CN105113260B - A kind of method of carbon fiber surface functional amido - Google Patents
A kind of method of carbon fiber surface functional amido Download PDFInfo
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- CN105113260B CN105113260B CN201510512182.5A CN201510512182A CN105113260B CN 105113260 B CN105113260 B CN 105113260B CN 201510512182 A CN201510512182 A CN 201510512182A CN 105113260 B CN105113260 B CN 105113260B
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Abstract
The present invention relates to a kind of method of carbon fiber surface functional amido, this method, by a step solution dipping method, is coated copolymer coated containing a large amount of active amines using the Michael's addition and schiff base reaction of dopamine and many amido molecules in fiber surface.Compared with prior art, the method technique that provides of the present invention is simple, mild condition, do not damage fiber bodies structure, the active group of carbon fiber surface can be effectively increased, so as to improve the interfacial combined function of fiber and interlaminar resin.
Description
Technical field
Field is modified the invention belongs to carbon material, more particularly, to a kind of method of carbon fiber surface modification.
Background technology
Carbon fiber (CF) is high with specific strength as high-performance fiber of new generation, and specific modulus is high, and creep-resistant property is good, close
Degree is low, and heat endurance and chemical stability are good, and thermal coefficient of expansion is low and a series of excellent performances such as hot and electrical conductivity height, its
Composite is widely used to the fields such as Aero-Space, military project, communications and transportation, medical treatment and sports goods.
The performance of carbon fibre reinforced composite is the performance itself and interface cohesion between the two by CF and matrix
Performance is together decided on.Interface is mutually very important microstructure in composite, is connected as between reinforcement CF and matrix
" bridge ", have very important influence to every mechanical performance of composite.
Because CF surfaces are smooth and chemical inertness, lack active functional group, cause fiber and matrix compatibility not good enough,
Interface adhesion is poor, have impact on the mechanical property of composite, so as to greatly hinder the process of composite material high performance.
It then becomes necessary to carry out surface modification to CF using suitable method, to improve its surface-active and roughness, strengthen itself and tree
The Chemical bonding and physics inlay resultant force of fat, and then improve its wellability and caking property with matrix, it can just give full play to CF's
Humidification, obtains the composite of excellent combination property.
Mainly there are gaseous oxidation, liquid phase oxidation, electrochemical oxidation using more CF surface treatment methods at present
(CN104562631A), corona treatment, vapour deposition, electrochemical deposition, coupling agent coating, polymer coating
(CN104018355A, CN103015163A), surface aggregate and grafting (CN104195835A, CN103850124A) etc..These
Method improves interface cohesion situation to a certain extent, but often has that handling process is comparatively laborious, cost is high, easily to fibre
Dimension body causes the shortcomings of damage and interface binding power are weaker.
Dopamine causes extensive concern as a kind of new material modified recent years.Dopamine in alkaline aqueous solution very
It is oxidized easily, then triggers from poly- cross-linking reaction, in a kind of the poly- many of substantially any solid material surface formation close attachment
Bar amine layer.Solid material to be modified need to be only put into the dopamine solution of fresh configuration by this method of modifying, soak one section
Taken out after time, you can obtain the material modified of surface attachment poly-dopamine coating.Whole modifying process is completed in aqueous,
Reaction condition is gentle, it is to avoid use organic solvent pollution on the environment, and the modification of material surface settled at one go, grasps
Make step simple, reaction condition is easily controllable with modifying process.Chinese patent CN103572591A is using this method to carbon fiber
Surface modification is carried out, but dopamine is during the course of the reaction, a large amount of amidos are consumed, and cause residual amine less.But in material
The poly-dopamine coating of material Surface Creation has the adjacent benzene diquinone group that the catechol enriched and catechol are oxidized to, it
Can pass through the groups such as Michael's addition and schiff base reaction and amido, sulfydryl and act on.It therefore, it can using this reaction,
In dopamine system, the molecule of other amino-containeds is introduced, to improve the amine groups content of fiber surface, is conducive to fiber and resin
Surface chemistry combine, so as to improve the macro property of composite.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of technique is simple, condition
Gently, fiber bodies structure is not damaged, the active group of carbon fiber surface can be effectively increased, so as to improve fiber and resin boundary
The method of the carbon fiber surface functional amido of face binding ability, this method only needs step solution dipping to can be achieved.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method of carbon fiber surface functional amido, this method is by a step solution dipping method, in fiber surface bag
Cover and contain the copolymer coated of a large amount of active amines, comprise the following steps：
(1) Tris buffer solutions are configured：A certain amount of tri methylol amino methane (Tris) is weighed in volumetric flask, plus go from
Sub- water dissolving, obtains 10mmol/L Tris solution, pH is adjusted to 8.5 or so by few drops of enriching hydrochloric acid, that is, obtains Tris bufferings
Liquid；
(2) surface treatment of carbon fiber：Mass ratio is weighed for (0.1~10):1 many amido molecules and dopamine, dissolving
In the Tris buffer solutions that step (1) is configured, by impregnated carbon fiber in reaction system, 2~48h of processing is stirred at room temperature,
After processing terminates, fully washed with deionized water, be put into 50~70 DEG C of vacuum drying oven and dry 12~24h, that is, obtain surface
The carbon fiber of functional amido.
A described step solution dipping method, is that DOPA amine component and many amido molecules are disposably added in cushioning liquid,
The copolymerization of bi-component occurs in the solution.During the auto polymerization of dopamine, the amino in polyethyleneimine can join
With into Michael's addition or schiff base reaction, while further can be crosslinked instead with the phenolic hydroxyl group on base material and quinonyl unit
Should, so as to be adhered to together with poly-dopamine on fiber surface.Wherein, the amino of polyethyleneimine amine component both take part in copolymer
The formation of coating, also provides enough amino for fiber surface.
Described many amido molecules are ethylenediamine, hexamethylene diamine, polyethylene polyamine, polyethyleneimine, dendritic interphase
Or the one or more in chitosan, preferably polyethyleneimine, it is water soluble polymer, and degree of branching is high, containing a large amount of amine
Base, with higher reactivity.
The molecular weight of described polyethyleneimine is 600~100000, and preferred molecular weight is 5000~20000.Polyethylene
When the molecular weight of imines is less than 600, the crosslinking copolymers density of formation is too high, causes coating too crisp, lacking toughness, easily produces
Interfacial stress is concentrated.When polyethyleneimine is higher than 100000, the motility of molecule is poor, is unfavorable for being penetrated into matrix resin
Portion.
Described polyethyleneimine and the mass ratio of dopamine are (0.1~10):1, preferred mass ratio is 0.5:1~2:1.
In copolymerization composition, the ratio of polyethyleneimine and dopamine is less than 0.1:1, dopamine can largely consume polyethyleneimine in reaction
On amino, cause the free amino group amount for being finally introducing fiber surface less.The ratio of polyethyleneimine and dopamine is higher than
10:When 1, the growth of polymerization initial stage molecular dimension can be caused too fast, and influence poly-dopamine in effective adhesion of fiber surface.
Described dopamine concentration be 0.1mg/ml~10mg/ml (in i.e. every milliliter Tris buffer solution addition 0.1mg~
10mg dopamines), preferred concentration is 0.5mg/ml~4mg/ml.When the concentration of dopamine is less than 0.1mg/ml, copolymer is difficult
Fiber surface is coated on completely, causes interface cohesion uneven.When the concentration of dopamine is higher than 10mg/ml, fiber surface is total to
Polymers coating is too thick, and the boundary layer of formation is corresponding also partially thick, and the thickness of interface phase is thick generally between tens to hundreds of nm
After degree exceedes to a certain degree, the interface between fiber and resin can be influenceed spread etc. and interacted, on the contrary can attacking material it is whole
Body performance.
Described carbon fiber includes polyacrylonitrile-based carbon fibre, asphalt base carbon fiber or viscose-based carbon fiber.
Compared with prior art, the present invention has advantages below：
1st, the present invention directly can be modified to commercialized CF, the pretreatment such as CF need not be extracted, aoxidized, thus will not
CF body construction is destroyed, the high-strength and high-modulus characteristics of CF in itself are remained；
2nd, in the present invention, the introducing of polyethyleneimine considerably increases the amine groups content of fiber surface；
3rd, carbon fiber modifying process control of the invention is preferable, by the molecular weight, the polyethylene that adjust polyethyleneimine
The process conditions such as ratio, concentration, the time of imines and dopamine, can be achieved the controllableization processing of CF surface amine groups quantity, so that
Obtain different types of interface；
4th, the present invention is using a step solution dipping method and reacts progress, simple and fast, condition temperature in room temperature and the aqueous solution
With environmental protection；
5th, the invention is not restricted to improve CF to strengthen the interface performance of thermosetting resin, such as epoxy resin, phenolic resin, span
Come sub- amide resin, for CF strengthen polarity thermoplastic resin, such as acid modified polyolefin, polyester, polyamide, polyimides,
Also there is interface humidification.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of obtained modified carbon fiber in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of unmodified carbon fiber.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Used raw material and method of testing are as follows in embodiment and comparative example：
Carbon fiber is the T700 of toray, and density is 1.8g/cm3, stretch modulus is 230GPa, and tensile strength is
4.9GPa.Epoxy resin (EP) is the E51, viscosity 2500mPas (40 DEG C), epoxide number 0.48- of Wuxi blue star petrochemical industry
0.54eq/100g, curing agent is methyl tetrahydro phthalic anhydride, and the mass ratio of epoxy resin and curing agent is 100:70.Maleic anhydride connects
Branch polypropylene (MPP) is the liter production of Shanghai day, and the wherein grafting rate of maleic anhydride is 1wt%.Nylon 6 (PA6) is Japan east
Beautiful CM1017, density is 1.13g/cm3, tensile strength is 85MPa, and bending strength is 120MPa.Use the flourish strain formula in Japanese east
Commercial firm HM410 type composite material interface evaluating apparatus, the interface shear strength of monofilament and interlaminar resin is tested using micro- unsticking method
(IFSS) interfacial bond property of material can directly be weighed.Wherein, the IFSS between the CF and EP, MPP, PA6 of long time without surface modification
Respectively 30.5MPa, 10.2MPa, 22.4MPa.
Embodiment 1
Weighing the polyethyleneimine and 200mg dopamines that 100mg molecular weight is 10000, (mass ratio is 0.5:1, dopamine
Concentration be 2mg/ml), be dissolved in 100ml pH be 8.5 Tris buffer solutions in, 5g CF are immersed in reaction system therewith
In, the magnetic agitation 24h under room temperature environment.After processing terminates, fully washed with deionized water, in the vacuum drying oven for being put into 60 DEG C
Dry 24h.CF manufactured in the present embodiment stereoscan photograph is as shown in figure 1, unmodified CF stereoscan photograph such as Fig. 2
It is shown, it can be seen that modified CF Surface coatings have uniform polymer coating.CF manufactured in the present embodiment and EP, MPP, PA6
Between IFSS be respectively 72.8MPa, 32.3MPa, 47.5MPa, be non-modified CF and above-mentioned three kinds of interlaminar resin IFSS
238.7%th, 316.7%, 212.1%, interface enhancing effect is notable.
Embodiment 2
The polyethyleneimine molecular weight that the present embodiment is used as different from Example 1 is 15000, other and embodiment 1
It is identical.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 65.3MPa, 29.7MPa, 42.7MPa, be without
214.1%, 291.2%, the 190.6% of modified CF and above-mentioned three kinds of interlaminar resin IFSS, interface enhancing effect is notable.
Embodiment 3
The polyethyleneimine and the mass ratio of dopamine that the present embodiment is used as different from Example 1 are 2:1, other with
Embodiment 1 is identical.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment be respectively 70.2MPa, 35.6MPa,
48.6MPa, is 230.2%, 291.2%, the 217.0% of non-modified CF and above-mentioned three kinds of interlaminar resin IFSS, interface enhancing
Effect is notable.
Embodiment 4
The concentration for the dopamine that the present embodiment is used as different from Example 1 is 4mg/ml, other and the phase of embodiment 1
Together.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 60.1MPa, 26.0MPa, 40.3MPa, is comparative example
160.7%, 144.4%, the 136.6% of the CF that is prepared in 1 and above-mentioned three kinds of interlaminar resin IFSS is non-modified CF with it is above-mentioned
197.0%, 254.9%, the 179.9% of three kinds of interlaminar resin IFSS, interface enhancing effect is notable.
Embodiment 5
Many amido molecules that the present embodiment is used as different from Example 1 are hexamethylene diamine, and other are same as Example 1.
IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 42.6MPa, 21.5MPa, 34.4MPa, is non-modified
CF and above-mentioned three kinds of interlaminar resin IFSS 139.7%, 210.8%, 153.6%, interface enhancing effect preferably, but not strictly according to the facts
Apply the CF that a 1-4 uses polyethyleneimine to prepare.
Comparative example 1
The molecular weight for the polyethyleneimine that this comparative example is used as different from Example 1 is 200, other and embodiment 1
It is identical.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 31.3MPa, 11.5MPa, 21.0MPa, be without
102.6%, 112.7%, the 93.8% of modified CF and above-mentioned three kinds of interlaminar resin IFSS, boundary strength essentially unchangedization.
Comparative example 2
The molecular weight for the polyethyleneimine that this comparative example is used as different from Example 1 is 200000, other and implementation
Example 1 is identical.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 28.6MPa, 8.9MPa, 20.7MPa, is not
93.8%, 87.3%, the 92.4% of modified CF and above-mentioned three kinds of interlaminar resin IFSS, boundary strength declines on the contrary.
Comparative example 3
The polyethyleneimine and the mass ratio of dopamine that this comparative example is used as different from Example 1 are 0.05:1,
Other are same as Example 1.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment be respectively 39.0MPa, 13.5MPa,
27.2MPa, is 127.9%, 132.4%, the 121.4% of non-modified CF and above-mentioned three kinds of interlaminar resin IFSS, boundary strength
Slightly improve.
Comparative example 4
The polyethyleneimine and the mass ratio of dopamine that this comparative example is used as different from Example 1 are 20:1, its
He is same as Example 1.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment be respectively 34.8MPa, 12.9MPa,
25.7MPa, is 114.1%, 126.5%, the 114.7% of non-modified CF and above-mentioned three kinds of interlaminar resin IFSS, boundary strength
Increase rate is little.
Comparative example 5
The concentration for the dopamine that this comparative example is used as different from Example 1 is 0.05mg/ml, other and embodiment 1
It is identical.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 26.3MPa, 9.1MPa, 20.5MPa, be without
86.2%, 89.2%, the 91.5% of modified CF and above-mentioned three kinds of interlaminar resin IFSS, boundary strength is slightly decreased.
Comparative example 6
The concentration for the dopamine that this comparative example is used as different from Example 1 is 20mg/ml, other and the phase of embodiment 1
Together.IFSS between CF and EP, MPP, PA6 manufactured in the present embodiment is respectively 22.0MPa, 7.3MPa, 17.2MPa, is without changing
Property CF and above-mentioned three kinds of interlaminar resin IFSS 72.1%, 71.6%, 76.8%, boundary strength has a certain degree of decline.
Table 1
From table 1 it was found from embodiment 1-5 result, CF produced by the present invention and resin have more preferable boundary strength, be because
Increase for the CF surface polar groups that prepare of the present invention, chemical action that can be stronger with interlaminar resin formation so that matrix resin with
Good interface cohesion is reached between CF, thus boundary strength is greatly enhanced.Comparative example 1-6 interface shear strength knot
Fruit shows, in one-step method solution dipping process, the molecular weight of polyethyleneimine, the mass ratio of polyethyleneimine and dopamine,
The concentration of dopamine will be controlled within the scope of certain, otherwise general to interface performance improvement, or even can damage interface
Intensity.
Embodiment 6
Weighing the polyethyleneimine and 10mg dopamines that 100mg molecular weight is 100000, (mass ratio is 10:1, dopamine
Concentration is 0.1mg/ml), it is dissolved in the Tris buffer solutions that 100ml pH are 8.5,5g CF is immersed in reaction system therewith
In, the magnetic agitation 24h under room temperature environment.After processing terminates, fully washed with deionized water, in the vacuum drying oven for being put into 50 DEG C
Dry 24h.Modified CF Surface coatings have uniform polymer coating.CF manufactured in the present embodiment and EP, MPP, PA6 interface
Enhancing effect is notable.
Embodiment 7
Weighing the polyethyleneimine and 1000mg dopamines that 100mg molecular weight is 600, (mass ratio is 0.1:1, dopamine
Concentration is 10mg/ml), it is dissolved in the Tris buffer solutions that 100ml pH are 8.5,5g CF is immersed in reaction system therewith,
The magnetic agitation 2h under room temperature environment.After processing terminates, fully washed with deionized water, be put into 70 DEG C of vacuum drying oven and dry
12h.Modified CF Surface coatings have uniform polymer coating.CF manufactured in the present embodiment and EP, MPP, PA6 interface strengthen
Effect is notable.
Embodiment 8
Weighing 100mg ethylenediamines and 200mg dopamines, (mass ratio is 0.5:1, the concentration of dopamine is 2mg/ml), dissolving
In the Tris buffer solutions that 100ml pH are 8.5,5g polyacrylonitrile-based carbon fibres are immersed in reaction system therewith, in room temperature
Magnetic agitation 24h under environment.After processing terminates, fully washed with deionized water, be put into 60 DEG C of vacuum drying oven and dry 24h.
Modified CF Surface coatings have uniform polymer coating.Interface enhancing effect is notable.
Embodiment 9
The present embodiment is substantially the same manner as Example 8, and difference is, many amido molecules are that hexamethylene diamine and ethylenediamine (rub
You are than being 1:1), carbon fiber is asphalt base carbon fiber.Modified CF Surface coatings have uniform polymer coating.The present embodiment system
Standby CF and EP, MPP, PA6 interface enhancing effect are notable.
Embodiment 10
The present embodiment is substantially the same manner as Example 8, and difference is, many amido molecules are polyethylene polyamine, carbon fiber
For viscose-based carbon fiber.Modified CF Surface coatings have uniform polymer coating.CF manufactured in the present embodiment and EP, MPP,
PA6 interface enhancing effect is notable.
Embodiment 11
The present embodiment is substantially the same manner as Example 8, and difference is, many amido molecules are dendritic interphase.Change
CF Surface coatings have uniform polymer coating after property.CF manufactured in the present embodiment and EP, MPP, PA6 interface enhancing effect show
Write.
Embodiment 12
The present embodiment is substantially the same manner as Example 8, and difference is, many amido molecules are chitosan.Modified CF tables
Bread is covered with uniform polymer coating.CF manufactured in the present embodiment and EP, MPP, PA6 interface enhancing effect are notable.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It is noted that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (8)
1. a kind of method of carbon fiber surface functional amido, it is characterised in that this method is by a step solution dipping method, in fibre
Tie up Surface coating copolymer coated containing a large amount of active amines, specifically include following steps：Mass ratio is weighed for (0.1~10):1
Many amido molecules and dopamine, be dissolved in Tris buffer solutions, formed reaction system, by impregnated carbon fiber in reaction system
In, 2~48h of processing is stirred at room temperature, is washed out, dries, that is, obtains the carbon fiber of surface amine groups functionalization；
Described carbon fiber includes polyacrylonitrile-based carbon fibre, asphalt base carbon fiber or viscose-based carbon fiber；
Described many amido molecules be selected from ethylenediamine, hexamethylene diamine, polyethylene polyamine, polyethyleneimine, dendritic interphase or
One or more in chitosan.
2. a kind of method of carbon fiber surface functional amido according to claim 1, it is characterised in that described polyamines
Base molecule is polyethyleneimine, and the molecular weight of polyethyleneimine is 600~100000.
3. a kind of method of carbon fiber surface functional amido according to claim 2, it is characterised in that described poly- second
Alkene imines molecular weight is 5000~20000.
4. a kind of method of carbon fiber surface functional amido according to claim 1, it is characterised in that described DOPA
The concentration of amine is 0.1mg/ml~10mg/ml.
5. the method for a kind of carbon fiber surface functional amido according to claim 1 or 4, it is characterised in that described
The concentration of dopamine is 0.5mg/ml~4mg/ml.
6. a kind of method of carbon fiber surface functional amido according to claim 1, it is characterised in that described polyamines
The mass ratio of base molecule and dopamine is 0.5:1~2:1.
7. a kind of method of carbon fiber surface functional amido according to claim 1, it is characterised in that described Tris
The pH of buffer solution is 8.5.
8. a kind of method of carbon fiber surface functional amido according to claim 1, it is characterised in that described drying
It is that 12~24h is dried in 50~70 DEG C of vacuum drying oven.
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| CN104524986A (en) * | 2014-12-08 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of hydrophilic antimicrobial film of which surface is coated with dopamine and polyethyleneimine cations |
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