CN100556962C

CN100556962C - By aromatic condensation is the polymer coated carbon nanotube

Info

Publication number: CN100556962C
Application number: CNB2004800025022A
Authority: CN
Inventors: 畳开真之; 桑原广明; 大森智; 松村俊一; 佐藤和彦; 本多劝
Original assignee: Teijin Ltd
Current assignee: Teijin Ltd
Priority date: 2003-01-20
Filing date: 2004-01-19
Publication date: 2009-11-04
Anticipated expiration: 2024-01-19
Also published as: CN1738872A

Abstract

The present invention relates to a kind of is polymer coated carbon nanotube and manufacture method thereof by aromatic condensation, described aromatic condensation is that polymer is 0.01～100 weight part with respect to 100 weight part carbon nanotubes, and for be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a.The invention still further relates to and comprise and be coated with 0.01～100 weight part carbon nanotube and 100 weight part aromatic condensations are that high molecular aromatic condensation is polymeric composition and their molding.

Description

By aromatic condensation is the polymer coated carbon nanotube

Technical field

The present invention relates to by aromatic condensation is polymer coated carbon nanotube, its manufacture method, the composition that contains it and molding thereof.

Background technology

Carbon nanotube by very little adding, can expect to improve greatly intensity, the spring rate that resin has because its structure has shown good intensity, spring rate in resin.But carbon nanotube is insoluble to resin and solvent, is difficult to be scattered in fully in resin and the solvent.

So the someone has inquired into and imported functional group or the dispersiveness of raising in solvent in carbon nanotube.For example, Science 280,1253 (1998) has reported and has utilized sulfuric acid etc. to import the carboxylic acid group in carbon nanotube.

Introduced among the Science 282,95 (1998) and utilized acid treatment to cut off carbon nanotube, import carboxylic acid after, utilize thionyl chloride carboxylic acid halides carboxylic acid and obtain etheride, and it is reacted with amine obtain aminoderivative.But aforesaid method uses halogenide such as thionyl chloride in reaction, and therefore contaminate environment not only, and the etheride reactive behavior that obtains is high to be to be difficult to separate obtaining by unsettled material.

In addition, as the report example of miniaturization carbon fiber, for example reported in the presence of nitric acid, sulfuric acid etc. among the Science 280,1253 (1998),, cut off and the miniaturization single-layer carbon nano-tube by heating or applying ultrasonic wave.Even by cut-out carbon nanotubes such as acid treatment, aggegation also can take place when handling carbon nanotube in separation such as utilization filtration, need further carry out dispersion treatment when using as the mixture with polymkeric substance.

As the example with the polymer overmold carbon fiber surface, the spy opens in flat 3-287821 number and reports the surface that coats superfine carbon fibrils with polyolefine such as polystyrene, polyethylene, polyacrylic acid, comes the wettability of improved surface.

Reported in the Te Kaiping 5-106163 communique carbodiimide reagent is being paid on carbon fiber surface, improved interface with thermoplastic resins such as polymeric amide, polycarbonate.

Summary of the invention

The object of the present invention is to provide by aromatic condensation is polymer coated carbon nanotube, its manufacture method, the composition that contains it and molding thereof.By being the polymer enveloped carbon nanometer tube with aromatic condensation, it is well-dispersed in resin and the solvent, can obtain the good composition of dispersiveness and orientation.

Embodiment

(for carbon nanotube)

Among the present invention, be the polymer coated carbon nanotube as being used for by aromatic condensation, mean diameter is below the 300nm, preferred 0.3～250nm, more preferably 0.3～200nm, further preferred 0.4～100nm.In fact being difficult to make diameter is the following carbon nanotube of 0.3nm, and that the above carbon nanotube dispersive of 300nm improves effect is little, is not preferred therefore.

In addition, as the preferred value of mean aspect ratio, the restriction of no maximum, but lower limit is preferably more than 5.0 more preferably more than 10.0, and further preferred more than 50.0.

Can obtain the mean diameter and the long-width ratio of carbon nanotube by the observation of electron microscope.For example, carry out TEM (transmission electron microscope) and measure, can directly measure the length of the diameter and the long axis direction of carbon nanotube by its image.In addition, can by for example with fibre axis abreast the TEM in staple fiber cross section (transmission electron microscope) measure to grasp the form of the carbon nanotube in the composition.

Preferred median size is 0.01～5 μ m, more preferably 0.5～3 μ m, further preferred 0.1～1.0 μ m.

Need to prove that median size can utilize known in the past size-grade distribution meter, particle size determination device to try to achieve.Measuring method can list light scattering method, laser diffractometry etc., but is not limited to this.

It is cylindric that being shaped as of carbon nanotube is rolled into graphite flake, and this cylinder can also can be multilayer for individual layer.And graphite flake can be laminated with cup-shaped.That is,, can enumerate preferred single layer carbon nanotube, multilayer carbon nanotube, capstan winch type carbon nanotube as carbon nanotube of the present invention.

These carbon nanotubes can be used known method manufacturing in the past, can list gas phase flow method, catalyst loading type gas phase flow method, laser cutting method, high pressure carbon monoxide method, arc discharge method etc., but be not limited thereto.

(pre-treatment of carbon nanotube)

When being the polymer enveloped carbon nanometer tube, preferably in advance carbon nanotube is implemented physical treatment and/or chemical treatment with aromatic condensation.

Chemically treated preferred example specifically can list, and uses the strong acid of pH0.01～2 to carry out surface treatment.Can obtain to have with carboxylic acid, hydroxyl by strong acid treatment is substituent carbon nanotube, can improve the affinity and the raising of solvent, fully aromatic polyamide dispersed.Strong acid as spendable pH0.01～2, can list for example nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, dichromic acid and their nitration mixture etc., wherein preferably use nitration mixture, dichromic acid and the vitriolic nitration mixture of nitric acid, sulfuric acid and nitric acid, the preferred especially high acid of working concentration.The preferred ratio of mixture of nitric acid and sulfuric acid is not particularly limited, and preferred nitric acid/sulfuric acid (weight ratio) is 10/1～1～10.Chemical treatment is preferably further handled in the presence of ultrasonic wave.

The preferred example of physical treatment can list, ball mill, ball mill, clarifixator, ultrasonication, powerful shearing treatment etc.Utilize physical treatments such as ball mill, clarifixator dispersing Nano carbon tubes in advance in solvent, be modulated into the carbon nanotube dispersion liquid, preferably use this dispersion liquid to use as carbon nanotube.

Physical treatment also can be for the dry type of not using solvent, with an organic solvent, the wet type of acid etc. any.Also further preferred also with physical treatment and ultrasonication.Solvent is also preferred also with the mixed solution of sulfuric acid nitric acid, the strong solvents of chemical oxidation ability such as mixed solution of sulfuric acid hydrogen peroxide.

(by the fully aromatic polyamide coated carbon nanotube)

Aromatic polyamide of the present invention be preferably comprise following formula (A) and (B),

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

Wherein, among above-mentioned general formula (A), (B), Ar ¹, Ar ²Represent alone that separately carbon number is 6～20 divalent aromatic base.

And satisfy the fully aromatic polyamide of following formula (1),

0.8≤a/b≤4/3 (1)

Wherein, a is the mole number of repeating unit of the aromatic diamine of formula (A) expression, and b is the mole number of repeating unit of the dicarboxylic acid of formula (B) expression.

Above-mentioned Ar ¹, Ar ²Represent alone that separately carbon number is 6～20 divalent aromatic base, specifically can enumerate metaphenylene, to phenylene, adjacent phenylene, 2,6-naphthylidene, 2,7-naphthylidene, 4,4 '-isopropylidene diphenylene, 4,4 '-biphenylene base, 4,4 '-diphenylene thioether group, 4,4 '-diphenylene sulfuryl, 4,4 '-diphenylene ketone group, 4,4 '-diphenylene ether, 3,4 '-diphenylene ether, an xylylene, terephthaldehyde's base, O-phthalic base etc.

In the hydrogen atom of these aromatic bases one or more are replaced by following groups respectively independently: halogen radicals such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; The aromatic base of carbon numbers such as phenyl 6～10.Need to prove that above-mentioned formula (A) and/or structural unit (B) also can be for comprising the multipolymer of the aromatic base more than 2 kinds.

Wherein, preferred Ar ¹For metaphenylene, to phenylene, 3,4 '-diphenylene ether, further preferably to phenylene or and use phenylene and 3,4 '-diphenylene ether, and use phenylene and 3, during 4 '-diphenylene ether, its mol ratio is preferably in 1: 0.8～1: 1.2 scope.

Ar ²Preferred metaphenylene, to phenylene, further preferably to phenylene.

That is,, specifically can list Ar as the preferred material that uses among the present invention ¹For to phenylene and/or 3,4 '-diphenylene ether, Ar ²Be fully aromatic polyamide to phenylene.Wherein, can list Ar ¹For to phenylene and 3,4 '-diphenylene ether, Ar ²Be multipolymer, its copolymerization ratio (Ar to phenylene ¹To phenylene and 3, the mol ratio of 4 '-diphenylene ether) be the fully aromatic polyamide in 1: 0.8～1: 1.2 the scope.

These fully aromatic polyamides can utilize solution polymerization process, interfacial polymerization, melt phase polycondensation etc. in the past known method make.The polymerization degree can be controlled by the ratio of aromatic diamine composition and aromatic dicarboxylic acid composition, molecular weight as the polymkeric substance that obtains, preferred 30 ℃ of concentration with 0.5g/100mL of measuring down are dissolved in the 98 weight % vitriol oils and intrinsic viscosity (inherent viscosity) the η inh of the solution that obtains is 0.05～20dL/g, more preferably between 1.0～10dL/g.

As by the manufacture method of fully aromatic polyamide coated carbon nanotube, preferably list following method: to satisfy the ratio of following formula (2) simultaneously

0.8≤c/d≤4/3 (2)

C is that aromatic diamine, the d of following formula (H) expression is the aromatic dicarboxylic acid diaryl of following formula (J) expression or the mole number of respectively feeding of aromatic dicarboxylic acid two etherides that following formula (K) is represented,

The aromatic dicarboxylic acid diaryl of at least a and following formula (J) expression of the aromatic diamine of the following formula of feeding (H) expression or aromatic dicarboxylic acid two etherides of following formula (K) expression at least a,

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

X ¹OC-Ar ²-COX ² (K)

R ⁹, R ¹⁰The aromatic base of representing carbon number 6～20 independently of one another, Ar ¹, Ar ²The divalence aromatic base of representing carbon number 6～20 independently of one another, X ¹, X ²The expression halogen,

And then add carbon nanotube (N) and react, then with the reactants dissolved that obtains in organic solvent or acid solvent, filter, separate and be aggregated the thing coated carbon nanotube.

In addition, preferably list following method: to satisfy following formula (2) simultaneously ' ratio,

1＜c/d≤4/3 (2)’

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

X ¹OC-Ar ²-COX ² (K)

React, synthetic amine end is more than the fully aromatic polyamide of the end that comprises carboxylic acid derivative, the carbon nanotube (N) that carries out surface treatment afterwards in the acidic solution of pH 0.01～2 and obtain reacts, the reactants dissolved that obtains in organic solvent or acid solvent, is filtered, separated and be aggregated the thing coated carbon nanotube.

That is, aforesaid by the fully aromatic polyamide coated carbon nanotube, utilize [method 1] of the present invention, [method 2], [method 3] or [method 4] to carry out industrial manufacturing with good productivity.

[method 1] reaches (J) monomer of expression with the regulation following formula of ratio reacting by heating (H), obtains the method for polymkeric substance:

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

Ar among (H), (J) in the above-mentioned formula ¹, Ar ²Respectively with to the Ar in the explanation of the composition of fully aromatic polyamide ¹, Ar ²Identical, in addition, R in the formula (J) ⁹, R ¹⁰The 1 valency aromatic base of representing carbon number 6～20 independently of one another is in particular phenylene, naphthyl, biphenylene base, isopropylidene phenyl, hexichol ether, diphenyl sulfide based, diphenyl sulfone, benzophenone based etc.In the hydrogen atom of these aromatic bases one or more also can be replaced by following radicals independently of one another: halogeno-groups such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; Carbalkoxy such as methoxycarbonyl, ethoxycarbonyl etc.Wherein, Ar ¹Preferred metaphenylene, to phenylene, 3,4 '-diphenylene ether is further preferably to phenylene or and use to phenylene and 34 '-diphenylene ether.Ar ²Preferred metaphenylene, to phenylene, further preferably to phenylene.

In above-mentioned [method 1], the mole number of each monomer (reacted constituent) is necessary to satisfy simultaneously following mathematical expression (2),

0.8≤c/d≤4/3 (2)

Wherein, c is that aromatic diamine, the d of above-mentioned formula (H) expression are the mole number of respectively feeding of the aromatic dicarboxylic acid diaryl of above-mentioned formula (J) expression.

That is, c/d is difficult to obtain the polymkeric substance of enough polymerization degree less than 0.8 or greater than 4/3 o'clock.The lower limit of c/d is preferred more than 0.9, and is more preferably more than 0.93, further preferred more than 0.95.The upper limit of c/d is preferred below 1.25, more preferably below 1.2.Therefore, the optimum range of c/d can be 0.95≤c/d≤1.2 among the present invention.

In [method 1], reaction can be adopted any of the reaction of carrying out, solvent-free heating and melting reaction in solvent, and preference is as, reacting by heating under agitation in the aftermentioned reaction solvent.Preferred 100 ℃～380 ℃ of temperature of reaction, more preferably 180 ℃～350 ℃.Reaction was not carried out when temperature was lower than 100 ℃, when being higher than 380 ℃ temperature be higher than reaction diamines boiling point or be easy to cause side reaction such as decomposition.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction can be carried out adding to depress under the decompression, carries out under decompression at normal pressure usually.The monohydroxy compounds such as phenol of generation are removed in the distillation of preferred limit, and react on the limit.Can under reduced pressure react during the heating and melting reaction, preferably under normal pressure, react when using reaction solvent.

Reaction is carried out under catalyst-free usually, also can use transesterification catalyst as required.The transesterification catalyst that the present invention uses can list antimony compoundss such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, tin compounds such as stannous acetate, stannous octoate, dibutyl tin oxide, dibutyl tin diacetate esters, alkali earth metal salts such as lime acetate, an alkali metal salt such as yellow soda ash, salt of wormwood etc., phosphorous acid esters such as phosphorous acid diphenyl ester, triphenyl phosphite.In addition, preferred and with various additives such as oxidation inhibitor during reaction.

Except that (H), (J), before the preferred reaction, add carbon nanotube (N) in advance with the ratio that satisfies formula (3) and react,

0.001≤(n)/(x)≤100 (3)

In the formula, (x) the weight part summation of expression aromatic diamine (H) and aromatic dicarboxylic acid diaryl (J), (n) weight part of expression carbon nanotube (N).

At this, carbon nanotube (N) is with noted earlier identical.

Above-mentioned weight ratio (n)/(x) is difficult to the carbon nanotube composition in the isolating polymer if less than 0.001, is not preferred therefore.And weight ratio (n)/(x) is if greater than 100, and the coating of the polymkeric substance of carbon nanotube is insufficient, so be not preferred.By present inventor's research, learn in the above-mentioned formula (3) preferred 0.01≤(n)/(x)≤10 scope, preferred especially 0.01≤(n)/(x)≤1.0 scope.

Above-mentioned reaction can be carried out under solvent-free, also can use N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE, sulfobenzide, methylene dichloride, chloroform, tetrahydrofuran (THF), water equal solvent as required.These solvents can be used alone or in combination of two or more kinds.

Once be dissolved in organic solvent or acid solvent, for example sulfuric acid, 1-Methyl-2-Pyrrolidone, 1-cyclohexyl-2-Pyrrolidone, the N,N-DIMETHYLACETAMIDE etc. and filter by the reactant that will obtain, can obtain by the fully aromatic polyamide coated carbon nanotube.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

[method 2] makes each reacted constituent (monomer) of following general formula (H), (K) react the method that obtains polymkeric substance simultaneously with the regulation ratio:

NH ₂-Ar ¹-NH ₂ (H)

X ¹OC-Ar ²-COX ² (K)

Among above-mentioned general formula (H), (K), Ar ¹, Ar ²Represent that independently of one another carbon number is 6～20 divalent aromatic base, its details respectively with the Ar that in the explanation of fully aromatic polyamide, narrates ¹, Ar ²Identical.X in the above-mentioned general formula (K) ¹, X ²The expression halogen specifically can list fluorine, chlorine, bromine, iodine.Wherein, consider reactivity, stability, cost, preferred chlorine.

In [method 2] of the present invention, make each reacted constituent (monomer) reaction with the ratio that satisfies following mathematical expression (2).

0.8≤c/d≤4/3 (2)

C is that aromatic diamine, the d of above-mentioned formula (H) expression is the mole number of respectively feeding of aromatic dicarboxylic acid two etherides of formula (K) expression.

Above-mentioned c/d is difficult to obtain the polymkeric substance of enough polymerization degree less than 0.8 or greater than 4/3 o'clock.The lower limit of c/d is preferred more than 0.9, and is more preferably more than 0.93, further preferred more than 0.95.The upper limit of c/d is preferred below 1.25, more preferably below 1.2.Therefore, the optimum range of c/d can be 0.95≤c/d≤1.2 among the present invention.

Preferred-20 ℃～100 ℃ of temperature of reaction in should [method 2], more preferably-5 ℃～50 ℃.Reaction was not carried out when temperature was lower than-20 ℃, was easy to cause the side reactions such as decomposition of raw material when being higher than 10 ℃.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction is reacting by heating in the aftermentioned reaction solvent preferably.

Utilize the alkaline matter neutralization to remove the hydrogen halide that dereaction generates, the desirable fully aromatic polyamide that goes out to generate.Can be in requisition for washing, refining this polymkeric substance, the reaction soln concentration that also can adjust after the neutralization is used as shaping stoste.

In above-mentioned [method 2], during reaction, use N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE, sulfobenzide, methylene dichloride, chloroform, tetrahydrofuran (THF), water equal solvent.These solvents can be used alone or in combination of two or more kinds.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

The invention is characterized in, except that (H), (K), before the preferred reaction, add carbon nanotube (N) in advance with the ratio that satisfies formula (3) and react,

0.001≤(n)/(x)≤100 (3)

In the formula, x represents to comprise the weight part summation of the monomer component of aromatic diamine (J) and aromatic dicarboxylic acid two etherides (K), (n) weight part of expression carbon nanotube (N).

At this, carbon nanotube (N) is with noted earlier identical.

, can obtain in organic solvent or acid solvent, for example sulfuric acid, N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE etc. and filter by the reactants dissolved that will obtain by the fully aromatic polyamide coated carbon nanotube.

[method 3] reaches (J) monomer of expression with the regulation following formula of ratio reacting by heating (H), obtains the method for amine end more than the polymkeric substance of the end that comprises carboxylic acid derivative:

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

Ar among (H), (J) in the above-mentioned formula ¹, Ar ²Respectively with to the Ar in the explanation of the composition of fully aromatic polyamide ¹, Ar ²Identical, in addition, R in the formula (J) ⁹, R ¹⁰The 1 valency aromatic base of representing carbon number 6～20 independently of one another is in particular phenylene, naphthyl, biphenylene base, isopropylidene phenyl, hexichol ether, diphenyl sulfide based, diphenyl sulfone, benzophenone based etc.In the hydrogen atom of these aromatic bases one or more also can be replaced by following radicals independently of one another: halogeno-groups such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; Carbalkoxy such as methoxycarbonyl, ethoxycarbonyl etc.Wherein, Ar ¹Preferred metaphenylene, to phenylene, 3,4 '-diphenylene ether further preferably to phenylene, or and is used to phenylene, 34 '-diphenylene ether.Ar ²Preferred metaphenylene, to phenylene, further preferably to phenylene.

In above-mentioned [method 3], each reacted constituent (monomer) is to satisfy following mathematical expression (2) ' ratio reaction.

1＜c/d≤4/3 (2)’

Above-mentioned c/d can't obtain the many fully aromatic polyamides of amine end less than 1 o'clock.Above-mentioned c/d was difficult to obtain the polymkeric substance of enough polymerization degree greater than 4/3 o'clock.The upper limit of c/d is preferred below 1.25, more preferably below 1.2.Therefore, the optimum range of the c/d of [method 3] can be 1＜c/d≤1.2 among the present invention.

At this, the fully aromatic polyamide that the amine end is many is meant, the complete terminal fully aromatic polyamide that more than 60%, more preferably is made of amino more than 80%.

In [method 3], reaction can be adopted any of the reaction of carrying out, solvent-free heating and melting reaction in solvent, and preference is as, reacting by heating under agitation in the aftermentioned reaction solvent.Preferred 100 ℃～380 ℃ of temperature of reaction, more preferably 180 ℃～350 ℃.Reaction was not carried out when temperature was lower than 100 ℃, when being higher than 380 ℃ temperature be higher than reaction diamines boiling point or be easy to cause side reaction such as decomposition.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction can be carried out adding to depress under the decompression, carries out under decompression at normal pressure usually.The monohydroxy compounds such as phenol of generation are removed in the distillation of preferred limit, and react on the limit.Can under reduced pressure react during the heating and melting reaction, preferably under normal pressure, react when using reaction solvent.

The invention is characterized in, add the above-mentioned amine end that obtains many fully aromatic polyamide and carbon nanotube (N) with the ratio that satisfies formula (3) and react,

0.001≤(n)/(x)≤100 (3)

In the formula, x represents the weight part of the fully aromatic polyamide that the amine end is many, (n) weight part of expression carbon nanotube (N).

At this, carbon nanotube (N) obtains for carry out surface treatment in the acidic solution of pH0.01～2 with noted earlier identical.

In the above-mentioned formula (3), weight ratio (n)/(x) is difficult to the carbon nanotube composition in the isolating polymer if less than 0.001, is not preferred therefore.And weight ratio (n)/(x) is if greater than 100, and the coating of the polymkeric substance of carbon nanotube is insufficient, so be not preferred.By present inventor's research, learn in the above-mentioned formula (3) preferred 0.01≤(n)/(x)≤10 scope, preferred especially 0.01≤(n)/(x)≤1.0 scope.

In [method 3], the method as making many fully aromatic polyamides of amine end and carbon nanotube (N) reaction is not particularly limited, and preferably in the solvent solution of the many fully aromatic polyamides of amine end, makes carbon nanotube (N) reaction.The thermotolerance height of fully aromatic polyamide is so need high temperature to come fusion.Also having not, fused exists.Consider that this point also preferably reacts in solution.

Temperature of reaction when making many fully aromatic polyamides of this [method 3] middle amine end and carbon nanotube (N) reaction is not particularly limited, and preferred 0 ℃～250 ℃, more preferably 30 ℃～200 ℃.Reaction was not carried out when temperature was lower than 0 ℃, was easy to cause the side reactions such as decomposition of raw material when being higher than 250 ℃.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction is reacting by heating in the aftermentioned reaction solvent preferably.

When making many fully aromatic polyamides of above-mentioned amine end and carbon nanotube (N) reaction, use N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE, sulfobenzide, methylene dichloride, chloroform, tetrahydrofuran (THF), water equal solvent.These solvents can be used alone or in combination of two or more kinds.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

, can obtain in organic solvent or acid solvent, for example sulfuric acid, N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE etc. and filter by the reactants dissolved that will obtain by the fully aromatic polyamide coated carbon nanotube.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

The amine of fully aromatic polyamide C-terminal terminal and surface treated carbon nanotube in acidic solution, interaction by covalent linkage and/or ionic interaction, obtain in [method 3] by the many fully aromatic polyamide coated carbon nanotube of amine end, coated by fully aromatic polyamide.

[method 4] makes each reacted constituent (monomer) of following general formula (H), (K) react with the ratio of regulation simultaneously, obtains the method for amine end more than the polymkeric substance of carboxylic acid derivative end:

NH ₂-Ar ¹-NH ₂ (H)

X ¹OC-Ar ²-COX ² (K)

In [method 4] of the present invention, to satisfy following mathematical expression (2) ' ratio make each reacted constituent (monomer) reaction.

1＜c/d≤4/3 (2)’

Above-mentioned c/d is 1 when following, can't obtain the many fully aromatic polyamides of amine end.Above-mentioned c/d was difficult to obtain the polymkeric substance of enough polymerization degree greater than 4/3 o'clock.The upper limit of c/d is preferred below 1.25, more preferably below 1.2.Therefore, the optimum range of [method 4] middle c/d can be 1＜c/d≤1.2 among the present invention.

At this, the fully aromatic polyamide that the amine end is many is meant, the terminal fully aromatic polyamide that more than 60%, more preferably is made of amino more than 80%.

Preferred-20 ℃～100 ℃ of temperature of reaction in should [method 4], more preferably-5 ℃～50 ℃.Reaction was not carried out when temperature was lower than-20 ℃, was easy to cause the side reactions such as decomposition of raw material when being higher than 10 ℃.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction is reacting by heating in the aftermentioned reaction solvent preferably.

In above-mentioned [method 4], during reaction, use N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE, sulfobenzide, methylene dichloride, chloroform, tetrahydrofuran (THF), water equal solvent.These solvents can be used alone or in combination of two or more kinds.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

[method 4] of the present invention is characterised in that, adds the many fully aromatic polyamides of the above-mentioned amine end that obtains and preferably carry out the carbon nanotube (N) that surface treatment obtains in the acidic solution of pH0.01～2 with the ratio that satisfies formula (3), react,

0.001≤(n)/(x)≤100 (3)

In the formula, (x) weight part of the fully aromatic polyamide that expression amine end is many (n) is illustrated in the weight part that carries out the carbon nanotube (N) that surface treatment obtains in the acidic solution of pH0.01～2.

In [method 4], the method as making many fully aromatic polyamides of amine end and carbon nanotube (N) reaction is not particularly limited, and preferably in the solvent solution of the many fully aromatic polyamides of amine end, makes carbon nanotube (N) reaction.The thermotolerance height of fully aromatic polyamide is so need high temperature to come fusion.Also having not, fused exists.Consider that this point also preferably reacts in solution.

Temperature of reaction when making many fully aromatic polyamides of this [method 4] middle amine end and carbon nanotube (N) reaction is not particularly limited, and preferred 0 ℃～250 ℃, more preferably 30 ℃～200 ℃.Reaction was not carried out when temperature was lower than 0 ℃, was easy to cause the side reactions such as decomposition of raw material when being higher than 250 ℃.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction is reacting by heating in the aftermentioned reaction solvent preferably.

When making many fully aromatic polyamides of above-mentioned amine end and carbon nanotube (N) reaction, use N-N-methyl-2-2-pyrrolidone N-, 1-cyclohexyl-2-Pyrrolidone, N,N-DIMETHYLACETAMIDE, sulfobenzide, methylene dichloride, chloroform, tetrahydrofuran (THF), water equal solvent.These solvents can use separately, use more than 2 kinds also capable of being combined.Also can and use an alkali metal salt or the alkali earth metal salt that dissolves in lithium chloride, the calcium chloride equal solvent in the above-mentioned solvent.

The amine of fully aromatic polyamide C-terminal terminal and surface treated carbon nanotube in acidic solution, interaction by covalent linkage and/or ionic interaction, obtain in [method 4] by the many fully aromatic polyamide coated carbon nanotube of amine end, coated by fully aromatic polyamide.

(by (entirely) aromatic polyester/carbonic ether coated carbon nanotube)

Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate among preferred the present invention comprise following structural unit

Ar ³For can substituted carbon number being 6～20 aromatic base, R ¹, R ²For separately can substituted phenylene, Y ¹For being selected from the group in the following formula group (E),

R ³～R ⁸Be a kind of group in the aralkyl of the aryl of the alkyl, carbon number 5 of hydrogen atom, halogen atom, carbon number 1～6 or 6 cycloalkyl, carbon number 6～12 and carbon number 6～12 independently of one another.Q represents 4～10 integer.

To the quilt manufacture method of (entirely) aromatic polyester/carbonic ether coated carbon nanotube, details are as follows.

Described carbon nanotube is obtained by following method: satisfying following formula (4), and the mol ratio of (5) simultaneously,

0≤e/f≤1.05 (4)

0.9≤g/(e+f)≤1.1 (5)

E is the aromatic dicarboxylic acid composition, and f is that diol component, g are each mole number of diaryl carbonate,

The aromatic diol composition of the aromatic dicarboxylic acid composition of the following formula of feeding (L) expression, following formula (O) expression, and (P) two diaryl carbonates of expression,

HOOC-Ar ³-COOH (L)

Ar ³It is identical with definition in the above-mentioned formula (C),

HO-R ¹-Y ¹-R ²-OH (O)

R ¹, R ², Y ¹It is identical with definition among above-mentioned formula (C), (D),

Two R ¹¹Difference is identical or different, is selected from the alkyl of hydrogen atom, halogen atom, hydroxyl, carboxyl, ester group or carbon number 1～6,

And then add carbon nanotube (N) and react, then with the reactants dissolved that obtains in organic solvent, filter, separate and be aggregated the thing coated carbon nanotube.

As the aromatic dicarboxylic acid composition, can list, for example, terephthalic acid, m-phthalic acid, methyl terephthalic acid, methyl m-phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, dicarboxylic acid diphenyl ester, diphenyl ether dicarboxylic acid, sulfobenzide dicarboxylic acid etc.These aromatic dicarboxylic acids can use separately, also can use a plurality of simultaneously.Wherein, obtaining on the good amorphism polymkeric substance, terephthalic acid and m-phthalic acid are used in special hope simultaneously.

As aromatic diol, can list, for example, 2, two (4-hydroxyphenyl) propane, 1 of 2-, two (4-hydroxyphenyl) hexanaphthenes, 2 of 1-, two (3, the 5-dimethyl-4-hydroxyphenyl) propane of 2-, 2-(4-hydroxyphenyl)-2-(3,5-two chloro-4-hydroxyphenyl) propane etc., wherein preferred 2, two (4-hydroxyphenyl) propane, 1 of 2-, two (4-hydroxyphenyl) hexanaphthenes of 1-.These aromatic diol compositions can use separately, also can use a plurality of simultaneously.

In the method for the present invention, in not damaging the scope that generates polymer property (for example, 1 mole % is above, 15 moles of % are following), can be with the part Resorcinol, 4 of above-mentioned aromatic diol composition, other aromatic diol compositions such as 4 '-dihydroxybiphenyl base replace.

As diaryl carbonate, can list, for example, diphenyl carbonate, two pairs of toluene esters of carbonic acid, two pairs of chlorobenzene esters of carbonic acid, carbonic acid phenyl be to toluene ester, carbonic acid dinaphthyl ester etc., wherein preferred especially diphenyl carbonate.These diaryl carbonates can use separately, also can use a plurality of simultaneously.

In the formula (5), if less than 0.9, the polymerization of the polymkeric substance of generation is easily slack-off than g/ (e+f) for this, and greater than 1.1 o'clock, and therefore the polymkeric substance that obtains painted violent be not preferred.In the formula (5), preferred range is 0.95≤g/ (e+f)≤1.1, more preferably 0.97≤g/ (e+f)≤1.1.

The invention is characterized in,, before reaction, add carbon nanotube (N) in advance with the ratio that satisfies following formula (6) and react except monomer component,

0.001≤(n)/(m)≤100 (6)

M is the summation of the monomer component weight part of aromatic dicarboxylic acid composition (e), diol component (f), diaryl carbonate (g), (n) is the weight part of carbon nanotube (N).

At this, carbon nanotube (N) and foregoing same meaning.

Above-mentioned weight ratio (n)/(m) is difficult to the carbon nanotube composition in the isolating polymer if less than 0.001, is not preferred therefore.And weight ratio (n)/(m) is if greater than 100, and the coating of the polymkeric substance of carbon nanotube is insufficient, so be not preferred.By present inventor's research, learn in the above-mentioned formula (6) preferred 0.01≤(n)/(m)≤10 scope, preferred especially 0.01≤(n)/(m)≤1.0 scope.

The preferred above-claimed cpd of method of the present invention (L), (O), (P) and carbon nanotube react in the presence of the pyridine based compound of following formula (T) expression,

R ¹⁴, R ¹⁵Be a kind of group in the aralkyl of the aryl of cycloalkyl, carbon number 6～12 of alkyl, the carbon number 5～10 of hydrogen atom, carbon number 1～6 and carbon number 6～12 independently of one another.R ¹⁴And R ¹⁵Between also can bonding.R ¹⁶Be at least a group in the aralkyl of the aryl of the cycloalkyl of the alkyl that is selected from carbon number 1～6, carbon number 5～10, carbon number 6～12 and carbon number 6～12.N represents 0～4 integer.

As this pyridine based compound, can list, for example, 4-aminopyridine, 4-Dimethylamino pyridine, 4-diethylin pyridine, 4-tetramethyleneimine pyridine, 4-piperidines alkane pyridine, 4-pyrroline pyridine, 2-methyl-4-Dimethylamino pyridine etc.Wherein, preferred especially 4-Dimethylamino pyridine, 4-tetramethyleneimine pyridine.

In this reaction, at first mainly be that diaryl carbonate and aromatic dicarboxylic acid composition and aromatic diol composition react the generation phenols.Generally speaking, the aromatic dicarboxylic acid solvability is low, so the reaction at this initial stage needs high temperature when beginning, and it is long-time to finish needs to initial reaction.But if use above-mentioned specific pyridine based compound, the phenols that is surprised to find that the phenols at this initial stage is produced as low temperature very, and promptly finishes in the short period of time.Surprising again discovery even make the later stage at aromatic polyester carbonate, can be used as transesterification catalyst and works, and obtains the polymkeric substance of high-polymerization degree in the short period of time.

Though the consumption of above-mentioned pyridine based compound gets final product with so-called catalytic amount,, be preferably 0.00001 mole～0.05 mole, more preferably 0.0001 mole～0.005 mole with respect to 1 mole of mentioned component (a).

In the method for the invention, the polymerization temperature under the existence of above-mentioned pyridine based compound during heated polymerizable, it is suitable being 200～400 ℃.At this, polymerization temperature is meant the temperature of the reaction system when polymerization later stage or its finish.If polymerization temperature is lower than 200 ℃, because the melt viscosity of polymkeric substance uprises, can't obtains the polymkeric substance of high-polymerization degree, and when being higher than 400 ℃, polymer deterioratoin etc. easily take place, so be not preferred.

Among the present invention,,, also can use an alkali metal salt, alkali earth metal salt except above-mentioned pyridine based compound in order to improve polymerization velocity.

As the object lesson of these catalyzer, can list oxyhydroxide, halogenide, carbonate, the supercarbonate of basic metal classes such as lithium, sodium, potassium, caesium and/or alkaline-earth metal classes such as magnesium, calcium.The disodium salt of wherein preferred especially salt of wormwood, yellow soda ash, dihydroxyphenyl propane.

Among the present invention, except that above-mentioned pyridine based compound, an alkali metal salt, alkali earth metal salt, can also use known in the past transesterification catalyst.

Though the consumption of these basic metal classes, alkaline-earth metal class gets final product with so-called catalytic amount, with respect to 1 mole of above-mentioned aromatic diol composition, be preferably 0.01 μ mol%～0.05mol%, more preferably 0.01 μ mol%～0.005mol%.

In the method for the present invention, the initial stage of preferred polymeric temperature of reaction is than lower temperature, and slowly heating up finally reaches above-mentioned polymerization temperature.The polymerization temperature of the initial stage polyreaction of this moment is preferably 160～320 ℃.

This polyreaction can in normal pressure down or decompression implement down, preferred initial stage is under the normal pressure during polyreaction, slowly decompression.In addition, reaction system is under the inert gas atmospheres such as nitrogen, argon during preferred normal pressure.Polymerization reaction time is not particularly limited, and is about about 0.2～20 hour.

Need to prove, in the inventive method, preferred autoreaction above-mentioned each composition of in reaction vessel, packing into originally, but also autoreaction begins branch imports molar equivalent part for several times in reaction vessel diaryl carbonate.

Wholly aromatic polyester in the invention described above, aromatic polyester carbonate and aromatic copolycarbonate are the amorphism polymkeric substance, use it for example can obtain molding by melt-shaping methods such as injection moldeds.And the polymkeric substance that is obtained by method of the present invention is that amorphism can be confirmed by phenomenons such as for example can't recording its fusing point with DSC.

The reducing viscosity separately of Wholly aromatic polyester, aromatic polyester carbonate and the aromatic copolycarbonate that is obtained by aforesaid method is 0.05～3.0, is preferably 0.3～2.5.If reducing viscosity is less than 0.05, can't obtain the mechanical characteristics expected as resin combination, if greater than 3.0, is difficult to basically make.

To be dissolved in organic solvent or acid solvent by the reactant that aforesaid method obtains, and once dissolve, separate and be aggregated the thing coated carbon nanotube.Can list preferred methylene dichloride, phenol/sym.-tetrachloroethane mixed solvent etc. as solvent.

(by the semi-aromatic polyester coated carbon nanotube)

Semi-aromatic polyester among the present invention preferably includes the semi-aromatic polyester of aromatic dicarboxylic acid composition, aliphatic diol composition.

It can be obtained by following method: satisfying the mol ratio of following formula (7),

0.8≤e’/f’≤1.2 (7)

E ' is the aromatic dicarboxylic acid composition, and f ' is each mole number of diol component,

Charging aromatic dicarboxylic acid composition and aliphatic diol composition, and then add carbon nanotube (N) with the ratio that satisfies following formula (8) and react, then with the reactants dissolved that obtains in organic solvent, filter, separate and be aggregated the thing coated carbon nanotube,

0.001≤(n)/(m)≤100 (8)

M is the summation of the monomer component weight part of aromatic dicarboxylic acid composition (e), diol component (f), (n) is the weight part of carbon nanotube (N).

As the aliphatic diol composition, preferred ethylene glycol, 1,2-propylene glycol, 1,3-three methylene glycols, 1,3 butylene glycol, 1,4-butyleneglycol, 2,2-dimethyl propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, three methylene glycols, tetramethyl glycol, five methylene glycols, eight methylene glycols, Diethylene Glycol, dipropylene glycol.These aliphatic diols can use separately or use multiple simultaneously.

The preferred reducing viscosity of the molecular weight of semi-aromatic polyester (in the solution of phenol/sym.-tetrachloroethane of 1.2g/dL=4/6 (weight ratio), 35 ℃ of values of measuring down) is 0.1～20g/dL, more preferably 0.2～10g/dL, further preferred 0.3～5g/dL.

(by all aromatic pyrrole coated carbon nanotube)

All aromatic pyrrole among the present invention is preferably and satisfies following formula (F) and/or all aromatic pyrrole (G),

Wherein, Y ², Y ³Independently be selected from O, S respectively, reach NH, Ar ⁴4 valency aromatic bases of expression carbon number 6～20, Ar ⁵The divalent aromatic base of expression carbon number 6～20.

(F), (G) can use separately also can and usefulness, (F): mol ratio (G) can be selected 0: 100～100: 0 arbitrary ratio aptly.

Ar among above-mentioned (F), (G) ⁴Represent the tetravalence aromatic base of carbon number 6～20 independently of one another, its object lesson can list following groups etc.

Wherein, Y4 is selected from O, S, SO, SO2, NH, C (CH ₃) ₂In any,

But be not limited thereto.In the hydrogen atom of these aromatic bases one or more are replaced by following groups respectively independently: halogen radicals such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; The aromatic base of carbon numbers such as phenyl 6～10 etc.

Ar among above-mentioned formula (F), (G) ⁵, represent independently of one another specifically to list the divalent aromatic base of carbon number 6～20, metaphenylene, to phenylene, adjacent phenylene, 2,6-naphthylidene, 2,7-naphthylidene, 4,4 '-isopropylidene diphenylene, 4,4 '-biphenylene base, 4,4 '-diphenylene thioether group, 4,4 '-diphenylene sulfuryl, 4,4 '-diphenylene ketone group, 4,4 '-diphenylene ether, 3,4 '-diphenylene ether, an xylylene, terephthaldehyde's base, O-phthalic base etc.In the hydrogen atom of these aromatic bases one or more can be replaced by following groups independently: halogen radicals such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; The aromatic base of carbon numbers such as phenyl 6～10 etc.Need to prove that above-mentioned formula (F) and/or structural unit (G) can be the multipolymers that comprises the aromatic base more than 2 kinds.

Wherein preferably to phenylene, 2, the 6-naphthylidene.

Preferred all aromatic condensation be polymer specifically can list following polyphenyl and two oxazoles,

Or following polyphenyl and double thiazole,

These all aromatic condensations be polymer can utilize solution polymerization process, melt phase polycondensation etc. in the past known method make.The preferred 30 ℃ of concentration with 0.5g/100mL measured down of the polymerization degree of polymkeric substance are dissolved in the 98 weight % vitriol oils and intrinsic viscosity (inherent viscosity) the η inh of the solution that obtains is 0.05～100dl/g, more preferably between 1.0～80 (dl/g).

The all aromatic pyrrole can carry out industry manufacturing with good productivity according to the methods below according to the present invention.

That is, can followingly obtain: satisfying the mol ratio of following formula (9) simultaneously,

0.8≤(h+i)/j≤1.2 (9)

In the formula, h is the aromatic amine derivant of above-mentioned formula (Q) expression, and i is the aromatic amine derivant of above-mentioned formula (R) expression, and j is the mole number of respectively feeding of the aromatic dicarboxylic acid derivative of above-mentioned formula (S) expression,

Charging is selected from aromatic dicarboxylic acid derivative at least a of the aromatic amine derivant of following formula (Q), (R) expression and the expression of at least a and following formula (S) in the hydrochloride thereof,

In the formula, Y ², Y ³Independently be selected from O, S respectively, reach NH, Ar ⁴4 valency aromatic bases of expression carbon number 6～20, or (Q), (R) also can be hydrochloride,

R ¹²-O ₂C-Ar ⁵-CO ₂-R ¹³ (S)

In the formula, Ar ⁵The divalent aromatic base of representing carbon number 6～20 independently of one another, R ¹², R ¹³The aromatic base of representing hydrogen or carbon number 6～20 independently of one another,

And then add carbon nanotube (N) and react, then with the reactants dissolved that obtains in organic solvent, filter, the separating carbon nano-tube composition.

Ar among above-mentioned formula (Q), (R), (S) ⁴, Ar ⁵, respectively with Ar about the explanation of the composition of all aromatic pyrrole ⁴, Ar ⁵Identical, R in the formula (S) ¹², R ¹³Represent 1 valency aromatic base of carbon number 6～20 independently of one another, the object lesson of aromatic base has, phenylene, naphthyl, biphenylene base, isopropylidene diphenylene, hexichol ether, diphenyl sulfide based, diphenyl sulfone, phenylbenzene ketone group etc.In the hydrogen atom of these aromatic bases one or more can be replaced by following groups independently: halogen radicals such as fluorine, chlorine, bromine; The alkyl of carbon numbers 1～6 such as methyl, ethyl, propyl group, hexyl; The cycloalkyl of carbon number such as cyclopentyl, cyclohexyl 5～10; Alkoxy carbonyls such as methoxycarbonyl, oxyethyl group carboxyl etc.

The mole number of each monomer (reacted constituent) preferably satisfies the mol ratio of following formula (9) simultaneously,

0.8≤(h+i)/j≤1.2 (9)

In the formula, h is the aromatic amine derivant of above-mentioned formula (Q) expression, and i is the aromatic amine derivant of above-mentioned formula (R) expression, and j is the mole number of respectively feeding of the aromatic dicarboxylic acid derivative of above-mentioned formula (S) expression.

(h+i)/j is less than 0.8 or 1.2 o'clock, is difficult to obtain the polymkeric substance of the abundant polymerization degree sometimes.(h+i)/lower limit of j is preferably more than 0.9, and is more preferably more than 0.93, further preferred more than 0.95.(h+i)/upper limit of j is preferred below 1.1, more selects excellent more than 1.07, further preferred below 1.05.Therefore, the optimum range of (h+i)/j can be 0.95≤(h+i)/j≤1.05 among the present invention.

(Q), (R) can distinguish separately and to use, also can and usefulness, (Q): the selection that can suit with 0: 100～100: 0 arbitrary ratio of mol ratio (R).

Reaction can be adopted any of the reaction of carrying out, solvent-free heating and melting reaction in solvent, preference is as, reacting by heating under agitation in the aftermentioned reaction solvent.Preferred 50 ℃～500 ℃ of temperature of reaction, more preferably 100 ℃～350 ℃.Reaction was not carried out when temperature was lower than 50 ℃, was easy to cause side reactions such as decomposition when being higher than 500 ℃.It is fixed that reaction times also comes according to temperature condition, but be generally 1 hour to tens of hours.Reaction can be carried out adding to depress under the decompression.

, preferably in as above-mentioned (Q), (R) of polymer raw, (S), before reaction, added carbon nanotube (N) in advance and react by all aromatic pyrrole coated carbon nanotube for of the present invention with the ratio that satisfies following formula (10),

0.001≤(n)/(m)≤100 (10)

In the formula, m is aromatic amine derivant composition (Q), (R), and the summation of the weight part of aromatic dicarboxylic acid derivative composition (S), (n) is the weight part of carbon nanotube (N).

Above-mentioned weight ratio (n)/(m) is difficult to the carbon nanotube composition in the isolating polymer if less than 0.001.And weight ratio (n)/(m) is if greater than 100, and the coating of the polymkeric substance of carbon nanotube is insufficient, so be not preferred.By present inventor's research, learn in the above-mentioned formula (10) preferred 0.01≤(n)/(m)≤10 scope, preferred especially 0.01≤(n)/(m)≤1.0 scope.

(comprising that being become the condensation of all aromatic of matrix is that polymer and aromatic condensation are the composition of polymer coated carbon nanotube)

The present invention is a polymeric composition for a kind of aromatic condensation, it comprises: 100 weight parts be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be that polymer and 0.1～100 weight part are the polymer coated carbon nanotube by above-mentioned aromatic condensation.With respect to 100 weight aromatic condensations is polymer, is preferably 0.1～60 weight part by coated carbon nanotube, more preferably 1～10 weight part., if being difficult to observe the effect that improves mechanical characteristics, less than 0.01 weight part then is difficult to be shaped by coated carbon nanotube greater than 100 weight parts.

This aromatic condensation is that polymeric composition makes by coated carbon nanotube dispersed good in resin, so intensity, spring rate are good.

Wherein, the aromatic condensation that is used for enveloped carbon nanometer tube is that the aromatic condensation of polymer and the matrix that becomes composition is that polymer is preferably a kind of fully aromatic polyamide, and this fully aromatic polyamide comprises that following formula (A) reaches (B)

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

In the formula, Ar ¹, Ar ²Represent that independently of one another carbon number is 6～20 divalent aromatic base,

And satisfy following formula (1)

0.8≤a/b≤4/3 (1)

In the formula, a is the mole number of repeating unit of the aromatic diamine of formula (A) expression, and b is the mole number of repeating unit of the aromatic dicarboxylic acid of formula (B) expression.

(molding)

By above-mentioned this aromatic condensation that obtains is that polymeric composition can obtain moldinies such as fiber or film.In molding, carbon nanotube can obtain the good molding of mechanical characteristics by being orientated in the long axis direction of molding or face.

Promptly, the molding that the present invention is orientated in the long axis direction of molding or face for carbon nanotube, the composition that this molding comprises comprises: be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be polymer 100 weight parts and above-mentioned be polymer coated carbon nanotube 0.01～100 weight part by aromatic condensation; It is characterized in that utilizing the orientation coefficient F of the carbon nanotube that following formula (11) tries to achieve is more than 0.1,

< \cos^{2} φ > = \frac{{&Integral;}_{0}^{π / 2} I (φ) \cos^{2} φ \sin φdφ}{{&Integral;}_{0}^{π / 2} I (φ) \sin φdφ}

F = \frac{3 < \cos^{2} φ > - 1}{2} - - - (11)

In the formula, φ is the position angle during X-ray diffraction is measured, and I is 002 diffracted intensity of graphite.

More preferably more than 0.2, more preferably more than 0.3.The F value is high more preferred more, and the theoretic higher limit when multilayer carbon nanotube is orientated fully is 1.0.

The present invention is the molding of carbon nanotube orientation in the long axis direction of molding or face, the composition that this molding comprises comprises: be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be polymer 100 weight parts and above-mentioned be polymer coated carbon nanotube 0.01～100 weight part by aromatic condensation; It is characterized in that the orientation degree P of the carbon nanotube of following formula (12) expression is more than 0 below 0.7,

P＝I _YY/I _XX (12)

In the formula, in the Raman spectrum of measuring by the polarisation raman spectroscopy, be I with the G band strength laser polarization light face is parallel with the long axis direction of molding or during with the face configured in parallel from carbon nanotube _XX, be I with the G band strength long axis direction of laser polarization light face and molding is vertical or during with the face arranged perpendicular _YY

Preferably provide fiber or film as molding.

Wherein preferred fully aromatic polyamide, its aromatic condensation that is used for enveloped carbon nanometer tube be polymer and the aromatic condensation that becomes composition matrix be polymer for comprise following formula (A) and (B),

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

Ar ¹, Ar ²The divalent aromatic base of representing carbon number 6～20 independently of one another,

And satisfy the fully aromatic polyamide of following formula (1),

0.8≤a/b≤4/3 (1)

A is the mole number of repeating unit of the aromatic diamine of formula (A) expression, and b is the mole number of repeating unit of the aromatic dicarboxylic acid of formula (B) expression.

Embodiment

Below, by embodiment the inventive method is carried out further specifically describing in detail.But these embodiment do not have any qualification to scope of the present invention.

(1) (centrifugation): use a MILLIPORE corporate system human-like whizzer to carry out.

(2) mensuration of median size

The median size of the carbon nanotube in the dispersion solvent is used a day machine dress corporate system microtrackMT3000, measures with light scattering method.The median size that it should be noted that the product of being untreated is carried out 1 minute ultrasonication in N-N-methyl-2-2-pyrrolidone N-(below be sometimes referred to as NMP) before mensuration, measure.

(3) mean diameter of carbon nanotube and mean aspect ratio

Use the H-800 of Hitachi, measure TEM (transmission electron microscope) photo, the diameter and the length of all carbon nanotubes that mensuration can be observed in long 7.5 μ m * wide 9 μ m (20000 times), with the mean value of its diameter mean diameter, be mean aspect ratio with the mean value of the long-width ratio of each carbon nanotube as carbon nanotube.

(4) aromatic condensation of enveloped carbon nanometer tube is high molecular amount

With aromatic condensation is that the polymer coated carbon nanotube uses differential heat scan heat balance TG-8120 that Ligaku company makes in air, be heated to 150 ℃ with 10 ℃/min of heat-up rate, by because the value that the ratio that the weight that aromatic condensation is the decomposition of polymer and carbon nanotube to be caused reduces is tried to achieve.

(5) mechanical characteristics: use the system Tensilon of Orientic Co., Ltd. universal testing machine 1225A, carry out tension test, obtain Young's modulus and tensile strength.

(6) X-ray diffraction is measured: use X-ray generator (motor corporate system RU-B type of science) to measure under the condition of subject matter CuK alpha-ray, voltage 45Kv, electric current 70mA.Incident X-rays utilizes vertical through transmission technique to measure the cross section of sample by Osumic corporate system multilayer film lens light harvesting and monochromatization.Use the imaging plate (Fuji's photographic film system) of big or small 200mm * 250mm, detection of diffracted X ray under the condition of phase captain 250mm.

(7) the polarization raman spectroscopy is measured: the raman spectroscopy device uses micro laser raman spectroscopy determinator (hole field Jobanibon makes LabRamHR).As the excitation laser light source, use the semiconductor laser of wavelength 785nm, laser beam diameter light harvesting is about 1 μ m.Use described device, the following polarization raman spectroscopy that carries out is measured.Make the side of incident laser irradiation fiber composition by the orthogonal directions of fibre axis, when measuring the Raman spectrum of carbon nanotube, measure the Raman shift wavelength 1580cm when disposing laser polarizing face abreast with fibre axis ^-1Near G band strength (I from graphite-structure _XX), with the G band strength (I of fibre axis when vertically disposing laser polarizing face _YY).

Reference example 1: single-layer carbon nano-tube synthetic

With y-type zeolite powder (eastern Cao's system; HSZ-320NAA) as porous carrier, with iron acetate and Cobaltous diacetate as the catalyst metal compound, with the Fe/Co catalyst loading on zeolite.The loading of catalyzer is modulated to 2.5 weight % respectively.Afterwards, on quartz container, place catalyst fines and be arranged in the silica tube of CVD device and carry out vacuum exhaust, flow 10mL/ minute under lead Ar gas and on one side by room temperature be warming up to 800 ℃ on one side.After reaching 800 ℃ of regulation, import alcohol vapour with flow 3000mL/ minute, under the Ar/ alcohol atmosphere, kept 30 minutes.The resultant of the black that obtains with laser raman optical spectroscopy and transmission electron microscope analysis, results verification has generated single-layer carbon nano-tube.Then, the resultant (single-layer carbon nano-tube/zeolite/metal catalyst) that dipping obtains in 10% hydrofluoric acid to neutral, is removed zeolite and metal catalyst and refined carbon nanotubes with the ion-exchange water washing after 3 hours thus.The carbon nanotube that utilizes tem observation to obtain, its mean diameter is that 1.2nm, mean aspect ratio are more than 100 as a result.But, most fascircular textures that are about 10nm for width.

Reference example 2: multilayer carbon nanotube synthetic

Except that the temperature of reaction in the CVD device is made as 600 ℃, similarly react with reference example 1, results verification has generated multilayer carbon nanotube.With reference example 1 similarly make with extra care remove zeolite and metal catalyst after, (field, storehouse skill is ground (strain) system, SCC-U-90/150) carries out graphitization processing to use electric sintering furnace.At first under vacuum, be warming up to 1000 ℃ through 30 minutes by room temperature, under argon atmospher, pressure 5atm, be warming up to 2000 ℃ through 30 minutes then by 1000 ℃, and then be warming up to 2800 ℃ by 2000 ℃ through 1 hour and carry out sintering, obtain multilayer carbon nanotube thus through graphitization processing.The carbon nanotube that utilizes tem observation to obtain, its mean diameter is 58nm as a result, mean aspect ratio is 36.

Reference example 3: the acid treatment of carbon nanotube

In reference example 1, obtain carbon nanotube 1 weight part in add 30 weight parts after, slowly drip nitric acid 10 weight parts.After drip finishing, in 70 ℃ warm water bath, utilize the ultrasonication 1 hour of 28kHz.Solution after the interpolation reaction finishes in the water of 100 weight parts dilutes, and is Te Fulong system filter membrane filter suction filtration and the water washing separation of 0.22 μ m with the aperture.

Reference example 4: the phenyl esterization of carbon nanotube

The phenol that in acid-treated carbon nanotube 0.1 weight part, adds 0.5 weight part that in reference example 3, obtains, in mortar, handle after 10 minutes down for about 60 ℃, in the warm water bath under 70 ℃ with the ultrasonication of 28kHz 10 minutes, add diphenyl carbonate 10 weight parts, Dimethylamino pyridine 0.0061 weight part therein, begin reaction under following 200 ℃ of the normal pressure.Be warming up to 220 ℃ under the normal pressure after 30 minutes, slowly decompression in the system in addition.After the reaction beginning 3 hours, further heat up, decompression, the reaction beginning is after 5 hours, making outlet temperature in the system is that 320 ℃, vacuum tightness are about 0.5mmHg (66.7Pa), to system outside slowly except that the phenol and the diphenyl carbonate of dereaction generation.Reaction is added methylene dichloride after finishing in residue, use the Te Fulong system filter membrane filter suction filtration of aperture 0.22 μ m, removes residual phenol and diphenyl carbonate, isolates the carbon nanotube of 0.55 weight part.

Reference example 5: the physical treatment of carbon nanotube

In NMP (N-N-methyl-2-2-pyrrolidone N-) 300 weight parts, add carbon nanotube 0.909 weight part that obtains in the reference example 1, use NETZSCH corporate system ball mill MINIZETA (air), microballon with the diameter 0.8mm of zirconium system, carry out 1 hour processing in 2500rmp, obtain the dispersion liquid of carbon nanotube.

Reference example 6:

Use the carbon nanotube that obtains in the reference example 2, in addition identical with reference example 3, obtain through acid-treated multilayer carbon nanotube.

Reference example 7:

Use the carbon nanotube that obtains in the reference example 6, in addition identical with reference example 4, obtain multilayer carbon nanotube through phenyl esterization.

Reference example 8:

Use carbon nanotube 4.680 weight parts that obtain in the reference example 2, in addition identical with reference example 5, obtain the dispersion liquid of multilayer carbon nanotube.

Reference example 9:

Use carbon nanotube VGCF clear and that electrician company makes, in addition identical with reference example 3, obtain through acid-treated multilayer carbon nanotube.

Reference example 10:

Use the carbon nanotube that obtains in the reference example 9, in addition identical with reference example 4, obtain multilayer carbon nanotube through phenyl esterization.

Reference example 11:

The carbon nanotube VGCF4.680 weight part that uses clear and electrician company to make, in addition identical with reference example 5, obtain the dispersion liquid of multilayer carbon nanotube.

Reference example 12: the preparation example of polymkeric substance dope (dope)

In the three-necked bottle that whipping appts is housed of thorough drying, add N-Methyl pyrrolidone 1717.38 weight parts, Ursol D 18.82 weight parts and 3 at normal temperatures, 4 '-diamino phenylate, 34.84 weight parts and in nitrogen the dissolving after, add terephthalic acid dichloride 70.08 weight parts while stir.Finally make it add calcium hydroxide 12.85 weight parts after 60 minutes and carry out neutralization reaction in reaction under 80 ℃.The polymkeric substance dope redeposition in water that obtains is separated out polymkeric substance, and its intrinsic viscosity is 3.5 (dl/g).

Reference example 13: the preparation example of the fully aromatic polyamide that the amine end is many

In the three-necked bottle that whipping appts is housed of thorough drying, add N-Methyl pyrrolidone 1717.38 weight parts, Ursol D 18.82 weight parts and 3 at normal temperatures, 4 '-diamino phenylate, 34.84 weight parts and in nitrogen the dissolving after, add terephthalic acid dichloride 63.07 weight parts while stir.Finally make it add calcium hydroxide 11.57 weight parts after 60 minutes and carry out neutralization reaction, obtain the many fully aromatic polyamide solution of amine end in reaction under 80 ℃.。The polymkeric substance dope redeposition in water that obtains is separated out polymkeric substance, and its intrinsic viscosity is 0.32 (dl/g).

Reference example 14: the preparation example of the fully aromatic polyamide that the amine end is many

In the three-necked bottle that whipping appts is housed of thorough drying, add N-Methyl pyrrolidone 1717.38 weight parts, 3 at normal temperatures, 4 '-diamino phenylate, 69.68 weight parts and in nitrogen the dissolving after, add terephthalic acid dichloride 63.07 weight parts while stir.Finally make it add calcium hydroxide 11.57 weight parts after 60 minutes and carry out neutralization reaction in reaction under 80 ℃.The polymkeric substance dope redeposition in water that obtains is separated out polymkeric substance, and its intrinsic viscosity is 0.28 (dl/g).

Embodiment 1

In the three-necked bottle that whipping appts is housed of thorough drying, after adding dissolving of obtaining in N-Methyl pyrrolidone 500 weight parts, calcium chloride 20 weight parts, Ursol D 3.406 weight parts and the reference example 3 at normal temperatures, add terephthalic acid dichloride 6.395g while stir through 0.5 weight part of the single-layer carbon nano-tube after the acid treatment and in nitrogen.Finally make it add calcium hydroxide 2.3 weight parts after 60 minutes and carry out neutralization reaction in reaction under 80 ℃.Utilizing the aperture is the polymkeric substance dope that the Teflon system filter membrane filter suction filtration of 0.22 μ m obtains, and washing is isolated by fully aromatic polyamide coated carbon nanotube 0.55 weight part.

Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 19.3wt%.

Embodiment 2

In the NMP of 40 weight parts, add single-layer carbon nano-tube 0.52 weight part that obtains in the reference example 4, add terephthaldehyde's diphenyl phthalate of 1.337 weight parts, the Ursol D of 0.454 weight part, 200 ℃ of heated and stirred 3 hours through phenyl esterization.Utilizing the aperture is the polymkeric substance that the Teflon system filter membrane filter suction filtration of 0.22 μ m obtains, and washing is isolated by fully aromatic polyamide coated carbon nanotube 0.58 weight part.Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 22.3wt%.

Embodiment 3

Ursol D 0.227 weight part, 3 that uses, in addition 4 '-diaminodiphenyl oxide, 0.421 weight part carries out same operation with embodiment 2.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the NMP of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.02 weight part.

Embodiment 4

200 ℃ of NMP dispersion liquid 244 weight parts that heat the carbon nanotube that obtained in the reference example 5 in 1 hour down, after fully removing the moisture that contains in the dispersion liquid, add Ursol D 0.730 weight part, 3,4 '-diaminodiphenyl oxide, 1.330 weight parts, carry out the ultrasonication of 28kHz under 0 ℃, add phthalic acid dichloride 2.639 weight parts behind the amine solvent, 0 ℃ of bottom carries out the ultrasonication limit of 28kHz and continues reaction 60 minutes, finally after making it to react 60 minutes under the same ultrasonic wave condition under 80 ℃, add calcium hydroxide 0.48 weight part, carry out neutralization reaction.Utilizing the aperture is the polymkeric substance that the Teflon system filter membrane filter suction filtration of 0.22 μ m obtains, and washing is isolated by fully aromatic polyamide coated carbon nanotube 3.91 weight parts.

Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the NMP of 100 weight parts to obtain thus, the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.01 weight part.Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 24.5wt%.

Embodiment 5

Use many fully aromatic polyamide solution 200 weight parts of polymeric amine end in the reference example 13, with the NMP dilution of 1000 weight parts, the many fully aromatic polyamide solution of 1wt% amine end of preparation homogeneous.In above-mentioned polymers soln, add carbon nanotube 2 weight parts that obtain in the reference example 6, make its dispersion with ultrasonic wave, and then 100 ℃ of following stirring reactions 24 hours.Reaction solution with the NMP dilution obtains filters with 0.2 μ filter, repeats 3 NMP washings, finally uses washing with alcohol, and drying under reduced pressure obtains by many fully aromatic polyamide coated carbon nanotube 2.52 weight parts of amine end.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the NMP of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.008 weight part.Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 26.0wt%.

Embodiment 6

Use many fully aromatic polyamide solution 200 weight parts of polymeric amine end in the reference example 14, with the NMP dilution of 1000 weight parts, the many fully aromatic polyamide solution of 1wt% amine end of preparation homogeneous.In above-mentioned polymers soln, add carbon nanotube 2 weight parts that obtain in the reference example 6, make its dispersion with ultrasonic wave, and then 100 ℃ of following stirring reactions 24 hours.Reaction solution with the NMP dilution obtains filters with 0.2 μ filter, repeats 3 NMP washings, finally uses washing with alcohol, and drying under reduced pressure obtains by many fully aromatic polyamide coated carbon nanotube 2.52 weight parts of amine end.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the NMP of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.006 weight part.Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 24.5wt%.

Embodiment 7

Use the carbon nanotube of reference example 6, in addition carry out same operation with embodiment 1, carbon nanotube 0.1 weight part that in 98% sulfuric acid of 100 weight parts, obtains with ultrasonic dispersing, the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.02 weight part.Utilize differential heat scan heat balance to measure, result, the amount of the fully aromatic polyamide of enveloped carbon nanometer tube are 21.1wt%.

Embodiment 8

Use the carbon nanotube of reference example 7, in addition, carry out same operation, estimated the dispersion in the sulfuric acid solvent similarly to Example 7 with embodiment 2.

Embodiment 9

Use the carbon nanotube of reference example 7, in addition, carry out same operation with embodiment 3.

Embodiment 10

Use the carbon nanotube of reference example 8, in addition, carry out same operation with embodiment 4.

Embodiment 11

Use the carbon nanotube of reference example 9, in addition, carry out same operation with embodiment 1.

Embodiment 12

Use the carbon nanotube of reference example 10, in addition, carry out same operation with embodiment 2.

Embodiment 13

Use the carbon nanotube of reference example 10, in addition, carry out same operation with embodiment 3.

Embodiment 14

Use the carbon nanotube of reference example 11, in addition, carry out same operation with embodiment 4.

Each of embodiment 1～14 the results are shown in Table 1.

Table 1

	Use CNT	Solvent dispersion is estimated	Sedimentation (weight part)	Carbon fiber through dissolving mutually (weight part)	Covering amount (wt%)
	Use CNT	Solvent dispersion is estimated	Sedimentation (weight part)	Carbon fiber through dissolving mutually (weight part)	Covering amount (wt%)	Embodiment 1	Reference example 3				19.3
Embodiment 2	Reference example 4				22.3	Embodiment 1	Reference example 3				19.3
Embodiment 2	Reference example 4				22.3	Embodiment 3	Reference example 4	NMP	0.02	0.08	29.8
Embodiment 4	Reference example 5	NMP	0.01	0.09	24.5	Embodiment 3	Reference example 4	NMP	0.02	0.08	29.8
Embodiment 4	Reference example 5	NMP	0.01	0.09	24.5	Embodiment 5	Reference example 6	NMP	0.008	0.092	26.0
Embodiment 6	Reference example 6	NMP	0.006	0.094	24.5	Embodiment 5	Reference example 6	NMP	0.008	0.092	26.0
Embodiment 6	Reference example 6	NMP	0.006	0.094	24.5	Embodiment 7	Reference example 6	Sulfuric acid	0.02	0.08	21.1
Embodiment 8	Reference example 7	Sulfuric acid	0.01	0.09	24.4	Embodiment 7	Reference example 6	Sulfuric acid	0.02	0.08	21.1
Embodiment 8	Reference example 7	Sulfuric acid	0.01	0.09	24.4	Embodiment 9	Reference example 7	NMP	0.005	0.095	31.1
Embodiment 10	Reference example 8	NMP	0.01	0.09	19.8	Embodiment 9	Reference example 7	NMP	0.005	0.095	31.1
Embodiment 10	Reference example 8	NMP	0.01	0.09	19.8	Embodiment 11	Reference example 9	Sulfuric acid	0.01	0.09	19.3
Embodiment 12	Reference example 10	Sulfuric acid	0.02	0.08	22.3	Embodiment 11	Reference example 9	Sulfuric acid	0.01	0.09	19.3
Embodiment 12	Reference example 10	Sulfuric acid	0.02	0.08	22.3	Embodiment 13	Reference example 10	NMP	0.01	0.09	33.4
Embodiment 14	Reference example 11	NMP	0.005	0.095	27.7	Embodiment 13	Reference example 10	NMP	0.01	0.09	33.4

Embodiment 15

In NMP (N-N-methyl-2-2-pyrrolidone N-) 300 weight parts, add obtain in the reference example 1 by fully aromatic polyamide coated carbon nanotube 0.909 weight part, the ultrasonication of utilizing the ultrasonic wave of 28kHz to carry out 1 hour.In this NMP dispersion liquid, add NMP dope 1500 weight parts of the polymkeric substance that obtains in the reference example 12, stirred 1 hour down at 90 ℃, make the polymkeric substance dope of homogeneous.The polymkeric substance dope that uses the lid of 5 of aperture 0.3mm, hole count to keep obtaining thus is 80 ℃, extrudes in 56 ℃ the precipitation bath of the aqueous solution of NMP30 weight % most.Distance between capping and the precipitation bath face is 10mm.Fiber through spinning is washed down at 50 ℃, and 120 ℃ dry down, obtains ultimate fibre (filament).The ultimate fibre stretching ratio with 10 times on 500 ℃ hot plate that obtains is stretched, obtain the ultimate fibre that stretches.The measurement result of physical data has been shown in the table 2.

Embodiment 16

Use among the embodiment 3 and obtain carbon nanotube, in addition, carry out same operation with embodiment 15.

Embodiment 17

200 ℃ of NMP dispersion liquid 300 weight parts that heat the carbon nanotube that obtained in the reference example 5 in 1 hour down, after fully removing the moisture that contains in the dispersion liquid, add Ursol D 0.168 weight part, 3,4 '-diaminodiphenyl oxide, 0.318 weight part, carry out the ultrasonication of 28kHz under 0 ℃, add phthalic acid dichloride 0.630 weight part behind the amine solvent, 0 ℃ of bottom carries out the ultrasonication limit of 28kHz and continues reaction 60 minutes, finally make it to react 60 minutes under the same ultrasonic wave condition down at 80 ℃, add calcium hydroxide 0.115 weight part, carry out neutralization reaction.

Add obtaining the polymkeric substance dope thus in NMP dope 1500 weight parts of the polymkeric substance that obtains in reference example 12,90 ℃ were stirred 1 hour down, make the polymkeric substance dope of homogeneous.Carry out spinning with program similarly to Example 15, obtain ultimate fibre.

Embodiment 18

Use among the embodiment 7 and obtain carbon nanotube 4.680 weight parts, in addition, carry out same operation with embodiment 15.

Embodiment 19

Use among the embodiment 3 and obtain carbon nanotube 4.680 weight parts, in addition, carry out same operation with embodiment 18.

Embodiment 20

200 ℃ of NMP dispersion liquid 300 weight parts that heat the carbon nanotube that obtained in the reference example 5 in 1 hour down, after fully removing the moisture that contains in the dispersion liquid, add Ursol D 0.864 weight part, 3,4 '-diaminodiphenyl oxide, 1.635 weight parts, carry out the ultrasonication of 28kHz under 0 ℃, add phthalic acid dichloride 3.245 weight parts behind the amine solvent, 0 ℃ of bottom carries out the ultrasonication limit of 28kHz and continues reaction 60 minutes, finally make it to react 60 minutes under the same ultrasonic wave condition down at 80 ℃, add calcium hydroxide 0.59 weight part, carry out neutralization reaction.

Embodiment 21

Use among the embodiment 11 and obtain carbon nanotube 4.680 weight parts, in addition, carry out same operation with embodiment 15.

Embodiment 22

Use among the embodiment 13 and obtain carbon nanotube 4.680 weight parts, in addition, carry out same operation with embodiment 15.

Embodiment 23

Use the NMP dispersion liquid that obtains carbon nanotube among the embodiment 11, in addition, carry out same operation with embodiment 20.

The measurement result of each physical data of embodiment 15～23 sees Table 2.

Table 2

	Young's modulus	Tensile strength	Orientation coefficient F	Raman P=I _YY/I _XX
	Young's modulus	Tensile strength	Orientation coefficient F	Raman P=I _YY/I _XX		GPa	(gf/de)
Embodiment 15	76	27		0.18		GPa	(gf/de)
Embodiment 15	76	27		0.18	Embodiment 16	77	26		0.21
Embodiment 17	79	29		0.16	Embodiment 16	77	26		0.21
Embodiment 17	79	29		0.16	Embodiment 18	71	25	0.523
Embodiment 19	73	22	0.512		Embodiment 18	71	25	0.523
Embodiment 19	73	22	0.512		Embodiment 20	72	24	0.563
Embodiment 21	69	24	0.498		Embodiment 20	72	24	0.563
Embodiment 21	69	24	0.498		Embodiment 22	72	23	0.538
Embodiment 23	70	25	0.549		Embodiment 22	72	23	0.538

Embodiment 24

In NMP (N-N-methyl-2-2-pyrrolidone N-) 300 weight parts, add clear and electrician's corporate system carbon nanotube VGCF9.360 weight part, use NETZSCH corporate system ball mill MINIZETA (air), the microballon of the 0.8mm diameter of the zirconium system of use, under 2500rmp, handled 1 hour, obtain the dispersion liquid of carbon nanotube.200 ℃ of NMP dispersion liquid 300 weight parts that heat the carbon nanotube that obtained thus in 1 hour down, after fully removing the moisture that contains in the dispersion liquid, add Ursol D 1.728 weight parts, 3,4 '-diaminodiphenyl oxide, 3.270 weight parts, carry out the ultrasonication of 28kHz under 0 ℃, add phthalic acid dichloride 6.490 weight parts behind the amine solvent, 0 ℃ of bottom carries out the ultrasonication limit of 28kHz and continues reaction 60 minutes, finally after making it to react 60 minutes under the same ultrasonic wave condition under 80 ℃, add calcium hydroxide 1.18 weight parts, carry out neutralization reaction.

Embodiment 25

In the reaction unit that possesses whipping appts, reliever and distillation tower etc., pack 2 into, multilayer carbon nanotube 0.5 weight part, dihydroxyphenyl propane disodium salt 0.014 weight part, Dimethylamino pyridine 0.061 weight part that obtain in 2 '-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane), 25.08 weight parts, diphenyl carbonate 23.54 weight parts, the reference example 6,180 ℃, N ₂Under the atmosphere, stirred 30 minutes dissolving.

Then, under uniform temp, under the decompression of 100mmHg, the limit distillation was removed phenol 1 hour, and the limit makes its reaction.And then the limit is warming up to 200 ℃, and the limit is decompressed to 30mmHg, synthermal, with reaction under the pressure 1 hour.And then reaction system is warming up to 280 ℃, and be decompressed to 0.5mmHg (6.67Pa), with carrying out polymerization in 0.3 hour under the condition, obtain containing the aromatic copolycarbonate of carbon nanotube.

Then, methylene dichloride 2000 weight parts are added in these aromatic copolycarbonate 20 weight parts, the dissolving aromatic copolycarbonate, utilizing the aperture is the Teflon system filter membrane filter suction filtration of 0.22 μ m, washing obtains by the aromatic copolycarbonate coated carbon nanotube.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the methylene dichloride of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.03 weight part, can confirm that 0.07 weight part is dissolved in the methylene dichloride.The aromatic copolycarbonate that has coated carbon nanotube is 23.3wt%.

Embodiment 26

Distillate in the reaction vessel of system and put into phthalic acid 5.81 weight parts, m-phthalic acid 2.49 weight parts, 2 having the vacuum that whipping appts and nitrogen introducing port are housed, two (4-hydroxyphenyl) propane of 2-(are commonly called as: multilayer carbon nanotube 0.2 weight part and 4-Dimethylamino pyridine 0.0061 weight part that obtains in 12.56 weight parts, diphenyl carbonate 22.49 weight parts, the reference example 6 dihydroxyphenyl propane), make in the reaction vessel to after the nitrogen atmosphere, begin reaction under following 200 ℃ of the normal pressure.Be warming up to 220 ℃ under the normal pressure after 30 minutes, after the synthermal phenol of affirmation down gold-plating goes out, slowly reduce the system internal pressure.The reaction beginning confirmed that raw material dissolves equably after 3 hours.

Afterwards, heat up, decompression, the reaction beginning is after 5 hours, and outlet temperature is 320 ℃ in the system, and vacuum tightness is about 0.5mmHg (66.7Pa).With carrying out polymerization in 0.3 hour under the condition, obtain containing aromatic polyester carbonate 19 weight parts of carbon nanotube.

Then, with phenol/1,1,2,2-tetrachloromethane mixing solutions (weight ratio 60/40) 2000 weight parts are added in these aromatic polyester carbonate 19 weight parts, the dissolving aromatic polyester carbonate, and utilizing the aperture is the Teflon system filter membrane filter suction filtration of 0.22 μ m, washing obtains by the aromatic polyester carbonate coated carbon nanotube.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the methylene dichloride of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.04 weight part, can confirm that 0.06 weight part is dissolved in the methylene dichloride.The aromatic polyester carbonate that has coated carbon nanotube is 32.5wt%.

Embodiment 27

Use phthalic acid 5.81 weight parts, m-phthalic acid 2.49 weight parts, 2, two (4-hydroxyphenyl) propane of 2-(are commonly called as: dihydroxyphenyl propane) 11.42 weight parts, diphenyl carbonate 21.75 weight parts, in addition, carry out same operation with embodiment 26, obtain by the Wholly aromatic polyester coated carbon nanotube.Carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the methylene dichloride of 100 weight parts to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.05 weight part, can confirm that 0.05 weight part is dissolved in the methylene dichloride.The aromatic polyester carbonate that has coated carbon nanotube is 26.9wt%.

Embodiment 28

In the ethylene glycol of 10 weight parts, handle the multilayer carbon nanotube of 3 weight parts that obtained in the reference example 6 in 1 hour with clarifixator, the dispersion liquid that obtains is added in the bishydroxyethyl terephthalate of 40 weight parts, add ANTIMONY TRIOXIDE SB 203 99.8 PCT 0.014 weight part, begin reaction under 200 ℃.Be warming up to 270 ℃ through 30 minutes, through 2 hours the pressure in the system be reduced to 0.3mmHg by normal pressure afterwards, finally under 270 ℃, 0.3mmHg, reacted 30 minutes, obtain containing the polyethylene terephthalate of carbon nanotube.

Then, with phenol/1,1,2,2-tetrachloromethane mixing solutions (weight ratio 60/40) 2000 weight parts are added in these polyethylene terephthalate 20 weight parts, the dissolving polyethylene terephthalate, utilizing the aperture is the Teflon system filter membrane filter suction filtration of 0.22 μ m, obtains by the polyethylene terephthalate coated carbon nanotube.

In phenol/1,1,2 of 100 weight parts, carbon nanotube 0.1 weight part that utilizes ultrasonic wave to make in the 2-tetrachloromethane mixing solutions (weight ratio 60/40) to obtain thus disperses, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.02 weight part.The polyethylene terephthalate that has coated carbon nanotube is 25.8wt%.

Embodiment 29

In polyphosphoric acid 9.37 weight parts, add 4,6-diamino resorcin 2 hydrochlorides 0.21306 weight part, 176mmHg, 80 ℃ of following stirrings 24 hours.Reactant is cooled to 60 ℃, adds multilayer carbon nanotube 0.23421 weight part that obtains in five phosphorus oxide, 6.82 weight parts, terephthalic acid 0.16613 weight part, the reference example 6,2 hours, 140 ℃ were stirred 18 hours down.In the water of 100 weight parts, add the reactant that obtains, make it redeposition.With 100 weight part sulfuric acid scrubbing throw outs 3 times, utilizing the aperture is the Teflon system filter membrane filter suction filtration of 0.22 μ m, and washing obtains by all aromatic pyrrole coated carbon nanotube 0.21 weight part.That utilizes ultrasonic wave to make in 98% sulfuric acid of 100 weight parts to obtain thus is disperseed by enveloped carbon nanometer tube 0.1 weight part, and the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.02 weight part, can confirm that the carbon nanotube of 0.08 weight part is dissolved in the sulfuric acid.Carry out same processing in the methanesulfonic of 100 weight parts, the throw out that the result obtains is 0.01 weight part, can confirm that the carbon nanotube of 0.09 weight part is dissolved in the methanesulfonic.

Utilize differential heat scan heat balance to measure, the result, the amount that has coated all aromatic pyrrole of carbon nanotube is 8.39wt%.

Comparative example 1

Utilize ultrasonic wave that carbon nanotube (VGCF) 0.1 weight part clear and that the electrician makes is disperseed in 98% sulfuric acid of 100 weight parts, the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.08 weight part, can confirm that 0.02 weight part is dissolved in the sulfuric acid.

Comparative example 2

Utilize ultrasonic wave that carbon nanotube (VGCF) 0.1 weight part clear and that the electrician makes is disperseed in the NMP of 100 weight parts, the centrifugal acceleration of carrying out 1 minute is 51000m/s ²Centrifugation handle, the throw out that obtains is 0.085 weight part, can confirm that 0.015 weight part is dissolved among the NMP.

Comparative example 3

Use the lid of 5 of aperture 0.3mm, hole count to keep the polymkeric substance dope that obtains in the reference example 12, keeping the dope temperature is 80 ℃, extrudes in 56 ℃ the precipitation bath of the aqueous solution of NMP30 weight % most.Distance between capping and the precipitation bath face is 10mm.Fiber through spinning is washed down at 50 ℃, and 120 ℃ dry down, and the stretching ratio with 10 times stretches on 500 ℃ hot plate afterwards, obtains the ultimate fibre that stretches.Young's modulus is 60Gpa, and tensile strength is 18gf/de.

Claims

1. one kind by coated carbon nanotube, it is that polymer coats with respect to 100 weight part carbon nanotubes by 0.01～100 weight part aromatic condensation, described aromatic condensation be polymer be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a.

2. as claimed in claim 1 by coated carbon nanotube, wherein, aromatic condensation is that polymer is a fully aromatic polyamide, this fully aromatic polyamide comprise following formula (A) and (B),

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

Ar ¹, Ar ²Represent that independently of one another carbon number is 6～20 divalent aromatic base,

And satisfy following formula (1)

0.8≤a/b≤4/3 (1)

3. as claimed in claim 2 by coated carbon nanotube, wherein, the Ar of fully aromatic polyamide ¹For

And/or

Ar ²For

4. as claimed in claim 2 by coated carbon nanotube, wherein, fully aromatic polyamide is Ar ¹For

With

Ar ²For

Multipolymer, its copolymerization ratio is 1: 0.8～1: 1.2.

5. as claimed in claim 1 by coated carbon nanotube, wherein, aromatic condensation is that polymer is to comprise in following structural unit (C) and/or Wholly aromatic polyester (D), aromatic polyester carbonate, the aromatic copolycarbonate any,

Ar ³For replacing or unsubstituted carbon number is 6～20 aromatic base, R ¹, R ²Respectively do for oneself and replace or unsubstituted phenylene Y ¹For being selected from the group in the following formula group (E),

R ³～R ⁸Be at least a group in the aralkyl of the aryl of the cycloalkyl of the alkyl, carbon number 5 that are selected from hydrogen atom, halogen atom, carbon number 1～6 or 6, carbon number 6～12 and carbon number 6～12 independently of one another, q represents 4～10 integer.

6. as claimed in claim 1 by coated carbon nanotube, wherein, aromatic condensation is that polymer is the semi-aromatic polyester that comprises the aromatic dicarboxylic acid composition, reaches the aliphatic diol composition.

7. as claimed in claim 1 by coated carbon nanotube, wherein, aromatic condensation is that polymer is to satisfy following formula (F) and/or all aromatic pyrrole (G),

Y ², Y ³Be independently selected from O, S respectively, reach NH, Ar ⁴4 valency aromatic bases of expression carbon number 6～20, Ar ⁵The divalent aromatic base of expression carbon number 6～20.

8. as claimed in claim 2 by the manufacture method of coated carbon nanotube, wherein, satisfying the ratio of following formula (2) simultaneously,

0.8≤c/d≤4/3 (2)

C is the aromatic diamine of following formula (H) expression, and d is the aromatic dicarboxylic acid diaryl of following formula (J) expression or the mole number of respectively feeding of aromatic dicarboxylic acid two etherides that following formula (K) is represented,

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

X ¹OC-Ar ²-COX ² (K)

And then add carbon nanotube (N) with the ratio that satisfies following formula (3) and react, then with the reactants dissolved that obtains in organic solvent or acid solvent, filter, separate and be aggregated the thing coated carbon nanotube,

0.001≤(n)/(x)≤100 (3)

X represents to comprise aromatic diamine (H), aromatic dicarboxylic acid diaryl (J), and the weight part summation of the monomer component of aromatic dicarboxylic acid two etherides (K), (n) weight part of expression carbon nanotube (N).

9. as claimed in claim 2 by the manufacture method of coated carbon nanotube, wherein, to satisfy following formula (2) simultaneously ' ratio,

1＜c/d≤4/3 (2)’

NH ₂-Ar ¹-NH ₂ (H)

R ⁹-O ₂C-Ar ²-CO ₂-R ¹⁰ (J)

X ¹OC-Ar ²-COX ² (K)

React, synthetic amine end is more than the fully aromatic polyamide of the end that comprises carboxylic acid derivative, afterwards and then be added on the carbon nanotube (N) that carries out surface treatment in the acidic solution of pH 0.01～2 and obtain with the ratio that satisfies following formula (3) and react, then with the reactants dissolved that obtains in organic solvent or acid solvent, filtration, separation are aggregated the thing coated carbon nanotube

0.001≤(n)/(x)≤100 (3)

(x) weight part of the terminal fully aromatic polyamide of expression amine, (n) weight part of expression carbon nanotube (N).

10. as claimed in claim 5 by the manufacture method of coated carbon nanotube, described carbon nanotube is obtained by following method: satisfying following formula (4), and the mol ratio of (5) simultaneously,

0≤e/f≤1.05 (4)

0.9≤g/(e+f)≤1.1 (5)

The aromatic diol composition of the aromatic dicarboxylic acid composition of the following formula of feeding (L) expression, following formula (O) expression, and (P) diaryl carbonate of expression,

HOOC-Ar ³-COOH (L)

Ar ³It is identical with definition in the above-mentioned formula (C),

HO-R ¹-Y ¹-R ²-OH (O)

And then add carbon nanotube (N) with the ratio that satisfies following formula (6) and react, then with the reactants dissolved that obtains in organic solvent, filter, separate and be aggregated the thing coated carbon nanotube,

0.001≤(n)/(m)≤100 (6)

M is as the summation of the monomer component weight part of aromatic dicarboxylic acid composition (e), diol component (f), diaryl carbonate (g), (n) is the weight part of carbon nanotube (N).

11. as claimed in claim 6 by the manufacture method of coated carbon nanotube, described carbon nanotube is obtained by following method: satisfying the mol ratio of following formula (7),

0.8≤e’/f’≤1.2 (7)

Charging aromatic dicarboxylic acid composition, aliphatic diol composition, and then add carbon nanotube (N) with the ratio that satisfies following formula (8) and react, then with the reactants dissolved that obtains in organic solvent, filter, separate and be aggregated the thing coated carbon nanotube,

0.001≤(n)/(m)≤100 (8)

M is as the summation of the monomer component weight part of aromatic dicarboxylic acid composition (e), diol component (f), (n) is the weight part of carbon nanotube (N).

12. as claimed in claim 7 by the manufacture method of coated carbon nanotube, wherein, satisfying the mol ratio of following formula (9) simultaneously,

0.8≤(h+i)/j≤1.2 (9)

H is the aromatic amine derivant of following formula (Q) expression, and i is the aromatic amine derivant of following formula (R) expression, and j is the mole number of respectively feeding of the aromatic dicarboxylic acid derivative of following formula (S) expression,

Y ², Y ³Be independently selected from O, S respectively, reach NH, Ar ⁴4 valency aromatic bases of expression carbon number 6～20, or (Q), (R) also can be hydrochloride,

R ¹²-O ₂C-Ar ⁵-CO ₂-R ¹³ (S)

Ar ⁵The divalent aromatic base of representing carbon number 6～20 independently of one another, R ¹², R ¹³The aromatic base of representing hydrogen or carbon number 6～20 independently of one another,

And then add carbon nanotube (N) with the ratio that satisfies following formula (10) and react, then with the reactants dissolved that obtains in organic solvent, filter, the separating carbon nano-tube composition,

0.001≤(n)/(m)≤100 (10)

M is aromatic amine derivant composition (Q), (R), and the summation of the weight part of aromatic dicarboxylic acid derivative composition (S), (n) is the weight part of carbon nanotube (N).

13., use the carbon nanotube that in the acidic solution of pH 0.01～2, carries out surface treatment and obtain as each describedly be is characterized in that by the manufacture method of coated carbon nanotube in the claim 8～12.

14. as each is described by the manufacture method of coated carbon nanotube in the claim 8～12, it is characterized in that, utilize physical treatments such as ball mill, ball mill, clarifixator that carbon nanotube is disperseed in solvent, modulating the monomer of feeding in the carbon nanotube dispersion liquid that forms thus, make it reaction.

15. as each describedly be is characterized in that by the manufacture method of coated carbon nanotube in the claim 8～12, using median size is the carbon nanotube of 0.01～5 μ m.

16. as each describedly be is characterized in that by the manufacture method of coated carbon nanotube in the claim 8～12, using median size is the carbon nanotube of 0.3～200nm.

17. an aromatic condensation is a polymeric composition, it comprises: be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be polymer 100 weight parts and as claimed in claim 1 by coated carbon nanotube 0.01～100 weight part.

18. aromatic condensation as claimed in claim 17 is a polymeric composition, the aromatic condensation that is used for enveloped carbon nanometer tube be polymer and the aromatic condensation that becomes composition matrix be polymer for comprise following formula (A) and (B),

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

And satisfy the fully aromatic polyamide of following formula (1),

0.8≤a/b≤4/3 (1)

19. the molding of a carbon nanotube orientation in the long axis direction of molding or face, the composition that this molding comprises comprises: be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be polymer 100 weight parts and as claimed in claim 1 be polymer coated carbon nanotube 0.01～100 weight part by aromatic condensation; It is characterized in that utilizing the orientation coefficient F of the carbon nanotube that following formula (11) tries to achieve is more than 0.1,

< co s^{2} φ > = \frac{{&Integral;}_{0}^{π / 2} I (φ) \cos^{2} φ \sin φdφ}{{&Integral;}_{0}^{π / 2} I (φ) \sin φdφ}

F = \frac{3 < \cos^{2} φ > - 1}{2} - - - (11)

20. molding in the long axis direction carbon nanotube orientation of molding, the composition that this molding comprises comprises: be selected from fully aromatic polyamide, Wholly aromatic polyester, aromatic polyester carbonate, aromatic copolycarbonate, semi-aromatic polyester, and all aromatic pyrrole at least a aromatic condensation be polymer 100 weight parts and as claimed in claim 1 by coated carbon nanotube 0.01～100 weight part; It is characterized in that, be more than 0 below 0.7 by the orientation degree P of the carbon nanotube of following formula (12) expression,

P＝I _YY/I _XX (12)

21. as claim 19 or 20 described moldinies, the aromatic condensation that is used for enveloped carbon nanometer tube be polymer and the aromatic condensation that becomes composition matrix be polymer for comprise following formula (A) and (B),

-NH-Ar ¹-NH- (A)

-OC-Ar ²-CO- (B)

And satisfy the fully aromatic polyamide of following formula (1),

0.8≤a/b≤4/3 (1)

A is the mole number of repeating unit of the aromatic diamine of formula (A) expression, and b is a formula

(B) mole number of the repeating unit of Biao Shi aromatic dicarboxylic acid.

22. as claim 19 or 20 described moldinies, wherein, molding is a fiber.

23. as claim 19 or 20 described moldinies, wherein, molding is a film.