CN103993484A - Carbon-fiber-surface modifying emulsion, preparation method thereof, and modified carbon fiber and polyamide complex prepared from same - Google Patents
Carbon-fiber-surface modifying emulsion, preparation method thereof, and modified carbon fiber and polyamide complex prepared from same Download PDFInfo
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Abstract
The invention provides a carbon-fiber-surface modifying emulsion, a preparation method thereof, and modified carbon fiber and polyamide complex prepared from the same. The carbon-fiber-surface modifying emulsion comprises the following compositions: 2-10 wt% of a surface modifier, 1-15 wt% of polyamide, 0.7-3 wt% of an emulsifier, 0-25 wt% of an organic solvent and 47-96.3 wt% of water. The surface modifier has a structural formula shown in the specification, and in the structural formula, R1, R2, R1' and R2' independently represent hydrogen, hydroxyl or a C1-C3 alkyl. The invention also provided the preparation method of the carbon-fiber-surface modifying emulsion, the modified carbon fiber obtained by employing the above emulsion and a preparation method, and the polyamide complex containing the modified carbon fiber and a preparation method and application of the polyamide complex. The carbon fiber modified by employing the carbon-fiber-surface modifying emulsion is high in surface resin content and good in compatibility with resin, and the prepared polyamide complex is good in mechanical properties.
Description
Technical field
The present invention relates to a kind of modifier, relate in particular to a kind of carbon fiber surface modification emulsion and preparation method thereof, apply polyamide compound prepared by carbon fiber, modified carbon fiber and the polyamide of this carbon fiber surface modification emulsion.
Background technology
Carbon fiber has outstanding mechanical property, is widely used carbon fiber and strengthens in composite, and improving in recent years interface performance between carbon fiber and base polyamide becomes the focus of research.Carbon fiber surface activity functional group is few, and effective chemical bond of forming with base polyamide compound tense is few, compatibility is poor, causes in carbon fibre composite easily forming fragility interface structure.For improving the interface performance between carbon fiber and base polyamide, industrially conventionally carbon fiber surface is carried out to oxidation processes, give carbon fiber surface hydroxyl, carbonyl isoreactivity oxygen-containing functional group, common are anodizing, nitric acid oxidation method, potassium permanganate oxidation method etc., but these class methods are easily damaged carbon fiber surface, destroy its mechanical property.Improve the interface performance between carbon fiber and matrix in order not damage fiber surface, Chinese patent application CN1944783A uses polymer graft technology to carbon nano-fiber surface modification, make fiber surface be rich in various active functional group, but, this method complex process, condition harshness, production run cost is high, has limited to a certain extent suitability for industrialized production.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of carbon fiber surface modification emulsion of improving carbon fiber surface activity.
In addition, the present invention also provides a kind of modified carbon fiber of applying above-mentioned emulsion.
In addition, the present invention also provides a kind of polyamide compound that comprises above-mentioned modified carbon fiber.
In addition, the present invention also provides a kind of preparation method of above-mentioned carbon fiber surface modification emulsion.
In addition, the present invention also provides a kind of preparation method of above-mentioned modified carbon fiber.
In addition, the present invention also provides a kind of application of above-mentioned polyamide compound.
A kind of carbon fiber surface modification emulsion, comprises the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyamide: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl.
A kind of carbon fiber surface modification emulsion, is made up of the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyamide: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl.
Wherein, R
1, R
2, R
1', R
2' can be methyl, ethyl, propyl group or hydrogen independently of one another, preferable methyl, ethyl or hydrogen, be particularly preferably methyl or hydrogen.
The present invention is necessary to provide the preparation method of above-mentioned surface modifier, comprises the steps:
Component A is provided:
and B component:
wherein, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl;
Make described surface modifier according to following reaction equation reaction:
Reaction equation comprises the step of condensation reaction and reduction reaction:
Condensation reaction: by component A and B component in molar ratio 1:2-1:4 be dissolved in ethanolic solution, temperature is 0-70 DEG C, the reaction time is 1-8h;
Reduction reaction: after condensation reaction completes, add excessive sodium borohydride (NaBH
4) and dimethyl sulfoxide (DMSO) (DMSO) continuation reaction, reaction temperature is 0-10 DEG C, and the reaction time is 1-6h, and product is again through extraction, and dry, solution revolves steaming, makes described surface modifier.
Wherein, described component A can be ethylene diamine derivative.Preferably ethylenediamine, 1,1-dimethyl-ethylenediamine, 1, at least one in 2-dimethyl-ethylenediamine, hydroxy-ethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine.
Wherein, described polyamide can comprise at least one in PA6, PA66, PA46, PA610, PA612, PAl010, PA10T, PA9T, PA6T.
Wherein, described emulsifying agent can for non-ionic surface active agent, anion surfactant, cationic surfactant and amphoteric surfactant form group in select at least one more than.
Wherein, described emulsifying agent can be fatty alcohol-polyoxyethylene ether.
Wherein, described organic solvent can comprise at least one in dimethyl formamide, dimethylacetylamide, dimethylbenzene, formic acid, trichloroacetaldehyde, dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide is called for short DMSO).
A preparation method for carbon fiber surface modification emulsion, comprises the following steps:
In proportion described surface modifier and described polyamide are mixed, add stirring and emulsifying after the organic solvent of described ratio, add the emulsifying agent of described ratio and water to stir after 1-3h, make carbon fiber surface modification emulsion.
Wherein, preferably distilled water of described water.
Wherein, adding the speed of stirring and emulsifying after organic solvent can be 12000r/min.
A kind of emulsion modified modified carbon fiber obtaining of above-mentioned carbon fiber surface modification of applying.
Wherein, the surface resin content of described modified carbon fiber can be 0.1-5%.
Further, the surface resin content of described modified carbon fiber can be 0.96-5%.
A preparation method for modified carbon fiber, comprises the following steps:
Carbon fiber is inserted in carbon fiber modifying emulsion and infiltrated, after taking out, drying, obtain modified carbon fiber.
A kind of polyamide compound, comprises above-mentioned modified carbon fiber and polyamide.
Wherein, in described polyamide compound, the content of described modified carbon fiber is preferably no more than the 35wt% of described polyamide compound.
Wherein, described polyamide can comprise at least one in PA6, PA66, PA46, PA610, PA612, PAl010, PA10T, PA9T, PA6T.
Wherein, the polyamide in described polyamide compound is preferably identical with the polyamide in described carbon fiber surface modification emulsion.
Wherein, described polyamide compound further can also comprise processing aid, and the content of described processing aid is no more than the 10wt% of described polyamide compound.
Described processing aid comprises conventional processing aid, as fire retardant, flexibilizer, conductive agent, antioxidant, light stabilizer, lubricant, colouring agent, nucleator, antistatic additive, filler etc.
A preparation method for polyamide compound, comprises the following steps:
In proportion described modified carbon fiber, polyamide, processing aid are mixed, add extruding pelletization in extruder, make polyamide compound.
Being widely used of a kind of above-mentioned polyamide compound, is mainly used in the fields such as communications and transportation equipment, sports equipment, civil construction material, daily life and medical equipment.
Compare prior art, the present invention uses surface modifier
wherein, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl, make carbon fiber surface modification emulsion, described modified emulsion is for modified carbon fiber, surface damage to carbon fiber is little, Effect on Mechanical Properties to carbon fiber is little, make the modified carbon fiber making there is good mechanical property and good with polyamide compatibility, and the polyamide compound being strengthened by described modified carbon fiber have good tensile strength, flexural strength, impact strength and good electric conductivity.And preparation method's technique of the preparation method of carbon fiber surface modification emulsion of the present invention, the preparation method of modified carbon fiber, polyamide compound is simple.
Brief description of the drawings
Fig. 1 is the electron microscope photo scanning of the modified carbon fiber that makes in embodiment 1;
Fig. 2 is the electron microscope photo scanning of the modified carbon fiber that makes in comparative example 1;
Wherein, the electron microscope photo scanning of modified carbon fiber is selected the Japanese field emission scanning electron microscope HitachiS-4800 that uses, and multiplying power is 35000-50000.
Detailed description of the invention
The modified carbon fiber, the polyamide compound that carbon fiber surface modification emulsion of the present invention and preparation method thereof and its are prepared below in conjunction with some detailed description of the invention are described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Modified carbon fiber of the present invention and polyamide compound carry out performance test in accordance with the following methods, have testing according to standard batten of testing standard:
Fiber surface resin content calculates: platinum crucible is placed in to baking oven, and oven temperature is controlled within the scope of 120 DEG C ± 3 DEG C.Platinum crucible clamping is placed on and in drier, is cooled to room temperature with clamp.Claim its quality m
0, be accurate to 0.01mg.Get modified carbon fiber in a certain amount of embodiment or comparative example as sample, claim its quality m
1, the quality of each sample, between 5g-10g, is accurate to 0.01mg.Sample is put into platinum crucible, platinum crucible is inserted together with sample in Muffle furnace, nitrogen protection, 750 DEG C of muffle furnace controls, constant temperature 1h, is cooled to room temperature, takes out platinum crucible and sample, takes its quality m
2, really to 0.01mg.Each sample need do two groups of Duplicate Samples, averages.
In formula:
J---fiber surface resin content, unit is %;
M
0---the quality of platinum crucible, unit is g;
M
1---the quality of sample before high-temperature process, unit is g;
M
2---after high-temperature process, sample adds the quality of platinum crucible, and unit is g.
The tensile strength of polyamide compound and elongation at break test: undertaken by GB GB/T1040-2006, specimen shape is dumb-bell shape.
The anti-interlaminar shear strength test of polyamide compound: by JC/T773-82(96) carry out, specimen shape is dumb-bell shape.
The bending resistance test of polyamide compound: undertaken by GB GB/T9341-2008, specimen shape is dumb-bell shape.
The impact strength test of polyamide compound: undertaken by GB GB/T1043.1-2008, test on pendulum radial-boom impact tester, breach type is A.
The specific insulation test of polyamide compound: carry out according to GB GB/T15662-1995.
Raw material of the present invention all can be from buying on the market, wherein,
PA66: be selected from German BASF, the trade mark is A3K.
PA6T: be selected from Mitsui chemistry, the trade mark is C230.
PA46: be selected from Dutch Di Si Man, the trade mark is TW300.
Emulsifier O-20: Jiangsu Hai'an Petrochemical Plant manufactures.
Emulsifier O-30: Jiangsu Hai'an Petrochemical Plant manufactures.
Emulsifying agent s-60: Jiangsu Hai'an Petrochemical Plant manufactures.
Emulsifying agent T-20: Jiangsu Hai'an Petrochemical Plant manufactures.
Emulsifying agent 1601: Hangzhou Xiaoshan three river Fine Chemical Co., Ltd manufacture.
The bisphenol A type epoxy resin that one-sided terminal methyl group is acrylic acid modified: be selected from Mitsubishi Rayon Co., Ltd.
Alkyl dimethyl betaine amphoteric surfactant: Shanghai Jinshan longitude and latitude Chemical Co., Ltd., trade mark BS-12.
Phosphite: Chengdu Hai Chuan chemical industry, hydrogen phosphite disodium.
Cocoamidopropyl betaine: Shanghai Jinshan longitude and latitude Chemical Co., Ltd., trade mark CAB-35.
Fatty alcohol polyoxyethylene ether sulfate: Guangzhou Kang Ci Chemical Co., Ltd., the trade mark is AES.
Embodiment 1
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1,1-dimethyl-1,2-diamines 0.1mol, adds ethanol 300mL, dissolve, drip and contain 0.2mol3 again, the ethanolic solution 300mL of 5-dihydroxy salicylide, controls 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
By 40gPA66 and 9.5g surface modifier
be placed in 1000mL beaker, add 100ml DMSO, stir, with high-shearing dispersion emulsifying machine, (Shanghai Fu Luke mechanical & electronic equipment corporation, Ltd manufactures, model is FA40) stir, rotating speed is 12000r/min, gets distilled water 300g, 1g Emulsifier O-20,4g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, is added in system, stirs 1.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtain a kind of modified carbon fiber, use and Japanese observe described modified carbon fiber with field emission scanning electron microscope HitachiS-4800, its multiplying power is 35000-50000, the electron-microscope scanning figure of described carbon fiber is shown in Fig. 1, and one deck PA66 polyamide is contained on this modified carbon fiber surface.
Get 15 weight portion modified carbon fibers, 85 weight portion PA66 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Embodiment 2
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1,1,2-trimethyl-1,2-diamines 0.1mol, add ethanol 300mL, dissolve, then dropping contains 0.3mol3, the ethanolic solution 300mL of 5-dihydroxy salicylide, control 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
By 71.25g PA66 and 47.5g surface modifier
be placed in 1000mL beaker, add 100ml DMSO, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 232g, 4.75g Emulsifier O-20, the emulsifying agent s-60 that 9.5g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 3h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C, and this carbon fiber surface contains one deck PA66 polyamide.
Get 35 weight portion modified carbon fibers, 65 weight portion PA66 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Embodiment 3
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1,1-dimethyl-1,2-diamines 0.1mol, adds ethanol 300mL, dissolve, drip and contain 0.4mol3 again, the ethanolic solution 300mL of 5-dihydroxy salicylide, controls 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
By 4.75g PA66 and 9.5g surface modifier
be placed in 1000ml beaker, add 100mLDMSO, stir, with the capable stirring of high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 298.5g, 0.95g Emulsifier O-20, the emulsifying agent s-60 that 2.375g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C, and this carbon fiber surface contains one deck PA66 polyamide.
Get 37 weight portion modified carbon fibers, 63 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Embodiment 4
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1-hydroxy-2-methyl-1,2-diamines 0.1mol, add ethanol 300mL, dissolve, then dropping contains 0.2mol3, the ethanolic solution 300mL of 5-dihydroxy salicylide, control 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
By 57g PA6T and 23.75g surface modifier
be placed in 1000ml beaker, add 100ml dimethylbenzene, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 278.55g, 0.95g Emulsifier O-20, the emulsifying agent s-60 that 4.75g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C, and this carbon fiber surface contains one deck PA6T polyamide.
Get 8 weight portion modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion PA6T mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Embodiment 5
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1-methyl isophthalic acid, 2-diamines 0.1mol, adds ethanol 300mL, dissolve, then dropping contains 0.2mol3, the ethanolic solution 300mL of 5-dihydroxy salicylide, control 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, add again the NaBH4 of 4 equivalents, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
By 28.5g PA46 and 14.25g surface modifier
be placed in 1000ml beaker, add 60ml trichloroacetaldehyde, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 356.75g, 3.8g Emulsifier O-30,5.7g emulsifying agent 1601, is added in system, stirs 1h, finally obtains the white emulsion of desired concn, is carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C, and this carbon fiber surface contains one deck PA46 polyamide.
Get 13 weight portion modified carbon fibers, 10 weight portion carbon blacks, 77 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Embodiment 6
In the polymeric kettle of the preparation of surface modifier: 1.5L, add 1,1-dimethyl-1,2-diamines 0.1mol, adds ethanol 300mL, dissolve, drip and contain 0.2mol3 again, the ethanolic solution 300mL of 5-dihydroxy salicylide, controls 55 DEG C of polymeric kettle temperature, after backflow 6h, add 300mLDMSO solution, control 0 DEG C of polymeric kettle temperature, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.Add 500mL water, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4dry, leave standstill, filter, solution revolves steaming, obtains a kind of surface modifier
Prepare water soluble polyamide according to the embodiment 2 in patent CN200410026949.5.By water soluble polyamide described in 28.5g and 14.25g surface modifier
be placed in 1000ml beaker, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min, gets distilled water 356.75g, 3.8g Emulsifier O-30,5.7g emulsifying agent T20, is added in system, stirs 2h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C, and this carbon fiber surface contains one deck water soluble polyamide resin.
Get 20 weight portion modified carbon fibers, 80 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 1
40gPA66 and 9.5g alkyl dimethyl betaine amphoteric surfactant are placed in to 1000mL beaker, add 100ml DMSO, stir, with high-shearing dispersion emulsifying machine, (Shanghai Fu Luke mechanical & electronic equipment corporation, Ltd manufactures, model is FA40) stir, rotating speed is 12000r/min, get distilled water 300g, 1g Emulsifier O-20,4g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, is added in system, stirs 1.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtains a kind of modified carbon fiber, at carbon fiber described in electric Microscopic observation, as Fig. 2, the multiplying power of described Electronic Speculum is selected 35000-50000.
Get 15 weight portion modified carbon fibers, 85 weight portion PA66 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 2
71.25g PA66 and 47.5g phosphite are placed in to 1000mL beaker, add 100ml DMSO, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 232g, 4.75g Emulsifier O-20, the emulsifying agent s-60 that 9.5g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 3h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtains a kind of modified carbon fiber.
Get 35 weight portion modified carbon fibers, 65 weight portion PA66 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 3
4.75g PA66 and the acrylic acid modified bisphenol A type epoxy resin of the one-sided terminal methyl group of 9.5g are placed in to 1000ml beaker, add 100mLDMSO, stir, with the capable stirring of high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 298.5g, 0.95g Emulsifier O-20, the emulsifying agent s-60 that 2.375g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtains a kind of modified carbon fiber.
Get 37 weight portion modified carbon fibers, 63 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 4
57g PA6T and 23.75g Cocoamidopropyl betaine are placed in to 1000ml beaker, add 100ml dimethylbenzene, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 278.55g, 0.95g Emulsifier O-20, the emulsifying agent s-60 that 4.75g weight ratio is 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtains a kind of modified carbon fiber.
Get 8 weight portion modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion PA6T, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 5
28.5g PA46 and 14.25g fatty alcohol polyoxyethylene ether sulfate are placed in to 1000ml beaker, add 60ml trichloroacetaldehyde, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 356.75g, 3.8g Emulsifier O-30,5.7g emulsifying agent 1601, is added in system, stirs 1h, finally obtains the white emulsion of desired concn, is carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration is dried in the electric heating constant-temperature blowing drying box of 160 DEG C, obtains a kind of modified carbon fiber.
Get 13 weight portion modified carbon fibers, 10 weight portion carbon blacks, 77 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Comparative example 6
Prepare water soluble polyamide according to the embodiment 2 in patent CN200410026949.5.Water soluble polyamide described in 28.5g and the acrylic acid modified bisphenol A type epoxy resin of the one-sided terminal methyl group of 14.25g are placed in to 1000ml beaker, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min, gets distilled water 356.75g, 3.8g Emulsifier O-30,5.7g emulsifying agent T20, is added in system, stirs 2h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configuring to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 DEG C of emulsion temperature, infiltrate 10min, the carbon fiber after infiltration obtains a kind of modified carbon fiber after drying in the electric heating constant-temperature blowing drying box of 160 DEG C.
Get 20 weight portion modified carbon fibers, 80 weight portion PA46 mixing, add double screw extruder, extruding pelletization, makes polyamide compound.
Modified carbon fiber and polyamide compound are carried out performance test and be recorded in table 1.
Following table 1 is the performance test table of modified carbon fiber and polyamide compound in above embodiment and comparative example.In table 1, the value of specific insulation is less, illustrates that the electric conductivity of sample is better.
Table 1
Each embodiment 1-6 all can prepare carbon fiber modifying emulsion of the present invention, uses the modified carbon fiber of this modified emulsion modification and add the polyamide compound of this modified carbon fiber above.Comparative example 1-6 is and adopts the carbon fiber modifying emulsion that makes of surface modifier of the prior art, use the modified carbon fiber of this modified emulsion modification and add the polyamide compound of this modified carbon fiber.
In table 1, from embodiment 1-6 and comparative example 1-6 contrast, can find out, the surface resin content of the modified carbon fiber that the modified carbon fiber that embodiment 1-6 makes makes compared with comparative example 1-6 is high, and the compatibility of itself and matrix resin is better.From the contrast of Fig. 1 and Fig. 2, also can find out, the surface resin content of the carbon fiber in Fig. 1 is many compared with the surface resin content of the carbon fiber in Fig. 2.
Embodiment 1-6 and comparative example 1-6 contrast, can find out, compared with the polyamide compound making with comparative example, the polyamide compound that the present invention makes has good tensile strength, elongation at break, anti-interlaminar shear strength, flexural strength, impact strength and electric conductivity.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a carbon fiber surface modification emulsion, comprises the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyamide: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl.
2. a carbon fiber surface modification emulsion, is made up of the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyamide: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3alkyl.
3. carbon fiber surface modification emulsion as claimed in claim 1 or 2, is characterized in that: described R
1, R
2, R
1', R
2' be methyl, ethyl, propyl group or hydrogen independently of one another.
4. a preparation method for the carbon fiber surface modification emulsion as described in claims 1 to 3 any one, comprises the following steps:
In proportion described surface modifier and described polyamide are mixed, add stirring and emulsifying after the organic solvent of described ratio, add the emulsifying agent of described ratio and water to stir after 1-3h, make carbon fiber surface modification emulsion.
5. an application emulsion modified modified carbon fiber obtaining of carbon fiber surface modification as described in claims 1 to 3 any one.
6. modified carbon fiber as claimed in claim 5, is characterized in that: the surface resin content of described modified carbon fiber is 0.1-5%.
7. a preparation method for modified carbon fiber as claimed in claim 5, comprises the following steps:
Carbon fiber is inserted in carbon fiber modifying emulsion and infiltrated, after taking out, drying, obtain modified carbon fiber.
8. a polyamide compound, comprises modified carbon fiber as claimed in claim 5 and polyamide.
9. a polyamide compound as claimed in claim 8, is characterized in that: the polyamide in described polyamide compound is identical with the polyamide in described carbon fiber surface modification emulsion.
10. an application for polyamide compound as claimed in claim 8, is characterized in that: described polyamide compound is applied to communications and transportation equipment, sports equipment, civil construction material, daily life and area of medical devices.
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| CN111876995A (en) * | 2020-06-10 | 2020-11-03 | 齐鲁工业大学 | Modification method for preparing fibers for carbon fiber paper and application of modification method |
| CN112877950A (en) * | 2021-01-12 | 2021-06-01 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Preparation system and method of filament carbon fiber 3D printing wire |
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