CN103321048A - Carbon fiber surface modified emulsion, preparation method thereof, and modified carbon fiber and polyester compound prepared thereby - Google Patents
Carbon fiber surface modified emulsion, preparation method thereof, and modified carbon fiber and polyester compound prepared thereby Download PDFInfo
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- CN103321048A CN103321048A CN2013102877649A CN201310287764A CN103321048A CN 103321048 A CN103321048 A CN 103321048A CN 2013102877649 A CN2013102877649 A CN 2013102877649A CN 201310287764 A CN201310287764 A CN 201310287764A CN 103321048 A CN103321048 A CN 103321048A
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- ZYMJLHKLNKQAHZ-UHFFFAOYSA-N CC(C)(CNCc(cccc1CC(OC)=O)c1O)NCc1cccc(CC(OC)=O)c1O Chemical compound CC(C)(CNCc(cccc1CC(OC)=O)c1O)NCc1cccc(CC(OC)=O)c1O ZYMJLHKLNKQAHZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides carbon fiber surface modified emulsion, a preparation method thereof, and a modified carbon fiber and polyester compound prepared thereby. The carbon fiber surface modified emulsion comprises 2-10 wt% of surface modifier, 1-15 wt% of polyester, 0.7-3 wt% of emulsifier, 0-25% of organic solvent, and 47-96.3 wt% of water, wherein the modifier is shown in specification; R1, R2, R1' and R2' respectively are hydrogen, hydroxyl or C1-C3 alkyl; R3 and R4 respectively are hydrogen, hydroxyl or C1-C8 alkyl, C1-C18 alkoxy, alkyl containing a silicon-oxygen bond or a group containing the following functional groups of hydroxyl, amino, halogen, acylamino or ester group; and R3 and R4 are not hydrogen at the same time. The invention also provides the preparation method of the modified emulsion, and the prepared modified carbon fiber and polyester compound. The modified carbon fiber prepared by the preparation method is good in compatibility with the polyester; and the mechanical property of the polyester compound is good.
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, use the standby polyester complexes of carbon fiber, modified carbon fiber and polyester of this carbon fiber surface modification emulsion.
Background technology
Carbon fiber has outstanding mechanical property, is widely used carbon fiber and strengthens in composite, improves in recent years the focus that interface performance between carbon fiber and matrix resin becomes research.Carbon fiber surface activity functional group is few, and the effective chemical bond that forms with the matrix resin compound tense is few, compatibility is poor, causes easily forming in the carbon fibre composite fragility interface structure.For improving the interface performance between carbon fiber and matrix resin, industrially usually carbon fiber surface is carried out 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.In order not damage the interface performance between fiber surface raising carbon fiber and the matrix, Chinese patent application CN1944783A uses the polymer graft technology to the carbon nano-fiber surface modification, make fiber surface be rich in various active functional group, but, this method complex process, condition is harsh, and the 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 using above-mentioned emulsion.
In addition, the present invention also provides a kind of polyester complexes 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 polyester complexes.
A kind of carbon fiber surface modification emulsion comprises the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyester: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in the formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3Alkyl; R
3, R
4Represent independently of one another hydrogen, hydroxyl, C
1-C
18Alkyl, C
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3And R
4Be not hydrogen simultaneously.
A kind of carbon fiber surface modification emulsion is comprised of the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyester: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in the formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3Alkyl; R
3, R
4Represent independently of one another hydrogen, hydroxyl, C
1-C
18Alkyl, C
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3And R
4Be not hydrogen simultaneously.
Wherein, in the described formula 1, 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 are particularly preferably methyl or hydrogen.
Wherein, in the described formula 1, R
3, R
4Can be hydrogen, hydroxyl, C independently of one another
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from amino, amide groups or ester group, and R
3, R
4Be not hydrogen simultaneously.
Wherein, described R
3, R
4Can be C independently of one another
1-C
10Alkoxyl or C
1-C
10Alkyl.
Wherein, described surface modifier is preferred
Or
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; R
3, R
4Represent independently of one another hydrogen, hydroxyl, C
1-C
18Alkyl, C
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3And R
4Be not hydrogen simultaneously;
Make described surface modifier according to following reaction equation reaction:
The step that comprises condensation reaction and reduction reaction in the reaction equation:
Condensation reaction: with component A and B component in molar ratio 1:2-1:4 be dissolved in the ethanolic solution, temperature is 0-70 ℃, the reaction time is 1-8h;
Reduction reaction: after condensation reaction is finished, add excessive NaBH
4And dimethyl sulfoxide (DMSO) (DMSO) continues reaction, and reaction temperature is 0-10 ℃, and the reaction time is 1-6h, and product is again through extraction, drying, and solution revolves steaming, makes described surface modifier.
Wherein, described component A can be ethylene diamine derivative.Preferred ethylenediamine, 1,1-dimethyl-ethylenediamine, 1, at least a in 2-dimethyl-ethylenediamine, hydroxy-ethylenediamine, tetramethylethylenediamine, the tetraethylethylenediamine.
Wherein, described polyester can be the polymer that is formed by dicarboxylic acids and dihydroxylic alcohols polycondensation.
What wherein, described dicarboxylic acids can be in chain type saturated aliphatic dicarboxylic acid, chain type unsaturated aliphatic dicarboxylic acid, alicyclic dicarboxylic acids or the aromatic binary carboxylic acid is at least a.
Wherein, described chain type saturated aliphatic dicarboxylic acid can be straight chain saturated aliphatic dicarboxylic acid or the branch's chain type saturated aliphatic dicarboxylic acid of 2-22 for carbon number.Described chain type saturated aliphatic dicarboxylic acid is at least a in the preferred following material further: oxalic acid, malonic acid, succinic acid, glutaric acid, dimethyl succinic acid, ethyl succinic acid, dimethyl malonic acid, the Alpha-Methyl glutaric acid, the Beta-methyl glutaric acid, 2,4-diethyl glutarate, isopropyl-malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, the decane dioctyl phthalate, the hendecane dioctyl phthalate, the dodecane dioctyl phthalate, the tridecane dioctyl phthalate, tetradecane dioctyl phthalate, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, eicosane dicarboxylic acid, the decyl succinic acid, the dodecyl succinic acid, the octadecyl succinic acid.
Wherein, described chain type unsaturated aliphatic dicarboxylic acid can be straight chain unsaturated aliphatic dicarboxylic acid or the branch's chain type unsaturated aliphatic dicarboxylic acid of 4-22 for carbon number.Described chain type saturated aliphatic dicarboxylic acid is at least a in the preferred following material further: maleic acid, fumaric acid, methyl-maleic acid, mesaconic acid, dodecenylsuccinic acid, ten pentaene base succinic acid, octadecylene base succinic acid.
Wherein, described alicyclic dicarboxylic acids can be the alicyclic dicarboxylic acids of 7-14 for carbon number.Described alicyclic dicarboxylic acids is at least a in the preferred following material further: 1,3-pentamethylene dioctyl phthalate, 1,2-pentamethylene dioctyl phthalate, 1,2-cyclohexane cyclohexanedimethanodibasic, 1,3-cyclohexane cyclohexanedimethanodibasic, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 1,2-cyclohexanediacetic, 1,3-cyclohexanediacetic, Isosorbide-5-Nitrae-cyclohexanediacetic, dicyclohexyl-4, the 4'-dioctyl phthalate.
Wherein, described aromatic binary carboxylic acid can be the aromatic binary carboxylic acid of 8-14 for carbon number.Described aromatic binary carboxylic acid is at least a in the preferred following material further: terephthalic acid (TPA), M-phthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, beta-phenyl glutaric acid, α-phenyl adipic acid, beta-phenyl adipic acid, biphenyl-2,2'-dioctyl phthalate and biphenyl-4,4'-dioctyl phthalate, naphthalenedicarboxylic acid.
Wherein, described dihydroxylic alcohols can be aliphatic alkane dihydroxylic alcohols and/or alicyclic dihydroxylic alcohols.
Wherein, described aliphatic alkane dihydroxylic alcohols can be the aliphatic alkane dihydroxylic alcohols of 2-16 for carbon number.Described aliphatic alkane dihydroxylic alcohols is at least a in the preferred following material further: ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6-hexylene glycol, ethohexadiol, decanediol, dodecanediol, hexadecane glycol, neopentyl glycol, 2,2-diethyl-1,3-PD.
Wherein, described alicyclic dihydroxylic alcohols can be the alicyclic dihydroxylic alcohols of 4-16 for carbon number.Described alicyclic dihydroxylic alcohols is at least a in the preferred following material further: Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, hydrogenated bisphenol A.
Wherein, described polyester optimization aromatic dicarboxylic acids and aliphatic alkane dihydroxylic alcohols are through the polymer of polycondensation formation.
Wherein, at least a in the preferred polybutylene terephthalate (PBT) of described polyester or the polyethylene terephthalate.
Wherein, select among the group that described emulsifying agent can form for non-ionic surface active agent, anion surfactant, cationic surfactant and amphoteric surfactant at least a more than.
Wherein, described emulsifying agent can be fatty alcohol-polyoxyethylene ether.
Wherein, described organic solvent can comprise at least a in the phenol, tetrachloroethanes, dimethyl formamide, dimethylacetylamide, dimethylbenzene, formic acid, trichloroacetaldehyde, dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide is called for short DMSO).
A kind of preparation method of carbon fiber surface modification emulsion may further comprise the steps:
In proportion described surface modifier and described polyester are mixed, add stirring and emulsifying behind the organic solvent of described ratio, add after the emulsifying agent of described ratio and water stirs 1-3h, make the carbon fiber surface modification emulsion.
Wherein, described water distilled water preferably.
Wherein, the speed of stirring and emulsifying can be 12000r/min behind the adding organic solvent.
A kind of emulsion modified modified carbon fiber that obtains of above-mentioned carbon fiber surface modification of using.
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 1.3-5%.
A kind of preparation method of modified carbon fiber may further comprise the steps:
Carbon fiber inserted in the carbon fiber modifying emulsion infiltrate, take out, after the oven dry, obtain modified carbon fiber.
A kind of polyester complexes comprises above-mentioned modified carbon fiber and polyester.
Wherein, described polyester can be the polymer that is formed by dicarboxylic acids and dihydroxylic alcohols polycondensation.
What wherein, described dicarboxylic acids can be in chain type saturated aliphatic dicarboxylic acid, chain type unsaturated aliphatic dicarboxylic acid, alicyclic dicarboxylic acids or the aromatic binary carboxylic acid is at least a.
Wherein, described chain type saturated aliphatic dicarboxylic acid can be straight chain saturated aliphatic dicarboxylic acid or the branch's chain type saturated aliphatic dicarboxylic acid of 2-22 for carbon number.Described chain type saturated aliphatic dicarboxylic acid is at least a in the preferred following material further: oxalic acid, malonic acid, succinic acid, glutaric acid, dimethyl succinic acid, ethyl succinic acid, dimethyl malonic acid, the Alpha-Methyl glutaric acid, the Beta-methyl glutaric acid, 2,4-diethyl glutarate, isopropyl-malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, the decane dioctyl phthalate, the hendecane dioctyl phthalate, the dodecane dioctyl phthalate, the tridecane dioctyl phthalate, tetradecane dioctyl phthalate, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, eicosane dicarboxylic acid, the decyl succinic acid, the dodecyl succinic acid, the octadecyl succinic acid.
Wherein, described chain type unsaturated aliphatic dicarboxylic acid can be straight chain unsaturated aliphatic dicarboxylic acid or the branch's chain type unsaturated aliphatic dicarboxylic acid of 4-22 for carbon number.Described chain type saturated aliphatic dicarboxylic acid is at least a in the preferred following material further: maleic acid, fumaric acid, methyl-maleic acid, mesaconic acid, dodecenylsuccinic acid, ten pentaene base succinic acid, octadecylene base succinic acid.
Wherein, described alicyclic dicarboxylic acids can be the alicyclic dicarboxylic acids of 7-14 for carbon number.Described alicyclic dicarboxylic acids is at least a in the preferred following material further: 1,3-pentamethylene dioctyl phthalate, 1,2-pentamethylene dioctyl phthalate, 1,2-cyclohexane cyclohexanedimethanodibasic, 1,3-cyclohexane cyclohexanedimethanodibasic, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 1,2-cyclohexanediacetic, 1,3-cyclohexanediacetic, Isosorbide-5-Nitrae-cyclohexanediacetic, dicyclohexyl-4, the 4'-dioctyl phthalate.
Wherein, described aromatic binary carboxylic acid can be the aromatic binary carboxylic acid of 8-14 for carbon number.Described aromatic binary carboxylic acid is at least a in the preferred following material further: terephthalic acid (TPA), M-phthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, beta-phenyl glutaric acid, α-phenyl adipic acid, beta-phenyl adipic acid, biphenyl-2,2'-dioctyl phthalate and biphenyl-4,4'-dioctyl phthalate, naphthalenedicarboxylic acid.
Wherein, described dihydroxylic alcohols can be aliphatic alkane dihydroxylic alcohols and/or alicyclic dihydroxylic alcohols.
Wherein, described aliphatic alkane dihydroxylic alcohols can be the aliphatic alkane dihydroxylic alcohols of 2-16 for carbon number.Described aliphatic alkane dihydroxylic alcohols is at least a in the preferred following material further: ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6-hexylene glycol, ethohexadiol, decanediol, dodecanediol, hexadecane glycol, neopentyl glycol, 2,2-diethyl-1,3-PD.
Wherein, described alicyclic dihydroxylic alcohols can be the alicyclic dihydroxylic alcohols of 4-16 for carbon number.Described alicyclic dihydroxylic alcohols is at least a in the preferred following material further: Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, hydrogenated bisphenol A.
Wherein, described polyester optimization aromatic polyester.
Wherein, at least a in the preferred polybutylene terephthalate (PBT) of described polyester or the polyethylene terephthalate.
Wherein, in the described polyester complexes, the content of described modified carbon fiber preferably is no more than the 35wt% of described polyester complexes.
Wherein, the polyester in the described polyester complexes is preferably identical with polyester in the described carbon fiber surface modification emulsion.
Wherein, described polyester complexes further can also comprise processing aid, and the content of described processing aid is no more than the 10wt% of described polyester complexes.
Described processing aid comprises processing aid commonly used, such as fire retardant, flexibilizer, conductive agent, antioxidant, light stabilizer, lubricant, colouring agent, nucleator, antistatic additive, filler etc.
A kind of preparation method of polyester complexes may further comprise the steps:
In proportion described modified carbon fiber, polyester, processing aid are mixed, add extruding pelletization in the extruder, make polyester complexes.
Being widely used of a kind of above-mentioned polyester complexes 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; R
3, R
4Represent independently of one another C
1-C
18Alkyl, C
1-C
18Alkoxyl or contain the group of following functional group: hydroxyl, amino, halogen, hydrogen, amide groups, ester group or siloxy, and R
3, R
4Be not hydrogen simultaneously; Make the carbon fiber surface modification emulsion, described modified emulsion is used for modified carbon fiber, surface damage to carbon fiber is little, Effect on Mechanical Properties to carbon fiber is little, so that the modified carbon fiber that makes has good mechanical property and good with the compatibility of polyester, and the polyester complexes that is strengthened by described modified carbon fiber has 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, polyester complexes is simple.
The specific embodiment
The modified carbon fiber, the polyester complexes that carbon fiber surface modification emulsion of the present invention and preparation method thereof and its are prepared below in conjunction with some specific embodiment 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 polyester complexes carry out performance test in accordance with the following methods, and testing according to the standard batten of testing standard arranged:
The fiber surface resin content calculates: platinum crucible is placed baking oven, and oven temperature is controlled in 120 ℃ ± 3 ℃ scopes.With clamp the platinum crucible clamping is placed on and is cooled to room temperature in the drier.Claim its quality m
0, be accurate to 0.01mg.Get modified carbon fiber in a certain amount of embodiment or the Comparative Examples as sample, claim its quality m
1, the quality of each sample is accurate to 0.01mg between 5g-10g.Sample is put into platinum crucible, platinum crucible is inserted in the Muffle furnace with sample, nitrogen protection, 750 ℃ of muffle furnace controls, constant temperature 1h is cooled to room temperature, takes out platinum crucible and sample, takes by weighing its quality m
2, really to 0.01mg.Each sample need be done two groups of Duplicate Samples, averages.
In the formula:
J---fiber surface resin content, unit are %;
m
0---the quality of platinum crucible, unit is g;
m
1---the quality of sample before the high-temperature process, unit is g;
m
2---sample adds the quality of platinum crucible after the high-temperature process, and unit is g.
The tensile strength of polyester complexes and elongation at break test: undertaken by GB GB/T1040-2006, specimen shape is dumb-bell shape.
The anti-interlaminar shear strength test of polyester complexes: by JC/T773-82(96) carry out, specimen shape is dumb-bell shape.
The bending resistance test of polyester complexes: undertaken by GB GB/T9341-2008, specimen shape is dumb-bell shape.
The impact strength test of polyester complexes: undertaken by GB GB/T1043.1-2008, test at the pendulum radial-boom impact tester, the breach type is A.
The specific insulation test of polyester complexes: carry out according to GB GB/T15662-1995.
Raw material of the present invention all can be from buying on the market, wherein,
Polyethylene terephthalate-1: China Petrochemical Industry Hainan, the trade mark 800.
Polyethylene terephthalate-2: Shanghai is far spun, trade mark CB-602.
Polybutylene terephthalate (PBT)-1: blue in the Nantong, the trade mark 1084.
Polybutylene terephthalate (PBT)-2: German BASF, trade mark B4500.
Polybutylene terephthalate (PBT)-3: China Petrochemical Industry's Yizheng Fiber Optical plant, trade mark L2100.
Unsaturated polyester (UP)-1: be metaphenylene unsaturated polyester resin, Shanghai Xin Tianhe Resin Co., Ltd., trade mark DS-608N.
Unsaturated polyester (UP)-2: be adjacent benzene type unsaturated polyester resin, Shanghai Xin Tianhe Resin Co., Ltd., trade mark DS-629.
Unsaturated polyester (UP)-3: be the unsaturated polyester resin that phthalic anhydride and standard dihydroxylic alcohols are made, Shanghai Xin Tianhe Resin Co., Ltd., trade mark DS-199.
Emulsifier O-20: Jiangsu Hai'an Petrochemical Plant makes.
Emulsifier O-30: Jiangsu Hai'an Petrochemical Plant makes.
Emulsifying agent s-60: Jiangsu Hai'an Petrochemical Plant makes.
Emulsifying agent T-20: Jiangsu Hai'an Petrochemical Plant makes.
Emulsifying agent 1601: Hangzhou Xiaoshan three river Fine Chemical Co., Ltd make.
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 industry Co., Ltd, trade mark BS-12.
Phosphite: Chengdu Hai Chuan chemical industry, hydrogen phosphite disodium.
Cocoamidopropyl betaine: Shanghai Jinshan longitude and latitude chemical industry Co., Ltd, trade mark CAB-35.
Fatty alcohol polyoxyethylene ether sulfate: the Guangzhou health is grant chemical industry Co., Ltd, and the trade mark is AES.
Embodiment 1
Add 1,1,2 in the polymeric kettle of the preparation of surface modifier: 1.5L; 2-tetramethyl-1; 2-diamines 0.1mol adds ethanol 300mL, dissolving; drip again the ethanolic solution 300mL that contains 0.2mol1-formoxyl-2-hydroxyl-4-benzyl carbinol ethyl ester; 55 ℃ of control polymeric kettle temperature behind the backflow 6h, add 300mLDMSO solution; control 0 ℃ of polymeric kettle temperature, add again 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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
With 40g polyethylene terephthalate-1 and 9.5g surface modifier
Place the 1000mL beaker, add 100mlDMSO, stir, (Fu Luke mechanical ﹠ electronic equipment corporation, Ltd in Shanghai makes with high-shearing dispersion emulsifying machine, model is FA40) stir, rotating speed is 12000r/min, gets distilled water 300g, 1g Emulsifier O-20, the 4g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, is added in the system, stirs 1h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber, and one deck polyethylene terephthalate-1 resin is contained on this modified carbon fiber surface.
Get 15 weight portion modified carbon fibers, the mixing of 85 weight portion polyethylene terephthalate-1, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Embodiment 2
Add 1-ethyl-1 in the polymeric kettle of the preparation of surface modifier: 1.5L, 2-diamines 0.1mol, add ethanol 300mL, dissolving drips the ethanolic solution 300mL that contains 0.2mol6-chloro-4-propoxyl group salicylide again, 55 ℃ of control polymeric kettle temperature, behind the backflow 6h, add 300mLDMSO solution, control 0 ℃ of polymeric kettle temperature, add again 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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
With 71.25g unsaturated polyester (UP)-1 and 47.5g surface modifier
Place the 1000mL beaker, add 100mlDMSO, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 232g, 4.75g Emulsifier O-20, the 9.5g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box, this carbon fiber surface contains one deck unsaturated polyester (UP)-1.
Get 35 weight portion modified carbon fibers, the mixing of 65 weight portion polyethylene terephthalate-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Embodiment 3
Add 1 in the polymeric kettle of the preparation of surface modifier: 1.5L; 2-dimethyl-1; 2-diamines 0.1mol adds ethanol 300mL, dissolving; drip again the ethanolic solution 300mL that contains 0.2mol3-formoxyl-4-hydroxyl-hydrocinnamamide; 55 ℃ of control polymeric kettle temperature behind the backflow 6h, add 300mLDMSO solution; control 0 ℃ of polymeric kettle temperature, add again 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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
With 4.75g unsaturated polyester (UP)-2 and 9.5g surface modifier
Place the 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 2.375g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box, this carbon fiber surface contains one deck unsaturated polyester (UP)-2.
Get 37 weight portion modified carbon fibers, the mixing of 63 weight portion polybutylene terephthalate (PBT)s-1, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Embodiment 4
Add 1,2-dimethyl-1 in the polymeric kettle of the preparation of surface modifier: 1.5L, 2-diamines 0.1mol adds ethanol 300mL, and dissolving drips and contains 0.2mol
Ethanolic solution 300mL, 55 ℃ of control polymeric kettle temperature behind the backflow 6h, add 300mLDMSO solution, 0 ℃ of control polymeric kettle temperature adds the NaBH of 4 equivalents again
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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
With 57g unsaturated polyester (UP)-3 and 23.75g surface modifier
Place the 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 4.75g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box, this carbon fiber surface contains one deck unsaturated polyester (UP)-3 resin.
Get 8 weight portion modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Embodiment 5
Add 1 in the polymeric kettle of the preparation of surface modifier: 1.5L; 1-dimethyl-1; 2-diamines 0.1mol adds ethanol 300mL, dissolving; drip again the ethanolic solution 300mL that contains 0.2mol5-formoxyl-6-hydroxyl-methyl phenylacetate; 55 ℃ of control polymeric kettle temperature behind the backflow 6h, add 300mLDMSO solution; control 0 ℃ of polymeric kettle temperature, add again 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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
With 28.5g polybutylene terephthalate (PBT)-2 and 14.25g surface modifier
Place the 1000ml beaker, add the 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 T20, be added in the system, stir 1.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box, this carbon fiber surface contains one deck polybutylene terephthalate (PBT)-2 resin.
Get 13 weight portion modified carbon fibers, 10 weight portion carbon blacks, the mixing of 77 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Embodiment 6
Add 1-hydroxyl-1 in the polymeric kettle of the preparation of surface modifier: 1.5L, 2-diamines 0.1mol, add ethanol 300mL, dissolving drips the ethanolic solution 300mL that contains 0.2mol5-hydroxyl-3-n-pro-pyl salicylide again, 55 ℃ of control polymeric kettle temperature, behind the backflow 6h, add 300mLDMSO solution, control 0 ℃ of polymeric kettle temperature, add again 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
4Drying leaves standstill, and filters, and solution revolves steaming, obtains a kind of surface modifier
Prepare a kind of water-soluble polyester according to the embodiment 1 among the patent CN200510038276.X.With the described water-soluble polyester of 28.5g and 14.25g surface modifier
Place the 1000ml beaker, 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 the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box, this carbon fiber surface contains the described water-soluble polyester resin of one deck.
Get 20 weight portion modified carbon fibers, the mixing of 80 weight portion polybutylene terephthalate (PBT)s-3, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 1
40g polyethylene terephthalate-1 and 9.5g alkyl dimethyl betaine amphoteric surfactant are placed the 1000mL beaker, add 100ml DMSO, stir, (Fu Luke mechanical ﹠ electronic equipment corporation, Ltd in Shanghai makes with high-shearing dispersion emulsifying machine, model is FA40) stir, rotating speed is 12000r/min, get distilled water 300g, 1g Emulsifier O-20, the 4g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, is added in the system, stirs 1h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber.
Get 15 weight portion modified carbon fibers, the mixing of 85 weight portion polyethylene terephthalate-1, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 2
71.25g unsaturated polyester (UP)-1 and 47.5g phosphite are placed the 1000mL beaker, add 100mlDMSO, stir, stir with high-shearing dispersion emulsifying machine, rotating speed is 12000r/min.Get distilled water 232g, 4.75g Emulsifier O-20, the 9.5g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber.
Get 35 weight portion modified carbon fibers, the mixing of 65 weight portion polyethylene terephthalate-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 3
4.75g unsaturated polyester (UP)-2 and the acrylic acid modified bisphenol A type epoxy resin of the one-sided terminal methyl group of 9.5g are placed the 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 2.375g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber.
Get 37 weight portion modified carbon fibers, the mixing of 63 weight portion polybutylene terephthalate (PBT)s-1, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 4
57g unsaturated polyester (UP)-3 and 23.75g Cocoamidopropyl betaine are placed the 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 4.75g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber.
Get 8 weight portion modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 5
28.5g polybutylene terephthalate (PBT)-2 and the acrylic acid modified bisphenol A type epoxy resin of the one-sided terminal methyl group of 14.25g are placed the 1000ml beaker, add the 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 T20, be added in the system, stir 1.5h, finally obtain the white emulsion of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration obtains a kind of modified carbon fiber after drying in 160 ℃ electric heating constant-temperature blowing drying box.
Get 13 weight portion modified carbon fibers, 10 weight portion carbon blacks, the mixing of 77 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Comparative Examples 6
Prepare a kind of water-soluble polyester according to the embodiment 1 among the patent CN200510038276.X.The described water-soluble polyester of 28.5g and 14.25g fatty alcohol polyoxyethylene ether sulfate are placed the 1000ml beaker, 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 the 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 that configures to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa infiltrates modification, 45 ℃ of emulsion temperature, infiltrate 10min, the carbon fiber after the infiltration is dried in 160 ℃ electric heating constant-temperature blowing drying box, obtains a kind of modified carbon fiber.
Get 20 weight portion modified carbon fibers, the mixing of 80 weight portion polybutylene terephthalate (PBT)s-3, add double screw extruder, extruding pelletization makes polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in the table 1.
Following table 1 is the performance test table of modified carbon fiber and polyester complexes in above embodiment and the Comparative Examples.Wherein, the value of the specific insulation in the table 1 is less, illustrates that the electric conductivity of sample is better.
Table 1 specification
Above each embodiment 1-6 all can prepare carbon fiber modifying emulsion of the present invention, use the modified carbon fiber of this modified emulsion modification and add the polyester complexes of this modified carbon fiber.Comparative Examples 1-6 is the carbon fiber modifying emulsion that adopts surface modifier of the prior art to make, use the modified carbon fiber of this modified emulsion modification and add the polyester complexes of this modified carbon fiber.
In the table 1, from embodiment 1-6 and Comparative Examples 1-6 contrast, can find out, the modified carbon fiber that embodiment 1-6 makes is high than the surface resin content of the modified carbon fiber that Comparative Examples 1-6 makes, and the compatibility of itself and matrix resin is better.
In the table 1, embodiment 1-6 and Comparative Examples 1-6 contrast, can find out, compare with the polyester complexes that Comparative Examples makes, the polyester complexes that the present invention makes has good tensile strength, elongation at break, anti-interlaminar shear strength, flexural strength, impact strength and electric conductivity.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. carbon fiber surface modification emulsion comprises the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyester: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in the formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3Alkyl; R
3, R
4Represent independently of one another hydrogen, hydroxyl, C
1-C
18Alkyl, C
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3And R
4Be not hydrogen simultaneously.
2. carbon fiber surface modification emulsion is comprised of the component of following percetage by weight:
Surface modifier: 2-10wt%;
Polyester: 1-15wt%;
Emulsifying agent: 0.7-3wt%;
Organic solvent: 0-25wt%;
Water: 47-96.3wt%;
Wherein, described surface modifier is
(formula 1), in the formula 1, R
1, R
2, R
1', R
2' represent independently of one another hydrogen, hydroxyl or C
1-C
3Alkyl; R
3, R
4Represent independently of one another hydrogen, hydroxyl, C
1-C
18Alkyl, C
1-C
18Alkoxyl, contain the alkyl of silicon oxygen bond or contain the group of the G of functional group, the described G of functional group is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3And R
4Be not hydrogen simultaneously.
3. carbon fiber surface modification emulsion as claimed in claim 1 or 2, it is characterized in that: described polyester is aromatic polyester.
4. preparation method such as each described carbon fiber surface modification emulsion of claims 1 to 3 may further comprise the steps:
In proportion described surface modifier and described polyester are mixed, add stirring and emulsifying behind the organic solvent of described ratio, add after the emulsifying agent of described ratio and water stirs 1-3h, make the carbon fiber surface modification emulsion.
5. an application such as the emulsion modified modified carbon fiber that obtains of each described carbon fiber surface modification of claims 1 to 3.
6. modified carbon fiber as claimed in claim 5, it is characterized in that: the surface resin content of described modified carbon fiber is 0.1-5%.
7. the preparation method of a modified carbon fiber as claimed in claim 5 may further comprise the steps:
Carbon fiber inserted in the carbon fiber modifying emulsion infiltrate, take out, after the oven dry, obtain modified carbon fiber.
8. a polyester complexes comprises modified carbon fiber as claimed in claim 5 and polyester.
9. polyester complexes as claimed in claim 8 is characterized in that: the polyester in the described polyester complexes is identical with polyester in the described carbon fiber surface modification emulsion.
10. the application of a polyester complexes as claimed in claim 8 is characterized in that: described polyester complexes is applied to communications and transportation equipment, sports equipment, civil construction material, daily life and area of medical devices.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106382149A (en) * | 2016-08-31 | 2017-02-08 | 芜湖恒耀汽车零部件有限公司 | Preparing method for surface treating agent for carbon fiber arc plate for decoration tail pipe of automobile exhaust pipe |
| CN110982232A (en) * | 2019-12-17 | 2020-04-10 | 江苏裕兴薄膜科技股份有限公司 | Antistatic PET/nano carbon fiber composite material and preparation method thereof |
| CN112724607A (en) * | 2020-12-26 | 2021-04-30 | 广东九彩新材料有限公司 | High-content pigment carbon black-thermoplastic polyester master batch and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0284577A (en) * | 1988-07-29 | 1990-03-26 | Tonen Corp | Surface-treated carbon fiber |
| EP0965679A1 (en) * | 1998-01-06 | 1999-12-22 | Toray Industries, Inc. | Carbon fibers and process for the production thereof |
| JP2006124847A (en) * | 2004-10-26 | 2006-05-18 | Toho Tenax Co Ltd | Method for producing carbon fiber strand for reinforcement of thermoplastic resin |
| CN101074542A (en) * | 2006-05-21 | 2007-11-21 | 淄博矿业集团有限责任公司 | Method for modifying and producing waste asphalt bamboo fibre and its apparatus |
| CN101280475A (en) * | 2008-05-21 | 2008-10-08 | 威海东方润德新材料有限公司 | Lubricating antistatic high-performance oil for drawing production of carbon fibre |
| CN102206919A (en) * | 2011-04-22 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof |
| CN102229747A (en) * | 2011-06-08 | 2011-11-02 | 深圳市科聚新材料有限公司 | Carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN102505449A (en) * | 2011-11-05 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Electrochemical modification treatment method of carbon fiber surface |
| CN103046347A (en) * | 2012-12-24 | 2013-04-17 | 金发科技股份有限公司 | Sizing agent for emulsion type carbon fiber, preparation method and application thereof |
-
2013
- 2013-07-09 CN CN201310287764.9A patent/CN103321048B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0284577A (en) * | 1988-07-29 | 1990-03-26 | Tonen Corp | Surface-treated carbon fiber |
| EP0965679A1 (en) * | 1998-01-06 | 1999-12-22 | Toray Industries, Inc. | Carbon fibers and process for the production thereof |
| JP2006124847A (en) * | 2004-10-26 | 2006-05-18 | Toho Tenax Co Ltd | Method for producing carbon fiber strand for reinforcement of thermoplastic resin |
| CN101074542A (en) * | 2006-05-21 | 2007-11-21 | 淄博矿业集团有限责任公司 | Method for modifying and producing waste asphalt bamboo fibre and its apparatus |
| CN101280475A (en) * | 2008-05-21 | 2008-10-08 | 威海东方润德新材料有限公司 | Lubricating antistatic high-performance oil for drawing production of carbon fibre |
| CN102206919A (en) * | 2011-04-22 | 2011-10-05 | 中国科学院宁波材料技术与工程研究所 | Graphene modified carbon fiber emulsion sizing agent and preparation method thereof |
| CN102229747A (en) * | 2011-06-08 | 2011-11-02 | 深圳市科聚新材料有限公司 | Carbon fiber reinforced polyamide composite material and preparation method thereof |
| CN102505449A (en) * | 2011-11-05 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Electrochemical modification treatment method of carbon fiber surface |
| CN103046347A (en) * | 2012-12-24 | 2013-04-17 | 金发科技股份有限公司 | Sizing agent for emulsion type carbon fiber, preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106382149A (en) * | 2016-08-31 | 2017-02-08 | 芜湖恒耀汽车零部件有限公司 | Preparing method for surface treating agent for carbon fiber arc plate for decoration tail pipe of automobile exhaust pipe |
| CN106382149B (en) * | 2016-08-31 | 2019-09-10 | 深圳市平驰实业有限公司 | The preparation method of the decorative tail tube of the automobile exhaust pipe surface treating agent of carbon fiber arc panel |
| CN110982232A (en) * | 2019-12-17 | 2020-04-10 | 江苏裕兴薄膜科技股份有限公司 | Antistatic PET/nano carbon fiber composite material and preparation method thereof |
| CN112724607A (en) * | 2020-12-26 | 2021-04-30 | 广东九彩新材料有限公司 | High-content pigment carbon black-thermoplastic polyester master batch and preparation method thereof |
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|---|---|
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Effective date of registration: 20151214 Address after: 510000, Guangdong, Guangzhou new Guangzhou knowledge city nine Buddha building 18 new street, 210 rooms Patentee after: GUANGZHOU KINGFA CARBON FIBER NEW MATERIAL DEVELOPMENT CO., LTD. Address before: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 510663 Patentee before: Kingfa Technology Co., Ltd. |