-ethyl is own) ester with appropriate vol, and described amount is generally about 50 to the 400ppm titanium, based on the finished product gross weight meter.Poly-(1,4 cyclohexane dimethanol-1,4-cyclohexanedicarboxyester ester) usually and polycarbonate form suitable blend.

The number-average molecular weight of preferred this copolyestercarbonates or this polyester is about 3,000 to about 1,000,000g/mole.In this scope, it is desirable to have more than or equal to about 10,000, be preferably greater than or equal about 20,000, and more preferably greater than or equal about 25, the number-average molecular weight of 000g/mole.It is about 100,000 for being less than or equal to it is desirable to number-average molecular weight equally, preferably is less than or equal to approximately 75,000, be more preferably less than or equal about 50,000, and most preferably be less than or equal to about 35,000g/mole.

Another kind of preferred polyester is a polyarylester.The polyester of polyarylester ordinary representation aromatic dicarboxylic acid and bis-phenol.The polyarylester multipolymer that comprises the carbonic acid ester bond except that the aryl ester bond is known as polyester-carbonic ether, and also can use easily with the form of mixture.This polyarylester can by aromatic dicarboxylic acid or their one-tenth ester derivative and bis-phenol or their derivative in solution or melt polymerization prepare.

Usually, it is desirable to comprise at least a and at least a aromatic dicarboxylic acid residue bonded diphenol residue for polyarylester.The exemplary diphenol residue of explanation is derived from 1 in the structural formula (X), and 3-dihydroxy-benzene part runs through this specification sheets and is called Resorcinol or resorcinol moiety.It is unsubstituted 1 that Resorcinol or resorcinol moiety comprise, 1 of 3-dihydroxy-benzene and replacement, 3-dihydroxy-benzene.

In the structural formula (X), R is C _1-12Alkyl or halogen at least a, and n is 0 to 3.Suitable dicarboxylic acid residue comprises derived from the monocycle part, the mixture of preferred m-phthalic acid, terephthalic acid or m-phthalic acid and terephthalic acid, or derived from many loop sections, for example diphenyldicarboxylic acid, diphenyl ether dicarboxylic acid and naphthalene-2,6-dicarboxylic acid etc., and the aromatic dicarboxylic acid residue that comprises at least a combination of above-mentioned many loop sections.Preferred many ring portions are divided into naphthalene-2, the 6-dicarboxylic acid.

Preferred this aromatic dicarboxylic acid residue derived from as the m-phthalic acid of the middle general remark of structural formula (XI) and/or the mixture of terephthalic acid.

Therefore, this polyarylester comprises the Resorcinol virtueization polyester that illustrates as in the structural formula (XII) in one embodiment.

Wherein R is C _1-12Alkyl or halogen at least a, n is 0 to 3, and m is at least about 8.Preferred R is a hydrogen.Preferred n is zero and m is about 10 and about 300.The mol ratio of isophthalic acid ester and terephthalate is about 0.25: 1 to about 4.0: 1.

In another embodiment, this polyarylester comprises the thermally-stabilised Resorcinol virtueization polyester that has the polycyclic aromatic base shown in structural formula (XIII).

Wherein R is C _1-12Alkyl or halogen at least a, n is 0 to 3, and m is at least about 8.

In another embodiment, this polyarylester is formed block copolyestercarbonatecomprise by copolymerization, and it comprises carbonic ether and virtueization block.They comprise the polymkeric substance that comprises structural formula (XIV) structural unit.

Each R wherein ¹Be halogen or C independently _1-12Alkyl, m is at least 1, and p is about 0 to about 3, each R ²Be divalent organic base independently, and n is at least about 4.It is about 10 that preferred n is at least, and more preferably is at least about 20 and most preferably be about 30 to about 150.It is about 3 that preferred m is at least, and more preferably is at least about 10 and most preferably be about 20 to about 200.In an exemplary, m exists with about 20 and 50 numerical value.

Usually the weight-average molecular weight that it is desirable to this polyarylester is about 500 to about 1,000,000 gram/mole (g/mol).In one embodiment, the weight-average molecular weight of this polyarylester is about 10,000 to about 200,000g/mol.In another embodiment, the weight-average molecular weight of this polyarylester is about 30,000 to about 150,000g/mol.In another embodiment again, the weight-average molecular weight of this polyarylester is about 50,000 to about 120,000g/mol.The example molecule amount that is used for the polyarylester of tectum (cap layer) is 60,000 and 120,000g/mol.

In one embodiment, polymer precursor comprises the ethylenic unsaturated group.The ethylenic unsaturated group that uses can be for can any ethylenic unsaturated functional group of polymeric.Suitable ethylenic unsaturated functional group comprises can be via group polymerization or cationoid polymerisation and the functional group that is aggregated.The specific examples of suitable ethylenic unsaturated group is for containing acrylate, methacrylic ester, vinylaromatic polymer, for example vinylbenzene; The group of the acrylamide that vinyl ether, vinyl ester, N-replace, N-vinylamide, maleic acid ester, fumarate etc.Preferred ethylenic is unsaturated is provided by the group that contains acrylate, methacrylic ester or styrenic functionality, and vinylbenzene most preferably.

Vinyl aromatic resin is preferably derived from containing the polymer precursor derived from the monomeric structural unit of structural formula (XV) of 25wt% at least:

R wherein ⁵Be hydrogen, low alkyl group or halogen; Z ¹Be vinyl, halogen or low alkyl group; And p is 0 to about 5.These polymkeric substance comprise homopolymer, vinylbenzene and one or more monomeric random copolymerss of being given an example by vinyl cyanide, divinyl, alpha-methyl styrene, vinyl xylene, ethyl vinyl benzene, Vinylstyrene and maleic anhydride of vinylbenzene, chloro-styrene and Vinyl toluene, and comprise blend and the polystyrene that connects the modified rubber of skill thing, wherein this rubber is the rubbery copolymer of polyhutadiene or about 98-70% vinylbenzene and about 2-30% diene monomers.Polystyrene can with polyphenylene oxide with any ratio mixing, and any this blend can contain and have an appointment 5 to about 95wt%, and the most frequent about 25 polystyrene that arrive 75wt%, based on this total polymer weight meter.

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

Wherein " a " is more than or equal to about 1, and ideal is more than or equal to about 10, and better be more than or equal to about 1000; And wherein V is hard-core tetravalence linking group, as long as this linking group does not hinder the synthetic of this polyimide or uses.Suitable linking group comprise (a) have about 5 to the replacement of about 50 carbon atoms or do not replace, saturated, unsaturated or aromatic monocyclic and many cyclic groups, (b) have 1 to the replacement of about 30 carbon atoms or not replacement, linearity or branching, saturated or unsaturated alkyl; Or its combination.Suitable replacement group and/or linking group include but not limited to ether, epoxy compounds, acid amides, ester and combination thereof.Preferred linking group includes but not limited to the tetravalence aromatic group of structural formula (XVII), for example:

Wherein W is a divalent moiety, be selected from-O-,-S-,-C (O)-,-SO ₂-,-SO-,-C _yH _2y-(y is 1 to 5 integer) with and halo derivatives, comprise the perfluoro alkylidene group, or the group of structural formula-O-Z-O-, wherein should-O-or should-two valence links of O-Z-O-group are positioned at 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position, and wherein Z includes, but are not limited to the divalent radical of structural formula (XVIII).

R in the structural formula (XVI) comprises and replacing or unsubstituted divalent organic base that for example (a) has about 6 aromatic hydrocarbyl and halo derivatives thereof to about 20 carbon atoms; (b) have about 2 straight or branched alkylidene groups to about 20 carbon atoms; (C) have about 3 to the ring alkylidene groups of about 20 carbon atoms, or (d) divalent radical of general formula (XIX).

Wherein Q comprises divalent moiety, be selected from-O-,-S-,-C (O)-,-SO ₂-,-SO-,-C _yH _2y-(y is 1 to 5 integer) with and halo derivatives, comprise perfluorinated alkylidene.

The preferred type of polyimide comprises polyamidoimide and polyetherimide, particularly the machinable polyetherimide of those fusions.

Preferred polyetherimide polymer comprises more than 1, typically about 10 to about 1000 or more a plurality of, and 10 structural units to about 500 structural formulas (XX) more preferably from about.

Wherein T is-group of O-or structural formula-O-Z-O-, wherein should-O-or should-two valence links of O-Z-O-group 3,3 ', 3,4 ', 4,3 ' or 4,4 ' position, and wherein Z includes, but are not limited to the divalent radical of the structural formula (XVIII) as above definition.

In one embodiment, this polyetherimide can be multipolymer, and it further contains the polyimide structures unit of structural formula (XXI) except that ether imide unit as mentioned above.

The definition of R such as front structure formula (XVI) and the M group that includes, but are not limited to structural formula (XXII) wherein.

This polyetherimide can be by comprising any method preparation of the aromatics two (ether acid acid anhydride) that makes structural formula (XXIII) and the organic diamine reaction of structural formula (XIV).

H ₂N-R-NH ₂ (XXIV)

Wherein T and R such as above structural formula (XVI) and (XX) described in the definition.

The illustrative example of the aromatics two of structural formula (XXIII) (ether acid acid anhydride) comprises 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dicarboxylic anhydrides of 2-; 4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride; 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride; 4,4 '-two (3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride; 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride; 2, two [4-(2, the 3-di carboxyl phenyloxy) phenyl] the propane dicarboxylic anhydrides of 2-; 4,4 '-two (2, the 3-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride; 4,4 '-two (2, the 3-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride; 4,4 '-two (2, the 3-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride; 4,4 '-two (2, the 3-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride; 4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenylbenzene-2,2-propane dicarboxylic anhydride; 4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) phenyl ether dicarboxylic anhydride; 4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) diphenyl sulfide dicarboxylic anhydride; 4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) benzophenone dicarboxylic anhydride and 4-(2, the 3-di carboxyl phenyloxy)-4 '-(3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride, and various mixture.

This two (ether acid acid anhydride) can be by making nitro substituted-phenyl dintrile and dihydric phenolic compounds the reaction product of metal-salt, hydrolysis in the presence of the bipolarity aprotic solvent, then dehydration preparation.The preferred type of the aromatics two (ether acid acid anhydride) that is comprised by above structural formula (XXIII) includes but not limited to that wherein T has structural formula (XXV)

And ehter bond for example preferably 3,3 ', 3,4 ', 4,3 ' or the compound of 4,4 ' position and composition thereof, and wherein Q such as above definition.

Any diamino compounds can be used to prepare this polyimide and/or polyetherimide.The example of suitable compound is an ethylene diamine, trimethylene diamine, the trimethylene diamines, diethylenetriamine, Triethylenetetramine (TETA), hexamethylene-diamine, the heptamethylene diamines, eight methylene diamine, nine methylene diamine, decamethylene diamine, 1,12-dodecane diamines, 1, the 18-octadecamethylene diamine, 3-methyl heptamethylene diamines, 4, the two methyl heptamethylene diamines of 4-, 4-methyl nine methylene diamine, 5-methyl nine methylene diamine, 2, the two methyl hexamethylene-diamines of 5-, 2, the two methyl heptamethylene diamines of 5-, 2, the two methyl trimethylene diamines of 2-, N-methyl-two (3-aminopropyl) amine, 3-methoxyl group hexamethylene-diamine, 1,2-two (the amino propoxy-of 3-) ethane, two (3-aminopropyl) sulfide, 1,4-cyclohexyl diamines, two (4-aminocyclohexyl) methane, mphenylenediamine, Ursol D, 2, the 4-diaminotoluene, 2, the 6-diaminotoluene, m-xylene diamine, the p dimethylamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamines, 5-methyl-4,6-diethyl-1,3-phenylene-diamines, p-diaminodiphenyl, 3,3 '-tolidine, 3,3 '-dimethoxy benzidine, 1, the 5-diaminonaphthalene, two (4-aminophenyl) methane, two-(2-chloro-4-amino-3,5-diethyl phenyl) methane, two (4-aminophenyl) propane, 2,4-two (b-amino-tertiary butyl) toluene, two (right-b-amino-tert-butyl-phenyl) ether, two (right-b-methyl-o-aminophenyl) benzene, two (the amino amyl group of right-the b-methyl-o-) benzene, 1,3-diamino-4-isopropyl benzene, two (4-aminophenyl) sulfide, two (4-aminophenyl) sulfone, two (4-aminophenyl) ether and 1, two (3-aminopropyl) tetramethyl disiloxanes of 3-.The mixture that also can have these compounds.Preferred diamino compounds is aromatic diamine, particularly mphenylenediamine and Ursol D and composition thereof.

In an exemplary, this polyetherimide resin comprises the structural unit of structural formula (XX), and wherein each R is to phenylene or metaphenylene or its mixture independently, and T is the divalent group of structural formula (XXVI).

Usually, reaction can be used solvent, and for example orthodichlorobenzene, meta-cresol/toluene etc. carry out, and between the diamines of the acid anhydrides of structural formula (XVIII) and structural formula (XIX), implements reaction with about 100 ℃ to about 250 ℃ temperature.In addition, this polyetherimide can pass through the aromatics two (ether acid acid anhydride) of structural formula (XVIII) and the diamines of structural formula (XIX), follows stirring to carry out the melt polymerization preparation by heating this mixture of raw material simultaneously to high temperature.Usually, melt polymerization uses about 200 ℃ to arrive about 400 ℃ temperature.Chain terminator and branching agent also can be used for this reaction.When using polyetherimide/polyimide copolymer, dicarboxylic anhydride, for example pyromellitic acid acid anhydride and this two (ether acid acid anhydride) are used in combination.This polyetherimide polymer can be chosen the prepared in reaction by aromatics two (ether acid acid anhydride) and organic diamine wantonly, and wherein this diamines exists with about 0.2 molar excess at the most in reaction mixture, and preferably less than about 0.2 molar excess.Under this condition, this polyetherimide resin has less than the sour titratable group of the every gram of about 15 microequivalents (μ eq/g), and preferably have less than the titratable group of about 10 μ eq/g acid, as adopting chloroformic solution with shown in the hydrobromic glacial acetic acid solution titration of 33 weight percents (wt%).The titratable group of acid substantially should be owing to the amine end groups in this polyetherimide resin.

Usually, useful polyetherimide has about 0.1 melting index to about 10 grams per minutes (g/min), as by ASTM (American society for testing materials) (ASTM) D1238, uses 6.6 kilograms of (kg) weight determinatioies down at 295 ℃.In a kind of exemplary, this polyetherimide resin has about 10,000 weight-average molecular weight (Mw) to about 150,000 grams every mole (g/mol), as by gel permeation chromatography, uses polystyrene standards to measure.This polyetherimide polymer typically has the limiting viscosity greater than about 0.2 deciliter of every gram (dl/g), and is preferably about 0.35 to about 0.7dl/g, measures in 25 ℃ of following meta-cresols.

In another embodiment, polymeric amide can be as the organic polymer in the said composition.Polymeric amide is usually derived from the polymerization of the organic lactan with 4 to 12 carbon atoms.Exemplary lactan is represented by structural formula (XXVII).

Wherein n is about 3 to about 11.Highly preferred lactan is the ε-Ji Neixianan that n equals 5.

Polymeric amide also can be synthetic by the amino acid with 4 to 12 carbon atoms.Preferred amino acid is represented by structural formula (XXVIII).

Wherein n is about 3 to about 11.Highly preferred amino acid is the epsilon-amino caproic acid that n equals 5.

Polymeric amide also can be by aliphatic dicarboxylic acid with 4 to 12 carbon atoms and the aliphatie diamine polymerization with 2 to 12 carbon atoms.

Suitable and preferred aliphatic dicarboxylic acid is identical with above-mentioned those aliphatic dicarboxylic acids that are used for synthesizing polyester.Exemplary aliphatie diamine is represented by structural formula (XXIX)

H ₂N-(CH ₂) _n-NH ₂ (XXIX)

Wherein n is about 2 to about 12.Highly preferred aliphatie diamine is hexanediamine (H ₂N (CH ₂) ₆NH ₂).Preferably the mol ratio of dicarboxylic acid and diamines is about 0.66 to about 1.5.In this scope, it is desirable to usually have more than or equal to about 0.81, be preferably greater than or equal about 0.96 mol ratio.In this scope, it is desirable to quantity equally and be less than or equal to approximately 1.22, preferably be less than or equal to about 1.04.Preferred polymeric amide is nylon 6, nylon 6,6, nylon 4,6, nylon 6,12, nylon 10 etc., or comprises at least a combination of above-mentioned nylon.

The synthetic of polymeric amide fat can also be finished by aliphatic lactone with 4 to 12 carbon atoms and the aliphatics lactan with 4 to 12 carbon atoms.This aliphatic lactone is with to be used for above-mentioned those aliphatic lactones of polyester synthetic identical, and this aliphatics lactan is with to be used for above-mentioned those aliphatics lactan of polymeric amide synthetic identical.Aliphatic lactone can change to a great extent to the ratio of aliphatics lactan, and it depends on the required composition of final copolymer, and the relative response speed of this lactone and this lactan.The at present preferred initial molar ratio of aliphatics lactan and aliphatic lactone is about 0.5 to about 4.In this scope, it is desirable to mol ratio more than or equal to about 1.It is desirable to mol ratio equally and be less than or equal to about 2.

Said composition may further include catalyzer or initiator.Usually, be applicable to that any known catalysts of corresponding thermopolymerization or initiator can use.In addition, this polymerization can be implemented under the situation that does not have catalyzer or initiator.For example, in by aliphatic dicarboxylic acid and aliphatie diamine synthesizing polyamides, do not need catalyzer.

For by the lactan synthesizing polyamides, appropriate catalyst comprise water and be used for the corresponding omega-amino acid of this synthetic open loop (hydrolysis) lactan.Other appropriate catalyst comprises metallic aluminium alkylate (MAl (OR) ₃H; Wherein M is basic metal or alkaline-earth metal, and R is C ₁-C ₁₂Alkyl), two (2-methoxy ethoxy) sodium aluminates of dihydro, two (tert.-butoxy) lithium aluminates of dihydro, al-alkyl compound (Al (OR) ₂R; Wherein R is C ₁-C ₁₂Alkyl), the magnesium chloride of N-sodium caprolactam(ate), ε-Ji Neixianan or bromination magnesium salts (MgXC ₆H ₁₀NO, X=Br or Cl), the dialkoxy alanate.Suitable initiator comprises the two hexanolactams of isophthaloyl, N-acetal hexanolactam, isocyanic ester ε-Ji Neixianan adducts, alcohol (ROH; Wherein R is C ₁-C ₁₂Alkyl), glycol (HO-R-OH; Wherein R is C ₁-C ₁₂Alkylidene group), omega-amino-caproic acid and sodium methylate.

For by lactone and lactan synthesizing polyamides fat, appropriate catalyst comprises metal hydride compound, and for example structural formula is LiAl (H) _x(R ¹) _yThe lithium aluminium hydride catalyzer, wherein x is about 1 to about 4, y is about 0 to about 3, x+y equals 4, and R ¹Be selected from C ₁-C ₁₂Alkyl and C ₁-C ₁₂Alkoxyl group; Highly preferred catalyzer comprises LiAl (H) (OR ²) ₃, R wherein ²Be selected from C ₁-C ₈Alkyl; Particularly preferred catalyzer is LiAl (H) (OC (CH ₃) ₃) ₃Other appropriate catalyst and initiator comprise and are used to gather (ε-Ji Neixianan) and gather above-mentioned those catalyzer of (6-caprolactone) polymeric and initiator.

The preferred type of polymeric amide is the reaction person of obtaining by first polymeric amide and polymer materials, and described polymer materials is selected from second polymeric amide, poly-(arylene ether), poly-(alkenyl aromatic) homopolymer, modified rubber poly-(alkenyl aromatic) resin, acrylonitrile-butadiene-styrene (ABS) (ABS) graft copolymer, segmented copolymer and comprises above-mentioned two or more combination.This first polymeric amide comprises the repeating unit of structural formula (XXX):

R wherein ¹Be branching or nonbranched alkyl with nine carbon.R ¹Be preferably 1,9-nonane and/or 2-methyl isophthalic acid, 8-octane.Polyamide resin is characterised in that the amide group (C (O) NH-) that has the condensation product that belongs to carboxylic acid and amine.This first polymeric amide comprises the prepared in reaction of the diamines and the terephthalic acid (1,4-dicarboxyl benzene) of nine carbon moieties usually by one or more.When using more than a kind of diamines, the ratio of this diamines may influence some physicalies of the polymkeric substance that obtains, for example melt temperature.Diamines is generally equimolar to the ratio of dicarboxylic acid, but can excessive one or another kind of usefulness decide terminal functionality.In addition, this reaction monoamine and monocarboxylic acid of may further include as chain terminator and determining terminal functionality at least to a certain extent.In some embodiments, preferably have more than or equal to about 30meq/g, and more preferably greater than or equal the amine end groups content of about 40meq/g.

This 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 aromatic group or branching with four to seven carbon or nonbranched alkyl with six carbon.R ²Preferably be 1 in structural formula XXXI, the 6-hexane is 1 in structural formula XXXII, the 5-pentane.R ³Be preferably 1, the 4-butane.

This first polymeric amide is compared with other polymeric amide, has better dimensional stability, thermotolerance, moisture-resistant gas absorptivity, wear resistance and chemical resistant properties.Therefore, when with analogous composition when contrast of containing other polymeric amide that replaces this first polymeric amide, comprise these identical performances of improving of composition exhibiting of first polymeric amide.In some embodiments, the combination of this first and second polymeric amide improved in the heterogeneous compositions polymeric amide with other mutually, for example the consistency of poly-(arylene ether) has been improved shock resistance thus.Bound by theory not it is believed that this second polymeric amide has improved the amount of available terminal amino group.In some cases, this terminal amino group can with other mutually component reaction or functionalised with other phase reaction, improve consistency thus.

This organic polymer exists with about 5 amounts to about 99.999 weight percents (wt%) in composition usually.In this scope, it is desirable to usually with about 10wt% more than or equal to composition total weight, be preferably greater than or equal about 30wt%, and more preferably greater than or the amount that equals about 50wt% use organic polymer or blend polymer.Organic polymer or blend polymer usually to be less than or equal to about 99.99wt% of composition total weight, preferably are less than or equal to about 99.5wt% in addition, are more preferably less than or equal the amount use of about 99.3wt%.

The SWNT that is used for composition can produce by the laser synthetic or high pressure carbon monoxide conversion process (HIPCO) of graphite, carbon arc that volatilizees.These SWNT have the single wall that comprises graphite flake usually, have about 0.7 outside diameter to about 2.4 nanometers (nm).In composition, usually use aspect ratio more than or equal to about 5, be preferably greater than or equal about 100, more preferably greater than or equal about 1000 SWNT.When SWNT is generally when each terminal of respective tube has the enclosed construction of semisphere cap, what it is contemplated that is also to use the SWNT with single opening end or two opening ends.SWNT generally includes centre portions, and it is a hollow, but can be full of amorphous carbon.

In an exemplary, disperseing the purpose of SWNT in organic polymer is to make the SWNT disentanglement, so that obtain as far as possible the effective aspect ratio near the SWNT aspect ratio.Effectively aspect ratio is to ratio the measuring for dispersion validity of aspect ratio.Effectively aspect ratio is the twice of single SWNT rotation radius divided by the value of corresponding each nanotube outside diameter.Usually it is desirable to effective aspect ratio to the mean value of the ratio of aspect ratio more than or equal to about 0.5, be preferably greater than or equal about 0.75, and more preferably greater than or equal about 0.90, as what measure in more than or equal to about 10,000 electron photomicrograph in magnification.

In one embodiment, SWNT can exist with the form of rope form aggregate.These aggregates so-called " rope " and form as the result of the Van der Waals force between each SWNT.Each nanotube in the rope can slide relative to one another and self reset in rope, so that free energy minimizes.Usually have 10 to 10 ⁵The rope of individual nanotube can be used for said composition.In this scope, it is desirable to rope usually and have more than or equal to about 100, be preferably greater than or equal about 500 nanotubes.It is desirable to equally restricts to have is less than or equal to about 10 ⁴Individual nanotube preferably is less than or equal to about 5,000 nanotubes.

In another embodiment, it is desirable to the SWNT rope is connected to each other with branch's form after disperseing.This causes sharing the rope between the SWNT network branches, to form three-dimensional network in organic polymer matrix.About 10 nanometers can be separated tapping point to about 10 microns distance in this network type.Usually it is desirable to the intrinsic thermal conductivity that SWNT has at least 2000 watts every meter Kelvin (W/m-K), and the SWNT rope has 10 ⁴The intrinsic conductivity of Siemens/cm (S/cm).Usually it is desirable to equally that this SWNT has the tensile strength of at least 80 gigapascals (GPa) and at least about 0.5 pascal's (TPa) stiffness too.

In another embodiment, SWNT can comprise the mixture of metal nano-tube and semiconducting nanotubes.Metal nano-tube is similar to the nanotube of the electrical characteristic of metal for those demonstrations, and semiconducting nanotubes is to be semi-conductive nanotube on those electricity.Usually the mode of rolling graphite flake produces the nanotube of various spirane structures.Two kinds that can also confirm have zig-zag and armchair shape nanotube.For the quantity that makes the SWNT that uses in the composition minimizes, it is desirable to the metal SWNT that composition comprises major part usually.Usually the SWNT that it is desirable to be used for composition comprises that quantity accounts for the SWNT gross weight more than or equal to about 1wt%, be preferably greater than or equal about 20wt%, more preferably greater than or equal about 30wt%, more preferably greater than or equal about 50wt%, and most preferably more than or equal to the metal nano-tube of about 99.9wt%.In some cases, usually the SWNT that it is desirable to be used for composition comprises and accounts for the SWNT gross weight more than or equal to about 1wt%, be preferably greater than or equal about 20wt%, more preferably greater than or equal about 30wt%, more preferably greater than or equal about 50wt%, and most preferably more than or equal to the semiconducting nanotubes of about 99.9wt%.

When needing, SWNT arrives the amount use of about 80wt% usually with about 0.001 of composition total weight.In this scope, SWNT is usually with more than or equal to the about 0.25wt% of composition total weight, be preferably greater than or equal about 0.5wt%, more preferably greater than or the amount that equals about 1wt% use.SWNT to be less than or equal to the about 30wt% of composition total weight, preferably is less than or equal to about 10wt% usually in addition, is more preferably less than or equals the amount use of about 5wt%.

In one embodiment, SWNT can contain production and relate to impurity.The production that exists among the SWNT relates to impurity and be defined herein as the impurity that those produce in relevant with SWNT production basically technological process.As mentioned above, SWNT is for example producing in the technologies such as laser ablation, chemical vapor deposition, carbon arc, high pressure carbon monoxide conversion method.Production relates to impurity for produce those impurity that form naturally or have a mind to form in the SWNT process in above-mentioned technology or similar manufacturing process.Naturally to relate to the suitable example of impurity be the granules of catalyst that is used to produce SWNT in the production of Xing Chenging.The suitable example that the production that have a mind to form relates to impurity is for by having a mind to add the dangling bonds that the small amounts agent forms on the SWNT surface in process for making.

Production relates to impurity and comprises for example carbon containing byproduct of reaction, for example inferior SWNT, multi-walled carbon nano-tubes, branching or curling multi-walled carbon nano-tubes, decolorizing carbon, cigarette ash, nanometer green onion ball (nona-onion), nanometer angle (nanohorns), coke etc.; From the catalyst residue of the catalyzer that uses in the production process, for example metal, metal oxide, metallic carbide, metal nitride etc., or comprise at least a combination of above-mentioned byproduct of reaction.A kind of relevant with carbon nanotube production basically technology is for when comparing with any other mark that production relates to impurity, wherein the bigger technology of SWNT mark.In order to make technology relevant with SWNT production basically, the SWNT mark must be greater than any mark of byproduct of reaction listed above or catalyst residue.For example, the SWNT mark must be greater than many walls nanotube mark or cigarette ash mark or carbon black mark.The SWNT mark needn't relate to the mark summation of any combination of impurity greater than the production of thinking to relate to basically this technology that SWNT produces.

Production relates to impurity and comprises for example carbon containing byproduct of reaction, for example inferior SWNT, multi-walled carbon nano-tubes, branching or curling multi-walled carbon nano-tubes, amorphous carbon, carbon black, nanometer green onion ball, nanometer angle, coke etc.; From the catalysis residue of the catalyzer that uses in the production process, for example metal, metal oxide, metallic carbide, metal nitride etc., or comprise at least a combination of above-mentioned byproduct of reaction.A kind ofly produce relevant technology for when comparing with SWNT basically, wherein the more technology of SWNT mark with any other mark that production relates to impurity.In order to be used for producing relevant technology with SWNT basically, the SWNT mark must be greater than any mark of byproduct of reaction listed above or catalysis residue.For example, the SWNT mark must be greater than many walls nanotube mark or cigarette ash mark or carbon black mark.The SWNT mark will needn't think that the production of this relevant with SWNT production substantially technology relates to the mark summation of any combination of impurity greater than being used to.

Usually, the SWNT that is used for composition can comprise that quantity is about 0.1 to about 80wt% impurity.In this scope, SWNT can have more than or equal to the about 3wt% of SWNT gross weight, be preferably greater than or equal about 7wt%, and more preferably greater than or equal the foreign matter content of about 8wt%.In this scope, it is desirable to about 50wt% that foreign matter content is less than or equal to the SWNT gross weight equally, preferably be less than or equal to about 45wt%, and be more preferably less than or equal about 40wt%.

In one embodiment, the SWNT that is used for composition can comprise that quantity is about 0.1 to about 50wt% catalysis residue.In this scope, SWNT can have more than or equal to the about 3wt% of SWNT gross weight, be preferably greater than or equal about 7wt%, and more preferably greater than or equal about 8wt% the catalysis residue.In this scope, it is desirable to about 50wt% that the catalysis residuals content is less than or equal to the SWNT gross weight equally, preferably be less than or equal to about 45wt%, and be more preferably less than or equal about 40wt%.

During the polymerization precursor polymeric, also other carbon nanotube of for example multi-walled carbon nano-tubes (MWNT) and VGCF can be joined in the composition.Do not think that the MWNT and the VGCF that join in the composition are impurity, because they do not produce in the SWNT production process.Also can be used for composition derived from the MWNT that does not relate to SWNT production such as laser ablation and carbon arc synthesis technique.MWNT has at least two graphite linings that connect around the inner hollow core.The semisphere cap seals the two ends of MWNT usually, but it is desirable to use the MWNT that only has a semisphere cap or do not have the MWNT of two caps.MWNT has about 2 to about 50nm diameter usually.In this scope, it is about 40 to it is desirable to use diameter to be less than or equal to usually, preferably be less than or equal to about 30, and the MWNT that is more preferably less than or equals about 20nm.When using MWNT, preferably have more than or equal to about 5, be preferably greater than or equal about 100, more preferably greater than or equal about 1000 average aspect ratio.

When needing, MWNT arrives the amount use of about 50wt% usually with about 0.001 of composition total weight.In this scope, MWNT is usually with more than or equal to the about 0.25wt% of composition total weight, be preferably greater than or equal about 0.5wt%, more preferably greater than or the amount that equals about 1wt% use.MWNT to be less than or equal to the about 30wt% of composition total weight, preferably is less than or equal to about 10wt% usually in addition, is more preferably less than or equals the amount use of about 5wt%.

Other electroconductive stuffing, for example vapor-grown carbon fibers, carbon black, conductive metal filler, solid-state nonmetal electroconductive stuffing etc., or comprise that above-mentioned at least a combination can be chosen wantonly and be used for said composition.Also can use diameter for about 3.5 to about 2000 nanometers (nm) and aspect ratio more than or equal to about 5 vapor-grown carbon fibers or small graphite or part celion, be also referred to as vapor-grown carbon fibers (VGCF).When using VGCF, preferred diameter is about 3.5 to about 500nm, and more preferably diameter is about 3.5 to about 100nm, and most preferred diameters is about 3.5 to about 50nm.Equally preferably have more than or equal to about 100 and more preferably greater than or equal about 1000 average aspect ratio.

When needing, VGCF arrives the amount use of about 50wt% usually with about 0.001 of composition total weight.In this scope, VGCF is usually with more than or equal to the about 0.25wt% of composition total weight, be preferably greater than or equal about 0.5wt%, more preferably greater than or the amount that equals about 1wt% use.VGCF to be less than or equal to the about 30wt% of composition total weight, preferably is less than or equal to about 10wt% usually in addition, is more preferably less than or equals the amount use of about 5wt%.

The SWNT that uses in the composition and other carbon nanotube can also be used functional group's derivatize, mix with organic polymer to improve consistency and promotion.SWNT and other carbon nanotube can or carry out functionalized on sidewall and semisphere end cap on the graphite flake that constitutes sidewall, semisphere cap.Functionalized SWNT and other carbon nanotube have the carbon nanotube of structural formula (XXXIII) for those

Wherein n is an integer, and L is the number less than 0.1n, and m is the number less than 0.5n, and wherein each R is all identical and be selected from-SO ₃H ,-NH ₂,-OH ,-C (OH) R ' ,-CHO ,-CN ,-C (O) Cl ,-C (O) SH ,-C (O) OR ' ,-SR ' ,-SiR ₃' ,-Si (OR ') _yR ' _(3-y),-R " ,-AlR ₂', halogenide, ethylenic unsaturated functional group, epoxy functionality etc., wherein y is equal to or less than 3 integer, and R ' is that hydrogen, alkyl, aryl, cycloalkyl, aralkyl, cyclophane base, poly-(alkyl oxide) etc. and R " are fluoroalkyl, fluoro aryl, fluorine cycloalkyl, fluorine aralkyl, cyclophane base etc.Carbon atom C _nSurface carbon for carbon nanotube.In the SWNT and other carbon nanotube of all even inhomogeneous replacements, surface atom C _nReact.

The SWNT of non-homogeneous replacement and other carbon nanotube also can be used for composition.These comprise above shown in the composition of structural formula (I), wherein n, L, m, R and carbon nanotube as above define itself, condition is the equal oxygen-free of each R, if perhaps each R is an oxy radical, does not have COOH so.

Also comprise SWNT and other functionalized carbon nanotubes with structural formula (XXXIV):

Wherein n, L, m, R ' and R have identical meanings as above.Most of carbon atoms in the carbon nano tube surface layer are basal plane carbon.Basal plane carbon is relative inertness for chemical erosion.At defective locations, for example wherein graphite plane can not fully be expanded around carbon nanotube, exists and the similar carbon atom of graphite plane edge carbon atom.This edge carbon be reactive behavior and must contain some and make saturated heteroatoms of carbon atom valency or group.

The SWNT of above-mentioned replacement and other carbon nanotube can be easily by further functionalized.These compositions comprise the composition of structural formula (XXXV):

Wherein n, L and m as mentioned above, A is selected from-OY ,-NHY ,-CR ' ₂-OY ,-C (O) OY ,-C (O) NR ' Y ,-C (O) SY or-C (O) Y, wherein Y is an appropriate functional group, for example the transition state analog of albumen, peptide, enzyme, antibody, Nucleotide, oligonucleotide, antigen or enzyme substrates, enzyme inhibitors or enzyme substrates or be 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 ₂H ₄O) _wY ,-(C ₃H ₆O) _wH ,-(C ₂H ₄O) _wR ' ,-(C ₃H ₆O) _wR ' and R ", wherein w is greater than 1 and less than 200 integer.

The functionalized SWNT of structure (XXXIV) and other carbon nanotube also can functionalised the composition that has structural formula (XXXVI) with production:

Wherein n, L, m, R ' and A as above define.

Composition also comprises SWNT and other carbon nanotube of some ring compound of absorption on it.These comprise the composition of the material of structural formula (XXXVII):

Wherein n is an integer, and L is the number less than 0.1n, and m is less than 0.5n, and a is zero or less than 10 number, X be polynuclear aromatic family, many heteronuclears aromatic series or many heteronuclears of metal aromatic series part and R as previously discussed.Preferred ring compound is the big ring in plane, for example porphyrin (re porphyrin) and phthalocyanine.

The ring compound of this absorption can functionalised.This composition comprises the compound of structural formula (XXXVIII)

Wherein m, n, L, a, X and A as defined above and carbon on the SWNT or on other carbon nanotube such as MWNT, VGCF etc.

Be not limited to particular theory, functionalized SWNT and other carbon nanotube are better disperseed to advance in the organic polymer, because the surface properties of this modification can make this carbon nanotube become more compatible with this organic polymer, perhaps because functional group's (particularly hydroxyl or amido) of this modification is directly connected to this organic polymer as end group.In this way, organic polymer, for example polycarbonate, polymeric amide, polyester, polyetherimide etc. are directly connected to this carbon nanotube, make that thus this carbon nanotube is easier to disperse, and have the adhesivity that organic polymer is improved.

By contacting the time that one section of respective outer surfaces is enough to oxidation SWNT and other carbon nano tube surface with strong oxidizer, and further contacting this respective outer surfaces with the reactant that is suitable for functional group is added oxidized surface, functional group be directed on SWNT and other carbon nanotube outside surface usually.Preferred oxygenant is made up of the alkali metal chlorite solution in the strong acid.Preferred alkaline metal chlorate is sodium chlorate or Potcrate.A kind of applied exemplary strong acid is sulfuric acid.The for some time that is enough to oxidation is about 0.5 hour to about 24 hours.

Carbon black also can be chosen wantonly and be used for composition.Preferred carbon black is lower than about 200nm for those have, and preferably is lower than about 100nm, more preferably less than the carbon black of the mean particle size of about 50nm.Preferred conductive carbon black can also have greater than about 200 square metres of every gram (m ²/ g), be preferably greater than about 400m ²/ g is more preferably greater than about 1000m ²The surface-area of/g.Preferred conductive carbon black can have greater than about 40 cubic centimetres of every hectogram (cm ³/ 100g), be preferably greater than about 100cm ³/ 100g is more preferably greater than about 150cm ³The pore volume of/100g (dibutyl phthalate absorption).Exemplary carbon black comprises and is purchased the Chemicals from Columbian that trade mark is Conductex ^Carbon black; Available from Chevron Chemical, trade mark is the Shawinigan black of S.C.F. (SuperConductive Furnace) and E.C.F. (Electric Conductive Furnace); Available from Cabot Corp., trade mark is the carbon black of Vulcan XC72 and Black Pearls; And being purchased Co.Ltd from Akzo, trade mark is the carbon black of Ketjen Black EC 300 and EC 600.Preferred conductive carbon black can use to the amount of about 25wt% with the about 2wt% based on composition total weight.

Solid-state conductive metal filler also can be chosen wantonly and be used for conductive composition.These can be for being used to be introduced into organic polymer and making under the condition of finished product not fused conductive metal or alloy from it.Metal, for example aluminium, copper, magnesium, chromium, tin, nickel, silver, iron, titanium and comprise that any mixture of above-mentioned metal can be introduced into organic polymer as electroconductive stuffing.Physical mixture and true alloy, for example stainless steel, bronze etc. also can be used as the electroconductive stuffing particle.In addition, some intermetallic compounds of these metals, for example boride, carbide etc. (for example TiB2) also can be used as the electroconductive stuffing particle.Solid-state nonmetal electroconductive stuffing particle, for example stannic oxide, tin indium oxide etc. also can be made this organic polymer conduction that becomes by optional the adding.This solid metal and nonmetal electroconductive stuffing can exist with the form of powder, wire drawing, line material, fiber, pipe, nanotube, thin slice, laminating material, flap, spheroid, disk and other commercially available geometry.

Its surface quite non-conductive non-metallic fillers that has been coated with the adhesion layer of solid-state conductive metal of major part also can be chosen wantonly and is used for conductive composition.This non-conductive non-metallic fillers is commonly referred to base material, and the base material that scribbles solid-state conductive metal layer can be called " metallizing filler ".Typical conductive metal, for example aluminium, copper, magnesium, chromium, tin, nickel, silver, iron, titanium and comprise that any mixture of above-mentioned metal can be used for being coated with this base material.The example of base material comprises that those are recorded in " Plastic Additives Handboot " (plastics additive handbook), and the 5th edition, Hans Zweifel compiles, Carl Hanser Verlag press, Munich, the base material in 2001.The example of this base material comprises SiO 2 powder, for example fused silica and crystalline silica, boron nitride powder, the borosilicate powder, aluminum oxide, magnesium oxide (or magnesia), wollastonite comprises the surface-treated wollastonite, and calcium sulfate is (with its acid anhydrides, the form of dihydrate or trihydrate), lime carbonate comprises chalk, Wingdale, marble and common to grind the synthetic precipitated chalk of particle form, talcum, comprise fibrous, cordwood, acicular and lamellated talcum, hollow and solid glass ball, kaolin comprises hard, soft, calcined kaolin and the kaolin that comprises the coating of various promotions known in the art and polymeric matrix consistency, mica, feldspar, silicate spheroid, cigarette ash, cenosphere, the inert silicate microballoon, silico-aluminate (armouring ball (armospheres)), natural quartzite, quartzy, quartzite, perlite, tripoli, diatomite, synthetic silica and comprise above-mentioned any mixture.Above-mentioned all base materials can be coated with the metal material layer that is used for conductive composition.

Do not consider solid metal and nonmetal electroconductive stuffing particulate accurate dimension, shape and composition, they can disperse in the organic polymer with about add-on of 0.001 to about 50wt% of composition total weight when needing.In this scope, it is desirable to usually have more than or equal to the about 1wt% of composition total weight, be preferably greater than or equal about 1.5wt% and more preferably greater than or equal solid metal and the nonmetal electroconductive stuffing particle of about 2wt%.Solid metal and nonmetal electroconductive stuffing particulate add-on can be less than or equal to the 40wt% of composition total weight, preferably are less than or equal to about 30wt%, are more preferably less than or equal about 25wt%.

In one embodiment, in the preparation method for compositions, the polymer precursor of monomer, oligopolymer or polymer form is added in the reaction vessel.The suitable example of reaction vessel is pot, thin-film evaporator, list or multiple screw extruder, this kneader of cloth, Han Xieer mixing machine, helicones, Ross mixing machine, Banbury mixer, roller refining machine, mold apparatus, for example injection moulding machine, vacuum forming machine, blow moulding machine etc., or comprise at least a combination of aforesaid device.Between the polymer precursor polymerization period, the conductive composition that comprises SWNT and optional other carbon nanotube and electroconductive stuffing can be joined in the reaction vessel then.

In the embodiment, can before the polymer precursor polymerization, SWNT be added reaction vessel.The polymerization of polymer precursor can be carried out in solvent, or carries out with melt form in the presence of the solvent not having if desired.In another embodiment, can between the polymer precursor polymerization period, SWNT be added reaction vessel.In another embodiment, can before the polymer precursor polymerization, SWNT be added reaction vessel, and can after the polymerization other electroconductibility and non-conductive filler be added reaction vessel fully basically at organic precursor.In another embodiment, reaction vessel can contain a high proportion of SWNT and other electroconductibility and non-conductive filler in polymerization technique initial stage process, so that regulate the viscosity of reacting in the container, with effective promotion SWNT and other filler disentanglement.After one section required time of stirring reaction solution, in reaction vessel, add other polymer precursor to continue polymerization process.

In one embodiment, SWNT and other electroconductibility and non-conductive filler can add reaction vessel with master batch form.In the embodiment of another relevant use masterbatch, first masterbatch that comprises SWNT added in the reaction vessel in the very first time, and comprised that second masterbatch of other non-conductive filler can add reaction vessel in second time in the polymer precursor polymerization technique process.

As mentioned above, said composition can be with melt or to comprise the solution form manufacturing of solvent.The frit reaction of composition comprises at least a combination of using shearing force, drawing force, pressure, ultrasonic energy, electromagnetic energy, heat energy or comprising above-mentioned power or form of 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 sieve screw rod is arranged, have pin machine barrel, roller, percussion hammer, helical rotor, retaining to pull or comprises that above-mentioned at least a combination applies above-mentioned power.

In one embodiment, can use ultrasonic energy to disperse SWNT.Polymer precursor and SWNT and other optional electroconductibility or non-conductive filler at first carry out sonication to disperse SWNT in ultra-sonic generator.After sonic treatment, make the polymer precursor polymerization.If desired, can during polymerization technique, proceed ultrasonication.Ultrasonic energy can be applied to wherein can carry out polymeric different reactor, for example pot, forcing machine etc.

The frit reaction that relates to above-mentioned power can be carried out in following equipment, such as but not limited to list or multiple screw extruder, this kneader of cloth, Han Xieer mixing machine, helicones, Ross mixing machine, Banbury mixer, roller refining machine, mold apparatus, for example injection moulding machine, vacuum forming machine, blow moulding machine etc., or comprise at least a combination of aforesaid device.Solution reaction carries out in the container of for example pot usually.

In one embodiment, be admitted to reactor, for example before this kneader of forcing machine or cloth, the polymer precursor of Powdered, particulate state, sheet etc. can at first be done in Han Xieer mixing machine or roller refining machine with SWNT and other optional filler if desired and mix.Though the shearing force that it is desirable to usually in this reactor causes that usually the SWNT in the polymer precursor disperses, and wishes to keep the aspect ratio of SWNT equally in reaction process.In order to accomplish this point, may it is desirable to SWNT is introduced reactor with the form of masterbatch.In this technology, this masterbatch can be introduced into reactor in the polymer precursor downstream.

Masterbatch can include organic polymer or polymer precursor and SWNT.When using masterbatch, SWNT can be present in the masterbatch with about amount of 0.01 to about 50wt%.In this scope, it is desirable to usually use more than or equal to the about 0.1wt% of masterbatch gross weight, be preferably greater than or equal about 0.2wt%, more preferably greater than or equal the SWNT of about 0.5wt%.The amount that it is desirable to SWNT equally is less than or equal to about 30wt% of masterbatch gross weight, preferably is less than or equal to about 10wt%, is more preferably less than or equals about 5wt%.Relate in the embodiment of using masterbatch at one, though when extruding with line material form or being molded as dumbbell shape, the masterbatch that contains SWNT may not have integral body or the surface resistivity that can survey, but the composition of wherein introducing masterbatch that obtains has integral body or the surface resistivity that can survey, even the weight fraction of SWNT is lower than the weight fraction of SWNT in the masterbatch in the composition.Preferably organic polymer is hemicrystalline in this masterbatch.The example that shows these characteristics and can be used for the hypocrystalline organic polymer of masterbatch is polypropylene, polymeric amide, polyester etc., or comprises at least a combination of above-mentioned hypocrystalline organic polymer.

If desired, said composition also can be used as masterbatch.When said composition was used as masterbatch, SWNT can be present in the masterbatch with about amount of 0.01 to about 50wt%.In this scope, it is desirable to usually use more than or equal to the about 0.1wt% of masterbatch gross weight, be preferably greater than or equal about 0.2wt%, more preferably greater than or equal the SWNT of about 0.5wt%.The amount that it is desirable to SWNT equally is less than or equal to about 30wt% of masterbatch gross weight, preferably is less than or equal to about 10wt%, is more preferably less than or equals about 5wt%.

Relate in manufacturing at another and to include in the embodiment of using masterbatch in the composition of organic polymer blend, often it is desirable to have the masterbatch that comprises with derived from the identical organic polymer of polymer precursor polymeric organic polymer.This feature allows to use the SWNT of remarkable smaller scale, because only the external phase of organic polymer has SWNT, provides required volume specific resistance of said composition and surface resistivity.Relate in the embodiment of in polymeric blend, using masterbatch at another, may it is desirable to have the masterbatch of organic polymers different on the chemical property of being included in other polymkeric substance that is used for said composition.In this case, the organic polymer of this masterbatch will form external phase in blend.In another embodiment, may it is desirable to use independently masterbatch, it comprises many walls nanotube, vapor-grown carbon fibers, carbon black, conductive metal filler, solid-state nonmetal electroconductive stuffing etc., or comprises combination at least a in the above-mentioned composition.

If desired, the composition that includes organic polymer and SWNT can carry out repeatedly blend and forming step.For example, particle can at first be extruded and be shaped to said composition.This particle can be admitted to mold apparatus then, and it can be shaped to desired shape there, for example counter body, can static the car panel etc. of paint.In addition, sheet material or line material be can be formed as, and back technology, for example annealing, single shaft or diaxial orientation extruded from the effusive conductive composition of independent melt blending device.

In one embodiment, the organic polymer precursor can be at first with SWNT at reactor, for example mix in the pot, and polymerization in the equipment of the combination of between polymerization period, using shearing, stretching and/or extending force subsequently.Carry out the polymeric suitable equipment for those 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 arranged, the sieve screw rod is arranged, have pin machine barrel, roller, percussion hammer, helical rotor, retaining to pull or comprise the equipment of above-mentioned at least a combination.

Solution blending also can be used to prepare said composition.Solution blending can use auxiliary energy equally, for example shears, compression, ultrasonic vibration etc., promotes homogenizing of SWNT and organic polymer.In one embodiment, polymer precursor can be introduced into ultrasonic generator with SWNT.This mixture can be before polymer precursor be synthetic or during, carry out solution blending by one period that SWNT is distributed on the organic polymer particles effectively of ultrasonication.If desired, then organic polymer can be dry with SWNT, extrude and molding.

Can choose wantonly along with SWNT and organic polymer precursor are introduced into ultrasonic generator such as the fluid of solvent.The time cycle of ultrasonication is generally the amount that effective promotion SWNT is disperseed and/or seals by the organic polymer precursor.After sealing, organic polymer precursor polymerization then forms the organic polymer that wherein is dispersed with SWNT.This maintenance that disperses the method promotion SWNT aspect ratio of SWNT in organic polymer, therefore it make said composition improve electric conductivity with lower SWNT add-on.

Usually, it is desirable to the mixture ultrasonication of organic polymer, organic polymer precursor, fluid and/or SWNT about 1 minute to about 24 hours.In this scope, it is desirable to the mixture ultrasonication more than or equal to about 5 minutes, be preferably greater than or equal about 10 minutes, and more preferably greater than or equal about 15 minutes.It is desirable to the time cycle in this scope equally is less than or equal to about 15 hours, preferably is less than or equal to about 10 hours, and is more preferably less than or equals about 5 hours.

Relate to dispersion at one and have in the embodiment of producing the SWNT that relates to impurity, compare, have higher impurity fractional SWNT composition and can use less energy to disperse with having low impurity fractional SWNT composition.Bound by theory not it is believed that in some organic polymer, and impurity interacts and promotes reducing of Van der Waals force, promotes the easier dispersion of nanotube in the organic polymer thus.

Relate to dispersion at another and have in the embodiment of producing the SWNT that relates to impurity, have low impurity fractional composition with those and compare, having higher impurity fractional SWNT composition may need bigger combined amount.But, have the composition that hangs down impurity fractional SWNT and when additional the mixing, lose electroconductibility usually, and have higher SWNT impurity fractional composition usually along with combined amount improves and raising electroconductibility.These compositions wherein needing can be used for flowability, impact and excellent electric conductivity equilibrated to use.They also can be used for wherein using conductive material and wherein conductive material have the application of extremely low-level electroconductive stuffing, for example fuel cell, electrostatic applications application etc.

Aforesaid composition can be used for multiple industrial application.They can need avoid the film of the electronic component of electrostatic dissipation easily as packing, described electronic component is computer, electronic product, semiconductor device, wiring board etc. for example.They also can innerly use in computer and other electronic product, and for personnel provide electromagnetic shielding with other electronics that is positioned at the computer outside, and protection inner computer element is avoided other external electromagnetic interference.They also can be used in the automotive body panels that is used for automotive interior and external component easily, and it can be painted by static if desired.

Following examples are intended to illustrative, and not restrictive, illustrate some preparation method of the various embodiments of composition described herein and this conductive composition.

Embodiment 1

Carry out present embodiment SWNT is dispersed in the polycarbonate (PC), and the masterbatch that in PC, forms SWNT.At first, will be dispersed in 120 milliliters of (ml) 1 available from 250 milligrams of (mg) SWNT of Carbon Nanotechnologies Incorporated, in the 2-ethylene dichloride by using the ultrasonication buzzer 30 minutes.This ultrasonic wave buzzer use the processor for ultrasonic wave that is in 80% amplitude (600 watts, the 13mm probe diameter is available from Sonics ﹠amp; MaterialsIncorporated).30gms carbonic acid two (methyl salicyl) ester (BMSC) and 20.3467gms dihydroxyphenyl propane (BPA) (BMSC mole/BPA mole=1.02) are joined among dispersion and the SWNT, again with this reaction mixture ultrasonication 30 minutes.Change the material of ultrasonication over to glass reactor, this reactor is at first by soaking 24 hours and passivation in the bath that contains 1 volumetric molar concentration aqueous hydrochloric acid, then with the abundant rinsing of deionized water.By in the presence of the flowing nitrogen in low pressure glass reactor being heated to 100 ℃ of dry solvents.Use the catalyst solution injecting reactor of syringe then with appropriate amount.The amount of catalyzer comprises every mole of BPA 4.5 * 10 ^-6NaOH and every mole of BPA (dihydroxyphenyl propane) 3.0 * 10 of mole ^-4The TBPA (tetrabutylphosphoniuacetate acetate ) of mole.

Use vacuum source to find time and with the air in the nitrogen purging reactor then.Repeat this circulation 3 times, afterwards the reactor content heating is made monomer mixture carbonic acid (two (methyl salicyl) ester (BMSC) and dihydroxyphenyl propane (BPA)) fusion.When mixture temperature reaches about 180 ℃, open the agitator in the reactor and be adjusted to about 60 rev/mins (rpm), to guarantee the complete fusion of entire solid matters, this process needs about 15 to about 20 minutes usually.Then reaction mixture is heated to about 220 ℃, uses vacuum source that the pressure in the reactor slowly is adjusted to about 100 millibars simultaneously.Under this condition after about 15 minutes of the stirring reaction material, temperature of reaction is elevated to about 280 ℃ of whiles again pressure is adjusted to about 20 millibars.After under this condition, keeping about 10 minutes, the temperature of reaction mixture is elevated to 300 ℃, makes pressure reduce to about 1.5 millibars simultaneously.Make reaction carry out about 2 under these conditions after about 5 minutes, make the pressure in the reactor reach normal atmosphere and, discharge any overpressure reactor emptying.Carry out the product separation by open glass tube joint and collection material at reactor bottom.Remove glass reactor and take out residual polymer from reaction tubes.

For determining molecular weight, the polycarbonate that obtains is dissolved in methylene dichloride, then from methyl alcohol redeposition polymkeric substance.Measure polymericular weight by gel permeation chromatography with respect to polystyrene standard.Weight-average molecular weight is 55756g/mole, and number-average molecular weight is 23,938g/mole, and polydispersity index is 2.32.

Embodiment 2

Carrying out present embodiment makes SWNT be dispersed in PCCD (in poly-(1,4-hexanaphthene-dimethanol-1,4 cyclohexanedicarboxylic acid ester) polymkeric substance and form the masterbatch of SWNT in PCCD.This PCCD polymkeric substance is synthetic by carry out melt phase polycondensation in the presence of the SWNT available from Carbon Nanotechnologies Incorporated.By with SWNT and 1,4-dimethyl cyclohexane dicarboxylic acid esters (14.01gm, 0.07 mole) (DMCD), 1,4-cyclohexanedimethanol (10.09gm, 0.07 mole) (CHDM) and 1,2-ethylene dichloride (50mL) under high-speed stirring, be mixed with the SWNT slip (0.24gm, 1wt%).Change this slip over to glass reaction tube.This reaction tubes is assembled on the melt polycondensation reaction device, the mechanical stirrer that this reactor is equipped with side arm, is driven by top formula stirring motor, and side arm has stopcock.Side arm is used to purge nitrogen and is used to apply vacuum.At first, reaction tubes is heated eliminating 1,2-ethylene dichloride, and cool to room temperature under nitrogen.Find time and with the content in the nitrogen purging reactor three times, to get rid of any trace oxygen.With this reactor of nitrogen purging and make it reach normal atmosphere, and follow constant agitation (100rpm) that the content of reaction mixture is heated to 200 ℃.Add different third titanium oxide (IV) of 400 parts of per 1,000,000 (ppm) via side arm, and transesterification reaction follows the methyl alcohol distillation to carry out, in graduated cylinder (receptor), collect methyl alcohol via side arm as catalyzer.Make melt temperature be elevated to 250 ℃ and under nitrogen, stirred 1 hour.Carry out polycondensation by progressively the pressure in the reactor being reduced to 700,500,300,100,50,25 and 10 mmhg (mmHg) from 900mm Hg.At last, reactor is applied 0.5 to 0.1mbar perfect vacuum, and continued polyase 13 0 minute.After polymerization is finished, reach normal atmosphere by make the pressure in the reactor with nitrogen purging, and remove polymer composition from reaction tubes.Polymkeric substance is dissolved in methylene dichloride, service performance viscosimetry determining molecular weight.The soltion viscosity that is determined in phenol/tetrachloroethane (25 ℃ of lower volume ratios are 2: 3) solution is 0.58 deciliter/gram (dL/g), and it is corresponding to 50, the viscosity-average molecular weight of 000g/mole.

The masterbatch that makes in embodiment 1 and 2 preparation then and polymkeric substance the small test chamber mixes with molding forming machine in melt blending, with the add-on of minimizing SWNT.Line material from molding forming machine is ruptured under liquid nitrogen, and exposed ends is painted to carry out conductivity measurement with the conductive silver lacquer.Conductivity values is shown in the following table 1.

Table 1

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

From last table as seen, sample 2-4 is made by the PC masterbatch (sample 1) of embodiment 1, and sample 6-9 is made by the masterbatch (sample 5) of embodiment 2.Can be clear that from embodiment along with the SWNT level increases, resistivity reduces.Can see that in addition masterbatch can be advantageously used in disperseing SWNT in polymkeric substance.

Embodiment 3

Present embodiment is used for preparing at nylon 6 masterbatch of SWNT during polymerizing polyamide.In beaker, get the ε-Ji Neixianan of 24.8gm and be heated to 90 ℃.After the compound fusion, in ε-Ji Neixianan, add the SWNT (being purchased Incorporated) that 250 milligrams (mg) contain the 10wt% impurity of having an appointment from Carbon Nanotechnologies.Use be in 80% amplitude processor for ultrasonic wave (600 watts, the 13mm probe diameter is available from Sonics﹠amp; MaterialsIncorporated) at uniform temp with this mixture ultrasonication half an hour.Then the SWNT dispersion in the fusion ε-Ji Neixianan is changed over to reaction tubes and keep spending the night gelling (formation network) so that SWNT restricts.Add the 1.5gm hexosamine then in reactor, and following under the nitrogen of slow stirring, making caprolactam polymerization at 260 ℃ in 9 hours by ring-opening polymerization is nylon-6.

Embodiment 4

Carry out this experiment in PCCD, to prepare the SWNT matrix material by the in-situ polymerization that does not use solvent.In the present embodiment, the 1,4 cyclohexane dimethanol of 1,4 cyclohexanedicarboxylic acid ester, the 24.03gms of 17.29gm is mixed and be incorporated in 80 ℃ of following fusions.In beaker, add the SWNT (being purchased Incorporated) that 33mg contains the 10wt% impurity of having an appointment from CarbonNanotechnologies.Use be in 80% amplitude processor for ultrasonic wave (600 watts, 13mm probe diameter, Sonics ﹠amp; Materials Incorporated, U.S.) at uniform temp with mixture ultrasonication half an hour.Then the SWNT dispersion in the molten monomer mixture is changed over to reaction tubes and keep spending the night gelling (formation network) so that SWNT restricts.Use the method identical to make monomer polymerization be PCCD then with embodiment 2.

The PCCD matrix material that made the nylon 6 composite material of embodiment 3 reach 240 ℃ (fusing points that are higher than nylon 6) and embodiment 4 in one hour respectively a part of matrix material heating of above preparation reaches 230 ℃.Then with the slow cool to room temperature of matrix material, and measurement electric conductivity as shown in table 2.Similarly, the matrix material that makes embodiment 3 and 4 mixes with other polymer melt, and compacting mixes and molding forming machine by the small test chamber, forms the line material that is used for carrying out the conductivity measurement that described in detail as embodiment 2 subsequently.These results also are shown in table 4.

Table 4

Sample number	The final composition	Resistivity (kOhm-cm) (S.D. *)
			10	0.1wt%SWNT among the PCCD of embodiment 4	---
11	0.1wt% SWNT (annealing) among the PCCD of embodiment 4	10,030
			12	1wt%SWNT in the nylon 6 of embodiment 3	33(13)
13	1wt%SWNT (annealing) in the nylon 6 of embodiment 3	24(14)
			14	0.5wt%SWNT (melting mixing in the nylon 6; Sample 12 is as masterbatch)	14715(3986)
15	0.5wt%SWNT in the nylon 6 (melting mixing is also used sample 13 as masterbatch)	4075(2390)
			16	0.5wt%SWNT in the nylon 6 (melting mixing and annealing in mould)	702

^*S.D. represent that the numerical value in the bracket is standard deviation.

From above data as seen, compare with those annealed samples, the annealed sample shows excellent electric property.Annealing can make SWNT rope reset in polymeric matrix and improve the SWNT branched reunion/distribution of restricting, and forms long-range network form widely, and it causes the electric conductivity of matrix material higher conversely.

Although the present invention's reference example embodiment is described, those skilled in the art of the present technique are appreciated that and can do various changes without departing from the scope of the invention and can carry out Equivalent for its key element to substitute.In addition, under the prerequisite that does not break away from essential scope of the present invention, many improvement can be carried out so that particular case or material adapt to instruction of the present invention.Therefore, mean that the present invention is not limited to the disclosed particular of implementing best mode of the present invention as expection.

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.