CN106149383B - A kind of colored carbon fiber based on ring group poly phosphazene film - Google Patents
A kind of colored carbon fiber based on ring group poly phosphazene film Download PDFInfo
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- CN106149383B CN106149383B CN201510127348.1A CN201510127348A CN106149383B CN 106149383 B CN106149383 B CN 106149383B CN 201510127348 A CN201510127348 A CN 201510127348A CN 106149383 B CN106149383 B CN 106149383B
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Abstract
The present invention provides a kind of colored carbon fibers based on ring group poly phosphazene film, and specifically, colour carbon fiber provided by the invention includes: carbon fiber ontology, and is located on the carbon fiber ontology, and the poly phosphazene film layer in conjunction with the carbon fiber ontology covalence graft；And the reflection spectrum peak of the colored carbon fiber can be within the scope of 390~750nm.Golden, red, green and blue (predominantly blue) can be presented in the colored carbon fiber under natural light, and there is no need to carry out chemical staining, and preparation method is simple, is suitble to industrialized production and application.
Description
Technical field
The invention belongs to stock-dye fields, and specifically, it is color based on the preparation of ring group poly phosphazene that the present invention is more particularly directed to one kind
The method of color carbon fiber.
Background technique
In nature, in riotous profusion colorful color, a part is due to pigment coloring, that is, these chemical substances can choose
The light of certain colors in white light is absorbed to property, and the light of other colors is reflected, to bring in riotous profusion colorful vision
Impression.These chemical substances are exactly so-called pigment or dyestuff.Such as carrotene, carrotene selective absorbing 400~
The blue light and green light of 500nm range, so, carrot shows orange red.In the Nature, some color is not needed
By chemical dye coloring, but by the special institutional framework of object itself, white light is allowed to interfere, diffraction, the objects such as scattering
Reason process generates color to make the light of certain color is stronger to reflect.Here it is so-called schemochromes, this is one
Kind physics coloring.Oil film, peacock feather on soap bubble, the water surface are all to show gorgeous color due to its own special structure
It is color.
Currently, in worldwide, fiber, textile coloration main means be exactly using physicochemical method,
Fiber and fabric surface absorption dyestuff or fixed dyestuff.However, dyeing process often use a large amount of toxic chemical dyes and
A large amount of water resource results in traditional dyeing and finishing industry and causes serious pollution to our environment.This is that we are urgently to be resolved
The problem of.On the other hand, some special fibres, such as carbon fiber, due to the special physicochemical characteristics of fiber itself, using tradition
Dyeing method, the dyeing effect that can not be got well.This also results in carbon fiber and its composite product, often only a kind of
Single black.
For these problems, schemochrome may provide a kind of good solution, that is, introduce one layer of knot in fiber surface
Structure chromatograph, needs not rely on dyestuff, so that it may obtain fiber lucuriant in design.Recently, domestic in schemochrome fiber research field
Outer scientist is in the method for active development preparation structure color fibre.Hongzhi Wang of Donghua University etc. is in Chemical
It is reported in Communications Vol.47 (2011) pp.12801-12803 and assembles one layer of opal in fiberglass surfacing
The SiO of structure2The glass fibre of schemochrome has been made in nanosphere.They are also in Nanoscale Vol.5 (2013)
It is reported in pp.6917-6922 using PMMA microsphere in one layer of opal structural of carbon fiber surface electro-deposition, to realize carbon
The target of fiber surface structure color.However, being not very well ordered, and microballoon in these nanospheres of fiber surface assembling
Between binding force and unstable.In industry, Japanese Di Ren company develops the Morphotex fiber (US with schemochrome
6,326,094).This fiber is made of multiple layer polymer thin layer, and each layer fiber membrane makes certain light that constructive interference occur, thus
The colourama of reflected wavelengths.The technology is the thin-layers interference coloring based on light, similar in nature butterfly's wing it is more
Tunic interferes coloring.But, manufacture craft is extremely complex, cannot achieve volume production.
In conclusion this field, which still lacks, can efficiently, simply prepare the colored carbon fiber that surface has structure chromatograph
Method.
Summary of the invention
The object of the present invention is to provide the colored carbon fibers that a kind of surface has structure chromatograph.
It is a further object of the present invention to provide one kind can efficiently, simply prepare the colored carbon that surface has structure chromatograph
The method of fiber.
The first aspect of the present invention provides a kind of colored carbon fiber, which is characterized in that the colored carbon fiber packet
It includes: carbon fiber ontology, and be located on the carbon fiber ontology, and the poly phosphazene in conjunction with the carbon fiber ontology covalence graft
Film layer；And the reflection spectrum peak of the colored carbon fiber within the scope of 390~750nm of visible light (preferably 400~500
In range).
In another preferred example, the colored carbon fiber is by carbon fiber ontology and to be located at the carbon fiber ontology
On, and the poly phosphazene film layer composition in conjunction with the carbon fiber ontology covalence graft.
In another preferred example, the colored carbon fiber only has single layer poly phosphazene film layer.
In another preferred example, color selected from the group below is presented in the colored carbon fiber under natural light: blue, green
Color, gold, or combinations thereof；Blue is preferably presented.
In another preferred example, the poly phosphazene film layer with a thickness of 10~1000nm, preferably 100~500nm.
In another preferred example, the poly phosphazene film layer includes: the chlordene ring being covalently attached with carbon fiber body surface
Triphosphine nitrile layer, and the bifunctional compound and hexachlorocyclotriphosphazene condensation polymer that are covalently attached with the hexachlorocyclotriphosphazene layer
Layer.
In another preferred example, the bifunctional compound is diamine or dihydric alcohol；Preferably: the binary
Amine (NH2-R-NH2) it is Diaminoalkane class compound N H2-(CH2)n-NH2And/or diamino aromatic compound, NH2-A-
NH2；Preferably, the diamino aromatic compound is selected from the group: 4,4 '-diaminodiphenyl ethers, para diaminobenzene, diamino
Base biphenyl, 4,4'-diaminodiphenyl sulfone, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminobenzophenones, or combinations thereof；With/
Or the dihydric alcohol is dihydroxy alkane compound HO- (CH2)n- OH and/or dihydroxy aromatic compounds HO-A-OH；Preferably
Ground, the dihydroxy aromatic compounds are selected from the group: 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxybiphenyls, and 4,4 '-two
Dihydroxy benaophenonel, 4,4 '-dihydroxy diphenyl sulfides, 4,4 '-dihydroxy diphenyl ethers, 4,4 '-dihydroxy diphenyl propanes, 2,2 '-
Double-(4- hydroxyphenyl) hexafluoropropane, or combinations thereof；Wherein, the n is 2~50, preferably 2~10；The A is to take
Generation or unsubstituted C6~C20 arlydene.
In another preferred example, the infrared spectroscopy of the colored carbon fiber has one or more features selected from the group below
Peak: 3416cm-1Near, 1631cm-1Nearby, 1502cm-1Nearby, 1249cm-1Nearby, 1206cm-1Nearby, 1167cm-1Near；
Wherein, described to refer to " near X " in X ± 10cm-1In range, preferably in X ± 5cm-1In range.
The second aspect of the present invention provides a kind of preparation side of colored carbon fiber as described in the first aspect of the invention
Method, the method includes the steps:
(1) (preferably, the carbon fiber of the surface oxidation is by carbon fiber surface to the carbon fiber of offer surface oxidation
Face carries out oxidation processes and obtains)；
(2) gathered with the carbon fiber of the surface oxidation with phosphine nitrile monomer compound and bifunctional compound
Reaction is closed, the colored carbon fiber of surface grafting cladding poly phosphazene film layer is obtained；
In another preferred example, in the step (2), the polymerization reaction is home position polymerization reaction.
In another preferred example, the carbon fiber of the surface oxidation is by carrying out oxidation processes for carbon fiber surface
It obtains.
In another preferred example, the oxidation processes include: by carbon fiber and strong acid hybrid reaction, and filtration drying obtains
To the carbon fiber of surface oxidation.
In another preferred example, the strong acid is oxidisability strong acid.
In another preferred example, the mixed weight of the carbon fibre precursor and strong acid ratio is carbon fibre precursor: strong acid=1
~10:100.
In another preferred example, the strong acid is selected from the group: nitric acid, sulfuric acid, or combinations thereof.
In another preferred example, the nitric acid is the nitric acid of concentration >=50%, the preferably nitric acid of concentration >=60%.
In another preferred example, the sulfuric acid is the sulfuric acid of concentration >=90%, the preferably sulfuric acid of concentration >=95%.
In another preferred example, the strong acid is the nitric acid that mass concentration is 60% and the sulfuric acid that mass concentration is 98%
The mixed acid being made by 1:4 volume ratio.
In another preferred example, the oxidation processes reaction temperature is 50~150 DEG C, preferably 60~120 DEG C.
In another preferred example, the oxidation processes reaction time is 0.5~4 hour.
In another preferred example, before the carbon fiber is dried, with deionized water by fiber wash to washing lotion
For neutrality.
In another preferred example, the drying temperature is 60~100 DEG C.
In another preferred example, the step (2) includes:
(2a) reacts the carbon fiber of the surface oxidation with hexachlorocyclotriphosphazene, obtains surface grafting hexachlorocyclotriphosphazene
Carbon fiber；With
(2b) is by the carbon fiber of the surface grafting hexachlorocyclotriphosphazene and bifunctional compound and hexachlorocyclotriphosphazene
Reaction, obtains the carbon fiber of surface grafting poly phosphazene layer.
In another preferred example, the step (2a) includes: to be put into the carbon fiber of the first acid binding agent and surface oxidation
In solvent, then hexachlorocyclotriphosphazene is added in above-mentioned solution and reacted, obtains the carbon fiber of surface grafting hexachlorocyclotriphosphazene；
And/or
The step (2b) includes: (to add monomer hexachlorocyclotriphosphazene and bifunctional compound after preferably mixing again
Enter) it is added in the reaction solution for the carbon fiber that placement surface is grafted hexachlorocyclotriphosphazene, it adds the second acid binding agent and is reacted, obtained
To the colored carbon fiber of surface grafting cladding poly phosphazene film layer.
In another preferred example, in the step (2a),
First acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof (preferably
Triethylamine)；And/or
The weight ratio of the carbon fiber of first acid binding agent and the surface oxidation is 20~300:100；And/or
The weight ratio of the hexachlorocyclotriphosphazene and carbon oxide fiber is 5~100:100.
In another preferred example, in the step (2a), the solvent is selected from the group: tetrahydrofuran, toluene, anhydrous
Acetonitrile (preferably anhydrous acetonitrile), acetone, or combinations thereof.
In another preferred example, in the step (2a), reaction reaction 2~24 under conditions of 30~80 DEG C is small
When.
In another preferred example, in the step (2b),
Second acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof (preferably
Triethylamine)；And/or
The carbon fiber of the grafting hexachlorocyclotriphosphazene and the gross weight of the hexachlorocyclotriphosphazene and bifunctional compound
The weight ratio of amount is 100:50~600；And/or
The mol ratio of the bifunctional compound and hexachlorocyclotriphosphazene is 3.0~4.5:1.0；And/or
The weight ratio of the grafting hexachlorocyclotriphosphazene carbon fiber and the second acid binding agent is 100:50~1000, preferably
100:120~500, more preferably 100:150~300.
In another preferred example, in the step (2b), the solvent is selected from the group: tetrahydrofuran, toluene, anhydrous
Acetonitrile (preferably anhydrous acetonitrile), acetone, or combinations thereof.
In another preferred example, in the step (2b), the reaction reacts 0.2~24 under conditions of 30~80 DEG C
Hour.
In another preferred example, in the step (2b), the reaction is super in 30~80 DEG C of constant temperature stirrings or water-bath
It is reacted 0.5~24 hour under the conditions of sound.
In another preferred example, the method also includes: after the step (2) or the step (2b), to acquired
Carbon fiber post-processed as follows: taking out fiber solvent or/and water, supersound washing is multiple repeatedly, under the conditions of 50~100 DEG C,
Vacuum drying.
In another preferred example, the method also includes: after the step (2) or the step (2b), to acquired
Carbon fiber post-processed as follows: take out fiber solvent or/and water and carry out soxhlet type, under the conditions of 50~100 DEG C, vacuum
It is dry.
In another preferred example, it after taking out the carbon fiber, is washed repeatedly with solvent, and in the case where temperature is 50~100 DEG C
It is dried.
In another preferred example, the first acid binding agent used in step (2a) and (2b) and the second acid binding agent can be identical or not
Together.
In another preferred example, the bifunctional compound is diamine or dihydric alcohol；Preferably:
Diamine (the NH2-R-NH2) it is Diaminoalkane class compound N H2-(CH2)n-NH2And/or diamino virtue
Fragrant compounds of group, NH2-A-NH2；Preferably, the diamino aromatic compound is selected from the group: 4,4 '-diamino hexichol
Ether, para diaminobenzene, benzidine, 4,4'-diaminodiphenyl sulfone, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino two
Benzophenone, or combinations thereof；With
The dihydric alcohol is dihydroxy alkane compound HO- (CH2)n- OH and/or dihydroxy aromatic compounds HO-A-
OH；Preferably, the dihydroxy aromatic compounds are selected from the group: 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxybiphenyls,
4,4'-Dihydroxybenzophenone, 4,4 '-dihydroxy diphenyl sulfides, 4,4 '-dihydroxy diphenyl ethers, 4,4 '-dihydroxy, two phenylpropyl alcohol
Alkane, 2,2 '-bis--(4- hydroxyphenyl) hexafluoropropane, or combinations thereof；
Wherein, the n is 2~50, preferably 2~10；
The A is substituted or unsubstituted C6~C20 arlydene.
The third aspect of the present invention provides a kind of preparation side of colored carbon fiber as described in the first aspect of the invention
Method, the method includes the steps:
(2b) has the carbon fiber and bifunctional compound of hexachlorocyclotriphosphazene grafting layer with surface in atent solvent
Polymerization reaction is carried out with hexachlorocyclotriphosphazene, obtains the carbon fiber of surface grafting poly phosphazene film layer.
The fourth aspect of the present invention, provides a kind of composite material, and the composite material has such as first aspect present invention
The colored carbon fiber or the composite material are prepared with colored carbon fiber as described in the first aspect of the invention.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
The SEM picture for the blue structural colour carbon fiber that Fig. 1 in-situ polymerization obtains.
The optical microscope photograph for the blue carbon fiber that Fig. 2 in-situ polymerization obtains.Wherein Fig. 2 a is a branch of blue carbon fiber,
Fig. 2 b is single blue carbon fiber.
The reflectance spectrum figure of Fig. 3 blue structural colour carbon fiber.
The infrared spectrogram of Fig. 4 carbon fiber.Wherein Fig. 4 a is the infrared spectroscopy of carbon oxide fiber, and Fig. 4 b is blue schemochrome
The infrared spectroscopy of carbon fiber.
Specific embodiment
The present inventor is based on for a long time and in-depth study, it has unexpectedly been found that, it is coated with by a kind of surface of preparation and is covalently connect
The carbon fiber for the poly phosphazene film layer that branch combines, it is unexpectedly available that blue colored carbon fiber is showed under natural light.And
The colored carbon fiber production method is simple, is easy to volume production, therefore have good industrial application value.Based on above-mentioned hair
Existing, inventor completes the present invention.
The colored carbon fiber of surface cladding poly phosphazene film layer
The present invention provides a kind of carbon fiber based on poly phosphazene film preparation schemochrome, the structural colour carbon fiber has
Good optical property, and it is dyed without using chemical dye colour can be presented under natural light, thus for
The dyeing of the environmental pollution and carbon fiber that reduce Dyeing & Finishing Industry has important reference value.
The colored carbon fiber one layer of hundred nano-scale of carbon fiber body surface grafting and coating (thickness is about 10~
Poly phosphazene film layer 1000nm).Since poly phosphazene film layer is to the interference effect of light, blue can be presented in carbon fiber, it might even be possible to
It is golden, green and red.
Specifically, the colored carbon fiber includes: carbon fiber ontology, and is located on the carbon fiber ontology, and with
The poly phosphazene film layer that the carbon fiber ontology covalence graft combines, the reflection spectrum peak of the colored carbon fiber can 390~
Within the scope of 750nm, it is therefore preferable between 400~480nm.The colored carbon fiber does not have in other regions of visible region
There is reflection spectrum peak, or only there is very weak reflection spectrum peak, therefore face selected from the group below can be usually presented in it under natural light
Color: blue, green, gold, or combinations thereof；Blue is preferably presented.
In the colored carbon fiber, the poly phosphazene film layer refers to total with hexachlorocyclotriphosphazene and bifunctional compound
Polycondensation monomer is formed by poly- in carbon fiber (preferably first passing through the carbon fiber of oxidation processes in advance) surface progress home position polymerization reaction
Compound film layer, a kind of preferred poly phosphazene film layer include: the hexachlorocyclotriphosphazene layer being covalently attached with carbon fiber body surface, with
And the polymeric layer for the bifunctional compound and hexachlorocyclotriphosphazene being covalently attached with the hexachlorocyclotriphosphazene layer.
In the colored carbon fiber, the poly phosphazene film layer with a thickness of 10~1000nm, preferably 100~
500nm。
The oxidation processes of carbon fiber
The oxidation of carbon fiber can be carried out by conventional technique, such as gaseous oxidation technology, liquid phase oxidation technology, electrochemistry oxygen
Change technology etc..In the present invention, the oxidation of carbon fiber uses liquid phase oxidation technology, and by carbon fiber and strong acid hybrid reaction, filtering is dried
It is dry, obtain the carbon fiber of surface oxidation.
The carbon fibre precursor specification is unlimited, optionally obtains or is prepared by a conventional method by commercially available approach.
Preferably, the carbon fibre precursor is unsized carbon fibre precursor.
In the present invention, the oxidation processes can use methods known in the art, for example, in another preference
In, the oxidation processes include: that carbon fiber and strong acid hybrid reaction, filtration drying are obtained the carbon fiber of surface oxidation.
The strong acid is oxidisability strong acid, such as nitric acid, sulfuric acid, or combinations thereof.In another preferred example, the nitric acid
For the nitric acid of concentration >=50%, the preferably nitric acid of concentration >=60%.In another preferred example, the sulfuric acid be concentration >=
90% sulfuric acid, the preferably sulfuric acid of concentration >=95%.In another preferred example, it is 60% that the strong acid, which is mass concentration,
Nitric acid and mass concentration be 98% the mixed acid that is made by 1:4 volume ratio of sulfuric acid.
In another preferred example, the mixed weight of the carbon fibre precursor and strong acid ratio is carbon fibre precursor: strong acid=
0.1~20:100, preferably 1~15:100.
The condition of the oxidation processes is not particularly limited, and in another preferred example, the oxidation processes react temperature
Degree is 50~150 DEG C, preferably 60~120 DEG C.In another preferred example, the oxidation processes reaction time is 2~4 small
When.
In another preferred example, before the carbon fiber is dried, with deionized water by fiber wash to washing lotion
For neutrality.
In another preferred example, the drying carries out at being 60~100 DEG C in temperature.
Surface coats the preparation of the colored carbon fiber of poly phosphazene film layer
The present invention also provides the preparation methods of the colored carbon fiber described in one kind, which is characterized in that comprising steps of
(1) (preferably, the carbon fiber of the surface oxidation is by carbon fiber surface to the carbon fiber of offer surface oxidation
Face carries out what oxidation processes obtained)；
(2) gathered with the carbon fiber of the surface oxidation with phosphine nitrile monomer compound and bifunctional compound
Reaction is closed, the colored carbon fiber of surface grafting cladding poly phosphazene film layer is obtained；
In another preferred example, in the step (2), the polymerization reaction is home position polymerization reaction.
In another preferred example, the carbon fiber of the surface oxidation is by carrying out oxidation processes for carbon fiber surface
It obtains.The oxidation processes can use methods known in the art, for example, in another preferred example, at the oxidation
Reason includes: that carbon fiber and strong acid hybrid reaction, filtration drying are obtained the carbon fiber of surface oxidation.
The strong acid is oxidisability strong acid, such as nitric acid, sulfuric acid, or combinations thereof.In another preferred example, the nitric acid
For the nitric acid of concentration >=50%, the preferably nitric acid of concentration >=60%.In another preferred example, the sulfuric acid be concentration >=
90% sulfuric acid, the preferably sulfuric acid of concentration >=95%.In another preferred example, it is 60% that the strong acid, which is mass concentration,
Nitric acid and mass concentration be 98% the mixed acid that is made by 1:4 volume ratio of sulfuric acid.
In another preferred example, the mixed weight of the carbon fibre precursor and strong acid ratio is carbon fibre precursor: strong acid=
0.1~20:100, preferably 1~15:100.
The condition of the oxidation processes is not particularly limited, and in another preferred example, the oxidation processes react temperature
Degree is 50~150 DEG C, preferably 60~120 DEG C.In another preferred example, the oxidation processes reaction time is 2~4 small
When.
In another preferred example, before the carbon fiber is dried, with deionized water by fiber wash to washing lotion
For neutrality.
In another preferred example, the drying carries out at being 60~100 DEG C in temperature.
In the preferred embodiment of the present invention, the step (2) is further comprised the steps of:
(2a) reacts the carbon fiber of the surface oxidation with hexachlorocyclotriphosphazene, obtains surface grafting hexachlorocyclotriphosphazene
Carbon fiber；With
(2b) is by the carbon fiber of the surface grafting hexachlorocyclotriphosphazene and bifunctional compound and hexachlorocyclotriphosphazene
Comonomer reaction, obtains the carbon fiber of surface grafting poly phosphazene film layer by in-situ polymerization.
In another preferred example, the colored carbon fiber can also by using it is commercially available or pass through existing method prepare
, there is the carbon fiber of hexachlorocyclotriphosphazene grafting layer directly to carry out instead with bifunctional compound and hexachlorocyclotriphosphazene on surface
It answers, obtains the carbon fiber of surface grafting cladding poly phosphazene layer.
The poly phosphazene film layer for being arbitrarily capable of forming colored carbon fiber of the invention can be selected in the step (2a) and (2b)
Method, after disclosing the contents of the present invention, it is such selection it would have been obvious for a person skilled in the art.
In another preferred example, the step (2a) includes: to be put into the carbon fiber of the first acid binding agent and surface oxidation
In solvent, then hexachlorocyclotriphosphazene is added in above-mentioned solution and reacted, obtains the carbon fiber of surface grafting hexachlorocyclotriphosphazene；
And/or
The step (2b) includes: (to add monomer hexachlorocyclotriphosphazene and bifunctional compound after preferably mixing again
Enter) it is added in the laying reaction solution of the carbon fiber of surface grafting hexachlorocyclotriphosphazene, it adds the second acid binding agent and is reacted,
Obtain the colored carbon fiber of surface grafting cladding poly phosphazene film layer.
In another preferred example, in the step (2a),
First acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof；And/or
The weight ratio of the carbon fiber of first acid binding agent and the surface oxidation be 20~300 (preferably 60~250,
More preferably 65~250): 100；And/or
The weight ratio of the hexachlorocyclotriphosphazene and carbon oxide fiber is 5~100 (preferably 20~250, more preferably 25
~250): 100.
In another preferred example, in the step (2a), the solvent is selected from the group: tetrahydrofuran, toluene, anhydrous
Acetonitrile (preferably anhydrous acetonitrile), acetone, or combinations thereof.
In another preferred example, in the step (2a), reaction reaction 2~24 under conditions of 30~80 DEG C is small
When.
In another preferred example, in the step (2b),
Second acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof；And/or
The carbon fiber of the grafting hexachlorocyclotriphosphazene and the gross weight of the hexachlorocyclotriphosphazene and bifunctional compound
The weight ratio of amount is 100:50~600；And/or
The mol ratio of the bifunctional compound and hexachlorocyclotriphosphazene is 3.0~4.5:1.0；And/or
The weight ratio of the grafting hexachlorocyclotriphosphazene carbon fiber and the second acid binding agent is 100:50~1000, preferably
100:120~500, more preferably 100:150~300.
In another preferred example, in the step (2b), the solvent is selected from the group: tetrahydrofuran, toluene, anhydrous
Acetonitrile (preferably anhydrous acetonitrile), acetone, or combinations thereof.
In another preferred example, in the step (2b), the reaction reacts 0.2~24 under conditions of 30~80 DEG C
Hour.
In another preferred example, in the step (2b), the reaction is super in 30~80 DEG C of constant temperature stirrings or water-bath
It is reacted 0.5~24 hour under the conditions of sound.
In another preferred example, the method also includes: after the step (2) or the step (2b), to acquired
Carbon fiber post-processed as follows: taking out fiber solvent or/and water, supersound washing is multiple repeatedly, under the conditions of 50~100 DEG C,
Vacuum drying.
In another preferred example, the method also includes: after the step (2) or the step (2b), to acquired
Carbon fiber post-processed as follows: take out fiber solvent or/and water and carry out soxhlet type, under the conditions of 50~100 DEG C, vacuum
It is dry.
In another preferred example, it after taking out the carbon fiber, is washed repeatedly with solvent, and in the case where temperature is 50~100 DEG C
It is dried.
In another preferred example, the first acid binding agent used in step (2a) and (2b) and the second acid binding agent can be identical or not
Together.
In another preferred example, the bifunctional compound is diamine or dihydric alcohol；Preferably:
Diamine (the NH2-R-NH2) it is Diaminoalkane class compound N H2-(CH2)n-NH2And/or diamino virtue
Fragrant compounds of group, NH2-A-NH2；Preferably, the diamino aromatic compound is selected from the group: 4,4 '-diamino hexichol
Ether, para diaminobenzene, benzidine, 4,4'-diaminodiphenyl sulfone, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino two
Benzophenone, or combinations thereof；With
The dihydric alcohol is dihydroxy alkane compound HO- (CH2)n- OH and/or dihydroxy aromatic compounds HO-A-
OH；Preferably, the dihydroxy aromatic compounds are selected from the group: 4,4 '-dihydroxydiphenylsulisomers, 4,4 '-dihydroxybiphenyls,
4,4'-Dihydroxybenzophenone, 4,4 '-dihydroxy diphenyl sulfides, 4,4 '-dihydroxy diphenyl ethers, 4,4 '-dihydroxy, two phenylpropyl alcohol
Alkane, 2,2 '-bis--(4- hydroxyphenyl) hexafluoropropane, or combinations thereof；
Wherein, the n is 2~50, preferably 2~10；
The A is substituted or unsubstituted C6~C20 arlydene.
Compared with prior art, main advantages of the present invention include:
1. providing a kind of colored carbon fiber, the colored carbon fiber, can be in natural light without carrying out chemical staining
Lower presentation blue, and preparation method is simple, is suitble to industrialized production.
2. a kind of preparation method of colored carbon fiber is provided, compared with existing colored carbon fiber production method, this hair
Bright preparation method is more easy, and product quality is easily controllable.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Those skilled in the art makes some nonessential according to the content of aforementioned present invention
Modifications and adaptations still fall within the scope of the present invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to
Normal condition, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Embodiment 1
Step (1) carbon fibre precursor oxidation processes: 1 parts by weight of carbon fibers is added in the nitric acid of 100 parts by weight 60%, so
It flows back 2 hours under conditions of temperature is 80 DEG C afterwards, taking out carbon fiber and being washed with deionized to washing lotion is neutrality, in temperature
It is dried under conditions of being 60 DEG C, obtains the carbon fiber of surface oxidation；
Step (2) preparation surface is connected to the carbon fiber of hexachlorocyclotriphosphazene: by acid binding agent and carbon oxide fiber according to 90:
100 weight ratios are put into anhydrous acetonitrile, then the hexachlorocyclotriphosphazene of 50 parts by weight is dissolved in solvent and is slowly added to above-mentioned reaction
It in solution, is reacted 12 hours under conditions of 40 DEG C, takes out the washing of carbon fiber Wesy solvent repeatedly, under the conditions of temperature is 60 DEG C,
Vacuum oven is spare.
Step (3) carbon fiber surface grafted polyphosphazene: the carbon fiber of the grafting hexachlorocyclotriphosphazene of 100 parts by weight is put into
In anhydrous acetonitrile, then gross weight is molten for the above-mentioned reaction of 4,4 '-diaminodiphenyl ethers and hexachlorocyclotriphosphazene addition of 450 parts by weight
In liquid, wherein 4, the mol ratio of 4 '-diaminodiphenyl ethers and chlordene ring triphosphine is 3.6:1.0, and 300 weight are added after dissolution
Part acid binding agent, be stirred to react 10 hours in 40 DEG C of constant temperature, taking out carbon fiber Wesy solvent and water, supersound washing is repeatedly or rope repeatedly
Family name extracts, and under the conditions of 60 DEG C, vacuum oven obtains the blue carbon fiber of surface cladding poly phosphazene film layer.Fig. 1 is to obtain
Blue carbon fiber scanning electron microscope (SEM) picture.Fig. 2 and Fig. 3 is respectively that the optical microscopy of obtained blue carbon fiber shines
The reflectance spectrum figure of piece and blue carbon fiber.It is the carbon fiber of blue as we can clearly see from the figure.Reflectance spectrum peak exists
Near 450nm, the spectrum peak of blue is corresponded to.
Embodiment 2
Step (1) carbon fibre precursor oxidation processes: 10 parts by weight of carbon fibers are put into 100 parts by weight, 98% sulfuric acid, so
It flows back 2 hours under conditions of temperature is 80 DEG C afterwards, filtering and being washed with deionized to washing lotion later is neutrality, is in temperature
Drying obtains the carbon fiber of surface oxidation under conditions of 80 DEG C；
Step (2) preparation surface is connected to the carbon fiber of hexachlorocyclotriphosphazene: by acid binding agent and carbon oxide fiber according to 40:
100 weight ratios are put into anhydrous tetrahydro furan, then the hexachlorocyclotriphosphazene of 15 parts by weight is dissolved in solvent be slowly added to it is above-mentioned
It in reaction solution, is reacted 12 hours under conditions of 50 DEG C, takes out the washing of carbon fiber Wesy solvent repeatedly, be 60 DEG C of conditions in temperature
Under, vacuum oven is spare.
Step (3) carbon fiber surface grafted polyphosphazene: the carbon fiber of the grafting hexachlorocyclotriphosphazene of 100 parts by weight is put into
In anhydrous acetonitrile, then gross weight is molten for the above-mentioned reaction of 4,4 '-diaminodiphenyl ethers and hexachlorocyclotriphosphazene addition of 250 parts by weight
In liquid, wherein 4, the mol ratio of 4 '-diaminodiphenyl ethers and chlordene ring triphosphine is 4.5:1.0, and 150 weight are added after dissolution
The acid binding agent of part, is stirred to react 24 hours in 40 DEG C of constant temperature, and supersound washing is multiple repeatedly for taking-up carbon fiber Wesy solvent and water, and 60 DEG C
Under the conditions of, vacuum oven obtains the blue carbon fiber of surface cladding poly phosphazene film layer.The blue carbon fiber that Fig. 4 is
Infrared spectroscopy (FT-IR) picture of dimension can see the ring group poly phosphazene that ODA and HCCP are copolymerized from FT-IR map
Characteristic peak: 3416cm-1(ν N-H), 1631cm-1With 1502cm-1(ν Phenyl ring C=C)；1249cm-1(νC-O-C)；
1206cm-1With 1167cm-1(ν Phosphazene ring P=N).
Embodiment 3
Step (1) carbon fibre precursor oxidation processes: 10 parts by weight of carbon fibers are put into 100 parts by weight, 60% nitric acid, so
It flows back 2 hours under conditions of temperature is 60 DEG C afterwards, filtering and being washed with deionized to washing lotion later is neutrality, is in temperature
Drying obtains the carbon fiber of surface oxidation under conditions of 80 DEG C；
Step (2) preparation surface is connected to the carbon fiber of hexachlorocyclotriphosphazene: by acid binding agent and carbon oxide fiber according to 20:
100 weight ratios are put into anhydrous tetrahydro furan, then the hexachlorocyclotriphosphazene of 10 parts by weight is dissolved in solvent be slowly added to it is above-mentioned
It in reaction solution, is reacted 6 hours under conditions of 60 DEG C, takes out the washing of carbon fiber Wesy solvent repeatedly, be 60 DEG C of conditions in temperature
Under, vacuum oven is spare.
Step (3) carbon fiber surface grafted polyphosphazene: the carbon fiber of the grafting hexachlorocyclotriphosphazene of 100 parts by weight is put into
In anhydrous acetonitrile, then gross weight is molten for the above-mentioned reaction of 4,4 '-dihydroxydiphenylsulisomers and hexachlorocyclotriphosphazene addition of 400 parts by weight
In liquid, wherein 4, the mol ratio of 4 '-dihydroxydiphenylsulisomers and chlordene ring triphosphine is 4.0:1.0, and 250 weight are added after dissolution
The acid binding agent of part, is stirred to react 12 hours in 50 DEG C of constant temperature, and supersound washing is multiple repeatedly for taking-up carbon fiber Wesy solvent and water, 50~
Under the conditions of 100 DEG C, vacuum oven obtains the blue carbon fiber of surface cladding poly phosphazene film layer.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (9)
1. a kind of colour carbon fiber, which is characterized in that the colored carbon fiber includes: carbon fiber ontology, and is located at described
On carbon fiber ontology, and the poly phosphazene film layer in conjunction with the carbon fiber ontology covalence graft；And the colored carbon fiber
Reflection spectrum peak is within the scope of 390~750nm of visible light, and the poly phosphazene film layer includes: total with carbon fiber body surface
The hexachlorocyclotriphosphazene layer of valence connection, and the bifunctional compound and chlordene that are covalently attached with the hexachlorocyclotriphosphazene layer
Ring triphosphine nitrile polycondensation nitride layer；
Wherein, the bifunctional compound is diamine or dihydric alcohol；
Diamine (the NH2-R-NH2) it is Diaminoalkane class compound N H2-(CH2)n-NH2And/or diamino aromatic series
Compound, NH2-A-NH2；The dihydric alcohol is dihydroxy alkane compound HO- (CH2)n- OH and/or dihydroxy aromatic
Close object HO-A-OH；
And wherein, the n is 2~50；The A is substituted or unsubstituted C6~C20 arlydene；The poly phosphazene film
Layer with a thickness of 10~1000nm.
2. colour carbon fiber as described in claim 1, which is characterized in that choosing is presented in the colored carbon fiber under natural light
From the color of the following group: blue, green, gold, or combinations thereof.
3. colour carbon fiber as described in claim 1, which is characterized in that indigo plant is presented in the colored carbon fiber under natural light
Color.
4. colour carbon fiber as described in claim 1, which is characterized in that the poly phosphazene film layer with a thickness of 100~
500nm。
5. the preparation method of colour carbon fiber as described in claim 1, which is characterized in that comprising steps of
(1) carbon fiber of surface oxidation is provided；
(2a) reacts the carbon fiber of the surface oxidation with hexachlorocyclotriphosphazene, obtains the carbon of surface grafting hexachlorocyclotriphosphazene
Fiber；With
(2b) in atent solvent, by the carbon fiber of the surface grafting hexachlorocyclotriphosphazene and bifunctional compound and chlordene
The reaction of ring triphosphine nitrile, obtains the carbon fiber of surface grafting poly phosphazene layer；
And the step (2a) includes: that the carbon fiber of the first acid binding agent and surface oxidation is put into solvent, then by chlordene ring
Triphosphine nitrile is added in above-mentioned solution and reacts, and obtains the carbon fiber of surface grafting hexachlorocyclotriphosphazene；The reaction is 30~80
It is reacted 2~24 hours under conditions of DEG C；The weight ratio of the carbon fiber of first acid binding agent and the surface oxidation be 20~
300:100；The weight ratio of the hexachlorocyclotriphosphazene and carbon oxide fiber is 5~100:100；
And the step (2b) includes: that placement surface grafting six is added in monomer hexachlorocyclotriphosphazene and bifunctional compound
It in the reaction solution of the carbon fiber of chlorine ring triphosphine nitrile, adds the second acid binding agent and is reacted, obtain surface grafting cladding poly phosphazene
The colored carbon fiber of film layer；In the step (2b), the reaction is reacted 0.2~24 hour under conditions of 30~80 DEG C；
The weight ratio of the grafting hexachlorocyclotriphosphazene carbon fiber and the second acid binding agent is 100:50~1000.
6. method as claimed in claim 5, which is characterized in that in the step (2a),
First acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof；
Or in the step (2b),
Second acid binding agent is selected from the group: triethylamine, sodium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof；And/or
The total weight of the carbon fiber and hexachlorocyclotriphosphazene and bifunctional compound of the grafting hexachlorocyclotriphosphazene
Weight ratio is 100:50~600；And/or
The mol ratio of the bifunctional compound and hexachlorocyclotriphosphazene is 3.0~4.5:1.0.
7. method as claimed in claim 6, which is characterized in that the carbon fiber and second of the grafting hexachlorocyclotriphosphazene is tied up
The weight ratio of sour agent is 100:120~500.
8. method as claimed in claim 6, which is characterized in that the carbon fiber and second of the grafting hexachlorocyclotriphosphazene is tied up
The weight ratio of sour agent is 100:150~300.
9. a kind of composite material, which is characterized in that the composite material has colored carbon fiber as described in claim 1, or
The composite material is prepared with colored carbon fiber as described in claim 1.
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