CN103321048B - 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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- CN103321048B CN103321048B CN201310287764.9A CN201310287764A CN103321048B CN 103321048 B CN103321048 B CN 103321048B CN 201310287764 A CN201310287764 A CN 201310287764A CN 103321048 B CN103321048 B CN 103321048B
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- CWPGGYPOCMOJQK-UHFFFAOYSA-N CC(C)(C(C)(C)NCc1ccc(CCOC(C)=O)cc1O)NCc(ccc(CCOC(C)=O)c1)c1O Chemical compound CC(C)(C(C)(C)NCc1ccc(CCOC(C)=O)cc1O)NCc(ccc(CCOC(C)=O)c1)c1O CWPGGYPOCMOJQK-UHFFFAOYSA-N 0.000 description 1
- VGTQTKPDHUCMDH-MXBGMFSPSA-N CC[C@@H](C)O/C=C1/C(O)=C(CNC[I](C)N)C(Cl)=CC1 Chemical compound CC[C@@H](C)O/C=C1/C(O)=C(CNC[I](C)N)C(Cl)=CC1 VGTQTKPDHUCMDH-MXBGMFSPSA-N 0.000 description 1
- ZEFIJBGNBMFFDX-KHRKXTPDSA-N C[C@H](/C=C(\C=C(/C)\Cl)/O)O Chemical compound C[C@H](/C=C(\C=C(/C)\Cl)/O)O ZEFIJBGNBMFFDX-KHRKXTPDSA-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, particularly relate to a kind of carbon fiber surface modification emulsion and preparation method thereof, apply the standby polyester complexes of the carbon fiber of this carbon fiber surface modification emulsion, modified carbon fiber and polyester.
Background technology
Carbon fiber has outstanding mechanical property, widely uses carbon fiber in the composite and strengthens, and the interface performance improved in recent years between carbon fiber and matrix resin becomes the focus of research.Carbon fiber surface activity functional group is few, and the effective chemical bond formed with matrix resin compound tense is few, poor compatibility, causes easily forming brittle interface Rotating fields in carbon fibre composite.For improving the interface performance between carbon fiber and matrix resin, industrially usually oxidation processes is carried out to carbon fiber surface, 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 easily damage carbon fiber surface, destroy its mechanical property.In order to not damage the interface performance between fiber surface raising carbon fiber and matrix, Chinese patent application CN1944783A uses polymer graft technology to carbon nano-fiber surface modification, fiber surface is made to be rich in various active functional group, but, this method complex process, condition is harsh, and production run cost is high, limits suitability for industrialized production to a certain extent.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of carbon fiber surface modification emulsion improving carbon fiber surface activity.
In addition, the present invention also provides a kind of modified carbon fiber applying above-mentioned emulsion.
In addition, the present invention also provides a kind of polyester complexes comprising 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 formula 1, R
1, R
2, R
1', R
2' represent hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent hydrogen, hydroxyl, C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3and R
4be asynchronously hydrogen.
A kind of carbon fiber surface modification emulsion, is made up 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 formula 1, R
1, R
2, R
1', R
2' represent hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent hydrogen, hydroxyl, C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3and R
4be asynchronously hydrogen.
Wherein, in 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, be particularly preferably methyl or hydrogen.
Wherein, in described formula 1, R
3, R
4can be hydrogen, hydroxyl, C independently of one another
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from amino, amide groups or ester group, and R
3, R
4be asynchronously hydrogen.
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 the preparation method providing above-mentioned surface modifier, comprises the steps:
Component A is provided:
and B component:
wherein, R
1, R
2, R
1', R
2' represent hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent hydrogen, hydroxyl, C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3and R
4be asynchronously hydrogen;
According to the obtained described surface modifier of 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, and the reaction time is 1-8h;
Reduction reaction: after condensation reaction completes, adds excessive NaBH
4continue reaction with dimethyl sulfoxide (DMSO) (DMSO), 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, obtained described surface modifier.
Wherein, described component A can be ethylene diamine derivative.At least one in preferred ethylenediamine, 1,1-dimethyl-ethylenediamine, 1,2-dimethyl-ethylenediamine, hydroxy-ethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine.
Wherein, described polyester can be the polymer by dicarboxylic acids and dihydroxylic alcohols polycondensation.
Wherein, described dicarboxylic acids can be at least one in chain type saturated aliphatic dicarboxylic acid, chain type unsaturated aliphatic dicarboxylic acid, Cycloaliphatic dicarboxylic acids or aromatic binary carboxylic acid.
Wherein, described chain type saturated aliphatic dicarboxylic acid can be straight chain saturated aliphatic dicarboxylic acid or branch's chain type saturated aliphatic dicarboxylic acid of 2-22 for carbon number.At least one in the further preferred following material of described chain type saturated aliphatic dicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, dimethyl succinic acid, ethyl succinic acid, dimethyl malonic acid, Alpha-Methyl glutaric acid, Beta-methyl glutaric acid, 2, 4-diethyl glutarate, isopropyl-malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, decane dicarboxylic, undecane, dodecanedicarboxylic acid, tridecane dioctyl phthalate, tetradecane dioctyl phthalate, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, eicosane dicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid.
Wherein, described chain type unsaturated aliphatic dicarboxylic acid can be straight chain unsaturated aliphatic dicarboxylic acid or branch's chain type unsaturated aliphatic dicarboxylic acid of 4-22 for carbon number.At least one in the further preferred following material of described chain type saturated aliphatic dicarboxylic acid: maleic acid, fumaric acid, methyl-maleic acid, mesaconic acid, dodecenylsuccinic acid, 15 alkenyl succinic acids, octadecylene base succinic acid.
Wherein, described Cycloaliphatic dicarboxylic acids can be the Cycloaliphatic dicarboxylic acids of 7-14 for carbon number.At least one in the further preferred following material of described Cycloaliphatic dicarboxylic acids: 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-4,4'-dioctyl phthalate.
Wherein, described aromatic binary carboxylic acid can be the aromatic binary carboxylic acid of 8-14 for carbon number.At least one in the further preferred following material of described aromatic binary carboxylic acid: 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 cycloaliphatic diols.
Wherein, described aliphatic alkane dihydroxylic alcohols can be the aliphatic alkane dihydroxylic alcohols of 2-16 for carbon number.At least one in the further preferred following material of described aliphatic alkane dihydroxylic alcohols: ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6-hexylene glycol, ethohexadiol, decanediol, dodecanediol, hexadecane diol, neopentyl glycol, 2,2-diethyl-1,3-PD.
Wherein, described cycloaliphatic diols can be the cycloaliphatic diols of 4-16 for carbon number.At least one in the further preferred following material of described cycloaliphatic diols: Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, hydrogenated bisphenol A.
Wherein, the polymer that formed through polycondensation of described polyester optimization aromatic dicarboxylic acids and aliphatic alkane dihydroxylic alcohols.
Wherein, at least one in the preferred polybutylene terephthalate (PBT) of described polyester or polyethylene terephthalate.
Wherein, more than at least one selected in the group that described emulsifying agent can form for non-ionic surface active agent, anion surfactant, cationic surfactant and amphoteric surfactant.
Wherein, described emulsifying agent can be fatty alcohol-polyoxyethylene ether.
Wherein, described organic solvent can comprise at least one in phenol, tetrachloroethanes, 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 by described surface modifier and the mixing of described polyester, add stirring and emulsifying after the organic solvent of described ratio, add after the emulsifying agent of described ratio and water stirs 1-3h, obtained carbon fiber surface modification emulsion.
Wherein, described water is preferably distilled water.
Wherein, after adding organic solvent, the speed of stirring and emulsifying can be 12000r/min.
A kind ofly apply the emulsion modified modified carbon fiber obtained of above-mentioned carbon fiber surface modification.
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 preparation method for modified carbon fiber, comprises the following steps:
Carbon fiber is inserted in carbon fiber modifying emulsion and infiltrate, after taking-up, 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 by dicarboxylic acids and dihydroxylic alcohols polycondensation.
Wherein, described dicarboxylic acids can be at least one in chain type saturated aliphatic dicarboxylic acid, chain type unsaturated aliphatic dicarboxylic acid, Cycloaliphatic dicarboxylic acids or aromatic binary carboxylic acid.
Wherein, described chain type saturated aliphatic dicarboxylic acid can be straight chain saturated aliphatic dicarboxylic acid or branch's chain type saturated aliphatic dicarboxylic acid of 2-22 for carbon number.At least one in the further preferred following material of described chain type saturated aliphatic dicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, dimethyl succinic acid, ethyl succinic acid, dimethyl malonic acid, Alpha-Methyl glutaric acid, Beta-methyl glutaric acid, 2, 4-diethyl glutarate, isopropyl-malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, decane dicarboxylic, undecane, dodecanedicarboxylic acid, tridecane dioctyl phthalate, tetradecane dioctyl phthalate, hexadecane dicarboxylic acid, octadecane dicarboxylic acid, eicosane dicarboxylic acid, decyl succinic acid, dodecyl succinic acid, octadecyl succinic acid.
Wherein, described chain type unsaturated aliphatic dicarboxylic acid can be straight chain unsaturated aliphatic dicarboxylic acid or branch's chain type unsaturated aliphatic dicarboxylic acid of 4-22 for carbon number.At least one in the further preferred following material of described chain type saturated aliphatic dicarboxylic acid: maleic acid, fumaric acid, methyl-maleic acid, mesaconic acid, dodecenylsuccinic acid, 15 alkenyl succinic acids, octadecylene base succinic acid.
Wherein, described Cycloaliphatic dicarboxylic acids can be the Cycloaliphatic dicarboxylic acids of 7-14 for carbon number.At least one in the further preferred following material of described Cycloaliphatic dicarboxylic acids: 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-4,4'-dioctyl phthalate.
Wherein, described aromatic binary carboxylic acid can be the aromatic binary carboxylic acid of 8-14 for carbon number.At least one in the further preferred following material of described aromatic binary carboxylic acid: 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 cycloaliphatic diols.
Wherein, described aliphatic alkane dihydroxylic alcohols can be the aliphatic alkane dihydroxylic alcohols of 2-16 for carbon number.At least one in the further preferred following material of described aliphatic alkane dihydroxylic alcohols: ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,6-hexylene glycol, ethohexadiol, decanediol, dodecanediol, hexadecane diol, neopentyl glycol, 2,2-diethyl-1,3-PD.
Wherein, described cycloaliphatic diols can be the cycloaliphatic diols of 4-16 for carbon number.At least one in the further preferred following material of described cycloaliphatic diols: Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, hydrogenated bisphenol A.
Wherein, described polyester optimization aromatic polyester.
Wherein, at least one in the preferred polybutylene terephthalate (PBT) of described polyester or polyethylene terephthalate.
Wherein, in described polyester complexes, the content of described modified carbon fiber is preferably more than the 35wt% of described polyester complexes.
Wherein, the polyester in described polyester complexes is preferably identical with the polyester in described carbon fiber surface modification emulsion.
Wherein, described polyester complexes can also comprise processing aid further, and the content of described processing aid is no more than the 10wt% of described polyester complexes.
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 polyester complexes, comprises the following steps:
In proportion by described modified carbon fiber, polyester, processing aid mixing, add extruding pelletization in extruder, obtained 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 hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl or the group containing following functional group: hydroxyl, amino, halogen, hydrogen, amide groups, ester group or siloxy, and R
3, R
4be asynchronously hydrogen; Obtained carbon fiber surface modification emulsion, described modified emulsion is used for modified carbon fiber, little to the surface damage of carbon fiber, little to the Effect on Mechanical Properties of carbon fiber, make the modified carbon fiber obtained have good mechanical property and good with the compatibility of polyester, and the polyester complexes 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 the preparation method of carbon fiber surface modification emulsion of the present invention, modified carbon fiber, polyester complexes is simple.
Detailed description of the invention
Below in conjunction with some detailed description of the invention, carbon fiber surface modification emulsion of the present invention and preparation method thereof and its modified carbon fiber prepared, polyester complexes 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, have testing according to standard batten of testing standard:
Fiber surface resin content calculates: platinum crucible is placed in baking oven, and oven temperature controls within the scope of 120 DEG C ± 3 DEG C.With clamp, platinum crucible clamping is placed in drier and is cooled to room temperature.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 in Muffle furnace together with sample, nitrogen protection, muffle furnace controls 750 DEG C, and 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 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, pendulum radial-boom impact tester is tested, 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 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 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: the unsaturated polyester resin made for phthalic anhydride and standard dyadic alcohol, Shanghai Xin Tianhe Resin Co., Ltd., trade mark DS-199.
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 manufactures.
The bisphenol A type epoxy resin that one-side ends is acrylic 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
1 is added, 1,2 in the polymeric kettle of the preparation of surface modifier: 1.5L; 2-tetramethyl-1; 2-diamines 0.1mol, adds ethanol 300mL, dissolves; drip the ethanolic solution 300mL containing 0.2mol1-formoxyl-2-hydroxyl-4-benzyl carbinol ethyl ester again; control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution; control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
By 40g polyethylene terephthalate-1 and 9.5g surface modifier
be placed in 1000mL beaker, add 100mlDMSO, 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 1h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, infiltrate 10min, 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, and this modified carbon fiber surface is containing one deck polyethylene terephthalate-1 resin.
Get 15 part by weight modified carbon fibers, 85 weight portion polyethylene terephthalate-1 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Embodiment 2
1-ethyl-1 is added in the polymeric kettle of the preparation of surface modifier: 1.5L, 2-diamines 0.1mol, add ethanol 300mL, dissolve, then drip the ethanolic solution 300mL containing 0.2mol6-chloro-4-propoxyl group salicylide, control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution, control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
By 71.25g unsaturated polyester (UP)-1 and 47.5g surface modifier
be placed in 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-20,9.5g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 unsaturated polyester (UP)-1.
Get 35 part by weight modified carbon fibers, 65 weight portion polyethylene terephthalate-2 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Embodiment 3
1 is added in the polymeric kettle of the preparation of surface modifier: 1.5L; 2-dimethyl-1; 2-diamines 0.1mol, adds ethanol 300mL, dissolves; drip the ethanolic solution 300mL containing 0.2mol3-formoxyl-4-hydroxyl-hydrocinnamamide again; control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution; control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
By 4.75g unsaturated polyester (UP)-2 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-20,2.375g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2.5h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 unsaturated polyester (UP)-2.
Get 37 part by weight modified carbon fibers, 63 weight portion polybutylene terephthalate (PBT)-1 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Embodiment 4
Add 1,2-dimethyl-1,2-diamines 0.1mol in the polymeric kettle of the preparation of surface modifier: 1.5L, add ethanol 300mL, dissolve, then drip containing 0.2mol
ethanolic solution 300mL, control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution, control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
By 57g unsaturated polyester (UP)-3 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-20,4.75g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 3h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 unsaturated polyester (UP)-3 resin.
Get 8 part by weight modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Embodiment 5
1 is added in the polymeric kettle of the preparation of surface modifier: 1.5L; 1-dimethyl-1; 2-diamines 0.1mol, adds ethanol 300mL, dissolves; drip the ethanolic solution 300mL containing 0.2mol5-formoxyl-6-Hydroxy-phenyl-acetic acid methyl esters again; control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution; control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
By 28.5g polybutylene terephthalate (PBT)-2 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 T20, be added in system, stir 1.5h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 polybutylene terephthalate (PBT)-2 resin.
Get 13 part by weight modified carbon fibers, 10 parts by weight of carbon black per, 77 weight portion polybutylene terephthalate (PBT)-2 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Embodiment 6
1-hydroxyl-1 is added in the polymeric kettle of the preparation of surface modifier: 1.5L, 2-diamines 0.1mol, add ethanol 300mL, dissolve, then drip the ethanolic solution 300mL containing 0.2mol5-hydroxyl-3-n-pro-pyl salicylide, control polymeric kettle temperature 55 DEG C, after backflow 6h, add 300mLDMSO solution, control polymeric kettle temperature 0 DEG C, then add the NaBH of 4 equivalents
4, stir, until reactant liquor is colourless, react complete.500mL water is added, separatory to reaction system.Water layer CH
2cl
2extraction, merges organic layer, uses anhydrous Na
2sO
4drying, leaves standstill, and filter, solution revolves steaming, obtains a kind of surface modifier
A kind of water-soluble polyester is prepared according to the embodiment 1 in patent CN200510038276.X.By water-soluble polyester 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.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 " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, intensity 3.5GPa, the carbon fiber surface of modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 water-soluble polyester resin described in one deck.
Get 20 part by weight modified carbon fibers, 80 weight portion polybutylene terephthalate (PBT)-3 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 1
40g polyethylene terephthalate-1 and 9.5g alkyl dimethyl betaine amphoteric surfactant are 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, 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, be added in system, stir 1h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 15 part by weight modified carbon fibers, 85 weight portion polyethylene terephthalate-1 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 2
71.25g unsaturated polyester (UP)-1 and 47.5g phosphite are placed in 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-20,9.5g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 part by weight modified carbon fibers, 65 weight portion polyethylene terephthalate-2 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 3
4.75g unsaturated polyester (UP)-2 and the acrylic modified bisphenol A type epoxy resin of 9.5g one-side ends are placed in 1000ml beaker, and 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-20,2.375g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 2.5h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 part by weight modified carbon fibers, 63 weight portion polybutylene terephthalate (PBT)-1 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 4
57g unsaturated polyester (UP)-3 and 23.75g Cocoamidopropyl betaine are 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-20,4.75g weight ratio is the emulsifying agent s-60 of 1.27:1 and the mixture of emulsifying agent T-20, be added in system, stir 3h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 part by weight modified carbon fibers, 3 weight portion antioxidant 1010s, 89 weight portion polybutylene terephthalate (PBT)s-2, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 5
28.5g polybutylene terephthalate (PBT)-2 and the acrylic modified bisphenol A type epoxy resin of 14.25g one-side ends are 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 T20, be added in system, stir 1.5h, finally obtain the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 13 part by weight modified carbon fibers, 10 parts by weight of carbon black per, 77 weight portion polybutylene terephthalate (PBT)-2 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Comparative example 6
A kind of water-soluble polyester is prepared according to the embodiment 1 in patent CN200510038276.X.Water-soluble polyester described in 28.5g and 14.25g fatty alcohol polyoxyethylene ether sulfate are placed in 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 system, stirs 1h, finally obtains the white " milky " liquid of desired concn, be carbon fiber modifying emulsion of the present invention.
Utilize the above-mentioned emulsion configured to 12k, the carbon fiber surface of intensity 3.5GPa, modulus 230GPa carries out infiltration modification, emulsion temperature 45 DEG C, 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 20 part by weight modified carbon fibers, 80 weight portion polybutylene terephthalate (PBT)-3 mixing, add double screw extruder, extruding pelletization, obtained polyester complexes.
Modified carbon fiber, polyester complexes are carried out performance test, and be recorded in table 1.
Following table 1 is the performance test table of modified carbon fiber and polyester complexes in above embodiment and comparative example.Wherein, the value of the specific insulation in table 1 is less, illustrates that the electric conductivity of sample is better.
Table 1 description
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 polyester complexes of this modified carbon fiber above.Comparative example 1-6 be adopt surface modifier of the prior art obtain carbon fiber modifying emulsion, use the modified carbon fiber of this modified emulsion modification and add the polyester complexes of this modified carbon fiber.
In table 1, contrast from embodiment 1-6 and comparative example 1-6, can find out, the surface resin content of the modified carbon fiber that the modified carbon fiber that embodiment 1-6 obtains obtains compared with comparative example 1-6 is high, and the compatibility of itself and matrix resin is better.
In table 1, embodiment 1-6 and comparative example 1-6 contrasts, can find out, compared with the polyester complexes that comparative example is obtained, the polyester complexes that the present invention obtains 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 the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; 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%;
Polyester: 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 hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent hydrogen, hydroxyl, C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3and R
4be asynchronously hydrogen.
2. a carbon fiber surface modification emulsion, is made up 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 formula 1, R
1, R
2, R
1', R
2' represent hydrogen, hydroxyl or C independently of one another
1-C
3alkyl; R
3, R
4represent hydrogen, hydroxyl, C independently of one another
1-C
18alkyl, C
1-C
18alkoxyl, the alkyl containing silicon oxygen bond or the group containing functional group G, described functional group G is selected from hydroxyl, amino, halogen, amide groups or ester group, and R
3and R
4be asynchronously hydrogen.
3. carbon fiber surface modification emulsion as claimed in claim 1 or 2, is characterized in that: described polyester is aromatic polyester.
4. a preparation method for the carbon fiber surface modification emulsion as described in any one of claims 1 to 3, comprises the following steps:
In proportion by described surface modifier and the mixing of described polyester, add stirring and emulsifying after the organic solvent of described ratio, add after the emulsifying agent of described ratio and water stirs 1-3h, obtained carbon fiber surface modification emulsion.
5. the carbon fiber surface modification emulsion modified modified carbon fiber that obtain of an application as described in any one of claims 1 to 3.
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 infiltrate, after taking-up, oven dry, obtain modified carbon fiber.
8. a polyester complexes, comprises modified carbon fiber as claimed in claim 5 and polyester.
9. a polyester complexes as claimed in claim 8, is characterized in that: the polyester in described polyester complexes is identical with the polyester in described carbon fiber surface modification emulsion.
10. an application for 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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| CN110982232B (en) * | 2019-12-17 | 2021-08-17 | 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 |
| CN112724607B (en) * | 2020-12-26 | 2021-08-24 | 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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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. |